JP2001215741A - Electrophotographic photoreceptor - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To obtain a high resolution and long life electrophotographic photosensitive member. SOLUTION: An electrophotographic photoreceptor having a compound represented by the following general formula (1) as a charge transporting agent in a photosensitive layer and containing a polymer represented by the following general formula (3) as a binder resin. Embedded image (In the general formula (1), Ar _{1 to} Ar ₆ represent an arylene group, a condensed polycyclic group, a heterocyclic group, and the like, and X _{1 to} X ₄ represent a hydrogen atom, a butadiene derivative residue, and the like.) ]

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. More specifically, the present invention relates to a higher sensitivity and higher performance electrophotographic photosensitive member.

[0002]

2. Description of the Related Art Electrophotographic technology is widely used not only in conventional copying machines but also in various printers and facsimile machines because of its immediacy and high-quality images. At present, some inorganic photoconductive materials such as amorphous silicon and arsenic-selenium are used for photoconductors which form the core of electrophotographic technology, but the mainstream is organic photoconductors. Although several layer configurations have been devised as organic photoconductors, a so-called stacked photoconductor in which charge generation and charge transport functions are separated and a charge generation layer and a charge transport layer are stacked,
It has been researched and developed vigorously due to its ease of design, high productivity, and higher-performance photoreceptors.Currently, the range of use is expanding to medium- and high-speed copiers and printers. .

However, for use in high-speed machines, the optical characteristics are insufficient in light sensitivity, high in residual potential, poor in photoresponsiveness, and further, the chargeability decreases when used repeatedly. There are various problems such as accumulation, fluctuation in sensitivity, and deterioration of various characteristics when used at low temperatures, and it cannot be said that the film has sufficient characteristics. Among them, development of a higher-performance photoconductor is widely desired for use in high-speed copying machines, printers, and the like.

For example, in the case of a photoreceptor having a charge transporting layer comprising a charge transporting agent and a binder resin disposed thereon, toner adheres to the surface of the charge transporting layer, and the developer and transfer paper and the photoreceptor There are problems such as abrasion and scratches caused by contact with the surface, and there are many examples of using polycarbonate resin, polymethyl methacrylate resin, etc. as the binder resin in the charge transport layer to improve these problems. Although reported, there were still problems, especially in terms of durability. Therefore, various photoconductors using a polyester resin have been reported as improvements.

However, JP-A-62-135840, JP-A-63-256961, JP-A-3-6567, and JP-A-4
-274434, JP-A-6-27692, JP-A-9-2
2126, JP-A-10-20517, JP-A-10-26
When the photoreceptor exemplified in 8535 and the like is used at a low temperature, electrical characteristics are significantly deteriorated. Also, Japanese Patent Application Laid-Open No. 5-3
41539, JP-A-7-114191, JP-A-8-11
A photoreceptor using a polyester resin as exemplified by 0646 or the like may have poor ozone resistance.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has been studied. The present invention provides an electrophotographic photosensitive member using a polyester resin having excellent friction resistance and exhibiting good sensitivity and electric characteristics. Is to do.

[0007]

Means for Solving the Problems As a result of intensive studies on the above-mentioned problems, the present inventors have selected a specific polyester resin as a binder resin and a specific arylamine compound as a charge transport compound. As a result, it has been found that the excellent properties of the charge transport agent can be utilized without being adversely affected by the binder resin, and the present invention has been completed. That is, the electrophotographic photoreceptor of the present invention comprises, in an electrophotographic photoreceptor having at least a photosensitive layer on a conductive support, a charge transport agent represented by the following general formula (1) and the following general formula ( An electrophotographic photoreceptor comprising a polyester resin having a structural unit represented by 3).

[0008]

Embedded image (In the general formula (1), Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ and Ar
₆ represents an arylene group which may have a substituent, a condensed polycyclic group which may have a substituent, or a heterocyclic group which may have a substituent, (Ar ₁ to Ar ₃ or Ar ₄ or Ar
₆ may combine with each other to form a carbocyclic or heterocyclic group. X) X ₁ to X _{4 each} represent a hydrogen atom or the following general formula (2), and at least one has a structure represented by the following general formula (2).

