JP2009288629A - Method for manufacturing electrophotographic photoreceptor and electrophotographic photoreceptor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing an electrophotographic photoreceptor having good film thickness uniformity of an intermediate layer, and an electrophotographic photoreceptor obtained by the manufacturing method. <P>SOLUTION: The method for manufacturing the electrophotographic photoreceptor having a support and an intermediate layer and a photosensitive layer over the support includes: a step of forming the intermediate layer by applying an aqueous dispersion containing polyolefin resin particles having a particle diameter of 50-500 nm and a metal oxide, and heating the resultant coating film to fuse the polyolefin resin particles; and a step of forming the photosensitive layer on the intermediate layer. The electrophotographic photoreceptor obtained by the manufacturing method is also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing an electrophotographic photoreceptor and an electrophotographic photoreceptor produced by the method. Specifically, the present invention relates to a method for producing an electrophotographic photoreceptor using a specific intermediate layer coating solution containing a metal oxide, and an electrophotographic photoreceptor obtained by the production method.

  When producing an electrophotographic photoreceptor (hereinafter, 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 chargeability, image contrast, and reversal development method cause black spots and fogging on a white background, resulting in a significant decrease in image quality.

  As an intermediate layer having an electric resistance characteristic in an appropriate range and a blocking function, 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, since the metal oxide is dispersed, a coating defect is generated without being uniformly applied, or the blocking function is not sufficient due to an increase in surface roughness, resulting in a decrease in charging ability, a decrease in image contrast, In the case of the reversal development method, black spots or background fog may occur on a white background.

  Patent Document 3 clearly states that a dry film of a polymer emulsion in which conductive material particles are dispersed is provided as an intermediate layer of an electrostatic recording body. However, even when an intermediate layer is formed 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 not affected by the resolution. It was still 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.

  Also, in response to the recent demand for higher image quality, it is effective to reduce the thickness of the photoreceptor. 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 clearly shows 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. Yes. However, when forming an upper film in contact with the corresponding film, particularly when there is a dielectric layer in the upper layer, there are problems that occur, such as electrophotographic photosensitivity such as a coating layer defect of the corresponding film and a decrease in chargeability of the dielectric layer due to surface roughness. There is no clear statement regarding the specific issues in body preparation.
JP-A-56-52757 JP-A-2-43175 JP-A-56-80048 JP 2003-268164 A JP 2003-105145 A Japanese Patent Laid-Open No. 2003-147028 New Polymer Experimental Studies 2 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 intermediate layer containing a resin and a metal oxide, a method for producing an electrophotographic photosensitive member having good film thickness uniformity of the intermediate layer, and an electrophotographic photosensitive member obtained by the production method Is to provide.

According to the present invention, in a method for producing a support, and an electrophotographic photoreceptor having an intermediate layer and a photosensitive layer on the support,
A step of applying an aqueous dispersion containing a polyolefin resin particle 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 particle to form an intermediate layer;
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, there is provided an electrophotographic photoreceptor obtained by the above-described method for producing an electrophotographic photoreceptor.

  According to the present invention, aggregation of metal oxides during film formation (drying) is suppressed, and the film thickness uniformity of the intermediate layer is improved. Furthermore, even a long-term storage coating solution is excellent in film thickness uniformity. As a result, the blocking function can be enhanced while maintaining the electrical resistance characteristics, and a good image can be provided as a photoreceptor.

  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 metal oxide are dispersed in a solvent having a ratio of water to the total amount of the solvent of 50% by mass or more.

In order to suppress the aggregation of the metal oxide during the film formation (drying), it is necessary to suppress the fluidity in a state where the solvent is still present immediately after the dispersion is applied, and the present invention. It came to.
After applying an aqueous dispersion containing a polyolefin resin particle having a particle size of 50 nm or more and 500 nm or less and a metal oxide, the coating film is heated to melt the polyolefin resin particle to form an intermediate layer, thereby forming a uniform film thickness. The reason for the improvement is estimated as follows. One is that the dispersibility of the polyolefin resin particles and the metal oxide in the dispersion is good, and a good dispersion state is maintained even if the solvent in the dispersion is volatilized after coating. One is that the polyolefin resin particles are heated and dissolved after the solvent in the dispersion is volatilized and the metal oxides do not aggregate, and the adhesion of each particle is improved. For these reasons, it is possible to form a film in a state where the metal oxide is uniformly dispersed.

