JP2000075515A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photoreceptor small in wear in repeating use through a long period, excellent in cleaning property and the durability against scratch, improved in slidability to a blade and free from the deterioration of other properties such as electrical property and coating property by giving a group having charge transfer property to a lubricating material. SOLUTION: In the photoreceptor having a charge transfer material and a charge generating material on a conductive supporting body, at least one kind of the lubricating material having the group having charge transfer property is used. In such a case, the lubricating material is used in a photosensitive layer composed particularly of 2 layers of a charge generating layer and a charge transfer layer (charge moving layer). Concretely, the charge generating layer is formed usually by vapor depositing the charge generating material directly or applying as a dispersion with a binder and casting an organic solvent solution containing the lubricating material having the group having charge transfer property thereon or the charge transfer layer is preferably formed by dissolving a charge transfer medium with the binder and applying the dispersion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor having excellent printing durability and slipperiness for use in copiers and printers using an electrophotographic process.

[0002]

2. Description of the Related Art In an electrophotographic image forming method based on the Carlson method, after uniformly charging a surface of a photoreceptor, the charge is eliminated by performing exposure in accordance with image information forming the surface. An electrostatic latent image is formed on the surface.
Next, the electrostatic latent image is developed and visualized with toner, and the toner image is transferred from a photoreceptor to a transfer paper or the like and then fixed. On the other hand, the surface of the photoreceptor after the transfer is initialized by removing toner remaining on the surface, removing static electricity, and the like, and is used repeatedly.

Accordingly, the electrophotographic photoreceptor is required to have photosensitive characteristics such as good charging characteristics and sensitivity and low dark decay characteristics, and to have printing durability, abrasion resistance, scratch resistance and the like when repeatedly used. It is also required to have good mechanical properties, active species such as ozone generated during corona discharge, and good resistance to ultraviolet rays during exposure. In recent years, low pollution,
Studies on the use of an organic photoconductive material having a feature of being easy to produce for a photosensitive layer have been actively conducted, and practical use thereof has been promoted.
In particular, a stacked photoreceptor composed of a charge generation layer and a charge transfer layer in which the function of generating charge by absorbing light and the function of transporting the generated charge are separated has become mainstream. These photoconductors are widely used in fields such as copying machines and laser printers.

[0004] Further, in electrophotographic copying machines and printers, it is required that a large amount of images can be formed quickly and that maintenance is not troublesome. Although printing durability is indispensable, organic photoreceptors have the disadvantage that they have poorer mechanical properties than inorganic photoreceptors, and are liable to be worn and damaged when used repeatedly.

Various studies have been made to improve such disadvantages. Decreasing the amount of charge transport material reduces the amount of wear, but degrades the photosensitivity. As another means, when the molecular weight of the binder in the charge transport layer increases, the amount of wear decreases, but the viscosity of the coating solution increases, so that defects such as sagging and unevenness are likely to occur at the coating stage. Recently, a method of dispersing inorganic fillers and lubricating particles in the charge transport layer has been devised.However, since the incident light is scattered by the particles, the sensitivity is greatly degraded, or the dispersed particles in the coating liquid are left unattended. However, at present, there is no electrophotographic photoreceptor having improved mechanical properties without deteriorating properties such as photosensitive properties and coating properties.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to reduce wear during long-term repeated use, to provide excellent cleaning properties and durability against scratches, An object of the present invention is to provide an electrophotographic photoreceptor that has good slipperiness and does not impair other characteristics such as electric characteristics and coatability.

[0007]

As a result of intensive studies on the above problems, in an electrophotographic photoreceptor having a photosensitive layer on a conductive support, at least the lubricating substance of the present invention is contained in the outermost layer of the photoreceptor. It has been found that by containing one kind, abrasion resistance, printing durability, and slipperiness can be improved without impairing photosensitive properties such as chargeability and sensitivity, and coating properties. That is, the gist of the present invention is to provide an electrophotographic photosensitive member having a photosensitive layer containing a charge transporting substance and a charge generating substance on a conductive support, wherein a lubricating substance having a charge transporting group in the photosensitive layer is provided. An electrophotographic photosensitive member characterized by containing at least one kind.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In an electrophotographic photoreceptor having a charge transporting substance and a charge generating substance on a conductive support, abrasion resistance and printing durability were improved by using at least one kind of lubricating substance having a charge transporting group. Thus, an electrophotographic photosensitive member is obtained. The present inventors have considered the reason why the photoreceptor having the above specific lubricant exhibits excellent performance as follows. In other words, conventional lubricants using wax, polysiloxane, etc. can certainly improve the lubricating ability, but have the potential to cause changes in electrical properties and coating liquid properties due to large amounts of addition. Was. This is considered to be because these lubricants had a problem in compatibility with the charge transport material and the binder polymer.