[0009]

Embedded image

(In the general formula (2), s represents an integer of 0 to 4, and R ₁ to R ₅ each represent a hydrogen atom, an alkyl group which may have a substituent, Represents an optionally substituted aryl group or an optionally substituted heterocyclic group, which may be the same or different from each other.) Y is a direct bond or a divalent organic residue Represents )

[0011]

Embedded image

(In the general formula (3), ring A, ring B and ring C represent a benzene ring which may have a substituent, and R ₆ and R
₇ represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a cyclic alkylidene or cyclic ester group in which R ₆ and R ₇ are linked. )

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The electrophotographic photoreceptor of the present invention contains a charge transporting agent represented by the general formula (1) and a polyester resin having a structural unit represented by the general formula (3) in a photosensitive layer. I do. In the general formula (1), Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ and
Ar ₆ is an arylene group such as a phenylene group, a naphthylene group or a pyrenylene group; a fused polycyclic residue such as fluorene, dihydrophenanthrene, or tetralin; a pyridine group,
Represents a heterocyclic residue such as thiophene and carbazole.

These may have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a methyl group, an ethyl group, a propyl group;
Alkyl groups such as butyl group, hexyl group and isopropyl group; alkoxy groups such as methoxy group, ethoxy group and propyloxy group; aralkyl groups such as allyl group, benzyl group, naphthylmethyl group and phenethyl group; phenoxy group and toloxy group Aryloxy group; benzyloxy group,
Arylalkoxy groups such as phenethyloxy group; aryl groups such as phenyl group and naphthyl group; arylvinyl groups such as styryl group and naphthylvinyl group; acyl groups such as acetyl group and benzoyl group; dialkyl groups such as dimethylamino group and diethylamino group Amino group; diarylamino group such as ditolylamino group, diphenylamino group and dinaphthylamino group; diaralkylamino group such as dibenzylamino group and diphenethylamino group; diheterocyclic amino group such as dipyridylamino group and dithienylamino group A substituted allyl group such as a diallylamino group or a disubstituted amino group obtained by combining the above-mentioned amino group substituents. These substituents are condensed with each other to form a single bond, a methylene group, ethylene, or the like. Group, carbonyl group, vinylidene group, ethylenylene group, etc. Oxygen atom, a sulfur atom, including the nitrogen atom and the like, may form a heterocyclic group.

Further, Ar ₁ to Ar ₃ or Ar ₄ to Ar ₄
Ar ₆ may combine with each other to form a carbocyclic or heterocyclic group. Ar ₁ to Ar ₆ are preferably an aryl group which may have a substituent, and more preferably a phenylene group, from the viewpoint of electrical properties. In the general formula (1), X ₁ to X ₄ represent a hydrogen atom or the following general formula (2), and at least one of them has a structure represented by the following general formula (2).

[0016]

Embedded image

In the general formula (2), s represents an integer of 0 to 4, and R ₁ to R ₅ are each a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, a phenyl group, a naphthyl group, Represents an aryl group such as a pyrenyl group, or a heterocyclic group such as a thienyl group, a pyridyl group, or a carbazolyl group;
These may be the same or different from each other. Further, these alkyl group, aryl group and heterocyclic group may have a substituent, and the substituent is the same as the substituent for the arylene group of Ar _{1 to} Ar ₆ . It is preferable that at least one of R ₄ and R ₅ is not a hydrogen atom from the viewpoint of electric characteristics. Further, R ₁ to R ₃ are preferably a phenyl group which may have a substituent or a hydrogen atom from the viewpoint of ease of synthesis, and more preferably a hydrogen atom. X ₂ and X ₄ are preferably hydrogen atoms from the viewpoint of production. In the general formula (1), Y represents a direct bond or an organic residue. Here, the organic residue represents a residue derived from a known organic compound, and has, for example, the following structure.

[0018]

Embedded image

In the above formula, Z may have a substituent.
Examples thereof include an aliphatic hydrocarbon residue, an aromatic hydrocarbon residue, a heterocyclic residue, and a condensed polycyclic residue. Of these, as Y
Preferred are methylene groups which may be directly bonded or substituted in terms of electrical characteristics. In the general formula (3), ring A, ring B and ring C represent a benzene ring which may have a substituent. From the viewpoint of durability, the ring A and the ring B preferably have a substituent at the ortho position of the ester group, and the substituent is preferably a methyl group. Ring C is preferably unsubstituted from the viewpoint of production.

