JP2001117252A - Organic semiconductor film, electrophotographic photoreceptor and image forming device using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an organic semiconductor film having satisfactory photoconductivity as an electronic device and excellent in mechanical strength and to obtain an electrophotographic photoreceptor and an image forming device using the photoreceptor. SOLUTION: The organic semiconductor film contains at least a material obtained by crosslinking and hardening an electric charge transferring polymer having a reactive group at an end or contains at least a material obtained by crosslinking and hardening an electric charge transferring polymer having a reactive group at an end and a crosslinkable compound. Or the organic semiconductor film is formed on the surface of an electrically conductive substrate to obtain the objective electrophotographic photoreceptor.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an organic semiconductor film which can be used as a photosensitive layer of an electrophotographic photosensitive member called an organic photosensitive member (OPC), and the organic semiconductor film is formed on the surface of a conductive support. An electrophotographic photoreceptor, and
The present invention relates to an image forming apparatus using the same.

[0002]

2. Description of the Related Art In recent years, so-called organic electronic devices such as an electrophotographic photosensitive member and an organic electroluminescent element have been put to practical use and widely used. As organic materials have become more sophisticated, organic materials have been used in areas where inorganic materials have been used, but problems with the inherent mechanical strength of organic materials have become apparent. I have.

For example, an organic electroluminescent device has a disadvantage that a low-molecular charge transporting material is melted by the generated Joule heat, and the morphology of the film is easily changed by crystallization or the like. Abrasion of the surface layer is a problem.

Hereinafter, the electrophotographic photosensitive member will be described in detail. At present, organic photoconductors have come to be used in high-speed copiers and printers as their performances have improved. In particular, when an organic photoreceptor is used in a high-speed copying machine, the current performance is not always sufficient, and a longer life is desired. One of the important factors that determines the life of the organic photoreceptor is the wear of the surface layer. Current organic photoconductors are mainly of the laminated type in which a charge transport layer is laminated on a charge generation layer, and the charge transport layer is often a surface layer. In the current mainstream low molecular dispersion charge transporting layer, sufficient electrical properties are being obtained, but the low molecular compound is dispersed in the binder polymer, and the inherent mechanical performance of the binder polymer is reduced. However, there is a disadvantage that the wear is essentially weak.

[0005] In order to improve the above drawbacks, various methods as described below have been proposed. (1) Addition of filler A method of adding strong resin fine particles to the photosensitive layer has been proposed. For example, JP-A-60-177349 discloses an example in which melamine resin fine particles are added.
However, since the compatibility between the charge transporting material and the binder resin and the fine particles is poor, there is a problem that phase separation occurs in the photosensitive layer, resulting in an opaque film, which may cause deterioration of electrical characteristics.

(2) Addition of a lubricating substance A method of adding a lubricating substance has been proposed for the purpose of enhancing the lubricity of the surface of the photosensitive layer. For example, Japanese Patent Laid-Open No. 2-14
It has been proposed to add fluorine-based polymer fine particles to JP-A No. 4550, and to add silicone-based fine particles to JP-A-63-65449. However, in any of the proposals, the charge transport material and the binder resin have poor compatibility with the lubricating substance,
There is a problem in that phase separation occurs in the photosensitive layer, resulting in an opaque film, which may cause deterioration of electrical characteristics.

(3) Curing of Binder Polymer A number of methods have been proposed in which a low molecular charge transport material is dispersed in a binder polymer or a polymer precursor, and then the binder polymer or the polymer precursor is cured by reaction. For example, JP-A-56-48637,
JP-A-56-42863 discloses a system using an acrylic polymer, and JP-A-5-66581 discloses a system for photocuring a vinyl monomer. Also,
JP-B 5-47104, JP-B-60-22347
And JP-B-7-120051 disclose systems using a silicon-based polymer or a polymer precursor, respectively.

However, in order to obtain sufficient characteristics as an electrophotographic photoreceptor, the concentration of the low-molecular charge transport material must be 3
Although it is necessary to increase the value to 0 to 50%, the curing reaction of the binder may not proceed sufficiently, and there is a problem that it is difficult to obtain a film having sufficient strength.

(4) Lamination of Surface Protective Layer An electrophotographic photosensitive member provided with a surface protective layer has been proposed to protect the surface of the photosensitive layer. For example, JP-A-61-
Japanese Patent Application No. 217052 proposes a system provided with a melamine resin, and Japanese Patent Application Laid-Open No. 8-15886 proposes a system provided with a silicon resin. However, since these electrophotographic photoreceptors do not have charge transport ability, they have a drawback that the residual potential may be increased.

(5) Use of charge transporting polymers Charge transporting polymers typified by polyvinyl carbazole (PVK) have the potential to achieve both high charge transporting ability and strength. I have. The present inventors have proposed in JP-A-8-253568 a charge-transporting polyester and an electrophotographic photosensitive member using the same. This electrophotographic photoreceptor has improved abrasion resistance as compared with the low molecular weight dispersion type organic photoreceptor. However, in order to further reduce the size of copiers and printers in the future, further improvements in durability are desired.

(6) Curing of low molecular charge transport material and crosslinkable compound A low molecular charge transport material having a functional group capable of forming a crosslinked structure and a method of curing a crosslinkable compound capable of reacting with the functional group have been proposed. ing. For example, JP-A-8-27864
JP-A-10-177 discloses that a polyfunctional oxirane compound and a charge transport material having an epoxy group are cured.
No. 268 proposes to cure a polyfunctional isocyanate compound and a charge transport material having a hydroxyl group. In addition, US Pat.
No. 0004 and Japanese Patent Application Laid-Open No. 9-124665 propose to cure a charge transporting material having a curable organosilicon polymer and an alkoxysilyl group. Since the charge transport material is directly chemically bonded to the crosslinkable compound serving as a binder, a surface layer with superior mechanical strength can be obtained compared to the current mainstream low molecular dispersion charge transport layer. Since many residual unreactive groups remain, there has been a problem in image characteristics under high temperature and high humidity.

(7) Curing of charge transporting oligomer A method of curing a charge transporting oligomer alone or a charge transporting oligomer and a crosslinkable compound has been proposed. Specifically, JP-A-6-250423 proposes a polycarbonate having a molecular structure three-dimensionally formed by a carbonate bond by curing a charge transporting oligomer. The transesterification method is used for the curing reaction, and a polymer chain splitting reaction occurs along with a crosslinking reaction in the reaction system.
There is a drawback that the mechanical strength inherent to the polymer of the charge transporting oligomer is not used, and it is difficult to obtain sufficient mechanical strength.

[0013]

SUMMARY OF THE INVENTION Accordingly, the present invention has been made to solve the above-mentioned problems in the prior art. That is, an object of the present invention is to have sufficient photoconductivity as an electronic device, an organic semiconductor film having excellent mechanical strength, and an electrophotographic photoreceptor,
Another object of the present invention is to provide an image forming apparatus using the same.

