JP2003107910A - Method for surface-treating developer carrier and developer carrier and developing device using the method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for surface-treating a developer carrier used for developing an electrostatic latent image formed on an electrostatic latent image carrier such as an electrophotographic photoreceptor or an electrostatic recording dielectric, thereby rendering the latent image visible, and to provide a developer carrier and developing device that use the surface treating method. SOLUTION: In the surface treating method for the developer carrier, the developer carrier is rotated while magnetic particles harder than the binding resin of a resin coat layer is held on the resin coat layer by a magnetization generating means disposed in the developer carrier, and thus the surface of the resin coat layer is treated by slide-frictional force between the surface of the resin coat layer and the magnetic particles.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic method, in which an electrostatic latent image formed on an electrostatic latent image holding member such as an electrophotographic photosensitive member or an electrostatic recording dielectric is developed and visualized. The present invention relates to a method of treating a surface of a developer carrier used in carrying out the method, a developer carrier using the surface treatment method, and a developing device.

[0002]

2. Description of the Related Art Conventionally, a large number of electrophotographic methods are known, but generally, a photoconductive material is used, and various means are used to electrically connect an electrostatic latent image holding member (photosensitive drum) to an electrical surface. After forming a latent image, the electrostatic latent image is developed with a developer (toner) to make it a visible image, and if necessary, the toner image is transferred to a transfer material such as paper, and then heat or pressure is applied. The toner image is fixed on the transfer material to obtain a copy.

The developing method in electrophotography is mainly divided into a one-component developing method and a two-component developing method. In recent years, a developing device using a one-component developing system is often used because it is necessary to reduce the size of a copying device in order to reduce the weight and size of an electrophotographic device.

Unlike the two-component developing method, the one-component developing method does not require carrier particles such as glass beads and iron powder.
The developing device itself can be made smaller and lighter. Furthermore, since the two-component developing system needs to keep the toner concentration in the developer constant, a device for detecting the toner concentration and supplying a required amount of toner is required. Therefore, also in this case, the developing device becomes large and heavy. The one-component developing method is preferable because such a device is not necessary and can be made small and light.

As a developing device using the one-component developing system, an electrostatic latent image is formed on the surface of a photosensitive drum as an electrostatic latent image holding member, friction between a developer carrying member (developing sleeve) and toner, and And / or a positive or negative electric charge is applied to the toner by friction with the developer layer thickness regulating member for regulating the toner coat amount on the developing sleeve, and the toner is thinly applied on the developing sleeve and developed on the photosensitive drum. It is known that the toner is conveyed to a developing area opposite to the sleeve, and toner is made to fly and adhere to the electrostatic latent image on the surface of the photosensitive drum in the developing area to develop the electrostatic latent image as a toner image. There is.
However, when such a one-component developing method is used, it is difficult to adjust the toner charge, and although various measures have been taken with the toner, the problems relating to the non-uniformity of the toner charge and the durability stability of the charge are not completely solved. Has not been resolved.

Particularly, while the developing sleeve is repeatedly rotated, the charge amount of the toner coated on the developing sleeve becomes too high due to the contact with the developing sleeve, and the toner is reflected by the surface of the developing sleeve. A so-called charge-up phenomenon, in which the toner attracts each other and becomes immobile on the surface of the developing sleeve and does not move from the developing sleeve to the latent image on the photosensitive drum, is likely to occur particularly in low humidity. When such a charge-up phenomenon occurs, the toner in the upper layer is less likely to be charged and the developing amount of the toner decreases,
Problems such as thin line images and low image density of solid images occur.

Further, the toner that is not properly charged due to charge-up becomes defective in regulation and flows out onto the sleeve,
A so-called blotch phenomenon, which causes uneven spots and waves, also occurs. Further, since the toner layer forming state of the image portion (toner consuming portion) and the non-image portion are different and the charging state is different, for example, the position where a solid image having a high image density is once developed is next to the developing sleeve. When the halftone image is developed at the developing position during the rotation of, the so-called sleeve ghost phenomenon in which a trace of a solid image appears on the image easily occurs.

Further, recently, in order to digitize the electrophotographic apparatus and further improve the image quality, the particle size and the particle size of the toner have been reduced. For example, in order to improve resolution and character sharpness and faithfully reproduce a latent image, it is general to use a toner having a weight average particle diameter of about 5 to 12 μm. Further, from the viewpoint of ecology and for the purpose of further reducing the weight and size of the apparatus, the transfer efficiency of the toner has been improved in order to reduce the waste toner. For example, a transfer efficiency improver having an average particle size of 0.1 to 3 μm and B
By containing the hydrophobic silica fine powder having an ET specific surface area of 50 to 300 m ² / g, the volume resistance of the toner is reduced,
There is known a method of improving transfer efficiency by forming a thin film layer of a transfer efficiency improver on a photosensitive drum, and further improving the transfer efficiency by sphericalizing the toner itself by a mechanical impact force. .

Further, the fixing temperature of toner tends to be lowered for the purpose of shortening the first copy time and saving power. Under such circumstances, the toner especially under low temperature and low humidity is more likely to electrostatically adhere to the developing sleeve because the amount of electric charge per unit mass increases, and the toner under high temperature and high humidity can be physically removed from the outside. Since it uses a material that has high power and is easily fluidized, the quality of the material is easily changed, and the sleeve is liable to be contaminated by the toner and the sleeve is easily fused.

As a method for solving such a phenomenon, Japanese Patent Laid-Open Nos. 02-105181 and 03-036573 are available.
No. 0, etc. proposes a method of using a developing sleeve in which a coating layer in which a conductive lubricant such as a solid lubricant and carbon is dispersed in a resin is provided on a metal substrate in a developing device. . It is recognized that by using this method, the above-mentioned phenomenon is significantly reduced. However, in this method, when a large amount of the above powder is added, it is good against charge-up and sleeve ghost, but the coating layer is easily scraped, and when the durability is promoted, the surface roughness is When the amount of addition is small, the charge becomes uneven.
The effect of the solid lubricant and conductive fine powder such as carbon is small, and there remains a problem that it is insufficient for charge-up and sleeve ghost.

In Japanese Unexamined Patent Publication (Kokai) No. 03-252679, the surface of a conductive coating layer in which a conductive fine powder such as a solid lubricant and carbon is dispersed in a resin is blasted or polished with abrasive grains having a constant particle size distribution. There is proposed a method of using the developed developing sleeve in a developing device. By using this method, the exposure rate of solid lubricant and conductive fine powder such as carbon on the surface of the coating layer increases, and although it is effective against charge-up and sleeve ghost, it can be used for a longer period of time. However, the problem of insufficient wear resistance and surface roughness uniformity remains.

JP-A-04-246673, JP-A-04-246674, JP-A-04-246675
Japanese Patent Laid-Open No. 04-246676 and the like propose a method of using a developing sleeve in which a surface of a conductive coating layer in which at least graphite is dispersed in a resin is polished in a developing device. Even in this method, the rate of graphite exposure on the surface of the coating layer is still large, but there is a problem that the wear resistance and the uniformity of the surface roughness are insufficient in the durability for a longer period of time. .

Further, in Japanese Unexamined Patent Publication No. 03-200986, a developing sleeve in which a conductive coating layer in which a conductive fine powder such as a solid lubricant and carbon and spherical particles are dispersed in a resin is provided on a metal substrate Is proposed. In this developing sleeve, the abrasion resistance of the coating layer is improved, the surface shape of the coating layer is uniform, and the change in surface roughness is small. Is uniformed, and the image quality such as sleeve ghost, image density, and streaks and unevenness such as solid images is further stabilized.

However, even this developing sleeve does not have perfect wear resistance, and during long-term durability, the coating layer is abraded, in which case the charging of the toner becomes unstable and causes image defects. . Also in this developing sleeve, the ratio of exposure of the solid lubricant and conductive fine powder such as carbon to the surface of the coating layer is insufficient, and the surface treatment method as described above promotes wear and detachment of spherical particles. Therefore, when the low temperature fixing toner as described above is used, sleeve contamination and sleeve fusion due to the toner may occur due to abrasion and drop-off of spherical particles, which also causes image defects. Cheap.

In Japanese Unexamined Patent Publication No. 08-240981, the spherical particles dispersed in the conductive coating layer are conductive spherical particles, and the wear resistance of the coating layer is further improved, whereby the surface of the coating layer is improved. There is proposed a developing sleeve having a surface layer that further stabilizes the shape of the toner, further improves the toner charging, and can suppress sleeve contamination and sleeve fusion due to the toner even when the coating layer is slightly worn.
However, even in this developing sleeve, the ratio of the exposure of the solid lubricant and the conductive fine powder such as carbon to the surface of the coating layer is insufficient.

On the other hand, Japanese Unexamined Patent Publication No. 09-325616 proposes a surface treatment method for polishing the surface of a conductive resin layer using a strip-shaped abrasive having abrasive particles adhered to the surface. In the conductive resin coating layer in which the conductive spherical particles having improved abrasion resistance are dispersed, the strip-shaped abrasive can polish only a part of the convex portion of the conductive resin coating layer surface, The rate of exposure of solid lubricant and conductive fine powder such as carbon to the uniform coating layer surface is insufficient.

Further, by increasing the polishing conditions of the above-mentioned strip-shaped abrasive, it is possible to improve the exposure ratio of the conductive fine powder to some extent even in the conductive resin coating layer in which the conductive spherical particles are dispersed. In such a method, the convex portion in which the conductive spherical particles are formed is scraped on the surface of the conductive coating layer, and as a result, it becomes difficult to obtain uniform chargeability of the toner for a long period of time, and further, the conductive property is further reduced. The difference in the amount of wear of the conductive coating layer and the amount of wear of the conductive spherical particles may cause a large change in the surface roughness of the coating layer during the initial period of durability and the latter period of durability. The amount may change, which may cause image deterioration. Further, when the small particle diameter toner having high transferability as described above is used, the influence of the change in the surface roughness of the coating layer on the toner coating amount is more likely to be remarkable, which also causes the image deterioration. easy.

[0018]

SUMMARY OF THE INVENTION It is an object of the present invention to prevent a toner charge-up phenomenon and blotch, and to carry a developer capable of giving an appropriate charge amount to a toner for a long period of time even under different environments. It is an object of the present invention to provide a body surface treatment method, a developer carrier and a developing device using the surface treatment method.

Further, the object of the present invention is to stably obtain a high quality image without causing problems such as image density reduction and fog over a long period of time even under different environments. Further, a method of treating a surface of a developer carrier that does not cause sleeve contamination and fusion of the sleeve with toner on the surface of the developer carrier and does not generate a defective image such as streaks and unevenness, and a developer carrier using the surface treatment method. And a developing device.

Further, the object of the present invention is to make the amount of toner coating on the developer carrier constant by reducing the change of the surface roughness of the developer carrier over a long period of time even under different environments. It is an object of the present invention to provide a surface treatment method for a developer carrier which can be controlled in amount, a developer carrier and a developing device using the surface treatment method.

[0021]

The above object can be achieved by the present invention described below. That is, the present invention provides a resin coating layer containing a binder resin, a solid lubricant and / or conductive fine powder, and particles for forming irregularities on the surface of a cylindrical substrate surface made of at least a non-magnetic material. In the method for surface treatment of a developer carrying member (developing sleeve), the surface of the coating layer is coated on the surface of the resin coating layer by a magnetism generating means arranged in the developer carrying body. A developer characterized in that the surface of the resin coating layer is treated by a rubbing force between the surface of the resin coating layer and the magnetic particles by supporting magnetic particles harder than the hardness and rotating the developer carrier. Provided is a surface treatment method for a carrier.

Further, according to the present invention, the irregularity-forming particles existing on the surface of the resin coating layer and in the vicinity thereof form irregularities on the surface of the resin coating layer without being worn and removed, and the solid lubricant and / or Alternatively, there is provided a method for surface-treating a developer carrier as described above, wherein the conductive fine powder is uniformly exposed on the surface of the resin coating layer. The present invention further provides the method for surface treatment of the developer carrying member, wherein the magnetism generating means is a magnet roll having a plurality of magnetic poles.

Further, according to the present invention, the surface of the resin coating layer is formed by disposing a magnetic particle regulating member on the developer carrying member.
There is provided a method of treating the surface of a developer carrying member, wherein the rubbing force with respect to the magnetic particles is strengthened for treatment. Further, the present invention is
The number average particle size (A) of the magnetic particles satisfies the relationship of the following expression (1) with the average interval Sm value (Sm ₁ ) of the irregularities on the surface of the resin coating layer formed before the surface treatment. A method for treating the surface of the developer carrier is provided. A / Sm ₁ ≦ 0.5 (1)

Furthermore, the present invention provides the film thickness of the surface of the resin coating layer.
Was polished to a thickness of 0.4 to 2.5 μm by the surface treatment.
Surface treatment of the developer carrier described above to be treated to be polished
Provide a way. Furthermore, the present invention provides the resin before the surface treatment.
Ra value of the arithmetic mean roughness of the coating layer surface (Ra ₁) And the surface treatment
The arithmetic mean roughness Ra value (R
a₂) Is processed so as to satisfy the relationship of the following formula (2).
The above method for treating the surface of a developer carrier is provided. 0.7 ≦ Ra₂/ Ra₁≦ 1.3 (2)

Further, the present invention is formed after the surface treatment.
The average spacing Sm value (Sm of irregularities on the surface of the resin coating layer₂)
Is 20 to 200 μm.
Provide a surface treatment method. Furthermore, the present invention provides the
Ra value of the arithmetic mean roughness of the surface of the resin coating layer (Ra ₂)But,
The surface of the developer carrier, which is 0.3 to 3.5 μm.
Provide a processing method.

The present invention further provides the above-mentioned method for treating a surface of a developer carrier, wherein the hardness of particles for forming irregularities on the surface of the resin coating layer is harder than that of the binder resin. Further, in the present invention, the number average particle diameter (A) of the magnetic particles is 5 to 60 μm.
A method for treating the surface of the developer-carrying member, wherein m is m. Furthermore, in the present invention, the true density of the magnetic particles is 2500 k
There is provided a method for treating the surface of the developer carrier as described above, wherein the surface treatment is at least g / m ³ . Further, in the present invention, the number average particle diameter of particles for forming irregularities on the surface of the resin coating layer is 2 to 30 μm.
And a method for treating the surface of the developer carrier as described above.

Further, in the present invention, the particles for forming irregularities on the surface of the resin coating layer are spherical, and the true density is 300.
There is provided a surface treatment method for the developer carrier, which is 0 kg / m ³ or less. Further, the present invention provides the above-mentioned method for treating a surface of a developer carrier, wherein particles for forming irregularities on the surface of the resin coating layer are conductive particles. Further, the present invention provides the method for surface-treating the developer carrier, wherein the resin coating layer has a volume resistance of 10 ^{-2 to} 10 ³ Ω · cm.

Further, according to the present invention, a resin coating containing a binder resin, a solid lubricant and / or conductive fine powder, and particles for forming irregularities on the surface of a cylindrical substrate made of at least a non-magnetic material. In the developer carrier having a layer,
On the surface of the coating layer, magnetic particles having a hardness higher than the hardness of the binder resin of the resin coating layer are carried on the surface of the resin coating layer by the magnetism generating means arranged in the developer bearing body to rotate the developer carrying body. By doing so, a developer carrying member is provided, wherein the surface of the resin coating layer is treated by the rubbing force between the surface of the resin coating layer and the magnetic particles.

Further, according to the present invention, the irregularity-forming particles present on the surface of the resin coating layer and in the vicinity thereof form irregularities on the surface of the resin coating layer without being worn and removed, and the solid lubricant and The above-mentioned developer carrying body in which the conductive fine powder is uniformly exposed on the surface of the resin coating layer is provided. Furthermore, the present invention provides the developer carrying member, wherein the magnetism generating means is a magnet roll having a plurality of magnetic poles. Further, the present invention provides the developer carrying body, wherein the surface of the resin coating layer is treated by arranging a magnetic particle regulating member on the developer carrying body so that the rubbing force with the magnetic particles is strengthened. I will provide a.