In the general formula (3), R ₆ and R ₇ each represent a hydrogen atom, an alkyl group such as a methyl group, an ethyl group or an isopropyl group, an aryl group such as a phenyl group, a naphthyl group or a pyrenyl group; ₆ and R ₇ are linked to form a cyclic alkylidene group or a cyclic ester group such as cyclohexylidene and cyclopentylidene. These may have a substituent, and these substituents are condensed with each other to form a single bond, a methylene group, an ethylene group, a carbonyl group, a vinylidene group, a carbon ring group via an ethylenylene group, or the like, an oxygen atom And a heterocyclic group containing a sulfur atom, a nitrogen atom and the like. From the viewpoint of durability of the photoreceptor, a hydrogen atom or a cyclic alkylidene group is preferable.

In the present invention, the photosensitive layer is provided on a conductive support. As the conductive support, any of those used in known electrophotographic photoreceptors can be used. Specifically, for example, aluminum, stainless steel, copper, a drum made of a metal material such as nickel, a sheet, or a laminate of these metal foils, a deposited material, or a polyester film, aluminum on the surface of an insulating support such as paper,
One provided with a conductive layer of copper, palladium, tin oxide, indium oxide, or the like is given.

Further, a conductive film such as a metal powder, carbon black, copper iodide, a polymer electrolyte or the like is coated with a suitable binder to conduct a conductive treatment.
Examples include a plastic drum, paper, and a paper tube. Also,
Examples of the sheet include a conductive plastic sheet or drum containing a conductive substance such as metal powder, carbon black, and carbon fiber. Further, plastic films and belts which have been subjected to conductive treatment with a conductive metal oxide such as tin oxide or indium oxide may be used. Among them, an endless pipe made of metal such as aluminum is a preferable support.

A known barrier layer, which is usually used, may be provided between the conductive support and the photosensitive layer. As the barrier layer, for example, an anodized aluminum film, an inorganic layer such as aluminum oxide and aluminum hydroxide, an organic layer such as polyvinyl alcohol, casein, polyvinylpyrrolidone, polyacrylic acid, celluloses, gelatin, starch, polyurethane, polyimide, and polyamide. Is used. When the organic layer is used as a barrier layer, a metal oxide such as titania, alumina, silica, zirconium oxide, or a fine metal powder such as copper, silver, or aluminum may be dispersed and used as necessary. The thickness of these barrier layers can be set as appropriate,
5 μm to 20 μm, preferably 0.1 μm to 10 μm
Use in the range of m.

As the photoconductive layer, a charge generation layer and a charge transport layer may be laminated in this order, or may be laminated in the reverse order, or a so-called dispersion type in which a charge generation substance is dispersed in a charge transport medium may be used. Can be. Specifically, the charge generation material is directly deposited, or applied as a dispersion with a binder to form a charge generation layer, and on that,
A layered photoreceptor having a charge transport layer formed by applying a coating solution containing the amine compound represented by the general formula (1) and a binder represented by the general formula (3), or a charge generation layer The order of lamination of the charge transport layer and the charge transport layer may be reversed, or a single layer type photoreceptor in which a coating solution containing a charge generating material, a charge transport material, and a binder is applied on a conductive support.

Examples of the charge generating material include inorganic photoconductive particles such as selenium, selenium-tellurium alloy, selenium-arsenic alloy, cadmium sulfide, and amorphous silicon; metal-free phthalocyanines, metal-containing phthalocyanines, perinone pigments, thioindigo, quinacridone, perylene-based Organic photoconductive particles such as pigments, anthraquinone pigments, azo pigments, bisazo pigments, trisazo pigments, tetrakis azo pigments, and cyanine pigments are exemplified.

