JPH06222581A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To provide an electrophotographic sensitive body having high bending strength of a coating film on the surface of the sensitive body, not causing defects such as cracks in the coating film even when the sensitive body is repeatedly used as a beltlike sensitive body and having improved wear resistance and original electrical characteristics and image quality characteristics. CONSTITUTION:This electrophotographic sensitive body contains polycarbonate resin whose repeating units are represented by the formula as a bonding resin in the photosensitive layer. The viscosity average mol.wt. of the polycarbonate resin is usually within the range of 10,000-200,000 and polycarbonate resin having 20,000-100,000 viscosity average mol.wt. is preferably used when the mol.wt. distribution is relatively uniform. A mixture or copolymer of different polycarbonate resins may be used. In the formula, each of X1, X1' and X2 is H, a halogen, alkyl, cycloalkyl, aryl or arylalkyl.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor, and more specifically, it uses a specific polycarbonate resin as a binder resin, and the coating film of the surface layer has high bending strength and excellent abrasion resistance. And a highly durable electrophotographic photoreceptor.

[0002]

2. Description of the Related Art In recent years, electrophotographic technology has been remarkably developed in the fields of copying machines, laser beam printers and the like because it has the advantage that high speed and high printing quality can be obtained. As electrophotographic photoreceptors used in these electrophotographic techniques, selenium, selenium-
Those using an inorganic photoconductive material such as tellurium alloy, selenium-arsenic alloy, and cadmium sulfide are widely known. on the other hand,
Research on electrophotographic photoconductors using organic photoconductive materials, which are cheaper and have superior advantages in terms of manufacturability and disposability as compared with electrophotographic photoconductors using these inorganic photoconductive materials, has also been activated. . Among them, the function-separated organic laminate type photoreceptor in which a charge generation layer that generates a charge upon exposure and a charge transport layer that transports a charge is laminated is preferable in terms of electrophotographic characteristics such as sensitivity, chargeability and repeated stability thereof. It is excellent, and various proposals have been made and put into practical use. On the other hand,
The single-layer type organic photoconductor has the manufacturability, the manufacturing cost, and the system advantage of positive charging (reduction of ozone generation, uniform charging property), but the electrical performance is inferior to that of the laminated photoconductor. However, there is still plenty of room for research and development.

An organic laminated type photoreceptor has been developed which has sufficient performance with respect to the above-mentioned electrophotographic characteristics. However, since the photosensitive layer is made of an organic material, the durability against mechanical external force, That is, toner, developer, paper,
Problems such as abrasion and scratches on the surface of the photoconductor due to direct load from the cleaning member and adhesion of foreign matter such as toner filming may cause image quality defects, or ozone, nitrogen oxides, etc. generated by corona discharge. There is a problem such as image deletion in a high humidity environment caused by a low-resistance substance or paper dust generated from copy paper adhering and accumulating on the surface of the photoconductor, which limits the life of the photoconductor. In addition, with the increase in color and speed of copying machines and printers,
The process is becoming more complicated and the stress is increasing, and high durability is required also from these points. In addition, a flexible electrophotographic photosensitive member having a photosensitive layer coating film formed on a film such as polyethylene terephthalate having a conductive layer formed by a method such as vapor deposition can be processed into a belt and repeatedly used in a copying machine. Although it has the advantage that the shape freedom of the hardware of the copying machine can be expanded, there is a demand that the photosensitive layer must sufficiently follow the flexible movement. In order to solve these problems, various materials have been conventionally studied for the binder resin of the photosensitive layer in the electrophotographic photosensitive member. For example, various polycarbonate resins were used as the binder resin of the surface layer. A photoconductor has been proposed (JP-A-60-1).
72044, JP-A-62-247374,
JP-A-63-148263).

