JP2011095672A - Method for manufacturing electrophotographic photoreceptor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing an electrophotographic photoreceptor having good uniformity of a film thickness of an intermediate layer. <P>SOLUTION: The method for manufacturing an electrophotographic photoreceptor having a support and an intermediate layer and a photosensitive layer formed on the support includes steps of: forming a coating film by applying an aqueous dispersion liquid containing polyolefin resin particles having a particle diameter of 50 nm or more and 500 nm or less and a metal oxide, followed by heating the coating film to melt the polyolefin resin particles to form the intermediate layer; and forming the photosensitive layer on the intermediate layer. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing an electrophotographic photoreceptor.

  When producing an electrophotographic photoreceptor (hereinafter, sometimes simply referred to as “photoreceptor”), a layer called an intermediate layer (sometimes called an undercoat layer) is interposed between the photosensitive layer and the support. Has been done.

  If the electrical resistance of the intermediate layer is too high, the charge generated in the photosensitive layer stays in the photosensitive layer, resulting in an increase in residual potential and potential fluctuation due to repeated use. Therefore, the electrical resistance characteristics should not change greatly in any environment from low temperature and low humidity to high temperature and high humidity.

  On the other hand, an electrical blocking function is also required so that charge injection does not occur from the support when a voltage is applied to the electrophotographic photosensitive member. If there is charge injection from the support, the charging ability, the image contrast, and the reversal development method cause black spots on the white background and fogging, thereby degrading the image quality.

  As an intermediate layer having an electric resistance characteristic and a blocking function within an appropriate range, many intermediate layers (Patent Documents 1 and 2) containing a metal oxide such as titanium oxide in a resin have been studied.

  Many studies have been made on the production of an intermediate layer containing a resin and a metal oxide by a coating solution in which the metal oxide is dispersed in a solution in which the resin is dissolved. However, the dispersion of the metal oxide causes a coating defect without being uniformly applied, or the surface roughness becomes large and the blocking function is insufficient. In the case of the decrease in color and the reversal development method, black spots and background fog may occur on a white background.

  Patent Document 3 describes that a dry film of a polymer emulsion in which particles of a conductive material are dispersed is provided as an intermediate layer of an electrostatic recording body. However, even when the intermediate layer is formed by using a coating solution in which a metal oxide is dispersed in a conventional polymer emulsion to produce a photoreceptor, the surface uniformity of the intermediate layer is still satisfactory, although there is no problem in resolution. It was insufficient. For this reason, in the case of a decrease in charging ability, a decrease in image contrast, or a reversal development method, black spots or background fog may occur on a white background.

  In addition, in response to the recent demand for higher image quality, it is effective to reduce the thickness of the photosensitive layer. However, reducing the thickness of the photosensitive layer is advantageous for improving the image quality, but promotes the injection of charges from the support. Therefore, it was necessary to further enhance the blocking function while maintaining the electrical resistance characteristics.

  On the other hand, Patent Document 4 describes that by drying a polyolefin resin dispersion having excellent liquid stability, an antistatic film having good water resistance, transparency, and adhesion to a base film can be obtained. ing. However, when forming an upper film in contact with the antistatic film, it is caused by a problem caused when a dielectric layer such as a photosensitive layer is present on the upper layer, a coating defect of the antistatic film, or a surface roughness. There is no description regarding a specific problem at the time of producing an electrophotographic photosensitive member such as a decrease in charging ability of the dielectric layer.

JP-A-56-52757 Japanese Patent Laid-Open No. 2-181158 JP-A-56-80048 JP 2003-268164 A JP 2003-105145 A Japanese Patent Laid-Open No. 2003-147028

New Polymer Experiments 2 Chapter 1 to Chapter 4 of Polymer Synthesis and Reaction (1), Kyoritsu Publishing Co., Ltd.

  An object of the present invention is to provide a method for producing an electrophotographic photosensitive member having good thickness uniformity of the intermediate layer in a method for producing an electrophotographic photosensitive member having an intermediate layer containing a resin and a metal oxide. is there.

According to the present invention, in a method for producing an electrophotographic photoreceptor having a support and an intermediate layer and a photosensitive layer formed on the support,
An aqueous dispersion containing polyolefin resin particles having a particle size of 50 nm or more and 500 nm or less and a metal oxide is applied to form a coating film, and then the coating film is heated to melt the polyolefin resin particles to form an intermediate layer And the process of
There is provided a method for producing an electrophotographic photosensitive member, comprising the step of forming the photosensitive layer on the intermediate layer.

  According to the present invention, the aggregation of the metal oxide during layer formation (during drying) is suppressed, so that the film thickness uniformity of the intermediate layer is improved. Furthermore, even when the intermediate layer is formed using the aqueous dispersion stored for a long period of time, the film thickness uniformity of the intermediate layer is excellent. As a result, the blocking function can be enhanced while maintaining the electrical resistance characteristics of the intermediate layer in an appropriate range, and the manufactured electrophotographic photoreceptor can provide a good image.

  Hereinafter, embodiments of the present invention will be described in detail.

  The aqueous dispersion according to the present invention refers to a liquid in which polyolefin resin particles and a metal oxide are dispersed in a dispersion medium (aqueous dispersion medium) in which the ratio of water to the total amount of the dispersion medium is 50% by mass or more.

In order to suppress the aggregation of the metal oxide at the time of layer formation (during drying), it is necessary to suppress the fluidity in the state where the dispersion medium is still present immediately after the dispersion is applied, The present invention has been reached. Uniformity of film thickness by applying an aqueous dispersion containing polyolefin resin particles having a particle size of 50 nm or more and 500 nm or less and a metal oxide, and then heating the coating film to melt the polyolefin resin particles to form an intermediate layer. The reason for the improvement is estimated as follows. That is, one has good dispersibility of the polyolefin resin particles and the metal oxide in the aqueous dispersion, and good dispersion even if the dispersion medium in the aqueous dispersion volatilizes after the aqueous dispersion is applied. The state is maintained. The other is that the polyolefin resin particles are melted by heating after the dispersion medium in the aqueous dispersion is volatilized and the metal oxide is not agglomerated, thereby improving the adhesion of each particle. For these reasons, it is assumed that the intermediate layer can be formed in a state where the metal oxide is uniformly dispersed.

  When the particle diameter of the polyolefin resin particles is less than 50 nm, the effect of suppressing the aggregation of metal oxides during layer formation (during drying) cannot be obtained. When the particle size is more than 500 nm, the adhesion between the particles becomes low, and a partial defect in which no intermediate layer is formed occurs.

  The polyolefin resin used in the present invention refers to a polymer obtained by polymerizing an olefin. Olefin means a hydrocarbon compound having one or more C═C (double bond between carbons). The polyolefin resin used in the present invention may be a polymer obtained by polymerizing only an olefin, or a polymer (polyolefin copolymer) obtained by copolymerizing an olefin and another monomer. May be.