[0014]

Means for Solving the Problems As a result of diligent studies on the above problems, the present inventors have found that the terminal of the charge transporting polymer is cross-linked and cured, particularly preferably three-dimensionally cross-linked and cured. The present inventors have found that an organic semiconductor film having excellent mechanical strength can be obtained, and have completed the present invention.

That is, the present invention provides <1> an organic semiconductor film containing at least a charge-transporting polymer having a reactive group at a terminal crosslinked and cured. <2> An organic semiconductor film comprising at least a charge-transporting polymer having a reactive group at a terminal and a crosslinkable compound crosslinked and cured.

<3> An electrophotographic photosensitive member characterized in that at least the organic semiconductor film according to <1> or <2> is formed on the surface of a conductive support. <4> charging means for charging the electrophotographic photosensitive member with a charging member, latent image forming means for forming a latent image on the electrophotographic photosensitive member using coherent light, and electrostatic latent on the surface of the electrophotographic photosensitive member with toner Developing means for developing the image to obtain a toner image;
A transfer unit for transferring the formed toner image to the surface of the transfer material, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to <3>. It is.

In the organic semiconductor film of the present invention, it is preferable that the terminal of the charge transporting polymer is three-dimensionally cross-linked and cured. By using the charge transporting polymer, a three-dimensional crosslinked structure is formed by utilizing the mechanical strength unique to the polymer and further forming a chemical bond between the charge transporting polymers or between the charge transporting polymer and the crosslinkable compound. Therefore, it is possible to dramatically increase the mechanical strength.

In the present invention, since the main chain of the polymer is not split during the crosslinking and curing reaction, the intrinsic mechanical strength of the polymer is efficiently enhanced. Another advantage of using the charge transporting polymer is that the number of crosslinking reaction sites is small, so that image deterioration due to residual unreactive groups is unlikely to occur. Since it is easy to increase the density of the transport unit, there is an advantage that it is possible to cope with a further increase in the speed of the electrophotographic process.

[0019]

Embodiments of the present invention will be described below in detail. As the charge transporting polymer used in the present invention, generally known charge transporting polymers can be used, and among these, charge transporting polyesters and charge transporting polycarbonates are preferable.
Further, those containing at least one structural unit represented by the following general formula (I) or (II) are preferable, and charge transport represented by the following general formulas (III) to (VII) is preferable. Polyester or charge transporting polycarbonate is particularly preferred.

First, the structural unit represented by formula (I) or (II) will be described. The general formulas (I) and (II) are as follows.

[0021]

Embedded image

In the above formula, R _{1 to} R ₆ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a substituted amino group, a halogen atom, or a substituted or unsubstituted aryl group. k and l are each independently 0 or 1. X represents a substituted or unsubstituted aryl group. T represents a divalent hydrocarbon group having 1 to 10 carbon atoms which may be branched, and specifically, T-1 to T-32 shown below are exemplified.

[0023]

Embedded image

The above general formula (I) or general formula (I
The arylamine skeleton of I) may be bonded to any side of T. Specific examples of the structural unit (partial structure) represented by the general formula (I) are shown in Tables 1 to 12 below, and specific examples of the structural unit (partial structure) represented by the general formula (II) are shown in Tables 13 to 21 below. Each of the substituents is shown in a specific form. In addition,
When there is no item of "T" in the table, it indicates that "l" is 0 in the above general formula (I) or general formula (II).

[0025]

[Table 1]

[0026]

[Table 2]

[0027]

[Table 3]

[0028]

[Table 4]

[0029]

[Table 5]

[0030]

[Table 6]

[0031]

[Table 7]

[0032]

[Table 8]

[0033]

[Table 9]

[0034]

[Table 10]

[0035]

[Table 11]

[0036]

[Table 12]

[0037]

[Table 13]

[0038]

[Table 14]

[0039]

[Table 15]

[0040]

[Table 16]

[0041]

[Table 17]

[0042]

[Table 18]

[0043]

[Table 19]

[0044]

[Table 20]

[0045]

[Table 21]

Next, the charge-transporting polyester or polycarbonate represented by the general formula (III), (IV), (V) or (VI) will be described. The general formulas (III), (IV), (V) and (VI) are as follows.

[0047]

Embedded image

In the above formula, A represents a structural unit represented by the aforementioned general formula (I) or (II), and B represents —O—
_{(Y'-O) m '-} , or Z' represents, Y, Y ', Z and Z' each represents a divalent hydrocarbon group. m and m ′ are each independently an integer of 1 to 5, and n is 0 or 1. p is an integer of 5-500, q is 1-500
The integer of 0 and r show the integer of 1-3500, respectively. Here, q + r is an integer of 5 to 5,000, and 0.
3 ≦ q / (q + r) <1.

Specific examples of the compound represented by the general formula (III) are shown in Table 22 below, specific examples of the compound represented by the general formula (IV) are shown in Table 23 below, and specific examples of the compound represented by the general formula (V) are shown below. Examples are shown in Table 24 below, and specific examples of the compound represented by the general formula (IV) are shown in Tables 25 to 30 below, each of which specifies a substituent.

[0050]

[Table 22]

[0051]

[Table 23]

[0052]

[Table 24]

[0053]

[Table 25]

[0054]

[Table 26]

[0055]

[Table 27]

[0056]

[Table 28]

[0057]

[Table 29]

[0058]

[Table 30]

Next, the charge-transporting polyester or the charge-transporting polycarbonate represented by the general formula (VII) will be described. The general formula (VII) is as follows.

[0060]

Embedded image

In the above formula, R ₉ represents hydrogen, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group;
R ₇ and R ₈ each independently represent hydrogen, an alkoxy group, a halogen, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. T1 represents a divalent aliphatic group which may be branched, and n1 represents 0 or 1.
Ar ₁ and Ar ₂ each independently represent a substituted or unsubstituted aryl group. m1 represents an integer of 5 to 5000. Further, Y1 represents a substituted or unsubstituted divalent alkyl group, a substituted or unsubstituted divalent aryl group, or a divalent linking group represented by the following general formula (VIII).

[0062]

Embedded image

In the above formula, R ₁₁ and R ₁₂ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a halogen atom. a and b each independently represent an integer of 0 to 4; B represents a linear, branched or cyclic divalent hydrocarbon group having 1 to 12 carbon atoms, -O-, -S-, -SO-; , -SO _2- , -CO
— Or —CO—O—Z—O—CO— (where Z is 2
Represents a monovalent hydrocarbon group).

Specific examples of the compound represented by formula (VII) are shown in the following Tables 31 to 45 in a form in which each substituent is specified.

