JPH0690539B2 - Electrophotographic photoreceptor - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor having a surface protective layer.

<Prior Art> In an image forming apparatus such as a copying machine utilizing a so-called Carlson process, an electrophotographic photoreceptor having a photosensitive layer formed on a conductive base material is used.

The electrophotographic photosensitive member is repeatedly subjected to electrical, optical and mechanical shocks during the image forming process. Therefore, for the purpose of improving durability against these shocks, a surface made of a binder resin is formed on the photosensitive layer. Laminating a protective layer is performed.

As the binder resin, a thermosetting silicone resin is mainly used in order to improve the hardness of the surface protective layer. However, the thermosetting silicone resin alone has problems that it is brittle against sliding friction and is easily damaged.

Therefore, an electrophotographic photosensitive member (see JP-A-63-18354) using a thermosetting silicone resin as a binder resin for the surface protective layer and a thermoplastic resin such as polyvinyl acetate, or a thermosetting silicone An electrophotographic photosensitive member using a resin and an acrylic polymer in combination has been proposed (see JP-A-60-3639).

<Problems to be Solved by the Invention> However, in the former combination system, the sensitivity of the photoconductor is not sufficient, and the surface hardness is low as compared with the case of using the thermosetting silicone resin alone, and it is rather easily damaged. Etc., there is a problem in terms of the physical properties of the surface protective layer, and especially in a system in which polyvinyl acetate is used in combination with a thermosetting silicone resin,
There is also a problem that the coating solution for forming the surface protective layer lacks stability, and whitening of the film occurs after the pot life.

On the other hand, the latter combination system uses an acrylic polymer having excellent optical properties and compatibility with a thermosetting silicone resin, which is superior to polyvinyl acetate.
The photosensitivity can be improved as compared with the combined use system of polyvinyl acetate. However, since the above-mentioned combination type acrylic polymer has a high molecular weight of 8,000 to 60,000, it cannot be easily dissolved in the coating liquid. Therefore, if the acrylic polymer is insufficiently dissolved in the coating liquid, a uniform layer cannot be formed, resulting in unevenness, turbidity, etc., resulting in poor transparency of the surface protective layer. There is a problem in that the photosensitive characteristics of No. 1 are deteriorated, or the strength of the surface protective layer is reduced, so that the surface becomes brittle against sliding friction and cracks easily occur.

The present invention has been made in view of the above circumstances, and does not adversely affect the photosensitive characteristics and physical properties of the electrophotographic photosensitive member, and is more fragile to sliding friction than the case of using a thermosetting silicone resin alone. It is an object of the present invention to provide an electrophotographic photosensitive member having a surface protective layer with improved roughness and the like.

<Means and Actions for Solving the Problems> In order to solve the above problems, the electrophotographic photoreceptor of the present invention comprises a thermosetting silicone resin and an acrylic polymer having an average molecular weight of 6000 or less. Acrylic polymer 0.1 to 30 per 100 parts by weight of non-volatile solid content of silicone resin
It is characterized in that it has a surface protective layer formed by applying a coating liquid contained in a proportion of parts by weight onto the photosensitive layer and curing it.

Further, it is preferable that the conductive metal oxide particles are uniformly dispersed in the surface protective layer by mixing a colloidal solution of conductive metal oxide particles as a conductivity imparting agent with the coating liquid. .

In the electrophotographic photoreceptor of the present invention having the above-mentioned constitution, the average molecular weight of the acrylic polymer contained in the coating liquid is as small as 6000 or less, so that it is easily dissolved in the coating liquid as compared with the conventional one. The surface protective layer formed is uniform and has excellent optical characteristics and physical properties.

The reason why the content of the acrylic polymer is limited to 0.1 to 30 parts by weight with respect to 100 parts by weight of the nonvolatile solid content of the thermosetting silicone resin in the coating liquid is as follows. That is, the content of the acrylic polymer is 0.
If the amount is less than 1 part by weight, the effect of adding the acrylic polymer is not sufficiently obtained, and the cured surface protective layer is deteriorated in physical properties such as cracks and brittleness against sliding friction. On the other hand, when the content of the acrylic polymer exceeds 30 parts by weight, it becomes difficult to dissolve it in the coating liquid and unevenness occurs, the transparency of the surface protective layer deteriorates, and the photosensitive characteristics of the photoreceptor deteriorate. To do. The content of the acrylic polymer is more preferably 0.1 to 15 parts by weight.

