JPH11174698A - Electrophotographic photoreceptor and electrophotographic device using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an excellently durable electrophotographic photoreceptor, having high abrasion resistance, holding satisfactory durability if it is used in a contact-charging mode, having high folding strength in a coating film on a surface of the photoreceptor, and free from mechanical deterioration if it is repeatedly used as a belt-shaped photoreceptor. SOLUTION: A polyester resin obtained by polymerizing a dicarboxyl acid expressed by an expression or its ester-forming derivative with a diole, is used as a photosensitive-layer binding resin in an electrophotographic photoreceptor made up by providing the photosensitive layer on a conductive support body. In the formula, R1 stands for H, an alkyl radical of 1 to 4C, or an aryl radical of 6 to 10C, R2 and R3 each for a radical selected from among an alkylene radical that may be branched, an aryl-substituted alkylene radical or an alkylene-arylene-alkylene radical, each of 1 to 10C (where, for the aryl radical, an alkyl radical may be substituted).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member, and more particularly, to an electrophotographic photosensitive member having excellent electrophotographic characteristics by using a polyester polymer having a specific structure as a binder resin, and an electrophotographic photosensitive member having the same. The present invention relates to an electrophotographic apparatus using a photoconductor.

[0002]

2. Description of the Related Art In recent years, electrophotographic photosensitive members have been widely used in the fields of copiers, laser beam printers, and the like because high-quality images can be obtained at high speed.
The electrophotographic photoreceptor used in these electrophotographic devices is more manufacturable and more disposable than conventional ones using inorganic photoconductive materials such as selenium, selenium-tellurium alloy, selenium-arsenic alloy, and cadmium sulfide. Electrophotographic photoreceptors using excellent and inexpensive organic photoconductive materials have become the mainstream. Above all, a function-separated-type laminated organic photoconductor in which a charge generation layer that generates charges by exposure and a charge transport layer that transports charges are laminated has excellent electrophotographic properties such as electrical sensitivity, chargeability, and repetition stability. Since then, many research and development have been carried out, and as a result, various proposals have been made,
It has already been put to practical use.

[0003]

However, in general, the organic photoreceptor is inferior in mechanical strength to the inorganic photoreceptor, and when subjected to a mechanical external force such as a cleaning blade, a developing brush and paper, scratches and scratches may occur. Wear tends to occur, and when these occur, the electrical characteristics of the photoreceptor are degraded, and there is a problem that the life of the photoreceptor is short. further,
In recent years, from the viewpoint of ecology, a contact charging type electrophotographic system has been adopted. However, in this system, abrasion of a photoreceptor is significantly increased as compared with a normal charging method using a corotron. Is an even more serious problem. In particular, as the wear of the photoreceptor surface progresses, the sensitivity of the photoreceptor decreases, so that the obtained copied image fogs or the image density decreases with a decrease in the charging potential. Therefore, development of a surface layer material for forming a photosensitive layer having sufficient durability in an organic photoreceptor is required.

A flexible electrophotographic photosensitive member having a photosensitive layer coated on a film of polyethylene terephthalate or the like, on which a conductive layer is formed by a method such as vapor deposition, is processed into a belt shape and repeatedly uses an electrophotographic apparatus. Therefore, there is an advantage that the degree of freedom of the shape of the electrophotographic apparatus can be increased. However, the photoreceptor used therein is required to be able to sufficiently follow a flexible movement, and in order to satisfy this requirement, for example, a photoreceptor using various polycarbonate resins as a binder resin for a surface layer has been proposed. (Japanese Patent Application Laid-Open No. Sho 60-172444, Japanese Patent Application Laid-Open No. Sho 62-24)
7374, JP-A-63-148263)
However, when these are repeatedly rotated for a long period of time in a belt driving device in a copying machine, cracks are generated in the photosensitive layer, and the problem that cracks appear on a copy image remains.

[0005] The present invention has been made in view of the above situation, and has as its object to solve the problems in the prior art. That is, an object of the present invention is to provide an electrophotographic photoreceptor that has high abrasion resistance, has high durability even when using a process such as a contact charging device, and maintains excellent electrical characteristics. It is in. Another object of the present invention is that the coating film on the surface of the photoreceptor has high flexibility, and even when used repeatedly as a belt-shaped photoreceptor, there is no occurrence of defects such as cracks in the coating film, and it is preferable. An object of the present invention is to provide an electrophotographic photoreceptor having excellent durability by having excellent abrasion resistance.

[0006]

Means for Solving the Problems The present inventors have made intensive studies on the above-mentioned problems of the electrophotographic photosensitive member, and as a result,
By using a polyester polymer obtained by using a dicarboxylic acid having a specific chemical structure or an ester thereof as a binder resin for a photosensitive layer, a photosensitive member having excellent durability and electrical properties related to mechanical strength can be obtained. In addition, the drum-shaped photoreceptor and the belt-shaped photoreceptor using the polyester polymer as a binder resin for the photosensitive layer can be used for a long period of time in an electrophotographic apparatus. The inventors have found that the problem of deterioration can be solved, and have completed the present invention.

That is, the present invention relates to an electrophotographic photoreceptor comprising a photosensitive layer provided on a conductive support, wherein the photosensitive layer has a dicarboxylic acid represented by the following general formula (I) or an ester-forming dicarboxylic acid thereof. It is characterized by containing a polyester resin obtained by polymerization of a derivative and a diol.

Embedded image [Wherein, R ₁ represents a hydrogen atom, an alkyl group or an aryl group having 6 to 10 carbon atoms having 1 to 4 carbon atoms, R ₂ and R
₃ is independently an alkylene group having 1 to 10 carbon atoms which may be branched, an aryl-substituted alkylene group or an alkylene arylene alkylene group (however, the aryl group may be substituted with an alkyl group). Represents a group selected from Further, the present invention provides an electrophotographic photoreceptor comprising a photosensitive layer provided on a conductive support, wherein the photosensitive layer contains a dicarboxylic acid group containing the dicarboxylic acid represented by the general formula (I) or a dicarboxylic acid group containing the same. And a polyester resin obtained by polymerization of an ester-forming derivative of the above with a diol.

In the present invention, the polyester resin used in the photosensitive layer is preferably such that the dicarboxylic acid represented by the general formula (I) or its ester-forming derivative accounts for at least 30 mol% of the total dicarboxylic acid or its ester-forming derivative component. Are preferably included.

In the above photosensitive layer, as a charge transport material,
It is preferable to use a benzidine compound represented by the following general formula (II).

Embedded image (Wherein, R ₄ and R ₅ may be the same or different and each represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom; R _{6 to} R ₉ may be the same or different; , An alkyl group, an alkoxy group, a halogen atom or a substituted amino group, and k to n are each 1 or 2.)

In the photosensitive layer, a triarylamine compound represented by the following general formula (III) is preferably used as a charge transporting material.