[0004]

However, when the conventionally proposed resin is used as the binder resin for the photosensitive layer, an electrophotographic photosensitive member having relatively good durability can be obtained, but none of them is still sufficiently satisfactory. . That is, the mechanical strength of the coating film formed by using these resins is not always sufficient, and when it is repeatedly used in a copying machine for a long period of time, the surface of the photosensitive layer is abraded and The thickness of the body changes and the sensitivity changes. Therefore, fog occurs in the copy, the charge potential and the copy density decrease, or scratches occur.
There is a problem that an image quality defect occurs due to adhesion of foreign matter such as toner filming. When the belt-shaped photoconductor is repeatedly rotated by a belt driving device in a copying machine, it cannot respond to its flexible movement, and a crack occurs in the photosensitive layer, which appears as a crack pattern on the copy image quality. There was a problem left. In addition, when the photosensitive layer is formed, the compatibility of the charge transport material with the binder resin is important, and if the compatibility is low, some charge transport materials may crystallize or precipitate, resulting in electrical characteristics and image quality characteristics. Has been found to have a significant impact on. The present invention has been made in view of the above circumstances, and its purpose is to:
The coating film on the surface of the photoconductor has high bending strength, does not cause defects such as cracks in the coating film even when it is repeatedly used as a belt-shaped photoconductor, and further improves abrasion resistance and original electrical characteristics and The present invention is intended to provide an electrophotographic photosensitive member having both compatible image quality characteristics.

[0005]

Means for Solving the Problems As a result of intensive studies on the binder resin, the present inventors have found that by incorporating a bisphenol-based polycarbonate resin in the photosensitive layer of an electrophotographic photoreceptor, the original electrical characteristics and The inventors have found that even when used as a belt-shaped photoreceptor, crack defects do not occur and excellent abrasion resistance is achieved while achieving both image quality characteristics, and the present invention has been completed.

That is, the present invention relates to an electrophotographic photoreceptor in which a photosensitive layer is coated on a conductive support, and the photosensitive layer contains a polycarbonate resin having a repeating unit represented by the following structural formula (I) as a binder resin. It is in the electrophotographic photoreceptor.

[Chemical 3] (In the formula, X ₁ , X ₁ ′ and X ₂ may be the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group or an arylalkyl group.)

The electrophotographic photoreceptor of the present invention will be described in detail below. The conductive support in the electrophotographic photosensitive member of the present invention, metals such as aluminum, nickel, chromium, stainless steel, and aluminum, titanium, nickel, chromium, stainless steel, gold, vanadium, tin oxide, indium oxide, Examples thereof include a plastic film coated with a thin film of ITO or the like, or paper and a plastic film coated or impregnated with a conductivity-imparting agent. These conductive supports are used in a suitable shape such as a drum shape, a sheet shape, and a plate shape, but are not limited thereto. Further, if necessary, 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, chemical treatment, coloring treatment, or irregular reflection treatment such as graining can be performed.

In the electrophotographic photoreceptor of the present invention, it is preferable to provide an undercoat layer between the conductive support and a photosensitive layer described later. This undercoat layer prevents the injection of charges from the conductive support to the photosensitive layer during charging of the photosensitive layer, and also acts as an adhesive layer that integrally adheres and holds the photosensitive layer to the conductive support, Alternatively, in some cases, the conductive support exhibits the antireflection function of light.

As the material for forming the undercoat layer, polyamide resin, vinyl chloride resin, vinyl acetate resin, phenol resin, polyurethane resin, melamine resin, benzoguanamine resin, polyimide resin, polyethylene resin, polypropylene resin, polycarbonate resin, acrylic resin. Resin, methacrylic resin, vinylidene chloride resin, polyvinyl acetal resin, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol resin, water-soluble polyester resin, nitrocellulose, casein, gelatin, polyglutamic acid, starch, starch acetate, amino starch, poly In addition to resins such as acrylic acid and polyacrylamide, zirconium chelate compounds, titanyl chelate compounds, organic titanyl compounds such as titanyl alkoxide compounds, silane coupling agents, etc. Known materials can be used. These materials can be used alone or in combination of two or more. Furthermore, titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, barium titanate,
It can be mixed with fine particles such as silicone resin. As a coating method for forming the undercoat layer, a usual method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method or a curtain coating method is adopted. It The thickness of the undercoat layer is 0.
A value of 01 to 10 μm, preferably 0.05 to 2 μm is suitable.