Further, various organic pigments and dyes such as polycyclic quinone, pyrylium salt, thiopyrylium salt, indigo, anthantrone and pyranthrone can be used. Among them, metal-free phthalocyanine or copper, indium, gallium, tin, oxytitanium, zinc, metals such as vanadium,
The oxides, phthalocyanines coordinated with chlorides, or azo pigments such as monoazo, bisazo, trisazo and polyazo are preferred. Preferred azo components of the azo pigment include the following structures,

[0027]

Embedded image

Preferred couplers have the following structures.

[0029]

Embedded image

These azo components and couplers may have a substituent. Such azo pigments are disclosed in
-79632, JP-A-54-145142, JP-A-55-145142
-117151, JP-A-57-176055, JP-A-Showa-6
3-192627 and JP-A-63-282743. Further, among phthalocyanines, Cu
The black angle 2θ ± (0.2
°) Oxytitanium phthalocyanine showing a characteristic diffraction peak at 27.3 ° or 2θ (± 0.2 °)
9.3 °, 13.2 °, 26.2 °, and 27.1 °
Oxytitanium phthalocyanine showing a diffraction peak at
Bragg angle 2θ (± 0.3 ゜) 9.2, 14.1, 15.3, 19.7,
27.1 (± 0.2 °) 8.5 °, 12.2 having a diffraction peak at 27.1 °
°, 13.8 °, 16.9 °, 22.4 °, 28.4 °
And dichlorotin phthalocyanine which shows a main diffraction peak at 30.1 ° is preferred as the charge generator.

The electrophotographic photoreceptor thus obtained has a high sensitivity, a low residual potential, a high chargeability, a small variation due to repetition, and particularly a good charge stability which affects the image density. Therefore, it can be used as a highly durable photoconductor. Further, since the sensitivity is high in the range of 750 to 850 nm, it is particularly suitable for a photoconductor for a semiconductor laser printer. The charge-generating material is dissolved or dispersed in a solvent together with a binder polymer and other organic photoconductive compounds, dyes, electron-withdrawing compounds and the like as necessary, and the thus-obtained coating solution is applied and dried to obtain a charge-generating layer. .

That is, the charge generation layer in the laminated type photosensitive layer is made of fine particles of these substances, for example, polyester resin, polyvinyl acetate, polyester, polycarbonate, polyvinyl acetoacetal, polyvinyl propional, polyvinyl butyral, phenoxy resin,
Epoxy resin, urethane resin, cellulose ester, cellulose ether, etc., or polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylate, methacrylate, vinyl alcohol, ethyl vinyl ether, polyamide, silica It is obtained by forming a dispersion layer in a form bound with a binder resin such as a base resin. In this case, the use ratio of the charge generation material (charge generation substance) is usually 20 to 2,000 parts by weight, preferably 30 to 50 parts by weight, per 100 parts by weight of the binder resin.
0 parts by weight, more preferably from 33 to 500 parts by weight, and the thickness of the charge generation layer is usually 0.05 to 5 μm.
m, preferably 0.1 μm to 2 μm, more preferably 0.15 μm to 0.8 μm. Further, the charge generation layer may contain various additives such as a leveling agent, an antioxidant, and a sensitizer for improving applicability, if necessary. Furthermore, the charge generation layer may be a deposited film of the above-described charge generation material.

In the case of the dispersion type photosensitive layer, the particle size of the charge generating material must be sufficiently small, and is preferably 1 μm or less, more preferably 0.5 μm or less. The amount of the charge generating material dispersed in the photosensitive layer is, for example, 0.5 to 5
Although it is in the range of 0% by weight, if the amount is too small, sufficient sensitivity cannot be obtained. If the amount is too large, there are adverse effects such as a decrease in chargeability and a decrease in sensitivity. . Next, in the present invention, dye dyes optionally added to the photosensitive layer include, for example, methyl violet, brilliant green, triphenylmethane dyes such as crystal violet, thiazine dyes such as methylene blue, quinone dyes such as quinizarin, and cyanine dyes. Examples include a beryllium salt, a thiavirilium salt, and a benzobrillium salt.