Embedded image (Wherein, R ₁₀ and R ₁₁ may be the same or different, represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, p and q is 1 or 2. Further, R ₁₂
Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or 6 to
And 12 aryl groups. )

In order to adapt the electrophotographic photosensitive member of the present invention to a high-speed electrophotographic apparatus requiring high durability,
At least 7.4 °, 16.6 °, 25.5 °, at the Bragg angle (2θ ± 0.2 °) of the X-ray diffraction spectrum using Cukα ray as the charge generating material of the photosensitive layer.
Chlorgallium phthalocyanine having a diffraction peak at 28.3 °, at least 7.5 °, 9.9 °, 1
2.5 °, 16.3 °, 18.6 °, 25.1 °, 2
Hydroxygallium phthalocyanine having a diffraction peak at 8.1 ° and at least 9.5 °, 11.7
It is preferable to contain at least one phthalocyanine compound selected from titanyl phthalocyanines having diffraction peaks at the positions of °, 15.0 °, 24.1 °, and 27.3 °. The electrophotographic photoreceptor of the present invention can be used for an electrophotographic apparatus charged by contact charging.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. 1 to 7 are schematic cross-sectional views showing the layer structure of the electrophotographic photosensitive member according to the present invention. 1 to 4 show the case where the photosensitive layer has a laminated structure.
In the above, the charge generation layer 1 is provided on the conductive support 3, and the charge transport layer 2 is provided thereon. In FIG. 2, an undercoat layer 4 is further provided between the conductive support 3 and the charge generation layer 1. Further, in FIG. 3, a protective layer 5 is further provided on the surface of the layer configuration of FIG. Further, in FIG. 4, both the undercoat layer 4 and the protective layer 5 are provided on the layer configuration of FIG. 5 to 7 each show a case where the photosensitive layer has a single-layer structure. In FIG. 5, the photosensitive layer 6 is provided on the conductive support 3, and in FIG. , FIG.
Further, an undercoat layer 4 is provided between the conductive support 3 and the photosensitive layer 6 in the above-described layer structure. Further, in FIG. 7, both the undercoat layer 4 and the protective layer 5 are provided in the layer configuration of FIG.

Hereinafter, each layer of the electrophotographic photosensitive member according to the present invention will be described in detail. As the conductive support, aluminum, copper, iron, zinc, nickel or SUS stainless steel or other metal drum or metal sheet, paper, plastic or glass on aluminum, copper, gold,
A metal such as silver, platinum, palladium, titanium, nickel-chromium, stainless steel, copper-indium, or a conductive metal compound such as indium oxide or tin oxide is deposited, a metal foil is laminated, or carbon is deposited. Black, indium oxide, tin oxide-antimony oxide powder, metal powder, copper iodide, and the like are dispersed in a binder resin, and a known drum-shaped, sheet-shaped, plate-shaped, or the like, which has been subjected to a conductive treatment by coating the same. Of an appropriate shape is used.

When a metal pipe is used as a conductive support, it is necessary to perform mirror-cutting beforehand even if the surface is bare.
Processing such as etching, anodizing, rough cutting, centerless grinding, sand blasting, and wet honing may be performed. In particular, those obtained by roughening the surface of the base material by surface treatment are preferable because grain-like density unevenness due to interference light in the photoconductor generated when a coherent light source such as a laser beam is used can be prevented. .

As the undercoat layer, acetal resins such as polyvinyl butyral, polyvinyl alcohol resin, casein, polyamide resin, cellulose resin, gelatin, polyurethane resin, polyester resin, methacryl resin,
In addition to high molecular compounds such as acrylic resin, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, and melamine resin, zirconium and titanium , An organometallic compound containing aluminum, manganese, silicon atoms and the like. These compounds can be used alone or as a mixture or a polycondensate of a plurality of compounds. Among them, those containing organometallic compounds containing zirconium or silicon,
It is excellent in performance such as low residual potential and little change in potential due to environment, and little change in potential due to repeated use.

Examples of the silicon compound used for the undercoat layer include vinyltrimethoxysilane, γ-methacryloxypropyl-tris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ
-Aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethylmethoxysilane, N, N-bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxy Examples include silane. Further, more preferably used, vinyl triethoxysilane,
Vinyltris (2-methoxyethoxysilane), 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N
-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane Examples include silane coupling agents such as methoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-chloropropyltrimethoxysilane. Further, as the organic zirconium compound, for example, zirconium butoxide, ethyl zirconium acetoacetate, zirconium triethanolamine, acetylacetonate zirconium butoxide, ethyl zirconium butoxide acetoacetate, zirconium acetate, zirconium oxalate, zirconium lactate, zirconium phosphonate, octanoic acid Zirconium, zirconium naphthenate, zirconium laurate, zirconium stearate, zirconium isostearate, zirconium butoxide methacrylate, zirconium butoxide stearate, zirconium butoxide isostearate, and the like are used. Examples of the organic titanium compound include tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, titanium acetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, and titanium lactate ammonium salt , Titanium lactate, titanium lactate ethyl ester, titanium triethanol aminate, polyhydroxytitanium stearate and the like are used. As the organic aluminum compound, for example, aluminum isopropylate, monobutoxyaluminum diisopropylate, aluminum butyrate, diethylacetoacetate aluminum diisopropylate, aluminum tris (ethylacetoacetate) and the like are used.

In the undercoat layer, various organic fine powders or inorganic fine powders can be mixed for the purpose of improving electric properties and light scattering properties. Specifically, titanium oxide, zinc oxide, zinc white, zinc sulfide, lead white, white pigments such as lithopone, alumina, calcium carbonate, inorganic pigments as constitutional pigments such as barium sulfate, Teflon resin particles, benzoguanamine resin particles, It is preferable to use styrene resin particles and the like. These fine powders are added as needed, and the amount of addition is 10 to 80% by weight, more preferably 30 to 7% by weight, based on the solid content of the undercoat layer.
0% by weight, and the particle size is 0.01 to 2 μm. The thickness of the undercoat layer is 0.1 to 10 μm
Is desirable. In the formation of the undercoat layer coating liquid, when the added fine powder is mixed, it is added to a solution in which a resin component is dissolved to perform a dispersion treatment. In order to disperse the added fine powder in the resin, a method such as a roll mill, a ball mill, a vibration ball mill, an attritor, a sand mill, a colloid mill, and a paint shaker can be used.

The photosensitive layer in the present invention may have a single-layer structure or a laminated structure in which a charge generation layer and a charge transport layer are functionally separated. In the case of a stacked structure, any of the charge generation layer and the charge transport layer may be formed in an upper layer. In the present invention, as a binder resin for the photosensitive layer, a polyester resin obtained by polymerizing a dicarboxylic acid or an ester-forming derivative thereof represented by the following general formula (I) with a diol, or a resin represented by the following general formula (I) A polyester resin obtained by polymerization of a dicarboxylic acid or an ester-forming derivative thereof and another dicarboxylic acid or an ester-forming derivative thereof (hereinafter referred to as “other dicarboxylic acid raw materials”) with a diol is used. You.

[0019]

Embedded image In the general formula (I), R ₁ is a hydrogen atom or has 1 to 4 carbon atoms selected from methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl and t-butyl.
Or an aryl group having 6 to 10 carbon atoms such as phenyl and naphthyl. Also, R ₂ and R
₃ may be the same or different and each is independently a chained alkylene group having 1 to 10 carbon atoms, which may be branched, or an alkylene having an aryl group such as phenyl in the side chain. Or an arylenealkylene group, the aryl group including those substituted with an alkyl group. The dicarboxylic acid represented by the general formula (I) or the ester-forming derivative thereof does not have a carbonyl group directly bonded to an aromatic ring, and thus can improve the poor electric characteristics specific to polyester. Yes,
This is the main part of the present invention.

