JP2002063978A - Anisotropic electric conducting component and its manufacturing method, and electronic photography sensitive body using its anisotropic electric conducting component, and electronic photographic image forming equipment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of an anisotropic electrical conducting component having sufficiently high anisotropic conductivity which can arrange conductive grains in a predetermined direction in an adhesive component, and makes it possible to obtain efficiently and certainly the anisotropic electrical conducting body, even when a conductive grains having no magnetism are used, and the anisotropic electrical conducting element, obtained by it, and an electronic photography sensitive body and a photoelectric image forming equipment. SOLUTION: The manufacturing method of the anisotropic conducting component includes processing in which charged particles 5 or the like from an electrification means 4 not contacting adhesive components 2, are supplied to the adhesive components having fluidity or pliability in which the conductive grains 1 are dispersed, and the conductive grains 1 are arranged in the direction of an electric field by generating the electric field inside the adhesive components 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anisotropic conductive member and a method for manufacturing the same, and an electrophotographic photosensitive member and an electrophotographic image forming apparatus using the anisotropic conductive member.

[0002]

2. Description of the Related Art Conventionally, anisotropic conductive members in which conductive particles are dispersed in a binder have been known, and are used in electronic parts such as electrophotographic photosensitive members, laminated connectors, and semiconductive rolls. Application is in progress.

For example, in the case of an electrophotographic photosensitive member that is repeatedly used in an electrophotographic process in which charging, exposure, development, transfer, image fixing, and cleaning steps are sequentially performed, if the durability is insufficient, the cleaning step is not performed. The friction between the photoreceptor and the blade makes the surface of the photoreceptor easy to wear, resulting in a problem that the characteristics of the photoreceptor deteriorate. As a means for avoiding such a phenomenon, a method has been proposed in which a surface protective layer is laminated on the photosensitive layer of the photoreceptor to impart durability to the surface of the photoreceptor. When the value of is increased, the charge formed on the surface of the photoreceptor is easily diffused, and a phenomenon that the electrostatic latent image is blurred (latent image blur) occurs.

Therefore, as a means for achieving both the electrophotographic characteristics and durability of the electrophotographic photosensitive member, an electrophotographic photosensitive member having a surface protective layer made of an anisotropic conductive member on the surface of the photosensitive member has been proposed. For example, Japanese Unexamined Patent Publication No. 7-181705 discloses that a surface resistance of 1 × 10 ¹⁵ Ω or more and a volume resistance of 1
An electrophotographic photoreceptor having a surface protective layer (abrasion-resistant layer) having a thickness of 1 × 10 ¹² Ω or less and a thickness of 1 to 10 μm has been disclosed. As a method for imparting anisotropic conductivity to the surface protective layer, insulating needle-like fine particles have been disclosed. A technique for dispersing in a hydrophilic polymer is described.

[0005] In general, even a member in which conductive particles are simply dispersed in a binding member, the electric resistance in the voltage application direction decreases due to the non-linearity of the electric resistance value, and a certain degree of anisotropic conductivity is obtained. Is shown. However, such a member usually has a certain degree of conductivity even in a predetermined direction in a plane perpendicular to the depth direction. Cannot be sufficiently prevented from being caused by image diffusion. Therefore, in such an anisotropic conductive member, it is necessary to improve the anisotropic conductivity by arranging the conductive particles in a predetermined direction in the binding member.

As a method of arranging the conductive particles dispersed in the binding member, for example, Japanese Patent Application Laid-Open No. 7-161236 discloses a method in which a binding member in which conductive particles are dispersed is sandwiched between a pair of conductive plates. A method of applying a voltage to both conductive plates is disclosed. However, in such a method, when the voltage applied to the conductive plate is large or when the thickness of the member is small, dielectric breakdown often occurs and the device becomes inoperable, and the dielectric breakdown is prevented. Therefore, when a small voltage is applied, a vicious cycle occurs in which the processing time becomes extremely long.

When the conductive particles have magnetism, the particles can be arranged by applying a magnetic field to a binding member in which the conductive particles are dispersed.
Such a method is not sufficient in terms of versatility, for example, the conductive particles that can be used as a material are limited.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and does not cause dielectric breakdown even when conductive particles having no magnetism are used. Manufacture of an anisotropic conductive member in which conductive particles can be arranged in a predetermined direction in a binding member, and an anisotropic conductive member having sufficiently high anisotropic conductivity can be efficiently and reliably obtained. It is an object to provide a method, an anisotropic conductive member obtained by the method, and an electrophotographic photosensitive member and an electrophotographic image forming apparatus using the anisotropic conductive member.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, supplied charged particles or charged particles to a binding member in which conductive particles are dispersed to bind. When an electric field is generated in the member, the conductive particles are arranged in the direction of the electric field in the binding member without causing dielectric breakdown, and an anisotropic conductive member having sufficiently high anisotropic conductivity is efficiently and reliably formed. Thus, the present invention has been completed.

That is, according to the method of manufacturing an anisotropic conductive member of the present invention, a charged member having no fluidity or flexibility in which conductive particles are dispersed is charged from a charging means that is not in contact with the binder. Alternatively, the method further comprises a step of supplying charged particles, generating an electric field inside the binding member, and arranging the conductive particles in the direction of the electric field.