Therefore, as in the present invention,
By having a charge transporting group, the compatibility between the charge transporting substance and the lubricant and between the binder polymer and the lubricant in the film is improved, and changes in electrical properties and coating liquid properties are minimized. It is considered possible. For the above reasons, the lubricating substance of the present invention is a substance that can be added from a small amount to a large amount depending on the situation.

The lubricant preferably has a structure of triarylamine, stilbene, hydrazone, triarylmethane or the like from the viewpoint of charge transport ability and charge separation ability, and has a molecular ionization potential (IP) of 4. 7 ~
Preferably, it is 5.7 eV. The value of this IP is more preferably 4.9 to 5.5 eV. In this lubricating substance molecule, the sum SP of the bond orders is represented by the number of atoms N
SP / N is 1.15 or less, and 6
It is preferable for abrasion resistance and printing durability to have a group in which two or more atoms are connected in series by a primary bond.

Here, the calculation method of SP / N will be described with an example. For example, the following compound:

[0012]

The number of atoms (N) is 18, and the sum of bond orders (SP)
18, which has a site in which six atoms are connected in series by a primary bond. Note that the number of atoms includes hydrogen atoms.

The following reasons can be considered as the reason why the lubricant having the above specific parameters exhibits excellent performance. That is, when a molecule having improved lubricity at the molecular level is designed, it is considered that the greater the degree of freedom of the molecular structure, the higher the lubricity. For this purpose, substances having more double bonds, triple bonds, and ring-closed structures in the molecule that may increase the rigidity of the molecule are disadvantageous for lubricity because the structural freedom of the molecule is reduced. is expected. Therefore, the smaller the bond order per unit constituent atom (the larger the value of a compound containing a structure such as a double bond, a triple bond, or a closed ring structure), the greater the degree of structural freedom of the molecule and the lubricity. Expected to work favorably. The bond order per unit constituent atom is represented by the following formula: SP / N (SP: total sum of bond orders of molecules, N: number of constituent elements) This value is preferably 1.15 or less, More preferably, it is 1.14 or less.

Since it is desirable to have at least one double bond site or aromatic site in the molecule from the viewpoint of charge transport ability, this value is preferably more than 1.00.
From the same viewpoint as above, an electrophotographic photoreceptor having improved abrasion resistance and printing durability can be obtained by using at least one organic charge transporting substance having a long-chain alkyl moiety.

It is preferable that the long-chain alkyl serving as a lubricating site be linked to an ether bond, an ester bond, or the like, from the viewpoint of easy synthesis. This long-chain alkyl has preferably 11 or more carbon atoms, more preferably 13 or more, still more preferably 16 or more, further preferably,
It is 17 or more and 40 or less. The lubricating site may be located anywhere in the molecule, but is preferably located at the terminal of the molecule in terms of improving abrasion and ease of synthesis.

Further, more preferably, from the viewpoint of lubricity, it is preferable to have an endothermic peak at 130 ° C. or lower in the thermal analysis measurement. In the photoreceptor, the inclusion of at least one kind of charge transporting substance other than the lubricating substance is compatible with the polymer, in the sense of enhancing coatability, in the sense that the electrical properties can be easily controlled.
More preferred.

If the amount of the lubricant having a charge transporting group of the present invention is too small, there is no effect on the mechanical properties, and if it is too large, the surface of the coating film may be uneven. Therefore,
The amount of addition is preferably in the range of 0.01% to 80%, more preferably 0.1% to 40%, based on the total solid weight of the surface layer. Specific examples of the organic charge transport material in the present invention include the following.