[0065]

[Table 31]

[0066]

[Table 32]

[0067]

[Table 33]

[0068]

[Table 34]

[0069]

[Table 35]

[0070]

[Table 36]

[0071]

[Table 37]

[0072]

[Table 38]

[0073]

[Table 39]

[0074]

[Table 40]

[0075]

[Table 41]

[0076]

[Table 42]

[0077]

[Table 43]

[0078]

[Table 44]

[0079]

[Table 45]

The charge transporting polymer in the present invention has a reactive group at the terminal. The reactive group at the terminal includes a reactive substituent and a reactive group capable of forming a crosslinked structure. Can be

In the present invention, the following three means (1) to (3) can be mentioned as means for crosslinking the charge transporting polymer. (1) Crosslinking and curing of a charge transporting polymer having a reactive substituent at the terminal and a crosslinkable compound (2) Crosslinking and curing of a charge transporting polymer having a reactive group capable of forming a crosslinkable structure at a terminal alone (3) ) Cross-linking and curing of a charge transporting polymer having a reactive group capable of forming a cross-linkable structure at the terminal and a cross-linkable compound Among these, the means (3) is particularly preferable.

In the case of the means (1), examples of the reactive substituent at the terminal of the charge transporting polymer include a substituent having an active hydrogen group and a substituent capable of reacting with a crosslinkable compound. Among them, a hydroxyl group, a carboxyl group, an amino group and the like are preferable. When the reactive substituent is a hydroxyl group or a carboxyl group, a polyester,
The terminal residue of polycarbonate can be used as it is. Other reactive groups can be introduced by modifying the terminal functional group derived from the polymer. For example, as a method for introducing a functional group into the hydroxyl group at the terminal of the polyester, it is preferable to react an acid chloride, a carboxylic acid, an acid anhydride, an isocyanate or the like having a desired functional group as a substituent.

When the desired functional group is active in the reaction introduced into the polymer terminal, it is also possible to carry out the introduction reaction with a desired functional group provided with a protective group and then carry out the deprotection reaction. It is. In the cross-linking and curing reaction, it is preferable that the charge-transporting polymer having a terminal-reactive group, the terminal-reactive group and a reactive cross-linkable compound are mixed and cross-linked and cured.

In the case of the above-mentioned means (2) and (3), a reactive group capable of forming a crosslinked structure is introduced into the charge transporting polymer prior to the crosslinking curing reaction. Specific examples of the reactive group capable of forming a crosslinked structure include an alkoxysilyl group, a methacryl group, and an epoxy group. The substituent capable of forming a crosslinked structure can be introduced by modifying a hydroxyl group or a carboxyl group which is a terminal functional group of polyester or polycarbonate. For example, as a method of introducing an alkoxysilyl group into the hydroxyl group at the polyester terminal, specifically, an addition reaction of an alkyl isocyanate having an alkoxysilyl group at the other end, or a reaction with an acid chloride having a vinyl group at the other end Followed by an addition reaction of an alkoxysilyl group by hydroxysilylation of a vinyl group at the terminal. In the cross-linking curing reaction, the cross-linking and curing can be performed by using the charge transporting polymer alone (the means (2)) or by further adding a cross-linkable compound (the means (3)).

As the crosslinkable compound used in the means (1) and (3), a polyfunctional compound having a plurality of functional groups is preferable. In particular, it is desired that the number of functional groups is 3 or more, which enables formation of a three-dimensional crosslinked structure. Examples include polyfunctional isocyanate compounds, polyfunctional epoxy compounds, polyfunctional vinyl compounds, alkoxysilane compounds and the like. Among these, a crosslinkable compound capable of reacting with the reactive group at the terminal of the charge transporting polymer may be appropriately selected. For example, a polyfunctional isocyanate compound is used for a charge-transporting polyester or polycarbonate, and a polyfunctional epoxy compound is used for a charge-transportable polymer containing an epoxy group at a terminal, and a charge-transporting polymer having an alkoxysilyl group at a terminal. On the other hand, alkoxysilane compounds are listed as preferable combinations.

The addition amount of the crosslinking compound is preferably about 0.01 to 50% by weight, more preferably about 0.1 to 30% by weight. The ratio of the reactive group of the crosslinkable compound to the reactive group at the end of the charge transporting polymer is 0.01 to 10
It is preferably 0 equivalent, more preferably 0.1 to 50 equivalent. As shown in the examples below, partial three-dimensional crosslinking is formed even when the reactive group of the crosslinkable compound is equal to or less than the reactive group at the terminal of the charge transporting polymer. With this, the mechanical strength is improved. further,
When the reactive group of the crosslinkable compound is equal to or more than the terminal functional group of the charge transportable polymer, in addition to the three-dimensional crosslinking and curing of the charge transportable polymer and the crosslinkable compound, the bonding between the crosslinkable compounds, An interpenetrating polymer network is formed, further improving mechanical strength.

Examples of the polyfunctional isocyanate compound include 1,3,6-hexamethylene triisocyanate, lysine ester triisocyanate, 1,6,11
And polyisocyanate monomers such as -undecane triisocyanate, 1,8-isocyanate-4-isocyanatomethyloctane, triphenylmethane triisocyanate, and tris (isocyanatephenyl) thiophosphate.

Further, among compounds containing three or more isocyanate groups, a film-forming property of a finally obtained crosslinked film,
It is more preferable to use a modified product such as a derivative or a prepolymer obtained from a polyisocyanate monomer from the viewpoint of crack generation resistance and easy handling.

Examples of these are urethane modified products obtained by modifying a polyol with an excess of an isocyanate compound, buret modified products obtained by modifying a compound having a urea bond with an isocyanate compound, and allophanate modified products obtained by adding an isocyanate to a urethane group. Preferably, a modified isocyanurate, a modified carbodiimide, etc. are used. Furthermore, although it is included in the above-mentioned modified polyisocyanate, a blocked isocyanate reacted with a blocking agent for temporarily masking the activity of the isocyanate group can also be preferably used. Here, the isocyanate used for the modification may have two functional groups, such as tolylene diisocyanate (TDI),
Diphenylmethane diisocyanate (MDI), 1,5
-Naphthylene diisocyanate, tolidine diisocyanate, 1,6-hexamethylene diisocyanate, xylene diisocyanate, lysine diisocyanate, tetramethyl xylene diisocyanate and the like.

Commercially available polyfunctional isocyanate compounds include Sumidur N-75, Sumidur N3200,
Death module N3400, Sumidur N3500,
Sumidur HT, Sumidur BL3175, Desmodur BL4165, Desmodur TPLS-20
10, Death Module TPLS-2759, Death Module E3265, Death Module Z4370, Death Module E41 (manufactured by Sumitomo Bayer Urethane Co., Ltd.), and the like.

As the alkoxysilane compound, various silane coupling agents and commercially available silicon-based hard coat agents can be used. Examples of the silane coupling agent include vinyl trichlorosilane, vinyl trimethoxy silane, vinyl triethoxy silane, γ-
Glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyl Dimethoxysilane,
N-β (aminoethyl) γ-aminopropyltriethoxysilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane and the like can be mentioned.