The thermosetting silicone resin contained in the coating liquid is tetraalkoxysilane, trialkoxyalkylsilane,
A hydrolyzate (so-called organopolysiloxane) of a silane compound such as an organosilane such as dialkoxydialkylsilane, a trichloroalkylsilane, an organohalogensilane such as a dichlorodialkylsilane, or a mixture thereof (so-called organopolysiloxane), or an initial stage thereof. The condensation reaction product is dissolved or dispersed in a solvent as a non-volatile solid content, and the alkoxy group and the alkyl group of the silane compound include a methoxy group, an ethoxy group, an isopropoxy group, and t-
Examples thereof include lower groups having about 1 to 4 carbon atoms such as butoxy group, glycidoxy group, methyl and ethyl.

Examples of the acrylic polymer used in combination with the thermosetting silicone resin include homopolymers or copolymers of acrylic monomers such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and butyl methacrylate. The average molecular weight of the acrylic polymer is limited to 6000 or less, when the average molecular weight exceeds 6000, as described above, the solubility in the coating liquid is reduced, it is not possible to form a uniform film .

As the solvent constituting the coating solution for the surface protective layer by dissolving or dispersing the thermosetting silicone resin and the acrylic polymer, for example, isopropyl alcohol; n-hexane, octane, aliphatic hydrocarbons such as cyclohexane Aromatic hydrocarbons such as benzene, toluene, xylene; halogenated hydrocarbons such as dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene; ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether Ketones such as acetone, methyl ethyl ketone and cyclohexanone; esters such as ethyl acetate and methyl acetate; dimethylformamide; dimethyl sulfoxide and the like, These are used alone or in two or more.

The coating solution for the surface protective layer containing the thermosetting silicone resin and the acrylic polymer can be cured by heating without a catalyst depending on the conditions, but usually the curing reaction is smooth. In addition, a catalyst is often used in order to achieve uniform completion.

As the curing catalyst, various ones such as inorganic acids or organic acids, alkalis such as amines, etc. can be used.
Further, if necessary, a conventionally known curing aid and the like can be used in combination.

In the surface protective layer composed of both resins, a conductivity-imparting agent is preferably dispersed for the purpose of facilitating the injection of charges into the lower layer in the image forming process.

The conductivity imparting agent, tin oxide, titanium oxide, indium oxide, simple metal oxides such as antimony oxide,
A conductive metal oxide such as a solid solution of tin oxide and antimony oxide can be used. The conductive metal oxide is generally
In the state of fine particles, it is stirred and mixed in the coating liquid before curing, and it is dispersed in the surface protective layer by curing the coating film, but in the state of fine particles it easily aggregates, and it takes a long time to uniformly disperse in the coating liquid. As mentioned above, since it takes time to stir,
It is preferable to mix the colloidal solution in the coating solution. In the colloidal solution, the fine particles of the conductive metal oxide repel each other due to the surface charge of each, and the aggregation in the coating liquid is prevented. Can be dispersed in.

The method for producing a colloidal solution of conductive metal oxide particles depends on the type of conductive metal oxide. For example, a colloidal solution of antimony pentoxide (Sb ₂ O ₅ ) is prepared by mixing anhydrous antimony trioxide and nitric acid. After heating, α-hydroxycarboxylic acid and an organic solvent such as N, N-dimethylformamide (DMF) are added in this order, and water as a by-product is removed by distillation (JP-A-47-11382). (See issue)
Or hydrogen halide such as hydrogen chloride, monovalent or divalent alcohol represented by ethylene glycol, DMF
A method in which a hydrophilic organic solvent such as α-hydroxycarboxylic acid is added, and antimony trioxide is dispersed therein and then oxidized with hydrogen peroxide solution (Japanese Patent Laid-Open No. 38395/52/38495). (See Japanese Patent No. 38496) and the like.