In order to obtain an aqueous dispersion using the polyolefin resin particles, the polyolefin resin particles have the following (A1), (A2) and (A3), and (A1), (A2) and (A3) It is preferably a polyolefin resin particle whose mass ratio satisfies the following formula:
0.01 ≦ (A2) / {(A1) + (A2) + (A3)} × 100 ≦ 30
55/45 ≦ (A1) / (A3) 99/1
More preferably, it is a polyolefin resin particle satisfying the following formula,
0.01 ≦ (A2) / {(A1) + (A2) + (A3)} × 100 ≦ 10
55/45 ≦ (A1) / (A3) ≦ 99/1
More preferred are polyolefin resin particles satisfying the following formula.
0.01 ≦ (A2) / {(A1) + (A2) + (A3)} × 100 ≦ 5
55/45 ≦ (A1) / (A3) ≦ 99/1

  (A1): Repeating structural unit represented by the following formula (11)

（式（１１）中、Ｒ^１１〜Ｒ^１４は、それぞれ独立に、水素原子またはアルキル基を示す。）

(In formula (11), R ^{11 to} R ¹⁴ each independently represents a hydrogen atom or an alkyl group.)

  (A2): Repeating structural unit represented by the following formula (21) or (22)

(In the formulas (21) and (22), R ^{21 to} R ²⁴ are each independently a hydrogen atom, an alkyl group, a phenyl group or —Y ²¹ COOH (wherein Y ²¹ is a single bond, an alkylene group or an arylene) R ²⁵ and R ²⁶ each independently represents a hydrogen atom, an alkyl group or a phenyl group, and X ²¹ represents —Y ²² COOCO.
Y ²³ — (wherein Y ²² and Y ²³ each independently represents a single bond, an alkylene group or an arylene group) represents a divalent group. However, at least one of R ^{21 to} R ²⁴ is a monovalent group represented by —Y ²¹ COOH. )

  (A3): repeating structural unit represented by the following formula (31), (32), (33) or (34)

(In formulas (31) to (34), R ^{31 to} R ³⁵ each independently represent a hydrogen atom or a methyl group, and R ^{41 to} R ⁴³ each independently represents an alkyl group having 1 to 10 carbon atoms. R ^{51 to} R ⁵³ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

In the formula (11), R ^{11 to} R ¹⁴ each independently represent a hydrogen atom or an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group. R ^{11 to} R ¹⁴ are preferably each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably each independently a hydrogen atom or a methyl group, and all are hydrogen atoms. More preferably it is. These repeating structural units can be introduced by a polymerization reaction in the presence of a monomer having a carbon-carbon double bond. Examples of the monomer include ethylene, propylene, 1-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 3-methyl-1-pentene, and 1-hexene. Among these, ethylene is used. It is preferable.

In the formula (21), R ^{21 to} R ²⁴ each independently represent a hydrogen atom, an alkyl group, a phenyl group, or —Y ²¹ COOH (wherein Y ²¹ represents a single bond, an alkylene group, or an arylene group). ) Represents a monovalent group. However, at least one of R ^{21 to} R ²⁴ is a monovalent group represented by —Y ²¹ COOH. Of R ^{21 to} R ²⁴ , three are hydrogen atoms, one is —COOH, or two of R ^{21 to} R ²⁴ are hydrogen atoms, one is an R ²² methyl group, and one is —COOH. It is preferable.
In the formula (22), R ²⁵ and R ²⁶ each independently represent a hydrogen atom, an alkyl group or a phenyl group, and X ²¹ represents —Y ²² COOCOY ²³ — (wherein Y ²² and Y ²³ represent Each independently represents a single bond, an alkylene group or an arylene group.). R ²⁵ and R ²⁶ are each preferably a hydrogen atom, and X ²¹ is preferably —COOCO—.

  These repeating structural units can be introduced by a polymerization reaction in the presence of a monomer having at least one carboxyl group or acid anhydride group in the molecule (in the monomer unit). Examples of the monomer include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid and crotonic acid, as well as unsaturated dicarboxylic acid half esters and half amides.

In the formula ^{(31), R 31} represents a hydrogen atom or a methyl ^{group, R 41} represents a methyl group, an ethyl group, a propyl group, an alkyl group having 1 to 10 carbon atoms such as butyl group. R ⁴¹ is preferably a methyl group or an ethyl group. These repeating structural units can be introduced by a polymerization reaction in the presence of a (meth) acrylic acid ester monomer. Examples of the monomer include methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate.
In the formula (32), R ³² and R ³³ each independently represent a hydrogen atom or a methyl group, and R ⁴² and R ⁴³ each independently represent a methyl group, an ethyl group, a propyl group, a butyl group, or the like. An alkyl group having 1 to 10 carbon atoms. R ⁴² and R ⁴³ are preferably a methyl group or an ethyl group. These repeating structural units can be introduced by a polymerization reaction in the presence of a maleate monomer. Examples of the monomer include dimethyl maleate, diethyl maleate, and dibutyl maleate.
In the above formula ^{(33), R 34} represents a hydrogen atom or a methyl ^{group, R 51} and ^{R 52} each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R ⁵¹ and R ⁵² are preferably a hydrogen atom. These repeating structural units can be introduced by a polymerization reaction in the presence of an acrylic acid amide monomer.
In the above formula (34), R ³⁵ represents a hydrogen atom or a methyl group, R ⁵³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group. Group and ethyl group are preferred. These repeating structural units can be introduced by a polymerization reaction in the presence of an alkyl vinyl ether monomer and a vinyl alcohol monomer. Examples of the monomer include methyl vinyl ether, ethyl vinyl ether, and vinyl alcohol obtained by saponifying vinyl ester with a basic compound, and a mixture thereof can also be used.
Of formulas (31) to (34), formula (31) is particularly preferred as the repeating structural unit.

  If (A2) / {(A1) + (A2) + (A3)} is 0.01 or more, it becomes easy to make the polyolefin resin aqueous (liquefaction) and obtain a good aqueous dispersion. Becomes easier. On the other hand, if (A2) / {(A1) + (A2) + (A3)} is 30 or less, erosion of the intermediate layer when the photosensitive layer is applied and formed on the intermediate layer is suppressed, and electrophotography Degradation of characteristics is suppressed.

  If (A1) / (A3) is 55/45 or more, when the photosensitive layer is applied and formed on the intermediate layer, erosion of the intermediate layer is suppressed, and deterioration of electrophotographic characteristics is suppressed. On the other hand, when (A1) / (A3) is 99/1 or less, it becomes easy to make the polyolefin resin aqueous (liquefaction) and to obtain a good aqueous dispersion.

  Preferred examples of the polyolefin resin include a structural unit represented by the following formula (111) as (A1), a structural unit represented by the following formula (221) as (A2), and the following formula as (A3): Examples thereof include a structural unit represented by (311) and / or a structural unit represented by the following formula (312).

  Further, the polyolefin resin used in the present invention may be one in which other monomers are copolymerized at 20% by mass or less of the entire resin. Examples of other monomers include alkyl vinyl ethers having 3 to 30 carbon atoms such as methyl vinyl ether and ethyl vinyl ether, dienes, (meth) acrylonitrile, halogenated vinyls, halogenated vinylidenes, carbon monoxide, and sulfur dioxide. Is mentioned. The molecular weight of the polyolefin resin used in the present invention is not particularly limited, but is preferably in the range of 10,000 to 100,000, more preferably 20,000 to 50,000.

  The polyolefin resin used in the present invention may be a synthetic resin or a commercially available resin.