Examples of the commercially available hard coat agent include:
KP-85, CR-39, X-12-2208, X-4
0-9740, X-41-1007, KNS-530
0, X-40-2239 (all manufactured by Shin-Etsu Silicone Co., Ltd.), and AY42-440, AY42-441,
AY49-208 (all manufactured by Dow Corning Toray),
And the like.

In order to form the organic semiconductor film of the present invention, an appropriate solvent is added to the above-mentioned charge-transporting polymer or further the crosslinkable compound to form a coating solution. The crosslinking and curing reaction is performed by heating. Solvents used in the preparation of the coating solution include those that sufficiently dissolve the charge transporting polymer, have a boiling point slightly lower than the heating temperature required for the crosslinking curing reaction, and have an active hydrogen group that inhibits crosslinking curing of the charge transporting polymer. It is desired not to include

If necessary, a catalyst for accelerating the crosslinking and curing reaction may be added to the coating solution. For example,
Examples of the catalyst for the crosslinking and curing reaction of the isocyanate include amines, metal acetates, metal chlorides, copper sulfate, and organotin compounds. Specifically, N, N, N ', N'-tetramethylbutanediamine, N, N, N', N'-tetramethylhexamethylenediamine, 1,4-diazabicyclo [2,2,2] octane, Triethylamine, N-ethylmorpholine, cobalt naphthenate, dibutyltin dilaurate, tin octoate, stannous chloride, tetra-n-
Butyltin, trimethyltin hydroxide, dimethyltin dichloride and the like.

Examples of the catalyst for the crosslinking curing reaction of alkoxysilane include acids, bases, organic tin compounds, organic titanium compounds, iron salts of organic carboxylic acids, manganese salts, cobalt salts, zinc salts, zirconium salts, metal acetylacetones and the like. Is mentioned. Specifically, hydrochloric acid, sulfuric acid, formic acid, acetic acid,
Examples include trifluoroacetic acid, ammonia, triethylamine, dibutyltin diacetate, dibutyltin dioctoate, stannous octoate, tetra-n-butyl titanate, and tetraisopropyl titanate.

The amount of the catalyst to be added is preferably 0.001 to 5% by weight based on the charge transporting polymer.
0.01 to 3% by weight is more preferred. Further, for the purpose of improving mechanical strength, stain resistance, and lubricity, fine particles can be added to the coating solution before coating. Examples of the fine particles include inorganic fine particles such as silica gel, colloidal silica, and alumina, and resin fine particles. It is also possible to use silica gel, colloidal silica, or the like in which a functional group capable of reacting with a reactive group at the terminal of the charge transporting polymer is modified.

After the application of the coating solution, a heat treatment can be performed simultaneously with the drying step or subsequent to the drying step. The temperature at the time of the crosslinking curing reaction is not particularly limited, but is preferably room temperature to 200 ° C, more preferably 50 to 200 ° C.
Set to 150 ° C.

When the organic semiconductor film of the present invention is used as the outermost surface layer of an electrophotographic photoreceptor, an antioxidant is added to a coating solution for the purpose of preventing deterioration by an oxidizing gas such as ozone generated from a charger. It may be added. As the antioxidant, hindered phenol-based or hindered amine-based antioxidants are preferably used, and organic sulfur-based antioxidants, phosphite-based antioxidants, dicarbamic acid-based antioxidants, thiourea-based antioxidants, benz Known substances such as imidazole antioxidants can be used. The addition amount of the antioxidant is preferably 15% by weight or less in the organic semiconductor film, more preferably 10% by weight or less.

The organic semiconductor film of the present invention may be applied to any layer of an electrophotographic photoreceptor. Specifically, an undercoat layer; A charge generation layer, a charge transport layer, and a charge transport layer.
A surface protective layer; or a photosensitive layer and a surface protective layer of a single-layer type photoreceptor (an electrophotographic photoreceptor having both functions of charge generation and charge transport in the photosensitive layer; the same applies hereinafter); Etc. can be used.

The organic semiconductor film of the present invention is desirably used for the outermost surface layer (not necessarily a surface protective layer) by utilizing its wear characteristics. In addition, it is also possible to utilize the solvent resistance for the intermediate layer. When the organic semiconductor film of the present invention is used as the outermost surface layer of an electrophotographic photoreceptor, the lower layer has at least a charge generation layer, or at least a charge generation layer and a charge transport layer, or at least a single layer type photoreceptor. It is preferable to have a photosensitive layer.

Hereinafter, each component of the electrophotographic photosensitive member of the present invention will be described in detail. The electrophotographic photoreceptor of the present invention is
At least the organic semiconductor film of the present invention described above is formed on the surface of a conductive support.

Examples of the conductive support used in the electrophotographic photoreceptor of the present invention include metals such as aluminum, nickel, chromium and stainless steel; aluminum, titanium, nickel, chromium, stainless steel, gold, vanadium, tin oxide, and the like. A plastic film provided with a film of indium oxide, ITO, or the like; or paper or a plastic film coated or impregnated with a conductivity-imparting agent.
These conductive supports are used in an appropriate shape such as a drum shape, a sheet shape, and a plate shape, but are not limited thereto.

Further, the surface of the conductive support can be subjected to various treatments, if necessary, within a range that does not affect the image quality. For example, the surface can be subjected to oxidation treatment, chemical treatment, coloring treatment, or the like, or irregular reflection treatment such as graining.

The electrophotographic photoreceptor of the present invention may have an undercoat layer between the conductive support and the photosensitive layer. The undercoat layer prevents the injection of charge from the conductive support into the photosensitive layer when charging the laminated photosensitive layer (charge generation layer and charge transport layer) or the single-layer photosensitive layer, It exhibits an action as an adhesive layer for integrally adhering and holding the conductive support, or, in some cases, an action of preventing the conductive support from reflecting light.

In the undercoat layer, polyethylene resin, polypropylene resin, acrylic resin, methacrylic resin, polyamide resin, vinyl chloride resin, vinyl acetate resin, phenol resin, polycarbonate resin, polyurethane resin, polyimide resin, Vinylidene resin, polyvinyl acetal resin, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol resin, water-soluble polyester resin, nitrocellulose, casein, gelatin,
Known materials such as polyglutamic acid, starch, starthiacetate, amino starch, polyacrylic acid, polyacrylamide, zirconium chelate compound, titanyl chelate compound, titanyl alkoxide compound, organic titanyl compound, and silane coupling agent are used. These materials can be used alone or as a mixture of two or more kinds, and can also be used as a mixture with fine particles such as titanium oxide, silicon oxide, zirconium oxide, barium titanate, and silicone resin.

The thickness of the undercoat layer is preferably about 0.01 to 10 μm, more preferably 0.05 to 2 μm. The undercoat layer is formed by applying a coating solution obtained by dissolving and dispersing the above-described materials in an appropriate solvent on the surface of the conductive support and drying the coating. As a method of applying the coating 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, a curtain coating method, or the like can be used.