As a dispersion medium for preparing the antimony pentoxide colloidal solution, so as not to attack the lower photosensitive layer,
Organic small methyl alcohol, ethyl alcohol,
It is preferable to use alcohols such as n-propyl alcohol, isopropyl alcohol and butyl alcohol.

In addition, tin oxide (SnO ₂ , SnO, etc.) and antimony oxide (Sb ₂
In the case of a colloidal solution of a solid solution with O ₅ , Sb ₂ O ₃ etc.), for example, as shown in FIG.
It can be prepared by a method of adsorbing silicon oxide particles 2 ... In the structure of FIG. 1, the silicon oxide particles 2 adsorbed on the surface of the solid solution particles 1 are OH when contacted with a polar solvent as a dispersion medium.
By generating a group to be negatively charged, the surface of the solid solution particle 1 is charged.

The solid solution particles of tin oxide and antimony oxide are usually formed by doping tin oxide fine particles with antimony, and are not particularly limited, but the content ratio of antimony in the solid solution particles is 0.001 to 30% by weight. It is preferably present, and more preferably 5 to 20% by weight.
When the content ratio of antimony in the solid solution particles is less than 0.001% by weight or exceeds 30% by weight, sufficient conductivity may not be obtained.

The particle size of the solid solution particles is not particularly limited, but 10
It is preferably ˜20 nm. Particle size of solid solution particles is 10 nm
If it is less than 20 nm, the electric resistance of the surface protective layer increases, and if it exceeds 20 nm, the light transmittance of the surface protective layer may decrease.

The ratio of silicon oxide to solid solution particles is not particularly limited, but is preferably 10 parts by weight or less with respect to 100 parts by weight of solid solution particles. When the ratio of silicon oxide to 100 parts by weight of the solid solution particles exceeds 10 parts by weight, sufficient conductivity may not be obtained.

As the dispersion medium that forms the colloidal solution with the solid solution particles, as described above, a polar solvent is used to negatively charge silicon oxide, and particularly, the compatibility with the protective layer coating liquid is excellent, and Alcohols, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and butyl alcohol, which do not damage the photosensitive layer as the base layer, are preferably used.

A thermosetting resin or a thermoplastic resin other than those described above can be used in combination with the binder resin forming the surface protective layer as long as the characteristics of the film are not impaired. Other binder resins other than the above are curable acrylic resins; alkyd resins; unsaturated polyester resins; diallyl phthalate resins; phenol resins; urea resins; benzoguanamine resins; melamine resins; styrene polymers; styrene-acrylic copolymers. Polymer; polyethylene, ethylene-vinyl acetate copolymer,
Olefinic polymers such as chlorinated polyethylene, polypropylene, ionomers; polyvinyl chloride; vinyl chloride-
Examples are vinyl acetate copolymers; polyvinyl acetate; saturated polyesters; polyamides; thermoplastic polyurethane resins; polycarbonates; polyarylates; polysulfones; ketone resins; polyvinyl butyral resins; polyether resins.

In the surface protective layer, conventionally known sensitizers such as terphenyl, halonaphthoquinones, and acenaphthylene; fluorene compounds such as 9- (N, N-diphenylhydrazino) fluorene and 9-carbazolyliminofluorene; conductive materials Various additives such as a property-imparting agent; an antioxidant such as an amine-based or phenol-based agent; a deterioration inhibitor such as an ultraviolet absorber such as a benzophenone-based agent; and a plasticizer can be contained.

The thickness of the surface protective layer is 0.1 to 10 μm, especially 2 to 5 μm.
It is preferably within the range of m.

The photoreceptor of the present invention can have the same structure as the conventional one by using the same material as the conventional material except for the surface protective layer.

First, the conductive base material will be described.

The conductive base material is formed into an appropriate shape such as a sheet shape or a drum shape according to the mechanism and structure of the image forming apparatus in which the electrophotographic photosensitive member is incorporated. Further, the conductive base material may be entirely composed of a conductive material such as metal, or the base material itself may be formed of a structural material having no conductivity, and the surface thereof may be provided with conductivity. .