  When the particle size is less than 50 nm, the effect of suppressing aggregation of metal oxides during film formation (drying) cannot be obtained. When the particle diameter exceeds 500 nm, the adhesion between the particles is lowered, and a defect in which the intermediate layer is not 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 may be a polymer obtained by polymerizing only an olefin, or a polymer obtained by copolymerizing with other monomers.

The polyolefin resin used in the present invention is water-based (liquefied)
(A1) one or both of an unsaturated carboxylic acid or its anhydride,
(A2) a hydrocarbon comprising a alkene having 2 to 6 carbon atoms as a constituent component,
(A3) At least one compound represented by any one of the above formulas (1) to (4)

(In Formulas (1) to (4), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkyl group having 10 or less carbon atoms, and R ₃ represents a hydrogen atom or an alkyl group having 10 or less carbon atoms. .)
In which the mass ratio of the components (A1) to (A3) satisfies the following formula:
0.01 ≦ (A1) / {(A1) + (A2) + (A3)} × 100 ≦ 30
(A2) / (A3) = 55/45 to 99/1
More preferably, the polyolefin copolymer satisfies the following formula:
0.01 ≦ (A1) / {(A1) + (A2) + (A3)} × 100 ≦ 10
(A2) / (A3) = 55/45 to 99/1
More preferably, 0.01 ≦ (A1) / {(A1) + (A2) + (A3)} × 100 ≦ 5
(A2) / (A3) = 55/45 to 99/1
It satisfies.

  One or both of the unsaturated carboxylic acid and its anhydride that can be used as the component (A1) are compounds having at least one carboxyl group or acid anhydride group in the molecule (in the monomer unit). is there. Specific examples include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid and the like, as well as unsaturated dicarboxylic acid half esters and half amides. Among these, acrylic acid, methacrylic acid, and (anhydrous) maleic acid are preferable, and acrylic acid and maleic anhydride are particularly preferable. Moreover, the unsaturated carboxylic acid should just be copolymerized in polyolefin resin, The form is not limited, For example, random copolymerization, block copolymerization, graft copolymerization etc. are mentioned.

  (A2) The hydrocarbons having 2 to 6 carbon atoms that can be used as the component are ethylene, propylene, 1-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 3-methyl. Examples include -1-pentene and 1-hexene. Among these, alkenes having 2 to 4 carbon atoms such as ethylene, propylene, isobutylene, and 1-butene are more preferable, ethylene and propylene are further preferable, and ethylene is particularly preferable.

As the component (A3),
Dimethyl maleate, maleic acid represented by (meth) acrylate ester formula (2) such as methyl (meth) acrylate represented by formula (1), ethyl (meth) acrylate, butyl (meth) acrylate, etc. Maleate esters such as diethyl and dibutyl maleate,
An acrylic amide represented by the formula (3),
Examples thereof include alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether represented by formula (4), vinyl alcohol obtained by saponifying vinyl ester with a basic compound, and the like, and a mixture thereof can also be used. Among these, a (meth) acrylic acid ester represented by the formula (1) is more preferable, and methyl acrylate or ethyl acrylate is particularly preferable.

  When (A1) / {(A1) + (A2) + (A3)} is less than 0.01, it becomes difficult to make the polyolefin resin aqueous (liquefaction) and obtain a good aqueous dispersion. Is difficult. On the other hand, when (A1) / {(A1) + (A2) + (A3)} exceeds 30, the aqueous layer becomes easy, but when the photosensitive layer is applied on the intermediate layer, the intermediate layer It may erode and deteriorate the electrophotographic characteristics.