Hereinafter, the respective layers formed on the surface of the conductive support or on the undercoat layer will be described separately for the case of the laminated photoreceptor and the case of the single-layer type photoreceptor. First, the case of a laminated photoconductor will be described.

In the present invention, the charge generation layer of the electrophotographic photosensitive member contains at least a charge generation material and a binder resin. As the charge generation material, amorphous selenium, crystalline selenium-tellurium alloy, selenium-arsenic alloy, other selenium compounds and selenium alloys, inorganic photoconductive materials such as zinc oxide and titanium oxide, phthalocyanine-based, squarylium-based And organic pigments and dyes such as an anthrone-based, perylene-based, azo-based, anthraquinone-based, pyrene-based, pyrylium salt, and thiapyrylium salt. Among these, from the viewpoint of the photosensitivity of the electrophotographic photoreceptor, it is preferable to use a phthalocyanine-based compound, and preferable examples thereof include metal-free phthalocyanine, titanyl phthalocyanine, chlorogallium phthalocyanine, and hydroxygallium phthalocyanine.

Among the phthalocyanine compounds, particularly,
Bragg angle (2θ ± 0.2) in X-ray diffraction spectrum
°) is 7.4 °, 16.6 °, 25.5 °, 28.3.
Chlorogallium phthalocyanine having a specific crystal form having a strong diffraction peak at 0 ° or a Bragg angle (2θ ± 0.2 °) in an X-ray diffraction spectrum of 7.5 °;
9.9 °, 12.5 °, 16.3 °, 18.6 °, 2
Hydroxygallium phthalocyanine having a specific crystal form having strong diffraction peaks at 5.1 ° and 28.3 ° has high charge generation efficiency with respect to a wide range of light from visible light to near infrared light. Is preferred in that

Examples of the binder resin for the charge generation layer include polyvinyl butyral resin, polyvinyl formal resin, partially modified polyvinyl acetal resin, polycarbonate resin,
A polyester resin, an acrylic resin, a polyvinyl chloride resin, a polystyrene resin, a polyvinyl acetate resin, a vinyl chloride-vinyl acetate copolymer, a silicone resin, a phenol resin, a poly-N-vinyl carbazole resin, and the like are used, but are not limited thereto. Not something. These binder resins can be used alone or in combination of two or more.

The mixing ratio (weight ratio) of the charge generating material to the binder resin is preferably in the range of 10: 1 to 1:10. Also,
The thickness of the charge generation layer used in the present invention is generally 0.1.
1 to 5 μm, preferably 0.2 to 2.0 μm is suitable.

The charge generation layer is formed by applying a coating solution obtained by dissolving and dispersing the above-mentioned materials in an appropriate solvent on the surface of the conductive support or on the undercoat layer and drying. As a method of applying the coating 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, a curtain coating method, or the like can be used.

Solvents used for preparing the coating solution for the charge generation layer include methanol, ethanol, n-propanol and n-propanol.
-Butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate,
Ordinary organic solvents such as dioxane, tetrahydrofuran, methylene chloride, and chloroform can be used alone or in combination of two or more.

When the layer containing the organic semiconductor film of the present invention is used as a charge transport layer, it is preferable to laminate the layer on the charge generation layer. The charge transport layer in the present invention contains at least a charge transport material and a binder resin. This charge transport layer may be either a low-molecular dispersion type charge transport layer or a polymer charge transport layer having a charge transport function itself.

Examples of the charge transport material include quinone compounds such as p-benzoquinone, chloranil, bromoanil, and anthraquinone; tetracyanoquinodimethane compounds;
Fluorenone compounds such as 2,4,7-trinitrofluorenone, xanthone compounds, benzophenone compounds, cyanovinyl compounds, electron-withdrawing substances such as ethylene compounds, triarylamine compounds, benzidine compounds, arylalkane compounds Compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, hydrazone compounds and the like. These charge transport materials can be used alone or in combination of two or more.

Examples of the binder resin used for the charge transport layer include a polycarbonate resin, a polyester resin, a methacrylic resin, an acrylic resin, a vinyl chloride resin, a vinylidene chloride resin, a polystyrene resin, a polyvinyl acetate resin, a styrene-butadiene copolymer, and a chloride resin. Vinylidene-
Acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin,
Known resins such as phenol-formaldehyde resin, styrene-acrylic resin, styrene-alkyd resin, poly-N-vinylcarbazole, polysilane and the like can be used.

Further, an antioxidant can be added to the charge transport layer. When the charge transport layer is not the outermost layer, it does not come into direct contact with the oxidizing gas, but since these oxidizing gases may penetrate the surface protective layer and penetrate into the charge transport layer, Is appropriately used to prevent the occurrence of As the specific examples of the antioxidant, those described above are used.
% By weight or less, more preferably 10% by weight or less. When a layer containing the organic semiconductor film of the present invention is used as a surface protective layer, it is preferable to use the layer over the charge transport layer.

Next, the case of a single-layer type photosensitive member will be described. In the electrophotographic photoreceptor of the present invention, the photosensitive layer (single-layer type photosensitive layer) of the single-layer type photoreceptor is formed using at least the charge generating substance and the binder resin described in the section of the multilayer type photoreceptor. . As the binder resin, those similar to the binder resins used for the charge generation layer and the charge transport layer described above are used. The content of the charge generating substance in the single-layer type photosensitive layer is preferably in the range of 10 to 85% by weight, and more preferably in the range of 20 to 50% by weight.

An antioxidant may be added to the single-layer type photosensitive layer if necessary for the same reason as in the case of the charge transport layer, and the same material as that of the charge transport layer can be used. The amount of addition is 15% by weight or less, preferably 10% by weight or less. In addition, the above-described charge transporting material may be added to the single-layer type photosensitive layer for the purpose of improving the photoelectric characteristics and the like. In this case, the addition amount is preferably 70% by weight, more preferably 50% by weight or less. When a layer containing the organic semiconductor film of the present invention is used as a surface protective layer, it is preferable to use the layer by laminating it on the photosensitive layer.

The electrophotographic photosensitive member of the present invention as described above can be applied to all conventionally known electrophotographic image forming apparatuses.

Hereinafter, the image forming apparatus of the present invention will be described in detail. The image forming apparatus of the present invention is a charging unit that charges an electrophotographic photosensitive member with a charging member, a latent image forming unit that forms a latent image on the electrophotographic photosensitive member using coherent light,
An image forming apparatus, comprising: a developing unit that develops an electrostatic latent image on a surface of an electrophotographic photoreceptor with a toner to obtain a toner image; and a transfer unit that transfers the formed toner image to a transfer material surface. The photographic photosensitive member is the electrophotographic photosensitive member of the present invention as described above.