In the electrophotographic photosensitive member of the present invention, the photosensitive layer coated on the conductive support may have a single-layer structure or a laminated structure in which the charge-generating layer and the charge-transporting layer are functionally separated. May be. These photosensitive layers are composed of a coating film containing a charge generating material, a charge transporting material, or both in a binder resin. When the photosensitive layer has a laminated structure, the charge generation layer and the charge transport layer may be laminated in either order, but the case where the charge transport layer is the upper layer will be mainly described below.

As the charge generating material contained in the charge generating layer, amorphous selenium, crystalline selenium-tellurium alloy, selenium-arsenic alloy, other selenium compounds and selenium alloys, inorganic oxides such as zinc oxide and titanium oxide are used. Organic pigments and dyes such as photoconductive materials, phthalocyanine-based, squarylium-based, anthanthrone-based, perylene-based, azo-based, anthraquinone-based, pyrene-based, pyrylium salts, and thiapyrylium salts are used. Further, as the binder resin in the charge generation layer, polyamide resin, polyvinyl butyral resin, polyvinyl formal resin, partially modified polyvinyl acetal resin, polyester resin, polycarbonate resin, acrylic resin, polyvinyl chloride resin, polystyrene resin, polyvinyl acetate resin , Vinyl chloride-vinyl acetate copolymer, silicone resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, polyurethane resin, poly-N-vinylcarbazole resin, etc., but a film can be formed in a normal state. If it is a resin, it is not limited to these. These binder resins may be used alone or in combination of two or more.

The volume ratio of the charge generating material to the binder resin is preferably in the range of 5: 1 to 1: 2. The charge generation layer is formed by vacuum deposition of the charge generation material or by dispersing and applying the charge generation material to a binder resin in an organic solvent. Solvents used when preparing a coating solution include methanol, ethanol, n
-Propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate,
Usual organic solvents such as methylene chloride and chloroform may be mentioned. These solvents can be used alone or in combination of two or more. As a method for applying the application liquid, a usual method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method is adopted. The thickness of the charge generation layer is generally 0.01 to 5 μm, preferably 0.1.
1 to 2.0 μm is suitable.

The charge transport material contained in the charge transport layer includes p-benzoquinone, chloranil, bromoanil,
Electron withdrawing properties of quinone compounds such as anthraquinone, tetracyanoquinodimethane compounds, fluorenone compounds such as 2,4,7-trinitrofluorenone, xanthone compounds, benzophenone compounds, cyanovinyl compounds, ethylene compounds Substance, benzidine compound,
Triphenylamine-based compounds, arylalkane-based compounds, aryl-substituted ethylene-based compounds, butadiene-based compounds, stilbene-based compounds, anthracene-based compounds, hydrazone-based compounds, or polymers having groups of these compounds in the main chain or side chain Electron donating substances such as These charge transport materials can be used alone or in combination of two or more.

Among these charge-transporting materials, a benzidine compound and a mixture of a benzidine compound and a triphenylamine compound are preferably used.
As the benzidine compound, a compound represented by the following general formula (II) is preferable.

[Chemical 4] (In the formula, R ₁ and R ₁ ′ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and R ₂ , R ₂ ′, R ₃ and R ₃ ′ are represented.
May be the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a substituted amino group. In addition, m, m'and n, n'are each 1
Or, it means an integer of 2. )

Among the benzidine compounds represented by the above general formula (II), the applicant of the present invention has already disclosed in JP-A-62-24737.
The following general formula (III) or general formula (I
When the compound represented by V) is used, solubility in a solvent and compatibility with the polycarbonate resin (I) are high, and a uniform coating film can be obtained. Therefore, the following compound (III) or (IV) is particularly preferable as the benzidine-based compound because a uniform interface can be formed, and an electrophotographic photosensitive member having a particularly high sensitivity and excellent repeated stability is produced.

[0016]

[Chemical 5] (In the formula, R ₄ , R ₄ ′, R ₅ and R ₅ ′, which may be the same or different, each represents a hydrogen atom or a methyl group.)