Further, the anisotropic conductive member of the present invention is characterized by being obtained by the above-mentioned manufacturing method of the present invention.

Although it is not clear why the manufacturing method of the present invention makes it possible to arrange conductive particles dispersed in a binding member efficiently and reliably, the present inventors speculate as follows. I do.

That is, in the conventional manufacturing method in which a voltage is applied across a binding member between a pair of conductive plates, if there is a low resistance portion in the depth direction of the binding member, the current from the conductive plate is reduced. Flows intensively in the low resistance area,
It is considered that dielectric breakdown easily occurs when a high voltage is applied or when the thickness of the member is small.

On the other hand, in the manufacturing method of the present invention, by supplying charged particles or charged particles from charging means not in contact with the binding member, a voltage is applied to the binding member in a non-contact manner. Therefore, it is considered that even when a high voltage is applied or when the thickness of the member is thin, the conductive fine particles can be efficiently and reliably arranged without causing dielectric breakdown.

Further, the electrophotographic photoreceptor of the present invention comprises a conductive support, a photosensitive layer laminated on the support, and a photoconductive layer laminated on the photosensitive layer. And a surface protective layer made of a conductive material.

Further, the electrophotographic image forming apparatus of the present invention comprises the above electrophotographic photosensitive member of the present invention, charging means for charging the electrophotographic photosensitive member, and an electrostatic latent on the electrophotographic photosensitive member. An exposure unit for forming an image, a developing unit for forming a toner image by attaching toner to the electrostatic latent image, and a transfer unit for transferring the toner image to a transfer material It is characterized by the following.

[0017]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below in detail with reference to the accompanying drawings. In the drawings, the same or corresponding parts have the same reference characters allotted.

The method for producing an anisotropic conductive member according to the present invention is characterized in that a flowable or flexible binding member in which conductive particles are dispersed is charged from charged means or charged particles not in contact with the binding member. Supplying particles, generating an electric field inside the binding member, and arranging the conductive particles in the direction of the electric field, wherein the applied voltage is large or the film thickness of the member is small. Also in this case, the conductive particles can be arranged in the binding member without causing dielectric breakdown, and a sufficiently high anisotropic conductive member can be efficiently and reliably obtained.

The manufacturing method of the present invention can be suitably performed using the apparatus shown in FIG. In the apparatus shown in FIG. 1A, first, a binding member 2 in which conductive particles 1 are dispersed is arranged on a grounded conductive substrate 3. Next, ionized ions 5 are supplied to the binding member 2 from the corona charger 4 arranged to face the conductive substrate 3 via the binding member 2, and the conductive substrate 3 and the ionized ions 5 Thus, the conductive particles 1 are arranged in the direction of the electric field by the electric field generated between them, and the desired anisotropic conductive member is obtained (FIG. 1B). In the above process, the binding member 2 can be heated by the heater 6 as necessary to maintain the fluidity or flexibility of the binding member.

Here, the conductive particles according to the present invention generally have a volume resistivity of 0 to 10 ⁸ Ωcm, preferably 1 to 10 ⁸ Ωcm.
0 ² to 10 ⁸ Ωcm, and includes semiconductive particles such as metal oxides described later. If the electrical resistance of the conductive fine particles exceeds 10 ⁸ Ωcm, the conductivity in the depth direction of the anisotropic conductive member tends to decrease, while the electrical resistance of the conductive particles decreases to 10 ² Ωcm.
If it is less than cm, the conductive particles in the member tend to be difficult to arrange with regularity, and in any case, it is difficult to obtain sufficient anisotropic conductivity.

As the material of the conductive particles according to the present invention, specifically, zinc, aluminum, alumel, antimony, iridium, indium, gold, silver, chromium, chromel, cobalt, constantan, zirconium,
Copper, tin, tungsten, tantalum, duralumin,
Metals such as iron, lead, nichrome, nickel, platinum, rhodium, palladium, beryllium, magnesium, manganin, molybdenum and alloys of two or more thereof; titanium oxide, tin oxide, iron oxide, antimony oxide, indium oxide, zirconium oxide , Copper oxide, tungsten oxide,
Metal oxides such as lead oxide and bismuth oxide or a mixture in which two or more thereof are compatible; tungsten carbide;
And carbon black. Also, various coatings on fine particles made of the above materials,
Insulating particles coated with a conductive substance can also be used. One kind of these conductive fine particles may be used alone, or two or more kinds may be used in combination.

The shape of the conductive fine particles used in the present invention is not particularly limited, and may have an elongated anisotropic shape such as a needle shape or an isotropic shape such as a spherical surface or a polyhedron. However, the average particle diameter of the conductive particles is preferably 0.01 to 100 μm.

Specific examples of the binder used in the present invention include polyvinyl butyral resin, polyamide resin, polyurethane resin, polyester resin, polycarbonate resin, acrylic resin, epoxy resin, silicone resin, alkyd resin, and phenol resin. , A binder resin such as a vinyl resin, glass, a silane coupling agent, an organometallic compound, ceramics, and clay. When a binder resin is used as the binding member, a compound containing a curing agent or a reaction initiator such as an isocyanate compound, a melamine compound, a silane coupling agent, and an organometallic compound can also be used.