As a means for forming a latent image by exposure such as a laser optical system or an LED array, and other developing means, transferring means and fixing means, any conventionally known means can be employed. In addition, if necessary, a static eliminator for removing an electrostatic latent image remaining on the surface of the electrophotographic photoreceptor, a cleaning unit for collecting residual toner and other foreign matters on the surface of the electrophotographic photoreceptor, etc., are conventionally known as necessary. The method can be applied in the following manner.

FIG. 1 is a schematic configuration diagram showing an example of the image forming apparatus of the present invention. Photoreceptor 10 which is an electrophotographic photoreceptor of the present invention, and charging roll 1 which is a charging means of a contact charging type
2. a laser exposure optical system 14 as a latent image forming unit, a developing device 16 as a developing unit using powder toner, a transfer roll 18 as a transferring unit, a charge removing device 19 as a charge removing unit,
It has a cleaning device 24 having a cleaning blade 20 which is a mechanical cleaning means, and a fixing roll 22.

The mechanical cleaning means is a means for directly contacting the surface of the photoreceptor and removing toner, paper dust, dust and the like adhering to the surface. In addition, a known type such as a brush and a roll can be applied.

As the charging means, the charging roll 12 which is a contact charging type is mentioned here, but any type such as a non-contact type such as a corotron and a scorotron may be used. The charging means of the contact charging type is a photoconductor 10
The surface of the photosensitive member is charged by applying a voltage to the conductive member brought into contact with the surface of the photosensitive member. The shape of the conductive member may be a roll shape such as the charging roll 12 in FIG. Any of a brush shape, a blade shape, a pin electrode shape, and the like may be used, but a roll-shaped conductive member is particularly preferable. Usually, the roll-shaped conductive member is formed by forming an elastic layer on the roll surface as a core material, and further forming a resistance layer thereon. Further, if necessary, a protective layer can be provided outside the resistance layer.

The material of the core material has conductivity, and generally, iron, copper, brass, stainless steel, aluminum, nickel or the like is used. In addition, a resin molded product or the like in which conductive particles or the like are dispersed can also be used. The material of the elastic layer is an elastic material having conductivity or semi-conductivity, and is generally a material in which conductive particles or semi-conductive particles are dispersed in a rubber material.

As rubber materials, EPDM, polybutadiene, natural rubber, polyisobutylene, SBR, CR, NB
R, silicone rubber, urethane rubber, epichlorohydrin rubber, SBS, thermoplastic elastomer, norbornene rubber, fluorosilicone rubber, ethylene oxide rubber and the like are used.

Examples of the conductive particles or semiconductive particles include carbon black, zinc, aluminum, copper, iron, and the like.
Metals such as nickel, chromium, and titanium, ZnO-Al
₂ O ₃ , SnO ₂ —Sb ₂ O ₃ , In ₂ O ₃ —SnO ₂ , ZnO
_{-TiO 2, MgO-Al 2 O} 3, FeO-TiO 2, Ti
Metal oxides such as O ₂ , SnO ₂ , Sb ₂ O ₃ , In ₂ O ₃ , ZnO, and MgO can be used, and these materials may be used alone or as a mixture of two or more.

The resistance layer and the protective layer are formed by dispersing conductive particles or semiconductive particles in a binder resin and controlling the resistance. Examples of the binder resin include an acrylic resin, a cellulose resin, a polyamide resin, and a methoxy resin. Methylated nylon, ethoxymethylated nylon, polyurethane resin, polycarbonate resin, polyester resin, polyethylene resin, polyvinyl resin, polyarylate resin, polythiophene resin, polyolefin resins such as PFA, FEP, PET, and styrene butadiene resin are used. As the conductive particles or semiconductive particles, the same carbon black, metal, and metal oxide as those of the elastic layer are used. The resistivity of the resistance layer and the protective layer is preferably 10 ³
Ωcm to 10 ¹⁴ Ωcm, more preferably 10 ⁵ to 1
0 ¹² Ωcm, more preferably 10 ⁷ to 10 ¹² Ωcm. The thicknesses of the resistance layer and the protective layer are preferably from 0.01 to 1,000 μm, more preferably from 0.1 to 1,000 μm.
1 to 500 μm, more preferably 0.5 to 100 μm
It is.

If necessary, hindered phenol,
Antioxidants such as hindered amines, fillers such as clay and kaolin, and lubricants such as silicone oil can be added.

A method for forming these layers can be carried out by dissolving and dispersing the above-mentioned materials in an appropriate solvent to prepare a coating solution, and applying the solution to an object to be coated. As a means for applying, conventionally known means 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 can be employed.

When the charging roll 12 is brought into contact with the surface of the photoreceptor 10, it rotates at the same peripheral speed as the photoreceptor 10 without having any driving means, and functions as a charging means. However, some type of driving means may be attached to the charging roll 12 and rotated at a peripheral speed different from that of the photoconductor 10 to charge the surface of the photoconductor 10.

In order to charge the photosensitive member by the conductive member of the charging means, it is necessary to apply a voltage to the conductive member. The applied voltage is a DC voltage or a voltage obtained by superimposing an AC voltage on a DC voltage. It is particularly preferable to superimpose an AC voltage on a DC voltage in terms of uniform charging and stabilizing the environment.

As the magnitude of the voltage, the DC voltage is positive or negative 50 to 2.0, depending on the required photosensitive member charging potential.
00V is preferable, and 100 to 1,500V is particularly preferable. When the AC voltage is superimposed, the peak-to-peak voltage is 400
To 3,000 V, more preferably 800 to 2,500 V, and still more preferably 1,200 to
2,500V. The frequency of the AC voltage is 50
２０20,000 Hz, preferably 100〜5,000 H
z.

[0135]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. In the following description, “parts” means “parts by weight”.

(Synthesis Example) The synthesis examples of the present invention and the precursor of the organic semiconductor film for comparison are shown below. [Synthesis Example 1: Synthesis of compound A (precursor of organic semiconductor film)] In a nitrogen atmosphere, the above-mentioned exemplified compound III was placed in a two-neck flask.
-8 (weight average molecular weight 2 × 10 ⁴ ; in terms of GPC styrene) 3 g was taken, and THF (tetrahydrofuran) 100
and dissolved in (C ₂ H ₅ O) ₃ Si (CH ₂ ) ₃ NCO
Was added in an amount of 0.79 g. 0.01 g of dibutyltin laurate
After the addition of g, the mixture was stirred at 80 ° C. for 20 hours. The completion of the reaction was confirmed by NMR, and the reaction solution was allowed to cool and then filtered. The obtained filtrate was dropped into 1.5 liters of stirring hexane to precipitate a polymer. The precipitated polymer was collected by filtration and sufficiently washed with hexane. The obtained polymer is
The polymer was dissolved in 70 ml of HF, and the reprecipitation washing treatment was repeated. The finally obtained polymer was dried, and the compound A represented by the following structural formula (precursor of the organic semiconductor film of the present invention) 2.7 was obtained.
8 g were obtained. FIG. 1 shows the IR absorption spectrum of the obtained Compound A.