  On the other hand, when (A2) / (A3) is less than 55/45, it becomes difficult to obtain an aqueous solution and it becomes difficult to obtain a good aqueous dispersion. On the other hand, when (A2) / (A3) exceeds 99/1, when the photosensitive layer is applied on the intermediate layer, the intermediate layer may be eroded and the electrophotographic characteristics may be deteriorated.

  Specific examples of the polyolefin resin are preferably ethylene-acrylic acid ester-maleic anhydride terpolymer or ethylene-methacrylic acid ester-maleic anhydride terpolymer. In particular, ethylene-methyl acrylate-maleic anhydride terpolymer or ethylene-ethyl acrylate-maleic anhydride terpolymer is preferred. Here, the acrylic ester unit may be converted into an acrylic acid unit by hydrolyzing a small part of the ester bond when the resin is made into an aqueous solution described later. It suffices if the ratio of each constituent component taking into account the change is within a specified range.

  In addition, unsaturated carboxylic anhydride units such as maleic anhydride units form an acid anhydride structure in which adjacent carboxyl groups are dehydrated in the dry state of the resin. However, particularly in an aqueous medium containing a basic compound, a part or all of the ring is opened to easily form a structure of a carboxylic acid or a salt thereof.

  In the present invention, when the amount is defined based on the amount of carboxyl groups of the resin, the calculation is performed assuming that all acid anhydride groups in the resin are ring-opened to form carboxyl groups.

  Further, in the polyolefin resin used in the present invention, other monomers may be copolymerized at 20% by mass or less of the entire resin. Examples thereof include alkyl vinyl ethers having 3 to 30 carbon atoms such as methyl vinyl ether and ethyl vinyl ether, dienes, (meth) acrylonitrile, halogenated vinyls, vinylidene halides, carbon monoxide, and sulfur dioxide.

  The polyolefin resin used in the present invention may be obtained by synthesis or a commercially available resin may be used.

  The method for synthesizing the polyolefin resin is not particularly limited, but it is generally obtained by high-pressure radical copolymerization of the monomer constituting the polyolefin resin in the presence of a radical generator. The synthesis method of the polyolefin resin is synthesized by a known method described in Non-Patent Document 1, Patent Document 5, Patent Document 6, and the like.

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

  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, or a composite oxide. 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 producing an aqueous dispersion containing polyolefin resin particles and a 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 separately prepared and mixed to be 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 capable of sealing 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 liquid can be charged and can appropriately stir the mixture of the resin and the aqueous solvent charged into the tank. As such an apparatus, an apparatus widely known to those skilled in the art 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 putting each raw material into the tank of this apparatus, it is preferably stirred and mixed at a temperature of 40 ° C. or lower. Next, the aqueous dispersion can be obtained by continuing the stirring for 5 to 120 minutes while maintaining the temperature in the tank at preferably 50 ° C. or higher and 200 ° C. or lower, more preferably 60 ° C. or higher and 200 ° C. or lower.

  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 times equivalent or more and 3.0 times equivalent or less with respect to the carboxyl group in the polyolefin resin (1 mol of acid anhydride group is regarded as 2 mol of carboxyl group), 0.8 times equivalent or more and 2.5 times equivalent or less are more preferable, and 1.0 times equivalent or more and 2.0 times equivalent or less are 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 long, or an aqueous dispersion may color.

  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- Examples thereof include ethyl morpholine.

  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, a vibration ball mill, a roll mill, a triter, a sand mill, a colloid mill, or the like to obtain a dispersion. Moreover, the slurry, the sol liquid, etc. which are disperse | distributed to the commercially available aqueous solvent can also be used as it is. In addition, a method of hydrolyzing or thermally hydrolyzing a metal oxide, a method of alkaline hydrolysis of an acidic solution containing metal ions, a method of ion exchange of a solution containing metal ions with an ion exchange membrane or an ion exchange resin, etc. are also used. be able to.

  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.