The electron-withdrawing compound optionally added to the photosensitive layer includes, for example, chloranil, 2,3-dichloro-1,4-naphthoquinone, 1-nitroanthraquinone, 1-chloro-5-nitroanthraquinone, Quinones such as chloroanthraquinone and phenanthrenequinone; aldehydes such as 4-nitrobenzaldehyde; 9
-Benzoylanthracene, indandione, 3,5-
Ketones such as dinitrobenzophenone, 2,4,7-trinitrofluorenone, 2,4,5,7-tetranitrofluorenone, 3,3 ', 5,5'-tetranitrobenzophenone; phthalic anhydride, 4-chloronaphthal Acid anhydrides such as acid anhydrides; tetracyanoethylene, terephthalalmalononitrile, 9-anthrylmethylidenemalononitrile, 4-nitrobenzalmalononitrile, 4- (p
-Nitrobenzoyloxy) cyano compounds such as benzalmalononitrile; 3-benzalphthalide, 3- (α-cyano-p-nitrobenzal) phthalide, 3- (α-cyano-p-nitrobenzal) -4,5,6,7 -Electron-withdrawing compounds such as phthalides such as tetrachlorophthalide.

As the binder resin used in the charge transport layer, in addition to the polyester represented by the general formula (3),
For example, vinyl polymers such as polymethyl methacrylate, polystyrene, and polyvinyl chloride, and copolymers thereof, polycarbonate, polyester, polyester carbonate, polysulfone, polyimide, phenoxy, epoxy, and silicone resin may be shared or copolymerized. These partially crosslinked cured products can also be used. When another resin is used as the binder resin, the polyester represented by the general formula (3) is preferably contained in an amount of 10% by weight or more of all the binder resins, more preferably 30% by weight or more, and further preferably 50% by weight or more. It is.

The ratio of the binder resin to the compound represented by the general formula (1) is in the range of 30 to 200 parts by weight, preferably 40 to 150 parts by weight, per 100 parts by weight of the binder resin. The charge transport layer may contain various additives such as an antioxidant and a sensitizer as needed. The thickness of the charge transport layer is 10 to 60 μm, preferably 10 to 45 μm.

The charge transporting layer in the case of the laminated type photosensitive layer may contain various additives such as an antioxidant and a sensitizer, and other charge transporting materials, if necessary. The thickness of the charge transport layer is usually 10 to 60 μm, preferably 10 to 45 μm,
More preferably, it is used in a thickness of 27 to 40 μm. As the outermost surface layer, a conventionally known overcoat layer mainly composed of, for example, a thermoplastic or thermosetting polymer may be provided. Usually, the charge transfer layer is formed on the charge generation layer, but the reverse is also possible. As a forming method of each layer, a known method such as sequentially applying a coating solution obtained by dissolving or dispersing a substance to be contained in a layer in a solvent can be applied.
In addition to the above, various additives for improving the mechanical strength and durability of the coating film can be used in the charge transport layer.

Examples of such additives include well-known plasticizers, various stabilizers, flowability-imparting agents, and crosslinking agents. Further, the photosensitive layer of the electrophotographic photoreceptor of the present invention may contain a well-known plasticizer in order to improve film formability, flexibility, and mechanical strength. Therefore, examples of the plasticizer added to the coating solution include phthalic acid esters, phosphate esters, epoxy compounds, chlorinated paraffins, chlorinated fatty acid esters, and aromatic compounds such as methylnaphthalene. When the arylamine-based compound is used as the charge transporting material in the charge transporting layer, the coating liquid may be the same as the above-described composition, but the photoconductive particles, the dye, and the electron-withdrawing compound are excluded from the composition. Or it is better to add a small amount. In this case, as the charge generation layer, a coating liquid obtained by dissolving or dispersing the above-mentioned photoconductive particles and a solvent such as a binder polymer or other organic photoconductive substance, a dye or an electron-withdrawing compound as necessary is applied. Examples include a dried thin layer or a layer in which the photoconductive particles are formed into a film by means such as vapor deposition.

The electrophotographic photoreceptor of the present invention is prepared by dissolving the amine derivative represented by the general formula (1) in a suitable solvent together with the binder represented by the general formula (3) according to a conventional method. A coating solution obtained by adding a well-known additive such as a suitable charge generating material, a sensitizing dye, an electron-withdrawing compound, another charge transporting material, or a plasticizer or a pigment onto a conductive support. Coating and drying, usually several μ to several tens μ, preferably 10 to 45 μm, particularly preferably 20 μ
It can be manufactured by forming a photosensitive layer having a thickness of at least m. In the case of a photosensitive layer comprising a charge generation layer and a charge transport layer, the above-mentioned coating solution is applied on the charge generation layer, or the charge generation layer is placed on the charge transport layer obtained by applying the above coating solution. Can be produced.