The dispersion of the conductive particles in the binder can be performed using a kneader, a mill, a stirrer, or the like.
When the resin, which is the material of the binding member, is liquid at room temperature, it can be used as it is. However, when the resin is solid at room temperature, it can be used after heating to make it liquid, or after adding water, methanol, ethanol, n- Propanol, n-butanol,
After dissolving the conductive particles in a solvent such as benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, and toluene. In addition, it is preferable to disperse.

When supplying charged particles or charged particles to the binder in which the conductive particles are dispersed as described above, the binder in which the conductive particles 1 are dispersed as shown in FIG. 2 is preferably disposed on the conductive substrate 3 because an electric field is easily generated inside the binding member. In this case, the conductive substrate is preferably grounded (grounded). In addition, as a method of arranging the binding member in which the conductive particles are dispersed on the conductive substrate, a dip coating method, a spray coating method, a blade drawing coating method, a spin coating method, and the like can be given.

The material of the conductive substrate 3 is not particularly limited, but specific examples thereof include the metals, metal oxides, and carbon black exemplified in the description of the conductive particles. When the anisotropic conductive member of the present invention is laminated on a molded body or a film formed with a conductive substrate, such as an electrophotographic photosensitive member described later, the molded body or the conductive substrate of the molded body is grounded. (Grounding) to obtain the conductive substrate 3 in FIG.

In the present invention, as shown in FIG. 1 (a), by ionizing air using a corona charger 4, the binder 2 in which the conductive particles 1 are dispersed is ionized as charged particles. The ions 5 can be efficiently and reliably supplied. Here, specific examples of the ionized ion 5 include a hydrated ion (H ⁺ (H ₂ O) _n ; n represents an integer of 1 or more), a carbonate ion (CO ₃ ⁻ ), and a nitrate ion (N
O ₃ ⁻ ), hydrogen anions (H ⁻ ), monovalent oxygen ions (O ⁻ ), and the like, and associations thereof. In the present invention, protons or electrons generated by a method such as thermal excitation emission, field emission, photoelectric effect, or emission from a radioactive substance may be used as charged particles.
In addition, instead of these charged particles, organic polymers such as polyvinyl butyral resin, polyamide resin, polyurethane resin, polyester resin, polycarbonate resin, acrylic resin, epoxy resin, silicone resin, alkyd resin, phenol resin, and vinyl resin are rubbed. Charged particles charged by the method described above can also be used.

When the charged particles or charged particles are supplied to the binding member, the applied voltage is appropriately selected according to the volume resistivity of the conductive particles and the binding member.

After arranging the conductive particles in the direction of the electric field in this manner, if necessary, the binder can be solidified to fix the conductive particles in the binder. The method of solidifying the binding member is appropriately selected depending on the properties of the binding member,
For example, if a thermoplastic resin is used, cool; if a thermosetting resin is used, heat; if a curable resin having room temperature reactivity is used, a predetermined curing time is passed; When used, it is brought into contact with a predetermined gas; When a solvent plastic resin is used, the solvent is removed; When a photocurable resin is used, light such as ultraviolet light having a predetermined wavelength is irradiated; In the case where is used, the binding member can be solidified by performing one kind of method such as irradiating an electron beam alone or in combination of two or more kinds.

The anisotropic conductive member obtained by the manufacturing method of the present invention has sufficiently high anisotropic conductivity, specifically, volume resistivity in the depth direction and a predetermined direction in a plane perpendicular to the depth direction. In the formula (1), R ¹ / R ² ≦ 1/2 (1) (In the above formula (1), R ¹ is the volume resistivity in the depth direction [Ωc]
m], and R ² represents a volume resistivity [Ωcm] in a predetermined direction in a plane perpendicular to the depth direction), an electrophotographic photosensitive member, a laminated connector It is suitably used for electronic components such as semiconductive rolls. In particular, when used as a surface protective layer of an electrophotographic photoreceptor, R ² preferably satisfies the condition represented by the following formula (2): R ² ≧ 10 ¹⁰ (2).

FIGS. 2A and 2B are schematic cross-sectional views each showing a preferred embodiment of the electrophotographic photosensitive member of the present invention. In FIG. 2A, the laminated photoconductor 201a
Has a structure in which an undercoat layer 203, a laminated photosensitive layer 206 including a charge generation layer 204 and a charge transport layer 205, and a surface protective layer 207 are sequentially laminated on a conductive support 202. In FIG. 2B, the single-layer type photoreceptor 201b has an undercoat layer 20 on a conductive support 202.
3, a single-layer photosensitive layer 208 and a surface protective layer 207 made of an anisotropic conductive member obtained by the production method of the present invention. By providing the surface protective layer made of an anisotropic conductive member obtained by the production method of the present invention on the surface of the electrophotographic photoreceptor, it is possible to achieve both high sensitivity and durability at a sufficiently high level. Become.

The thickness of the surface protective layer 207 is 0.1 to 30 μm.
m is preferable. If the thickness of the surface protective layer is less than the lower limit, sufficient strength cannot be obtained, and the life of the photoconductor tends to be shortened. On the other hand, if the thickness of the surface protective layer exceeds the above upper limit, the photosensitive characteristics tend to be insufficient.