  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 tin oxide ultrafine particles exceeds 50 nm in the aqueous dispersion, the film thickness uniformity may be impaired even if polyolefin resin particles are used.

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 100 arbitrary particles of polyolefin resin particles and metal oxides and determining the average value.

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

  The present invention is an electrophotography characterized in that the aqueous dispersion obtained as described above is applied on a conductive support or a conductive layer, heated and dissolved to form a film, and an intermediate layer is formed. This is a method for producing a photoreceptor.

  As a means for applying the intermediate layer coating solution, a method usually used in this field can be applied, but dip coating 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 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 below.

  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 lower than 80 ° C., the dissolution by heating becomes insufficient, and the effects of the present invention may not be sufficiently exhibited. On the other hand, when the temperature exceeds 120 ° C., the film contracts, and the film thickness may become uneven.

  The support used for the electrophotographic photosensitive member may be a conductive one (conductive support), and examples thereof include those made of metals or alloys such as aluminum, nickel, copper, gold and iron. Alternatively, a thin film 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 moderately used to suppress interference fringes. It is preferable to roughen the surface. 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 in which a suspension obtained by suspending a powdery abrasive in a liquid such as water is sprayed on the surface of a support at a high speed to roughen the surface. In the case of wet honing treatment, the surface roughness of the support can be controlled by the spraying pressure of the suspension, the speed, the amount of abrasive, the type, shape, size, hardness, specific gravity, suspension temperature, and the like. 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.

  Between the support and the intermediate layer of the present invention, a conductive layer may be provided for the purpose of suppressing interference fringes due to scattering of laser light or the like, and covering 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 the dispersibility of the conductive particles, and have good solvent resistance after film formation.

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

  An intermediate layer having a function such as an adhesive function may be provided between the intermediate layer of the present invention and the photosensitive layer. The intermediate layer of the present invention can be formed of, for example, casein, polyvinyl alcohol, nitrocellulose, polyamide (nylon 6, nylon 66, nylon 610, copolymer nylon, alkoxymethylated nylon, etc.), polyurethane, aluminum oxide, or the like. .

  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 phthalocyanine and non-metal phthalocyanine;
(3) Indigo pigments such as indigo and thioindigo,
(4) Perylene pigments such as perylene acid 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 substances 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) Zinc oxide and the like can be mentioned. 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; and
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 crystals 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, and
Strong peaks at Bragg angles (2θ ± 0.2 °) of 8.7 ° to 9.2 °, 17.6 °, 24.0 °, 27.4 ° and 28.8 ° in CuKα characteristic X-ray diffraction A chlorogallium phthalocyanine crystal is preferable.

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 having strong peaks at °, 21.9 ° and 25.5 °, and
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,
A 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; and
Bragg angles (2θ ± 0.2 °) of CuKα characteristic X-ray diffraction of 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 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, melamine resins, and the like. Of 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 of a suitable charge transport material, for example, a heterocyclic compound such as poly-N-vinylcarbazole or polystyrylanthracene or a polymer compound having a condensed polycyclic aromatic compound, or a complex such as pyrazoline, imidazole, oxazole, triazole or carbazole. Suitable binder resins such as ring compounds, triarylalkane derivatives such as triphenylmethane, triarylamine derivatives such as triphenylamine, phenylenediamine derivatives, N-phenylcarbazole derivatives, stilbene derivatives, hydrazone derivatives, etc. A solution dispersed / dissolved in a solvent (which can be selected from the aforementioned resin for charge generation layer) can be applied by the above-mentioned known method and dried. In this case, the ratio of the charge transport material to 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 transport material is less than that, the charge transport ability is lowered, and problems such as a decrease in sensitivity and an increase in residual potential are likely to occur. In this case, the thickness of the charge transport layer is preferably adjusted in the range of 1 μm to 50 μm, more preferably 3 μm to 30 μm.

  Furthermore, a surface protective layer may be formed on the 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”.