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

[Table 3]

[0022]

[Table 4]

[0023]

[Table 5]

[0024]

[Table 6]

[0025]

[Table 7]

[0026]

[Table 8]

[0027]

[Table 9]

[0028]

[Table 10]

[0029]

[Table 11]

[0030]

[Table 12]

[0031]

[Table 13]

[0032]

[Table 14]

[0033]

[Table 15]

[0034]

[Table 16]

[0035]

[Table 17]

[0036]

[Table 18]

[0037]

[Table 19]

[0038]

[Table 20]

[0039]

[Table 21]

[0040]

[Table 22]

[0041]

[Table 23]

[0042]

[Table 24]

[0043]

[Table 25]

[0044]

[Table 26]

[0045]

[Table 27]

[0046]

[Table 28]

[0047]

[Table 29]

[0048]

[Table 30]

[0049]

[Table 31]

[0050]

[Table 32]

[0051]

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[0052]

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The electrophotographic photoreceptor of the present invention comprises one or two lubricating substances having a charge transporting group in the photosensitive layer.
Contains more than one species. Further, other lubricating substances such as wax may be contained as long as the effects of the present invention are not impaired. The photosensitive layer is laminated on the conductive support, the conductive support is, for example, a metal material such as aluminum, stainless steel, copper, nickel, zinc, indium, gold, silver, or a surface of aluminum, copper, Examples thereof include polymers such as polyester provided with a conductive layer such as palladium, tin oxide, indium oxide or a conductive polymer, and insulating substrates such as paper and glass. The surface of the conductive support can be subjected to various treatments within a range that does not affect the image quality. For example, surface oxidation treatment or chemical treatment can be performed. A metal drum or the like that has been subjected to a metal oxidation treatment by electrode oxidation or the like corresponds to this. The shape can take any shape such as a drum, a sheet, a belt, and a seamless belt.

The photosensitive layer (photoconductive layer) is formed by laminating a charge generation layer and a charge transport layer in this order, or by laminating the charge generation layer and the charge transport layer in reverse order. Any configuration such as a so-called dispersion type in which particles of the (generating substance) are dispersed can be used. For example, a photosensitive layer containing a charge transport medium and, if necessary, a dye serving as a sensitizer or an electron-withdrawing compound in a binder, or a charge generating material (photoconductive material) that generates charge carriers with extremely high efficiency when absorbing light. Particles), a photosensitive layer in which a charge transport medium is added to a binder, a charge generation layer composed of a charge transport medium and a binder, and a charge generation material that generates charge carriers with extremely high efficiency when absorbing light, or a combination thereof with a binder. And a photosensitive layer in which a charge generation layer is laminated.

In the present invention, in particular, when the above-mentioned specific lubricating substance is used in a photosensitive layer comprising a charge generating layer and a charge transporting layer (charge transporting layer), abrasion is reduced during long-term repeated use. It is possible to obtain an electrophotographic photosensitive member which is excellent in cleaning properties and durability against scratches and which does not impair other properties such as electrical properties and coating properties.

More specifically, the charge generating material is usually formed by directly depositing the charge generating material or coating it as a dispersion with a binder to form a charge generating layer, on which an organic solvent containing a lubricating substance having a charge transporting group is formed. It is preferable to form a charge transport layer by casting a solution or dissolving a charge transport medium together with a binder or the like and applying a dispersion thereof. In addition, a function inversion type laminated photoconductor in which the stacking order of the charge generation layer and the charge transport layer is reversed may be used. In this case, the charge generation layer preferably contains the lubricating substance. Further, the charge generating material and the charge transporting material may be a single layer type photoreceptor in which the charge generating material and the charge transporting material are applied to a conductive support in a state of being dispersed and dissolved in a binder.

Selenium, selenium-
Inorganic photoconductive particles such as tellurium alloy, selenium-arsenic alloy, cadmium sulfide, amorphous silicon; metal-free phthalocyanine, metal-containing phthalocyanine, perinone pigment,
Organic photoconductive particles such as thioindigo, quinacridone, perylene pigment, anthraquinone pigment, azo pigment, bisazo pigment, trisazo pigment, tetrakis azo pigment, and cyanine pigment.

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 chloride, gallium chloride, tin, oxytitanium, zinc or a metal such as vanadium or an oxide thereof, phthalocyanines in which chloride is coordinated, or monoazo, bisazo, trisazo, or Azo pigments such as polyazos are preferred.

In particular, when a photoreceptor having improved sensitivity to laser light is desired, it is preferable to use a phthalocyanine as a charge generating agent. In particular, at least a charge generating material and a charge transport material are provided on a conductive support. And a black layer (2θ ± 0.2 °) of 9.7 °, 24.2 ° in the X-ray diffraction pattern of CuKα ray as the charge generating material.
An electrophotographic photoreceptor containing oxytitanium phthalocyanine showing a diffraction peak at 27.3 ° is preferred.