Tables 1 to 4 show specific examples of the dicarboxylic acid represented by the general formula (I) or an ester-forming derivative thereof used in the production of the polyester resin used in the present invention.

[Table 1]

[0021]

[Table 2]

[0022]

[Table 3]

[0023]

[Table 4]

In the present invention, the polyester resin used as the binder resin in the photosensitive layer is obtained by polymerization of a dicarboxylic acid represented by the general formula (I) or an ester-forming derivative thereof and other dicarboxylic acid raw materials with a diol. When a polyester resin is used, the proportion of the dicarboxylic acid or its ester-forming derivative component represented by the general formula (I) to the total dicarboxylic acid or its ester-forming derivative in the polyester resin is 30 mol% or more. Occupied is preferred, more preferably 50% or more. With a polyester resin having this ratio of less than 30%, it is difficult to achieve both high abrasion resistance and excellent electrical characteristics of the electrophotographic photosensitive member.

In the production of the polyester resin used in the present invention, "other dicarboxylic acid raw materials" used in combination with the dicarboxylic acid represented by the general formula (I) or an ester-forming derivative thereof include, for example, succinic acid, adipine acid,
Maleic acid, sebacic acid, aliphatic dicarboxylic acids such as decamethylene dicarboxylic acid, terephthalic acid, isophthalic acid,
2,6-, 1,6-, 1,7-, 1,4-, 1,5-,
2,3-, 2,7-naphthalenedicarboxylic acid, 4,4 '
-, 3,3'-, 2,2'-, 4,3'-, 4,2'-
Examples thereof include aromatic dicarboxylic acids such as biphenyldicarboxylic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and ester-forming derivatives thereof, and one or more of these are used.

In the present invention, the diol used for producing the polyester resin may be, for example, ethylene glycol
Aliphatic diols such as 1,4-butanediol,
Alicyclic diols such as 6-cyclohexanedimethanol and tricyclodecanedimethylol, 2,6-, 2,3-,
2,7-, 1,5-, 1,6-, 1,7-bis (hydroxyethoxy) naphthalene, 4,4-, 4,3'-,
Aromatic diols such as 4,2'-bishydroxyethoxybiphenylene, 1,1'-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane, 2,2'-bis [4- (2-hydroxyethoxy) phenyl ] Propane, 9,9'-bis [4- (2-hydroxyethoxy)
Bisphenol derivative diols such as [phenyl] fluorene, etc., and one or more of these are used. Among them, aromatic diols and bisphenol derivative diols are suitable for producing polyester resins having high abrasion resistance.

In the present invention, the polyester resin obtained by polymerization of the above-mentioned dicarboxylic acid or its ester-forming derivative with a diol may be used in any of a photosensitive layer having a single-layer structure and a charge generation layer and a charge transport layer having a multilayer structure. Although it can be used as a binder resin for the layer of
It is preferably used as a binder resin for the charge transport layer. In particular, when the photoreceptor is used for a photoreceptor having a structure in which the charge transport layer is a surface layer, the abrasion resistance of the photoreceptor can be improved and surface scratches can be reduced. When present at any position in the photosensitive layer, it contributes to the improvement of the mechanical life related to flexibility, and can form an image with excellent image quality while maintaining excellent electrical characteristics.

The binder resin used in the photosensitive layer of the present invention may further include, for the purpose of improving the compatibility of the charge transporting material, the solubility in a solvent, and the film forming property, with the polyester resin described above. Resins can be mixed and used. Examples of resins that can be mixed include bisphenol (A), bisphenol (Z), bisphenol (C), bisphenol (TP), and bisphenol (B
Various polycarbonate resins including P), other general polyester resins, polyarylate resins, methacrylic resins, acrylic resins, polyvinyl chloride resins, polystyrene resins, polyvinyl acetate resins, styrene-butadiene copolymers, vinylidene chloride-acrylics Nitrile copolymer, vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N-vinylcarbazole, and the like.

The molecular weight of the polyester resin used in the present invention is appropriately selected depending on the film thickness of the photosensitive layer, film forming conditions such as a solvent, and mechanical properties such as abrasion resistance. It is in the range of 200,000 to 200,000, preferably 40,000 to 100,000. Weight average molecular weight of 3
If it is less than 10,000, the abrasion resistance is reduced due to the low mechanical strength of the resin. On the other hand, if it exceeds 200,000, the function of the charge transport material is reduced, and not only the electrical sensitivity is reduced, but also the film formability is deteriorated and the surface properties of the photoreceptor are deteriorated.

The charge generating layer is formed by forming a charge generating substance by vacuum evaporation or by dispersing and applying the charge generating substance together with an organic solvent and a binder resin. As the charge generating material, amorphous selenium, crystalline selenium, selenium-tellurium alloy, selenium-arsenic alloy, other selenium compounds and selenium alloys, zinc oxide, inorganic photoconductors such as titanium oxide,
Various phthalocyanine pigments such as metal-free phthalocyanine, titanyl phthalocyanine, copper phthalocyanine, tin phthalocyanine, and gallium phthalocyanine;
Various organic pigments and dyes such as an anthrone-based, perylene-based, azo-based, anthraquinone-based, pyrene-based, pyrylium salt, and thiapyrylium salt are used. In addition, these organic pigments generally have several types of crystal forms. Particularly, in the case of phthalocyanine pigments, various crystal types such as α-type and β-type are known. Any crystal type can be used as long as the pigment can be obtained.

In the present invention, in connection with the polyester resin used for the photosensitive layer, the following phthalocyanine compounds are mentioned as charge generation materials which can obtain particularly excellent performance. (A) At least 7.4 in the Bragg angle (2θ ± 0.2 °) of the X-ray diffraction spectrum using Cuka radiation.
Chlorogallium phthalocyanine having diffraction peaks at the positions of °, 16.6 °, 25.5 ° and 28.3 ° (b) In the Bragg angle (2θ ± 0.2 °) of the X-ray diffraction spectrum using Cukα ray , At least 7.5
°, 9.9 °, 12.5 °, 16.3 °, 18.6 °,
Hydroxygallium phthalocyanine having diffraction peaks at 25.1 ° and 28.1 (c) At least 9.5 in the Bragg angle (2θ ± 0.2 °) of the X-ray diffraction spectrum using Cukα ray.
°, 11.7 °, 15.0 °, 24.1 °, 27.3 °
Titanyl phthalocyanine with diffraction peak at position

Examples of the binder resin in the charge generation layer include the following in addition to the polyester resin described above. Polyester resin, polyarylate resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polystyrene resin, polyvinyl acetate obtained using a raw material other than the dicarboxylic acid represented by the general formula (I) or an ester-forming derivative thereof. Resin, styrene
Butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N-vinyl Carbazole and the like, and these binder resins can be used alone or in combination of two or more. The mixing ratio (weight ratio) of the charge generation material and the binder resin is preferably in the range of 10: 1 to 1:10. The thickness of the charge generation layer is generally 0.0
1 to 5 μm, preferably 0.05 to 2.0 μm.
It is set in the range of μm.