[Chemical 6] (In the formula, R ₆ and R ₆ ′ may be the same or different and each represents an alkyl group having 2 or more carbon atoms, and R ₇ and R ₇ ′ may be the same or different and each is a hydrogen atom or an alkyl group. Represents a group, an alkoxy group or a substituted amino group.)

Further, the triphenylamine compound is preferably a compound represented by the following general formula (V).

[Chemical 7] (In the formula, R ₈ and R ₉ may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group, and R ₁₀ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms. Or represents an aryl group having 6 to 12 carbon atoms.)

Specific examples of benzidine compounds are shown in Tables 1 and 2, and specific examples of triphenylamine compounds are shown in Table 3, respectively.

[Table 1]

[0019]

[Table 2]

[0020]

[Table 3]

The benzidine compound and the triphenylamine compound are not limited to the compounds listed in Tables 1 to 3. For example, Tables 1 and 2 list benzidine compounds having the same R ₁ and R ₁ ′, R ₂ and R ₂ ′, and R ₃ and R ₃ ′ for convenience, but they do not necessarily have to be the same. , And further R ₁ ′, R ₂ ′ and R ₃ ′
The substitution position of may not be the same as R ₁ , R ₂ and R ₃ . The benzidine compound and the triphenylamine compound may be used alone or in combination of two or more.

As the binder resin in the charge transport layer, it is desirable to use a polycarbonate resin whose repeating unit is a polycarbonate resin represented by the structural formula (I) as a main component.

[Chemical 8] (Wherein X ₁ , X ₁ ′ and X ₂ are the same as above)

X ₁ , X ₁ 'and X _{2 in the} general formula (I)
As the above, the following substituents can be exemplified.
For example, as a halogen atom, a fluorine atom, a chlorine atom,
Examples thereof include a bromine atom and an iodine atom. The alkyl group may be linear or branched, a methyl group,
Examples thereof include ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group and octadecyl group. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and the like. Examples of the aryl group include a phenyl group and a naphthyl group. As the arylalkyl group, benzyl,
Examples thereof include a phenethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group, and a naphthylmethyl group. The alkyl group may have a branched chain structure, and in the alkyl group having 2 or more carbon atoms. The phenyl group can be substituted not only with the terminal carbon but also with another carbon. Further, these aryl groups include
One or two or more of the above-mentioned substituents such as a halogen atom and an alkyl group may be substituted.

As the polycarbonate resin (I), one having a viscosity average molecular weight in the range of 10,000 to 200,000 can be used. When the polycarbonate resin (I) having a relatively uniform molecular weight distribution is used, it is preferably in the range of 20,000 to 100,000. When the viscosity average molecular weight is less than 20,000, the viscosity of the coating liquid is low and the required film thickness cannot be obtained, so that the film thickness unevenness is likely to occur in the case of dip coating, for example. On the other hand, when the viscosity average molecular weight is more than 100,000, on the contrary, there is a problem that the viscosity of the coating liquid is high and it is difficult to control the required film thickness. However, this point is that the viscosity average molecular weight is 10,000 to 20.
Since it can be improved by appropriately mixing and using the polycarbonate resin (I) in the range of 100,000, the polycarbonate resin (I) having a significantly different viscosity average molecular weight may be mixed and used. Further, it is also possible to use a mixture of different polycarbonate resins or a copolymer thereof, as long as the effects and effects of the polycarbonate resin (I) are not impaired.

In the present invention, the polycarbonate resin which can be preferably used is exemplified by the one represented by the structural formula having a repeating unit as shown below. These polycarbonate resins are 1,3-bis [β- (4-
It can be produced by an ordinary synthetic method of reacting hydroxyphenyl) -β-propyl] benzene (hereinafter referred to as bisphenol compound (1)) or a derivative thereof with phosgene.