  The method for synthesizing the polyolefin resin used in the present invention is not particularly limited, but it can be obtained by a method in which a monomer constituting the polyolefin resin is subjected to high-pressure radical copolymerization in the presence of a radical generator. Specific methods for synthesizing polyolefin resins are described in Non-Patent Document 1, Patent Document 5, and Patent Document 6.

  Examples of commercially available polyolefin resins include “Bondyne (registered trademark)” manufactured by Sumitomo Chemical Co., Ltd. and “Primacol (registered trademark)” manufactured by Dow Chemical Co., Ltd.

  The metal oxide used in the present invention is aluminum oxide, titanium oxide, zinc oxide, cerium oxide, yttrium oxide, silicon oxide, zirconium oxide, iron oxide, tin oxide, magnesium oxide, copper oxide, manganese oxide, antimony-doped tin oxide , Indium-doped tin oxide, aluminum-doped tin oxide, a mixture of two or more of oxides, and composite oxides. The metal oxide can be surface-treated using a surface treatment agent as necessary.

Next, the manufacturing method of the aqueous dispersion concerning this invention is described.
The method for preparing the aqueous dispersion containing the polyolefin resin particles and the metal oxide is not particularly limited. However, from the viewpoint of the dispersibility of the metal oxide, a method in which the polyolefin resin particle dispersion and the metal oxide dispersion are prepared separately and mixed to prepare is preferable. Hereinafter, this method will be described in detail.

As a method for preparing the polyolefin resin particle dispersion, for example, a method of heating and stirring in a container that can be sealed with polyolefin resin, water, and if necessary, an organic solvent can be employed. At this time, the shape of the polyolefin resin is not particularly limited, but it is preferable to use a granular or powdery particle having a particle diameter of 1 cm or less, preferably 0.8 cm or less, from the viewpoint of increasing the particle formation rate.

  Any container may be used as long as it is equipped with a tank into which a liquid can be introduced and can appropriately stir the mixture of the resin and the aqueous dispersion medium introduced into the tank. As such an apparatus, an apparatus known as a solid / liquid stirring apparatus or an emulsifier can be used, and an apparatus capable of pressurization of 0.1 MPa or more is preferably used. The stirring method and the rotation speed of stirring are not particularly limited.

  After each raw material is put into the tank of this apparatus, it is preferably stirred and mixed at a temperature of 40 ° C. or lower. Subsequently, an aqueous dispersion can be obtained by continuing stirring for 5 to 120 minutes while maintaining the temperature in the tank preferably at a temperature of 50 ° C to 200 ° C, more preferably at a temperature of 60 ° C to 200 ° C. .

  At this time, it is preferable to add a basic compound in order to anionize the unsaturated carboxylic acid unit of the polyolefin resin. The addition amount of the basic compound is preferably 0.5 to 3.0 equivalents relative to the carboxyl group in the polyolefin resin (1 mol of acid anhydride group is regarded as 2 mol of carboxyl group). The equivalent of 8 times to 2.5 times equivalent is more preferable, and 1.0 time to 2.0 times equivalent is particularly preferable. If it is less than 0.5 times equivalent, the addition effect of a basic compound is not recognized, and if it exceeds 3.0 times equivalent, the drying time at the time of coating film formation may become longer or the aqueous dispersion may be colored. .

  As a basic compound added here, the compound which volatilizes at the time of coating film formation is preferable, and ammonia or various organic amine compounds are preferable. Specific examples of the organic amine compound include triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, and 3-ethoxypropylamine. , 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, methyliminobispropylamine, 3-methoxypropylamine, monoethanolamine, diethanolamine, triethanolamine, morpholine, N-methylmorpholine, N- Mention may be made of ethylmorpholine.

  The polyolefin resin particle dispersion obtained as described above is a uniform liquid in which the polyolefin resin is dispersed in an aqueous medium. “Uniform liquid” means that, in terms of appearance, a portion where the solid content concentration is locally different from other portions such as precipitation, phase separation or skinning is not found in the aqueous dispersion.

  As a method for preparing the metal oxide dispersion, for example, a commercially available metal oxide can be wet pulverized with a ball mill, vibration ball mill, roll mill, triter, sand mill or colloid mill to obtain a dispersion. Moreover, the slurry and sol liquid currently disperse | distributed to the commercially available aqueous dispersion medium can also be used as it is. Also, a method of hydrolyzing or thermally hydrolyzing metal oxides, a method of alkaline hydrolysis of an acidic solution containing metal ions, or a method of ion exchange of a solution containing metal ions with an ion exchange membrane or ion exchange resin is used. Can do.

  When mixing the polyolefin resin particle dispersion and the metal oxide dispersion obtained by separate operations in this manner, the metal oxide dispersion may be added to the polyolefin resin dispersion and mixed. Conversely, the polyolefin resin dispersion may be added to and mixed with the metal oxide dispersion.

In the present invention, setting the particle diameter of the polyolefin resin particles in the aqueous dispersion to 50 nm to 500 nm means that the stirring conditions such as the time, speed and temperature during the production of the resin particle dispersion and the aqueous dispersion This can be achieved by adjusting the solid content. When increasing the particle diameter of the polyolefin resin particles, for example, the stirring conditions during the production of the resin particle dispersion may be weakened, or the solid content of the aqueous dispersion may be increased. On the other hand, when the particle diameter of the polyolefin resin particles is reduced, for example, the stirring conditions during the production of the resin particle dispersion can be increased, or the solid content of the aqueous dispersion can be decreased.
The metal oxide contained in the aqueous dispersion according to the present invention preferably has a volume ratio of 0.5 to 2.0 with respect to the polyolefin resin particles. If the volume ratio is less than 0.5, metal oxides may not be uniformly present between the polyolefin resin particles, and if it exceeds 2.0, aggregation of metal oxides may occur.

The particle diameter of the metal oxide is preferably 5 nm or more and 50 nm or less. If the particle size of the metal oxide exceeds 50 nm in the aqueous dispersion, the film thickness uniformity may be reduced even if polyolefin resin particles are used. On the other hand, when the particle size of the metal oxide is less than 5 nm, the storage stability of the aqueous dispersion may be lowered.
The particle size of the metal oxide can be adjusted by using metal oxides having different particle sizes, or by adjusting the dispersion time at the time of preparing the coating liquid or adjusting the mass ratio of the dispersion medium. .

Moreover, it is preferable that the relationship between the particle diameter C1 of the polyolefin resin particles and the particle diameter C2 of the metal oxide satisfies the following formula.
1 ≦ C1 / C2 ≦ 20

  If C1 / C2 is less than 1, the polyolefin resin particles will be smaller than the metal oxide, so the metal oxide may not be uniformly present between the polyolefin resin particles, and if C1 / C2 exceeds 20, In some cases, aggregation of metal oxides may occur.

  The particle diameters of the polyolefin resin particles and the metal oxide are measured by TEM (transmission electron microscope) observation of the produced aqueous dispersion. Specifically, the aqueous dispersion is frozen using an TEM equipped with an energy filter equipped with a cryotransfer and observed with an electron microscope. It can be obtained by measuring the particle size of any 100 particles of polyolefin resin particles and metal oxides and determining the average value. The magnification was 40,000 times, the lower limit was 1 nm, and the upper limit was 1,500 nm.