Further, according to the present invention, the number average particle diameter (A) of the magnetic particles is defined by the following formula (Sm ₁ ) which is an average interval Sm of irregularities on the surface of the resin coating layer formed before the surface treatment. 1)
There is provided the above-mentioned developer carrying member satisfying the relationship of. A / Sm ₁ ≦ 0.5 (1) Further, in the present invention, the film thickness of the surface of the resin coating layer is treated so as to be polished to a thickness of 0.4 to 2.5 μm by the surface treatment. To provide a developer carrier.

The present invention further provides the resin coating before the surface treatment.
Ra average surface roughness Ra value (Ra ₁) And after the surface treatment
Arithmetic mean roughness Ra value (Ra₂)
Is processed so as to satisfy the relationship of the following formula (2).
The above developer carrier is provided. 0.7 ≦ Ra₂/ Ra₁≦ 1.3 (2) Furthermore, the present invention provides the resin coating layer formed after the surface treatment.
Average spacing Sm value of surface irregularities (Sm₂) Is 20 to 2
There is provided the developer carrier as described above, which is 00 μm.

The present invention further provides the resin coating after the surface treatment.
Ra average surface roughness Ra value (Ra ₂) Is 0.3 to
There is provided the developer carrier as described above, which is 3.5 μm. Further
The present invention provides particles for forming irregularities on the surface of the resin coating layer.
The hardness of the developer is higher than that of the binder resin.
provide. Furthermore, the present invention provides the number average particle diameter of the magnetic particles.
(A) is the above-mentioned developer carrying member having a thickness of 5 to 60 μm.
provide. Furthermore, in the present invention, the true density of the magnetic particles is 25
00 kg / m³The above-mentioned developer carrier is provided.
It

Further, in the present invention, the number average particle diameter of the particles for forming irregularities on the surface of the resin coating layer is 2 to 30 μm.
The above developer carrier is Further, the present invention is
There is provided the above developer carrier, wherein particles for forming irregularities on the surface of the resin coating layer are spherical, and the true density is 3000 kg / m ³ or less. Furthermore, the present invention provides the above-mentioned developer carrying member, wherein the particles for forming irregularities on the surface of the resin coating layer are conductive particles. Further, the present invention provides the above developer carrier, wherein the resin coating layer has a volume resistance of 10 ^{-2 to} 10 ³ Ω · cm.

Further, according to the present invention, a developing container, a developer carrying member for carrying and carrying the developer contained in the developing container, and a developer carrying member are disposed in proximity to or in pressure contact with the developer carrying member. A developer layer thickness regulating member for forming a thin layer of the developer on the developer carrying member, the developer carrying member carries the developer to a developing region facing the electrostatic latent image holding member, In a developing device which conveys and develops an electrostatic latent image formed on the electrostatic latent image holding member with a developer to form a visible image, the developer carrying member is one of the developer carrying members. There is provided a developing device.

In the present invention, the surface of the developing sleeve is provided with the specific resin coating layer shown in the present invention, and the surface of the coating layer is formed on the surface of the resin coating layer by the magnetism generating means arranged in the developer carrier. By rotating magnetic particles having an average particle size of not more than the average unevenness Sm value on the surface of the coating layer and harder than the hardness of the binder resin and rotating the developer carrier, the surface of the resin coating layer and the magnetic property The surface of the resin coating layer is treated by a rubbing force with the particles to form irregularities on the surface of the coating layer and the irregularity-forming particles present on the surface of the coating layer without being worn or removed, and the coating layer By uniformly exposing the solid lubricant and / or the conductive fine powder on the surface, the charge imparting property to the toner is stabilized, the toner coat amount is also stabilized, and the development three-dimensional image is formed by repeated copying or durability. Since the resin coating layer on the surface is less likely to wear and the sleeve is less likely to be contaminated and fused by toner, durability is improved over a long period of time, image density is reduced, sleeve ghosts and fog are exacerbated, and image streaks and image unevenness occur. It is possible to provide difficult high-quality images for a long period of time.

[0036]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below with reference to preferred embodiments. First, the material constitution of the resin coating layer used in the present invention will be described. In the present invention, it is preferable to add unevenness-forming particles in the resin coating layer in order to make the surface roughness uniform and maintain an appropriate surface roughness.

In the present invention, the particles for forming irregularities on the coating layer preferably have a higher hardness than the binder resin constituting the coating layer. When the hardness of the particles for forming the unevenness is larger than the hardness of the binder resin forming the coating layer, the particles for forming the unevenness are scraped by the rubbing with the magnetic particles. In addition, the solid lubricant and / or the conductive fine powder is uniformly exposed on the surface of the coating layer to stabilize the charge imparting property to the toner,
Even when the resin coating layer is worn due to long-term durability, the surface roughness of the resin coating layer surface hardly changes between the initial stage of durability and the latter stage of durability.

When the hardness of the particles for forming the irregularities is smaller than the hardness of the binder resin constituting the resin coating layer, the surface of the coating layer and its vicinity during the surface treatment with the magnetic particles are used. The unevenness-forming particles present in the toner are abraded and fallen off, which deteriorates toner transportability and charge uniformity, and destabilizes the toner coating of the resin coating layer due to long-term durability. It is not preferable because the charging becomes non-uniform and it tends to cause poor image quality such as sleeve ghost, image density, and streaks / unevenness such as solid images.

The irregularity-forming particles used in the present invention are preferably spherical. Since the particles are spherical particles, an uneven surface having a uniform surface shape is obtained as compared with the irregular particles, so that the durability of the coating layer and the uniform chargeability to the toner are improved. By adding such spherical particles, while maintaining a uniform surface roughness on the resin coating layer surface in the developer carrier of the present invention, even when the resin coating layer surface is worn, the surface roughness of the resin coating layer The thickness of the toner on the developer carrier is less likely to change, so that the toner is evenly charged, the sleeve ghost is good, and lines and unevenness are less likely to occur. It is possible to exert the effect of making it difficult for the sleeve to be contaminated and fused by the toner for a long time.

The number average particle size of the irregularity-forming particles used in the present invention is 2 to 30 μm, preferably 3 to 20 μm. When the number average particle diameter of the unevenness forming particles is less than 2 μm, the effect of imparting uniform surface roughness to the surface of the resin coating layer is small, and the toner is charged up due to the abrasion of the resin coating layer, and the sleeve is contaminated and melted by the toner. Adhesion is likely to occur, which tends to cause deterioration of the image and reduction of the image density due to the sleeve ghost, which is not preferable.
When the number average particle diameter exceeds 30 μm, the surface roughness of the resin coating layer becomes too large, and the amount of toner conveyed increases, so that the toner coat on the surface of the developing sleeve becomes uneven and the toner is not charged. It becomes difficult to be performed uniformly. In addition, the protrusion of coarse particles causes white spots and black spots due to image streaks and bias leak. Furthermore, the mechanical strength of the conductive resin coating layer is reduced, which is not preferable.

As the shape of the irregularity-forming particles used in the present invention, spherical particles having a major axis / minor axis ratio of about 1.0 to 1.5, preferably a major axis / minor axis ratio of 1. 0-1.
2 particles, more preferably spherical particles are used. When the ratio of the major axis / minor axis of the spherical particles exceeds 1.5, the dispersibility of the irregularity-forming particles in the resin coating layer is reduced, and a large number of particles are added to obtain the desired surface roughness. Therefore, the surface shape of the conductive resin coating layer becomes non-uniform, which is not preferable in terms of uniform charging of the toner and strength of the resin coating layer.

The material of the irregularity-forming particles used in the present invention is harder than the hardness of the binder resin of the resin coating layer,
It is preferable that durability against abrasion and abrasion is excellent, for example, resin particles having high mechanical strength, particles obtained by subjecting these resin particles to conductive treatment, carbon-based particles, metal or cerium oxide, chromium oxide, aluminum oxide, Metal oxide particles such as oxides of silicon oxide, zirconium oxide and titanium oxide, nitrides such as boron nitride, aluminum nitride and titanium nitride, silicon carbide, titanium carbide, boron carbide, tungsten carbide, vanadium carbide and zirconium carbide. And a boride such as zirconium boride, titanium boride, silicon boride, or tungsten boride.

Among these, the resin particles are preferable in that spherical particles can be easily obtained by a suspension polymerization method, a dispersion polymerization method or the like, and a suitable surface roughness can be obtained with a small amount added to the resin coating layer. Specific examples of suitable resin particles in the present invention include acrylic resin particles such as polyacrylate and polymethacrylate, polyamide resin particles such as nylon, polyethylene resin, polyolefin resin particles such as polypropylene, and silicone resin. Examples thereof include spherical particles made of generally known resins such as particles, phenol resin particles, polyurethane resin particles, styrene resin particles, and benzoguanamine resin particles.

The resin particles used in the present invention may have inorganic fine powder adhered or fixed to the surface thereof. For example, by treating the surface of the spherical resin particles with an inorganic fine powder as described below, the dispersibility of the spherical particles in the resin coating layer is improved, the surface uniformity of the formed coating layer, the coating layer Stain resistance, chargeability to toner,
The wear resistance and the like of the coating layer can be improved.

The inorganic fine powder used at this time is S
iO ₂ , SrTiO ₃ , CeO ₂ , CrO, Al ₂ O ₃ , Z
oxides such as nO and MgO, nitrides such as Si ₃ N ₄ , S
Carbides such as iC, CaSO ₄ , BaSO ₄ , CaCO ₃
Examples thereof include sulfates and carbonates. These inorganic fine powders may be treated with a coupling agent. That is, in particular, the inorganic fine powder treated with the coupling agent can be preferably used for the purpose of improving the adhesion with the binder resin or for the purpose of imparting hydrophobicity to the particles.

Examples of the coupling agent used in this case include a silane coupling agent, a titanium coupling agent and a zircoaluminate coupling agent. More specifically, for example, as the silane coupling agent, hexamethyldisilazane, trimethylsilane,
Trimethylchlorosilane, trimethylethoxysilane,
Dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane , Triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane,
Diphenylethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,
3-diphenyltetramethyldisiloxane, dimethylpolysiloxane having 2 to 12 siloxane units per molecule, and each terminal unit having a hydroxyl group bonded to a silicon atom are included. Can be mentioned.

The true density of the irregularity-forming particles used in the present invention is 3000 kg / m ³ or less, preferably 2700 kg.
/ M ³ or less, more preferably 900 to 2500 kg / m ³
Is. That is, the true density of the irregularity-forming particles is 3000 kg /
When it exceeds m ³ , it is necessary to add a large amount of particles in order to impart an appropriate surface roughness, and the density difference with the binder resin is too large, so that the unevenness-forming particles are dispersed in the resin coating layer. Property becomes insufficient, it becomes difficult to impart uniform roughness to the surface of the coating layer, and it becomes difficult to impart uniform charging to the toner.

Further, the concavo-convex formation used in the present invention
The conductivity of the particles has a volume resistance value of 10 ⁶Ω · cm or less is preferable
Better than 10³-10^-6More preferred to be Ω · cm
Good The volume resistance value of the irregularity-forming particles is 10⁶Over Ω · cm
If the particles are worn, the effect of making the particles conductive, that is, wear
Therefore, the spherical particles exposed on the surface of the coating layer are used as nuclei
The effect of suppressing sleeve contamination and fusion due to
Hard to get.

As a method for obtaining the conductive spherical particles used in the present invention, the following method is preferable,
It is not necessarily limited to these. As a method for obtaining particularly preferred conductive spherical particles used in the present invention, for example, carbon-based and / or graphitized by firing resin-based spherical particles or mesocarbon microbeads to give a low concentration and good conductivity. A method of obtaining spherical carbon particles can be mentioned. Examples of the resin used for the resin-based spherical particles include phenol resin, naphthalene resin, furan resin, xylene resin, divinylbenzene polymer, styrene-divinylbenzene copolymer, and polyacrylonitrile. In addition, the mesocarbon microbeads can be usually produced by washing spherical crystals produced in the process of heating and firing the medium pitch with a large amount of a solvent such as tar, medium oil or quinoline.

As a more preferable method for obtaining conductive spherical particles, a mechano-capsule is formed on the surface of spherical particles such as phenol resin, naphthalene resin, furan resin, xylene resin, divinylbenzene polymer, styrene-divinylbenzene copolymer and polyacrylonitrile. Examples include a method in which the bulk mesophase pitch is coated by a chemical method, and the coated particles are heat-treated in an oxidizing atmosphere and then fired to carbonize and / or graphitize to obtain conductive spherical carbon particles.

In any of the conductive spherical carbon particles obtained by the above-mentioned method, the conductivity of the obtained spherical carbon particles can be controlled to some extent by changing the firing conditions. It is preferably used in the invention. Further, the spherical carbon particles obtained by the above method,
In some cases, the conductive spherical particles may be plated with a conductive metal and / or a metal oxide in such a range that the true density of the conductive spherical particles does not exceed 3000 kg / m ³ .

As another method of obtaining the conductive spherical particles used in the present invention, conductive particles having a particle size smaller than the particle diameter of the core particles made of spherical resin particles are mixed in an appropriate mixing ratio. By mechanically mixing the conductive fine particles evenly around the core particles by the action of Van der Waals force and electrostatic force, a local temperature rise caused by, for example, applying mechanical impact force A method of softening the surface of the core particle by the method to obtain conductive resin particles on the surface of the core particle to obtain a spherical resin particle that has been subjected to a conductive treatment.

It is preferable to use spherical resin particles made of an organic compound and having a low true density as the core particles. Examples of the resin include PMMA (polymethylmethacrylate), acrylic resin, polybutadiene resin, polystyrene resin. , Polyethylene, polypropylene, polybutadiene, or copolymers thereof, benzoguanamine resin, phenol resin, polyamide resin, nylon, fluorine resin, silicone resin, epoxy resin, polyester resin. As the conductive fine particles (small particles) used when forming a film on the surface of the core particles (mother particles), in order to uniformly provide the conductive fine particle coating, the particle size of the small particles is smaller than that of the mother particles. It is preferable to use one-eighth or less.

As still another method of obtaining the conductive spherical particles used in the present invention, the conductive spherical particles in which the conductive fine particles are dispersed by uniformly dispersing the conductive fine particles in the spherical resin particles are prepared. The method of obtaining is mentioned. As a method for uniformly dispersing the conductive fine particles in the spherical resin particles, for example, the binder resin and the conductive fine particles are kneaded to disperse the conductive fine particles, followed by cooling and solidification, and pulverization to a predetermined particle size. And to obtain conductive spherical particles by spheroidizing by mechanical and thermal treatments; or adding a polymerization initiator, conductive fine particles and other additives into a polymerizable monomer, and uniformly using a disperser. The dispersed monomer composition is suspended in an aqueous phase containing a dispersion stabilizer by a stirrer so as to have a predetermined particle size and polymerized to obtain spherical particles in which conductive particles are dispersed. There is a method.

Also in the conductive spherical particles in which the conductive fine particles obtained by these methods are dispersed, the conductive fine particles having a particle size smaller than that of the above core particles are mechanically mixed at an appropriate mixing ratio, After the conductive fine particles are uniformly attached to the periphery of the conductive spherical particles by the action of the Van der Waals force and the electrostatic force, for example, the local spherical temperature rise of the conductive spherical particles caused by the mechanical impact force is applied to the conductive spherical particles. The surface may be softened, and conductive fine particles may be formed on the surface to further increase the conductivity before use.

As described above, the unevenness-forming particles dispersed in the resin coating layer constituting the developer carrying member of the present invention optimize the surface roughness of the developing sleeve surface, and further make the surface shape uniform, thereby making the sleeve uniform. By suppressing the decrease of the surface roughness when the resin coating layer is worn, the decrease of the transfer force due to the durability is suppressed, and the charge-up prevention effect is achieved, while making the transfer force of the upper toner layer uniform. Also, the effect of preventing sleeve ghost and the effect of preventing sleeve contamination and fusion due to toner can be exhibited over a long period of durability. Of these, spherical carbon particles are particularly preferably used because the conductivity of the resin coating layer is not impaired and toner adhesion / fusion with particles as cores can be prevented.