To disperse the charge generating material in the resin,
A method such as a roll mill, a ball mill, a vibrating ball mill, an attritor, a dyno mill, a sand mill, a colloid mill, and a homogenizer is used.

Examples of the charge transporting material used in the charge transporting layer include the following. 2,5-bis (p
Oxadiazole derivatives such as -diethylaminophenyl) -1,3,4-oxadiazole, 1,3,5-triphenyl-pyrazoline, 1- [pyridyl- (2)]-3
Pyrazoline derivatives such as-(p-diethylaminostyryl) -5- (p-diethylaminostyryl) pyrazoline;
Triphenylamine, tri (P-methyl) phenylamine, N, N-bis (3,4-dimethylphenyl) biphenyl-4-amine, dibenzylaniline, 9,9-dimethyl-N, N-di (p- Aromatic tertiary amino compounds such as tolyl) fluorenone-2-amine, N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,
1-biphenyl] -4,4'-diamine
Grade diamino compound, 3- (4'dimethylaminophenyl) -5,6-di (4'-methoxyphenyl) -1,
1,2,4-triazine derivatives such as 2,4-triazine, 4-diethylaminobenzaldehyde-1,1-diphenylhydrazone, 4-diphenylaminobenzaldehyde-1,1-diphenylhydrazone, [p- (diethylamino) phenyl] ( Hydrazone derivatives such as 1-naphthyl) phenylhydrazone, quinazoline derivatives such as 2-phenyl-4-styryl-quinazoline, benzofuran derivatives such as 6-hydroxy-2,3-di (p-methoxyphenyl) -benzofuran, p- ( Hole transporting substances such as α-stilbene derivatives such as 2,2-diphenylvinyl) -N, N-diphenylaniline, enamine derivatives, carbazole derivatives such as N-ethylcarbazole, poly-N-vinylcarbazole and derivatives thereof, chloranil , Bromoanil, Ant Quinone compounds quinone such as tetracyanoquinodimethane compounds, trinitrofluorenone, 2,4,5,7-tetranitro-9
Fluorenone compounds such as fluorenone, 2- (4-biphenyl) -5- (4-t-butylphenyl) -1,3,3
4-oxadiazole or 2,5-bis (4-naphthyl)
-1,3,4-oxadiazole, 2,5-bis (4-
Oxadiazole compounds such as diethylaminophenyl) -1,3,4-oxadiazole, xanthone compounds, thiophene compounds, 3,3 ′, 5,5′-tetra-
Examples thereof include an electron transporting substance such as a diphenoquinone compound such as t-butyl diphenoquinone, and a polymer having a group consisting of the compound shown above in a main chain or a side chain. These charge transport materials can be used alone or in combination of two or more.

In the laminated photoreceptor, the charging polarity of the photoreceptor varies depending on the charge transporting polarity of the charge transporting material. That is, when a hole transport material is used as the charge transport material, the photoreceptor is used in a negative charge, and when an electron transport material is used as the charge transport material, the photoreceptor is used in a positive charge. Furthermore, when both are used in combination, a photoreceptor having both charging polarities is possible.

In the present invention, as the charge transporting material which can obtain particularly excellent performance in relation to the binder resin containing the polyester resin used in the charge transporting layer, a benzidine compound represented by the following general formula (II): Or a triarylamine-based compound represented by the following general formula (III).

The benzidine compound used in the present invention is represented by the following general formula (II).

Embedded image (Wherein, R ₄ and R ₅ may be the same or different and each represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom; R _{6 to} R ₉ may be the same or different; , An alkyl group, an alkoxy group, a halogen atom or a substituted amino group, and k to n are each 1 or 2.)

Tables 5 to 7 show specific examples of the benzidine compound represented by the general formula (II).

[Table 5]

[0039]

[Table 6]

[0040]

[Table 7]

The triarylamine compound used in the present invention is represented by the following general formula (III).

Embedded image (Wherein, R ₁₀ and R ₁₁ may be the same or different, represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, p and q is 1 or 2. Further, R ₁₂
Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or 6 to
And 12 aryl groups. )

Tables 8 and 9 show specific examples of the triarylamine-based compound represented by the general formula (III).

[Table 8]

[0043]

[Table 9]

The electrophotographic photoreceptor of the present invention contains an antioxidant and a photo-oxidizing agent in the photosensitive layer for the purpose of preventing deterioration of the photoreceptor due to ozone, oxidizing gas, light or heat generated in the electrophotographic apparatus. Additives such as stabilizers and heat stabilizers can be added. As the antioxidant, for example, hindered phenol, hindered amine, paraphenylenediamine, arylalkane, hydroquinone, spirochroman, spiroidanone and derivatives thereof, organic sulfur compounds, organic phosphorus compounds and the like are used. Specific examples of the phenolic antioxidant include 2,6-di-t-butyl-4-methylphenol, styrenated phenol,
n-octadecyl-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate, 2,
2'-methylene-bis (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl Acrylate, 4,4'-butylidene-bis (3-methyl-6-t-butylphenol), 4,
4'-thio-bis (3-methyl-6-tert-butylphenol), 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, tetrakis [methylene- 3- (3 ', 5'-di-t
-Butyl-4'-hydroxyphenyl) propionate] -methane, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethyl Ethyl] -2,4
8,10-tetraoxaspiro [5,5] undecane and the like.

As the hindered amine compound, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- ｛3
-(3,5-Di-t-butyl-4-hydroxyphenyl) propionyloxy {ethyl] -4- {3- (3
5-di-t-butyl-4-hydroxyphenyl) propionyloxy {-2,2,6,6-tetramethylpiperidine, 8-benzyl-7,7,9,9-tetramethyl-
3-octyl-1,3,8-triazaspiro [4,5]
Undecane-2,4-dione, 4-benzoyloxy-
2,2,6,6-tetramethylpiperidine, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine succinate polycondensate, poly [｛6- ( 1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diimyl {(2,2,6,6-tetramethyl-4-piperidyl) imino {hexamethylene} (2,3,6,6-tetramethyl-4-piperidyl) imino}], 2- (3,5
-Di-t-butyl-4-hydroxybenzyl) -2-n
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) -butylmalonate, N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- ( 1,2,2,6,6-pentamethyl-4-
Piperidyl) amino] -6-chloro-1,3,5-triazine condensate and the like.

The organic sulfur-based antioxidants include:
Dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, pentaerythritol-tetrakis (β-lauryl-thiopropionate ), Ditridecyl-3,3'-thiodipropionate, 2-mercaptobenzimidazole, and the like.
As organophosphorus antioxidants, trisnonylphenylphosphite, triphenylphosphite, tris (2,
4-di-t-butylphenyl) phosphite and the like. Among the above antioxidants, organic sulfur-based and organic phosphorus-based antioxidants are called secondary antioxidants, and are used in combination with primary antioxidants such as phenol-based or amine-based compounds. By doing so, a synergistic effect can be obtained.

