JP3087994B2 - Developer carrier and developing device using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developer carrier applied to a developing apparatus for developing using a developer used in electrophotography, electrostatic recording, magnetic recording, and the like, and to a developer carrier using the same. The present invention relates to a developing device.

[0002]

2. Description of the Related Art Conventionally, many methods are known as electrophotography. In general, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means. The latent image is developed with a developer (hereinafter, referred to as "toner") to form a visible image, and if necessary, a toner image is transferred to a transfer material such as paper, and then fixed by heat, pressure, etc., and copied. Get things.

In recent years, devices using electrophotography have been increasing in number, such as printers and facsimile machines, in addition to conventional copying machines. Particularly in a printer or a facsimile, a developing device using a one-component toner is often used because it is necessary to reduce the size of a copying device.

The one-component developing system does not require carrier particles such as glass beads and iron powder, unlike the two-component developing system, so that the developing device itself can be reduced in size and weight. Further, in the two-component developing method, it is necessary to keep the toner concentration in the toner constant, so a device for detecting the toner concentration and replenishing a necessary amount of toner is required. . The one-component developing system is preferable because such a device is not required and can be made small and light.

As for printer devices, LED and LBP printers have become the mainstream in the recent market, and the direction of technology has been changed to higher resolution, that is, from 240 or 300 dpi to 400, 600 and 800 dpi. I have. Accordingly, the development system is also required to produce a higher definition recorded image. Also, the functions of the copying machines have been advanced, and the digital copying machines are moving toward digitalization. In this direction, since the method of forming an electrostatic charge image with a laser is mainly used, the direction is also proceeding to a higher resolution, and in electrophotography, similarly to these printers, high resolution and high definition development are performed. A method has been demanded, as disclosed in Japanese Patent Application Laid-Open Nos. 1-1112253 and 2-284158.
In Japanese Patent Application Publication No. JP-A-2005-163, a toner having a small particle size is proposed.

[0006] As a developer carrier used for the development of the above-described method, for example, a metal, an alloy thereof, or a compound thereof is formed into a cylindrical shape, and the surface thereof is made to have a predetermined surface roughness by electrolysis, blast, file, or the like. Is used. However, in this case, the toner present in the toner layer near the surface of the developer carrier in the toner layer formed on the surface of the developer carrier by the regulating member has a very high electric charge, and the toner has a high reflection power on the surface of the developer carrier. Since the toner is strongly attracted, and there is no chance of friction between the toner and the developer carrier, the toner cannot have a suitable charge. Under such circumstances, sufficient development and transfer are not performed, resulting in an image having many image density unevenness and character scattering.

[0007] In order to prevent the generation of such an excessively charged toner and the strong adhesion of the toner, a film in which a conductive substance such as carbon graphite or a solid lubricant is dispersed in a resin is used as the developer. A method of forming on a carrier has been proposed in JP-A-1-277265 and the like. Further, in order to stabilize the toner transportability due to the durability of the film, that is, stabilize the surface roughness of the developer carrying member, a method in which spherical particles are further included in the film is disclosed in JP-A-3-200986. Has been proposed. Also, Japanese Patent Application Laid-Open No. 5-6089 and the like have proposed that in order to increase the surface roughness, a metal cylindrical tube is formed with irregularities by blasting or the like, and then a coating is provided on the surface.

However, in recent years, a reduction in the energy consumption of the copying machine or the LBP body has been demanded again, and accordingly, the energy required for fixing has been reduced. I have.
Due to this effect, the number of toners that easily fuse to a sleeve or the like is increasing. Further, there is a demand for further improving the durability of the developing cartridge and the unit.

[0009]

Conventionally, for example, cartridges have been made under the concept of lightweight, compact and user-friendly, and the number of durable sheets has been about 2,000 to 8,000 due to the miniaturization. However, in recent years, as the number of prints from a personal computer or the like has increased, the toner capacity of the cartridge has increased, and the necessity of a toner replenishment method has arisen. In order to further improve the image quality, the regulation of the toner is strengthened, and the toner tends to be thin on the developer carrier, and the physical load on the toner and the developer carrier is increasing.
For example, the technique described in the above-mentioned Japanese Patent Application Laid-Open No. 1-277265 is an effective technique for a conventional low-durability cartridge. However, the surface irregularities are formed from graphite which is originally added, and a large amount of addition is required due to its shape, and since it has a brittle and irregularly shaped surface, it is easily shaved and smoothed. In this regard, in the technology disclosed in Japanese Patent Application Laid-Open No. 3-200986,
Since a preferable surface unevenness is formed by adding a small amount, progress is shown in the point of maintaining the unevenness. However, there are many aspects that are insufficient due to problems such as peeling and abrasion of added particles, dispersibility as a coating material, problems in production, proper adhesion of toner and proper charging of toner, and the like. As a result of various studies on this point, an improved point disclosed in the present invention was found.

Accordingly, it is an object of the present invention to provide a toner on a developer carrying member which has a stable and appropriate charge even in repeated image formation, is uniform and non-uniform, and has a reduced image density and ghost. It is an object of the present invention to provide a developer carrier that can obtain a high-quality image without any problem. Another object of the present invention is to provide a developer carrying member which can further improve the abrasion resistance of the resin coating layer and can obtain a long and stable image. Another object of the present invention is to provide a developer carrying member capable of obtaining a longer and stable image by reducing toner adhesion to a resin coating layer. It is a further object of the present invention to provide a developing device capable of obtaining a stable and high-quality image by using a developer carrier having a uniform surface state over a long period of time.

[0011]

The above object is achieved by the present invention described below. That is, the present invention relates to a developer carrier of an electrophotographic developing device, which has a conductive coating layer on the surface of a substrate, and the coating layer has at least a binder resin and a number average particle size of 0. .3 to 30 μm and is formed of a coating material containing resin particles having an inorganic fine powder adhered or fixed to the surface or the surface and the vicinity of the surface, and a conductive material ;
The inorganic fine powder includes SiO ₂ , SrTiO ₃ , CeO ₂ , C
rO, Al ₂ O ₃ , ZnO, MgO, Si ₃ N ₄ , SiC,
Group consisting of CaSO ₄ , BaSO ₄ and CaCO ₃
And a developer carrier selected from the group consisting of:
Also, a second aspect of the present invention is a container for storing at least a developer, a developer carrying member for carrying and transporting the developer in the developing container, and transporting the developer to a developing area close to the latent image carrier, A developer layer thickness regulating member that regulates the layer thickness of the developer on the developer carrier in close proximity or pressure contact with the carrier, wherein the developer carrier is electrically conductive on the surface of the substrate. Suffered
A cover layer, the cover layer comprising at least a binder resin and
The number average particle size is 0.3 to 30 μm and the surface or surface
Resin particles with inorganic fine powder attached or fixed on the surface and near the surface
And a coating material containing a conductive material,
The inorganic fine powder includes SiO ₂ , SrTiO ₃ , CeO ₂ , C
rO, Al ₂ O ₃ , ZnO, MgO, Si ₃ N ₄ , SiC,
Group consisting of CaSO ₄ , BaSO ₄ and CaCO ₃
A developing device selected from the group consisting of:

[0012]

[Action]

(1) In some cases, resin particles insoluble in a solvent may aggregate in a resin dispersion solution. When the resin particles in the coating material for forming the resin coating layer of the developer carrier agglomerate, the surface roughness after coating becomes excessively uneven. However, the aggregation is solved by the presence of the inorganic fine powder on the surface of the resin particles, and a resin coating layer of the developer carrier having a uniform surface can be obtained. (2) Due to the presence of the inorganic fine powder on the surface of the resin particles in the resin coating layer of the developer carrying member, the adhesion to the binder resin is improved, and the scraping from the resin particle portion can be prevented, and the developer carrying Improves body durability. In the case of an inorganic fine powder treated with a coupling agent, more preferable results are obtained. (3) When the inorganic fine powder is present on the surface of the resin particles in the resin coating layer of the developer carrier, the adhesion of the toner to the exposed portions of the resin particles or the resin particle portions exposed by the shaving is reduced, and the image quality is improved. Drop can be prevented. (4) To prevent the adverse effect on the toner from being negatively charged by selecting an inorganic fine powder to be adhered to the surface of the resin particles in the resin coating layer of the developer carrier. Can be. These effects can be obtained individually or in combination. Accordingly, the toner on the developer carrying member has stable and appropriate charge even in repeated image formation due to the above-mentioned action, so that the toner is uniform, has no unevenness, and is free from image density reduction and ghost. Image can be obtained. Therefore, according to the present invention, a high-quality image can be obtained,
It is possible to provide a developer carrying member having a further improved abrasion resistance and capable of obtaining a long and stable image. By mounting this developer carrying member, it becomes possible to provide a developing device for electrophotography having the above characteristics. .

[0013]

The developer carrying member of the electrophotographic developing apparatus of the present invention has a binder resin, at least a conductive substance and an inorganic fine powder coated on the surface of the substrate, that is, the surface carrying the developer. It is characterized in that a conductive coating layer containing resin particles having a specific particle diameter adhered or fixed to the surface or near the surface is provided. The electrophotographic developing device in the present invention means a developing device that performs development using a developer used in electrophotography, an electrostatic recording method, a magnetic recording method, or the like. The carrier carries such a developer. As the binder resin contained in the resin coating layer of the present invention, generally known resins can be used. For example, phenolic resin, epoxy resin, polyamide resin, alkali resin, polyester resin,
Polycarbonate resins, polyolefin resins, silicone resins, fluorine resins, styrene resins, vinyl resins, cellulose resins, melamine resins, urea resins, polyurethane resins, polyimide resins, and the like. Thermosetting resins are more preferable in consideration of mechanical strength, but thermoplastic resins are also applicable as long as they have sufficient mechanical strength.

Examples of the conductive substance which is added to the resin coating layer of the developer carrying member of the present invention and imparts conductivity to the resin coating layer include generally known conductive fine powders. For example,
Powders of metals or alloys such as copper, nickel, silver, and aluminum; metal oxides such as antimony oxide, indium oxide, tin oxide, and titanium oxide; and carbon-based conductive materials such as carbon fiber, carbon black, and graphite. . The amount of the conductive fine powder to be added varies depending on the developing system. For example, in the case of using a one-component insulating toner in the jumping developing method, the electric resistance of the resin coating layer may be 10 ³ Ω · cm or less. Is preferably added. Carbon black, especially amorphous carbon, is particularly excellent in conductivity, and can be given conductivity with a small amount of addition compared to other conductive materials. Since it can be used, it is particularly preferably used.