[0026]

[Chemical 9]

[0027]

[Chemical 10]

[0028]

[Chemical 11]

[0029]

[Chemical 12]

[0030]

[Chemical 13]

The composition ratio of the charge transport material to the binder resin is preferably in the range of 10:90 to 70:30 by weight, and 3
The range of 0:70 to 60:40 is preferable. The solvent used when forming the charge transport layer, benzene, toluene, aromatic hydrocarbons such as xylene, halogenated aromatic hydrocarbons such as monochlorobenzene, ketones such as acetone, methyl ethyl ketone, methylene chloride, Halogenated aliphatic hydrocarbons such as chloroform and ethylene chloride,
Usual organic solvents such as cyclic or linear ethers such as tetrahydrofuran and ethyl ether can be mentioned. These solvents can be used alone or in combination of two or more. Further, as a method for applying the coating solution, a usual method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method or the like is adopted. The thickness of the charge transport layer is generally 5 to 50 μm, preferably 10 to 30 μm.
m is suitable.

In the photoconductor of the present invention, an antioxidant, a light stabilizer, a heat stabilizer, a heat stabilizer and a heat stabilizer are added to the photosensitive layer for the purpose of preventing the photoconductor from deteriorating due to ozone, oxidizing gas, light or heat generated in the copying machine. Additives such as stabilizers can be added. Examples of antioxidants include hindered phenols, hindered amines, paraphenylenediamines, arylalkanes, hydroquinones, spirocoumarone, spiroindanone and their derivatives, organic sulfur compounds and organic phosphorus compounds. Examples of light stabilizers are benzophenone, benzotriazole, dithiocarbamate,
Examples thereof include derivatives such as tetramethylpiperidine.

When the photosensitive layer of the electrophotographic photosensitive member according to the present invention has a single layer structure, the same charge generating material and charge transport material as those used when the photosensitive layer has a laminated structure are used, and the binder resin is used. The polycarbonate resin described for the charge transport layer is used as the material. The polycarbonate resin may contain less than 50% by weight of the binder resin exemplified in the charge generation layer. Further, if necessary, additives such as the above-mentioned antioxidants, light stabilizers and heat stabilizers are contained in the photosensitive layer. In the single-layer type photoreceptor, the composition ratio of the charge generating material is 0.1 to 20% by weight, preferably 0.5 to 5% by weight, based on the total amount of the charge transporting material and the binder resin.
Is appropriate. The composition ratio of the charge transport material and the binder resin is preferably in the range of 60:40 to 30:70 by weight. To coat the photosensitive layer on the conductive support, after uniformly dissolving or dispersing the above-mentioned constituents in a solvent as exemplified when forming the charge transport layer, the above-mentioned usual coating method is used. It may be applied and dried. The thickness of the single-layer type photosensitive layer is generally 5 to 50 μm, preferably 10 to 25 μm.
Is appropriate.

The polycarbonate resin (I) used as the binder resin is preferably contained on the outermost surface of the photosensitive layer. That is, when the photosensitive layer of the electrophotographic photosensitive member has a single layer structure, the polycarbonate resin (I) is contained in the photosensitive layer as described above. On the other hand, when the photosensitive layer has a laminated structure, the polycarbonate resin (I) is preferably contained in the charge transport layer, but when the charge generating layer is coated on the upper layer, the polycarbonate resin (I) is contained in the charge generating layer. It is also possible to use the binder resin as described in the charge generation layer for the charge transport layer. The electrophotographic photosensitive member of the present invention is also a single layer type photosensitive member, on the photosensitive layer,
Further, a protective layer may be formed on the charge transport layer in the laminated photoreceptor.

[0035]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. In addition, "part" in an Example and a comparative example means a weight part. First, a representative synthesis example of the polycarbonate resin (I) used as a binder resin for the photosensitive layer in the electrophotographic photosensitive member of the present invention will be shown.