As the conductive material used in the conductive base material having the former structure, the surface was anodized,
Or untreated aluminum, copper, tin, platinum, gold,
A metal material such as silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, indium, stainless steel, or brass is preferable.

On the other hand, as the latter structure, on the surface of a synthetic resin base material or a glass base material, a thin film made of a conductive material such as the above-exemplified metals or aluminum iodide, tin oxide, indium oxide, a vacuum deposition method or Structures laminated by a known film forming method such as a wet plating method, structures in which a film such as the metal material is laminated on the surface of the synthetic resin molded product or the glass substrate, the synthetic resin molded product or the glass substrate A structure in which a substance imparting conductivity is injected into the surface is exemplified.

The conductive base material may be subjected to a surface treatment with a surface treatment agent such as a silane coupling agent or a titanium coupling agent, if necessary, to enhance the adhesion to the photosensitive layer.

Next, the photosensitive layer formed on the conductive substrate will be described.

The photosensitive layer may be made of a semiconductor material, an organic material, or a composite material thereof, having the following structure.

A single layer type photosensitive layer made of a semiconductor material.

A single-layer type organic photosensitive layer containing a charge generating material and a charge transporting material in a binder resin.

A charge generation layer containing a charge generation material in a binder resin,
A laminated organic photosensitive layer comprising a charge transport layer containing a charge transport material in a binder resin.

A composite type photosensitive layer in which a charge generation layer made of a semiconductor material and the organic charge transport layer are laminated.

As a semiconductor material that can be used alone as a charge generation layer in a composite type photosensitive layer to form a photosensitive layer,
Examples thereof include amorphous chalcogenides such as a-As ₂ Se ₃ , a-SeAsTe, amorphous selenium (a-Se), and amorphous silicon (a-Si). The photosensitive layer or charge generating layer made of the above semiconductor material can be formed by a known thin film forming method such as a vacuum vapor deposition method or a glow discharge decomposition method.

As the organic or inorganic charge generating material used for the charge generating layer in the single-layer type or laminated type organic photosensitive layer,
For example, the powder of the semiconductor material exemplified above; ZnO, CdS, etc. II-VI
Group crystallites; pyrylium salts; azo compounds; bisazo compounds; phthalocyanine compounds; ansanthrone compounds; perylene compounds; indigo compounds; triphenylmethane compounds; threnic compounds; toluidine compounds; pyrazoline compounds; Examples include quinacridone compounds; pyrrolopyrrole compounds. And among the above-exemplified compounds, α belonging to a phthalocyanine-based compound
Aluminum phthalocyanine, copper phthalocyanine, metal-free phthalocyanine, oxotitanyl phthalocyanine, etc. having various crystal types such as β-type, β-type, and γ-type are preferably used, and particularly, the above metal-free phthalocyanine and / or oxotitanyl phthalocyanine are often preferably used. . The charge generating materials may be used alone or in combination of plural kinds.

Examples of the charge transport material contained in the charge transport layer in the single-layer type or multilayer type organic photosensitive layer or the composite type photosensitive layer include tetracyanoethylene; 2,4,7-trinitro-9-fluorenone. Fluorenone compounds such as; nitration compounds such as dinitroanthracene; succinic anhydride; maleic anhydride; dibromomaleic anhydride; triphenylmethane compounds; 2,5-di (4-dimethylaminophenyl) -1,3, Oxadiazole compounds such as 4-oxadiazole; styryl compounds such as 9- (4-diethylaminostyryl) anthracene; carbazole compounds such as poly-N-vinylcarbazole; 1-phenyl-3-
Pyrazoline compounds such as (p-dimethylaminophenyl) pyrazolin; amine derivatives such as 4,4 ′, 4 ″ -tris (N, N-diphenylamino) triphenylamine; 1,1-bis (4-diethylaminophenyl) -4,4-diphenyl-
Conjugated unsaturated compounds such as 1,3-butadiene; hydrazone compounds such as 4- (N, N-diethylamino) benzaldehyde-N, N-diphenylhydrazone; indole compounds,
Nitrogen-containing cyclic compounds such as oxazole-based compounds, isoxazole-based compounds, thiazole-based compounds, thiadiazole-based compounds, imidazole-based compounds, pyrazole-based compounds, pyrazoline-based compounds, and triazole-based compounds; and condensed polycyclic compounds are exemplified. The above charge transport materials can be used alone or in combination of two or more. Among the above charge transport materials, the photoconductive polymer material such as poly-N-vinylcarbazole can also be used as the binder resin for the photosensitive layer.