The resin particles contained in the resin coating layer of the developer carrier of the present invention can be selected from known resins. As the resin particles, for example, resin particles obtained by a pulverization method, spherical resin particles by a suspension polymerization method or the like are used. Spherical resin particles can obtain a suitable surface roughness with a small amount of addition,
It is easy to obtain a uniform surface shape. Examples of such spherical resin particles include acrylic resin particles such as polyacrylate and polymethacrylate, polyamide resin particles such as nylon 6, polyolefin resin particles such as polyethylene and polypropylene, silicone resin particles, and phenol resin particles. And polyurethane-based resin particles, styrene-based resin particles, and benzoguanamine particles. The resin particles obtained by the pulverization method may be used after being subjected to thermal or physical sphering treatment.

The surface of the resin particles or the surface and the vicinity thereof
The inorganic fine powder to fix with Chakumatawa to, S iO _2,
SrTiO ₃ , CeO ₂ , CrO, Al ₂ O ₃ , ZnO, M
_{gO, S i 3 N 4,} S iC, C aSO 4, BaSO 4 and C
aCO _3, and the like. Such an inorganic fine powder may be used after being treated with a coupling agent, and for the purpose of improving the adhesion to the binder resin or imparting hydrophobicity to the particles, such an inorganic fine powder is particularly preferable. Used.
Examples of such a coupling agent include a silane coupling agent, a titanium coupling agent, and a zircoaluminate coupling agent. More specifically, for example, as a silane coupling agent, hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, Benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethyl Diethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane,
Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 siloxane units per molecule, each having a silicon unit as a terminal unit Examples include dimethylpolysiloxane having a hydroxyl group bonded to an atom.

As a method of adhering or fixing the inorganic fine powder on the surface of the resin particles, for example, using a mixer such as a Henschel mixer used for external addition of toner, etc.
There is a method of adhering or fixing by vigorous stirring. At this time, it is also possible to assist the adhesion to the particles by heating the jacket or the like. Also, a method of fixing powder to particles by mechanical impact by passing through a small gap by using an apparatus having a rotating piece and a fixed piece as disclosed in Japanese Patent Application Laid-Open No. 2-256062 is also applicable. It is possible.

The particle size of the resin particles whose surface has been treated with the inorganic fine powder as described above is 0.3 μm to 30 μm in number average particle size.
Is preferred. If the thickness is less than 0.3 μm, it is difficult to make the coating layer have uniform surface irregularities. If the surface roughness is to be increased, the addition amount becomes excessive, the resin coating layer becomes brittle, and the abrasion resistance is extremely reduced. Conversely, when it is larger than 30 μm,
Since the particles excessively protrude from the surface of the carrier, the thickness of the toner layer becomes too large, so that the charge of the toner tends to decrease or become non-uniform, and there is a possibility that the toner leaks to the photosensitive drum when a bias is applied. The resin particles treated with such an inorganic fine powder are preferably used in such an amount that the surface roughness of the coating layer falls within the following range.

In the measurement of the average particle diameter in the present invention, a 100 μm aperture is used for a Multisizer II manufactured by Coulter Co., Ltd. (particles having a diameter of 3.0 μm or less are 50 μm aperture).
Was attached and the measurement was performed. The measurement of the conductive particles was performed by attaching a liquid module to an LS-130 type particle size distribution analyzer manufactured by Coulter Corporation. The surface roughness of the resin coating layer to which the particles are added in this manner is 0.3 μm or more as the center line average roughness (Ra) in the notation method of JIS B0601.
It is preferably in the range of 5.0 μm. When the value of Ra is 0.3 μm or less, the thickness of the toner layer on the developer carrier is too small, and the amount of toner supplied is too small for developing a solid image on the latent image carrier, and is 5.0 μm or more. In this case, the thickness of the toner layer becomes too large, and the charge of the toner tends to decrease or become uneven. The measurement of the surface roughness in the present invention was performed using a surface roughness meter SE-3300H manufactured by Kosaka Laboratory, with a cutoff value of 0.8 mm, a specified distance of 2.5 mm, and a feed rate of 0.1 mm / sec. The measurement was performed at 12 points under the above measurement conditions, and the average value was used as the measured value.

It is preferred that the resin coating layer of the developer carrier of the present invention contains a fine lubricating powder in addition to the above-mentioned substances. Examples of such a lubricating fine powder include fluorinated polymers such as molybdenum disulfide, boron nitride, mica, graphite, graphite fluoride, silver-niobium selenide, calcium chloride-graphite, talc, Teflon, and PVDF; Zinc stearate, magnesium stearate,
Fatty acid metal salts such as aluminum stearate and zinc palmitate; Among them, graphite is particularly preferably used because it has conductivity as well as lubricity.

Next, a developing device in which the developer carrying member of the present invention is incorporated will be described with reference to FIG. 2, which is an example of a developing device. In FIG. 2, an image carrier for carrying an electrostatic latent image formed by a known process, for example, an electrophotographic photosensitive drum 1 is rotated in the direction of arrow B. The developing sleeve 8 as a developer carrying member is composed of a metal cylindrical tube (base) 6 and a resin coating layer 7 formed on the surface thereof. A stirring blade 10 for stirring the magnetic toner 4 is provided in the hopper 3. By carrying the magnetic toner 4 as a one-component magnetic toner supplied from the hopper 3 and rotating in the direction of arrow A, the magnetic toner 4 is conveyed to the developing section where the developing sleeve 8 and the photosensitive drum 1 are opposed to each other. A magnet 5 is disposed in the developing sleeve 8 to magnetically attract and hold the magnetic toner 4 on the developing sleeve 8. The magnetic toner 4 obtains a triboelectric charge capable of developing the electrostatic latent image on the photosensitive drum 1 by friction with the developing sleeve 8.

In order to regulate the thickness of the magnetic toner 4 conveyed to the developing section, a regulating blade 2 made of a ferromagnetic metal is used.
It is hung from the hopper 3 so as to face the developing sleeve 8 with a gap width of about 50 to 500 μm from the surface of the developing sleeve 8. When the lines of magnetic force from the magnetic pole N1 of the magnet 5 concentrate on the regulating blade 2, a thin layer of the magnetic toner 4 is formed on the developing sleeve 8. As the regulating blade 2, a non-magnetic blade can be used.

The thickness of the thin layer of the magnetic toner 4 formed on the developing sleeve 8 is preferably smaller than the minimum gap between the developing sleeve 8 and the photosensitive drum 1 in the developing section. The present invention is particularly effective for a developing device of a type that develops an electrostatic latent image with such a thin toner layer, that is, a non-contact type developing device. However, the present invention is also applicable to a developing device in which the thickness of the toner layer in the developing section is equal to or greater than the minimum gap between the developing sleeve 8 and the photosensitive drum 1, that is, a contact type developing device.

For the sake of simplicity, the following description will be made by taking a non-contact type developing device as an example. The developing sleeve 8
In order to cause the magnetic toner 4, which is a one-component magnetic toner carried thereon, to fly, a power supply 9 applies a developing bias voltage. When a DC voltage is used as the developing bias voltage, a voltage having a value between the potential of the image portion of the electrostatic latent image (the region where the magnetic toner 4 is adhered and visualized) and the potential of the background portion is used. Preferably, it is applied to the sleeve 8. On the other hand, in order to increase the density of the developed image or improve the gradation, an alternating bias voltage may be applied to the developing sleeve 8 to form an oscillating electric field in which the direction is alternately reversed in the developing unit. In this case, it is preferable to apply to the developing sleeve 8 an alternating bias voltage on which a DC voltage component having a value between the potential of the image portion and the potential of the background portion is superimposed.

In so-called regular development in which toner is adhered to a high potential portion of an electrostatic latent image having a high potential portion and a low potential portion to visualize the toner, toner charged to a polarity opposite to the polarity of the electrostatic latent image is used. On the other hand, in so-called reversal development in which toner is attached to a low potential portion of an electrostatic latent image to visualize the toner, a toner charged to the same polarity as the polarity of the electrostatic latent image is used. In addition, high potential,
Low potential is an expression based on an absolute value. In any case, the magnetic toner 4 is charged to a polarity for developing the electrostatic latent image by friction with the developing sleeve 8.

FIG. 3 is a block diagram showing another example of the developing device of the present invention, and FIG. 4 is a block diagram showing still another example of the developing device of the present invention. In the developing device shown in FIGS. 3 and 4, as a member for regulating the layer thickness of the magnetic toner 4 on the developing sleeve 8, a material having rubber elasticity such as urethane rubber or silicone rubber, or a metal elastic material such as phosphor bronze or stainless steel is used. An elastic plate 11 made of a material having
3 is characterized in that it is pressed against the developing sleeve 8 in the same direction as the rotation direction in the developing device of FIG. 3, and the developing device in FIG. 4 is pressed against the developing sleeve 8 in the direction opposite to the rotating direction. In such a developing device, a thinner toner layer can be formed on the developing sleeve 8. Other configurations of the developing device of FIGS. 3 and 4 are basically the same as those of the developing device shown in FIG. 2. In FIGS. 3 and 4, the same reference numerals as those shown in FIG.

The developing device for forming a toner layer on the developing sleeve 8 as described above as shown in FIG. 3 and FIG. It is also suitable for those using a one-component non-magnetic toner containing a magnetic toner as a main component.

Next, the toner used for obtaining a visible image by the developer carrier or the developing device of the present invention will be described. Toners are mainly resins, release agents, charge control agents,
It is a fine powder having a uniform particle size distribution by melting and kneading a colorant or the like, solidifying and then pulverizing, and then classifying or the like. As the binder resin used for the toner, generally known resins can be used. For example, styrene, α-methylstyrene, p
A homopolymer of styrene such as chlorostyrene and a substituted product thereof; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-
Octyl acrylate copolymer, styrene-dimethylaminoethyl copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate Copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer Styrene copolymers such as polymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenolic resin, aliphatic or alicyclic Hydrogen resins, aromatic petroleum resins, paraffin wax, carnauba wax and the like can be used alone or in combination.