The oxytitanium phthalocyanine particles are dissolved or dispersed in a solvent together with a binder polymer and, if necessary, other organic photoconductive compounds, dyes, electron-withdrawing compounds, and the like. Obtain a generating layer. In addition to the oxytitanium phthalocyanine, the black angle (2θ ± 0.2 °) of the X-ray diffraction pattern by CuKα ray is 9.3 °, 13.
Oxytitanium phthalocyanine showing diffraction peaks at 2 °, 26.2 ° and 27.1 °, black angle (2θ ±
0.2 °) 8.5 °, 12.2 °, 13.8 °, 16.
Dichlorotin phthalocyanine showing main diffraction peaks at 9 °, 22.4 °, 28.4 ° and 30.1 °, or black angle (2θ ± 0.3 °) 9.2 °, 14.1
°, 15.3 °, 19.7 °, dihydroxysilicon phthalocyanine compounds having peaks at 27.1 °, or a mixture thereof, or 9.7 ° with the above black angle (2θ ± 0.2 °). , 24.2 °, 27.3 °
A photosensitive layer containing a mixture with oxytitanium having a diffraction peak at the bottom is preferred.

When a charge transporting agent other than the above-mentioned lubricating substance having a charge transporting group is used in the photosensitive layer, the charge transporting agent may be polyvinyl carbazole, polyvinyl pyrene,
Polymer compounds such as polyacenaphthylene, polyvinylpyrene, polyvinylanthracene, or various pyrazoline derivatives, carbazole derivatives, oxazole derivatives, hydrazone derivatives, stilbene derivatives, arylamine derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives , Imidazole derivatives, imidazolone derivatives, imidazolidine derivatives,
Low molecular compounds such as styryl compounds, benzothiazole derivatives, benzimidazole, acridine derivatives, and phenazine derivatives can be used. In addition to the above hole transport type charge transport agents, benzoquinone derivatives, naphthoquinone derivatives,
Electron transporting agents such as anthraquinone derivatives, diphenoquinone derivatives, and fluorenone derivatives are also used as needed.
These charge transporting agents are used singly or in combination of two or more in consideration of the combination with the charge generating agent, the polarity and the like.

When the charge generating agent and the charge transporting agent contained in the photosensitive layer have poor film-forming ability, they may be formed using a binder polymer. In this case, the charge generation layer can be obtained by applying and drying a coating solution obtained by dissolving or dispersing these substances and a binder polymer in a solvent.
As the binder, for example, polymers and copolymers of vinyl compounds such as butadiene, styrene, vinyl acetate, vinyl chloride, acrylates, methacrylates, vinyl alcohol, or ethyl vinyl ether, polyvinyl acetal, polycarbonate, polyester, polyamide, Polyurethane, cellulose ether,
Phenoxy resins, silicon resins, epoxy resins, and the like. These can be used after being crosslinked by heat, light or the like using an appropriate curing agent or the like. These binders can be used alone or in combination of two or more.

In the case of the function-separated type photoreceptor, the ratio of the charge generating agent to the binder polymer in the charge generating layer is not particularly limited, but is generally 5 to 500 parts by weight, preferably 100 parts by weight of the charge generating agent. Uses 20 to 300 parts by weight of a binder polymer. The charge generating agent is usually dispersed and dissolved in an appropriate dispersion medium using a ball mill, an ultrasonic disperser, a paint shaker, an attritor, a sand grinder, or the like, and if necessary, a coating solution is prepared by adding a binder resin. Liquid dipping method, spray method, bar coater method, blade method, roll coater method,
The coating is performed by a coating method such as a wire bar coating method or a knife coater coating method, and then dried. Further, the charge generation layer may be formed by depositing the above-mentioned charge generation agent by a vapor deposition method such as vapor deposition or sputtering. The thickness of the charge generation layer is 0.01
To 5 μm, preferably 0.05 to 2 μm.

The ratio of the total charge transporting agent to the binder polymer in the charge transporting layer is not particularly limited, but is generally 10 to 500 parts by weight, preferably 30 to 300 parts by weight, per 100 parts by weight of the total charge transporting agent. Is used. The charge transport layer is mixed with the above polymer having excellent performance as a binder, dissolved in an appropriate solvent together with the charge transport agent, and the obtained coating solution is applied by the same method as the charge generation layer, Can be manufactured. The thickness of the charge transport layer is usually 10 μm to 50 μm.
m, preferably in the range of 15 μm to 35 μm.