Further, the single-layer type or laminated type organic photosensitive layer, the layer such as the charge transport layer in the composite type photosensitive layer, the sensitizer, a fluorene compound, an antioxidant, a deterioration inhibitor such as an ultraviolet absorber, Additives such as plasticizers may be included.

In the single-layer organic photosensitive layer, the content ratio of the charge generation material to 100 parts by weight of the binder resin is preferably in the range of 2 to 20 parts by weight, particularly preferably 3 to 15 parts by weight,
On the other hand, the content ratio of the charge transport material to 100 parts by weight of the binder resin is preferably in the range of 40 to 200 parts by weight, and particularly preferably in the range of 50 to 100 parts by weight. If the charge generating material is less than 2 parts by weight or the charge transporting material is less than 40 parts by weight, the sensitivity of the photoconductor becomes insufficient and the residual potential becomes large. This is because if the amount exceeds or the amount of the charge transport material exceeds 200 parts by weight, the abrasion resistance of the photoreceptor cannot be sufficiently obtained.

The single-layer type photosensitive layer can be formed to have an appropriate thickness, but it is usually preferably formed in the range of 10 to 50 μm, particularly 15 to 25 μm.

On the other hand, in the layers constituting the laminated organic photosensitive layer, the content ratio of the charge generating material to the binder resin 100 parts by weight in the charge generating layer is in the range of 5 to 500 parts by weight, particularly 10 to 250 parts by weight.
It is preferably within the range of parts by weight. This is because if the amount of the charge generating material is less than 5 parts by weight, the charge generating ability is too small, and if it exceeds 500 parts by weight, the adhesiveness with other adjacent layers or substrates is deteriorated.

The thickness of the charge generation layer is 0.01 to 3 μm, particularly 0.1 to 2 μm.
It is preferably in the range of μm.

Further, among the layers constituting the laminated organic photosensitive layer and the composite type photosensitive layer, in the charge transport layer, the content ratio of the charge transport material relative to 100 parts by weight of the binder resin is in the range of 10 to 500 parts by weight, and particularly, It is preferably in the range of 25 to 200 parts by weight. This is because if the charge transport material is less than 10 parts by weight, the charge transport ability is insufficient, and if it exceeds 500 parts by weight, the mechanical strength of the charge transport layer is lowered.

The thickness of the charge transport layer is 2 to 100 μm, particularly 5 to 30 μm.
It is preferably within the range of m.

As described above, the organic layer such as the single-layer type or laminated type organic photosensitive layer, the charge transport layer of the composite type photosensitive layer, and the surface protective layer is a coating liquid for each layer containing the above-mentioned components. Is prepared, and each of these layers is sequentially coated on a conductive base material so that the above-mentioned layer constitution can be formed, and dried or cured to form a laminate.

When preparing the above-mentioned coating liquid, various solvents can be used depending on the type of binder resin or the like used. Examples of the solvent include aliphatic hydrocarbons such as n-hexane, octane and cyclohexane; benzene, xylene,
Aromatic hydrocarbons such as toluene; halogenated hydrocarbons such as dichloromethane, carbon tetrachloride, chlorobenzene, methylene chloride; methyl alcohol, ethyl alcohol, isopropyl alcohol, allyl alcohol, cyclopentanol, benzyl alcohol, furfuryl alcohol, diacetone Alcohols such as alcohols; ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone;
Examples of various solvents include esters such as ethyl acetate and methyl acetate; dimethylformamide; dimethylsulfoxide and the like, and these are used alone or in combination of two or more. In addition, a surfactant, a leveling agent, or the like may be used together in order to improve dispersibility, coatability, and the like when preparing the coating liquid.