The toner may contain a pigment. For example, carbon black, nigrosine dye, lamp black, Sudan Black SM, First Yellow G, Benzidine Yellow, Pigment Yellow, India First Orange, Irgazine Red, Paranitroaniline Red, Toluidine Red, Carmine FB, Permanent Bordeaux FRR, Pigment
Orange R, Risor Red 2G, Lake Red C, Rhodamine FB, Rhodamine B Lake, Methyl Bio Red B Lake, Phthalocyanine Blue, Pigment Blue, Brilliant Green B, Phthalocyanine Green, Oil Yellow GG, Pomelo First Yellow CGG, Kaya set Y963, Kaya set Y
G, Pomelo First Orange RR, Oil Scarlet, Orazol Brown B, Pomelo First Scarlet CG, Oil Pink OP, etc. can be applied.

In order to use the toner as a magnetic toner, a magnetic powder may be contained in the toner. As such a magnetic powder, a substance that is magnetized in a magnetic field is used, and a powder of a ferromagnetic metal such as iron, cobalt, and nickel is used.
Alternatively, alloys and compounds such as magnetite, hematite, and ferrite may be used. The content of the magnetic powder is preferably 15 to 70% by weight based on the weight of the toner.

Various release agents may be used in the toner. Such release agents include polyfluoroethylene,
Fluororesin, fluorocarbon oil, silicone oil, low molecular weight polyethylene, low molecular weight polypropylene, various waxes, and the like. Further, if necessary, a charge control agent for facilitating positive or negative charging may be added.

As the substrate used for the developer carrier, a cylindrical tube is preferable, and a non-magnetic metal or alloy such as aluminum, stainless steel, brass or the like formed into a cylindrical shape and subjected to polishing, grinding, or the like is preferably used. Can be These metal cylindrical tubes are molded or processed with high precision in order to improve the uniformity of images. For example, the straightness in the longitudinal direction is 30
μm or less, preferably 20 μm or less, when the developing sleeve and the photosensitive drum are rotated by abutting the developing sleeve and the photosensitive drum through a uniform spacer against a vertical surface, for example, when the developing sleeve is rotated. Is also 30 μm or less, preferably 20 μm or less.

The resin coating layer of the developer carrier of the present invention can be obtained, for example, by a method in which the components for forming the resin coating layer are dispersed and mixed in a solvent to form a coating, and the composition is coated on the substrate. It is. A sand mill,
A known dispersing apparatus using beads such as a paint shaker, a dyno mill, and a pearl mill can be suitably used. As the coating method, a known method such as a dipping method, a spray method, and a roll coating method can be applied. The thickness of the coating layer is preferably in the range of 0.2 μm to 50 μm from the viewpoint that a film having a uniform thickness is easily formed, but is not particularly limited thereto.

[0034]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. Example 1 [Production of developing sleeve] Number average particle diameter D1 = 8.54 μm
The polymethyl methacrylate (hereinafter, referred to as “PMMA”) particles cross-linked by m cross-linking agents were prepared. The PMMA particles were produced by suspension polymerization and had a spherical form. In order to fix the silica on the surface of the PMMA particles, a 75 liter Henschel mixer is heated by circulating hot water, and BET is added to 10 kg of the PMMA particles.
G of dry silica having a specific surface area of 200 m ² / g
Was added, and the mixture was stirred at an atmosphere temperature of 90 ° C. to fix the dry silica on the surface of the PMMA particles. PMMA obtained
When the particles were observed with an electron microscope (FE-SEM),
The surface of the PMMA particles was sufficiently covered with silica.

Next, paints were prepared using the materials and compounding ratios shown below. Phenol resin intermediate 100 parts by weight PMMA particles 12 parts by weight Conductive carbon black 25 parts by weight Methanol 60 parts by weight isopropyl alcohol 230 parts by weight The above-mentioned raw material was dispersed by a sand mill using glass beads as a medium by the following method. After diluting the methanol solution of the phenol resin intermediate with isopropyl alcohol, conductive carbon black is added and dispersed with a sand mill.
Further, the above-mentioned PMMA particles were added and dispersed to prepare a paint. After the dispersion, the mixture was separated from the glass beads and the viscosity was measured at room temperature. The result was 42.5 mPa · s.

Using this coating material, a developing sleeve was coated. As a coating method, an aluminum cylindrical tube with an outer diameter of 16 mm is set up on a work stand, rotated by a motor, and coated while lowering a spray gun at a constant speed.
After drying and curing at 140 ° C. for 30 minutes in a drying oven, a developing sleeve of the present invention having a resin coating layer having a uniform film thickness was obtained. The adhesion weight of the paint after drying was 5,700 mg / m ² . When the surface roughness of this developing sleeve was measured, it was 1.75 μm on average in terms of Ra. Wrap an OHP sheet around another cylindrical tube and apply it in the same way.
The volume resistance of the coating film measured using this OHP sheet was 1.53 Ω · cm. The volume resistance value was measured by attaching a four-terminal probe to Lourester AP manufactured by Mitsubishi Yuka.

[Image Destruction Durability Test] The image development durability test was performed on the obtained developing sleeve using a laser jet IV manufactured by Hewlett-Packard (HP). First, the above-mentioned developing sleeve was processed and attached to an EP-E cartridge for laser jet IV so as to be attachable. An image endurance test was performed on a total of 30,000 sheets while replenishing 100 g of toner every time 100 g of toner was consumed. EP-
The vicinity of the developing sleeve of the E cartridge is of a type in which an elastic blade elastically contacts the sleeve, as schematically shown in FIG. . 15 ° C / 10% RH
(Low temperature and low humidity), 23 ° C / 55% RH (normal temperature and normal humidity), 30
C./80% RH (high temperature and high humidity) were performed in three environments.

Incidentally, in this image formation durability test, a toner having the following materials and compounding ratio was used. Styrene-butyl acrylate-maleic acid-n-butyl half ester copolymer 100 parts by weight Magnetite 90 parts by weight Charge control agent 5 parts by weight Low molecular weight polypropylene 5 parts by weight After mixing these materials using a Henschel mixer, The mixture was kneaded using a shaft-type extruder, cooled, ground by a hammer mill, and then ground by a jet mill. This was classified by an elbow jet classifier, and particles having a weight average particle size D4 of 6.58 μm and particles of 4.0 μm or less were 1%.
7.5% by number, 1.2% by weight of particles of 10.1 μm or more
Was obtained. To 100 parts by weight of the classified product, 1.2 parts by weight of hydrophobic colloidal silica was externally added and mixed to obtain a toner used in the present test.

[Evaluation Method] (1) Change in Solid Black Image Density Reflection density was measured at 10 points in a page when solid black printing was performed using a reflection densitometer RD918 (manufactured by Macbeth), and the average of the 10 points was calculated. To obtain the image density.

(2) Density Rise The image density was measured in the same manner as in (1), initially or after a pause during durability (based on standing for 3 days), and the change in image density was observed. The evaluation results are shown by the following indices. A: Sufficient image density was shown from the start, and there was no change in density. : About 10 sheets from the start show a slight rise, but the image density is sufficient. △: Slightly rising at the start, image density slightly inferior, but practically no problem. Δ ○: intermediate between ○ △ and △. Δ: The image density is lower than the practical level, and the rise of the density is slow. Δ ×: The image density is inferior to the practical level, and the rise of the density is very slow. ×: The image density is extremely low, and the density does not rise.
Below practical level.

(3) Ghost An image in which a solid white portion and a solid black portion are adjacent to each other is developed at the leading end of the image (first rotation of the sleeve), a halftone image is developed for the second and subsequent laps, and a halftone image is developed for the second and subsequent laps. The density difference between the solid white mark and the solid black mark appearing on the halftone was compared mainly visually, and evaluated with reference to the measurement result of the image density by a reflection densitometer. The evaluation results were indicated by the following indices. : No difference in shade was observed. ：: A slight difference in shading can be confirmed depending on the viewing angle. △: The density difference can be visually confirmed, but the image density difference is within 0.01. Δ ○: A difference in shading such that the edge is not clear can be confirmed, but practical. Δ: Difference in shading is somewhat clear, and the lower limit of the practical level. Δ ×: The density difference can be clearly confirmed and the image density difference can be confirmed. Inferior to practical level. X: The difference in density is considerably large, and the difference in density with a reflection densitometer is 0.05 or more, which is below a practical level.

(4) Fading A solid black image and a line image (with a uniform width of 5 mm) are printed, and the density difference of the image density appearing as a vertical band in the transfer paper traveling direction appearing in the image is mainly visually determined. The evaluation was made with reference to the measurement results of the image density by a reflection densitometer. The evaluation results were indicated by the following indices. A: Solid black with no density difference visually. ：: Solid black, no difference in image density, but a slight difference in shading can be seen when viewed through. ○ △: Solid black, slightly different in image density, but little difference in image density. Δ ○: Image density difference can be slightly confirmed visually (index, ○ △)
And between △). Δ: The image density difference exists within 0.05 in the case of solid black on the entire surface, but does not cause a problem in the case of solid black having a small area (within a practical level). C: Solid black with some vertical bands clearly visible (inferior to practical level). × △: About half of a solid black image has a light image density portion in a vertical band shape. ×: Difference in shading can be confirmed even in a line image. Alternatively, there is a vertical band-like dark part in a part of the solid black.

(5) Fog The reflectivity of a solid white image is measured, and the reflectivity of an unused transfer paper is measured. [The worst value of the reflectivity of a solid white image−the best reflectivity of an unused transfer paper] Value] was evaluated as the fog density. However, the measurement of the reflectance was performed 10 times at random.
The reflectance was measured with TC-6DS (manufactured by Tokyo Denshoku).
The evaluation results were indicated by the following indices. ◎: 1.0 or less. : 1.0 to 1.5. △: 1.5 to 2.3. Δ ○: 2.3 to 3.0. Δ: 3.0 to 4.0 (4.0 is a practical level lower limit). C: 4.0 to 5.0. X: 5.0 or more. However, when visually judging the above numerical values, it is hardly understood that the value is 1.5 or less, and about 2.3 is a level that can be confirmed by looking closely. If it exceeds 4.0, fog can be confirmed at a glance.

(6) Unevenness After confirming various images such as solid black, halftone, and line images, images such as wavy unevenness and blotches (spotted unevenness) on the developing sleeve are caused by poor coating of the developer on the sleeve. The evaluation results of unevenness (wave, blotch, etc.) were indicated by the following indices. : Does not appear at all. ：: About one out of several to dozens of images can be confirmed by seeing through the image. There is no practical problem at all. Δ: Wavy or spot-like unevenness is observed in the first rotation of the first sleeve of the halftone image or solid black image. No problem with photographic images. Δ ×: One to several solid images appear as uneven images. Not practical. X: Unevenness also appears on solid white.