Solvents for preparing a coating solution include ethers such as tetrahydrofuran and 1,4-dioxane; ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; N, N-dimethylformamide, acetonitrile; N-methylpyrrolidone,
Aprotic polar solvents such as dimethyl sulfoxide; esters such as ethyl acetate, methyl formate, and methyl cellosolve acetate; solvents that dissolve amine compounds such as chlorinated hydrocarbons such as dichloroethane and chloroform. Of course, those which dissolve the binder are selected from these.

The photoreceptor thus formed may also be provided with, if necessary, an improvement in electrical and mechanical properties such as a barrier layer, an adhesive layer, an intermediate layer such as a blocking layer, a transparent insulating layer or a protective layer. It is needless to say that a layer may be provided. As the outermost layer, a conventionally known overcoat layer mainly composed of, for example, a thermoplastic or thermosetting polymer may be provided. As a method for forming each layer, a known method such as sequentially applying a coating solution obtained by dissolving or dispersing a substance to be contained in a layer in a solvent can be applied.

Examples of the method of applying the photosensitive layer include a spray coating method, a spiral coating method, a ring coating method, and a dip coating method. Spray coating methods include air spray, airless spray, electrostatic air spray, electrostatic airless spray, rotary atomizing electrostatic spray, hot spray, hot airless spray, etc., but fine particles to obtain a uniform film thickness Considering the degree of adhesion, adhesion efficiency, etc., in the case of a rotary atomization type electrostatic spray, the conveying method disclosed in Japanese Patent Laid-Open Publication No. 1-805198, that is, a cylindrical work is rotated and spaced apart in the axial direction. By continuously transporting the electrophotographic photoreceptors, it is possible to obtain an electrophotographic photosensitive member excellent in uniformity of film thickness with high overall adhesion efficiency.

A spiral coating method is disclosed in
Japanese Patent Application Laid-Open No. H11-231966 discloses a method using a liquid injection coating machine or a curtain coating machine disclosed in Japanese Patent Application Publication No. 119651.
There is a method disclosed in Japanese Patent Application Laid-Open Publication No. H10-193, in which the coating material is continuously flew from the minute opening in a streak shape, and a method using a multi-nozzle body disclosed in Japanese Patent Application Laid-Open No. 3-193161. Hereinafter, the dip coating method will be described.

Using the amine derivative represented by the general formula (1), the binder represented by the general formula (3), a solvent and the like, the total solid content concentration is preferably 25% or more, more preferably 40%. A coating liquid for forming a charge transport layer having the following viscosity and usually having a viscosity of 50 to 300 centipoise or less, preferably 100 to 200 centipoise or less is prepared. Here, the viscosity of the coating liquid is substantially determined by the type and molecular weight of the binder polymer. However, if the molecular weight is too low, the mechanical strength of the polymer itself is reduced, so the binder polymer has a molecular weight that does not impair the mechanical strength. It is preferred to use The charge transport layer is formed by a dip coating method using the coating solution thus adjusted.

Thereafter, the coating film is dried, and the drying temperature and time are preferably adjusted so that necessary and sufficient drying is performed. The drying temperature is usually 100 to 250 ° C, preferably 110 to 17 ° C.
0 ° C, more preferably in the range of 120 to 140 ° C. As a drying method, a hot air dryer, a steam dryer, an infrared dryer, a far infrared dryer, or the like can be used.
Next, main specific examples of the compound represented by the general formula (1) will be shown, but it should not be construed that the invention is limited thereto.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

[Table 4]

[0050]

[Table 5]

[0051]

[Table 6]

[0052]

[Table 7]

[0053]

[Table 8]

[0054]

[Table 9]

[0055]

[Table 10]

[0056]

[Table 11]

[0057]

[Table 12]

[0058]

[Table 13]

[0059]

[Table 14]

[0060]

[Table 15]

[0061]

[Table 16]

[0062]

[Table 17]

[0063]

[Table 18]

[0064]

[Table 19]

[0065]

[Table 20]

[0066]

[Table 21]

[0067]

[Table 22]

[0068]

[Table 23]

[0069]

[Table 24]

Structure of Xa, Xb, Xc, Xd

[0071]

[Table 25]

Next, main specific examples of the compound represented by the formula (3) will be shown, but it should not be construed that the invention is limited thereto.