Further, the coating solution is a conventional method, for example, a mixer,
It can be prepared using a ball mill, paint shaker, sand mill, attritor, ultrasonic disperser, or the like.

<Examples> Hereinafter, the present invention will be described in more detail with reference to Examples.

Examples 1 to 4, Comparative Examples 1 and 2 100 parts by weight of polyarylate (manufactured by Unitika Ltd., trade name U-100) as a binder resin, 4- (N,
N-diethylamino) benzaldehyde-N, N-diphenylhydrazone 100 parts by weight and methylene chloride (CH ₂ Cl ₂ ) as a solvent 900 parts by weight to prepare a charge-transporting coating liquid, and this coating liquid was prepared to have an outer diameter of 78 mm × length. After coating on a 340 mm aluminum tube, it was heated and dried at 90 ° C. for 30 minutes to form a charge transport layer having a film thickness of about 20 μm.

Next, on the charge transport layer, 2,7 as a charge generating material
-80 parts by weight of dibromoanthanthurone (manufactured by ICI) and 20 parts by weight of metal-free phthalocyanine (manufactured by BASF), 50 parts by weight of polyvinyl acetate (manufactured by Nippon Gohsei Co., Ltd., trade name Y5-N) as a binder resin, and A charge generation layer coating solution consisting of 2000 parts by weight of diacetone alcohol as a solvent was applied and dried by heating at 110 ° C. for 30 minutes to form a charge generation layer having a thickness of about 0.5 μm.

Next, 57.4 parts by weight of 0.02N hydrochloric acid and isopropyl alcohol 3
After mixing with 6 parts by weight, 80 parts by weight of methyltrimethoxysilane and 20 parts by weight of glycidoxypropyltrimethoxysilane were gradually added dropwise while stirring while maintaining the liquid temperature of the mixed solution at 20 to 25 ° C. A silane hydrolyzate solution was obtained by allowing it to stand at room temperature for 1 hour, and based on 100 parts by weight of the non-volatile solid content in this silane hydrolyzate solution, the amount of acrylic acid ester-methacrylic acid ester shown in the following table A copolymer (manufactured by Nippon Shokubai Co., Ltd., trade name Alorone 450, average molecular weight 5000 to 6000) was mixed to prepare a coating solution for the surface protective layer.

Next, antimony-doped tin oxide fine powder (manufactured by Sumitomo Cement Co., containing solid solution particles of tin oxide and antimony oxide, containing 10% by weight of antimony) was used as a resin solid content in the coating liquid.
50 parts by weight to 100 parts by weight, 0.3 parts by weight of a silicone-based interfacial lubricant are mixed, and stirred for 150 hours with a ball mill,
Mixed. Then, 0.5 part by weight of triethylamine as a curing agent was added to the mixture of the coating liquid and the antimony-doped tin oxide fine powder, and the mixture was coated on the charge generation layer and cured by heating at 110 ° C. for 1 hour to form a film. A surface protective layer having a thickness of about 2.5 μm was formed to prepare a drum-type electrophotographic photosensitive member having a laminated photosensitive layer.

Comparative Examples 3 and 4, in place of the acrylic acid ester-methacrylic acid ester copolymer having an average molecular weight of 5000 to 6000, except that polyacrylate having an average molecular weight of 55000 (manufactured by Mitsubishi Rayon Co., Ltd., trade name Dianal BR105) was blended. Electrophotographic photoreceptors were produced in the same manner as in Examples 1 to 4 above.

The following tests were carried out on the electrophotographic photosensitive members produced in the above-mentioned Examples and Comparative Examples.

Surface potential measurement Each of the above electrophotographic photoconductors was loaded into an electrostatic copying tester (Gentec Cynthia 30M model, manufactured by Gentec),
The surface was positively charged and the surface potential V ₁ sp (V) was measured.