(7) Sleeve Contamination After the endurance or when the image density is extremely lowered, the toner on the sleeve surface is removed by a vacuum cleaner and an air blow (by an air gun), observed with a SEM, and the evaluation result is indicated by the following index. Displayed with. A: No toner is present. ：: Fine toner powder is slightly observed in the dent on the sleeve surface. △: The toner particles remain in the dents on the sleeve, but the original shape of the toner particles remains. Δ ○: Intermediate level between indices ○ △ and △. Δ: Toner particles attached to the sleeve are present in some places, and the toner particles are crushed as if they were slightly melted. Δ ×: Toner sticking is observed in about 20% of the sleeve surface (intermediate level between indices Δ and Δ ×). × △: There is no streak-like fusion visually recognizable, but when viewed by SEM, toner particles which have been melt-smoothed exist in a considerable portion on the sleeve. X: Melted and smoothed toner particles are adhered to a considerable portion of the sleeve, and streak-like fusion is partially visible over the entire sleeve.

(8) Surface Roughness The method for measuring the surface roughness is as described above. The measurement was performed on the surface of the obtained developing sleeve before the endurance test (hereinafter, referred to as “initial”) and after the endurance of 30,000 sheets (hereinafter, referred to as “initial”).
"After endurance". ).

The above results are shown in Table 1 below. The relationship between the number of endurance sheets and the solid black image density is shown in a graph 1-1 in FIG. 7, and the relationship between the density rise and the graph 1-2 is shown in a graph 1-2. Regarding the solid black image density, a sufficient image density was maintained even after durability. Ghosts and fogging did not cause any problem even after 30,000 sheets were used. The surface roughness was Ra = 1.75 μm in an initial value under a normal temperature and normal humidity environment.
The value after durability was Ra = 1.53 μm, and the value did not change much. Observation of the surface of the developing sleeve after the image endurance test revealed that no exposure of the surface of the aluminum cylindrical tube under the resin coating layer was observed.

Example 2 The number average particle diameter D1 described in Example 1 was 8.54 μm.
Using the crosslinked PMMA particles having the dry silica fixed on the surface thereof, a coating material was prepared by the following materials, compounding ratios and methods.

Phenol resin intermediate 100 parts by weight PMMA particles 12 parts by weight Crystalline graphite having an average particle diameter of 2 μm 30 parts by weight Conductive carbon black 5 parts by weight Methanol 60 parts by weight Isopropyl alcohol 240 parts by weight

The above raw materials were dispersed in a sand mill in the same manner as in Example 1 to obtain a paint having a viscosity of 55.0 mPa · s at room temperature. In the same manner as in Example 1 using this paint, the outer diameter 16
5,400mg weight attached to aluminum cylindrical tube
/ M ² to give a developing sleeve of the present invention.
The surface roughness of the obtained developing sleeve was Ra = 1.80 μm.
And the volume resistance value of the OHP sheet described in Example 1 was 0.73 Ω · cm.

With respect to this developing sleeve, the same toner as used in Example 1 was used, and an image output durability test and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1 below.
The graph (2-1) in FIG. 7 shows the change in the density of the solid black image during the image endurance test. A good image was obtained through the image endurance test. (2) The results of the concentration rise are shown in the graph 2-2 in FIG. (3) With regard to ghosts, good results were obtained in Example 1, but better results were obtained in Example 2.

Example 3 The number average particle diameter D1 described in Example 1 was 8.54 μm.
, A dry silica having a specific surface area of 130 m ² / g by BET treated with a silane coupling agent was fixed to the surface of the PMMA particles in the same manner as in Example 1. Next, paints were prepared using the materials, compounding ratios and methods shown below. Phenol resin intermediate 100 parts by weight PMMA particles 12 parts by weight Crystalline graphite having an average particle diameter of 2 μm 30 parts by weight Conductive carbon black 5 parts by weight Methanol 60 parts by weight Isopropyl alcohol 240 parts by weight

The above raw materials were dispersed in a sand mill in the same manner as in Example 1 to obtain a coating material having a viscosity of 55.0 mPa · s at room temperature. In the same manner as in Example 1 using this paint, the outer diameter 16
5,400mg weight attached to aluminum cylindrical tube
/ M ² to obtain a developing sleeve of the present invention. The surface roughness of the obtained developing sleeve was Ra = 1.80.
μm, and the volume resistance value of the OHP sheet described in Example 1 was 0.73 Ω · cm. Using this developing sleeve, the same toner as used in Example 1 was used, and an image endurance test and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1 below. Also, the change in solid black image density during the image endurance test is shown in graph 3-1 in FIG.
Good image density was obtained through the image endurance test. The results of the concentration rise are shown in the graph 3-2 in FIG.
The ghost was as good as in Example 2. When the surface of the developing sleeve after the image output durability test was observed by FE-SEM, the exposure of PMMA particles was extremely small.
The change in surface roughness was also small.

Comparative Example 1 A coating material was prepared using the same materials, compounding ratio and method as in Example 2, except that PMMA particles not treated with fumed silica were used. The viscosity of the paint is 52.5mP at room temperature
a · s was almost the same as Example 2. Using this paint in the same manner as in Example 1, it was applied to an aluminum cylindrical tube having an outer diameter of 16 mm so as to have an adhesion weight of about 5,400 mg / m ² , to obtain a developing sleeve of Comparative Example. The surface roughness of the paint after curing was Ra = 1.83 μm, and the volume resistance was 0.76 Ω · cm, which was equivalent to that of Example 2. This developing sleeve was subjected to an image output durability test in the same manner as in Example 1. The results are shown in Table 1-1 below, and Comparative Example 1 is shown.
Although it was shown as -1, an image almost equivalent to that of Example 2 was obtained up to the durability of about 15,000 sheets, but thereafter the density gradually decreased (see graphs 4-3 and 4 in FIG. 8). 4-4
See also), the sleeve ghost also worsened. Although the results were better than Comparative Example 2 shown in Table 1-2 below, in the latter half of the endurance, there were some results that were lower than the practical level.

Further, after this coating material was allowed to stand in a laboratory at a maximum room temperature of 30 ° C. for 3 weeks, when the coating of the developing sleeve was performed again, the surface roughness increased to Ra = 2.84.
The particle size distribution of the paint was measured using a Coulter Counter LS-13.
When measured with Type 0, the peak due to PMMA particles was shifted to a coarser direction than the particle size distribution measured at the beginning of dispersion. FE-
Observation with an SEM revealed that many PMMA particles were localized and exposed on the surface of the coating layer.

With respect to this developing sleeve, an image endurance test and evaluation were performed in the same manner as in Example 2, and the results were shown in Table 1 below.
2 shows Comparative Example 1-2, however, a phenomenon in which the density is low at the initial stage and immediately after the printing is stopped for 20,000 sheets, and the density gradually rises (see graphs 4-1 and 4 in FIG. 8).
-2). That is, the resin particles are aggregated by storage, the surface roughness of the developing sleeve is increased, the thickness of the toner layer is increased, and due to the exposure of the resin particles on the surface of the developing sleeve, an appropriate charge amount cannot be given to the toner. It is thought that there is. Further, such a developing sleeve surface with poor resin particle dispersion has a large change in surface roughness due to an image endurance test, and Ra = 1.12 μm at the time of printing 10,000 sheets.
m, Ra = 0.97 μm when 30,000 sheets were printed.

COMPARATIVE EXAMPLE 2 In this comparative example, a developing sleeve was formed in which a coating layer having an uneven surface was formed using graphite having a large particle size without adding resin particles. First, a coating material was prepared by the following materials, compounding ratios and methods. Phenol resin intermediate 100 parts by weight Crystalline graphite having an average particle size of 15.2 μm 80 parts by weight Conductive carbon black 5 parts by weight Methanol 60 parts by weight Isopropyl alcohol 410 parts by weight The above raw materials are dispersed by a sand mill, and the viscosity is 47 at room temperature. .
A paint of 5 mPa · s was obtained. Since graphite has a plate-like or scale-like shape, it was necessary to increase the particle size and the amount of addition in comparison with PMMA particles in order to obtain an appropriate surface roughness. This coating material was applied to a 16 mm aluminum cylindrical tube in the same manner as in Example 1 to obtain a developing sleeve of Comparative Example. The surface roughness of the obtained developing sleeve is Ra = 1.78 μm, and the volume resistance value is 0.58 Ω · cm.
Met.

The developing sleeve was subjected to an image endurance test in the same manner as in Example 1 (the results are shown in Table 1 below).
In the initial stage, almost good images were obtained, but a phenomenon was observed in which the image density gradually decreased from about 10,000 sheets in each environment (see graph 5-1 in FIG. 9). In a low-temperature, low-humidity environment, wavy toner coat unevenness was observed in the latter half of the image output durability test, and an uneven image was observed on halftone. Regarding the surface roughness, the initial value was Ra = 1.84 μ, respectively.
m, 1.78 μm, and 1.87 μm (low temperature, low humidity, normal temperature, normal humidity, and high temperature, high humidity, respectively), whereas the values after durability were Ra = 1.10 μm, 1.03 μm, and 0.9, respectively.
7 μm, and a remarkable decreasing tendency was observed. Analysis of the surface composition by the laser Raman method revealed that the amount of graphite was lower than in the initial stage.
This is presumably because the graphite portion was preferentially shaved by the image endurance test and the surface roughness was reduced.

Table 1-1 Table 1-2

Example 4 Instead of the PMMA particles of Example 3, the number average particle diameter D1 =
Spherical PMM cross-linked by 12.32 μm cross-linking agent
B treated with a silane coupling agent using A particles
Crosslinked PMMA particles having dry silica fixed to the surface were obtained in the same manner as in Example 3 except that 150 g of dry silica having a specific surface area of 130 m ² / g by ET was used. Next, paints were prepared using the materials, compounding ratios and methods shown below. Phenol resin intermediate 100 parts by weight PMMA particles 12 parts by weight Crystalline graphite having an average particle size of 2 μm 30 parts by weight Conductive carbon black 3 parts by weight Methanol 60 parts by weight Isopropyl alcohol 240 parts by weight

The above raw materials were dispersed in a sand mill in the same manner as in Example 1 to obtain a paint having a viscosity of 50.0 mPa · s at room temperature. This coating was applied to an aluminum cylindrical tube in the same manner as in Example 1 to obtain a developing sleeve of the present invention. The coating weight of the paint on the developing sleeve is about 5.4.
00 mg / m ² , the surface roughness was Ra = 1.98 μm, and the volume resistivity was 0.92 Ω · cm. The image development durability test and evaluation of this developing sleeve were performed in the same manner as in Example 1. The result is shown in graph 6-1 in FIG.
6-2 and as shown in Table 2 below.