[0137]

Embedded image

[Synthesis Example 2: Synthesis of Compound B (precursor of organic semiconductor film)] In a two-necked flask, 2 g of the above exemplified compound III-8 (weight average molecular weight 2 × 10 ⁴ ; GPC styrene equivalent) was placed in a two-necked flask under a nitrogen atmosphere. The solution was dissolved in 30 ml of THF, and 10 g of triethylamine was added. A solution of 1.5 g of benzoyl chloride dissolved in 3 ml of THF was added dropwise thereto, and the mixture was stirred at room temperature for 3 hours. The completion of the reaction was confirmed by NMR, and the reaction solution was allowed to cool and then filtered. The obtained filtrate was dropped into 800 ml of stirring methanol to precipitate a polymer. The precipitated polymer was collected by filtration and sufficiently washed with methanol. The obtained polymer was dissolved in 70 ml of THF, and the reprecipitation washing treatment was repeated. The finally obtained polymer was dried, and 1.76 g of a compound B (precursor of an organic semiconductor film for comparison) represented by the following structural formula was obtained. I got FIG. 2 shows the IR absorption spectrum of Compound B thus obtained.

[0139]

Embedded image

(Example 1) Aluminum pipe (diameter 3)
10 parts of a zirconium compound (Orgatic ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.) and a silane compound (A1110, manufactured by Nippon Unicar) 1
, 10 parts of propanol, and 20 parts of butanol by a dip coating method.
After heating and drying at 0 ° C. for 10 minutes, a film thickness of 0.1 μm
Was formed.

Next, 1 part of an X-type metal-free phthalocyanine crystal and 1 part of polyvinyl butyral (Eslec BM-S, manufactured by Sekisui Chemical Co., Ltd.) were mixed with 100 parts of cyclohexanone, and dispersed together with glass beads by a sand mill for 1 hour. The undercoat layer was applied by dip coating to form a charge generation layer having a thickness of about 0.15 μm.

Further, 2.5 parts of the above exemplified compound III-8 (weight average molecular weight 2 × 10 ⁴ ) and 0.13 part of an isocyanate compound (N3500, manufactured by Sumitomo Bayer Urethane Co.) are dissolved in 7.5 parts of cyclohexanone. Then, a coating solution to which 0.01 part of dibutyltin dilaurate was added was applied on the charge generation layer by a spray coating method.
Surface layer (charge transport layer) with a thickness of 20 μm by heating for 1 hour
Was formed to obtain an electrophotographic photosensitive member of Example 1.

(Example 2) In the same manner as in Example 1, an undercoat layer and a charge generation layer were sequentially laminated on the surface of an aluminum pipe. Next, 2.4 parts of the compound A (weight average molecular weight = 2 × 10 ⁴ ) obtained in the above Synthesis Example was dissolved in 9.7 parts of 1,4-dioxane, and then 0.1 part of 10% hydrochloric acid was dissolved. This was added to prepare a coating solution. This coating solution was applied on the charge generation layer by a spray coating method, and heated at 150 ° C. for 1 hour to form a surface layer (charge transport layer) having a thickness of 20 μm. Obtained.

(Comparative Example 1) In the same manner as in Example 1, an undercoat layer and a charge generation layer were sequentially laminated on the surface of an aluminum pipe. Next, N, N-diphenyl-N, N'-bis (3-methylphenyl)-[1,1'-biphenyl]-
4 parts of 4,4′-diamine was dissolved in 40 parts of monochlorobenzene together with 6 parts of a polycarbonate Z resin to prepare a coating solution. This coating solution was applied on the charge generation layer by a dip coating method, and heated at 110 ° C. for 1 hour to form a surface layer (charge transport layer) having a thickness of 20 μm. Obtained.

(Comparative Example 2) In Example 1, an isocyanate compound (N3500, manufactured by Sumitomo Bayer Urethane Co., Ltd.) was prepared when preparing a coating solution for forming a surface layer (charge transport layer).
An electrophotographic photoreceptor of Comparative Example 2 was produced in the same manner as in Example 1 except that no dibutyltin dilaurate and dibutyltin dilaurate were added.

Comparative Example 3 The charge-transporting polyester used in the preparation of the coating solution for forming the surface layer (charge-transporting layer) in Example 1 was replaced with the compound B obtained in the above Synthesis Example.
An electrophotographic photoreceptor of Comparative Example 3 was prepared in the same manner as in Example 1, except that the weight average molecular weight was changed to 2 × 10 ⁴ .

(Examples 3 and 4) In Example 1,
Examples 3 and 4 were prepared in the same manner as in Example 1 except that the amount of the isocyanate compound used in preparing the coating solution for forming the surface layer (charge transport layer) was changed to the amount shown in Table 46 below. An electrophotographic photosensitive member was manufactured.

[0148]

[Table 46]

(Examples 5 to 7) In Example 1, the charge transporting polyester used in preparing the coating solution for forming the surface layer (charge transport layer) was changed to the above-mentioned compound III-9 (weight average molecular weight = 6). × 10 ⁴ ), and the electrophotographic photoreceptors of Examples 5 to 7 were produced in the same manner as in Example 1 except that the amount of the isocyanate compound added was changed to the amount shown in Table 47 below. .

[0150]

[Table 47]

Example 8 The procedure of Example 1 was repeated except that the isocyanate compound used in preparing the coating solution for forming the surface layer (charge transport layer) was changed to BL3175 (manufactured by Sumitomo Bayer Urethane Co., Ltd.). An electrophotographic photosensitive member of Example 8 was produced in the same manner as in Example 1.

(Example 9) In Example 1, the charge-transporting polymer used in preparing the coating solution for forming the surface layer (charge-transporting layer) was changed from the exemplified compound III-8 to the exemplified compound III-16 ( An electrophotographic photosensitive member of Example 9 was prepared in the same manner as in Example 1, except that the weight average molecular weight was changed to 2 × 10 ⁵ ).

Example 10 In Example 1, the charge-transporting polymer used in preparing the coating solution for forming the surface layer (charge-transporting layer) was changed from Exemplified Compounds III-8 to VII-79 (Ex. An electrophotographic photosensitive member of Example 10 was prepared in the same manner as in Example 1, except that the weight average molecular weight was changed to 1 × 10 ⁵ ).

(Example 11) In Example 1, the charge-transporting polymer used in preparing the coating solution for forming the surface layer (charge-transporting layer) was changed from the exemplified compound III-8 to the exemplified compound VII-80 ( Example 11 was repeated in the same manner as in Example 1 except that the weight average molecular weight was changed to 1.2 × 10 ⁵ ).
Was prepared.