Half-exposure amount measurement Each electrophotographic photosensitive member in the charged state is exposed under the conditions of an exposure intensity of 0.92 mW / cm ² and an exposure time of 60 msec using a halogen lamp which is an exposure light source of the electrostatic copying test apparatus. The half-exposure amount E1 / 2 (lux · Sec) was calculated by determining the time required for the surface potential V ₁ sp to become 1/2.

Measurement of change in surface potential after repeated exposure Each of the above electrophotographic photoconductors was copied by a copying machine (manufactured by Mita Kogyo Co., Ltd., DC-111
After performing a copying process on 500 sheets, the surface potential was measured as the surface potential V ₂ sp (V) after repeated exposure.

Further, from the surface potential measurement value V ₁ sp value and the surface potential measurement value V ₂ sp value after repeated exposure, according to the following formula [I],
The surface potential change value-ΔV (V) was calculated.

-ΔV (V) = V ₂ sp (V) -V ₁ sp (V) ... [I] Abrasion resistance test Each electrophotographic photosensitive member was subjected to a drum polishing tester (manufactured by Mita Kogyo Co., Ltd.).
And a drum tester installed on this drum polishing tester, which rotates once during 1000 revolutions of the photoconductor, has a polishing test paper (Sumitomo 3M, trade name Imperial Wrapping Film, particle size 12 μm) Aluminum oxide powder on the surface) was loaded and the polishing test paper was pressed against the surface of the photoconductor at a linear pressure of 10 g / mm,
The amount of wear (μm) when the photoconductor was rotated 100 times was measured.

Appearance The appearance of the surface protective layer was visually observed.

The above results are shown in the following table.

From the results in the above table, the electrophotographic photoreceptors of Examples 1 to 4 were
In both cases, the average molecular weight was smaller than that of Comparative Examples 3 and 4 in which the acrylic polymer was more than 6000, the amount of change in surface potential after repeated exposure was small, and the amount of wear was small. It was found that the surface protective layer in No. 4 was uniform and had excellent physical properties and photosensitivity.

In addition, from the results of Examples 1 to 4 and Comparative Examples 1 and 2 above,
It was found that when the amount of the acrylic polymer compounded in the coating liquid was less than 0.1 parts by weight, the physical properties of the surface protective layer deteriorated, and when it exceeded 30 parts by weight, the photosensitive characteristics deteriorated.

<Effects of the Invention> Since the electrophotographic photosensitive member of the present invention is configured as described above, it does not adversely affect the photosensitive characteristics, physical properties, etc. of the electrophotographic photosensitive member, and when the thermosetting silicone resin alone is used. In comparison, the surface protective layer has improved brittleness against sliding friction.

Further, the conductive metal oxide particles as a conductivity imparting agent,
If it is mixed with the coating solution in a colloidal solution,
It becomes easy to uniformly disperse the conductive metal oxide particles in the surface protective layer.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing a state where the solid solution particles of tin oxide and antimony oxide are charged by adsorbing the silicon oxide particles on the surface of the solid solution particles. 1 ... Solid solution particles, 2 ... Silicon oxide particles.

Claims (2)

[Claims] 1. A thermosetting silicone resin and an average molecular weight of 60.
A coating solution containing an acrylic polymer of 00 or less and 0.1 to 30 parts by weight of the acrylic polymer with respect to 100 parts by weight of the nonvolatile solid content of the thermosetting silicone resin is applied on the photosensitive layer. An electrophotographic photoreceptor having a surface protective layer formed by curing. 2. A thermosetting silicone resin and an average molecular weight of 60.
Acrylic polymer of 00 or less, containing 0.1 to 30 parts by weight of the acrylic polymer with respect to 100 parts by weight of the nonvolatile solid content of the thermosetting silicone resin, the conductive metal oxide particles of An electron characterized by having a surface protective layer in which the above-mentioned conductive metal oxide particles are uniformly dispersed as a conductivity-imparting agent by applying a coating solution containing a colloid solution to the photosensitive layer and curing it. Photoreceptor.