[0073]

[Table 26]

[0074]

[Table 27]

[0075]

[Table 28]

[0076]

[Table 29]

[0077]

[Table 30]

[0078]

[Table 31]

[0079]

[Table 32]

[0080]

[Table 33]

[0081]

[Table 34]

[0082]

[Table 35]

[0083]

[Table 36]

[0084]

[Table 37]

[0085]

[Table 38]

[0086]

[Table 39]

[0087]

[Table 40]

[0088]

[Table 41]

[0089]

[Table 42]

[0090]

The present invention will be described below in more detail with reference to Examples and Comparative Examples, but it should not be construed that the invention is limited thereto. Example-1 Black 2θ (± 0.2 °) 9.3 °, 13.2 °, 2
200 parts by weight of n-propanol was added to 10 parts by weight of oxytitanium phthalocyanine showing X-ray diffraction peaks by CuKα radiation at 6.2 ° and 27.1 °, and the mixture was pulverized for 10 hours by a sand blind mill to perform atomization and dispersion treatment. Was.
Next, polyvinyl butyral (manufactured by Denki Kagaku Kogyo Co., Ltd.
The product was mixed with 5 parts by weight of a 10% methanol solution (trade name “Denka Butyral” # 6000C) to prepare a dispersion.

Next, a charge generation layer was provided on an aluminum-deposited surface on which the dispersion was deposited on a polyester film so that the film thickness after drying was 0.4 μm by a bar coater. On top of this charge generation, 60 parts by weight of the compound (No. 1) shown in Table 1 and 1: 1 of the polyesters (P-1) and (M-1) shown in Table 2 above. Copolymer 1
00 parts by weight of tetrahydrofuran / toluene mixed solution
A solution dissolved in 1000 parts by weight was applied by a film applicator, and a charge transport layer was provided so that the film thickness after drying was 20 μm. The photoconductor formed in this manner is referred to as photoconductor A. The electrophotographic photoreceptor having the two-layered photosensitive layer obtained in this manner was obtained at 5 ° C. and 10% humidity.
0.48 μm
J / cm ² . First, the photoreceptor was negatively charged by a corona current of 50 μA in a dark place,
It was determined by exposing with 0 nm light (exposure energy: 10 μW / cm ² ) and measuring the amount of exposure required for the surface potential to attenuate from −700 V to −350 V. Further, when the surface potential when the exposure time was set to 9.9 seconds was measured as a residual potential, it was -39 V.

Comparative Example 1 Example 1 was the same as Example 1 except that the compound (No. 1) shown in Table 1 used in the charge transport layer was changed to a charge transport material having the following structure. Comparative Photoconductor 1 was prepared in the same manner as described above. Next, the sensitivity was determined in the same manner as in Example-1.
When the residual potentials were measured, they were 0.60 μJ /
cm2, -82V.

[0093]

Embedded image

Comparative Example 2 The results are shown in Table 1 above, which was used for the charge transport layer in Example 1.
N-methylcarbazole- in place of the compound (No. 1)
Other than changing to 3-carbaldehyde diphenylhydrazone
Was performed in the same manner as in Example 1 to prepare a comparative photoreceptor 2. Next
The sensitivity and residual potential were measured in the same manner as in Example 1.
However, each is 0.55 μJ / cm ^TwoAt -90V
there were. Half-exposure amount (E_1/2) (ΜJ / cm^Two)
And the residual potential (Vr) are shown in the table below.