The content of the irregularity-forming particles dispersed in the resin coating layer is preferably 2 to 120 parts by mass, more preferably 2 to 80 parts by mass with respect to 100 parts by mass of the binder resin. Gives good results. When the content of the unevenness-forming particles is less than 2 parts by mass, the effect of adding the unevenness-forming particles is small, and when it exceeds 120 parts by mass, the charging property of the toner may be too low.

Further, in the present invention, in order to further stabilize the chargeability of the toner in combination with the unevenness-forming particles in the resin coating layer, a generally known charge-imparting substance is added, if necessary. It is also possible to use. As the negatively chargeable control agent, for example, an organometallic complex and a chelate compound are effective, and examples thereof include a monoazo metal complex, an acetylacetone metal complex, a metal complex or a metal salt of an aromatic hydroxycarboxylic acid or an aromatic dicarboxylic acid. Can be mentioned.
Other examples include aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol. These may be used alone or in combination of two or more.

As the positive charge control agent, a modified product of nigrosine and a fatty acid metal salt or the like; a quaternary ammonium salt such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate or tetrabutylammonium tetrafluoroborate, And onium salts such as phosphonium salts which are analogs thereof and lake pigments thereof;
Triphenylmethane dyes and lake pigments thereof (as a laker, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanic acid, ferrocyanine compounds, etc.); higher fatty acids Metal salts of diorgano tin oxides such as dibutyl tin oxide, dioctyl tin oxide and dicyclohexyl tin oxide; and diorgano tin borate such as dibutyl tin borate, dioctyl tin borate and dicyclohexyl tin borate. These may be used alone or in combination of two or more.

In the present invention, any of them can be used, but as the charge-imparting substance used for the purpose of improving the chargeability of the negatively chargeable toner and suppressing the chargeability of the positively chargeable toner, a nitrogen-containing heterocyclic compound is used. Is preferably used. As the nitrogen-containing heterocyclic compound used in the present invention, imidazole, imidazoline, imidazolone, pyrazoline, pyrazole, pyrazolone, oxazoline, oxazole, oxazolone, thiazoline, thiazole, thiazolone, selenazoline, selenazole, selenazolone, oxadiazole, thiadiazole, Tetrazole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, benzoselenazole, pyrazine, pyrimidine, pyridazine, triazine, oxazine, thiazine, tetrazine, polyazain, pyridazine, pyrimidine, pyrazine, indole, isoindole, indazole, carbazole, quinoline , Pyridine, isoquinoline, cinnoline, quinazoline, quinaxaline, phthalazine, purine, pi Lumpur, triazole, include compounds having a nitrogen-containing heterocyclic group phenazine and the like.

In the present invention, an imidazole compound is particularly preferable because it promotes the effect of the interaction between the developer carrier and the toner used in the present invention. In particular, among the imidazole compounds, the following general formula (a) or (b) [In the formula, R ₁ and R ₂ represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and R ₁ and R ₂ may be the same or different. R ₃ and R ₄ have _{3 to 3} carbon atoms
0 represents a linear alkyl group, and R ₃ and R ₄ may be the same. ]

[0062] [In the formula, R ₅ and R ₆ represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and R ₅ and R ₆ may be the same. R ₇ represents a linear alkyl group having 3 to 30 carbon atoms. ] The imidazole compound represented by the above is more preferable from the viewpoints of rapid and uniform charging property of the toner and strength of the coating layer.

The reason is that the imidazole compound having the structure represented by the general formula (a) or (b) has a linear alkyl group having 3 to 30 carbon atoms as a substituent,
It is considered that this is because the dispersibility of the coating layer with respect to the resin is good, and the triboelectrification property with the toner having a dispersed state on the special surface used in the present invention is good. Further, the nitrogen-containing heterocyclic group constituting the nitrogen-containing heterocyclic compound,
It may be monocyclic, may be condensed with another group, and may be substituted.

When the nitrogen-containing heterocyclic group is substituted, examples of the substituent include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxyl group, an aryl group, a substituted amino group, a ureido group and a urethane group. Group, aryloxy group, sulfamoyl group, carbamoyl group,
Alkyl or aryl thio group, alkyl or aryl sulfonyl group, alkyl or aryl sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamido group, sulfonamide A group, a carboxyl group, a phosphoric acid amide group, a diacylamino group, an imide group or the like can be used. The above substituents may further have a substituent. As examples of the substituent, the substituents described above as the substituent of the nitrogen-containing heterocycle can be used.

The nitrogen-containing heterocyclic compound has a number average particle size of preferably 20 μm or less, more preferably 0.1 to 15 μm.
It is better to use m. When the number average particle diameter of the nitrogen-containing heterocyclic compound exceeds 20 μm, it is difficult to obtain a sufficient effect of improving charging performance due to poor dispersibility of the nitrogen-containing heterocyclic compound in the resin coating layer, which is not preferable.

The content of the nitrogen-containing heterocyclic compound dispersed in the resin coating layer is preferably 0.5 to 60 parts by mass, more preferably 1 part by mass with respect to 100 parts by mass of the binder resin.
A range of ˜50 parts by weight gives particularly favorable results. When the content of the nitrogen-containing heterocyclic compound is less than 0.5 parts by mass, the effect of adding the nitrogen-containing heterocyclic compound is small, and when it exceeds 60 parts by mass, it is difficult to control the volume resistance of the resin coating layer to be low. Therefore, the charge-up phenomenon is likely to occur, and it becomes difficult to obtain the abrasion resistance of the resin coating layer.

Further, in the present invention, it is preferable to contain a metal compound of benzylic acid as the charge imparting substance used for the purpose of suppressing the chargeability of the negatively chargeable toner and improving the chargeability of the positively chargeable toner, For example, by containing an aluminum compound of benzylic acid, the charge amount of the toner can be controlled within a preferable range, and thus it is preferably used.

The aluminum compound of benzylic acid which can be used in the present invention is represented by the following general formula (C):

[In the formula, R ₁ and R ₂ may be the same or different and each is a linear or branched alkyl group, alkenyl group, alkoxyl group, halogen atom, nitro group, cyano group, amino group. Represents a substituent selected from the group consisting of a group, a carboxyl group and a hydroxyl group, and m and n represent an integer of 0 to 5. ] The aluminum compound of the benzylic acid which has an unsubstituted group or a substituent shown by these is mentioned.

Further, the aluminum compound of benzylic acid is preferably an aluminum compound of benzylic acid represented by the following general formula (D).
It is not limited to the following general formula (D) as long as it is a complex and / or complex salt composed of ol and 1 mol of aluminum atom.

[0071]

[In the formula, R ₁ and R ₂ may be the same or different and each is a linear or branched alkyl group, alkenyl group, alkoxyl group, halogen atom, nitro group, cyano group, amino group. Represents a substituent selected from the group consisting of a group, a carboxyl group and a hydroxyl group, and m and n represent an integer of 0 to 5. X represents a monovalent cation, hydrogen, lithium, sodium, potassium, ammonium and alkylammonium. ]

As described above, by dispersing the aluminum compound of benzylic acid in the resin coating layer, it has the effect of suppressing the charge amount for negative toner having a high charge amount,
An appropriate amount of charge can be uniformly applied to the toner. As a result, it is possible to prevent a decrease in image density, sleeve ghost, fog, and the like, and also prevent blotches and the like due to charge-up.

The addition amount of the negative charge control agent used in the present invention as described above is 1 with respect to 100 parts by mass of the binder resin.
It is preferable to set to 100 mass parts. It is more preferably 2 to 50 parts by mass. If it is less than 1 part by mass, no improvement in charge imparting property is observed by addition, and if it exceeds 100 parts by mass, it is excessively dispersed in the binder resin and the coating strength is apt to be lowered.

Further, in the present invention, as one of the other charge-imparting substances used for the purpose of suppressing the chargeability of the negatively chargeable toner and improving the chargeability of the positively chargeable toner, there is disclosed in Japanese Patent Laid-Open No.
It is possible to use a resin coating layer containing a quaternary ammonium salt compound described in JP-A No. 0-326040, JP-A No. 11-052711, and JP-A No. 11-249414.

These methods use a quaternary ammonium salt compound conventionally known as a positive charge control agent for toner, that is, a quaternary ammonium salt compound which is itself positively charged with iron powder. As the binder resin, in particular, part or all of the binder resin has at least − in its molecular structure.
When the coating layer of the triboelectrification imparting member is formed by using one having any one of NH ₂ group, ═NH group, and —NH— bond, the quaternary ammonium salt compound is incorporated into the binder resin,
It has been found that the resin (resin layer) itself exhibits a strong negative charging property and exhibits a good charge imparting property to the positive charging toner.

Further, a proposal that a very good image can be obtained by using these methods as a triboelectric charging member in a developing device is disclosed in JP-A-10-326040 and JP-A-11-052711. Kaihei 11-24941
No. 4 publication. In this method, for example, silica, a fluororesin powder for imparting a positive chargeability to the toner,
The advantage compared with the system in which the negative charge control agent is added is that the quaternary ammonium salt compound can be dissolved in the solvent of the binder resin and can be uniformly present in the resin, so that the resin layer is formed. In this case, since the entire resin layer becomes a uniform negatively chargeable material and shows a good charge imparting property as compared with a silica-added system in which it is dispersed in a matrix, and further, it is not a powder-added system. The uniformity of the resin layer surface is further improved.

Further, in a developing device using a toner having a negative chargeability and a high chargeability, the quaternary ammonium salt compound known as a positive charge control agent for the toner,
That is, a quaternary ammonium salt compound, which is itself positively charged with iron powder, is used, and as a binder resin, in particular, a part or all of the binder resin has —NH in its molecular structure.
By forming the coating layer of the developer carrier using one having any of _two groups, = NH group, and -NH- bond, the charge-up of negatively chargeable toner having high chargeability, generation of blotch and development A method of effectively preventing the toner from firmly adhering to the surface of the agent carrier and adjusting the addition amount of the quaternary ammonium salt compound to charge the triboelectric charge amount of the negatively chargeable toner to a suitable level is a method. Have been found.

As the quaternary ammonium salt compound having the above-mentioned function, which is preferably used in the present invention, one having a positive charging property to iron powder is used. For example, the compound represented by the following general formula (e) is mentioned. [Wherein R ₁ , R ₂ , R ₃ , and R ₄ are each an alkyl group which may have a substituent, an aryl group which may have a substituent,
It represents an alkyl group, and R _{1 to} R ₄ may be the same or different. X ⁻ represents an anion of an acid. ]

Specific examples of the quaternary ammonium salt compound, which itself is positively charged with iron powder, which is preferably used in the present invention, include the following, but of course, The invention is not limited to these.

[0081]

[0082]

Fourth used in the present invention as shown above
The addition amount of the primary ammonium salt compound is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the binder resin.
It is more preferably 2 to 50 parts by mass. If the amount is less than 1 part by mass, the addition of charge cannot be improved by addition, and if the amount exceeds 100 parts by mass, the dispersion in the binder resin becomes poor and the coating strength is apt to decrease. In addition, since the positively-charged quaternary ammonium salt is present in excess with respect to the resin component, the effective effect of the present invention begins to decrease.

The binder resin used in the coating layer of the present invention is not particularly limited, but a part or all of the binder resin has at least -NH ₂ group, = NH group, or -NH-bond in its molecular structure. It is preferable to have any one of the above structures. The effect of the present invention can be easily exhibited by forming the coating layer using such a resin.

In the present invention, when the resin layer of the developer carrying member having the above-mentioned constitution is used, the clear reason why the developer itself becomes negative charge imparting property is not clear, but the present invention Used in, a quaternary ammonium salt compound which is itself positively charged with iron powder and -NH ₂
The quaternary ammonium salt is incorporated into the structure of the resin by forming the resin coating layer using the binder resin having at least one structure of the group, the ═NH group, and the —NH— bond. At that time, it is considered that the original structure of the quaternary ammonium salt having the positive polarity is lost, and the chargeability of the resin incorporating them becomes uniform and has sufficient negative chargeability.

Examples of the substance having a —NH ₂ group include R—N
The primary amine represented by H ₂ or a polyamine having the same, the primary amide represented by RCO-NH ₂ or the polyamide having them, etc. 2 amines or polyamines having them, (RCO) ₂ = second amide represented by NH or polyamides having them, etc., —NH
Examples of the substance having a -bond include polyurethanes having a -NHCOO- bond in addition to the above-mentioned polyamines, polyamides, etc., and one or more types of the above substances are contained, or they are industrially contained. The resin synthesized in 1. is preferably used.

Of these, from the viewpoint of versatility and the like, phenol resin, polyamide resin, urethane resin, etc. using ammonia as a catalyst are preferable. As a phenolic resin,
As a result of intensive studies by the present inventors, the use of a phenol resin in which a nitrogen-containing compound is used as a catalyst in the production process makes it easier for the quaternary ammonium salt compound to be incorporated into the structure of the phenol resin during heat curing. I understood it. Therefore, by using such a phenol resin as one of the materials forming the resin coating layer on the developer carrying member, a good developing device can be obtained.

Examples of the nitrogen-containing compound used as a catalyst in the process for producing a phenol resin include, for example, acidic catalysts such as ammonium sulfate, ammonium phosphate, ammonium sulfamate, ammonium carbonate, ammonium acetate, and ammonium maleate. Amino salts, and as a basic catalyst, ammonia, or dimethylamine, diethylamine, diisopropylamine, diisobutylamine, diamylamine, trimethylamine, triethylamine, tri-n-butylamine, triamylamine, dimethylbenzylamine, diethylbenzylamine, dimethylaniline. , Diethylaniline, n, n-di-n-butylaniline, n, n-diamylaniline, n, n-dit-amylaniline, n-methyl Tanolamine, n-ethylethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, diethylethanolamine, ethyldiethanolamine, n-butyldiethanolamine, di-n-butylethanolamine, triisopropanolamine, ethylenediamine, hexamethylenetetraamine, etc. Amino compounds, pyridine, α-picoline, β-picoline, γ-picoline, 2,4-lutidine,
Pyridine such as 2,6-lutidine and its derivatives, quinoline compounds, imidazole, 2-methylimidazole,
Nitrogen-containing heterocyclic compounds such as imidazole such as 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole and its derivatives, and the like. There is.

As the polyamide resin, for example,
Nylon 6,66,610,11,12,9,13, Q
Any of 2 nylon and the like, a copolymer of nylon having these as a main component, N-alkyl modified nylon, N-alkoxyl alkyl modified nylon and the like can be preferably used. Further, any resin modified with polyamide such as polyamide-modified phenol resin, or a resin containing a polyamide resin component such as an epoxy resin using a polyamide resin as a curing agent is suitable. Can be used for.

As the urethane resin, any resin containing a urethane bond can be preferably used. This urethane bond is obtained by a polymerization addition reaction of polyisocyanate and polyol. As the polyisocyanate which is the main raw material of this polyurethane resin, diphenylmethane-4,4′-diisocyanate (MD
I), isophorone diisocyanate (IPDI), polymethylene polyphenyl polyisocyanate, tolylene diisocyanate, hexamethylene diisocyanate,
1,5-naphthalene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, carbodiimide-modified diphenylmethane-4,4′-diisocyanate,
Trimethylhexamethylene diisocyanate, orthotoluidine diisocyanate, naphthylene diisocyanate, xylene diisocyanate, paraphenylene diisocyanate, lysine diisocyanate methyl ester,
Dimethyl diisocyanate or the like can be used.

As the polyol which is the main raw material of the polyurethane resin, polyethylene adipate ester,
Polyester polyols such as polybutylene adipate ester, polydiethylene glycol adipate ester, polyhexene adipate ester, and polycaprolactone ester, and polyether polyols such as polytetramethylene glycol and polypropylene glycol can be used.

As described above, the quaternary ammonium salt compound and the --NH ₂ group, ═NH group, or --NH-- bond are used in combination with the conductive spherical particles in the resin coating layer constituting the developer carrier of the present invention. By using a binder resin having at least one structure of, or modified by a group having those structures, the toner charge-up phenomenon and blotch are prevented, and the toner is adjusted to a suitable triboelectric charge level. It is possible to control, and even when the coating layer wears, sleeve contamination and sleeve fusion due to toner can be further suppressed.
The synergistic effect of further improving the developability can be exhibited.