Synthesis Example 1 0.2 mol of bisphenol compound (1), 400 ml of 4.7% aqueous sodium hydroxide solution and 35 methylene chloride.
0 ml was placed in a reaction vessel having a volume of 2 l, and phosgene was blown thereinto at a rate of 400 ml / min for 15 minutes while vigorously stirring. Keep the reaction temperature at 15 ℃, 13.7%
40 ml of an aqueous sodium hydroxide solution, 0.2 g of trimethylbenzylammonium chloride and 0.3 ml of triethylamine were added, and stirring was continued at 23 ° C. for 1 hour to carry out a polycondensation reaction. Then, the reaction product was diluted with 400 ml of methylene chloride, and 1 liter of water and 0.5 N of 0.01N hydrochloric acid were used.
1 and 1 l of water. The obtained organic layer was added to 5 l of methanol to precipitate a white polymer, which was separated by filtration,
After drying at 100 ° C. for 12 hours, about 55 g of the above-mentioned polycarbonate resin (1) (viscosity average molecular weight Mv; 43,000) was obtained.

Synthesis Example 2 Bisphenol compound (1) was added to 1,3-bis [β- (3
-Methyl-4-hydroxyphenyl) -β-propyl]
About 50 g of the above polycarbonate resin (8) (Mv; 46,000) was obtained in the same manner as in Synthesis Example 1 except that benzene was used instead. Synthesis Example 3 Bisphenol compound (1) was added to 1,3-bis [β- (3
-Methyl-4-hydroxyphenyl) -β-propyl]
The polycarbonate resin (10) (Mv; 4) was prepared in the same manner as in Synthesis Example 1, except that -5-ethylbenzene was used instead.
About 2,000) was obtained. Synthesis Example 4 The bisphenol compound (1) was treated with 1,3-bis [β- (3
-Methyl-4-hydroxyphenyl) -β-propyl]
Polycarbonate resin (17) (Mv; 4) in the same manner as in Synthesis Example 1 except that -5-phenylbenzene was used.
About 7,000) was obtained.

Example 1 An aluminum thin film of about 500 Å was formed on the surface of a polyethylene terephthalate film by vacuum evaporation. A coating solution consisting of 10 parts of a polyamide resin (Laccamide 5003; manufactured by Dainippon Ink and Chemicals, Inc.), 150 parts of methyl alcohol and 40 parts of water was applied onto this substrate, and dried by heating at 120 ° C. for 10 minutes to give a film thickness of 1 μm.
An undercoat layer was formed. Then, a mixture of 90 parts of trigonal selenium (manufactured by Xerox Co., USA), 10 parts of polyvinyl butyral resin (S-REC BM-S; manufactured by Sekisui Chemical Co., Ltd.) and 300 parts of n-butyl alcohol was dispersed to obtain a dispersion liquid. A liquid diluted with 1 part of 2 parts of n-butyl alcohol was applied on the undercoat layer and dried by heating at 120 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.2 μm. Next, 8 parts of a benzidine compound (Compound No. II-27) as a charge transport material and 12 parts of the polycarbonate resin (1) obtained in Synthesis Example 1 were dissolved in 85 parts of monochlorobenzene to obtain a coating liquid. Is coated on an aluminum substrate on which a charge generation layer is formed,
It was heated and dried at 5 ° C. for 1 hour to form a charge transport layer having a thickness of 25 μm. In this way, an electrophotographic photoreceptor containing the polycarbonate resin (1) in the charge transport layer was produced.

Example 2 Compound No. 3 was used as the charge transport material. Compound No. II-27 in place of A photoconductor was prepared in the same manner as in Example 1 except that the benzidine compound of II-15 was used. Example 3 10 parts of a triphenylamine compound (Compound No. III-6) was used as a charge transport material instead of a benzidine compound, and 10 parts of a polycarbonate resin (1) was used as a binder resin of a charge transport layer. A photoconductor was produced in the same manner as in Example 1 except that the above was adopted.

Example 4 A photoconductor was prepared in the same manner as in Example 3 except that a hydrazone compound represented by the following general formula (VI) was used as the charge transport material instead of the triphenylamine compound.

[Chemical 14]

Example 5 A photoconductor was prepared in the same manner as in Example 3 except that a stilbene compound represented by the following general formula (VII) was used in place of the triphenylamine compound as the charge transport material.