Examples of the material of the conductive support 202 include metals such as aluminum, nickel, chromium, and stainless steel; aluminum, titanium, nickel, chromium, stainless steel, gold, vanadium, tin oxide, indium oxide, and the like.
Plastic films provided with a conductive thin film such as ITO; paper and plastic films coated or impregnated with a conductivity-imparting agent; and the like. Further, the shape of the conductive support 202 is not particularly limited, but those having a shape such as a drum shape, a sheet shape, and a plate shape are preferably used. Further, in the present invention, the surface of the conductive support 202 can be subjected to an oxidation treatment, a chemical treatment, a coloring treatment, a diffuse reflection treatment (graining, etc.) as necessary.

In the electrophotographic photosensitive member of the present invention, FIG.
As shown in (a) and (b), an undercoat layer 203 is preferably provided on the conductive support 202. When the undercoat layer is provided on the conductive support, the following (i) to (vi): (i) unnecessary carrier injection from the conductive support into the photosensitive film is prevented, and the image quality is improved; (Ii) Stable image quality can be obtained by reducing the environmental dependence (temperature, humidity, etc.) of the light decay curve of the electrophotographic photoreceptor; (iii) Due to the appropriate charge transport ability, when used repeatedly over a long period of time. And (iv) the occurrence of image defects due to dielectric breakdown is prevented by the appropriate withstand voltage against the charging voltage; (v) a photosensitive layer as an adhesive layer (Vi) light reflection of the support is prevented, and the effect shown in (1) tends to be obtained.

Examples of the material of the undercoat layer 203 include organic zirconium compounds such as zirconium chelate compounds, zirconium alkoxide compounds, and zirconium coupling agents; organic titanium compounds such as titanium chelate compounds, titanium alkoxide compounds, and titanate coupling agents; Organic aluminum compounds such as compounds, aluminum coupling agents; organic indium compounds such as indium alkoxide compounds and indium chelate compounds; organic manganese compounds such as manganese alkoxide compounds and manganese chelate compounds; organic tin compounds such as tin alkoxide compounds and tin chelate compounds Compound; aluminum silicon alkoxide compound, aluminum titanium alkoxide compound, aluminum zirconium oxide An organoaluminum compound such as Kokishido compounds; antimony alkoxide compounds, germanium alkoxide compounds, and organometallic compounds such as. Among them, the use of an organic zirconium compound, an organic titanyl compound or an organic aluminum compound is particularly preferable since an electrophotographic photoreceptor having a low residual potential and excellent photosensitivity can be obtained.

In addition, the above-mentioned materials include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-2-methoxyethoxysilane,
Vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-2
-Aminoethylaminopropyltrimethoxysilane, γ
Silane coupling agents such as mercapropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, and β-3,4-epoxycyclohexyltrimethoxysilane. Furthermore, polyvinyl alcohol conventionally used as a material of the undercoat layer,
Polyvinyl methyl ether, poly-N-vinyl imidazole, polyethylene oxide, ethyl cellulose, methyl cellulose, ethylene-acrylic acid copolymer, polyamide, polyimide, casein, gelatin, polyethylene, polyester, phenolic resin, vinyl chloride-vinyl acetate copolymer, Known binder resins such as epoxy resin, polyvinylpyrrolidone, polyvinylpyridine, polyurethane, polyglutamic acid, and polyacrylic acid can also be used. The mixing ratio of these materials can be appropriately set as needed.

The undercoating layer 203 can also contain an electron transporting pigment. Here, as the electron transporting pigment used in the present invention, JP-A-47-3033 is used.
No. 0 publication, organic pigments such as perylene pigments, bisbenzimidazole perylene pigments, polycyclic quinone pigments, indigo pigments, quinacridone pigments, and electron-withdrawing substituents such as cyano groups, nitro groups, nitroso groups, and halogen atoms. Organic pigments such as bisazo pigments and phthalocyanine pigments, and inorganic pigments such as zinc oxide and titanium oxide. Among these, when using a perylene pigment, a bisbenzimidazole perylene pigment or a polycyclic quinone pigment,
This is preferable because higher electron mobility can be obtained. A method of dispersing an electron-transporting pigment in a solution containing the material of the undercoat layer; a method of dispersing the electron-transporting pigment in a solution containing the material of the undercoat layer; A method in which the material of the undercoat layer is added to and mixed with a liquid obtained by dispersing the electron transporting pigment in the binder resin; and a method in which the solution containing the binder resin is mixed A method of adding and mixing the material of the undercoat layer, and further dispersing the electron transporting pigment; a solution containing the above-mentioned binder resin after adding and mixing the material of the undercoat layer to the electron transporting pigment; The coating liquid obtained by a method of dispersing the conductive support on the conductive support 2 can be obtained by drying. It is obtained by forming a film. In addition,
When preparing a coating solution by the above method, a conventionally known mixing and dispersion method using a ball mill, a roll mill, a sand mill, an attritor, an ultrasonic wave, or the like can be applied. It is important to control so as not to cause gelation or aggregation when the reaction is performed. The compounding amount of the electron transporting pigment in the undercoat layer according to the present invention is preferably 20 to 95% by weight, more preferably 30 to 9% by weight, based on the total amount of the substances contained in the undercoat layer.
0% by weight. Further, as the solvent used in the above-mentioned coating liquid, those that dissolve the organometallic compound or the resin that is the material of the undercoat layer and do not cause gelation or aggregation when the electron transporting pigment is mixed and dispersed. Although there is no particular limitation as long as it is, specifically, methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methylcellosolve, ethylcellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acetate n-
Examples thereof include butyl, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, and toluene. One of these may be used alone, or a mixture of two or more thereof may be used. Furthermore, as a method of applying the above-mentioned coating liquid on the conductive support 2, there are a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method. And the like. The thickness of the undercoat layer 3 thus obtained is usually 0.1 to
It is 20 μm, preferably 0.2 to 10 μm.