As the light stabilizer, for example, benzophenone type, benzotriazole type, dithiocarbamate type,
Derivatives such as tetramethylpiperidine are used. As the benzophenone-based light stabilizer, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-
Octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, and the like. 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole
[2'-hydroxy-3 '-(3 ", 4", 5 ", 6"
-Tetra-hydrophthalimido-methyl) -5'-methylphenyl] benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5
-Chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2 '-Hydroxy-
3 ', 5'-di-t-amylphenyl) benzotriazole and the like. Other examples include 2,4-di-t-butylphenyl-3 ', 5'-di-t-butyl-4'-hydroxybenzoate, nickel dibutyl-dithiocarbamate, and the like.

Further, the photoreceptor of the present invention has improved sensitivity,
One or more electron-accepting substances can be contained as needed for the purpose of reducing residual potential, reducing fatigue when repeatedly used, and the like. Examples of the electron-accepting substance that can be used in the photoreceptor of the present invention include, for example, succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-Dinitrobenzene, m-dinitrobenzene, chloranil, dinitroanthraquinone, trinitrofluorenone, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, phthalic acid and the like. Among these, fluorenone compounds, quinone compounds,
Benzene derivatives having electron-withdrawing substituents such as Cl, CN and NO ₂ are particularly preferred.

The formation of the charge transport layer can be obtained by applying a solution obtained by dissolving the above-described charge transport material and the binder resin in a suitable solvent and drying the solution. As the solvent used for forming the charge transport layer, for example, benzene, toluene, aromatic hydrocarbons such as chlorobenzene, acetone,
Ketones such as 2-butanone, methylene chloride, chloroform, halogenated aliphatic hydrocarbons such as ethylene chloride, tetrahydrofuran, dioxane, ethylene glycol,
A cyclic or linear ether such as diethyl ether, an ester such as ethyl acetate, methyl acetate, or isopropyl acetate, a cellosolve such as ethyl cellosolve or methyl cellosolve, or a mixed solvent thereof is used. Further, a slight amount of silicone oil can be added to the coating liquid as a leveling agent for improving the smoothness of the coating film.

The mixing ratio of the charge transport material to the binder resin is preferably from 10: 1 to 1: 5. The thickness of the charge transport layer is usually set in the range of 5 to 50 μm, preferably 10 to 40 μm. If the film thickness is less than 5 μm, the effect of the deterioration of the electrical characteristics of the photoconductor due to abrasion becomes large, and the life of the photoconductor is shortened. On the other hand, if the film thickness exceeds 50 μm, the charge transportability is reduced.

The coating liquid is applied by a coating method such as a dip coating method, a ring coating method, a spray coating method, a bead coating method, a blade coating method, or a roller coating method according to the shape and use of the photoreceptor. Can be done. The drying is preferably performed by heat drying after touch drying at room temperature.
The heat drying is desirably performed at 30 to 200 ° C. for 5 minutes to 2 hours.

The dicarboxylic acid or its ester-forming derivative represented by the general formula (I) used in the electrophotographic photoreceptor of the present invention, or the dicarboxylic acid or its ester-forming derivative containing other dicarboxylic acid raw material and diol The polyester resin obtained by assembly has extremely high solubility in a solvent compared to various polycarbonate resins conventionally used as a binder resin of an electrophotographic photoreceptor, and the same amount of solid content is dissolved in the solvent. The solution prepared in this manner has the characteristic that the viscosity is significantly reduced. Therefore, when this polyester resin is used, the productivity of the electrophotographic photosensitive member is greatly improved, and the surface accuracy of the surface is extremely increased. Furthermore, in order to obtain a solution having the same viscosity, the amount of solvent used can be reduced as compared with various polycarbonates.
There are notable advantages such as enabling a production method with less environmental pollution.

In the photoreceptor of the present invention, a surface protective layer can be formed on the photosensitive layer if necessary. As the surface protective layer, there is an insulating resin protective layer or a low resistance protective layer obtained by adding a resistance adjuster to the insulating resin. In the case of the low-resistance protective layer, for example, a layer in which conductive fine particles are dispersed in an insulating resin is preferable, and the conductive fine particles are white, gray or blue-white with an electric resistance of 10 ⁹ Ω · cm or less. Fine particles having an average particle diameter of 0.3 μm or less, preferably 0.1 μm or less are suitable. For example, molybdenum oxide, tungsten oxide, antimony oxide, tin oxide, titanium oxide, indium oxide, tin oxide and antimony or antimony oxide And a mixture thereof, or a mixture of these metal oxides in a single particle, or a coating. Among them,
Tin oxide, a solid solution of tin oxide and antimony or antimony oxide are preferably used because the electrical resistance can be appropriately adjusted and the protective layer can be made substantially transparent ( JP-A-57-30847
No., JP-A-57-128344).

As the insulating resin, polyamide,
Condensed resins such as polyurethane, polyester, epoxy resin, polyketone, and polycarbonate, and vinyl polymers such as polyvinyl ketone, polystyrene, and polyacrylamide are used.

The electrophotographic photosensitive member obtained according to the present invention comprises:
Light lens type copier, laser beam printer that emits near-infrared light or visible light, digital copier, LE
It can be used for an electrophotographic apparatus such as a D printer and a laser facsimile. Further, the electrophotographic photoreceptor of the present invention can be used as a one-component or two-component regular developer or a reversal developer, and also has a current leakage even in a contact charging method using a charging roller or a charging brush. Good characteristics with little occurrence are obtained.

In the present invention, examples of the synthesis of a polyester resin used as a binder resin for the photosensitive layer are shown below. 30 mol of dicarboxylic acid ester and dimethyl 2,6-naphthalenedicarboxylate 10 shown in compound No. 1-1
Mol, 28 mol of 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane and 80 mol of ethylene glycol, and 0.008 mol of zinc acetate as a transesterification catalyst were charged into a 30-liter polymerization apparatus,
The reaction system is heated to 130 ° C. in a nitrogen gas atmosphere to completely dissolve the solid. Thereafter, the mixture is heated to 210 ° C. at a rate of 20 ° C./hour to perform a transesterification reaction, and methanol as a reaction distillate is distilled out of the system from a rectification column, a condenser, or the like. Next, after a theoretical amount of methanol was distilled off, a solution in which 0.032 mol of germanium oxide as a polymerization catalyst and 0.008 mol of trimethyl phosphate as an antioxidant were dispersed in ethylene glycol was added. After stirring to sufficiently disperse the catalyst and the additives in the reaction system, the temperature of the reaction system is gradually raised to 250 ° C. over 1 to 2 hours, and the pressure is reduced to a vacuum of 1 Torr or less.

Next, the reaction system was set at 280.degree.
While maintaining the temperature at rr or less, the increase in the stirring torque of the polymerization apparatus is recorded, and the polymerization is terminated when the stirring torque reaches a desired value. Further, the reaction system is pressurized with nitrogen to about 5 kgf / cm ² , and the polymer is extruded into a strand shape through a die (having a plurality of holes with an inner diameter of about 4 mm) installed at the lower part of the polymerization apparatus, and this is poured into a quench pool. And pelletized with a rotary cutter. The produced polymer is subjected to a purification treatment such as reprecipitation, if necessary, to obtain a polyester resin.