When the photosensitive layer has a single-layer structure, a coating solution obtained by dissolving and dispersing additives and the like in a solvent in addition to the above-described charge generating agent, charge transporting agent and binder polymer is applied on a substrate by the same method. Thereby, a photosensitive layer is obtained. Solvent used at the time of coating, as a dispersion medium, butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine,
N, N-dimethylformamide, acetone, methyl ethyl ketone, cyclohexanone, benzene, toluene, xylene, chloroform, 1,2-dichloroethane, 1,
2-dichloropropane, 1,1,2-trichloroethane, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethane, dichloromethane, tetrahydrofuran, dioxane, methyl alcohol, ethyl alcohol, isopropyl alcohol, ethyl acetate, acetic acid Butyl, dimethylsulfoxide, methylcellosolve and the like.

These solvents may be used alone or in combination of two or more. If necessary, an electron-withdrawing compound or a plasticizer, a pigment or other additives may be added. Examples of the electron-withdrawing compound include cyano compounds such as tetracyanoquinodimethane, dicyanoquinomethane, and aromatic esters having a dicyanoquinovinyl group; nitro compounds such as 2,4,6-trinitrofluorenone; and condensation of perylene and the like. Polycyclic aromatic compounds; diphenoquinone derivatives; quinones; aldehydes; ketones; esters;
Metal complexes of substituted and unsubstituted salicylic acids; metal salts of substituted and unsubstituted salicylic acids; metal complexes of aromatic carboxylic acids; and metal salts of aromatic carboxylic acids. Preferably, cyano compounds, nitro compounds, condensed polycyclic aromatic compounds, diphenoquinone derivatives, metal complexes of substituted and unsubstituted salicylic acids, metal salts of substituted and unsubstituted salicylic acids; metal complexes of aromatic carboxylic acids; It is preferable to use a metal salt.

Further, the photosensitive layer of the electrophotographic photoreceptor of the present invention has a well-known plasticizer and an antioxidant for improving film formability, flexibility, coatability, mechanical strength, film forming property, durability and the like. Agents, ultraviolet absorbers and leveling agents. It goes without saying that the photoreceptor thus formed may have an undercoat layer, an intermediate layer, and the like, if necessary.

The undercoat layer is usually used between the photosensitive layer and the conductive support, and a commonly used known layer can be used. Titanium oxide, aluminum oxide,
Inorganic fine particles such as zirconia and silicon oxide, organic fine particles,
Polyamide resin, phenol resin, melamine resin, casein, polyurethane resin, epoxy resin, cellulose,
Components such as resins such as nitrocellulose, polyvinyl alcohol, and polyvinyl butyral can be used. These fine particles and resin can be used alone or in combination of two or more. The thickness is usually 0.01-50μ
m, preferably 0.01 to 10 μm. A known blocking layer can be provided between the photosensitive layer and the conductive support. When a surface protective layer is provided on the present photoreceptor, the thickness of the protective layer can be 0.01 to 20 μm, preferably 0.1 to 10 μm. The above-mentioned binder can be used for the protective layer, but the protective layer may contain the above-mentioned charge generating agent, charge transporting agent, additive, conductive material such as metal and metal oxide. The electrophotographic photoreceptor thus obtained is a photoreceptor that maintains excellent printing durability over a long period of time, and is suitable for electrophotographic fields such as copying machines, printers, fax machines, and plate making machines.

In using the electrophotographic photoreceptor of the present invention, a corona charger such as a corotron and a scorotron, and a contact charger such as a charging roll and a charging brush are used. Exposure is performed using a halogen lamp, a fluorescent lamp, a laser (semiconductor, He-Ne), an LED, a photoconductor internal exposure method, or the like. The development process is cascade development, 1
Dry development methods such as component-insulated toner development, one-component conductive toner development, and two-component magnetic brush development, and wet development methods are used. For the transfer process, an electrostatic transfer method such as corona transfer, roller transfer, belt transfer, pressure transfer method, and adhesive transfer method are used. For fixing, heat roller fixing, flash fixing, oven fixing, pressure fixing and the like are used. For cleaning, a brush cleaner, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, and the like are used.