Example 5 In place of the PPMMA particles of Example 3, the number average particle diameter was D.
1 = 23.21 μm and PMMA particles passed through a 400-mesh sieve were treated with a silane coupling agent in the same manner as in Example 3 except that the amount of dry silica added in Example 3 was 100 g. Crosslinked PMMA particles having fumed silica fixed on the surface were obtained. Next, paints were prepared using the materials, compounding ratios and methods shown below. Phenol resin intermediate 100 parts by weight PMMA particles 6 parts by weight Crystalline graphite having an average particle diameter of 2 μm 30 parts by weight Conductive carbon black 3 parts by weight Methanol 60 parts by weight Isopropyl alcohol 240 parts by weight

The above raw materials were dispersed in a sand mill in the same manner as in Example 1 to obtain a coating material having a viscosity of 45.0 mPa · s at room temperature. This coating material was applied to an aluminum cylindrical tube in the same manner as in Example 1 to obtain a developing sleeve of the present invention. The coating weight of paint on this developing sleeve is about 7,700 mg / m
^{2. The} surface roughness was Ra = 2.26 μm, and the volume resistivity was 0.92 Ω · cm. The image development durability test and evaluation of this developing sleeve were performed in the same manner as in Example 1.
The results were good as shown in the graphs 7-1 and 7-2 in FIG. 10 and Table 2 below.

Example 6 In place of the PMMA particles of Example 3, the number average particle diameter was D1.
= 5.95 μm PMMA particles, and the amount of the dry silica added in Example 3 was set to 180 g.
In the same manner as in the above, crosslinked PMMA particles having dry silica treated with a silane coupling agent fixed to the surface were obtained. Next, paints were prepared using the materials, compounding ratios and methods shown below. Phenol resin intermediate 100 parts by weight PMMA particles 15 parts by weight Crystalline graphite having an average particle size of 2 μm 30 parts by weight Conductive carbon black 3 parts by weight Methanol 60 parts by weight Isopropyl alcohol 240 parts by weight

The above raw materials were dispersed in a sand mill in the same manner as in Example 1 to obtain a paint having a viscosity of 52.5 mPa · s at room temperature. This coating material was applied to an aluminum cylindrical tube in the same manner as in Example 1 to obtain a developing sleeve of the present invention. The coating weight of paint on this developing sleeve is about 4,800 mg / m
^{2. The} surface roughness was Ra = 1.99 μm, and the volume resistivity was 1.03 Ω · cm. The image development durability test and evaluation of this developing sleeve were performed in the same manner as in Example 1. The results were good as shown in graphs 8-1 and 8-2 in FIG. 10 and Table 2 below.

Comparative Example 3 In place of the PMMA particles of Example 3, the number average particle diameter was D1.
= 0.2 μm spherical PMMA particles and treated with a silane coupling agent to give a BET specific surface area of 20
Dry silica was fixed to the surface of the crosslinked PMMA particles in the same manner as in Example 3 except that 300 g of 0 m ² / g dry silica was used. Next, paints were prepared using the materials, compounding ratios and methods shown below. Phenol resin intermediate 100 parts by weight PMMA particles 30 parts by weight Crystalline graphite having an average particle diameter of 2 μm 30 parts by weight Conductive carbon black 3 parts by weight Methanol 60 parts by weight isopropyl alcohol 270 parts by weight

The above raw materials were dispersed in a sand mill in the same manner as in Example 1, to obtain a coating material having a viscosity of 60.0 mPa · s at room temperature. This coating material was applied to an aluminum cylindrical tube in the same manner as in Example 1 to obtain a developing sleeve of the present invention. The coating weight of paint on this developing sleeve is about 5,700 mg / m
² , and the surface roughness was as small as Ra = 0.75 μm. The volume resistance value was 2.11 Ω · cm. Using this developing sleeve, a subject durability test and evaluation were performed in the same manner as in Example 1. The result is shown in graph 9 in FIG.
As shown in Table 2 below, good image densities could not be obtained. The coating resin layer was brittle and the developing sleeve was greatly scraped. Also, the underlying aluminum was exposed at both ends of the developing sleeve. Regarding the surface roughness at room temperature and normal humidity, the initial value was Ra = 0.75 μm,
After the durability test, Ra was reduced to 0.45 μm.

Comparative Example 4 Instead of the PMMA particles of Example 3, the number average particle diameter was D1.
= 38.2 μm spherical PMMA particles, treated with a silane coupling agent and having a BET specific surface area of 1
Dry silica was fixed to the surface of the crosslinked PMMA particles in the same manner as in Example 3 except that 80 g of 30 m ² / g dry silica was used. Next, paints were prepared using the materials, compounding ratios and methods shown below. Phenol resin intermediate 100 parts by weight PMMA particles 5 parts by weight Crystalline graphite having an average particle diameter of 2 μm 30 parts by weight Conductive carbon black 3 parts by weight Methanol 60 parts by weight 220 parts by weight isopropyl alcohol

The above raw materials were dispersed in a sand mill in the same manner as in Example 1 to obtain a paint having a viscosity of 45.0 mPa · s at room temperature. This coating material was applied to an aluminum cylindrical tube in the same manner as in Example 1 to obtain a developing sleeve of the present invention. The coating weight of paint on this developing sleeve is about 5,400 mg / m
^{2. The} surface roughness was Ra = 2.78 μm, which was rather large. Further, the volume resistance value was 0.91 Ω · cm. The image development durability test and evaluation of this developing sleeve were performed in the same manner as in Example 1. The result is shown in graph 10 in FIG.
As shown in Table 2 below, the image density showed a rise, and was a lower value overall. Further, under a high-temperature and high-humidity environment, white spots on a solid black image, which are considered to be caused by leakage, occurred.

Table 2

Example 7 Spherical nylon resin particles having a number average particle diameter D1 = 8.35 μm were prepared. Using 200 g of silica having a specific surface area of 130 m ² / g by BET treated with a silane coupling agent with respect to 10 kg of the nylon particles,
It was fixed to the surface of the nylon particles in the same manner as in Example 1. When confirmed by FE-SEM, the surface of the particles was sufficiently covered with silica. Next, a coating material was prepared by the following materials, compounding ratios and methods. Phenol resin intermediate 100 parts by weight Nylon particles 14 parts by weight Crystalline graphite having an average particle diameter of 2 μm 30 parts by weight Methanol 60 parts by weight Isopropyl alcohol 230 parts by weight

The above raw materials were dispersed in a sand mill in the same manner as in Example 1 to obtain a paint having a viscosity of 52.5 mPa · s at room temperature. This coating material was applied to an aluminum cylindrical tube in the same manner as in Example 1 to obtain a developing sleeve of the present invention. The coating weight of paint on this developing sleeve is about 5,400 mg / m
^{2. The} surface roughness was Ra = 2.18 μm, and the volume resistivity was 15.2 Ω · cm. The image development durability test and evaluation of this developing sleeve were performed in the same manner as in Example 1.
The results were good as shown in the graphs 11-1 and 11-2 in FIG. 11 and Table 3 below.

Comparative Example 5 A coating material was prepared in the same manner as in Example 7, except that the nylon resin particles were used without any treatment with silica. The viscosity at room temperature of this paint is 50.0 mP
a · s. This coating material was applied to an aluminum cylindrical tube in the same manner as in Example 1 to obtain a developing sleeve of the present invention. The coating weight of paint on this developing sleeve is about 5,
The surface roughness was 300 mg / m ² , the Ra was 2.15 μm, and the volume resistivity was 16.1 Ω · cm. The image development durability test and evaluation of this developing sleeve were performed in the same manner as in Example 1. Under a normal temperature and normal humidity environment, a good image was obtained as in Example 7, but under a high temperature and high humidity environment, as the image output durability test progressed, the initial image density at the time of re-image after a pause was reduced. , A phenomenon that the concentration rises slowly occurred. In a low-temperature and low-humidity environment, the ghost deteriorated as the image output durability test progressed. The results are shown in graph 12 in FIG.
-1, 12-2 and Table 3 below.

Reference Example A Spherical nylon resin particles having a number average particle diameter D1 = 6.74 μm were prepared. Using 300 g of titanium oxide having a specific surface area of 100 m ² / g by BET treated with a silane coupling agent per 10 kg of nylon particles, the titanium oxide was fixed to the surface of the nylon particles in the same manner as in Example 1.
When confirmed by FE-SEM, the surface of the particles was sufficiently covered with titanium oxide. Next, the materials shown below,
A paint was prepared according to the mixing ratio and method. Phenol resin intermediate 100 parts by weight Nylon particles 14 parts by weight Molybdenum disulfide with an average particle size of 1.5 μm 20 parts by weight Conductive carbon black 15 parts by weight Methanol 60 parts by weight Isopropyl alcohol 240 parts by weight

The above raw materials were dispersed in a sand mill in the same manner as in Example 1 to obtain a paint having a viscosity of 37.5 mPa · s at room temperature. This coating material was applied to an aluminum cylindrical tube in the same manner as in Example 1 to obtain a developing sleeve of the present invention. The coating weight of the coating on the developing sleeve is about 5,100.
mg / m ² , the surface roughness was Ra = 1.85 μm, and the volume resistivity was 3.23 Ω · cm. The image development durability test and evaluation of this developing sleeve were performed in the same manner as in Example 1. The results are shown in graphs 13-1 and 13- in FIG.
2 and as shown in Table 3 below.

Example 9 Spherical PMMA particles having a number average particle diameter D1 = 9.82 μm were prepared. B treated with a silane coupling agent
Silica having a specific surface area of 130 m ² / g by ET,
Using 200 g per 10 kg of the PMMA particles, the particles were fixed to the surface of the PMMA particles in the same manner as in Example 1. When confirmed by FE-SEM, the surface of the particles was sufficiently covered with silica. Next, paints were prepared using the materials, compounding ratios and methods shown below. Phenol resin intermediate 100 parts by weight PMMA particles 12 parts by weight Boron nitride powder having an average particle diameter of 3.0 μm 30 parts by weight Conductive carbon black 22 parts by weight Methanol 60 parts by weight isopropyl alcohol 270 parts by weight

The above raw materials were dispersed in a sand mill in the same manner as in Example 1 to obtain a paint having a viscosity of 40 mPa · s at room temperature. This coating material was applied to an aluminum cylindrical tube in the same manner as in Example 1 to obtain a developing sleeve of the present invention. The coating weight of paint on this developing sleeve is about 5,300 mg / m
^{2. The} surface roughness was Ra = 1.92 μm, and the volume resistivity was 2.23 Ω · cm. The image development durability test and evaluation of this developing sleeve were performed in the same manner as in Example 1. The results were good as shown in graphs 14-1 and 14-2 in FIG. 12 and Table 3 below.