  The dispersion medium used in the present invention may contain a hydrophilic organic solvent in addition to water. When preparing the polyolefin resin particle dispersion, it is preferable to adjust appropriately when mixing the polyolefin resin particle dispersion and the metal oxide dispersion when preparing the metal oxide dispersion. Examples of the organic solvent include methyl ethyl ketone, acetone, diethyl ketone, propanol, butanol, methanol, ethanol, tetrahydrofuran, dioxane, and ethylene glycol monobutyl ether. The amount of these organic solvents in the total amount of the aqueous dispersion is preferably 40% by mass or less.

  The aqueous dispersion obtained as described above is applied onto a conductive support or a conductive layer to form a coating film. And the intermediate layer is formed by heating the coating film and melting (heating and melting) the polyolefin resin particles.

  As a method for applying the aqueous dispersion, which is a coating solution for the intermediate layer, various methods usually used in this field can be applied, and among them, the dip coating method is particularly preferable.

  In the method for producing a photoreceptor of the present invention, when the intermediate layer coating solution is applied by dip coating, the relative humidity at a temperature of 23 ° C. is 60% or less and the wind speed is 1 m / s. It is preferable to carry out with the dip coating apparatus installed in a certain environment.

  The thickness of the intermediate layer is preferably in the range of 0.1 μm to 20 μm.

  The heating temperature of the coating film is preferably 80 ° C. or higher and 120 ° C. or lower. If the temperature is 80 ° C. or higher, the heat-melting is sufficient, and the effects of the present invention can be sufficiently exerted. Moreover, if the temperature is 120 ° C. or lower, the contraction of the film of the intermediate layer is suppressed, and the film thickness uniformity is increased.

  The support used in the electrophotographic photosensitive member may be a conductive one (conductive support), and examples thereof include a metal or an alloy such as aluminum, nickel, copper, gold and iron. . Further, a thin film made of a metal such as aluminum, silver or gold, or a conductive material such as indium oxide or tin oxide may be formed on an insulating support such as polyester, polycarbonate, polyimide or glass. Moreover, the support body which disperse | distributed carbon and the electroconductive filler in resin, and provided electroconductivity may be sufficient.

  The surface of the support may be subjected to an electrochemical treatment such as anodization in order to improve electrical characteristics and adhesion. Further, the surface of the support may be subjected to chemical treatment with a solution obtained by dissolving a metal salt compound or a fluorine compound metal salt in an acidic aqueous solution mainly composed of alkali phosphate or phosphoric acid or tannic acid. .

  In addition, when the electrophotographic photosensitive member of the present invention is used in an electrophotographic apparatus using single-wavelength light such as laser light as exposure light (image exposure light), the surface of the support is used to suppress interference fringes. It is preferable that the surface is appropriately roughened. Specifically, it is preferable that the surface of the support is subjected to honing, blasting, cutting, and electropolishing, or a conductive film containing a conductive metal oxide and a binder resin is provided on the support.

  The honing process includes a dry process and a wet process, either of which may be adopted. The wet honing treatment is a method of roughening a suspension obtained by suspending a powdery abrasive in a liquid such as water on the surface of a support at a high speed. In the case of the wet honing treatment, the surface roughness of the support can be controlled by the spraying pressure of the suspension, the speed, the amount of the abrasive, the type, shape, size, hardness, specific gravity and suspension temperature. The dry honing treatment is a method in which an abrasive is sprayed onto the surface of a support with air at a high speed to roughen the surface. Also in the case of the dry honing treatment, the surface roughness of the support can be controlled in the same manner as the wet honing treatment. Examples of the abrasive used for the honing treatment include particles such as silicon carbide, alumina, iron, and glass beads.

  A conductive layer may be provided between the support and the intermediate layer of the present invention for the purpose of suppressing interference fringes due to scattering of laser light and covering the scratches on the support.

The conductive layer can be formed by dispersing conductive particles such as carbon black, metal particles, and metal oxide particles in a binder resin. Examples of the metal oxide particles include zinc oxide and titanium oxide particles. Further, barium sulfate particles coated with oxygen-deficient SnO ₂ can also be used as the conductive particles.

  Examples of the binder resin used for the conductive layer include a phenol resin, a polyurethane resin, and a polyamide resin. These have good adhesion to the support, improve dispersibility of the conductive particles, and have good solvent resistance after layer formation.

  Further, a leveling agent may be added to the conductive layer in order to improve the surface property of the conductive layer.

A second intermediate layer having an adhesive function may be provided between the intermediate layer of the present invention and the photosensitive layer. The second intermediate layer is formed of a material such as casein, polyvinyl alcohol, nitrocellulose, polyamide (for example, nylon 6, nylon 66, nylon 610, copolymer nylon, alkoxymethylated nylon), polyurethane, or aluminum oxide. can do.
A photosensitive layer is provided on the intermediate layer.
The photosensitive layer may be a single-layer type photosensitive layer containing a charge generation material and a charge transport material in a single layer, or a charge generation layer containing a charge generation material and a charge transport containing a charge transport material. It may be a laminate type (function separation type) photosensitive layer in which layers are laminated. From the viewpoint of electrophotographic characteristics, a laminate type photosensitive layer is preferable, and among them, a laminate type photosensitive layer in which a charge generation layer and a charge transport layer are laminated in this order from the support side is more preferable.
Hereinafter, a laminated type photosensitive layer will be described as an example.

  The charge generation layer can be formed by applying a charge generation layer coating solution obtained by dispersing a charge generation material together with a binder resin and a solvent and drying the coating solution.

As the charge generation material used in the present invention,
(1) Azo pigments such as monoazo, disazo, trisazo,
(2) phthalocyanine pigments such as metal phthalocyanines and non-metal phthalocyanines;
(3) Indigo pigments such as indigo and thioindigo,
(4) Perylene pigments such as perylene anhydride and perylene imide,
(5) polycyclic quinone pigments such as anthraquinone and pyrenequinone,
(6) squarylium dye,
(7) pyrylium salt, thiapyrylium salt,
(8) triphenylmethane dye,
(9) inorganic materials such as selenium, selenium-tellurium, amorphous silicon,
(10) quinacridone pigment,
(11) an azulenium salt pigment,
(12) cyanine dyes,
(13) a xanthene dye,
(14) quinoneimine dye,
(15) styryl dye,
(16) cadmium sulfide,
(17) Examples include zinc oxide. Among these, metal phthalocyanine pigments are particularly preferable, and among them, oxytitanium phthalocyanine, chlorogallium phthalocyanine, dichlorotin phthalocyanine, and hydroxygallium phthalocyanine are preferable. Of these, hydroxygallium phthalocyanine is particularly preferred.

As oxytitanium phthalocyanine,
An oxytitanium phthalocyanine crystal having strong peaks at 9.0 °, 14.2 °, 23.9 ° and 27.1 ° of the Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction;
Bragg angles (2θ ± 0.2 °) of 9.5 °, 9.7 °, 11.7 °, 15.0 °, 23.5 °, 24.1 ° and 27.3 in CuKα characteristic X-ray diffraction Oxytitanium phthalocyanine crystals having a strong peak at ° are preferred.