In addition to the above, generally known resins can be used as the binder resin material of the resin coating layer. For example, styrene resin, vinyl resin, polyether sulfone resin, polycarbonate resin, polyphenylene oxide resin, fluororesin, fibrin resin, acrylic resin, epoxy resin, polyester resin, alkyd resin, melamine resin, urea resin, silicone A resin, a thermoplastic resin such as a polyimide resin, or a photocurable resin can be used. Of these, those having releasability such as silicone resin and fluororesin, and those having mechanically excellent properties such as polyether sulfone, polycarbonate, polyphenylene oxide, polyester, styrene resin and acrylic resin are more preferable.

However, when a quaternary ammonium salt compound is used as the charge imparting substance, --NH is used as described above.
It is preferable to use a binder resin having at least one structure of _two groups, = NH group, or -NH- bond, or modified by a group having these structures.
It is also possible to mix and use the above-mentioned general binder resin.

Further, it is preferable to disperse the solid lubricant in the resin coating layer constituting the developer carrying member of the present invention together with the irregularity-forming particles because the effect of the present invention is further promoted. Examples of the solid lubricant include substances such as crystalline graphite, molybdenum disulfide, boron nitride, mica, graphite fluoride, silver-niobium selenide, calcium chloride-graphite, talc and fatty acid metal salts such as zinc stearate. Among them, crystalline graphite is particularly preferably used since the conductivity of the conductive coating layer is not impaired when used in combination with the conductive spherical particles.

The number average particle size of this solid lubricant is preferably about 0.2 to 20 μm, more preferably 1 to 15 μm.
It is better to use m. When the number average particle size of the solid lubricant is less than 0.2 μm, it is difficult to obtain sufficient lubricity, which is not preferable, and when the number average particle size exceeds 20 μm, the influence on the surface roughness becomes large. Further, it is not preferable because the surface roughness is likely to change due to abrasion, and the surface of the resin coating layer becomes unstable, resulting in unstable toner coating on the sleeve and unstable charging of the toner.

When the solid lubricant is used in combination with the conductive spherical particles in the resin coating layer, the content of the solid lubricant is preferably 5 to 120 parts by mass, more preferably 100 parts by mass of the binder resin. Gives particularly preferable results in the range of 10 to 100 parts by mass. When the content of the solid lubricant exceeds 120 parts by mass, the film strength and the charge amount of the toner decrease, and when it is less than 5 parts by mass, 7 μm.
When the following small particle size toners are used for a long time, toner contamination tends to occur on the surface of the resin coating layer.

In the present invention, the volume resistance of the resin coating layer of the developer carrying member is preferably 10 ³ Ω · cm or less, more preferably 10 ⁻² to 10 ³ Ω · cm. When the volume resistance of the resin coating layer exceeds 10 ³ Ω · cm, toner charge-up is likely to occur, and sleeve ghost is likely to deteriorate and the density is likely to decrease. In the present invention, in order to adjust the volume resistance of the resin coating layer, other conductive fine powder may be dispersed and contained in the resin coating layer in combination with the above conductive spherical particles.

The electrically conductive fine powder has a number average particle diameter of preferably 1 μm or less, more preferably 0.01 to.
The thickness is 0.8 μm. When the number average particle diameter of the conductive fine powder to be dispersedly contained in the resin coating layer in combination with the conductive spherical particles exceeds 1 μm, it becomes difficult to control the volume resistance of the resin coating layer to a low level, resulting in a toner charge. The up phenomenon is likely to occur.

Examples of the conductive fine powder that can be used in the present invention include carbon black such as furnace black, lamp black, thermal black, acetylene black and channel black; titanium oxide, tin oxide, zinc oxide, molybdenum oxide. Metal oxides such as, potassium titanate, antimony oxide and indium oxide;
Metals such as aluminum, copper, silver and nickel; inorganic fillers such as graphite, conductive metal fibers and conductive carbon fibers.

When the conductive fine powder is dispersedly contained in the conductive coating layer in combination with the irregularity-forming particles, the content of the conductive fine powder of 1 μm or less is preferably 100 parts by mass of the binder resin. 40 parts by mass or less, more preferably 2 to 3
Use in a range of 5 parts by weight gives particularly favorable results. That is, when the content of the conductive fine powder exceeds 40 parts by mass, a decrease in coating strength and a decrease in charge amount of toner are often observed.

Next, the surface treatment method for the surface of the resin coating layer in the present invention will be described. As the surface treatment method of the developing sleeve used in the present invention, a one-component developing device or a two-component developing device including a magnet roll is used, and a specific magnetic material is used instead of the developer on the developing sleeve of the resin coating layer. By carrying the particles and rotating the developing sleeve, the magnetic particles are conveyed following the minute irregularities formed on the surface of the resin coating layer, and the magnetic particles are evenly rubbed on the surface of the resin coating layer. This will be possible. Of course, the surface treatment method of the developing sleeve used in the present invention is not limited to these, and the magnetic particles uniformly coat the surface of the resin coating layer while following the minute irregularities formed in the resin coating layer. Any form may be used as long as it is a device that is rubbed.

By using the surface treatment of the developing sleeve as described above, the unevenness-forming particles existing on the surface of the resin coating layer of the developing sleeve and in the vicinity thereof are not uneven and are not removed, and thus the unevenness is formed on the surface of the resin coating layer. The formed solid lubricant and / or conductive fine powder can be uniformly exposed on the surface of the resin coating layer.

FIG. 3 is a schematic view of an embodiment used in the surface treatment apparatus for the developing sleeve used in the present invention. In FIG. 3, a developing sleeve 308 for surface treatment carries magnetic particles 404 supplied by a hopper 403 as a magnetic particle container, rotates in the direction of arrow B, and conveys the magnetic particles 404 while developing sleeve 308. The resin coating layer 307 is rubbed. As shown in FIG. 3, in the developing sleeve 308, in order to magnetically attract and hold the magnetic particles 404 on the developing sleeve 308, a magnet as a magnetism generating means is inscribed in the magnet roll 405. Are arranged. In the present invention, as the magnetism generating means, an electromagnet may be used instead of the magnet roll. Further, this magnetism generating means preferably has a plurality of magnetic poles in order to uniformly and effectively rub the developing sleeve and the magnetic particles.

In FIG. 3, the developing sleeve 308 used in the surface treating method of the developing sleeve of the present invention is a solid lubricant and / or conductive fine powder coated on a non-magnetic metal cylindrical tube 306 as a base. And a resin coating layer 307 containing particles for forming irregularities on the surface. The hopper 403 is provided with a stirring blade 410 for stirring the magnetic particles 404 and rubbing the resin coating layer 307 uniformly. Reference numeral 12 in the drawing denotes a gap indicating that the developing sleeve 308 and the magnet roll 405 are in a non-contact state.

In the example of FIG. 3, in order to strengthen the rubbing force between the magnetic particles 404 and the developing sleeve 308, the magnetic regulating blade 402 as a magnetic particle regulating member is in non-contact with the surface of the developing sleeve 308. It is suspended from the hopper 403 so as to face 308. As a result, the magnetic force lines from the magnetic pole N1 serving as the regulation pole of the magnet roll 405 are concentrated on the regulation blade 402, so that the magnetic particles 40 conveyed as the developing sleeve 308 rotates.
4 is a developing sleeve 308 in the regulation blade 402.
Is compressed in the hopper 403 located on the upstream side in the rotation direction of the.

In this region, the magnetic particles are appropriately compressed, and at the same time, the exchange of the magnetic particles 404 being conveyed and entering and the magnetic particles 404 flowing out from the regulating blade 402 can be dynamically generated. , Magnetic particles 40
It is preferable to perform uniform rubbing of the surface of the conductive coating layer 307 by No. 4.

In order to control such a proper compression state of the magnetic particles and the exchange of the magnetic particles, the magnetic pole configuration of the magnet roll, the magnetic field strength of the N1 magnetic pole, and the magnetic pole N1 are controlled.
This can be done by adjusting the position of the regulating blade, the distance between the regulating blade and the developing sleeve, the shape and magnetic characteristics of the regulating blade, the particle size of the magnetic particles, the magnetic characteristics, and the like.

Generally, the gap between the regulation blade and the developing roller is preferably 50 to 700 μm, and 1
More preferably, it is from 00 to 600 μm. The gap is 5
When it is less than 0 μm, the magnetic particles are likely to be clogged between the regulation blade and the developing roller, and the magnetic particles are likely to be unevenly conveyed on the developing sleeve, so that the surface of the resin coating layer may not be uniformly treated. On the other hand, if the gap exceeds 700 μm, it is difficult to form a proper compressed state of the magnetic particles in the vicinity of the regulation blade portion, it is difficult to obtain a uniform surface treatment, and it takes a long time for the surface treatment, and further the magnetic particles are scattered. It is not preferable because it causes

Generally, it is preferable that the position of the regulating blade is arranged so that the N1 magnetic pole, which is the regulating pole of the magnet roll, is located on the downstream side in the rotation direction of the developing sleeve. Further, when the half-value width of the N1 magnetic pole, which is the restricting pole, is x degrees, the restricting blade is located at a position between the facing position of the maximum magnetic flux density of the N1 magnetic pole and x / 2 degrees on the downstream side in the rotation direction of the developing sleeve, that is, More preferably, it is arranged near the facing position of the N1 magnetic pole. When the position of the regulating blade is arranged upstream of the range, it becomes difficult for the magnetic particles to be compressed, uneven transport of the magnetic particles occurs, and the rubbing force of the magnetic particles weakens, so that the magnetic particles are electrically conductive. The uniform coating layer may not be able to be rubbed uniformly. On the contrary, even if the magnetic field is arranged on the downstream side of the above range, the similar phenomenon is likely to occur because the magnetic field between the N1 magnetic pole and the regulating blade is weak.

As the peak value of the magnetic flux density of the N1 magnetic pole,
It is preferably 400 mT or higher, more preferably 600 mT or higher. The peak value of the magnetic flux density of the N1 magnetic pole is 40
When it is less than 0 mT, the rubbing force between the magnetic particles and the resin coating layer of the developing sleeve is weak, and the degree of compression of the regulation particles in the vicinity of the regulation blade becomes unstable, making it difficult to perform uniform surface treatment. .

For the magnetic poles other than the N1 magnetic pole, magnetic particles are conveyed onto the developing sleeve to promote uniform sliding of the magnetic particles and the resin coating layer of the developing sleeve. For example, as shown in FIG. It is preferable that a plurality of magnetic particles are arranged in the above-mentioned container and the magnetic particles are conveyed so as to roll on the developing sleeve.

FIG. 4 is a schematic diagram showing the configuration of another embodiment of the apparatus using the developing sleeve surface treatment method of the present invention, and FIG. 5 further shows the apparatus using the developing sleeve surface treatment method of the present invention. It is a structure schematic diagram which shows other embodiment. When the surface treatment apparatus shown in FIG. 4 is used particularly when the magnetic particles to be carried are strongly magnetized, a repulsive magnetic field is formed by using the repulsive pole N3 on the upstream side of the N1 magnetic pole as shown in FIG. When is used as a regulation pole, the degree of compression of the magnetic particles is reduced, the replacement of the magnetic particles is improved, and uniform surface treatment of the resin coating layer 307 can be performed. In addition, the restriction blade of FIG. 4 includes a non-magnetic restriction blade 402 and a magnetic plate 402.
b is provided, and the position of the restriction blade 402 is similar to that of the surface treatment apparatus of FIG. 3, when the half-value width of the N1 magnetic pole that is the restriction pole is x degrees, from the maximum magnetic flux density opposing position of the N1 magnetic pole. , X / on the downstream side of the developing sleeve in the direction of rotation.
It is arranged between two times.

When the surface treatment apparatus shown in FIG. 5 is used especially when the magnetic particles to be carried are weakly magnetized, since the regulation blade 402 is provided with the magnetic plate 402b and the regulation auxiliary member 402c, A proper compressed state can be easily obtained, and uniform surface treatment of the resin coating layer 307 can be performed. As the magnetic particle regulating blade used in the present invention, a non-magnetic blade may be used instead of the magnetic regulating blade 302 shown in FIG.

In the surface treatment as shown in FIGS. 3 to 5, the magnet roll is fixed, but it may be rotated and used. Further, in the surface treatment as shown in FIGS. 3 to 5, the rotation speed of the developing sleeve may be set arbitrarily, but considering the length of processing time, scattering of magnetic particles and the like,
The peripheral speed of the developing sleeve is preferably about 0.5 to 15 m / s.

The other basic constitutions of the surface treatment apparatus of FIGS. 4 and 5 are the same as those of the surface treatment apparatus shown in FIG. 3, and those having the same reference numerals are basically the same members. Show.
3 to 4 are merely schematic illustrations of the surface treatment method of the present invention, and it goes without saying that there are various forms of the shape of the hopper 403, the presence or absence of the stirring blades 410, the arrangement of the magnetic poles, and the like. .

In the present invention, the number average particle diameter (A) of the magnetic particles used for surface treatment is the average spacing Sm value (S) of the irregularities on the surface of the resin coating layer formed before the surface treatment.
It is preferable that the relationship of m ₁ ) and the following formula (1) is satisfied. A / Sm ₁ ≦ 0.5 (1) By satisfying the above relation, the unevenness-forming particles existing on the surface of the resin coating layer and in the vicinity thereof are not uneven and are not removed, and thus the surface of the resin coating layer is uneven. After being formed, the solid lubricant and / or the conductive fine powder is uniformly exposed on the surface of the resin coating layer, and the surface treatment of the developing sleeve can be performed.

When A / Sm ₁ > 0.5, it becomes difficult for the magnetic particles to sufficiently rub against the concave portions having the irregularities formed on the surface of the resin coating layer, and only the convex portions are preferentially rubbed. Since it is easily rubbed, the solid lubricant and / or the conductive fine powder is less likely to be uniformly exposed on the surface of the resin coating layer, and a convex portion on the surface of the resin coating layer is formed. It is not preferable because the unevenness imparting particles are worn and fallen off.

Further, in the present invention, the number average particle diameter (A) of the magnetic particles used for surface treatment is preferably 5 to 60 μm, more preferably 7 to 30 μm. When the average particle diameter is less than 5 μm, the rubbing force between the surface of the resin coating layer and the magnetic particles is weakened, and the solid lubricant and / or conductive fine powder becomes difficult to be uniformly exposed on the surface of the resin coating layer. , Surface treatment takes a long time. On the other hand, when the average particle size exceeds 60 μm, the unevenness forming particles existing on the surface of the resin coating layer and in the vicinity thereof are easily worn and removed, which is not preferable.

The hardness of the magnetic particles used in the present invention is preferably higher than that of the binder resin forming the resin coating layer. If the hardness of the magnetic particles is not harder than that of the binder resin, it becomes difficult to polish the surface of the resin coating layer by rubbing the magnetic particles, and the solid lubricant and / or the conductive fine powder becomes the resin coating layer. It is difficult to evenly expose the surface.

The true density of the magnetic particles used in the present invention is preferably 2500 kg / m ³ or more, more preferably 3000 kg / m ³ or more. The true density of the magnetic particles is 2500 kg / m
^When it is less than ³ , it becomes difficult to polish the surface of the resin coating layer by rubbing with the magnetic particles, and it becomes difficult to uniformly expose the solid lubricant and / or the conductive fine powder to the surface of the resin coating layer.

Further, regarding the material of the magnetic particles used in the present invention, iron magnetized by being placed in a magnetic field,
A ferromagnetic metal such as cobalt or nickel, an alloy or compound such as magnetite, γ-Fe ₂ O ₃ , or ferrite, or a dispersion of these ferromagnetic metals, alloys or compounds in a resin can be used.

The strength of magnetization of the magnetic particles used in the present invention is 1000 × (10 ³ / 4π) ·
The magnetization strength (σ ₁₀₀₀ ) measured under a magnetic field of A / m is 40.
~220Am ² / kg, preferably 50~200Am ² /
When the magnetic characteristics of the magnetic particles are within the above range, the magnetic particles can maintain an appropriate compressed state in the vicinity of the regulating blade under the magnetic field of the magnetic field generating means included in the developing sleeve, and the magnetic particles It is also easy for dynamic replacement of. Further, the magnetic particles are uniformly transported from the regulating blade, so that the surface treatment of the resin coating layer is uniformly performed.