Example 10 Instead of the PMMA particles of Example 1, the number average particle diameter D1 =
Using nylon particles of 11.8 μm, the specific surface area by BET treated with a silane coupling agent is 130 m ^2.
/ G of silica per 15 kg of the nylon particles.
0 g was added and fixed to the surface of the nylon particles in the same manner as in Example 1. Next, a coating material was prepared by the following materials, compounding ratios and methods. Phenol resin intermediate 100 parts by weight Nylon particles 11 parts by weight Crystalline graphite having an average particle diameter of 2 μm 32 parts by weight Conductive carbon black 3 parts by weight Methanol 60 parts by weight Isopropyl alcohol 240 parts by weight

The above raw materials were dispersed in a sand mill in the same manner as in Example 1 to obtain a paint having a viscosity of 62.5 mPa · s at room temperature. An aluminum cylindrical tube was spray-coated with this paint in the same manner as in Example 1 to obtain a developing sleeve of the present invention. At this time, the outer diameter of the aluminum cylindrical tube is 12m
m. The coating weight of the coating on the developing sleeve was about 5,100 mg / m ² , and the surface roughness was Ra = 1.65.
The volume resistance of the OHP sheet described in Example 1 was 0.88 Ω · cm. Next, for this sleeve, Canon LBP Laser Shot A404GII
Was used to perform an image output durability test and evaluation. A404G
This developing sleeve was processed and attached to an EP-P cartridge for II. An image endurance test was performed on a total of 30,000 sheets while replenishing 100 g of toner every time 100 g of toner was consumed.

The toner used had the following materials and compounding ratios. Styrene-butyl acrylate-maleic acid-n-butyl half ester copolymer (Tg decreased by 4 ° C. from Example 1 to 58 ° C.) 100 parts by weight Magnetite 95 parts by weight Charge control agent 3 parts by weight Low molecular weight polypropylene 8 parts by weight Part Using these materials, a toner was prepared in the same manner as in Example 1, and the weight average particle diameter D4 was 6.69 μm, 4.0 μm.
The following particles were 15.2% by number, and particles having a particle size of 10.1 μm or more were 0.9% by weight. To 100 parts by weight of the classified product, 1.0 part by weight of hydrophobic colloidal silica was externally added and mixed to obtain a toner used in the present test.

The image endurance test was conducted in three environments as in Example 1. The result of the solid black image density change is shown in a graph 15-1 in FIG. 12, and the result of the density rise is shown in a graph 15-2 in the same figure. Table 3 below shows all the evaluation results. After the endurance test, the surface of the developing sleeve is FE-
Observation with an SEM revealed that the binder resin on a portion of the surface layer of the nylon particles was shaved, and a face appeared on the surface of the developing sleeve.
However, toner fusion to the surface of the developing sleeve was hardly observed.

[0082]

Comparative Example 6 A coating material was prepared in the same manner as in Example 10, except that nylon particles not treated with silica were used. This coating material was applied to a 12 mm outer mold aluminum cylindrical tube in the same manner as in Example 10 to obtain a developing sleeve of Comparative Example. The coating weight of the coating on the developing sleeve was about 5,100 mg / m ² , the surface roughness was Ra = 1.63 μm, and the volume resistance was 0.85 Ω · cm. An image endurance test was performed on this developing sleeve in the same manner as in Example 10. The results are shown in Table 3 below. The result of the solid black image density change is shown in a graph 16-1 in FIG. In particular, a decrease in image density was observed at both ends of the image. Regarding the surface roughness of the developing sleeve, the initial value was Ra = 1.63 μm under a normal temperature and normal humidity environment.
After the endurance, Ra = 1.45 μm, which was not so reduced, but when the surface of the developing sleeve was observed by FE-SEM, the exposed portion of the nylon particles was larger than that of Example 7,
It was observed that the fusion of the toner, which began to occur from the particle portion, began to spread, and this tendency was particularly large at both ends of the developing sleeve.

Comparative Example 7 A coating material was prepared in the same manner as in Comparative Example 2 except that the average particle size of the crystalline graphite was 10.1 μm, and the amount of addition was 70 parts by weight. This coating material was applied to an aluminum cylindrical tube having an outer diameter of 12 mm in the same manner as in Example 6 to obtain a developing sleeve of Comparative Example. The coating weight of the coating on the developing sleeve was about 5,100 mg / m ² , the surface roughness was Ra = 1.54 μm, and the volume resistance was 0.63Ω ·
cm. The image development durability test and evaluation of this developing sleeve were performed in the same manner as in Example 1. The results are shown in Table 3 below, and almost good images were obtained up to around 10,000 sheets. However, in each environment, the density of the solid black image gradually decreases after 10,000 sheets have passed (see the graph 17- in FIG. 13).
1), the surface roughness of the developing sleeve after endurance in a normal temperature and normal humidity environment was Ra = 0.87 μm.
(Initial value Ra = 1.54 μm). Further, in a high-temperature and high-humidity environment, a fading phenomenon (a phenomenon in which a high-density part and a low-density part appear in a solid image in a vertical band) occurs in the latter half of the image endurance test. It has become thin. When the surface of the developing sleeve after this test was observed by FE-SEM, considerable fusion of toner was recognized at both ends of the developing sleeve.

Comparative Example 8 An aluminum cylindrical tube having an outer diameter of 12 mm was subjected to sandblasting, and the surface was roughened so as to have a surface roughness Ra = 1.63 μm to obtain a developing sleeve of a comparative example. The image development durability test and evaluation of this developing sleeve were performed in the same manner as in Example 1. The results are shown in Table 3 below. In each environment, a decrease in the solid black image density occurred (see graph 18- in FIG. 13).
In addition, ghosts were poor in a low-temperature and low-humidity environment and in a high-temperature and high-humidity environment.

Example 11 In the same manner as in Example 3 except that the fine silica powder having a specific surface area of 130 m ² / g by BET was used instead of the fumed silica of Example 3, the fine alumina powder was fixed to the surface. PMMA particles were obtained. Next, paints were prepared using the materials, compounding ratios and methods shown below. Methyl methacrylate homopolymer 100 parts by weight PMMA particles 12 parts by weight Crystalline graphite having an average particle diameter of 2 μm 30 parts by weight Conductive carbon black 5 parts by weight Toluene 440 parts by weight

The methyl methacrylate homopolymer was previously dissolved in toluene, and graphite and carbon black were added and dispersed in a sand mill. PM above
MA particles were added and dispersion continued. The viscosity of the paint after the dispersion was 32.5 mPa · s at room temperature. Using this coating material, an aluminum cylindrical tube having an outer diameter of 16 mm was applied in the same manner as in Example 1 and dried at 150 ° C. for 20 minutes. The applied weight of the coating material was about 5,400 mg / m ² and the surface roughness Ra =
A 1.84 μm developing sleeve of the present invention was obtained. The volume resistance value of the OHP sheet described in Example 1 was 0.65.
Ω · cm. Example 1 of this developing sleeve
Using the same toner as in Example 1, an image-drawing durability test and evaluation were performed in the same manner as in Example 1. The result is shown in FIG.
The results were good as shown in the graphs 19-1 and 19-2 and Table 4 below.

Example 12 A styrene resin cross-linked by a cross-linking agent was pulverized by a jet mill and further classified by an elbow jet classifier, and 32% by number of particles having a number average particle diameter D1 = 10.5 μm and 6.35 μm or less were obtained. 0% by number of particles of 25 μm or more
Resin particles were obtained. To 10 kg of the resin particles, 200 g of alumina fine powder having a BET specific surface area of 130 m ² / g was externally added and mixed. Furthermore, by setting the clearance between the blade and the liner of the apparatus having a rotating blade and a fixed liner to 2 mm, while rotating the blade, passing the resin particles a plurality of times by a circulation mechanism, the alumina fine powder It was immobilized on the surface of styrene resin particles.

Next, a coating material was prepared by the following materials, compounding ratios and methods. Phenol resin intermediate 100 parts by weight Styrene resin particles 9 parts by weight Crystalline graphite having an average particle diameter of 2 μm 30 parts by weight Conductive carbon black 5 parts by weight Methanol 60 parts by weight Isopropyl alcohol 230 parts by weight The above-mentioned raw materials were the same as in Example 1. In a sand mill to obtain a coating material having a viscosity at room temperature of 47.5 mPa · s. This coating material was applied to an aluminum cylindrical tube having an outer diameter of 16 mm in the same manner as in Example 1, and then dried and cured at 130 ° C. for 20 minutes to obtain a developing sleeve of the present invention. The coating weight of the coating on the developing sleeve was about 5,100 mg / m ² , and the surface roughness was Ra = 2.21 μm. The volume resistance value of the OHP sheet described in Example 1 is 0.77Ω · c.
m. Using the same toner as that used in Example 1 for this developing sleeve, an image endurance test and evaluation were performed in the same manner as in Example 1. The results were good as shown in graphs 20-1 and 20-2 in FIG. 14 and Table 4 below.

Table 4

Comparative Example 9 A coating material was prepared in the same manner as in Example 12, except that the styrene resin particles were used as they were without being treated with alumina fine powder. The coating was applied to a cylindrical tube to produce a developing sleeve of a comparative example. The coating weight of paint on this developing sleeve is about 5,
The surface roughness was 100 mg / m ² , the surface roughness was Ra = 2.25 μm, and the volume resistivity was 0.79 Ω · cm. The same evaluation as in Example 1 was performed using the same toner as that used in Example 1 for this developing sleeve. The results are shown in Table 5 below. The results were good up to around 10,000 sheets in the image endurance test, but thereafter fading occurred and the solid black image density was reduced (see the graph in FIG. 14). 21-1). When the surface of the developing sleeve after the image endurance test was observed by FE-SEM, it was found that the styrene resin particles were exposed.
More than 2, the decrease in surface roughness was also slightly large.