[0070]

The present invention will be described in more detail with reference to the following examples. In the examples, “parts” means “parts by weight”. Production Example 1

[0071]

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The above hydroxy compound H, 16 g (55 mmo)
l), stearyl bromide 23.9 g (72 mmo)
l), tetrabutylammonium bromide (TBA
B) 5.1 g was dissolved in 100 ml of tetrahydrofuran (THF) in a 300 mL four-necked flask, and cras
6.2 g of hed KOH was added, and the mixture was stirred under reflux for 4 hours. After cooling, 200 ml of toluene and 200 ml of water were added, and the mixture was separated. The organic layer was washed with 100 ml of water until neutral. After drying the organic layer over magnesium sulfate, the solvent was distilled off under reduced pressure, the residue was purified by a column, and the solvent was distilled off under reduced pressure.
13 g (24 mmol) of a white solid (W-1) was obtained.
(Yield 43%). FIG. 1 shows the IR spectrum of W-1.

Production Example 2

[0074]

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Ditolylaminobenzaldehyde F60.
3 g (0.2 mol) was placed in a 1 L four-necked flask and dissolved in 500 ml of THF. At 20 ° C ± 5 ° C,
5 g (0.15 mol) of NaBH ₄ was added, and the mixture was stirred for 2 hours. 200 ml of water was added little by little and stirred for 30 minutes. Thereafter, 300 ml of toluene and 200 ml of water were added, and liquid separation was performed. The organic layer was washed three times with 200 ml of water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to give pale yellow waxy crystal ditolylaminobenzyl alcohol A, 50.9 g.
(0.17 mmol) was obtained. (83.9% yield).

The obtained alcohol A, 16 g (53 m
mol), stearyl bromide 22.9 g (68.6 m
mol), 5.1 g of TBAB was dissolved in 200 ml of THF in a 500 mL four-necked flask, and the mixture was crashed.
6 g of KOH was added, and the mixture was stirred under reflux for 4 hours. After cooling, 200 ml of toluene and 200 ml of water were added, and the mixture was separated. The organic layer was washed with 200 ml of water until neutral. After the organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, the residue was purified by a column, and the solvent was distilled off under reduced pressure.
It was dissolved in 5 ml and released into 100 ml of hexane to obtain 8 g (14.4 mmol) of a jelly-like solid (W-2).
(Yield 27%). FIG. 2 shows the IR spectrum of W-2.

Production Example 3

[0078]

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Hydroxy Form A, 2 g (7 mmol) and 2.3 g (7.7 mmol) of stearic acid chloride were dissolved in 20 ml of THF in a 50 mL four-necked flask, 5 g of pyridine was added, and the mixture was stirred under reflux for 4 hours. .
After cooling, 50 ml of toluene and 50 ml of water were added, and the mixture was separated. The organic layer was washed with 100 ml of water until neutral. After the organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by a column. The solvent was distilled off under reduced pressure to obtain 2.5 g (4.5 mmol) of a white solid (W-3). (Yield 64%). FIG. 3 shows the IR spectrum of W-3.

Example 1 (Preparation of charge generation layer) Azo compound 10 having the following structure
Part is 150 parts of 4-methoxy-4-methylpentanone-
In addition to the above, pulverization and dispersion treatment was performed with a sand glide mill. The pigment dispersion obtained here was treated with polyvinyl butyral (trade name # 6000-C, manufactured by Denki Kagaku Kogyo KK).
100 parts of a 1,2-dimethoxyethane solution and 100 parts of a 5% dimethoxyethane solution of a phenoxy resin (PKHH, manufactured by Union Carbide Co., Ltd.)
Finally, a dispersion having a solid concentration of 4.0% was prepared.

[0081]

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This charge generation layer solution was prepared with an outer diameter of 30 mm and a length of 3 mm.
A 48 mm, 1.0 mm thick aluminum cylinder is dip-coated and its dry film thickness is 0.4 g / m ² (about 0.4 μm).
The charge generation layer was provided so as to satisfy m).

(Preparation of Charge Transfer Layer) Next, on this charge generation layer, 80 parts of the following charge transport agent (T-1) were added.