In the laminated photoconductor 201a shown in FIG. 2A, the charge generation layer 204 contains a charge generation material and a binder resin. Here, as the charge generation material used for the charge generation layer 204, a conventionally known charge generation material can be used. However, it is preferable to use a metal-containing or metal-free phthalocyanine pigment, and among them, hydroxygallium phthalocyanine, chlorogallium It is particularly preferred to use phthalocyanines, dichlorotin phthalocyanines or oxytitanyl phthalocyanines. When the phthalocyanine pigment is used, the effect of suppressing interference fringes is improved, and higher photosensitivity tends to be obtained. The amount of the charge generation material is preferably 20 to 90% by weight based on the total amount of the substances contained in the charge generation layer. When the amount of the charge generating material is less than the lower limit, the photosensitive characteristics of the electrophotographic photoreceptor tend to be insufficient. On the other hand, when the amount exceeds the upper limit, dark decay increases and the charging tends to be poor. .

As the binder resin used for the charge generation layer 204, a conventionally known insulating resin, poly-N-
Examples thereof include photoconductive polymers such as vinyl carbazole, polyvinyl anthracene, and polyvinyl pyrene. Examples thereof include polyvinyl acetal, polyvinyl arylate (a condensation polymer of bisphenol A and phthalic acid), polycarbonate, polyester, phenoxy resin, and vinyl chloride-acetic acid. Vinyl copolymer, polyvinyl acetate, acrylic resin, polyacrylamide, polyvinyl pyridine, cellulose resin, urethane resin, epoxy resin, casein,
It is preferable to use an insulating resin such as polyvinyl alcohol and polyvinylpyrrolidone, and a resin having a hydroxyl group which easily causes a crosslinking reaction with an organometallic compound is particularly preferable. Furthermore, the compounding ratio (weight ratio) of the charge generation material and the binder resin in the charge generation layer 4 is preferably 10: 1 to 1:10. The charge transport layer 5 is provided on the charge generation layer 4.
When further forming another layer such as, for example, the binder resin of the charge generation layer 204 and the charge generation layer 5 so that the solvent used for the coating solution does not dissolve or swell the charge generation layer 5. A combination with a solvent of a coating solution applied on the generating layer 205 is appropriately selected. Further, it is preferable that the binder resin of the charge generation layer 204 and the binder resin of the charge transport layer 205 described later be used in combination with those having similar refractive indexes. Is preferably 1 or less. When such a binder resin having a close refractive index is used in combination, light reflection at the interface between the charge generation layer and the charge generation layer is suppressed, and the effect of preventing interference fringes tends to be improved.

The charge generation layer 204 is a coating obtained by adding the above-mentioned charge generation material and binder resin to a predetermined solvent, and mixing and dispersing the mixture using a ball mill, a roll mill, a sand mill, an attritor, an ultrasonic wave or the like. The liquid can be obtained by applying the solution by a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, or the like, and drying. Here, as the solvent used for the coating solution for the charge generation layer, specifically, methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, Examples thereof include methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, and toluene. One of these may be used alone, or a mixture of two or more thereof may be used. The thickness of the charge generation layer 204 thus obtained is usually 0.1 to 5 μm, preferably 0.2 to 2 μm.
μm.

The charge transport layer 205 contains a charge transport material. Usually, the charge transport material is dispersed in a predetermined binder resin. Here, examples of the charge transporting material used for the charge transporting layer 205 include quinone-based compounds such as p-benzoquinone, chloroanilquinone, bromoanilquinone, and anthraquinone; tetracyanoquinodimethane-based compounds;
Electron transporting compounds such as fluorenone compounds such as 2,4,7-trinitrofluorenone, xanthone compounds, benzophenone compounds, cyanovinyl compounds, ethylene compounds; triarylamine compounds, benzidine compounds, arylalkane compounds Compounds, aryl-substituted ethylene-based compounds, stilbene-based compounds, anthracene-based compounds, hole-transporting compounds such as hydrazone-based compounds, and the like. These charge-transporting materials may be used alone or in combination of two or more. It may be used as a mixture of the above. Further, as the binder resin used for the charge transport layer 205, the binder resins exemplified in the description of the charge generation layer 204 can be given. Further, the charge transport layer 205 having such a configuration can be obtained by applying and drying a coating liquid containing a charge transport material and a binder resin in the same manner as in the method of forming the charge generation layer 204. Can be. The thickness of the charge transport layer 205 thus obtained is usually 5 to 50 μm, preferably 10 to 40 μm.
m.