Example 13 Spherical ethyl acrylate particles crosslinked with a crosslinking agent having a number average particle size of 9.53 μm were prepared. To 10 kg of the ethyl acrylate particles, 200 g of dry silica having a specific surface area of 200 m ² / g by BET was added, and the mixture was stirred at room temperature for 10 minutes with a Henschel mixer. Next, paints were prepared using the materials, compounding ratios and methods shown below. Methyl methacrylate-dimethylaminoethyl methacrylate (95: 5 mol%) copolymer 100 parts by weight 13 parts by weight of the above ethyl acrylate particles 30 parts by weight of crystalline graphite having an average particle size of 2 μm 30 parts by weight of carbon black 5 parts by weight of toluene 350 parts by weight

[0093] The above copolymer is dissolved in toluene in advance,
Sand mill with graphite and carbon black
And dispersed. Further, the above ethyl acrylate particles
The addition continued to disperse. The viscosity of the paint after dispersion is
It was 32.5 mPa · s. Example using this paint
In the same manner as in 1, to an aluminum cylindrical tube with an outer diameter of 16 mm
Apply and dry at 140 ° C for 20 minutes.
About 4,800mg / m^TwoAnd the surface roughness is Ra = 1.75μ
m was obtained. At this time, the embodiment
The volume resistance value of the OHP sheet described in 1 is 0.85Ω.
Cm. Example 1 of this developing sleeve
The same toner as used in Example 1 was used, and
An image endurance test and evaluation were performed. The result is shown in FIG.
As shown in the graphs 22-1 and 22-2 and Table 5 below.
It was good.

Example 14 1 kg of crosslinked PMMA particles having a number average particle size of 3.10 μm
Then, 30 g of dry silica treated with a silane coupling agent having a specific surface area of 300 m ² / g was added, and fixed on the PMMA particle surface at an ambient temperature of 90 ° C. using a 10-liter Henschel mixer. When confirmed by FE-SEM, the surface of the particles was covered with silica. Next, paints were prepared using the materials, compounding ratios and methods shown below. Phenol resin intermediate 100 parts by weight PMMA particles 20 parts by weight Crystalline graphite having an average particle diameter of 2 μm 25 parts by weight Conductive carbon black 3 parts by weight Methanol 60 parts by weight Isopropyl alcohol 240 parts by weight

The above raw materials were dispersed in a sand mill using glass beads as a medium by the following method. After diluting the methanol solution of the phenol resin intermediate with isopropyl alcohol, graphite and conductive carbon black are added and dispersed with a sand mill. Further, the above-mentioned PMMA particles were added and dispersed to prepare a paint. After the dispersion was completed, it was separated from the glass beads and the viscosity was measured at room temperature.
It was 62.5 mPa · s.

[0096] Use this paint to coat the developing sleeve.
Was. As the coating method, A3 size with outer diameter of 32mm
An aluminum cylindrical tube stands on a work stand and is used as a motor
Rotate more and lower the spray gun at a constant speed.
And dried and cured at 140 ° C for 30 minutes in a drying oven.
To obtain a developing sleeve having a resin coating layer having a uniform thickness.
Was. Paint weight after drying is about 9,300mg / m^Two
Met. The surface roughness of this developing sleeve is represented by Ra.
It was 1.05 μm. An OHP cylinder is attached to another cylindrical tube.
And apply it in the same way and use this OHP sheet
When the volume resistance was measured in the same manner as in Example 1,
1.03 Ω · cm.

The obtained developing sleeve was subjected to an image endurance test using a copying machine NP-6060 manufactured by Canon Inc. The developing sleeve was processed into a size that could be incorporated into a developing device for NP-6060, and was used by incorporating a magnet inside and a stainless steel flange at both ends. NP-
The toner was replenished every time a residual test (toner remaining amount warning) was made on the 6060 as usual, and an image endurance test was performed on 500,000 sheets. FIG. 2 is a schematic view showing the vicinity of the developing sleeve of NP-6060. 30,000 sheets continuously for one day, the environment at 23 ° C / 55% RH, 30 ° C / 80% RH, 15 ° C every two days
/ 10% RH.

Incidentally, in this image formation durability test, a toner having the following materials and compounding ratio was used. (Toner composition) 100 parts by weight of polyester resin 100 parts by weight of magnetite 3 parts by weight of charge control agent 4 parts by weight of low molecular weight polypropylene After mixing these materials using a Henschel mixer, kneading using a biaxial extruder. After cooling, the mixture was pulverized by a hammer mill and then pulverized by a jet mill. This was classified by an elbow jet classifier, and particles having a weight average particle size D4 of 6.86 μm and 4.0 μm or less were 1
6.5 number%, particles of 10.1 μm or more are 2.1% by weight
Was obtained. 1.3 parts by weight of hydrophobic colloidal silica was externally added to and mixed with 100 parts by weight of the classified product to obtain a toner used in this test.

The evaluation was the same as in Example 1, but in this example, (9) the abrasion resistance (abrasion amount) of the coating film was also evaluated. The evaluation method of this property is as follows. (9) Abrasion resistance (abrasion amount) of coating film The outer diameter of the developing sleeve before and after the image endurance test was measured by a laser length measuring machine, and the average value of the measured values before and after was obtained. The abrasion resistance of the coating film was confirmed by setting 1 to the shaving amount (μm).

[0100] The evaluation results are shown in Table 5 below. Also, solid black drawing
The result of the image density change is shown in a graph 23-1 in FIG.
The rise results are shown in graph 23-2 in FIG.
Show. The change in solid black image density is achieved through an image endurance test.
Good image density was obtained. Also for ghosts, fog, etc.
The surface roughness of the developing sleeve is also good.
In the normal temperature and normal humidity environment, the initial value is Ra = 1.05 μm.
On the other hand, after the endurance, Ra = 0.96 μm,
The value did not change much. Furthermore, the abrasion resistance of the coating film is also reduced.
The displacement was 4.8 μm.

Comparative Example 10 A coating was prepared in the same manner as in Example 14 except that PMMA particles not treated with fumed silica were used, and a developing sleeve of a comparative example was prepared using the coating. The coating weight of the coating on the developing sleeve is about 9,300 mg /
m ² , volume resistance value is 1.00Ω · cm, surface roughness is Ra
= 1.07 µm. The image development durability test and evaluation of this developing sleeve were performed in the same manner as in Example 14. The results are shown in graphs 24-1 and 24-2 in FIG. 15 and Table 5 below. A decrease in image density was observed in the latter half of the image endurance test. For the surface roughness of the developing sleeve, Ra =
The decrease was slightly large at 0.78 μm, and the abrasion resistance of the coating film was 8.9 μm, which was larger than that of Example 14.

Comparative Example 11 A coating material was prepared in the same manner as in Comparative Example 2 using the following materials and compounding ratios. Phenol resin intermediate 100 parts by weight Crystalline graphite having an average particle size of 7.0 μm 40 parts by weight Conductive carbon black 5 parts by weight Methanol 60 parts by weight Isopropyl alcohol 230 parts by weight The obtained paint was used in the same manner as in Example 14. Outer diameter 32m
m of an aluminum cylindrical tube to obtain a developing sleeve of a comparative example. Surface roughness Ra of this developing sleeve = 1.0
The adhesive weight was about 9,300 mg / m ² , and the volume resistivity was 0.92 Ω · cm.

[0103] About this sleeve, as in Example 14
An image durability test and evaluation were performed. The results are shown in Table 5 below.
Show. About the change of solid black image density during the image endurance test
Indicates the results of Comparative Example 10 as shown in the graph 25-1 in FIG.
The fluctuation of the concentration was larger than that of the case. Concentration rise
The results are shown in a graph 25-2 in FIG. About surface roughness
In the normal temperature and normal humidity environment, the initial value is Ra = 1.06 μm
On the other hand, after the endurance, Ra = 0.49 μm
Had declined. Regarding the abrasion resistance of the coating film,
2.9 μm.
I was starting to see.

Table 5

Example 15 1 kg of crosslinked PMMA particles having a number average particle size of 1.94 μm
Then, 40 g of alumina fine powder having a specific surface area of 200 m ² / g by BET treated with a silane coupling agent was added thereto, and fixed to the surface of PMMA particles in the same manner as in Example 14. Next, paints were prepared using the materials, compounding ratios and methods shown below. Homopolymer of methyl methacrylate 100 parts by weight PMMA particles 20 parts by weight Conductive carbon black 25 parts by weight Toluene 430 parts by weight

[0106] Homopolymer of methyl methacrylate
Dissolve in toluene and add conductive carbon black
And use glass beads as a medium in a sand mill.
Spread. Further, PMMA particles are added and dispersed to perform coating.
Is prepared. After dispersion, separate from glass beads
The viscosity was measured at 57.5 Pa · s.
Was.

Using this paint, an aluminum cylindrical tube having an outer diameter of 20 mm was applied in the same manner as in Example 14 to obtain a developing sleeve of the present invention. The coating weight of the coating on this developing sleeve was about 8,000 mg / m ² , and the surface roughness was Ra =
The volume resistivity was 0.96 μm and the volume resistivity was 0.99 Ω · cm. Next, with respect to this developing sleeve, an image output durability test and evaluation were performed using a copying machine GP-55 manufactured by Canon Inc. The developing sleeve was processed into a size that could be incorporated in a developing device for GP-55, and was used with a magnet inside and stainless steel flanges at both ends. The toner was replenished each time GP-55 was subjected to a residual test as usual, and a 200,000 sheet durability test was performed. 10,000 sheets continuously for one day, the environment is set to 23 ° C / 55% RH, 30 ° C / 8 every 2 days
The measurement was performed while changing 0% RH and 15 ° C./10% RH.

Incidentally, in this image formation durability test, a toner having the following materials and compounding ratio was used. Styrene butyl acrylate copolymer 100 parts by weight Magnetite 80 parts by weight Charge control agent 3 parts by weight Low molecular weight polypropylene 6 parts by weight After mixing these materials using a Henschel mixer, kneading using a biaxial extruder After cooling, the mixture was pulverized by a hammer mill and then pulverized by a jet mill. This was classified by an elbow jet classifier, and particles having a weight average particle diameter D4 of 8.85 μm and 4.0 μm or less were 1%.
0.5% by number, 1.2% by weight of particles of 12.7 μm or more
Was obtained. To 100 parts by weight of the classified product, 1.0 part by weight of hydrophobic colloidal silica was externally added and mixed to obtain a toner used in the present test.