[0084]

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1.5 parts of cyano compound

[0086]

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Lubricant (W-1) 20 parts

[0088]

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A solution obtained by dissolving 100 parts of a polycarbonate resin (trade name: Z-200, manufactured by Mitsubishi Gas Chemical Co., Ltd.) in a mixed solvent of tetrahydrofuran and dioxane was applied by dip coating, followed by drying at 125 ° C. for 25 minutes. The charge transfer layer was provided so that the dry film thickness became 21 μm. The electrophotographic photosensitive member thus obtained is designated as A1.

Example 2 A photoconductor was prepared in the same manner as in Example 1, except that the lubricant (W-1) was changed to the lubricant (W-2). This electrophotographic photosensitive member is designated as A2.

[0091]

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Example 3 A photoconductor was prepared in the same manner as in Example 1, except that the lubricant (W-1) was changed to the lubricant (W-3). This electrophotographic photosensitive member is designated as A3.

[0093]

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Comparative Example 1 A photoconductor was prepared by the same method as that of Example 1 except that the lubricant (W-1) was not used and the number of parts of the charge transporting agent (T-1) was changed to 100 parts. This electrophotographic photosensitive member is designated as P1.

Next, these electrophotographic photosensitive members were mounted on a commercially available copying machine (SF7850 manufactured by Sharp Corporation) and
A 00 sheet copy test was performed. Table 1 shows the change in the thickness of the photosensitive layer (converted per 10,000 sheets) at this time.

[0096]

[Table 33]

Example 4 A film obtained by evaporating aluminum on a 75 μm-thick polyester film was used as a conductive support, and the charge-generating layer liquid weighed 0.4 g / m ² (about 0.4 μm ) Was applied with a wire bar and dried to form a charge generation layer. Further, a charge transfer layer liquid having the same composition as in Example 1 is applied on the charge generation layer with an applicator. afterwards,
Drying was performed at room temperature for 30 minutes and at 125 ° C. for 20 minutes, and a charge transfer layer was provided so that the film thickness after drying was 20 μm. This electrophotographic photosensitive member is designated as A4.

Example 5 A charge transport agent (T-1) was prepared using 10 parts of a lubricant (W-1).
A photoconductor was prepared by the same way as that of Example 4 except that the number of copies was changed to 90 parts. This electrophotographic photosensitive member is designated as A5.

Example 6 A charge transport agent (T-1) was prepared using 30 parts of a lubricant (W-1).
A photoconductor was prepared by the same way as that of Example 4 except that the number of copies was changed to 70 parts. This electrophotographic photosensitive member is designated as A6.

Comparative Example 2 A photoconductor was prepared by the same way as that of Example 4 except that the lubricant (W-1) was not used and the number of parts of the charge transporting agent (T-1) was changed to 100 parts. This electrophotographic photosensitive member is designated as P2.

Comparative Example 3 A photoconductor was prepared in the same manner as in Example 5, except that stearyl stearate (WAX) having a similar alkyl chain length was used instead of the lubricant (W-1). This electrophotographic photosensitive member is designated as P3.

Example 7 (Preparation of charge generation layer) Black angle (2θ ± 0.2 °) 9.3 °, 1
10 parts of oxytitanium phthalocyanine having peaks at 3.2 °, 26.2 °, and 27.1 °, polyvinyl butyral (trade name # 6000-, manufactured by Denki Kagaku Kogyo KK)
C) To 5 parts, 500 parts of 1,2-dimethoxyethane were added,
The mixture was pulverized and dispersed by a sand grind mill to obtain a charge generation layer liquid. Next, a film obtained by evaporating aluminum on a 75 μm-thick polyester film was used as a conductive support, and the charge-generating layer liquid weighed 0.4 g / m ² after drying.
(Approximately 0.4 .mu.m) with a wire bar and dried to form a charge generation layer.

(Preparation of Charge Transfer Layer) Next, on this charge generation layer, 50 parts of the following charge transport agent (T-2) were added.

[0104]

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10 parts of the lubricant (W-1) and a polycarbonate resin (trade name: Z-20, manufactured by Mitsubishi Gas Chemical Co., Ltd.)
A solution prepared by dissolving 100 parts of 0) in a mixed solvent of tetrahydrofuran and dioxane is applied on the charge generation layer with an applicator. Thereafter, drying was performed at room temperature for 30 minutes and at 125 ° C. for 20 minutes, and a charge transfer layer was provided so that the film thickness after drying was 20 μm. This electrophotographic photosensitive member is designated as A7.

Example 8 A charge transport agent (T-2) was prepared by using 20 parts of the lubricant (W-1).
A photoconductor was prepared by the same way as that of Example 7 except that the number of copies was changed to 40 parts. This electrophotographic photosensitive member is designated as A8.