On the other hand, the single-layer type photoreceptor 20 shown in FIG.
1b, the single-layer type photosensitive layer 208 includes a charge generation material, a charge transport material, and a binder resin in the same layer. Here, as the charge generation material, the charge transport material, and the binder resin used for the single-layer type photosensitive layer 208, the charge generation material, the charge transport material, and the charge exemplified in the description of the charge generation layer 204 and the charge transport layer 205 are used. Binder resins are mentioned. Further, the single-layer type photosensitive film 8 having such a configuration
Can be obtained by applying and drying a coating liquid containing a charge transport material, a charge generation material and a binder resin in the same manner as in the method of forming the charge generation layer 204. The thickness of the single-layer type photosensitive film 208 thus obtained is usually 5 to 50 μm, preferably 10 to 40 μm.

With the electrophotographic photoreceptor of the present invention having such a configuration, it is possible to achieve both high sensitivity and durability at a high level. High image quality can be obtained.

FIG. 3 is a schematic diagram showing a preferred embodiment of the electrophotographic image forming apparatus of the present invention. In FIG. 3, the electrophotographic photosensitive member 201 of the present invention is held by a support 301, and the electrophotographic photosensitive member 201 is
It is rotationally driven at a predetermined rotational speed in the direction of the arrow around 01. During this rotation process, the peripheral surface of the electrophotographic photosensitive member 201 is uniformly charged with a predetermined positive or negative potential by the charging member 303 supplied with a voltage from the power supply 302. Next, the electrophotographic photosensitive member 201 is subjected to optical image exposure by the exposure means (image input means) 304, and an electrostatic latent image corresponding to the exposed image is formed on the peripheral surface of the electrophotographic photosensitive member 201. Thereafter, a toner image is formed by attaching toner to the electrostatic latent image by the developing unit 305, and the toner image is transferred to the transfer material P by the transfer unit 306. The transfer material P after the transfer of the toner image undergoes image fixing by the image fixing means 307 and is printed out as a copy. After the transfer process, the photosensitive member 201 is cleaned by the cleaning unit 308 to remove the toner remaining on its peripheral surface, and is repeatedly used for image formation.

Examples of the charging method of the charging means according to the present invention include a corotron method, a scorotron method, and a contact charging method. The contact charging method is preferable because generation of ozone and the like is prevented. In the contact charging method, a voltage is applied to a conductive charging member brought into contact with the surface of the electrophotographic photosensitive member to charge the surface of the electrophotographic photosensitive member. Here, examples of the shape of the charging member include a brush shape, a blade shape, a pin electrode shape, and a roller shape, and among them, the roller shape is preferable. The roller-shaped charging member according to the present invention has a configuration in which an elastic layer and a resistance layer are sequentially laminated on a core material, and a protective layer can be further laminated on the resistance layer as needed. The core material has conductivity, and as the material thereof, a resin molded product in which a metal such as iron, copper, brass, stainless steel, aluminum, nickel, or the like or conductive particles are dispersed can be used. The elastic layer is formed by dispersing conductive particles or semiconductive particles in a rubber material, and has conductivity or semiconductivity. Rubber materials used for the elastic layer according to the present invention include EPDM, polybutadiene, natural rubber, polyisobutylene, SBR, C
R, NBR, silicone rubber, urethane rubber, epichlorohydrin rubber, SBS, thermoplastic elastomer, norbornene rubber, fluorosilicone rubber, ethylene oxide rubber, etc .; conductive particles and semiconductive particles include carbon black, zinc, aluminum, copper, Metals such as iron, nickel, chromium and titanium, ZnO-Al
₂ O ₃ , SnO ₂ —Sb ₂ O ₃ , In ₂ O ₃ —SnO ₂ , ZnO
_{-TiO 2, MgO-Al 2 O} 3, FeO-TiO 2, Ti
Metal oxides such as O ₂ , SnO ₂ , Sb ₂ O ₃ , In ₂ O ₃ , ZnO, and MgO; and these materials may be used alone or as a mixture of two or more. You may. The resistance layer and the protective layer are formed by dispersing conductive particles or semiconductive particles in a binder resin to control the resistance. Here, the resistivity of the resistive layer and the resistivity of the protective layer according to the present invention are preferably 10 ³ to 10 ^14, respectively.
Ωcm, more preferably 10 ⁵ to 10 ¹² Ωcm, and even more preferably 10 ⁷ to 10 ¹² Ωcm. The thickness of each of the resistance layer and the protective layer is preferably 0.01 to 1 respectively.
000 μm, more preferably 0.1-500 μm, even more preferably 0.5-100 μm. As the binder resin used for the resistance layer and the protective layer according to the present invention, acrylic resin, cellulose resin, polyamide resin, methoxymethylated nylon, ethoxymethylated nylon, polyurethane resin, polycarbonate resin, polyester resin, polyethylene resin, polyvinyl Resin, polyarylate resin, polythiophene resin, PFA, FEP, PET
And polystyrene resins such as styrene butadiene resin. Examples of the conductive particles or semiconductive particles include carbon black, metals, and metal oxides exemplified in the description of the elastic layer. The resistive layer and the protective layer may contain an antioxidant such as hindered phenol and hindered amine, a filler such as clay and kaolin, and a lubricant such as silicone oil, if necessary. Examples of the method for forming the elastic layer, the resistance layer, and the protective layer include a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method.