At present, various polycarbonate resins widely used as binder resins for electrophotographic photoreceptors not only use a very harmful substance called phosgene in the production process but also produce harmful substances in the produced resin. Halogen often remains. However, as described above, the polyester resin obtained by using the dicarboxylic acid represented by the general formula (I) or the ester-forming derivative thereof used in the electrophotographic photoreceptor of the present invention completely eliminates such harmful substances during the production process. Since it is not used, there is no harmful element such as halogen in the obtained resin, and it is a clean electrophotographic material that is friendly to human body and environment.

Next, the electrophotographic apparatus of the present invention will be described. The electrophotographic photoreceptor of the present invention can be used for electrophotographic devices of both charging system of corona discharge and contact charging. However, since it has high wear resistance and bending strength, it is used for electrophotographic devices of contact charging system. However, excellent electrophotographic characteristics can be maintained. Specifically, an electrophotographic photoreceptor, a charging unit for charging the photoreceptor, an exposure unit for exposing the photoreceptor charged by the charging unit to form an electrostatic latent image, and an obtained electrostatic In an electrophotographic apparatus having a developing unit for visualizing a latent image, it can be advantageously used as a charging unit in a contact charging system for directly contacting and charging a photoreceptor.

FIG. 8 is a schematic view of an electrophotographic apparatus using the electrophotographic photosensitive member of the present invention. A photosensitive member 7 is provided with a charging member 8 of a corona discharge type for charging. A voltage is supplied to the charging member 8 from a power supply 9.
Around the photoreceptor, an image input device 10, a developing device 11,
A transfer device 12, a cleaning device 13, and a static eliminator 14 are provided. Reference numeral 15 denotes a fixing device. FIG.
1 is a schematic view of a contact charging type electrophotographic apparatus using the electrophotographic photoreceptor of the present invention. A contact charging member 16 is provided in contact with the photoreceptor 7. In this contact type electrophotographic apparatus, the static eliminator 14 may not be provided.

[0061]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. Example 1 The surface of a 30 mmφ ED tube aluminum substrate was coated on a conductive support by using a spherical alumina fine powder (D ₅₀ = 30 μm) by a liquid honing method to obtain a center line average roughness Ra =
A material having a surface roughness of 0.18 μm was used. An organic zirconium compound (acetylacetone zirconium butyrate) was added to 170 parts by weight of n-butyl alcohol obtained by dissolving 4 parts by weight of polyvinyl butyral resin (S-lec BM-S, manufactured by Sekisui Chemical Co., Ltd.)
30 parts by weight and 3 parts by weight of a mixture of organic silane compounds (γ-aminopropyltrimethoxysilane) were mixed and agitated using a coating liquid for forming an undercoat layer by dip coating. A one-hour curing treatment was performed to form a 1.2 μm-thick undercoat layer. Next, Cu
Bragg angle of X-ray diffraction spectrum using kα ray (2
θ ± 0.2 °), 7.4 °, 16.6 °, 2
3 parts by weight of chlorgallium phthalocyanine having clear diffraction peaks at 5.5 ° and 28.3 °, 2 parts by weight of vinyl chloride-vinyl acetate copolymer resin (VMCH, manufactured by Nippon Unicar) and 180 parts by weight of butyl acetate Part of the mixture was dispersed by a sand mill for 4 hours, and the resulting dispersion was applied on the undercoat layer by a dip coating method, and then dried to form a charge generation layer having a thickness of 0.2 μm. Was formed.

Next, the binder resin of the charge transport layer is a polyester resin polymerized according to the synthesis example, and the dicarboxylic acid ester 10 represented by compound No. 1-1 as an acid component.
0 mol%, 1,1-bis [4- (2
-Hydroxyethoxy) phenyl] -cyclohexane (ZE) 70 mol% and ethylene glycol (EG) 3
0 mol% polyester resin (weight average molecular weight 8
10,000) was used.

6 parts by weight of the polyester resin and N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1'-biphenyl] shown in Compound No. 2-1
4 parts by weight of -4,4'-diamine were dissolved in 80 parts by weight of tetrahydrofuran and 0.2 parts by weight of 2,6-di-t-butyl-4-methylphenol. An electrophotographic photoreceptor comprising three layers is formed by applying the obtained coating solution on the above-mentioned charge generating layer, and drying it at 120 ° C. for 40 minutes to form a charge transporting layer having a thickness of 25 μm. Was prepared. The obtained electrophotographic photoreceptor is connected to a contact charging type printer (PC-PR1000 / 4).
R, manufactured by NEC Corporation, and conducted a print test of 50,000 sheets to evaluate the image quality after printing 10,000 sheets. In addition, the residual potential, charging potential, and abrasion loss of the photoconductor after printing 50,000 sheets Was measured and evaluated.

Example 2 The binder resin of the charge transport layer was a polyester resin polymerized according to the synthesis example, and the acid component was Compound No. 1
-1 and 50 mol% of the dicarboxylic acid ester shown in FIG.
-Dimethyl naphthalenedicarboxylate (NDM) 50 mol%, and the diol component is 4,4'-bis [4- (2-
Hydroxyethoxy)]-1,1′-biphenylene (B
An electrophotographic photoreceptor having three layers was prepared and evaluated in the same manner as in Example 1 except that a polyester resin (weight average molecular weight: 60,000) comprising 70 mol% of PE) and 30 mol% of ethylene glycol was used. .

Example 3 The binder resin of the charge transport layer was a polyester resin polymerized according to the synthesis example, and the acid component was Compound No. 1
40 mol% of dicarboxylic acid ester shown in -1 and 2,6
An electron having three layers in the same manner as in Example 1, except that a polyester resin (weight average molecular weight: 65,000) consisting of 60 mol% of dimethyl naphthalenedicarboxylate and 100 mol% of ethylene glycol as a diol component was used. A photoreceptor was prepared and evaluated.

Example 4 The binder resin of the charge transport layer was a polyester resin polymerized according to the synthesis example, and the acid component was Compound No. 1
Polyester resin composed of 100 mol% of dicarboxylic acid ester represented by -1 and 80 mol% of 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane (AE) as a diol component and 20 mol% of ethylene glycol (weight) A three-layer electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that the average molecular weight was 70,000).
evaluated.

Example 5 The binder resin of the charge transport layer was a polyester resin polymerized according to the synthesis example, and the acid component was Compound No. 1
Polyester resin composed of 100 mol% of dicarboxylic acid ester shown in -12, 70 mol% of 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane and 30 mol% of ethylene glycol as diol components (weight average molecular weight 7 A three-layer electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that
evaluated.

Example 6 The binder resin of the charge transport layer was a polyester resin polymerized according to the synthesis example, and the acid component was Compound No. 1
Polyester resin composed of 100 mol% of dicarboxylic acid ester shown in -19, 70 mol% of 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane and 30 mol% of ethylene glycol as diol components (weight average molecular weight 6 A three-layer electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that
evaluated.

Example 7 The binder resin of the charge transport layer was a polyester resin polymerized according to the synthesis example, and the acid component was Compound No. 1
Polyester resin composed of 100 mol% of dicarboxylic acid ester represented by -25, 70 mol% of 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane and 30 mol% of ethylene glycol as diol components (weight average molecular weight 7 A three-layer electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that
evaluated.