As chlorogallium phthalocyanine,
Chlorogallium phthalocyanine crystals having strong peaks at 7.4 °, 16.6 °, 25.5 and 28.2 ° of the Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction,
Chlorogallium phthalocyanine crystal having strong peaks at 6.8 °, 17.3 °, 23.6 ° and 26.9 ° of the Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction, CuKα characteristic X-ray Chlorogallium phthalocyanine with strong peaks at 8.7 ° to 9.2 °, 17.6 °, 24.0 °, 27.4 ° and 28.8 ° of the Bragg angle (2θ ± 0.2 °) in diffraction Crystals are preferred.

As dichlorotin phthalocyanine,
Strong peaks at 8.3 °, 12.2 °, 13.7 °, 15.9 °, 18.9 ° and 28.2 ° of the Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction Having dichlorotin phthalocyanine crystals,
Dichlorotin phthalocyanine crystals having strong peaks at 8.5 °, 11.2 °, 14.5 ° and 27.2 ° of the Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction;
Bragg angles (2θ ± 0.2 °) of 8.7 °, 9.9 °, 10.9 °, 13.1 °, 15.2 °, 16.3 °, 17.4 in CuKα characteristic X-ray diffraction Dichlorotin phthalocyanine crystals with strong peaks at °, 21.9 ° and 25.5 °,
Strong peaks at 9.2 °, 12.2 °, 13.4 °, 14.6 °, 17.0 ° and 25.3 ° of the Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction The dichlorotin phthalocyanine crystal | crystallization which has is preferable.

As hydroxygallium phthalocyanine,
Hydroxygallium phthalocyanine crystal having strong peaks at 7.3 °, 24.9 ° and 28.1 ° of the Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction;
Bragg angles (2θ ± 0.2 °) of 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 in CuKα characteristic X-ray diffraction A hydroxygallium phthalocyanine crystal having a strong peak at 0 ° is preferred.

  Examples of the binder resin for the charge generation layer include butyral resin, polyester resin, polycarbonate resin, polyarylate resin, polystyrene resin, polyvinyl methacrylate resin, polyvinyl acrylate resin, polyvinyl acetate resin, polyvinyl chloride resin, polyamide resin, polyurethane Examples include resins, silicone resins, alkyd resins, epoxy resins, cellulose resins, and melamine resins. Among these, butyral resins are preferable.

  The dispersed particle diameter of the charge generation material in the charge generation layer is preferably 0.5 μm or less, more preferably 0.3 μm or less, and more preferably 0.01 μm or more and 0.2 μm or less.

  The film thickness of the charge generation layer is preferably from 0.01 μm to 2 μm, more preferably from 0.05 μm to 0.3 μm.

The charge transport layer is formed by applying a charge transport layer coating solution obtained by dispersing / dissolving a charge transport material in a solvent together with a binder resin (which can be selected from the aforementioned resin for charge generation layer) and drying it. Can be formed. Examples of the charge transport material include heterocycles such as poly-N-vinylcarbazole and polystyrylanthracene, polymer compounds having condensed polycyclic aromatics, and heterocycles such as pyrazoline, imidazole, oxazole, triazole, and carbazole. Examples thereof include low molecular weight compounds such as compounds, triarylalkane derivatives such as triphenylmethane, triarylamine derivatives such as triphenylamine, phenylenediamine derivatives, N-phenylcarbazole derivatives, stilbene derivatives, and hydrazone derivatives. Examples of the binder resin include the same binder resins as those described above for the charge generation layer. The ratio of the charge transport material and the binder resin is such that the mass of the charge transport material is preferably 20 to 100, more preferably 30 to 100, assuming that the total mass of both is 100. If the amount of the charge transporting material is too small, the charge transporting ability is lowered, and the problems of sensitivity reduction and increase in residual potential are likely to occur. The thickness of the charge transport layer is preferably 1 μm or more and 50 μm or less, and more preferably 3 μm or more and 30 μm or less.

  Furthermore, a surface protective layer may be formed on the photosensitive layer (charge transport layer).

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In the examples, “part” means “part by mass”.

  Examples of polyolefin resins used in the examples include commercially available resins (Bondaine HX-8290, Bondine HX-8210, Bondine AX-8390 (manufactured by Sumitomo Chemical Co., Ltd.), Primacol 5980I (manufactured by Dow Chemical Company)). And the resin (B1-B11) synthesize | combined by the well-known method was used.

  In addition, the synthesis method of resin B1-11 is the synthesis method described in the nonpatent literature 1, the patent documents 5, and the patent documents 6. FIG.

The composition of the polyolefin resin was measured by the following method. The results are shown in Tables 1 and 2.
(1) Composition of (A1) to (A3) in polyolefin resin Obtained by performing ¹ H-NMR, ¹³ C-NMR analysis (manufactured by Varian, 300 MHz) at a temperature of 120 ° C. in orthodichlorobenzene (d4). It was. ^{In 13} C-NMR analysis, measurement was performed using a gated decoupling method in consideration of quantitativeness.
(2) Composition of (A2) in polyolefin resin The acid value of the polyolefin resin was measured according to JIS K5407, and the mass of (A2) in the polyolefin resin was converted.

(Preparation of polyolefin resin particle dispersion 1)
A stirrer equipped with a heat-resistant 1-liter glass container with a heater was used.
Polyolefin resin 75.0g
(Bondyne HX-8290, manufactured by Sumitomo Chemical Co., Ltd.)
Isopropanol 60.0g
Triethylamine (TEA) 5.1g
Distilled water 159.9g
When the above materials were charged into a glass container and stirred at a rotation speed of the stirring blade of 300 rpm, no precipitation of resin particles was observed at the bottom of the container, and it was confirmed that the container was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 140 ° C. to 145 ° C., and further stirred for 20 minutes. Then, it was put in a water bath, cooled to room temperature (temperature about 25 ° C.) while stirring at a rotational speed of 300 rpm, and then pressure filtered (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave). And a milky white uniform polyolefin resin aqueous dispersion 1 was obtained.

(Polyolefin resin particle dispersion 2)
A polyolefin resin particle dispersion 2 was prepared in the same manner as in the polyolefin resin particle dispersion 1, except that the polyolefin resin (Bondaine HX-8290) was changed to a polyolefin resin (Bondaine HX-8210, manufactured by Sumitomo Chemical Co., Ltd.). Obtained.

(Polyolefin resin particle dispersion 3)
A stirrer equipped with a heat-resistant 1-liter glass container with a heater was used.
Polyolefin resin 60.0g
(Bondyne AX-8390, manufactured by Sumitomo Chemical Co., Ltd.)
n-propanol 100.0g
TEA 2.5g
Distilled water 137.5g
When the above materials were charged into a glass container and stirred at a rotation speed of the stirring blade of 300 rpm, no precipitation of resin particles was observed at the bottom of the container, and it was confirmed that the container was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 120 ° C. and further stirred for 20 minutes. Then, after cooling to room temperature (temperature: about 25 ° C.) with stirring at a rotational speed of 300 rpm, air filtration and pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave). ) To obtain a uniform polyolefin resin particle dispersion 3.