[0095]

[Table 43]

Example-2 The compound (No. 1) 60 shown in Table 1 above used in the examples.
A photoconductor was prepared in the same manner as in Example 1, except that 40 parts by weight of the photoreceptor was used. This is designated as photoconductor B. Photoconductor B
Was cut into a circular shape having a diameter of 10 cm, and the wear was evaluated by a Taber abrasion test. Test conditions are 23 ° C, 50% R
Under an atmosphere of H, using a worn wheel CS-10F, 250
The average value of the g load and the weight loss after 1000 rotations was taken.
The abrasion test was performed four times continuously for one sample, and the average value of three points excluding the initial value was taken as the abrasion loss of the sample. The smaller the value of the wear amount, the better the wear amount.

Comparative Example 3 The following structure was used in place of the 1: 1 copolymer of polyester (P-1) and (M-1) shown in Table 2 above and used for the charge transport layer in Example-2. A comparative photoreceptor 3 was prepared using the indicated polycarbonate, and abrasion was evaluated by a Taber abrasion test in the same manner as in Example-2.

[0098]

Embedded image

The measured values of wear of the respective photoconductors are shown in the following table.

[0100]

[Table 44]

As is clear from the above results, the photoreceptor according to the present invention shows very good sensitivity and residual potential with respect to the comparative photoreceptor. In particular, it has excellent characteristics at low temperature and low humidity. Further, it can be seen that the abrasion characteristics are also very excellent. That is, it is understood that the photoreceptor using the specific binder and the specific charge transporting agent according to the present invention has very excellent characteristics.

[0102]

The electrophotographic photoreceptor using a specific compound in the photoconductive layer of the present invention has extremely high photosensitivity and exhibits a low residual potential, and the residual potential is hardly accumulated even when used repeatedly. It has no change in chargeability and sensitivity, and has very good stability and excellent durability.Electrical characteristics do not deteriorate significantly even at low temperatures.Therefore, it can be used for high-speed copiers and printers without any problem. it can.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 5/05 101 G03G 5/05 101

Claims (5)

[Claims] 1. An electrophotographic photosensitive member having at least a photosensitive layer on a conductive support, wherein the photosensitive layer is represented by the following general formula (1) and a charge transporting agent represented by the following general formula (3). An electrophotographic photosensitive member comprising a polyester resin having a structural unit. Embedded image (In the general formula (1), Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ and Ar ₆ are
An arylene group which may have a substituent, a condensed polycyclic group which may have a substituent, or a heterocyclic group which may have a substituent (Ar ₁ to Ar ₃ , or Ar ₄ Or Ar
₆ may combine with each other to form a carbocyclic or heterocyclic group) X ₁ to X ₄ represent a hydrogen atom or the following general formula (2), and at least one of X _{1 to} X ₄ is , (2)
It is a structure represented by the formula. Embedded image (In the general formula (2), s represents an integer of 0 to 4, and R ₁
To R ₅ each represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent; May be the same or different from each other. ) Y
Represents a direct bond or a divalent organic residue. ) (In the general formula (3), ring A, ring B and ring C represent a benzene ring which may have a substituent, and R ₆ and R ₇ may each have a hydrogen atom and a substituent. Represents an alkyl group, an aryl group which may have a substituent, or a cyclic alkylidene group or a cyclic ester group in which R ₆ and R ₇ are linked.) 2. In the general formula (1), Ar ₁ to Ar ₁
2. The electrophotographic photoconductor according to claim 1, wherein Ar ₆ is a phenylene group which may have a substituent. 3. In the general formulas (1) and (2),
_3. The electrophotographic photoreceptor according to claim 1, wherein X ₂ , X ₄ , R ₁ , R ₂ , and R ₃ are hydrogen atoms. 4. An electrophotographic photoreceptor comprising at least a charge generation layer and a charge transport layer on a conductive support, wherein the charge transport agent and the polyester resin are contained in the charge transport layer. 4. The electrophotographic photosensitive member according to any one of 1 to 3, 5. In the general formula (3), ring A and ring B
And ring C is an unsubstituted benzene ring or a benzene ring substituted with one or two methyl groups, trifluoromethyl groups, halogen atoms or phenyl groups, and R ₆ and R ₇
Is a hydrogen atom, a methyl group, a trifluoromethyl group, a phenyl group, or R ₆ and R ₇ are linked to form a cyclic alkylidene group. Electrophotographic photoreceptor.