Evaluation was made in the same manner as in Example 14. The results are shown in Table 6 below. The result of the solid black image density change is shown in a graph 26-1 in FIG. 16, and the result of the density rise is shown in a graph 26-2 in the same figure. As the change in the solid black image density, a good image density was obtained through the image endurance test. Also good for ghosts, fog, etc.
Regarding the surface roughness of the developing sleeve, the initial value was Ra = 0.96 μm under the normal temperature and normal humidity environment, whereas the value after the endurance was Ra = 0.87 μm, and the value did not change much. Furthermore, the abrasion resistance of the coating film was 5.4 μm.

Reference Example B A coating material was prepared in the same manner as in Example 12 using the following materials and compounding ratios. Homopolymer of methyl methacrylate 100 parts by weight PMMA particles of Example 14 20 parts by weight Conductive carbon black 25 parts by weight Boron nitride fine powder having an average particle size of 1.5 μm 8 parts by weight Toluene 460 parts by weight Further using this paint In the same manner as in Example 12, a developing sleeve of the present invention was produced. The coating weight of the coating on this developing sleeve was about 8,000 mg / m ² , and the surface roughness was Ra =
0.98 μm, and the volume resistance was 1.03 Ω · cm. The image development durability test and evaluation of this developing sleeve were performed in the same manner as in Example 14. The results are shown in Table 5 below. The result of the change in the solid black image density is shown in a graph 27-1 in FIG.
This is shown in 7-2. As the solid black image density change,
Good image density was obtained through the image endurance test.
The ghost, fog, etc. were also good, and the surface roughness of the developing sleeve was Ra = 0.98 μm in the normal temperature and normal humidity environment.
a = 0.90 μm, and the value did not change much.
Further, the abrasion resistance of the coating film was 4.3 μm.

Comparative Example 12 A developing sleeve of a comparative example was produced in the same manner as in Example 16 except that PMMA particles not treated with fumed silica were used. The cured coating of the developing sleeve had an adhesion weight of about 8,000 mg / m ² , a volume resistivity of 1.00 Ω · cm, and a surface roughness Ra of 0.95 μm. This developing sleeve was subjected to an image-drawing durability test and evaluation in the same manner as in Example 14, and the results shown in Table 5 below were obtained. The result of the solid black image density change is shown by a graph 28 in FIG.
-1 shows the result of the concentration rise in the graph 28- in FIG.
2 respectively. Regarding the change in the solid black image density, a decrease in the image density was observed in the latter half of the image output durability test. Regarding the surface roughness of the developing sleeve, the initial value was Ra = 0.95 μm under a normal temperature and normal humidity environment.
a = 0.78 μm, the decrease was a little large, and the abrasion resistance of the coating film was 7.9 μm, which was a large value as compared with Example 16 as the scraping amount.

Comparative Example 13 A coating material was prepared using the following materials and compounding ratios. Homopolymer of methyl methacrylate 100 parts by weight 45 parts by weight of crystalline graphite having an average particle diameter of 7.0 μm 5 parts by weight of conductive carbon black 390 parts by weight of toluene

[0113] Methyl methacrylate previously dissolved in toluene
Graphite and conductive carbon in homopolymer of rate
Add black and disperse the paint by sand mill.
Using aluminum aluminum having an outer diameter of 20 mm in the same manner as in Example 15.
The developing sleeve of the comparative example was obtained by coating the cylindrical sleeve. This
The surface roughness of the developing sleeve is Ra = 1.00 μm
The amount is about 8,000mg / m^Two, Volume resistance is 0.88Ω
Cm.

[0114] About this developing sleeve, Example 14
In the same manner, an image endurance test and evaluation were performed, and the results are shown in Table 5 below.
The result was obtained. The change in solid black image density during the image endurance test
As shown in a graph 29-1 in FIG.
Also showed large fluctuations in concentration. Also, the concentration rise
The results are shown in graph 29-2 in FIG. Developing sleeve table
Regarding the surface roughness, the initial value under the normal temperature and normal humidity environment is Ra =
1.00 μm, while Ra = 0.5 after durability.
It was reduced to 1 μm. (9) The wear resistance of the coating film is also reduced.
The amount is 4.3 μm, and both ends of the developing sleeve are
I was starting to see.

[0115]

[0116]

As described above, according to the present invention, there is provided a developer carrier having improved durability over the prior art and capable of obtaining a good image for a long time, and a developing device using the same. Can be provided. That is, according to the present invention, even in repeated image formation, a stable and appropriate charge is applied,
It is possible to obtain a high-quality image that is uniform, has no unevenness, and is free from image density reduction and ghost. Further, the image can be maintained for a long time by improving the abrasion resistance of the resin coating layer or reducing the toner adhesion. Further, a developer carrier having the above performance can be provided stably, simply, and at low cost.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating an example of a conventional developing device having no resin film formed thereon.

FIG. 2 is a cross-sectional view illustrating an example of the developing device of the present invention.

FIG. 3 is a sectional view showing another example of the developing device of the present invention.

FIG. 4 is a sectional view showing another example of the developing device of the present invention.

FIG. 5 is a schematic diagram of a cross section of the developer carrying member of the present invention.

FIG. 6 is a schematic view of a cross section when a surface of a resin coating layer is scraped.

FIG. 7 is a graph showing the results of an image endurance test of Examples 1 to 3.

FIG. 8 is a graph showing the results of an image endurance test of Comparative Examples 1-2 and 1-1.

FIG. 9 is a graph showing the results of an image endurance test of Example 4 and Comparative Example 2.

FIG. 10 is a graph showing the results of an image endurance test of Examples 5, 6 and Comparative Example 3.

FIG. 11 is a graph showing the results of an image endurance test of Example 7 and Comparative Examples 4 and 5.

FIG. 12 is a graph showing the results of an image output durability test of Examples 8 to 10.

FIG. 13 is a graph showing the results of an image endurance test of Comparative Examples 6 to 8.

FIG. 14 is a graph showing the results of an image endurance test of Examples 11, 12 and Comparative Example 9.

FIG. 15 is a graph showing the results of an image-drawing durability test of Examples 13 and 14 and Comparative Example 10.

FIG. 16 is a graph showing the results of an image endurance test of Examples 15, 16 and Comparative Example 11.

FIG. 17 is a graph showing the results of an image-drawing durability test of Comparative Examples 12 and 13.

[Explanation of symbols]

 1: Electrophotographic photosensitive drum 2: Regulator blade 3: Hopper 4: Magnetic toner 5: Magnet 6: Metal cylindrical tube 7: Resin coating layer 8: Developing sleeve 9: Power supply 10: Toner stirring blade 11: Elastic plate 12: Resin Coating layer 13: spherical particles 14: inorganic fine powder

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Mayoko Maruko 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Michiko Orihara 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Kenji Fujishima 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Takuya Toyooka 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) References JP-A-63-183471 (JP, A) JP-A-5-232795 (JP, A) JP-A-1-102485 (JP, A) JP-A-3-163575 (JP, A) Japanese Unexamined Patent Publication No. Hei 4-301663 (JP, A) Japanese Unexamined Patent Publication No. Sho 54-86349 (JP, A) Japanese Unexamined Patent Publication No. Sho 58-68758 (JP, A) Japanese Unexamined Patent Publication No. Sho 58-211769 (JP, A) JP, A) JP-A-5-35073 JP, A) JitsuHiraku Akira 61-143155 (JP, U) (58 ) investigated the field (Int.Cl. ^7, DB name) G03G 15/08 - 15/095

Claims (12)

(57) [Claims] 1. A developer carrying member for an electrophotographic developing apparatus, comprising: a conductive coating layer on a surface of a substrate;
Is at least a binder resin, the number average particle size is 0.3 to
It is formed of a resin material having a thickness of 30 μm and containing a conductive substance and resin particles having an inorganic fine powder adhered or fixed on the surface or near the surface, and the inorganic fine powder is made of SiO ₂ , SrTiO ₃ , CeO ₂ , C
rO, Al ₂ O ₃ , ZnO, MgO, Si ₃ N ₄ , SiC,
Group consisting of CaSO ₄ , BaSO ₄ and CaCO ₃
A developer carrier selected from the group consisting of: 2. The developer carrier according to claim 1, wherein said coating material further contains a lubricating fine powder. Wherein said resin particles are spherical claim 1 or 2
3. The developer carrier according to item 1. 4. A developer carrying member according to any one of claims 1 to 3 wherein the inorganic fine powder has been treated coupling agent. 5. The coating layer comprises at least a binder resin,
The number average particle size is 0.3 to 30 μm and the surface or
Trees to which inorganic fine powder has previously adhered or fixed on the surface and near the surface
A coating agent containing fat particles, a conductive substance, and a solvent.
A contract formed by applying to the substrate surface
The developer carrier according to claim 1. 6. A container accommodating at least a developer, a developer carrier for carrying and transporting the developer in the developer container and transporting the developer to a development area close to the latent image carrier, and a developer carrier adjacent to the developer carrier. Or a developer layer thickness regulating member for regulating the layer thickness of the developer on the developer carrier by pressure contact, wherein the developer carrier has a conductive coating layer on the substrate surface. and, the coating layer comprises at least a binder resin, and the resin particles in which the number average particle diameter of the inorganic fine powder is and and in the vicinity of the surface or surfaces and the surface 0.3~30μm are attached or fixed, conductive
And a coating agent containing an inorganic substance, and the inorganic fine powder is made of SiO ₂ , SrTiO ₃ , CeO ₂ ,
rO, Al ₂ O ₃ , ZnO, MgO, Si ₃ N ₄ , SiC,
Group consisting of CaSO ₄ , BaSO ₄ and CaCO ₃
A developing device selected from the group consisting of: 7. The developing device according to claim 6 , wherein said coating agent further contains a lubricating fine powder. 8. A developing device according to claim 6 or 7 wherein the resin particles are resin particles spherical. 9. The method according to claim 1, wherein the inorganic fine powder is treated with a coupling agent.
The developing device according to any one of claims 6 to 8, wherein
Place. 10. The coating layer is at least a binder resin
Having a number average particle size of 0.3 to 30 μm and a surface or
The inorganic fine powder adheres or adheres to the surface or near the surface in advance.
Containing resin particles, conductive material, and solvent
On the surface of the substrate.
The developing device according to claim 6. 11. developer carrying member, the substrate is a cylindrical tube, the interior cylindrical tube magnetic field generating means is disposed Monodea
An apparatus according to any one of claims 6 to 10 that. 12. The developing device according to any one of claims 6 to 11 wherein the developer is a one component magnetic developer.