(Polyolefin resin particle dispersion 4)
A stirrer equipped with a heat-resistant 1-liter glass container with a heater was used.
Polyolefin resin 60.0g
(Primacol 5980I, manufactured by Dow Chemical Company)
TEA 16.8g
Distilled water 223.2g
When the above materials were charged into a glass container and stirred at a rotation speed of the stirring blade of 300 rpm, no precipitation of resin particles was observed at the bottom of the container, and it was confirmed that the container was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was maintained at 130 ° C., and further stirred for 30 minutes. Then, after cooling to room temperature (temperature: about 25 ° C.) with stirring at a rotational speed of 300 rpm, air filtration and pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave). And a polyolefin resin particle dispersion 4 was obtained.

(Polyolefin resin particle dispersion 5-15)
Except having changed polyolefin resin (Bondaine HX-8290) into polyolefin resin [B1]-[B11], it prepared similarly to polyolefin resin particle dispersion 1, and obtained polyolefin resin particle dispersions 5-15.

Example 1
10 parts of titanium oxide (trade name: TTO55N specific gravity 4.2, manufactured by Ishihara Sangyo Co., Ltd.) and 90 parts of isopropanol (IPA) were dispersed by a ball mill for 72 hours to obtain a titanium oxide dispersion.

  The polyolefin resin particle dispersion 1 was mixed in the titanium oxide dispersion so that the titanium oxide was 4.2 parts with respect to 1 part of the polyolefin resin solid content. Thereafter, the dispersion medium was added so that the mass ratio of the dispersion medium was 8/2 water / IPA and the solid content was 2.5%, and the aqueous dispersion 1 was obtained by stirring.

  The particle diameter of the polyolefin resin particles in the aqueous dispersion was 200 nm, and the particle diameter of titanium oxide was 30 nm.

  The film thickness uniformity was evaluated as follows.

By dip-coating the aqueous dispersion on a support that has been ultrasonically washed with an aluminum cylinder having a diameter of 30 mm and a length of 260.5 mm, and drying it at 100 ° C. for 30 minutes,
An intermediate layer having a thickness of 1.0 μm was formed.

  Surface roughness is measured using a surface roughness meter Surfcoder SE3500 manufactured by Kosaka Laboratory Ltd., with a cutoff of 0.8 mm, a measurement length of 8 mm, and a measurement speed of 0.5 mm / s. Average roughness (Ra) was determined. The results are shown in Table 3.

(Examples 2 to 15)
Except for changing the polyolefin resin particle dispersion 1 of Example 1 to the polyolefin resin particle dispersions 2 to 15, aqueous dispersions 2 to 15 were obtained in the same manner as in Example 1, and an intermediate layer was formed for evaluation. It was.

  Table 3 shows the results of the particle diameter of the polyolefin resin particles, the particle diameter of the titanium oxide, and the surface roughness in the aqueous dispersion.

(Examples 16 to 19)
Aqueous dispersion as in Example 1, except that the amount of titanium oxide in Example 1 was changed from 4.2 parts to 1.3 parts, 2.1 parts, 8.4 parts, and 12.6 parts, respectively. 16-19 were obtained and the intermediate | middle layer was formed and evaluated.

  Table 3 shows the results of the particle diameter of the polyolefin resin particles, the particle diameter of the titanium oxide, and the surface roughness in the aqueous dispersion.

(Example 20)
In Example 1, titanium oxide (trade name: TTO55N specific gravity 4.2, manufactured by Ishihara Sangyo Co., Ltd.) was changed to titanium oxide (product name: ST-01 specific gravity 4.2, manufactured by Ishihara Sangyo Co., Ltd.). Obtained the aqueous dispersion 20 similarly to Example 1, formed the intermediate | middle layer, and evaluated.
Table 3 shows the results of the particle diameter of the polyolefin resin particles, the particle diameter of the titanium oxide, and the surface roughness in the aqueous dispersion.

(Example 21)
In Example 1, except that titanium oxide (trade name: TTO55N specific gravity 4.2, manufactured by Ishihara Sangyo Co., Ltd.) was changed to titanium oxide (trade name PT401M specific gravity 4.2, manufactured by Ishihara Sangyo Co., Ltd.). An aqueous dispersion 21 was obtained in the same manner as in Example 1, and an intermediate layer was formed and evaluated.

  Table 3 shows the results of the particle diameter of the polyolefin resin particles, the particle diameter of the titanium oxide, and the surface roughness in the aqueous dispersion.

(Example 22)
In Example 1, except that titanium oxide (trade name: TTO55N specific gravity 4.2, manufactured by Ishihara Sangyo Co., Ltd.) was changed to titanium oxide (trade name: PT401L specific gravity 4.2, manufactured by Ishihara Sangyo Co., Ltd.), An aqueous dispersion 22 was obtained in the same manner as in Example 1, and an intermediate layer was formed and evaluated.

  Table 3 shows the results of the particle diameter of the polyolefin resin particles, the particle diameter of the titanium oxide, and the surface roughness in the aqueous dispersion.

(Example 23)
In Example 1, except that titanium oxide (trade name: TTO55N specific gravity 4.2, manufactured by Ishihara Sangyo Co., Ltd.) was changed to tin oxide (CI Chemical Co., Ltd. specific gravity 6.8), it was the same as Example 1. An aqueous dispersion 23 was obtained and an intermediate layer was formed for evaluation.

  Table 3 shows the results of the particle diameter of the polyolefin resin particles, the particle diameter of the titanium oxide, and the surface roughness in the aqueous dispersion.

(Example 24)
4. In Example 1, 4.2 parts of titanium oxide (trade name: TTO55N specific gravity 4.2, manufactured by Ishihara Sangyo Co., Ltd.) was added to zinc oxide (trade name: Passette 23K specific gravity 5.5, manufactured by Hakusui Tech Co., Ltd.). An aqueous dispersion 24 was obtained in the same manner as in Example 1 except that the amount was changed to 5 parts, and an intermediate layer was formed and evaluated.

  Table 3 shows the results of the particle diameter of the polyolefin resin particles, the particle diameter of the titanium oxide, and the surface roughness in the aqueous dispersion.

(Example 25)
In Example 1, 4.2 parts of titanium oxide (trade name: TTO55N specific gravity 4.2, manufactured by Ishihara Sangyo Co., Ltd.) was changed to 7.1 parts of cerium oxide (specific gravity 7.1 manufactured by CI Kasei Co., Ltd.). Except for the above, an aqueous dispersion 25 was obtained in the same manner as in Example 1, and an intermediate layer was formed for evaluation.

  Table 3 shows the results of the particle diameter of the polyolefin resin particles, the particle diameter of the titanium oxide, and the surface roughness in the aqueous dispersion.

(Example 26)
In Example 1, except that titanium oxide (trade name: TTO55N specific gravity 4.2, manufactured by Ishihara Sangyo Co., Ltd.) was changed to 3.6 parts of aluminum oxide (CI Chemical Co., Ltd. specific gravity 3.6). An aqueous dispersion 26 was obtained in the same manner as in Example 1, and an intermediate layer was formed and evaluated.

  Table 3 shows the results of the particle diameter of the polyolefin resin particles, the particle diameter of the titanium oxide, and the surface roughness in the aqueous dispersion.