The roller-shaped charging member according to the present invention may be rotated at the same peripheral speed as the electrophotographic photosensitive member by being brought into contact with the electrophotographic photosensitive member without using a driving means. Means may be attached to rotate at a peripheral speed different from that of the electrophotographic photosensitive member. The voltage applied to the charging means is preferably a DC voltage or a voltage obtained by superimposing an AC voltage on a DC voltage. When the applied voltage is a DC voltage, the voltage is preferably 50 to 2000 V, which is positive or negative, depending on the required photoconductor charging potential.
00 to 1500 V is preferred. On the other hand, when the applied voltage is obtained by superimposing an AC voltage on a DC voltage, the peak-to-peak voltage is preferably 400 to 1800 V, more preferably 800 to 1600 V, and still more preferably 1200 to 1600 V. The frequency of the AC voltage to be superimposed is preferably 50 to 20,000 Hz,
More preferably, the frequency is 100 to 5000 Hz.

Further, the developing system of the developing means according to the present invention includes a cascade developing system, a one-component insulating toner developing system, a one-component conductive toner developing system, a dry developing system such as a two-component magnetic brush developing and a wet developing system. A transfer method of the transfer means according to the present invention includes an electrostatic transfer method such as a corona transfer method, a roller transfer method, and a belt transfer method, a pressure transfer method, and an adhesive transfer method; Examples of the method include a heat roller fixing method, a flash fixing method, an oven fixing method, and a pressure fixing method; examples of the cleaning unit according to the present invention include a brush cleaner, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, and a blade cleaner. , And the like.

[0048]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Example 1 80 parts by weight of a polyvinyl butyral resin (Eslec BLS, manufactured by Sekisui Chemical Co., Ltd., glass transition temperature: 61.0 ° C.)
-Solution in 800 parts by weight of butyl alcohol
nO ₂ particles (S1, manufactured by Mitsubishi Materials Corporation, average particle size:
0.02 μm), add 20 parts by weight, and add
Time-dispersion treatment was performed to obtain a coating solution.

This coating solution was applied on the outer peripheral surface of an aluminum base (84 mmφ) of an ED tube whose surface was mirror-polished, air-dried at room temperature for 5 minutes, and then heated at 150 ° C. in a hot air dryer. A drying treatment was performed for 10 minutes to produce a conductive particle-dispersed film having a thickness of 7 μm.

Next, a heater was attached to the inside of the above-mentioned aluminum substrate and attached to the apparatus shown in FIG. A scorotron having an opening width of 2 cm (wire current: 850) while rotating the substrate at 30 rpm with the conductive fine particle dispersed film heated to 200 ° C. and softened by a heater.
(A, grid voltage: -700 V) for 5 minutes. Thereafter, the rotation of the substrate was stopped, and the dispersion film was cooled and solidified to obtain a target anisotropic conductive member.

When this anisotropic conductive member was cut and its cross section was observed with a transmission electron microscope, it was confirmed that SnO ₂ particles were arranged in the depth direction as shown in FIG. 1 (b). .

Comparative Example 1 A conductive particle-dispersed film was prepared in the same manner as in Example 1, and this was solidified as it was without performing a charging treatment to obtain an anisotropic conductive member. This member was cut, and its cross section was observed with a transmission electron microscope. As a result, the SnO ₂ particles were randomly dispersed and the regularity of the arrangement as shown in FIG. 1B was not observed.

Comparative Example 2 A conductive particle-dispersed film was prepared in the same manner as in Example 1,
A heater was attached inside the aluminum substrate, and the surface of the dispersion film was covered with aluminum foil. Next, when a voltage of 700 V was applied between the aluminum substrate and the aluminum foil in a state where the dispersion film was heated to 200 ° C. and softened by a heater, dielectric breakdown occurred, and the operation could not be continued. .

Example 2 n-butyl alcohol 1 in which 4 parts by weight of polyvinyl butyral resin (S-LEC BM-S, manufactured by Sekisui Chemical Co., Ltd.) was dissolved
30 parts by weight of acetylacetone zirconium butyrate and 3 parts by weight of γ-aminopropyltrimethoxysilane were added to 70 parts by weight, and mixed and stirred to obtain a coating liquid for an undercoat layer.

This coating solution was dip-coated on the outer peripheral surface of an aluminum substrate (84 mmφ) of an ED tube roughened by a honing treatment, and air-dried at room temperature for 5 minutes to obtain a substrate.
After the temperature was raised to 50 ° C. in 0 minutes, the temperature was raised to 50 ° C. and 85% RH.
(Dew point: 47 ° C.) and placed in a thermo-hygrostat for 20 minutes to perform humidification and curing acceleration treatment. Thereafter, the substrate was transferred into a hot air drier and dried at 170 ° C. for 10 minutes to produce an undercoat layer.

Next, 15 parts by weight of gallium chloride phthalocyanine and a vinyl chloride-vinyl acetate copolymer resin (VMC
H, manufactured by Nippon Unicar Co., Ltd.) and 10 parts by weight of n-butyl alcohol were mixed and dispersed in a sand mill for 4 hours. The resulting dispersion was dip-coated on the undercoat layer and dried to prepare a 0.2 μm-thick charge generation layer.

Further, N, N'-diphenyl-N, N '
-Bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine (4 parts by weight) and bisphenol Z
Polycarbonate resin (viscosity average molecular weight: 40000)
6 parts by weight was dissolved in 80 parts by weight of chlorobenzene, and a coating solution obtained by dip coating was applied onto the charge generation layer and dried to prepare a charge transport layer having a thickness of 25 μm.