[Chemical 15]

Examples 6 to 10 All of Examples 1 to 5 except that the polycarbonate resin (8) obtained in Synthesis Example 2 was used in place of the polycarbonate resin (1) as the binder resin for the charge transport layer. A photoconductor was prepared in the same manner as in. Examples 11 to 13 All were the same as Examples 1 to 3 except that the polycarbonate resin (10) obtained in Synthesis Example 3 was used in place of the polycarbonate resin (1) as the binder resin for the charge transport layer. To produce a photoconductor. Examples 14 to 16 All were the same as Examples 1 to 3 except that the polycarbonate resin (17) obtained in Synthesis Example 4 was used in place of the polycarbonate resin (1) as the binder resin for the charge transport layer. To produce a photoconductor.

Comparative Examples 1 to 5 In the formation of the charge transport layer, a polycarbonate resin (Mv; 3) having a repeating unit represented by the following structural formula (VIII) in place of the polycarbonate resin (1) as the binder resin is used.
Example 1 except that methylene chloride was used instead of monochlorobenzene as the coating solvent.
Photoreceptors were prepared in the same manner as in Steps 1 to 5.

[Chemical 16]

Comparative Examples 6 to 8 As a binder resin for the charge transport layer, a polycarbonate resin (Mv; 32,000) having a repeating unit represented by the following structural formula (IX) was used in place of the polycarbonate resin (1). A photoconductor was prepared in the same manner as in Examples 1 to 3.

[Chemical 17]

Each electrophotographic photosensitive member produced as described above was subjected to a bending repetition test up to 50,000 times by a film bending tester (manufactured by Nisshin Kagaku Co.). Further, a copying machine having a belt rotation driving device (Viv
ace800; made by Fuji Xerox Co., Ltd.) and each electrophotographic photoconductor is mounted with a belt tension tripled,
A copy running test up to 80,000 sheets was carried out without feeding the sheet, that is, without transferring to the sheet, and the image quality was evaluated every time 2000 sheets were copied. In addition, the state of the coating film on the surface (coating property) was visually observed during the production of each photoreceptor, and the results are shown in Table 4 together with the above evaluation.

[0046]

[Table 4] *: In each comparative example, the number of bends in which a crack is generated is shown. #: In each comparative example, the number of copies in which a minute crack is generated and an image defect is generated is shown.

Examples 17 to 22 Drum type photoconductors were prepared under the same conditions as in Examples 1 to 3 and Examples 6 to 8. Copy each electrophotographic photoreceptor to a copying machine (Vi
(Vace 500; made by Fuji Xerox Co., Ltd.) was mounted on a modified machine in which the ground pressure of the cleaning blade to the photoreceptor was tripled, and the copy running test was performed up to 30,000 times to measure the amount of abrasion of the photosensitive layer. did. At the same time, image quality defects after copying 30,000 sheets were evaluated. The results are shown in Table 5. Comparative Examples 9 to 14 Drum type photoreceptors were produced under the same conditions as in Comparative Examples 1 to 3 and Comparative Examples 6 to 8. In the same manner as in Example 17, each electrophotographic photosensitive member was measured for the amount of wear and evaluated for image quality defects. The results are shown in Table 5.

[0048]

[Table 5]

Example 23 10 parts of zirconium compound (Organix ZC540; manufactured by Matsumoto Pharmaceutical Co., Ltd.) and silane compound (A111)
0; manufactured by Nippon Unicar Co., Ltd.), a solution consisting of 1 part, 40 parts of i-propanol and 20 parts of butanol was applied onto a drum-shaped aluminum substrate by a dip coating method, and then at 150 ° C.
Was heated and dried for 10 minutes to form an undercoat layer having a film thickness of 0.1 μm. Then, 10 parts of a benzidine compound (Compound No. II-27) as a charge transport material and 12 parts of the polycarbonate resin (1) obtained in Synthesis Example 1 as a binder resin are mixed with 20 parts of monochlorobenzene and 80 parts of tetrahydrofuran. Dissolved in solvent. Next, 1 part of oxytitanyl phthalocyanine as a charge generating material was added, and the mixture was treated with glass beads for 1 hour in a sand mill to disperse, and the obtained coating solution was applied onto the undercoat layer by a dip coating method, It was heated and dried at 0 ° C. for 1 hour to form a single-layer type photosensitive layer having a film thickness of 25 μm. In this way, an electrophotographic photoreceptor containing the polycarbonate resin (1) in the single-layer type photosensitive layer was produced.