In the present invention, the film thickness of the resin coating layer polished before the surface treatment is preferably 0.4 to 2.5 μm. When the film thickness of the resin coating layer polished before the surface treatment is less than 0.4 μm, it becomes difficult to uniformly expose the solid lubricant and / or the conductive fine powder to the surface of the resin coating layer. On the other hand, when it exceeds 2.5 μm, the protrusions on the surface of the resin coating layer are excessively polished, resulting in poor toner transportability, and toner fusion is likely to occur due to durability starting from the polished protrusions. As a result, the chargeability of the toner becomes uneven.

The arithmetic mean roughness Ra value (Ra ₁ ) of the surface of the resin coating layer before the surface treatment and the arithmetic mean roughness Ra value (Ra ₂ ) of the surface of the resin coating layer after the surface treatment are represented by the following formulas. (2)
Is preferably processed so as to satisfy the relationship of 0.7 ≦ Ra ₂ / Ra ₁ ≦ 1.3 (2) When Ra ₂ / Ra ₁ is less than 0.7, the protrusions on the surface of the resin coating layer are excessively polished, resulting in poor toner transportability. When the convex portion is the polished portion, the toner fusion is likely to occur due to the durability due to the durability, and the chargeability of the toner becomes non-uniform, and when Ra ₂ / Ra ₁ exceeds 1.3, the resin coating layer surface The number of unevenness imparting particles in the toner is large, and the binder resin component and the solid lubricant are relatively too small, so that the toner on the developing sleeve tends to have low charge and become uneven.

The average spacing Sm value (Sm ₂ ) of the irregularities on the surface of the resin coating layer formed after the surface treatment is preferably 2
The thickness is 0 to 200 μm, more preferably 40 to 100 μm. When the Sm value (Sm ₂ ) is less than 20 μm, the toner conveyance amount becomes too large, and the toner is hard to be replaced on the surface of the resin coating layer, and the toner cannot be sufficiently charged. When the Sm value (Sm ₂ ) exceeds 200 μm, the toner conveyance amount is too small, and toner fusion on the surface of the resin coating layer is likely to occur.

The arithmetic mean roughness Ra value (Ra ₂ ) of the surface of the resin coating layer after the surface treatment is preferably 0.3 to 3.5.
μm, and more preferably 0.4 to 2.3 μm. Ra
When the value (Ra ₂ ) is less than 0.3 μm, the toner conveyance amount is too small, and toner fusion on the surface of the resin coating layer is likely to occur. Ra value (Ra ₂ ) is 3.5μ
When it exceeds m, the toner conveyance amount becomes too large and the toner cannot be sufficiently charged.

The layer thickness of the resin coating layer having the above structure is
The thickness is preferably 25 μm or less, more preferably 20 μm or less, and further preferably 5 to 20 μm in order to obtain a uniform layer thickness and uniform surface irregularities, but the layer thickness is not particularly limited.

In the present invention, a non-magnetic metal, an alloy thereof, or a compound thereof is preferably used as the substrate of the developer carrying member having the resin coating layer having the above-mentioned constitution, and particularly stainless steel and A cylindrical aluminum member is preferably used. The surface of these substrates may be treated by blasting, honing, sanding, cutting or the like so as to have a predetermined surface roughness.
It may be treated by electroless plating or the like. Further, the base body may be formed in the shape of a metal core such as stainless steel,
The surface of these substrates may be subjected to the surface treatment as described above.

Next, a developing device having the above-described developer carrying member of the present invention will be described. As a developing device, for example, a developing device as shown in FIGS. 1 and 2 is known. In FIG. 1, an electrostatic latent image holder that holds an electrostatic latent image formed by a known process, for example, an electrophotographic photosensitive drum 301 is rotated in the direction of arrow A. The developing sleeve 308 as a developer carrying member carries the developer 304 as the one-component magnetic toner contained in the developer container 303 and rotates in the direction of arrow B, whereby the developing sleeve 308 and the photosensitive drum 301 are rotated. The developer 304 is conveyed to the developing area D where and are opposed to each other. As shown in FIG. 1, the developing sleeve 308 has a resin coating layer 307 formed on a metal cylindrical tube 306 as a substrate, and the developer 304 is magnetically deposited on the developing sleeve 308. A magnetic roll 305 is arranged and fixed in order to attract and hold the magnetic field. The developing sleeve 308 and the magnet roll 305 are not in contact with each other.

Further, in the developer container 303, stirring blades 309 and 310 for stirring the developer 304 by rotating in the direction of the arrow C, and the developer 30 in the developer container 303.
A screw 311 for supplying 4 and a stirring wall 312 for adjusting the amount of the developer in the developer container 303 are provided. The developer 304 is formed between the magnetic toners and the developing sleeve 30.
8 by friction with the resin coating layer 307 on the photosensitive drum 3
A triboelectric charge is obtained that allows the electrostatic latent image on 01 to be developed.

In the example of FIG. 1, in order to regulate the layer thickness of the developer 304 conveyed to the developing area D, the magnetic regulation blade 302 made of a ferromagnetic metal as a developer layer thickness regulating member is
The developer container 303 hangs down from the surface of the developing sleeve 308 so as to face the developing sleeve 308 with a gap width of about 50 to 500 μm, and magnetic force lines from the N pole of the magnet roll 305 concentrate on the magnetic regulation blade 302. The developer 3 on the developing sleeve 308
04 thin layers are formed. In the present invention, a non-magnetic blade or an elastic blade as shown in FIG. 2 can be used instead of the magnetic regulation blade. The thickness of the thin layer of the developer 304 thus formed on the developing sleeve 308 is preferably thinner than the minimum gap between the developing sleeve 308 and the photosensitive drum 301 in the developing area D.

The developer carrying member of the present invention is particularly effective when incorporated in a developing device of the type in which an electrostatic latent image is developed by a thin layer of the developer as described above, that is, a non-contact type developing device. In the developing area D, the developer carrier of the present invention is also applied to a developing device in which the thickness of the developer layer is not less than the minimum gap between the developing sleeve 308 and the photosensitive drum 301, that is, a contact type developing device. can do. In order to avoid complication of the description, the non-contact type developing device as described above will be taken as an example in the following description.

A developing bias voltage is applied to the developing sleeve 308 by a developing bias power source 313 as a biasing means in order to fly the one-component developer 304 having magnetic toner carried on the developing sleeve 308. When a direct current voltage is used as the developing bias voltage, a voltage having a value between the potential of the image portion (the area where the developer 304 is attached and visualized) of the electrostatic latent image and the potential of the background portion is used as the developing sleeve. It is preferable to apply to 308.

In order to increase the density of the developed image or improve the gradation, an alternating bias voltage is applied to the developing sleeve 308 to form an oscillating electric field in which the direction is alternately reversed in the developing area D. May be. In this case, an alternating bias voltage in which a DC voltage component having an intermediate value between the potential of the developed image portion and the potential of the background portion is superimposed is applied to the developing sleeve 30.
8 is preferably applied. In the case of so-called normal development, in which toner is attached to the high potential part of an electrostatic latent image having a high potential part and a low potential part to make it visible, in the case of so-called normal development, toner charged to the opposite polarity to the polarity of the electrostatic latent image is used. To do. In the case of so-called reversal development, in which toner is attached to the low potential part of an electrostatic latent image having a high potential part and a low potential part to make it visible, a toner charged to the same polarity as the polarity of the electrostatic latent image is used. To do. High potential and low potential are expressions using absolute values. In any of these cases, the developer 304 is charged at least by friction with the developing sleeve 308.

FIG. 1 is a schematic illustration of the developing device of the present invention. The shape of the developer container 303,
It goes without saying that the presence or absence of the stirring blades 309 and 310 and the arrangement of the magnetic poles have various forms. Of course, these devices can also be used for development using a two-component developer containing toner and carrier.

Next, the developer (toner) used to obtain a visible image from the electrostatic latent image in the present invention will be described. The toner contained in the developer is roughly classified into a dry toner and a wet toner. However, since the wet toner has a large problem of solvent volatilization, the dry toner is currently the mainstream. The toner is a fine powder in which materials such as a binder resin, a release agent, a charge control agent and a coloring agent are melt-kneaded, and the melt is cooled and solidified and then pulverized, and then classified to have a uniform particle size distribution. Is.

The binder resin used in the toner is, for example, a homopolymer of styrene such as styrene, α-methylstyrene or p-chlorostyrene and a substitution product thereof; a styrene-propylene copolymer or a styrene-vinyltoluene copolymer. Polymer, 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 Coal, styrene-isoprene copolymer, styrene Styrene-based copolymers such as styrene-maleic acid copolymer and styrene-maleic acid ester copolymer; polymethyl methacrylate; polybutyl methacrylate; polyvinyl acetate; polyethylene; polypropylene; polyvinyl butyral; polyacrylic acid resin; rosin; A modified rosin, a terpene resin, a phenol resin, an aliphatic or alicyclic hydrocarbon resin, an aromatic petroleum resin, a paraffin wax, and a carnauba wax can be used alone or in combination.

When the toner is used as a color toner (non-magnetic toner), the toner may contain a pigment as a colorant. Examples of pigments include carbon black, nigrosine dye, lamp black, Sudan black SM, fast yellow G, benzidine.
Yellow, Pigment Yellow, India First
Orange, Irgadine Red, Paranitroaniline
Red, Toluidine Red, Carmine FB, Permanent Bordeaux FRR, Pigment Orange R, Resor Red 2G, Rake Red C, Rhodamine F
B, Rhodamine B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Pigment Blue, Brilliant Green B, Phthalocyanine Green, Oil Yellow GG, Pomelo First Yellow CG
G, Kayaset Y963, Kayaset YG, Pomelo Fast Orange RR, Oil Scarlet, Orazol Brown B, Pomelo First Scarlet C
G and oil pink OP can be mentioned, and it is possible to appropriately select and use from these.

When the toner is used as a magnetic toner, magnetic powder is contained in the toner. As such magnetic powder, a substance magnetized in a magnetic field is used. Examples of the magnetic powder include powders of ferromagnetic metals such as iron, cobalt, and nickel; alloys and compounds such as magnetite, hethamite, and ferrite. The content of these magnetic powders is 15 to 70 with respect to the toner mass.
It is preferably about mass%.

There are cases in which various releasing agents are added to the toner to be contained. Examples of such releasing agents include polyfluorinated ethylene, fluororesin, fluorocarbon oil, silicone oil,
Examples thereof include low molecular weight polyethylene, low molecular weight polypropylene and various waxes. Further, if necessary, various charge control agents may be added to facilitate positive or negative charging. In the present invention, the non-magnetic toner may be mixed with a carrier and used as a two-component developer, or may be mixed with a carrier and used as a non-magnetic one-component developer. Further, in the present invention, the magnetic toner can be used as a one-component developer.

The methods for measuring physical properties relating to the present invention will be described below. [Measuring method] (1) Measurement of average spacing Sm of irregularities and arithmetic average roughness Ra Based on the surface roughness of JIS B0601-1994, surf coder SE-3500 (manufactured by Kosaka Laboratory Ltd.), 3 points in the axial direction x Measured at 3 points in the circumferential direction = 9 points,
The average value was taken.

(2) Measurement of coating layer thickness Laser length measuring device (manufactured by KEYENCE: controller L
S-5500, sensor head LS5040T) was used to measure the outer diameter before and after the formation of the coating layer. From the measured values before and after that,
The average value of 30 points was taken as the film thickness (μm).

(3) Measurement of Volume Resistance of Coating Layer A resin coating layer having a thickness of 7 to 20 μm was formed on a PET sheet having a thickness of 100 μm, and the resin was applied to a resistivity meter Loresta AP or Hiresta IP (both manufactured by Mitsubishi Yuka). The volume resistance value was measured using a 4-terminal probe. The measurement environment is 20 to
It was set to 25 ° C. and 50 to 60% RH.

(4) Measurement of Volume Resistance of Concavo-Convex Forming Particles A granular sample was placed in a 40 mmφ aluminum ring and 2500
It was pressure-molded with N, and the volume resistance value was measured using a 4-terminal probe with a resistivity meter Loresta AP or Hiresta IP (both manufactured by Mitsubishi Yuka). The measurement environment is 20-25
C and 50 to 60% RH.

(5) Measurement of True Density of Concavo-Convex Forming Particles The true density of the spherical particles used in the present invention was measured using a dry densitometer Accupic 1330 (manufactured by Shimadzu Corporation).

(6) Measurement of number average particle size of irregularity-forming particles The number average particle size calculated from the number distribution was measured using a Coulter LS230 type particle size distribution meter (manufactured by Coulter) of a laser diffraction type particle size distribution meter. I asked.

(7) Ratio of major axis / minor axis of irregularity-forming particles Photographed at about 6000 times using an electron microscope, and the major axis and minor axis of the particles were measured on the photograph. This was measured for 100 samples, and the average value was defined as the major axis / minor axis ratio.

(8) Toner particle size measurement The weight average particle size was calculated using a Coulter counter, Multisizer II (manufactured by Coulter Co.), and the weight-based weight average diameter was calculated from the volume distribution.

(9) Measurement of number average particle size of magnetic particles 300 or more carrier particles having a particle size of 0.1 μm or more are randomly extracted by an optical microscope (100 to 5000 times),
The number average particle diameter is calculated by measuring the horizontal Feret diameter as a carrier particle diameter by an image processing analyzer Luzex3 manufactured by Nireco Corporation. From the number-based particle size distribution measured under these conditions, the cumulative proportion of the number average particle diameter of 1/2 times the diameter cumulative distribution or less is obtained, and the cumulative value of the 1/2 times diameter cumulative distribution or less is calculated.

(10) Measurement of Hardness of Binder Resin and Concavo-convex Forming Particles Used for Coating Layer and Magnetic Particles Used for Surface Treatment With a micro hardness meter MZT-4 manufactured by Akasi, a triangular pyramid indenter having a face angle with respect to the axis of 68 degrees. Is a universal hardness value HU measured by using the following formula. HU = K × F / (h2) ² [K: coefficient F: test load (mN) h2: maximum indentation depth (μm)]

In the sample prepared for measurement, with respect to the binder resin used for the coating layer, the coating layer was formed on the aluminum substrate so that the film thickness was 10 times or more the maximum indentation depth of the indenter. The surface is subjected to a polishing treatment.For unevenness forming particles and magnetic particles, the unevenness forming particles or magnetic particles are dispersed without any gap in the binder resin used for the coating layer, and the maximum indentation depth of the indenter on the aluminum substrate is obtained. The coating layer was formed so that the film thickness was 10 times or more, and the surface was subjected to polishing treatment. Further, the test load and the maximum indentation depth of the indenter are not affected by the surface roughness of the coating layer surface,
In addition, the range is preferably such that it is not affected by the base substrate, and in the present invention, the maximum indentation depth of the indenter is 1 to
The measurement was performed in the range of about 10 μm.

(11) Measurement of magnetic characteristics of magnetic particles The magnetic characteristics of the magnetic particles are measured using an oscillating magnetic field type automatic recording apparatus for magnetic characteristics BHV-30 manufactured by Riken Denshi Co., Ltd.
The magnetic characteristic value of the magnetic particle powder is determined by creating an external magnetic field of 1 kilo Oersted and determining the strength of magnetization at that time. The magnetic particles are prepared in a state of being packed in a cylindrical plastic container having a volume of about 0.07 cm ³ so as to be sufficiently dense.
In this state, the magnetization moment is measured, the actual volume when the sample is put in is measured, and the strength of the magnetization per unit volume is obtained from this.

[0154]

EXAMPLES Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the text, "%" and "part" mean
All are by weight unless otherwise noted.