(Example 27)
0.1 mol of stannic chloride pentahydrate was dissolved in 200 ml of water to make a 0.5 M aqueous solution, and 28% aqueous ammonia was added to adjust the pH to 1.5 while stirring. Then, after heating up to the temperature of 70 degreeC, after cooling naturally to the temperature of about 50 degreeC, the pure water was added and it adjusted to 1 liter, and solid-liquid separation was performed using the centrifuge. After adding 800 ml of pure water to this water-containing solid content, stirring and dispersing with a homogenizer, washing was performed by solid-liquid separation using a centrifuge. After adding 75 ml of pure water and 3.0 ml of triethylamine to the water-containing solid content after washing, the mixture is stirred and heated to a temperature of 70 ° C. when it becomes clear. Obtained.

  The polyolefin resin particle dispersion 1 was mixed with the tin oxide dispersion so that tin oxide was 6.8 parts relative to 1 part of the polyolefin resin solid content. Thereafter, the dispersion medium was added so that the mass ratio of the dispersion medium was 9/1 water / IPA and the solid content was 5%, and the aqueous dispersion liquid 27 was obtained by stirring. The obtained aqueous dispersion 27 was evaluated by forming an intermediate layer in the same manner as in Example 1.

  Table 3 shows the particle size of the polyolefin resin particles, the particle size of tin oxide, and the surface roughness in the aqueous dispersion.

(Example 28)
In Example 22, instead of adding the dispersion medium so that the mass ratio of the dispersion medium is 8/2 water / IPA and the solid content is 2.5%, the mass ratio of the dispersion medium is 9 / water / IPA. 1, solid content is 1.5
An intermediate layer was formed and evaluated in the same manner as in Example 22 except that the dispersion medium was added so as to be in%.

  Table 3 shows the results of the particle diameter of the polyolefin resin particles, the particle diameter of the titanium oxide, and the surface roughness in the aqueous dispersion.

(Example 29)
In Example 1, instead of adding the dispersion medium so that the mass ratio of the dispersion medium is 8/2 water / IPA and the solid content is 2.5%, the mass ratio of the dispersion medium is 7 / water / IPA. 3. An intermediate layer was formed and evaluated in the same manner as in Example 1 except that the dispersion medium was added so that the solid content was 10%.

  Table 3 shows the results of the particle diameter of the polyolefin resin particles, the particle diameter of the titanium oxide, and the surface roughness in the aqueous dispersion.

(Example 30)
In Example 1, instead of adding the dispersion medium so that the mass ratio of the dispersion medium is 8/2 water / IPA and the solid content is 2.5%, the mass ratio of the dispersion medium is 6 / water / IPA. 4. An intermediate layer was formed and evaluated in the same manner as in Example 1 except that the dispersion medium was added so that the solid content was 12%.

  Table 3 shows the results of the particle diameter of the polyolefin resin particles, the particle diameter of the titanium oxide, and the surface roughness in the aqueous dispersion.

(Examples 31-34)
In Example 1, the intermediate layer was formed in the same manner as in Example 1 except that the drying temperature of the intermediate layer was changed from 100 ° C. to 70 ° C., 80 ° C., 120 ° C., and 130 ° C., respectively. Evaluation was performed. Table 3 shows the results of the surface roughness.

(Comparative Example 1)
5 parts of N-methoxymethylated 6 nylon was dissolved in 95 parts of methanol to obtain a resin solution. Next, 10 parts of titanium oxide (trade name: TTO55N specific gravity 4.2, manufactured by Ishihara Sangyo Co., Ltd.) and 90 parts of methanol were dispersed by a ball mill for 72 hours to obtain a titanium oxide dispersion.

  The resin solution was mixed with the titanium oxide dispersion so that the titanium oxide content was 4.2 parts with respect to 1 part of the resin solid content. Then, methanol was added so that solid content might be 5%, and the dispersion liquid as a coating liquid for intermediate | middle layers was obtained.

  The obtained dispersion was evaluated by forming an intermediate layer in the same manner as in Example 1.

  In observation of the dispersion, N-methoxymethylated 6 nylon was completely dissolved and was not observed in the particle shape. Table 4 shows the results of the particle size and surface roughness of titanium oxide.

(Comparative Example 2)
A dispersion as an intermediate layer coating solution is obtained in the same manner as in Example 1 except that the aqueous dispersion 1 of Example 1 is changed to a polyester resin particle dispersion (trade name: Vylonal MD-1200, manufactured by Toyobo Co., Ltd.). It was. Table 4 shows the results of the particle size and surface roughness of titanium oxide in the dispersion.

"Production of electrophotographic photoreceptor"
<Photoreceptor Example 1-1>
An aluminum cylinder having a diameter of 30 mm and a length of 260.5 mm was ultrasonically washed with water as a support.

Next, 40 parts of barium sulfate particles coated with the following material oxygen-deficient SnO ₂ (powder resistivity 200Ω · cm, SnO ₂ coverage (mass ratio) is 60%)
Titanium oxide (trade name: TITANIX JR, manufactured by Teika Co., Ltd.) 8 parts Phenolic resin (as binder resin) (resin solid content 60%) 25 parts (trade name: Priorofen J-325, Dainippon Ink & Chemicals, Inc.) Made by Co., Ltd.)
Methoxypropanol 30 parts Methanol 30 parts The above materials were mixed and dispersed for 2 hours in a sand mill apparatus using glass beads having a diameter of 1 mm (1 mmφ) to prepare a dispersion for the conductive layer. In addition to this dispersion, the following materials: Silicone resin particles (as a surface roughening agent) 3.9 parts (trade name: Tospearl 120, manufactured by GE Toshiba Silicones Co., Ltd., average particle size 2 μm)
Silicone oil (as leveling agent) 0.002 parts (trade name: SH28PA, manufactured by Toray Dow Corning Silicone Co., Ltd.)
Was added and stirred to prepare a coating solution for a conductive layer. This conductive layer coating solution is dip-coated on a support at a temperature of 23 ° C. and a relative humidity of 60%, and dried and thermally cured at a temperature of 140 ° C. for 30 minutes. A layer was formed.

  Next, the aqueous dispersion 1 produced in Example 1 was dip-coated on the conductive layer, and this was dried at a temperature of 100 ° C. for 30 minutes to form an intermediate layer having a thickness of 1.0 μm.

Next, as a coating solution for the charge generation layer, first, the following materials: CuKα characteristic X-ray diffraction Bragg angle 2θ ± 0.2 ° 7.5 °, 9.9 °, 16.3 °, 18.6 ° , 25.1 ° and 28.3 ° in crystalline form of hydroxygallium phthalocyanine 10 parts Polyvinyl butyral resin 5 parts (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.)
0.1 part of a compound represented by the following structural formula (5)

Was added to 250 parts of cyclohexanone and dispersed in a sand mill using glass beads having a diameter of 1 mm for 4 hours. To this, 250 parts of ethyl acetate was added and diluted to prepare a charge generation layer coating solution. The charge generation layer coating solution thus prepared was applied on the intermediate layer, and then dried at a temperature of 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.16 μm.

Next, the following material 10 parts of the compound represented by the following structural formula (6)

10 parts of polyarylate resin having a repeating unit of the following structural formula (7) (weight average molecular weight Mw≈115000)

Was dissolved in a mixed solvent of 50 parts of monochlorobenzene and 30 parts of dichloromethane to prepare a charge transport layer coating solution. The charge transport layer coating solution thus prepared was dip-coated on the above-described charge generation layer and dried at a temperature of 120 ° C. for 1 hour to form a charge transport layer having a thickness of 12 μm.