Example 24 A photoconductor was prepared in the same manner as in Example 23 except that the polycarbonate resin (8) obtained in Synthesis Example 2 was used as the binder resin instead of the polycarbonate resin (1). .

Comparative Examples 15 and 16 As the binder resin, the repeating unit was replaced by the above-mentioned structural formula (VIII) and structural formula (IX) in place of the polycarbonate resin (1).
A photoconductor was produced in the same manner as in Example 23 except that the polycarbonate resin represented by was used.

Examples 23 and 24 and Comparative Examples 15 and 16
Each electrophotographic photoreceptor prepared in 1. was mounted on a modified machine of a laser beam printer (XP-11; Fuji Xerox Co., Ltd.), and 30,000 copies were made without feeding paper, that is, without transferring to paper. The print running test up to was carried out and the amount of abrasion of the photosensitive layer was measured. At the same time, the image quality defects of the obtained copies were evaluated. The results are shown in Table 6.

[0053]

[Table 6]

[0054]

INDUSTRIAL APPLICABILITY According to the present invention, a polycarbonate resin having the repeating unit represented by the structural formula (I) is used as a binder resin for the photosensitive layer. Therefore, the coating film of the formed photosensitive layer is extremely high. Has bending strength. Therefore, the electrophotographic photosensitive member of the present invention, when used in the form of a belt, has high durability without causing cracks or the like in the photosensitive layer even after repeated use for a long time in a copying machine. ing. Further, the drum type photoconductor also exhibits high abrasion resistance, and even if it is repeatedly used for a long time in a copying machine, a copy image having excellent image quality can be obtained for a long time. As described above, the electrophotographic photosensitive member of the present invention maintains excellent repeated stability and has excellent abrasion resistance, as is clear from the above tables.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tomozumi Uesaka 1600 Takematsu, Minamiashigara City, Kanagawa Prefecture, Fuji Xerox Co., Ltd. (72) Inventor Taketoshi Hoshizaki 1600 Takematsu, Minamiashigara City, Kanagawa Prefecture, Fuji Xerox Co., Ltd. (72 ) Inventor Fumio Kojima 1600 Takematsu, Minamiashigara City, Kanagawa Prefecture Fuji Xerox Co., Ltd.

Claims (7)

[Claims] 1. An electrophotographic photosensitive member comprising a conductive support and a photosensitive layer coated thereon, wherein the photosensitive layer contains a polycarbonate resin having a repeating unit represented by the following structural formula (I) as a binder resin. An electrophotographic photosensitive member. [Chemical 1] (In the formula, X ₁ , X ₁ ′ and X ₂ may be the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group or an arylalkyl group.) 2. The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer contains a benzidine compound represented by the following general formula (II) as a charge transport material. [Chemical 2] (In the formula, R ₁ and R ₁ ′ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and R ₂ , R ₂ ′, R ₃ and R ₃ ′ are represented.
May be the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a substituted amino group. In addition, m, m'and n, n'are each 1
Or, it means an integer of 2. ) 3. The electrophotographic photoreceptor according to claim 2, wherein a mixture of the benzidine compound and the triphenylamine compound is used as a charge transport material. 4. The electrophotographic photosensitive member according to claim 1, wherein the polycarbonate resin is contained on the outermost surface of the photosensitive layer. 5. The photosensitive layer has a single layer structure.
The electrophotographic photosensitive member according to any one of 1. 6. The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer has a structure in which a charge generation layer and a charge transport layer are sequentially laminated, and the polycarbonate resin is contained in the charge transport layer. . 7. The electrophotographic photosensitive member according to claim 1, wherein an undercoat layer is provided between the conductive support and the photosensitive layer.