  Polyolefin resins in the examples include commercially available resins (Bondaine HX-8290, Bondine HX-8210, Bondine AX-8390 (Sumitomo Chemical Co., Ltd.), Primacor 5980I (Dow Chemical Co.)), and Resin particles (B1 to B11) synthesized by a known method were used to prepare a resin particle dispersion and an electrophotographic photosensitive member.

  In addition, the synthesis | combining method of resin B1-1 is synthesize | combined by the method described in the nonpatent literature 1, patent document 5, patent document 6, etc. FIG.

The composition of the polyolefin resin was measured by the following method. The results are shown in Table 1.
(1) Content of unsaturated carboxylic acid component in polyolefin resin The acid value of the polyolefin resin was measured according to JIS K5407, and the content (graft ratio) of the unsaturated carboxylic acid was determined from the following formula.

Content (mass%) = (mass of grafted unsaturated carboxylic acid) / (mass of raw material polyolefin resin) × 100
(2) Composition of resin other than unsaturated carboxylic acid component It was determined by performing ¹ H-NMR and ¹³ C-NMR analysis (manufactured by Varian, 300 MHz) at 120 ° C. in orthodichlorobenzene (d4). ^{In 13} C-NMR analysis, measurement was performed using a gated decoupling method in consideration of quantitativeness.

(Preparation of polyolefin resin particle dispersion 1)
Using a stirrer equipped with a heat-resistant 1 liter glass container with a heater,
Polyolefin resin 75.0g
(Bondyne HX-8290, manufactured by Sumitomo Chemical Co., Ltd.)
Isopropanol 60.0g
Triethylamine (TEA) 5.1g
Distilled water 159.9g
Was stirred in a glass container and the stirring blade was rotated at a rotational speed of 300 rpm. As a result, 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. The system temperature was kept at 140 ° C. to 145 ° C. and further stirred for 20 minutes. Then, after putting in a water bath and cooling to room temperature (about 25 ° C.) while stirring at a rotational speed of 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) As a result, a milky white uniform polyolefin resin aqueous dispersion 1 was obtained.

(Polyolefin resin particle dispersion 2)
A polyolefin resin particle dispersion 2 was obtained 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.]. It was.

(Polyolefin resin particle dispersion 3)
Using a stirrer equipped with a heat-resistant 1 liter glass container with a heater,
Polyolefin resin 60.0g
[Bondane AX-8390, manufactured by Sumitomo Chemical Co., Ltd.]
n-propanol 100.0g
TEA 2.5g
Distilled water 137.5g
Was stirred in a glass container and the stirring blade was rotated at a rotational speed of 300 rpm. As a result, 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 (about 25 ° C.) while stirring with air rotation at 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) As a result, a uniform polyolefin resin particle dispersion 3 was obtained.

(Polyolefin resin particle dispersion 4)
Using a stirrer equipped with a heat-resistant 1 liter glass container with a heater,
Polyolefin resin 60.0g
[Primacol 5980I, manufactured by Dow Chemical Company]
TEA 16.8g
Distilled water 223.2g
Was stirred in a glass container and the stirring blade was rotated at a rotational speed of 300 rpm. As a result, 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 (about 25 ° C.) while stirring with air rotation at 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) As a result, a polyolefin resin particle dispersion 4 was obtained.

(Polyolefin resin particle dispersions 5 to 15)
Except having changed polyolefin resin (Bondaine HX-8290) into polyolefin resin [B1] thru | or [B11], it adjusted similarly to the polyolefin resin particle dispersion 1, and obtained polyolefin resin particle dispersion 5 thru | or 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, a solvent was added so that the solvent ratio 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 polyolefin resin particles in the aqueous dispersion was 210 nm, and the particle diameter of titanium oxide was 30 nm.

  The film thickness uniformity was evaluated as follows.

  The aqueous dispersion is dip-coated 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 this is dried at 100 ° C. for 30 minutes, whereby a film thickness of 1.0 μm is obtained. Layers were deposited.

  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 2.

(Examples 2 to 15)
Aqueous dispersions 2 to 15 were obtained in the same manner as in Example 1 except that the polyolefin resin particle dispersion 1 of Example 1 was changed to polyolefin resin particle dispersions 2 to 15, and an intermediate layer was formed and evaluated. It was.