<Production Example 1 of Surface Untreated Developer Sleeve> A coating material having the following composition for applying a resin coating layer on the surface of the developing sleeve was prepared. As the irregularity-forming particles, 100 parts of spherical phenol resin having a number average particle diameter of 5.6 μm was used with a Reika machine (automatic mortar, manufactured by Ishikawa Plant) to obtain coal-based bulk mesophase pitch powder 14 having a number average particle diameter of 2.1 μm.
Of the conductive spherical carbon particles obtained by graphitizing by uniformly coating the parts and subjecting them to heat stabilization treatment in an oxidizing atmosphere and then firing at 2,200 ° C. to obtain a number average particle size of 5 Spherical carbon particles B-1 having a true density of 1,500 μm, a true density of 1,500 kg / m ³ , a volume resistance of 7.5 × 10 ⁻² Ω · cm, and a major axis / minor axis ratio of 1.15 were obtained. The universal hardness value of the spherical carbon particles B-1 was larger than the hardness value of the coating layer binder resin.

[0156] ・ Resol type phenol resin (Containing 50% methanol) 500 parts ・ Carbon black 10 parts ・ Crystalline graphite (number average particle size 2.8 μm) 90 parts 25 parts of spherical carbon particles B-1 (number average particle diameter 5.1 μm) ・ Isopropanol 446 parts

The above materials were dispersed using a sand mill.
Carbon black and crystalline graphite (number average particle diameter of 2.8 μm) were added to a part of the resol type phenol resin (containing 50% of methanol), and the mixture was subjected to sand mill dispersion using glass beads as a medium. The remaining resol-type phenol resin (containing 50% of methanol) and spherical carbon particles B-1 (number average particle diameter 5.1 μm) were added thereto, and further sand mill dispersion was performed to obtain a coating material having a solid content of 35%.

This paint was sprayed to give an outer diameter of 24.5.
A resin coating layer having a thickness of about 12 to 13 μm is formed on the surface of a cylindrical aluminum base body (Ra = 0.35 μm) having a thickness of 12 mm, and the resin coating layer is dried and cured at 150 ° C. for 30 minutes with a hot air dryer, and then a predetermined flange Also, a magnet roll was attached, and a surface untreated developing sleeve C-1 was obtained. Table 2 shows the constitution and physical properties of the obtained resin coating layer.

<Preparation Example 2 of Surface Untreated Developing Sleeve> A developing sleeve was prepared in the same manner as in Preparation Example 1 of surface untreated developing sleeve, except that 15 parts of the imidazole compound represented by the following formula (A-1) was added to adjust the coating composition. A developing sleeve was produced in the same manner as in Production Example 1 and designated as surface untreated developing sleeve C-2. Table 2 shows the constitution and physical properties of the obtained resin coating layer.

[0160]

<Surface Untreated Developing Sleeve Production Example 3> In the surface untreated developing sleeve Production Example 1, the spherical carbon black shown in Table 1 was used in place of the spherical carbon particles B-1 having a number average particle diameter of 5.1 μm. A developing sleeve was prepared in the same manner as in Production Example 1 of surface untreated developing sleeve except that the coating material was adjusted by using the dispersed phenol resin particles to obtain a surface untreated developing sleeve C-3. Table 2 shows the constitution and physical properties of the obtained resin coating layer.

<Production Example 4 of Surface Untreated Developing Sleeve> In Production Example 1 of surface untreated developing sleeve, the spherical carbon particles B-1 having a number average particle diameter of 5.1 μm were replaced with the granular boron carbide shown in Table 1. A developing sleeve was produced in the same manner as in Production Example 1 of surface untreated developing sleeve except that the coating material was adjusted by using the particles B-3, to obtain a surface untreated developing sleeve C-4. Table 2 shows the constitution and physical properties of the obtained resin coating layer.

<Production Example 5 of Surface Untreated Development Sleeve> Development sleeve of Production Example 1 of surface untreated development sleeve, except that the coating material was prepared without using spherical carbon particles B-1 having a number average particle diameter of 5.1 μm. A developing sleeve was produced in the same manner as in Production Example 1 and designated as surface untreated developing sleeve D-1. Table 2 shows the constitution and physical properties of the obtained resin coating layer.

<Production Example 1 of surface-treated developing sleeve> The surface-untreated developing sleeve C-1 was subjected to surface treatment under the E-1 condition shown in Table 4 by using the surface treating apparatus shown in FIG. The developing sleeve is F-1. As magnetic particles,
Spherical ferrite powder A-1 having a number average particle size of 9.3 μm shown in Table 3 was used. The universal hardness value of the magnetic particles was larger than the hardness value of the coating layer binder resin. Tables 3 to 5 show the physical properties and structure of the magnetic particles, the surface treatment conditions, the surface roughness of the surface-treated developing sleeve, and the polished film thickness.

<Production Example 2 of surface-treated developing sleeve> In Production Example 1 of surface-treated developing sleeve, the surface treatment condition is E-
Surface treatment was performed in the same manner as in Surface Treatment Sleeve Manufacturing Example 1 except that the conditions were changed to two, and the surface treatment sleeve F
-2. Tables 3 to 5 show the physical properties and structure of the magnetic particles, the surface treatment conditions, the surface roughness of the surface-treated developing sleeve, and the polished film thickness.

<Production Example 3 of surface-treated developing sleeve> In Production Example 1 of surface-treated developing sleeve, the surface treatment condition is E-
The surface treatment was performed in the same manner as in Surface Treatment Sleeve Manufacturing Example 1 except that the conditions were changed to 3;
-3. Tables 3 to 5 show the physical properties and structure of the magnetic particles, the surface treatment conditions, the surface roughness of the surface-treated developing sleeve, and the polished film thickness.

<Production Example 4 of surface-treated developing sleeve> In Production Example 1 of surface-treated developing sleeve, the same surface treatment as in Production Example 1 of surface-treated sleeve except that the untreated surface developing sleeve is changed to C-2. Then, the surface-treated developing sleeve F-4 was obtained. Tables 3 to 5 show the physical properties and structure of the magnetic particles, the surface treatment conditions, the surface roughness of the surface-treated developing sleeve, and the polished film thickness.

<Production Example 5 of surface-treated developing sleeve> In Production Example 1 of surface-treated developing sleeve, the surface untreated developing sleeve was changed to C-2, and the surface treatment condition was changed to E-2 condition. The surface treatment was performed in the same manner as in Production Example 1 of treated sleeve to obtain a surface treated developing sleeve F-5. The physical properties and composition of the magnetic particles, the surface treatment conditions, the surface roughness of the surface-treated developing sleeve, and the polished film thickness are shown in Table 3 to Table 3, respectively.
5 shows.

<Production Example 6 of surface-treated developing sleeve> In Production Example 1 of surface-treated developing sleeve, the surface-undeveloped developing sleeve was changed to C-3, and the surface treatment condition was changed to E-2 condition. Surface treatment was performed in the same manner as in Processed Sleeve Production Example 1 to obtain a surface-treated developing sleeve F-6. The physical properties and composition of the magnetic particles, the surface treatment conditions, the surface roughness of the surface-treated developing sleeve, and the polished film thickness are shown in Table 3 to Table 3, respectively.
5 shows.

<Production Example 7 of surface-treated developing sleeve> In Production Example 1 of surface-treated developing sleeve, the surface-undeveloped developing sleeve was changed to C-4 and the surface-treatment condition was changed to E-2 condition. Surface treatment was performed in the same manner as in Processed Sleeve Production Example 1 to obtain a surface-treated developing sleeve F-7. The physical properties and composition of the magnetic particles, the surface treatment conditions, the surface roughness of the surface-treated developing sleeve, and the polished film thickness are shown in Table 3 to Table 3, respectively.
5 shows.

<Production Example 8 of surface-treated developing sleeve> In Production Example 1 of surface-treated developing sleeve, the surface treatment condition is E-
The surface treatment was performed in the same manner as in Surface Treatment Sleeve Manufacturing Example 1 except that the conditions were changed to 4;
It was set to -8. As magnetic particles, spherical ferrite powder A-2 shown in Table 3 having a number average particle size of 15.5 μm was used. The universal hardness value of the magnetic particles was larger than the hardness value of the coating layer binder resin. Tables 3 to 5 show the physical properties and structure of the magnetic particles, the surface treatment conditions, the surface roughness of the surface-treated developing sleeve, and the polished film thickness.

<Production Example 9 of surface-treated developing sleeve> In Production Example 1 of surface-treated developing sleeve, the surface treatment condition is E-
Surface treatment was performed in the same manner as in Surface Treatment Sleeve Manufacturing Example 1 except that the conditions were changed to 5
It was set to -9. As magnetic particles, spherical ferrite powder A-3 having a number average particle size of 21.4 μm shown in Table 3 was used. The universal hardness value of the magnetic particles was larger than the hardness value of the coating layer binder resin. Tables 3 to 5 show the physical properties and structure of the magnetic particles, the surface treatment conditions, the surface roughness of the surface-treated developing sleeve, and the polished film thickness.

<Production Example 10 of surface-treated developing sleeve> In Production Example 1 of surface-treated developing sleeve, the surface treatment condition is E.
The surface treatment was performed in the same manner as in Surface Treatment Sleeve Production Example 1 except that the conditions were changed to −6 to obtain a surface treatment developing sleeve F-10. As the magnetic particles, the spherical nickel fine particle-dispersed phenol resin particles A-4 having the number average particle diameter shown in Table 3 of 15.6 μm were used. The universal hardness value of the magnetic particles was slightly larger than the hardness value of the coating layer binder resin. Tables 3 to 5 show the physical properties and structure of the magnetic particles, the surface treatment conditions, the surface roughness of the surface-treated developing sleeve, and the polished film thickness.

<Production Example 11 of surface-treated developing sleeve> In Production Example 1 of surface-treated developing sleeve, the same surface treatment as in Production Example 1 of surface-treated sleeve except that the untreated surface developing sleeve is changed to D-1. Then, the surface-treated developing sleeve G-1 was obtained. Tables 3 to 5 show the physical properties and structure of the magnetic particles, the surface treatment conditions, the surface roughness of the surface-treated developing sleeve, and the polished film thickness.

<Production Example 12 of surface-treated developing sleeve> In Production Example 1 of surface-treated developing sleeve, the surface-undeveloped developing sleeve was changed to D-1 and the surface-treatment condition was changed to E-2 condition. Surface treatment was performed in the same manner as in Processed Sleeve Production Example 1 to obtain a surface-treated developing sleeve G-2. Table 3 shows the physical properties and composition of the magnetic particles, the surface treatment conditions, the surface roughness of the surface-treated developing sleeve, and the polished film thickness.
~ 5.

<Production Example 13 of surface-treated developing sleeve> In Production Example 1 of surface-treated developing sleeve, the surface-undeveloped developing sleeve was changed to D-1, and the surface treatment condition was changed to E-3 condition. Surface treatment was performed in the same manner as in Processed Sleeve Production Example 1 to obtain a surface-treated developing sleeve G-3. Table 3 shows the physical properties and composition of the magnetic particles, the surface treatment conditions, the surface roughness of the surface-treated developing sleeve, and the polished film thickness.
~ 5.

<Toner Production Example 1> Next, a magnetic negative toner as a one-component developer was produced. Styrene-acrylic resin 100 parts Magnetite 95 parts Negative charge control agent (chromic complex of salicylic acid) 2 parts Hydrocarbon wax 3 parts

The above materials were mixed by a Henschel mixer, and melt-kneaded and dispersed by a twin-screw extruder. After cooling the kneaded product, the mixture was finely pulverized by a pulverizer using a jet stream, and further classified by an air stream classifier, and the number ratio of particles having a weight average particle diameter of 6.8 μm and 4 μm or less was 12.9. %, A classified product having a distribution in which the weight ratio of particles of 10.1 μm or more was 4.6% was obtained. Next, the hydrophobic colloidal silica was added in an amount of 1.1 parts per 100 parts of the classified product.
External mixing was performed using a Henschel mixer to obtain a magnetic toner H-1 as a one-component developer.

<Embodiment 1> Surface-treated developing sleeve F-
1 and Toner H-1 were incorporated into a developing device as shown in FIG. 1 and evaluated for image formation. For image formation, a modified copier NP6350 manufactured by Canon was used, and a predetermined developing bias was applied to evaluate image formation. Images are generated at room temperature and low humidity (N / L) at 23 ° C. and 5% RH, and 30
25 degrees Celsius under high temperature and high humidity (H / H) environment of 80% RH
It went up to ten thousand sheets (250k). The evaluation results by the following evaluation methods are shown in Tables 6-8.

[Evaluation Method] (1) Image Density The density of a solid black image was measured by using a reflection densitometer RD918 (manufactured by Macbeth Co.), and the average value of 5 points was taken as the image density. (2) Fog and reversal fog The reflectance of a solid white image was measured, and the reflectance of an unused transfer paper was further measured (the worst value of the reflectance of a solid white image-the maximum value of the reflectance of an unused transfer paper. ) Is the fog density. The reflectance was measured by TC-6DS (manufactured by Tokyo Denshoku Co., Ltd.). However, when visually observing the measured values, 1.5 or less is a level that can hardly be visually confirmed, 2.0 to 3.0 is a level that can be confirmed by good observation, and if it exceeds 4.0, fogging is apparent at first glance. It is a level that can be confirmed.

(3) Toner charge amount on sleeve (Q / M)
And toner transport amount (M / S) The toner carried on the developing sleeve was sucked and collected by the metal cylindrical tube and the cylindrical filter, and at that time, the amount of charge Q accumulated in the condenser was collected through the metal cylindrical tube. The charge amount Q / M (mC / kg) per unit mass and the toner mass M / S (mg / cm ² ) per unit area are calculated from the toner mass M and the toner suction area S, and the toner charging The amount (Q / M) and the toner conveyance amount (M / S) were used.

(4) An image in which a ghost solid white and a solid black portion are adjacent to each other is developed at the image leading end portion (the first rotation of the sleeve rotation), and solid white marks and solid black marks appearing on the halftone image of the second and subsequent laps. The shade difference was visually observed, and the evaluation results were shown by the following indexes. ◯: No difference in shade is seen. ○ △: A slight difference in light and shade can be visually confirmed. Δ: The contrast is slightly clear, but it is at the lower limit of the practical level. △ ×: The density difference can be clearly confirmed and is at a level not practical. X: A remarkable difference in light and shade can be confirmed.

(5) Streaks and unevenness Solid black images and halftone (HT) images are developed, and streaks and unevenness are visually observed in each image,
The evaluation results are shown by the following indexes. ◯: No streaking or unevenness is observed. B: Minor streaks and unevenness are observed in the HT image. Δ: Streaks and unevenness are slightly seen in the HT image, but the lower limit of practical level. △ ×: Streaks and unevenness were observed in the solid black image, which is not practical. X: Remarkable streaks and unevenness are also seen in a solid black image.

(6) Abrasion amount (abrasion amount) of the conductive coating layer After image development and evaluation under each environment, the developing sleeve was removed, and a laser length measuring device (manufactured by KEYENCE: controller LS-5500, sensor head LS5040T) ) Was used to measure the outer diameter. The abrasion amount of the conductive coating layer was calculated from this measurement value and the measurement value of the outer diameter of the developing sleeve before image formation.
The film was scraped (μm) by taking the average value of 0 points.

(7) Sleeve contamination and fusion with toner (contamination resistance and fusion resistance) After image development and evaluation in each environment, the developing sleeve was removed, and a field emission-scanning microscope (FE-SEM) was used. The sleeve was observed and the evaluation results were shown by the following indexes. ◯: No contamination or fusion is observed. ○ △: Slight contamination and fusion are observed. Δ: Contamination and fusion are slightly observed, but the lower limit of practical level. Δx: Contamination and fusion were observed, and practically impossible level. X: Significant contamination and fusion are observed.

<Examples 2 to 10> Image formation and evaluation were performed in the same manner as in Example 1 except that the surface-treated developing sleeves F-2 to F-10 were used. The evaluation results are shown in Tables 6-8.

<Comparative Example 1> In Example 1, an untreated developing sleeve C- was used instead of the surface-treated developing sleeve F-1.
Image formation and evaluation were performed in the same manner as in Example 1 except that 1 was used. The evaluation results are shown in Tables 6-8.

<Comparative Examples 2 to 4> In Example 1, images were produced and evaluated in the same manner as in Example 1 except that the surface-treated developing sleeves G-1 to G-3 were used. Table 6 shows the evaluation results.
~ 8.