Example 12 In the same manner as in Example 1, an undercoat layer and a charge generation layer were sequentially laminated on the surface of an aluminum pipe. Next, the compound A obtained in the above synthesis example
After dissolving 2.4 parts (weight average molecular weight = 2 × 10 ⁴ ) and 0.2 parts of methyltrimethoxysilane in 9.7 parts of 1,4-dioxane, 0.1 part of 10% hydrochloric acid was dissolved. This was added to prepare a coating solution. This coating solution was applied onto the charge generation layer by a spray coating method, and heated at 150 ° C. for 1 hour to form a surface layer (charge transport layer) having a thickness of 20 μm. Formation was obtained.

Example 13 In the same manner as in Comparative Example 1, an undercoat layer, a charge generation layer, and a charge transport layer were sequentially laminated on the surface of an aluminum pipe. Next, the exemplified compound II
2.5 parts of I-9 (weight average molecular weight = 6 × 10 ⁴ ) and 0.13 part of an isocyanate compound (N3500, manufactured by Sumitomo Bayer Urethane Co., Ltd.) are dissolved in 7.5 parts of cyclohexanone, and dibutyltin dilaurate 0 is dissolved. 0.01 part was added to prepare a coating solution. This coating solution was applied on the charge generating layer by a spray coating method, and heated at 150 ° C. for 1 hour to form a surface protective layer having a thickness of 3 μm. Thus, an electrophotographic photosensitive member of Example 13 was obtained.

(Contents of Evaluation Test) Each of the electrophotographic photoreceptors of Examples and Comparative Examples obtained as described above was mounted on an XP-11 modified machine manufactured by Fuji Xerox Co., Ltd., and the following evaluation tests were performed. . The XP-11 remodeling machine includes a photoreceptor 10 as shown in FIG. 1, a charging roll 12, which is a contact charging type charging unit, a laser exposure optical system 14, a developing unit 16,
It has a static eliminator 19, which is an LED for static elimination, a cleaning device 24 having a cleaning blade 20, and a fixing roll 22, and the transfer roll 1
A corotron for transfer is used in place of 8.

[0158] 1. Image quality evaluation Using the image forming apparatus, image quality of an initial image, and 2
The image quality after the continuous copy printing test of 10,000 sheets was visually evaluated for sensory evaluation. The results are summarized in Table 48 below.

[0159] 2. Abrasion Amount A continuous copy printing test of 20,000 sheets was performed using the image forming apparatus, the film thickness before and after the test was measured, and the amount of decrease in the film thickness was calculated and used as the amount of abrasion. The charge is
DC-550V and AC 1.5kVpp for charging roll
(800 Hz) by applying a charging voltage superimposed thereon. The results are summarized in Table 48 below.

[0160]

[Table 48]

As can be seen from the above Table 48, Embodiment 1
The one using the electrophotographic photoreceptor had good image quality characteristics of the initial image and maintained good image quality characteristics even after copying 20,000 sheets. Further, since the amount of wear is small and no large streak-like scratches are observed on the surface, it is considered that the material has sufficient mechanical strength.

On the other hand, the electrophotographic photoreceptor of Comparative Example 1 has a charge transport layer in which a low molecular charge transport material is dispersed in a binder polymer. It can be seen that Example 1 has a smaller amount of wear under charging than Comparative Example 1, and has high durability against strong external stress such as the application of an AC voltage and a discharge gas. In Comparative Example 2, only Exemplified Compound III-8 was used for the surface layer. Compared with Comparative Example 2, a significant improvement in mechanical strength is seen in Example 1. It is thought that the mechanical strength was dramatically improved by the three-dimensional cross-linking structure by the direct chemical bond between the charge transporting polymer and the cross-linking compound. Comparative Example 3 was a compound B in which the terminal of the charge transporting polymer was benzoylated for the purpose of inhibiting the reaction between the charge transporting polymer and the crosslinkable compound,
A surface layer obtained by crosslinking and curing a polyfunctional isocyanate is used. Since the charge transporting polymer and the crosslinkable compound did not form a chemical bond, the mechanical strength did not improve much.

Example 2 is an example in which a compound having an alkoxysilyl group at the terminal of the charge transporting polymer was crosslinked and cured, and Examples 3 to 7 were the amounts of the crosslinkable compound of Example 1 and the charge transport This is an example in which the average molecular weight of the conductive polymer is changed. In Examples 2 to 7, good image quality characteristics were maintained both at the initial stage and after copying 20,000 sheets. In addition, the mechanical strength was also significantly improved as compared with Comparative Examples 2 and 3, which was due to the charge transporting polymers in Examples 2 and crosslinks with the charge transporting polymers in Examples 3 to 7. It is considered that the three-dimensional cross-link structure due to direct chemical bonding with the hydrophilic compound contributed.

[0164]

As described above, according to the present invention, an organic semiconductor film having sufficient photoconductivity as an electronic device and excellent in mechanical strength, an electrophotographic photosensitive member, and an image using the same are provided. A forming device can be provided.
In particular, in the electrophotographic photoreceptor of the present invention, the terminal of the charge transporting polymer has a crosslinked structure as the outermost surface layer (preferably three-dimensional)
It has good mechanical properties such as good photoelectric characteristics and excellent abrasion resistance, and further, against strong external stress such as application of AC voltage and discharge gas. Also have high durability. Therefore, the image forming apparatus using the electrophotographic photoreceptor of the present invention can maintain good quality images even after copying a large number of sheets.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus to which an electrophotographic photosensitive member of the present invention is applied.

FIG. 2 is a graph showing an IR absorption spectrum of Compound A which is a precursor of an organic semiconductor film of the present invention.

FIG. 3 is a graph showing an IR absorption spectrum of Compound B which is a precursor of an organic semiconductor film for comparison.

[Explanation of symbols]

 10: Photoreceptor 12: Charging roll (charging means) 14: Laser exposure optical system 16: Developing device 18: Transfer roll 19: Static eliminator 20: Cleaning blade (cleaning means) 22: Fixing roll

Continued on the front page (72) Inventor Wataru Yamada 1600 Takematsu, Minamiashigara, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd. (72) Inventor Mieko Seki 1600 Takematsu, Minamiashigara City, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd. 2H068 AA20 BA12 BB25 BB44

Claims (4)

[Claims] 1. An organic semiconductor film comprising at least a crosslinked and cured charge transporting polymer having a reactive group at a terminal. 2. An organic semiconductor film comprising at least a charge-transportable polymer having a reactive group at a terminal and a crosslinkable compound crosslinked and cured. 3. An electrophotographic photoreceptor comprising at least the organic semiconductor film according to claim 1 formed on the surface of a conductive support. 4. A charging means for charging an electrophotographic photosensitive member with a charging member, a latent image forming means for forming a latent image on the electrophotographic photosensitive member using coherent light, and a method for forming a latent image on the surface of the electrophotographic photosensitive member with toner. An image forming apparatus comprising: a developing unit that develops an electro-latent image to obtain a toner image; and a transfer unit that transfers the formed toner image to a transfer material surface, wherein the electrophotographic photoreceptor is an electrophotographic photosensitive member. An image forming apparatus comprising: an electrophotographic photoreceptor;