  Table 2 shows the results of the particle size of the polyolefin resin particles, the particle size of the titanium oxide, and the surface roughness in the aqueous dispersion.

(Examples 16 to 19)
Aqueous dispersion 16 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. To 19 were obtained, and an intermediate layer was formed and evaluated.

  Table 2 shows the results of the particle size of the polyolefin resin particles, the particle size 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 an aqueous dispersion 20 in the same manner as in Example 1, and formed an intermediate layer for evaluation.
Table 2 shows the results of the particle size of the polyolefin resin particles, the particle size of the titanium oxide, and the surface roughness in the aqueous dispersion.

(Example 21)
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.) in Example 1. In the same manner as in Example 1, an aqueous dispersion 21 was obtained, and an intermediate layer was formed and evaluated.

  Table 2 shows the results of the particle size of the polyolefin resin particles, the particle size 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 2 shows the results of the particle size of the polyolefin resin particles, the particle size of the titanium oxide, and the surface roughness in the aqueous dispersion.

(Example 23)
In Example 1, 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). An aqueous dispersion 23 was obtained, and an intermediate layer was formed and evaluated.

  Table 2 shows the results of the particle size of the polyolefin resin particles, the particle size 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 2 shows the results of the particle size of the polyolefin resin particles, the particle size 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 and evaluated.

  Table 2 shows the results of the particle size of the polyolefin resin particles, the particle size of the titanium oxide, and the surface roughness in the aqueous dispersion.

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

  Table 2 shows the results of the particle size of the polyolefin resin particles, the particle size 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 obtain a 0.5 M aqueous solution, and 28% aqueous ammonia was added to adjust the pH to 1.5 while stirring. Then, after heating to 70 degreeC, after cooling naturally to about 50 degreeC, pure water was added and it adjusted to 1L, 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 70 ° C. When it becomes clear, heating is stopped and natural cooling is performed to obtain a tin oxide dispersion. It was.

  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, a solvent was added so that the solvent ratio was 9/1 water / IPA and the solid content was 5%, and the mixture was stirred to obtain an aqueous dispersion 27. The obtained aqueous dispersion liquid 27 was evaluated by forming an intermediate layer in the same manner as in Example 1.

  Table 2 shows the results of 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 solvent so that the solvent ratio is 8/2 water / IPA and the solid content is 2.5%, the solvent ratio is 9/1 water / IPA and the solid content is 1. An intermediate layer was formed and evaluated in the same manner as in Example 22 except that the solvent was added to 5%.

  Table 2 shows the results of the particle size of the polyolefin resin particles, the particle size of the titanium oxide, and the surface roughness in the aqueous dispersion.

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

  Table 2 shows the results of the particle size of the polyolefin resin particles, the particle size of the titanium oxide, and the surface roughness in the aqueous dispersion.

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

  Table 2 shows the results of the particle size of the polyolefin resin particles, the particle size of the titanium oxide, and the surface roughness in the aqueous dispersion.

(Examples 31 to 34)
In Example 1, the intermediate layer was formed and evaluated 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. Table 2 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 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 3 shows the results of the particle size and surface roughness of titanium oxide.

(Comparative Example 2)
A dispersion for an intermediate layer was obtained in the same manner as in Example 1 except that the aqueous dispersion 1 of Example 1 was changed to a polyester resin particle dispersion (trade name: Vylonal MD-1200, manufactured by Toyobo Co., Ltd.). Table 3 shows the results of the particle size and surface roughness of titanium oxide in the intermediate layer dispersion.

"Production of photoconductor"
<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.)
30 parts of methoxypropanol 30 parts of methanol were mixed and dispersed for 2 hours in a sand mill apparatus using 1 mmφ glass beads 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 is dried and thermally cured at 140 ° C. for 30 minutes, whereby a conductive layer having a thickness of 20 μm. Formed.