Example 8 The binder resin of the charge transport layer was a polyester resin polymerized according to the synthesis example, and the acid component was Compound No. 1
Polyester resin comprising 100 mol% of dicarboxylic acid ester represented by -27, 70 mol% of 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane and 30 mol% of ethylene glycol as diol components (weight average molecular weight 7 A three-layer electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that
evaluated.

Example 9 The binder resin of the charge transport layer was a polyester resin polymerized according to the synthesis example, and the acid component was Compound No. 1
Polyester resin comprising 100 mol% of a dicarboxylic acid ester represented by -28, 70 mol% of 1,1-bis (4- (2-hydroxyethoxy) phenyl) cyclohexane and 30 mol% of ethylene glycol as diol components (weight average molecular weight 7 A three-layer electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that
evaluated.

Example 10 The binder resin of the charge transport layer was a polyester resin polymerized according to the synthesis example, and the acid component was Compound No. 1
Polyester resin comprising 100 mol% of a dicarboxylic acid ester represented by -30 and 70 mol% of 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane as a diol component and 30 mol% of ethylene glycol (weight average molecular weight: 6) A three-layer electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that
evaluated.

Comparative Example 1 Bisphenol A type polycarbonate (trade name: NOVAREX, manufactured by Mitsubishi Kasei Co., Ltd.)
An electrophotographic photosensitive member having three layers was prepared and evaluated in the same manner as in Example 1 except that the average molecular weight was 100,000).

Table 10 shows the evaluation results obtained in Examples 1 to 10 and Comparative Example 1.

[Table 10] In the table, the numbers in the column of "acid components of raw materials" are the compound numbers shown in Tables 1 to 4.

The photosensitive member obtained in each of the examples was subjected to a print test using a printer of a type in which the photosensitive member was charged by a contact charging device, and no image quality abnormality caused by leak discharge of the photosensitive member was observed. Further, these photoreceptors had stable electric characteristics without abrasion and no decrease in chargeability or increase in residual potential. On the other hand, in the photoreceptor obtained in Comparative Example 1, the abrasion was large, the dark decay increased, the chargeability was reduced, fogging was observed in a low density portion, and the film thickness was reduced by abrasion. In this case, there was a current leak from the contact charging device, and for that reason, it was necessary to repair the leaked portion with an insulating material and run. In addition, this part became an image quality defect.

Examples 11 to 20 The conductive support was provided with a center line average roughness Ra = 84 mmφ on a surface of an aluminum substrate by a liquid honing method.
A material having a surface roughness of 0.18 μm was used. On the aluminum substrate, 16 parts by weight of a polyvinyl butyral resin (Eslec BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 550 parts by weight of cyclohexanone were mixed and stirred.
5, Dainippon Ink and Chemicals Inc.) 8 parts by weight are added and stirred,
Further, 60 parts by weight of a titanium oxide pigment was added to the mixed solution, and the mixture was dispersed in a sand grind mill for 5 hours using a coating solution obtained. The mixture was cured at 170 ° C. for 1 hour to give a film thickness of 4 μm. Was formed. next,
9.5 °, 11.7 °, 1 in the Bragg angle (2θ ± 0.2 °) of the X-ray diffraction spectrum using Cukα ray
15 parts by weight of titanyl phthalocyanine having clear X-ray diffraction peaks at 5.0 °, 24.1 ° and 27.3 °, polyvinyl butyral resin (Eslec BM-S,
Sekisui Chemical Co., Ltd.) 10 parts by weight and n-butyl alcohol 3
A coating solution obtained by dispersing a mixture consisting of 00 parts by weight in a sand grind mill for 4 hours was coated on the undercoat layer, and dried to form a 0.2 μm-thick charge generation layer. did.

Next, Compound No. 3-
N, N-bis (3,4-dimethylphenyl) shown in 33
4 parts by weight of biphenyl-4-amine and Examples 11 to 20
6 parts by weight of the same polyester resin as used in Examples 1 to 10 were added to and dissolved in 80 parts by weight of chlorobenzene, and the obtained coating solution was applied on the charge generating layer. This was dried to form a charge transport layer having a thickness of 27 μm, thereby producing an electrophotographic photosensitive member having three layers. Each of the obtained electrophotographic photosensitive members was converted into a color copier (Ac) having an intermediate transfer drum system.
color-635, manufactured by Fuji Xerox Co., Ltd.), a printing operation was performed while adjusting the amount of light, and the image quality of the obtained image was evaluated.

Comparative Example 2 An electrophotographic photosensitive member was produced in the same manner as in Example 11, except that the binder resin used for the charge transport layer was changed to bisphenol A type polycarbonate. Example 1 was prepared using the obtained electrophotographic photosensitive member.
A printing operation was performed in the same manner as in Example 1, and the image quality of the obtained image was evaluated.

Table 11 shows the evaluation results obtained in Examples 11 to 20 and Comparative Example 2.

[Table 11]

When the photoreceptors obtained in the examples were used, no fogging occurred, and the occurrence of black spots was small, and good image quality was obtained. On the other hand, in the photoreceptor using the polycarbonate resin obtained in Comparative Example 2, fog occurred, black spots were frequently generated, and abnormal image quality was observed.

Examples 21 to 30 On a conductive support (Metal Me, manufactured by Toray Industries Co., Ltd.) having a polyethylene terephthalate film provided with an aluminum vapor-deposited film, 10 parts by weight of a polyamide resin, 150 parts by weight of methyl alcohol and water A coating solution consisting of 40 parts by weight was applied and dried to form an undercoat layer having a thickness of 1 μm. Next, at the Bragg angle (2θ ± 0.2 °) of the X-ray diffraction spectrum using Cukα ray, 7.5
°, 9.9 °, 12.5 °, 16.3 °, 18.6 °,
9 parts by weight of hydroxygallium phthalocyanine having diffraction peaks at positions of 25.1 ° and 28.1 °, polyvinyl butyral resin (Eslec BM-1, manufactured by Sekisui Chemical Co., Ltd.)
A mixture consisting of 2 parts by weight and 30 parts by weight of n-butyl alcohol was put into a ball mill pot, and SU was used as a mill member.
60 with S stainless steel ball (1/8 inch φ)
After milling for hours, n-butyl alcohol 30
The coating solution obtained by adding the parts by weight and diluting the mixture was stirred, and the obtained coating solution was applied on the undercoat layer and dried to obtain a film thickness of 0.3.
A μm charge generation layer was formed.

Next, Compound No. 2-
The N, N'-diphenyl-N, N'-bis (3-
Methylphenyl)-[1,1′-biphenyl] -4,
4′-diamine (4 parts by weight) and, in Examples 21 to 30, 6 parts by weight of the same polyester resin as used in Examples 1 to 10 were added to and dissolved in 55 parts by weight of methylene chloride. The resulting coating solution was applied onto the charge generation layer, and dried to form a charge transport layer having a thickness of 25 μm, thereby producing an electrophotographic photosensitive member. The photosensitive layer coating film of the obtained electrophotographic photosensitive member was peeled off from the conductive support, and a bending repetition test was performed up to 5000 times using a bending strength tester. Further, the electrophotographic photosensitive member is processed into a belt shape, and a copying machine (V
ibase800, manufactured by Fuji Xerox Co., Ltd.)
A copy running test was performed up to 100,000 cycles. Table 12 shows the obtained results.