<Production Example 6 of Surface Untreated Development Sleeve> In Production Example 1 of surface untreated development sleeve, the following coating composition and aluminum cylindrical substrate surface (Ra = 0.35 μm) having an outer diameter of 32.5 mmφ were prepared. A surface untreated development sleeve was prepared in the same manner as in Development Sleeve Production Example 1 except that it was used as a substrate, and was named surface untreated development sleeve C-5.
Table 2 shows the constitution and physical properties of the obtained resin coating layer.

[0190] ・ Resol type phenol resin (Containing 50% methanol) 460 parts ・ Carbon black 10 parts ・ Crystalline graphite (number average particle size 2.8 μm) 90 parts 25 parts of spherical carbon particles B-1 (number average particle diameter 5.1 μm) ・ Isopropanol 429 parts

<Production Example 7 of untreated surface developing sleeve> In Production Example 6 of untreated surface developing sleeve, except that 15 parts of an aluminum compound of benzylic acid containing 2 mol of benzylic acid and 1 mol of aluminum atom was further added to prepare a coating material, Surface untreated developing sleeve A surface untreated developing sleeve was prepared in the same manner as in Production Example 6 and designated as surface untreated developing sleeve C-6. Table 2 shows the constitution and physical properties of the obtained resin coating layer.

<Production Example 8 of Surface Untreated Developing Sleeve> In Production Example 6 of surface untreated developing sleeve, spherical carbon particles B were used.
-1 (number average particle diameter 5.1 μm), except that the coating material was not used, a surface untreated development sleeve was produced in the same manner as in Surface untreated development sleeve Production Example 6, and surface untreated development sleeve D-2. And Table 2 shows the constitution and physical properties of the obtained resin coating layer.

<Production Example 14 of surface-treated developing sleeve> In Production Example 1 of surface-treated developing sleeve, the surface-undeveloped developing sleeve was changed to C-5, and the surface treatment condition was changed to E-7 condition. The surface treatment was performed in the same manner as in Production and Development Sleeve Manufacturing Example 1 to obtain a surface-treated and development sleeve F-11. As magnetic particles, spherical iron powder A-5 having a number average particle size shown in Table 3 of 9.8 μm was used. The universal hardness value of the magnetic particles was larger than the hardness value of the coating layer binder resin. Tables 3 to 5 show the physical properties and structure of the magnetic particles, the surface treatment conditions, the surface roughness of the surface-treated developing sleeve, and the polished film thickness.

<Production Example 15 of surface-treated developing sleeve> In Production Example 1 of surface-treated developing sleeve, the surface-undeveloped developing sleeve was changed to C-5, and the surface treatment condition was changed to E-8 condition. The surface treatment was performed in the same manner as in Production and Development Sleeve Production Example 1 to obtain a surface-treated and development sleeve F-12. Tables 3 to 5 show the physical properties and structure of the magnetic particles, the surface treatment conditions, the surface roughness of the surface-treated developing sleeve, and the polished film thickness.

<Production Example 16 of surface-treated developing sleeve> In Production Example 1 of surface-treated developing sleeve, the surface-undeveloped developing sleeve was changed to C-6, and the surface treatment condition was changed to E-7 condition. The surface treatment was performed in the same manner as in Production and Development Sleeve Production Example 1 to obtain surface-treated development sleeve F-13. Tables 3 to 5 show the physical properties and structure of the magnetic particles, the surface treatment conditions, the surface roughness of the surface-treated developing sleeve, and the polished film thickness.

<Production Example 17 of surface-treated developing sleeve> In Production Example 1 of surface-treated developing sleeve, the surface-undeveloped developing sleeve was changed to C-6, and the surface treatment condition was changed to E-8 condition. The surface treatment was performed in the same manner as in Production and Development Sleeve Production Example 1 to obtain a surface-treated and development sleeve F-14. Tables 3 to 5 show the physical properties and structure of the magnetic particles, the surface treatment conditions, the surface roughness of the surface-treated developing sleeve, and the polished film thickness.

<Production Example 18 of surface-treated developing sleeve> In Production Example 1 of surface-treated developing sleeve, the surface-undeveloped developing sleeve was changed to D-2, and the surface treatment condition was changed to E-7 condition. A surface treatment was performed in the same manner as in Production and Development Sleeve Production Example 1 to obtain a surface-treated development sleeve G-4. Tables 3 to 5 show the physical properties and structure of the magnetic particles, the surface treatment conditions, the surface roughness of the surface-treated developing sleeve, and the polished film thickness.

<Production Example 19 of surface-treated developing sleeve> In Production Example 1 of surface-treated developing sleeve, the surface-undeveloped developing sleeve was changed to D-2, and the surface treatment condition was changed to E-8 condition. The surface treatment was performed in the same manner as in Production and Development Sleeve Production Example 1 to obtain a surface-treated and development sleeve G-5. Tables 3 to 5 show the physical properties and structure of the magnetic particles, the surface treatment conditions, the surface roughness of the surface-treated developing sleeve, and the polished film thickness.

<Toner Production Example 2> Next, a magnetic positive toner as a one-component developer was produced.・ Styrene-acrylic resin 100 parts ・ Magnetite 90 parts ・ Positive charge control agent (triphenylmethane compound) 2 parts ・ Hydrocarbon wax 3 parts

The above materials were mixed by a Henschel mixer, and melt-kneaded and dispersed by a twin-screw extruder. After cooling the kneaded product, it was finely pulverized by a pulverizer using a jet stream and further classified by an air stream classifier, and the number ratio of particles having a weight average particle diameter of 6.5 μm and 4 μm or less was 20.3. %, A classified product having a distribution in which the weight ratio of particles of 10.1 μm or more was 6.2% was obtained. Next, the hydrophobic colloidal silica was added in an amount of 1.1 parts per 100 parts of the classified product.
Part Henschel mixer was used for external addition mixing to obtain a magnetic toner H-2 as a one-component developer.

<Embodiment 11> Surface-treated developing sleeve F-
11 and toner H-2 were incorporated into a developing device as shown in FIG. To print out,
Using a remodeled machine of Canon Copier GP605, a predetermined developing bias was applied to evaluate images. Images are generated at room temperature and low humidity (N / L) at 23 ° C. and 5% RH, and 30
25 degrees Celsius under high temperature and high humidity (H / H) environment of 80% RH
It went up to ten thousand sheets (250k). Tables 6 to 8 show the evaluation results obtained by the same evaluation method as in Example 1.

[Evaluation Method] (1) Image Density The density of a solid black image was measured by a reflection densitometer RD918 (manufactured by Macbeth Co.), and the average value of 5 points was taken as the image density.

(2) Fog and reversal fog The reflectance of a solid white image was measured, and the reflectance of an unused transfer paper was further measured, (the worst value of the reflectance of a solid white image-the reflectance of an unused transfer paper). The highest value) was taken as the fog density. The reflectance was measured by TC-6DS (manufactured by Tokyo Denshoku Co., Ltd.). However, when visually observing the measured values, 1.5 or less is a level that can hardly be visually confirmed, 2.0 to 3.0 is a level that can be confirmed by good observation, and if it exceeds 4.0, fogging is apparent at first glance. It is a level that can be confirmed.

(3) Toner charge amount on sleeve (Q / M)
And toner transport amount (M / S) The toner carried on the developing sleeve was sucked and collected by the metal cylindrical tube and the cylindrical filter, and at that time, the amount of charge Q accumulated in the condenser was collected through the metal cylindrical tube. The charge amount Q / M (mC / kg) per unit mass and the toner mass M / S (mg / cm ² ) per unit area are calculated from the toner mass M and the toner suction area S, and the toner charging The amount (Q / M) and the toner conveyance amount (M / S) were used.

(4) An image in which a ghost solid white and a solid black portion are adjacent to each other is developed at the image front end portion (the first rotation of the sleeve), and solid white marks and solid black marks appearing on the halftone image after the second lap. The shade difference was visually observed, and the evaluation results were shown by the following indexes. ◯: No difference in shade is seen. ○ △: A slight difference in light and shade can be visually confirmed. Δ: The contrast is slightly clear, but it is at the lower limit of the practical level. △ ×: The density difference can be clearly confirmed and is at a level not practical. X: A remarkable difference in light and shade can be confirmed.

(5) Streaks and unevenness Solid black images and halftone (HT) images are developed, and streaks and unevenness are visually observed in each image,
The evaluation results are shown by the following indexes. ◯: No streaking or unevenness is observed. B: Minor streaks and unevenness are observed in the HT image. Δ: Streaks and unevenness are slightly seen in the HT image, but the lower limit of practical level. △ ×: Streaks and unevenness were observed in the solid black image, which is not practical. X: Remarkable streaks and unevenness are also seen in a solid black image.

(6) Abrasion amount of electrically conductive coating layer (abrasion amount) After image development and evaluation under each environment, the developing sleeve was removed, and a laser length measuring device (manufactured by KEYENCE: controller LS-5500, sensor head LS5040T) ) Was used to measure the outer diameter. The abrasion amount of the conductive coating layer was calculated from this measurement value and the measurement value of the outer diameter of the developing sleeve before image formation.
The film was scraped (μm) by taking the average value of 0 points.

(7) Sleeve contamination and fusion with toner (contamination resistance and fusion resistance) After image development and evaluation in each environment, the developing sleeve was removed, and a field emission-scanning microscope (FE-SEM) was used. The sleeve was observed and the evaluation results were shown by the following indexes. ◯: No contamination or fusion is observed. ○ △: Slight contamination and fusion are observed. Δ: Contamination and fusion are slightly observed, but the lower limit of practical level. Δx: Contamination and fusion were observed, and practically impossible level. X: Significant contamination and fusion are observed.

<Examples 12 to 14> In Example 11, images were evaluated in the same manner as in Example 11 except that the surface-treated developing sleeves F-12 to F-14 were used.
The evaluation results are shown in Tables 6-8.

<Comparative Example 5> Image formation and evaluation were carried out in the same manner as in Example 11 except that the untreated developing sleeve C-5 was used in place of the surface-treated developing sleeve F-11 in Example 11. The evaluation results are shown in Tables 6-8.

<Comparative Examples 6 and 7> Image formation and evaluation were carried out in the same manner as in Example 11 except that the surface-treated developing sleeves G-4 and G-5 were used. The evaluation results are shown in Tables 6-8.

<Production Example 9 of Surface Untreated Developing Sleeve> In Production Example 1 of surface untreated developing sleeve, the following coating composition and aluminum cylindrical substrate surface (R of 20 mmφ) (R
A surface-untreated development sleeve was prepared in the same manner as in Development Sleeve Production Example 1 except that a = 0.35 μm) was used as the substrate, to give a surface-untreated development sleeve C-7. Table 2 shows the constitution and physical properties of the obtained resin coating layer.

[0213] ・ Resol type phenol resin (Containing 50% methanol) 400 parts ・ Carbon black 10 parts ・ Crystalline graphite (number average particle size 2.8 μm) 90 parts ・ Spherical carbon particles B-4 (Number average particle size 13.1 μm) 30 parts ・ Isopropanol 413 parts

<Production Example 10 of Surface Untreated Development Sleeve> In Production Example 9 of surface untreated development sleeve, spherical carbon particles B-1 (number of particles) were used instead of spherical carbon particles B-4 (number average particle size 13.1 μm). An untreated surface developing sleeve was prepared in the same manner as in Production Example 6 of untreated surface developing sleeve except that the coating material was adjusted using 20 parts of an average particle size of 5.1 μm), and was designated as untreated developing sleeve C-8. Table 2 shows the constitution and physical properties of the obtained resin coating layer.

<Production Example 11 of untreated surface developing sleeve> In Production Example 9 of untreated surface developing sleeve, the coating material was prepared without using the spherical carbon particles B-4 (number average particle diameter 13.1 μm), and the outer diameter was further adjusted. A surface untreated developing sleeve was prepared in the same manner as in Surface Untreated Developing Sleeve Production Example 9 except that a 20 mmφ aluminum cylindrical substrate surface was blasted (Ra = 1.81 μm) as a substrate. The untreated developing sleeve D-3 was used. Table 2 shows the constitution and physical properties of the obtained resin coating layer.

<Production Example 12 of Surface Untreated Developing Sleeve> In Production Example 9 of surface untreated developing sleeve, the coating material was prepared without using the spherical carbon particles B-4 (number average particle diameter 13.1 μm), and the outer diameter was further adjusted. A surface untreated developing sleeve was prepared in the same manner as in Surface Untreated Developing Sleeve Production Example 9 except that a 20 mmφ aluminum cylindrical substrate surface was blasted (Ra = 1.34 μm) as a substrate. The untreated developing sleeve D-4 was used. Table 2 shows the constitution and physical properties of the obtained resin coating layer.

<Production Example 20 of surface-treated developing sleeve> In Production Example 1 of surface-treated developing sleeve, the surface-undeveloped developing sleeve was changed to C-7, and the surface treatment condition was changed to E-9 condition. The surface treatment was carried out in the same manner as in Production and Development Sleeve Production Example 1 to obtain surface-treated and development sleeve F-15. Tables 3 to 5 show the physical properties and structure of the magnetic particles, the surface treatment conditions, the surface roughness of the surface-treated developing sleeve, and the polished film thickness.

<Production Example 21 of surface-treated developing sleeve> In Production Example 1 of surface-treated developing sleeve, the surface-undeveloped developing sleeve was changed to C-7, and the surface treatment condition was changed to E-10 condition. The surface treatment was performed in the same manner as in Processed Development Sleeve Production Example 1 to obtain surface-treated development sleeve F-16. Tables 3 to 5 show the physical properties and structure of the magnetic particles, the surface treatment conditions, the surface roughness of the surface-treated developing sleeve, and the polished film thickness.

<Production Example 22 of surface-treated developing sleeve> In Production Example 1 of surface-treated developing sleeve, the surface-undeveloped developing sleeve was changed to C-8, and the surface treatment condition was changed to E-11 condition. The surface treatment was performed in the same manner as in Production and Development Sleeve Production Example 1 to obtain surface-treated development sleeve F-17. Tables 3 to 5 show the physical properties and structure of the magnetic particles, the surface treatment conditions, the surface roughness of the surface-treated developing sleeve, and the polished film thickness.

<Production Example 23 of surface-treated developing sleeve> In Production Example 1 of surface-treated developing sleeve, the surface-undeveloped developing sleeve was changed to C-8, and the surface treatment condition was changed to E-12 condition. A surface treatment was performed in the same manner as in Production and Development Sleeve Manufacturing Example 1 to obtain a surface-treated development sleeve F-18. Tables 3 to 5 show the physical properties and structure of the magnetic particles, the surface treatment conditions, the surface roughness of the surface-treated developing sleeve, and the polished film thickness.

<Production Example 24 of surface-treated developing sleeve> In Production Example 1 of surface-treated developing sleeve, the surface-undeveloped developing sleeve was changed to D-3, and the surface-treating condition was changed to E-9 condition. The surface treatment was performed in the same manner as in Processed Development Sleeve Production Example 1 to obtain a surface-treated development sleeve G-6. Tables 3 to 5 show the physical properties and structure of the magnetic particles, the surface treatment conditions, the surface roughness of the surface-treated developing sleeve, and the polished film thickness.

<Production Example 25 of surface-treated development sleeve> In Production Example 1 of surface-treated development sleeve, the surface was untreated except that the development sleeve was changed to D-4 and the surface treatment condition was changed to E-11. The surface treatment was performed in the same manner as in Processed Development Sleeve Production Example 1 to obtain a surface-treated development sleeve G-7. Tables 3 to 5 show the physical properties and structure of the magnetic particles, the surface treatment conditions, the surface roughness of the surface-treated developing sleeve, and the polished film thickness.

[0223] <Toner Production Example 3> ・ Styrene-butyl acrylate-butyl maleate   Fester copolymer 100 parts ・ Magnetite 90 parts ・ Negative charge control agent 2 parts ・ Low molecular weight polyethylene 6 parts

The above materials were mixed by a Henschel mixer, and melt-kneaded and dispersed by a twin-screw extruder. After cooling the kneaded product, the mixture was finely pulverized by a pulverizer using a jet stream and further classified by an air stream classifier, and the number ratio of particles having a weight average particle diameter of 6.2 μm and 4 μm or less was 22.6. %, A classified product having a distribution in which the weight ratio of particles of 10.1 μm or more was 6.1% was obtained. Next, a hydrophobic colloidal silica was added to 1.2 parts per 100 parts of the classified product.
Part Henschel mixer was used for external addition mixing to obtain a magnetic toner H-3 as a one-component developer.