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

Next, as a charge generation layer coating material, first, 10 parts of hydroxygallium phthalocyanine of the following material crystal form (7.5 °, 9.9 °, 16 of Bragg angle 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction) With strong peaks at 3 °, 18.6 °, 25.1 ° and 28.3 °)
5 parts of polyvinyl butyral resin (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 for 4 hours in a sand mill using glass beads having a diameter of 1 mm. This was diluted with 250 parts of ethyl acetate. The charge generation layer coating solution thus prepared was applied on the intermediate layer and then dried at 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 charge generation layer and dried at 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 4.

The fog evaluation was performed by sensual observation according to the following criteria.
A: No minute black spots are observed visually B: Only a few minute black spots (1 to 5 places) are observed C: Some minute black spots are visually recognized (6 or more places) D: Minute black spots on the entire surface In these, C and D judged that the effect of the present invention was not fully acquired.

<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 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 4.

<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 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 an intermediate layer coating material. This paint was dip-coated on the above intermediate layer and dried at 100 ° C. for 20 minutes to form a 0.5 μm intermediate layer.

  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 4.

<Photoreceptor Comparative Example 1>
In Photosensitive Example 1-1, electrophotography was performed in the same manner as in Photosensitive Example 1-1, except that the aqueous dispersion 1 prepared in Example 1 was changed to the intermediate layer prepared in Comparative Example 1. A photoconductor was prepared and evaluated. The results are shown in Table 4.

<Photoreceptor Comparative Example 2>
In Photoreceptor Example 1-1, electrophotography was performed in the same manner as for Photoreceptor Example 1-1 except that the aqueous dispersion 1 produced in Example 1 was changed to the intermediate layer dispersion produced in Comparative Example 2. A photoconductor was prepared and evaluated. The results are shown in Table 4.

Claims (10)

In a method for producing a support, an electrophotographic photoreceptor having an intermediate layer and a photosensitive layer on the support,
A step of applying an aqueous dispersion containing a polyolefin resin particle 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 particle to form an intermediate layer;
A method for producing an electrophotographic photoreceptor, comprising a step of forming the photosensitive layer on the intermediate layer. The polyolefin resin particles are (A1) one or both of an unsaturated carboxylic acid or an anhydride thereof,
(A2) a hydrocarbon comprising a alkene having 2 to 6 carbon atoms as a constituent component,
(A3) At least one compound represented by any of the following formulas (1) to (4)
(In Formulas (1) to (4), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkyl group having 10 or less carbon atoms, and R ₃ represents a hydrogen atom or an alkyl group having 10 or less carbon atoms. .)
A copolymer composed of
The method for producing an electrophotographic photosensitive member according to claim 1, wherein the mass ratio of each of the constituent components (A1) to (A3) satisfies the following formula.
0.01 ≦ (A1) / {(A1) + (A2) + (A3)} × 100 ≦ 30
(A2) / (A3) = 55/45 to 99/1 The method for producing an electrophotographic photosensitive member according to claim 2, wherein the mass ratio of (A1) to (A3) is a polyolefin copolymer satisfying the following formula.
0.01 ≦ (A1) / {(A1) + (A2) + (A3)} × 100 ≦ 10
(A2) / (A3) = 55/45 to 99/1 The method for producing an electrophotographic photosensitive member according to claim 3, wherein the mass ratio of (A1) to (A3) is a polyolefin copolymer satisfying the following formula.
0.01 ≦ (A1) / {(A1) + (A2) + (A3)} × 100 ≦ 5
(A2) / (A3) = 55/45 to 99/1   The electron according to any one of claims 1 to 4, wherein the polyolefin copolymer is an ethylene-acrylic acid ester-maleic anhydride terpolymer or an ethylene-methacrylic acid ester-maleic anhydride terpolymer. A method for producing a photographic 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 the heating temperature of the coating film is 80 ° C. or higher and 120 ° C. or lower.   An electrophotographic photosensitive member obtained by the method for producing an electrophotographic photosensitive member according to claim 1.