  The electrophotographic photoreceptor thus produced was left to stand for 24 hours under high temperature and high humidity (temperature 30 ° C., relative humidity 80%), and image evaluation was performed in the same environment.

  Image evaluation was performed by mounting an electrophotographic photosensitive member on an apparatus obtained by modifying a LBP “Laser Jet 2510” manufactured by Hewlett-Packard to a dark portion potential of −800 V, and setting the following process conditions.

  The image was evaluated by attaching the produced electrophotographic photosensitive member to a cyan process cartridge of LBP-2510, outputting solid white as an image, and visually evaluating the presence or absence of an image defect. The results are shown in Table 5.

The fog evaluation was performed according to the following criteria.
A: No minute black spots are observed visually. B: Only a few minute black spots are observed (1 to 5 places). C: Several small black spots are visually recognized (6 or more places). D: Small black spots are observed on the entire surface. Among these, C and D judged that the effects of the present invention were not sufficiently obtained.

<Photoreceptor Example 1-2>
The surface of an aluminum cylinder having a diameter of 30 mm and a length of 260.5 mm was subjected to a wet honing treatment and subjected to ultrasonic water cleaning as a support.

  Next, the aqueous dispersion 1 produced in Example 1 was dip-coated on a support and dried at a temperature of 100 ° C. for 30 minutes to form an intermediate layer having a thickness of 1.0 μm.

  Next, a charge generation layer and a charge transport layer were prepared in the same manner as in photoreceptor example 1-1 to obtain an electrophotographic photoreceptor. The image evaluation was also performed in the same manner as in photoconductor Example 1-1. The results are shown in Table 5.

<Photoreceptor Example 1-3>
The surface of an aluminum cylinder having a diameter of 30 mm and a length of 260.5 mm was subjected to a wet honing treatment and subjected to ultrasonic water cleaning as a support.

Next, the aqueous dispersion 18 produced in Example 18 was dip-coated on a support and dried at a temperature of 100 ° C. for 60 minutes to form an intermediate layer having a thickness of 10.0 μm.

  Next, 5 parts of N-methoxymethylated 6 nylon was dissolved in 95 parts of methanol to prepare a coating solution for the second intermediate layer. This second intermediate layer coating solution was dip-coated on the above intermediate layer and dried at a temperature of 100 ° C. for 20 minutes to form a 0.5 μm second intermediate layer.

  Next, a charge generation layer and a charge transport layer were sequentially formed on the second intermediate layer in the same manner as in Photoreceptor Example 1-1 to obtain an electrophotographic photoreceptor. The image evaluation was also performed in the same manner as in photoconductor Example 1-1. The results are shown in Table 5.

<Photoreceptor Comparative Example 1>
In Photoconductor Example 1-1, the same procedure as in Photoconductor Example 1-1 was performed, except that the aqueous dispersion 1 prepared in Example 1 was changed to the dispersion liquid as the intermediate layer coating liquid prepared in Comparative Example 1. An electrophotographic photosensitive member was prepared and evaluated. The results are shown in Table 5.

<Photoreceptor Comparative Example 2>
In Photoconductor Example 1-1, the same procedure as in Photoconductor Example 1-1 was performed, except that the aqueous dispersion 1 prepared in Example 1 was changed to the dispersion liquid as the intermediate layer coating solution prepared in Comparative Example 2. An electrophotographic photosensitive member was prepared and evaluated. The results are shown in Table 5.

Claims (9)

In a method for producing a support and an electrophotographic photoreceptor having an intermediate layer and a photosensitive layer formed on the support,
An aqueous dispersion containing polyolefin resin particles having a particle size of 50 nm or more and 500 nm or less and a metal oxide is applied to form a coating film, and then the coating film is heated to melt the polyolefin resin particles to form an intermediate layer And the process of
A method for producing an electrophotographic photoreceptor, comprising a step of forming the photosensitive layer on the intermediate layer. The polyolefin resin particles are polyolefin resin particles having the following (A1), (A2) and (A3),
The method for producing an electrophotographic photosensitive member according to claim 1, wherein a mass ratio of (A1), (A2) and (A3) of the polyolefin resin satisfies the following formula.
0.01 ≦ (A2) / {(A1) + (A2) + (A3)} × 100 ≦ 30
55/45 ≦ (A1) / (A3) ≦ 99/1
(A1): Repeating structural unit represented by the following formula (11)

(In formula (11), R ^{11 to} R ¹⁴ each independently represents a hydrogen atom or an alkyl group.)
(A2): Repeating structural unit represented by the following formula (21) or (22)

(In the formulas (21) and (22), R ^{21 to} R ²⁴ are each independently a hydrogen atom, an alkyl group, a phenyl group or —Y ²¹ COOH (wherein Y ²¹ is a single bond, an alkylene group or an arylene) R ²⁵ and R ²⁶ each independently represents a hydrogen atom, an alkyl group or a phenyl group, and X ²¹ represents —Y ²² COOCOY ²³ — (in the formula: , Y ²² and Y ²³ each independently represents a single bond, an alkylene group or an arylene group.) However, at least one of R ^{21 to} R ²⁴ is —Y ^21. (It is a monovalent group represented by COOH.)
(A3): repeating structural unit represented by the following formula (31), (32), (33) or (34)

(In formulas (31) to (34), R ^{31 to} R ³⁵ each independently represent a hydrogen atom or a methyl group, and R ^{41 to} R ⁴³ each independently represents an alkyl group having 1 to 10 carbon atoms. R ^{51 to} R ⁵³ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.) The method for producing an electrophotographic photosensitive member according to claim 2, wherein a mass ratio of (A1), (A2) and (A3) of the polyolefin resin satisfies the following formula.
0.01 ≦ (A2) / {(A1) + (A2) + (A3)} × 100 ≦ 10
55/45 ≦ (A1) / (A3) ≦ 99/1 The method for producing an electrophotographic photosensitive member according to claim 3, wherein a mass ratio of (A1), (A2) and (A3) of the polyolefin resin satisfies the following formula.
0.01 ≦ (A2) / {(A1) + (A2) + (A3)} × 100 ≦ 5
55/45 ≦ (A1) / (A3) ≦ 99/1 The polyolefin resin has a repeating structural unit represented by the following formula (111), a repeating structural unit represented by the following formula (221) and a repeating structural unit represented by the following formula (311), or a following formula ( The polyolefin resin having a repeating structural unit represented by (111), a repeating structural unit represented by the following formula (221), and a repeating structural unit represented by the following formula (312): A method for producing an electrophotographic photoreceptor.

  The method for producing an electrophotographic photosensitive member according to claim 1, wherein a volume ratio of the metal oxide to the polyolefin resin particles is 0.5 or more and 2.0 or less.   The method for producing an electrophotographic photosensitive member according to claim 1, wherein a particle diameter of the metal oxide is 5 nm or more and 50 nm or less. The method for producing an electrophotographic photosensitive member according to any one of claims 1 to 7, wherein a particle diameter C1 of the polyolefin resin particles and a particle diameter C2 of the metal oxide satisfy the following formula.
1 ≦ C1 / C2 ≦ 20   The method for producing an electrophotographic photosensitive member according to claim 1, wherein a heating temperature when heating the coating film is 80 ° C. or more and 120 ° C. or less.