<Embodiment 15> Surface-treated developing sleeve F-
15 and Toner H-3 were incorporated into a developing device as shown in FIG. 2 to evaluate images. To print out,
Using LBP-930 (manufactured by Canon Inc.), the surface-treated developing sleeve F-15 was attached to the EP-W cartridge for laser jet VSi, and the image formation was evaluated while further filling the toner H-3. Image output is 23 ° C, 5% RH
Under normal temperature and low humidity (N / L) and high temperature and high humidity (H / H) environment of 30 ° C. and 80% RH, up to 25,000 sheets (25 k). Tables 6 to 8 show the evaluation results obtained by the same evaluation method as in Example 1.

[Evaluation Method] (1) Image Density The density of a solid black image was measured by a reflection densitometer RD918 (manufactured by Macbeth Co.), and the average value of 5 points was taken as the image density.

(2) Fog and reversal fog The reflectance of a solid white image was measured, and the reflectance of an unused transfer paper was further measured, (the worst value of the reflectance of a solid white image-the reflectance of an unused transfer paper. The highest value) was taken as the fog density. The reflectance was measured by TC-6DS (manufactured by Tokyo Denshoku Co., Ltd.). However, when visually observing the measured values, 1.5 or less is a level that can hardly be visually confirmed, 2.0 to 3.0 is a level that can be confirmed by good observation, and if it exceeds 4.0, fogging is apparent at first glance. It is a level that can be confirmed.

(3) Toner charge amount on sleeve (Q / M)
And toner transport amount (M / S) The toner carried on the developing sleeve was sucked and collected by the metal cylindrical tube and the cylindrical filter, and at that time, the amount of charge Q accumulated in the condenser was collected through the metal cylindrical tube. The charge amount Q / M (mC / kg) per unit mass and the toner mass M / S (mg / cm ² ) per unit area are calculated from the toner mass M and the toner suction area S, and the toner charging The amount (Q / M) and the toner conveyance amount (M / S) were used.

(4) An image in which a ghost solid white and a solid black portion are adjacent to each other is developed at the image leading end portion (the first rotation of the sleeve rotation), and a solid white mark and a solid black mark appearing on the halftone image after the second lap. The shade difference was visually observed, and the evaluation results were shown by the following indexes. ◯: No difference in shade is seen. ○ △: A slight difference in light and shade can be visually confirmed. Δ: The contrast is slightly clear, but it is at the lower limit of the practical level. △ ×: The density difference can be clearly confirmed and is at a level not practical. X: A remarkable difference in light and shade can be confirmed.

(5) Streaks and unevenness Solid black images and halftone (HT) images are developed, and streaks and unevenness are visually observed in each image,
The evaluation results are shown by the following indexes. ◯: No streaking or unevenness is observed. B: Minor streaks and unevenness are observed in the HT image. Δ: Streaks and unevenness are slightly seen in the HT image, but the lower limit of practical level. △ ×: Streaks and unevenness were observed in the solid black image, which is not practical. X: Remarkable streaks and unevenness are also seen in a solid black image.

(6) Abrasion amount of electrically conductive coating layer (abrasion amount) After image development and evaluation under each environment, the developing sleeve was removed, and a laser length measuring device (manufactured by KEYENCE, Inc .: controller LS-5500, sensor head LS5040T) ) Was used to measure the outer diameter. The abrasion amount of the conductive coating layer was calculated from this measurement value and the measurement value of the outer diameter of the developing sleeve before image formation.
The film was scraped (μm) by taking the average value of 0 points.

(7) Sleeve contamination and fusion with toner (contamination resistance and fusion resistance) After image development and evaluation in each environment, the developing sleeve was removed, and a field emission-scanning microscope (FE-SEM) was used. The sleeve was observed and the evaluation results were shown by the following indexes. ◯: No contamination or fusion is observed. ○ △: Slight contamination and fusion are observed. Δ: Contamination and fusion are slightly observed, but the lower limit of practical level. Δx: Contamination and fusion were observed, and practically impossible level. X: Significant contamination and fusion are observed.

<Examples 16 to 18> In Example 15, images were evaluated in the same manner as in Example 15 except that the surface-treated developing sleeves F-16 to F-18 were used.
The evaluation results are shown in Tables 6-8.

<Comparative Example 8> Example 1 is the same as Example 15 except that the surface untreated developing sleeve D-3 is used instead of the surface treated developing sleeve F-15.
Image formation was evaluated in the same manner as in No. 5. The evaluation results are shown in Tables 6-8.

<Comparative Example 9> Image formation and evaluation were carried out in the same manner as in Example 15 except that the surface-treated developing sleeve G-6 was used. The evaluation results are shown in Tables 6-8.

<Comparative Example 10> An image was produced in the same manner as in Example 15 except that the surface-untreated developing sleeve D-15 was used in place of the surface-treated developing sleeve F-15 in Example 15. evaluated. The evaluation results are shown in Tables 6-8.

<Comparative Example 11> Image formation and evaluation were carried out in the same manner as in Example 15 except that the surface-treated developing sleeve G-7 was used. The evaluation results are shown in Tables 6-8.

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

As described above, according to the present invention, it is possible to prevent the toner charge-up phenomenon and the blotch, and to provide the toner with a proper charge amount for a long time even under different environments. It is possible to provide a developer carrier, a developing device using the same, and a surface treatment method for the developer carrier.

Further, the object of the present invention is to stably obtain a high-quality image without causing problems such as a decrease in image density and fog over a long period of time even under different environments. In addition, a developer carrier which does not cause sleeve contamination and sleeve fusion due to toner on the surface of the developer carrier and does not generate defective images such as streaks and unevenness, a developing device using the same, and a surface treatment of the developer carrier. A method can be provided.

The object of the present invention is to make the amount of toner coating on the developer carrier constant by reducing the change in the surface roughness of the developer carrier surface over a long period of time even under different environments. It is possible to provide a developer carrier which can be controlled in amount, a developing device using the same, and a surface treatment method for the developer carrier.

[Brief description of drawings]

FIG. 1 is a schematic view of a developing device using a developer carrier having a resin coating layer of the present invention.

FIG. 2 is a schematic diagram of a developing device using a developer carrying member having a resin coating layer of the present invention.

FIG. 3 is a schematic view of a surface treatment apparatus which is an example of a method for surface treatment of a resin coating layer used in the present invention.

FIG. 4 is another schematic view of the surface treatment apparatus which is an example of the surface treatment method of the resin coating layer used in the present invention.

FIG. 5 is another schematic view of the surface treatment apparatus which is an example of the surface treatment method of the resin coating layer used in the present invention.

[Explanation of symbols]

12: gap between developing sleeve and magnet roll 301: electrostatic latent image holder (photosensitive drum) 302: developer layer thickness regulating member (magnetic regulation blade and elastic blade) 303: developer container 304: developer (toner) 305 : Magnet (Magnet Roll) 306: Metal Cylindrical Tube 307: Resin Coating Layer 308: Developer Carrier (Developing Sleeve) 309, 310, 314: Developer Stirring Blade 311: Developer Conveying Screw 312: Stirring Wall 313: Development Bias Power supply 402: Magnetic particle regulation member (regulation blade) 402b: Magnetic plate 402c: Regulation auxiliary member 403: Hopper 404: Magnetic particles 405: Magnetism generating means (magnet roll) 410: Stirring blade A: Photosensitive drum rotation direction B: Development sleeve Rotation direction C: Rotation direction of stirring blade D: Development area

Continued front page    (72) Inventor Satoshi Otake             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Kyohisa Akashi             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Naoki Okamoto             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Ikki Saiki             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Kenji Fujishima             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation F-term (reference) 2H031 AA01 AA12 AB02 AB03 AB09                       AC10 AC11 AC14 AC18 AC19                       AC23 AC33 AD01 AD05 AD16                       BA01 BA05 BA09 BB01 CA07                       DA05                 2H077 AA11 AB02 AB03 AB13 AB14                       AB15 AB18 AC02 AC03 AD02                       AD06 AD13 AD17 AD18 AD35                       AE01 BA07 BA08 EA03 EA14                       FA00 FA01 FA03 FA13 FA14                       FA16 FA19 FA25 FA26 FA27                       GA03

Claims (33)

[Claims] 1. A resin coating layer containing a binder resin, a solid lubricant and / or conductive fine powder, and particles for forming irregularities on the surface, on a surface of a cylindrical substrate made of at least a non-magnetic material. In the method for surface treatment of a developer-carrying member having, magnetic particles harder than the hardness of the binder resin of the resin-coating layer on the surface of the coating layer by the magnetism generating means arranged in the developer-carrying member. The surface treatment of the developer carrier is characterized in that the surface of the resin coat layer is treated by a rubbing force between the surface of the resin coat layer and the magnetic particles by causing the carrier to be supported and rotating the developer carrier. Method. 2. The surface of the resin coating layer and the irregularity-forming particles existing in the vicinity thereof form irregularities on the surface of the resin coating layer without being worn or removed, and the solid lubricant and / or the conductive material. The surface treatment method for a developer carrying member according to claim 1, wherein the fine powder is uniformly exposed on the surface of the resin coating layer. 3. The surface treatment method for a developer carrying member according to claim 1, wherein the magnetism generating means is a magnet roll having a plurality of magnetic poles. 4. The surface of the resin coating layer is treated by arranging a magnetic particle regulating member on a developer carrying member to enhance the rubbing force with the magnetic particles. 2. The surface treatment method for a developer carrying member according to item 1. 5. The number average particle diameter (A) of the magnetic particles is
The average spacing Sm value (Sm ₁ ) of the irregularities on the surface of the resin coating layer formed before the surface treatment and the relationship of the following formula (1) are satisfied: Surface treatment method for developer carrier. A / Sm ₁ ≦ 0.5 (1) 6. The method according to claim 1, wherein the surface of the resin coating layer is processed to be polished to a thickness of 0.4 to 2.5 μm by the surface treatment. Surface treatment method for developer carrier. 7. The arithmetic mean roughness Ra value (Ra ₁ ) of the surface of the resin coating layer before the surface treatment and the arithmetic mean roughness Ra value (Ra ₂ ) of the surface of the resin coating layer after the surface treatment are: Claim 1 which is processed so that the relation of a following formula (2) may be satisfied.
5. The surface treatment method for the developer carrying member according to any one of 5 above. 0.7 ≦ Ra ₂ / Ra ₁ ≦ 1.3 (2) 8. The developer according to claim 1, wherein an average interval Sm value (Sm ₂ ) of irregularities on the surface of the resin coating layer formed after the surface treatment is 20 to 200 μm. Surface treatment method for carrier. 9. The arithmetic mean roughness Ra value (Ra ₂ ) of the surface of the resin coating layer after the surface treatment is 0.3 to 3.5 μm.
The method for surface treatment of a developer carrying member according to claim 1, wherein m is m. 10. The hardness of particles for forming irregularities on the surface of the resin coating layer is higher than that of the binder resin.
10. The surface treatment method for the developer carrying member according to any one of 9 above. 11. The number average particle diameter (A) of the magnetic particles
Is 5 to 60 μm. The method for surface treatment of a developer carrying member according to claim 1, wherein 12. The true density of the magnetic particles is 2500 k.
The surface treatment method of the developer carrying member according to any one of claims 1 to 11 is g / m ³ or more. 13. The surface treatment of the developer carrying member according to claim 1, wherein the number average particle diameter of particles for forming irregularities on the surface of the resin coating layer is 2 to 30 μm. Method. 14. Particles for forming irregularities on the surface of the resin coating layer are spherical and have a true density of 3000 kg /
The surface treatment method for the developer carrying member according to claim 1, wherein the surface treatment is m ³ or less. 15. The method for surface treatment of a developer carrying member according to claim 1, wherein the particles for forming irregularities on the surface of the resin coating layer are conductive particles. 16. The resin coating layer comprises 10 ^{−2 to} 10 ³
16. The volume resistance of Ω · cm according to claim 1.
Item 5. The method for surface treatment of a developer carrying member according to item. 17. A resin coating layer containing a binder resin, a solid lubricant and / or conductive fine powder, and particles for forming irregularities on the surface, on the surface of a cylindrical substrate made of at least a non-magnetic material. In the developer carrying member having the coating layer surface, magnetic particles harder than the hardness of the binder resin of the resin coating layer are carried on the resin coating layer surface by the magnetism generating means arranged in the developer carrying body. A developer carrier, wherein the surface of the resin cover layer is treated by a rubbing force between the surface of the resin cover layer and the magnetic particles by rotating the developer carrier. 18. The unevenness forming particles existing on the surface of the resin coating layer and in the vicinity thereof form unevenness on the surface of the resin coating layer without being worn and removed, and the solid lubricant and / or the conductive material. The developer carrying member according to claim 17, wherein the fine powder is uniformly exposed on the surface of the resin coating layer. 19. The developer carrier according to claim 17, wherein the magnetism generating means is a magnet roll having a plurality of magnetic poles. 20. The surface of the resin coating layer is treated by arranging a magnetic particle regulating member on a developer carrying member to enhance the rubbing force against the magnetic particles.
Item 20. The developer carrying member according to any one of Item 19. 21. The number average particle diameter (A) of the magnetic particles
21 satisfies the relationship between the average interval Sm value (Sm ₁ ) of the irregularities on the surface of the resin coating layer formed before the surface treatment and the following expression (1).
The developer carrying member according to any one of 1. A / Sm ₁ ≦ 0.5 (1) 22. The film thickness of the surface of the resin coating layer is treated by the surface treatment so as to be polished to a thickness of 0.4 to 2.5 μm. Developer carrier. 23. The arithmetic mean roughness Ra value (Ra ₁ ) of the surface of the resin coating layer before the surface treatment and the arithmetic mean roughness Ra value (Ra ₂ ) of the surface of the resin coating layer after the surface treatment are The developer carrier according to any one of claims 17 to 22, which is treated so as to satisfy the relationship of the following formula (2). 0.7 ≦ Ra ₂ / Ra ₁ ≦ 1.3 (2) 24. The average interval Sm value (Sm ₂ ) of irregularities on the surface of the resin coating layer formed after the surface treatment is 20.
The developer carrier according to any one of claims 17 to 23, having a thickness of from 200 to 200 µm. 25. The arithmetic mean roughness Ra value (Ra ₂ ) of the surface of the resin coating layer after the surface treatment is 0.3 to 3.5.
The developer carrying member according to any one of claims 17 to 24, which has a thickness of μm. 26. The hardness of particles for forming irregularities on the surface of the resin coating layer is higher than that of the binder resin.
25. The developer carrying member according to any one of 25 to 25. 27. The number average particle diameter (A) of the magnetic particles
Is 5 to 60 μm.
Item 6. The developer carrying member according to the item. 28. The true density of the magnetic particles is 2500 k.
The developer carrying member according to any one of claims 17 to 27, which has a g / m ³ or more. 29. The developer carrier according to claim 17, wherein the number average particle diameter of particles for forming irregularities on the surface of the resin coating layer is 2 to 30 μm. 30. The particles for forming irregularities on the surface of the resin coating layer are spherical and have a true density of 3000 kg /
developer carrying member according to any one of claims 17 to 29 m ³ or less. 31. The developer carrier according to claim 17, wherein the particles for forming irregularities on the surface of the resin coating layer are conductive particles. 32. The resin coating layer comprises 10 ^{−2 to} 10 ³
The developer carrier according to any one of claims 17 to 31, having a volume resistance of Ω · cm. 33. A developing container, a developer carrying member for carrying and carrying the developer contained in the developing container, and a developer carrying member arranged in proximity to or in pressure contact with the developer carrying member. Having a developer layer thickness regulating member for forming a thin layer of the developer on the body, the developer carrying member carries and conveys the developer to a developing area facing the electrostatic latent image holding member, 33. A developing device for developing a visible image by developing an electrostatic latent image formed on the electrostatic latent image holding member with a developer, wherein the developer carrying member is any one of claims 17 to 32. A developing device, which is the developer carrying member described above.