Comparative Example 3 An electrophotographic photosensitive member was produced in the same manner as in Example 21, except that the binder resin used for the charge transport layer was changed to bisphenol A type polycarbonate. Example 2 was prepared using the obtained electrophotographic photosensitive member.
A bending strength test and a copy running test were performed in the same manner as in Example 1. Table 12 shows the obtained results.

[0084]

[Table 12]

In the case of using the photoreceptor of each of the examples, the photoreceptor did not break even after the bending test, and good image quality was obtained even after the copy running test. On the other hand, the photoconductor using the photoconductor of the comparative example broke during the bending test, and many failures such as white spots caused by cracks occurred during the copy running test.

[0086]

The electrophotographic photoreceptor of the present invention uses a polyester resin obtained by using the dicarboxylic acid represented by the above general formula (I) or an ester-forming derivative thereof as the binder resin for the photosensitive layer. Therefore, the formed coating film has extremely high abrasion resistance and bending strength, has excellent electric characteristics even after repeated use, and can form a high-quality image. Therefore, the electrophotographic photoreceptor of the present invention can be used in a high-speed copying machine, and has high durability without causing cracks or the like in the photosensitive layer even when used in a belt-like form. I have. Further, the electrophotographic apparatus using the electrophotographic photoreceptor of the present invention can obtain a high-speed and stable high-quality image over a long period of time even in contact charging type charging.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view illustrating a layer configuration of an example of a laminated electrophotographic photosensitive member according to the present invention.

FIG. 2 is a schematic cross-sectional view illustrating a layer configuration of another example of the laminated electrophotographic photosensitive member according to the invention.

FIG. 3 is a schematic cross-sectional view illustrating a layer configuration of another example of the laminated electrophotographic photosensitive member according to the invention.

FIG. 4 is a schematic cross-sectional view illustrating a layer configuration of another example of a laminated electrophotographic photosensitive member according to the present invention.

FIG. 5 is a schematic cross-sectional view illustrating a layer configuration of an example of a single-layer type electrophotographic photosensitive member according to the invention.

FIG. 6 is a schematic cross-sectional view illustrating a layer configuration of another example of the single-layer type electrophotographic photosensitive member according to the invention.

FIG. 7 is a schematic cross-sectional view illustrating a layer configuration of another example of the single-layer electrophotographic photosensitive member according to the invention.

FIG. 8 is a schematic configuration diagram of an example of an electrophotographic apparatus used in the present invention.

FIG. 9 is a schematic configuration diagram of an example of a contact charging type electrophotographic apparatus used in the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Charge generation layer, 2 ... Charge transport layer, 3 ... Conductive support,
4 undercoat layer, 5 protective layer, 6 photosensitive layer, 7 photoconductor,
8 ... Charging member, 9 ... Power supply, 10 ... Image input device, 11
Developing device, 12 Transfer device, 13 Cleaning device, 14 Static eliminator, 15 Fixing device, 16 Contact charging member.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI G03G 15/02 101 G03G 15/02 101 (72) Inventor Masahiko Miyamoto 1600 Takematsu, Minamiashigara-shi, Kanagawa Prefecture Fuji Xerox Co., Ltd. (72 ) Inventor Hiroshi Nakamura 1600 Takematsu, Minamiashigara, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd.

Claims (11)

[Claims] 1. An electrophotographic photoreceptor comprising a photosensitive layer provided on a conductive support, wherein the photosensitive layer comprises a dicarboxylic acid represented by the following general formula (I) or an ester-forming derivative thereof and a diol: An electrophotographic photosensitive member comprising a polyester resin obtained by polymerization of Embedded image [Wherein, R ₁ represents a hydrogen atom, an alkyl group or an aryl group having 6 to 10 carbon atoms having 1 to 4 carbon atoms, R ₂ and R
₃ is independently an alkylene group having 1 to 10 carbon atoms which may be branched, an aryl-substituted alkylene group or an alkylene arylene alkylene group (however, the aryl group may be substituted with an alkyl group). Represents a group selected from ] 2. An electrophotographic photoreceptor comprising a photosensitive layer provided on a conductive support, wherein the photosensitive layer comprises a dicarboxylic acid group containing the dicarboxylic acid represented by the general formula (I) or an ester thereof. An electrophotographic photoreceptor comprising a polyester resin obtained by polymerization of a forming derivative and a diol. 3. The polyester resin contained in the photosensitive layer,
The ratio of the dicarboxylic acid or its ester-forming derivative represented by the general formula (I) to the total dicarboxylic acid or its ester-forming derivative component is 30 mol% or more. Electrophotographic photoreceptor. 4. The electrophotographic photoreceptor according to claim 1, wherein the polyester resin is contained on the outermost surface of the photosensitive layer. 5. The photosensitive layer according to claim 1, wherein a charge generating layer and a charge transporting layer are sequentially formed, and the polyester resin is contained in the charge transporting layer. Electrophotographic photoreceptor. 6. The electrophotograph according to claim 1, wherein the charge transport material contained in the photosensitive layer is a benzidine compound represented by the following general formula (II). Photoconductor. Embedded image (Wherein, R ₄ and R ₅ may be the same or different and each represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom; R _{6 to} R ₉ may be the same or different; , An alkyl group, an alkoxy group, a halogen atom or a substituted amino group, and k to n are each 1 or 2.) 7. The electron according to claim 1, wherein the charge transport material contained in the photosensitive layer is a triarylamine compound represented by the following general formula (III). Photoreceptor. Embedded image (Wherein, R ₁₀ and R ₁₁ may be the same or different, represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, p and q are each 1 or 2. Further, R ₁₂ is It represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms.) 8. The method according to claim 1, wherein the charge generation material contained in the photosensitive layer is a phthalocyanine compound.
8. The electrophotographic photoreceptor according to any one of items 7 to 7. 9. The charge generation material contained in the photosensitive layer is Cu
Bragg angle of X-ray diffraction spectrum using kα ray (2
θ ± 0.2 °), at least 7.4 °, 16.
Chlorogallium phthalocyanine having diffraction peaks at 6 °, 25.5 ° and 28.3 °, at least 7.5
°, 9.9 °, 12.5 °, 16.3 °, 18.6 °,
Hydroxygallium phthalocyanine having diffraction peaks at 25.1 ° and 28.1 ° and at least 9.5
°, 11.7 °, 15.0 °, 24.1 °, 27.3 °
The electrophotographic photoreceptor according to any one of claims 1 to 8, wherein the electrophotographic photoreceptor is one or more phthalocyanines selected from titanyl phthalocyanines having a diffraction peak at the position of (1). 10. The electrophotographic photoreceptor according to claim 1, wherein the conductive support has flexibility. 11. An electrophotographic photoreceptor, charging means for charging the photoreceptor, exposure means for exposing the photoreceptor charged by the charging means to form an electrostatic latent image, and An electrophotographic apparatus having a developing unit for visualizing a latent image, wherein the charging unit is contact charging for directly contacting and charging a photoconductor, and the electrophotographic photoconductor is any one of claims 1 to 10. An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1.