Example 9 A charge transport agent (T-2) was prepared using 30 parts of the lubricant (W-1).
A photoconductor was prepared by the same way as that of Example 7 except that the number of copies was changed to 30 parts. This electrophotographic photosensitive member is designated as A9.

Next, these electrophotographic photoreceptors were mounted on a photoreceptor characteristic measurement (Model EPA8100, manufactured by Kawaguchi Electric Co., Ltd.), and charged so that the current flowing into the aluminum surface became 50 μA. Exposure (Examples 7, 8,
9. In Comparative Example 4, monochromatic light exposure at 780 nm) was performed, charge was removed, the chargeability (Vo) at that time, the rate of decrease in potential after 2 seconds from the start of charging (dark decay DD), and the amount of half-decreased exposure (E1 / 2)
Reference potential: -450 V, lux · sec for white light,
At 780 nm, μJ / cm ² ) The residual potential (Vr) was measured.

Further, the friction coefficient of these electrophotographic photosensitive members is automatically determined by using a friction and wear analyzer (FACE, DFPM-SS).
(Kyowa Interface Science Co., Ltd.). From the friction coefficient thus obtained, a relative value was determined by setting the friction coefficient of the comparative example in which the corresponding lubricant was not added to 1.0. These are summarized in Tables 2 and 3.

[0110]

[Table 34]

[0111]

[Table 35]

The W-1, W-2, W
Table 4 shows the IP (eV), SP / N, and melting point (mp) of -3, T-1, and T-2.

[0113]

[Table 36]

The IP (ionization potential) of a substance is
The measurement was performed using a surface analyzer AC-1 manufactured by Riken Keiki Co., Ltd.

[0115]

By using the photoreceptor of the present invention, by using a lubricant having a charge transporting property, a low friction surface can be obtained without impairing the basic properties such as the electrical characteristics and coating properties of the photoreceptor. Thus, a photosensitive member having excellent mechanical properties such as abrasion resistance, cleaning properties, and scratch resistance can be obtained.

[Brief description of the drawings]

FIG. 1 is an IR spectrum of a lubricating substance (W-1) used in Examples.

FIG. 2 is an IR spectrum of a lubricating substance (W-2) used in Examples.

FIG. 3 is an IR spectrum of a lubricating substance (W-3) used in Examples.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Shinichi Suzuki 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Mitsubishi Chemical Corporation Yokohama Research Laboratory F-term (reference) 2H068 AA14 AA20 AA21 AA28 BA12 BA13 BA14 BA21 FA04

Claims (9)

[Claims] 1. An electrophotographic photosensitive member having a photosensitive layer containing a charge transporting substance and a charge generating substance on a conductive support, wherein said photosensitive layer contains at least one kind of lubricating substance having a charge transporting group. An electrophotographic photoreceptor characterized in that: 2. The lubricating substance having a charge transporting group has an ionization potential (IP) of 4.7 eV to 5.7 eV.
The electrophotographic photoreceptor according to claim 1, wherein 3. A value obtained by dividing a total number SP of bonding orders by a number N of atoms in a molecule of a lubricating substance having a charge transporting group;
3. The electrophotographic photoreceptor according to claim 1, wherein SP / N is 1.15 or less, and a group in which 6 or more atoms are connected in series by a primary bond. 4. The electrophotographic photoconductor according to claim 1, wherein the lubricating substance having a charge transporting group has a long-chain alkyl (having 11 or more carbon atoms). 5. The electrophotographic photosensitive member according to claim 4, wherein the long-chain alkyl having a charge transporting group has a molecular terminal. 6. The electrophotographic photosensitive member according to claim 1, wherein the lubricating substance having a charge transporting group has an ester group and / or an ether bond. 7. The method according to claim 1, wherein the lubricating substance having a charge transporting group has an arylamine, stilbene, hydrazone, or triarylmethane structure. The electrophotographic photosensitive member according to the above. 8. The electrophotographic photoreceptor according to claim 1, wherein the lubricating substance having a charge transporting group has an endothermic peak at 130 ° C. or lower in thermal analysis. 9. The photoconductor according to claim 1, wherein at least one kind of charge transporting substance other than the lubricating substance is contained.
9. The electrophotographic photoreceptor according to any one of items 1 to 8.