Further, a polyvinyl butyral resin (Eslec BLS, manufactured by Sekisui Chemical Co., Ltd., glass transition temperature: 61.
(0 ° C.) 20 parts by weight of SnO ₂ particles (S1, manufactured by Mitsubishi Materials Corporation, average particle size: 0.02 μm) were added to a solution in which 80 parts by weight of n-butyl alcohol was dissolved in 800 parts by weight of n-butyl alcohol. The coating liquid obtained by performing the time dispersion treatment is applied onto the charge transport layer, air-dried at room temperature for 5 minutes, and then dried at 150 ° C. for 10 minutes in a hot air drier to obtain a film thickness. A conductive particle-dispersed film having a thickness of 7 μm was prepared, and a laminate in which an undercoat layer, a charge generation layer, a charge transport layer, and a conductive particle-dispersed film were sequentially laminated on an aluminum substrate was obtained.

A heater was attached to the inside of the aluminum substrate of the laminate, and the laminate was attached to the apparatus shown in FIG. With the conductive fine particle dispersed film heated to 200 ° C. by a heater and softened, a scorotron (wire current: 85 cm) having an opening width of 2 cm is rotated while rotating the laminate at 30 rpm.
The charging treatment was performed at 0 μA, grid voltage: -700 V) for 5 minutes. Thereafter, the rotation of the laminate was stopped, and the dispersed film was cooled and solidified to form a surface protective layer, thereby obtaining an intended electrophotographic photosensitive member.

Using the electrophotographic photosensitive member thus obtained, an electrophotographic image forming apparatus having the structure shown in FIG. 3 was manufactured and a print test was performed. As a result, good image quality was obtained. When the surface potential of the photoreceptor in an electrophotographic process using this apparatus was measured, the charging potential was -650 V, and the potential after exposure was -240 V.
It was confirmed that the residual potential was sufficiently low.

Comparative Example 3 An electrophotographic photosensitive member was prepared in the same manner as in Example 3 except that after forming the conductive particle-dispersed film, the dispersion film was cooled and solidified to form a surface protective layer without performing charging treatment. The body was made.

Using the electrophotographic photosensitive member obtained in this way, an electrophotographic image forming apparatus having the structure shown in FIG. 3 was manufactured and a print test was carried out. It was blank. When the surface potential of the photoreceptor in the electrophotographic process using this apparatus was measured, the charging potential was -650 V, the potential after exposure was -460 V, and it was confirmed that the residual potential was high.

[0064]

As described above, according to the present invention,
Even when conductive particles having no magnetism are used, the conductive particles can be arranged in a predetermined direction in the binding member without causing dielectric breakdown, and have sufficiently high anisotropic conductivity. The anisotropic conductive member can be obtained efficiently and reliably. Furthermore, in the electrophotographic photoreceptor and the electrophotographic image forming apparatus using the anisotropic conductive member of the present invention obtained by the manufacturing method of the present invention, the electrophotographic characteristics and durability are compatible at a high level, and good image quality is obtained. Can be obtained.

[Brief description of the drawings]

FIGS. 1A and 1B are explanatory diagrams each showing an example of a production apparatus used in a production method of the present invention.

FIGS. 2A and 2B are schematic cross-sectional views each showing a preferred embodiment of the electrophotographic photosensitive member of the present invention.

FIG. 3 is a schematic configuration diagram showing a preferred example of an electrophotographic image forming apparatus of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Conductive particle, 2 ... Binding member, 3 ... Conductive substrate, 4 ...
Corona charger, 5 ionized ions, 6 ... heater, 201,
201a, 201b: electrophotographic photosensitive member, 202: conductive support, 203: undercoat layer, 204: charge generation layer, 20
5: charge transport layer, 206: laminated photosensitive layer, 207: surface protective layer, 208: single photosensitive layer, 301: support, 30
2 ... power supply, 303 ... charging member, 304 ... exposure means, 30
5 developing means, 306 transferring means, 307 image fixing means, 308 cleaning means.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Toshiyasu Yukawa 1600 Takematsu, Minamiashigara-shi, Kanagawa Prefecture Fuji Xerox Co., Ltd. F-term (reference) 2H068 AA05 CA37 5E051 CA10 5G307 HA02 HB01 HB03 HB05 HC01

Claims (4)

[Claims] 1. A method for supplying charged particles or charged particles from a charging unit not in contact with the binding member to a fluid or flexible binding member in which the conductive particles are dispersed, and A method of producing an anisotropic conductive member, the method comprising: arranging the conductive particles in the direction of the electric field by generating an electric field in the conductive member. 2. An anisotropic conductive member obtained by the manufacturing method according to claim 1. 3. A conductive support, a photosensitive layer laminated on the support, and a surface protective layer comprising the anisotropic conductive member according to claim 2 laminated on the photosensitive layer. An electrophotographic photoreceptor, comprising: 4. An electrophotographic photosensitive member according to claim 3, charging means for charging said electrophotographic photosensitive member, and exposing means for forming an electrostatic latent image on said electrophotographic photosensitive member. An electrophotographic image forming apparatus comprising: developing means for forming a toner image by attaching toner to the electrostatic latent image; and transfer means for transferring the toner image to a transfer material. .