JP3055115B2 - Developer carrier and developing device using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to electrophotography,
A developing device for developing and visualizing a latent image formed on a latent image holding member such as an electrophotographic photosensitive member or an electrostatic recording dielectric, and a developer carrier (developing roller) used in the developing device About.

[0002]

2. Description of the Related Art Conventionally, as an electrophotographic method, US Pat.
A number of methods are known as described in Japanese Patent Publication No. 297691, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748, but a photoreceptor made of a photoconductive substance is generally used. Forming an electrical latent image on the photoreceptor by various means, developing the latent image with a developer (toner), and transferring the toner image to a transfer material such as paper as necessary, The image is fixed by heating, pressure, or solvent vapor to obtain a copy.

The developing methods are generally classified into a dry developing method and a wet developing method. However, since the wet developing method involves evaporation of a solvent, it is hardly used at present. In the dry developing method, a two-component developing method such as a magnetic brush developing method mainly using a toner and a carrier has been used for a long time. The disadvantages of the two-component developing method are that it is difficult to keep the mixing ratio of the toner and the carrier constant, and that the carrier deteriorates quickly and the developer must be replaced frequently.

In order to avoid such disadvantages, various methods using a one-component developer consisting of only a toner have been proposed. As such a one-component developer, a one-component magnetic developer in which magnetic particles are contained in a high-resistance resin and toner is conveyed by magnetism is used. As a development method using a high-resistance magnetic toner, there is a method in which toner particles are frictionally charged by friction between toner particles, friction between the toner particles and a sleeve, and the like, and developed by contacting the toner particles with an electrostatic latent image holding member. Are known.

However, in these methods, the number of times of contact between the toner particles and the friction member is small and the triboelectric charging is apt to be insufficient, and the charged toner particles are liable to agglomerate the sleeve due to an increased Coulomb force between the sleeve and the sleeve. Has disadvantages.
Japanese Patent Application Laid-Open No. 54-43036 proposes a developing method in which the above-mentioned disadvantages are eliminated. This applies a very thin coating of magnetic toner on the sleeve, triboelectrically charges it, and then brings it very close to the electrostatic image under the action of the magnetic field,
In addition, they are developed without being in contact with each other.

According to this method, the magnetic toner is applied extremely thinly on the sleeve as the developer carrying member, so that the chance of contact between the sleeve and the toner is increased, and sufficient frictional charging is enabled. By supporting the toner and moving the magnet and the toner relatively, the aggregation of the toner particles is dissolved and the toner is sufficiently rubbed with the sleeve. The toner is supported by the magnet and the electrostatic image is formed. An excellent image can be obtained, for example, by developing the toner image while facing the surface without contacting the surface, thereby preventing background fog.

Conventionally, as a developing roller (developing sleeve) generally put to practical use, a metal cylindrical tube made of aluminum, stainless steel, or the like, and a magnet arranged as a magnetic field generating means inside the cylindrical tube are used. Used. The magnet is often used in the form of a magnet roll. The surface of the metal cylindrical tube is often used in a state in which unevenness is appropriately formed by means of sand blasting, sanding or the like to improve the toner conveying force.

However, in such a sleeve, various inconveniences such as uneven toner coat, poor coat, ghost, and reduced density may occur depending on environmental conditions, toner physical properties, sleeve surface conditions, and the like. For example, as the sleeve rotates repeatedly, the charge amount of the toner coated on the sleeve (tribo)
Becomes too high due to the contact with the sleeve, the toner is attracted by the mirror force of the sleeve surface, becomes immobile on the sleeve surface, and does not move from the sleeve to the latent image on the latent image holding member (drum). The charge-up phenomenon tends to occur particularly under low humidity. When such charge-up occurs, the toner in the upper layer becomes less likely to have a tribo, and the amount of developed toner is reduced, resulting in an image in which a line image is thinned, a solid black image has a low image density, and the like.

Further, since the toner layer forming state of the image area (toner consuming section) and the non-image area change and the charging state changes, the position where a solid image having a high image density is once developed is located next to the developing sleeve. When the halftone image is developed at the developing position during rotation, a phenomenon that a solid image appears on the image, that is, a so-called sleeve ghost phenomenon is likely to occur.

Recently, in order to improve the quality of electrophotography,
The toner has a small particle size and fine particles. In order to increase the resolution, sharpness and the like and faithfully reproduce a latent image, a toner having a weight average particle diameter of about 6 to 9 μm is generally used. Further, there is a tendency that the fixing temperature of the toner is lowered for the purpose of shortening the first copy time and saving power. In such a situation, the toner is more likely to adhere electrostatically to the sleeve, and the surface of the sleeve is more likely to be contaminated and the toner is fused due to an external physical force.

As a method for solving such a phenomenon, Japanese Patent Laid-Open No. 2-105 is used instead of the conventional sleeve of a metal cylindrical tube.
As described in JP-A-181 and JP-A-3-36570, there has been proposed a method of forming a resin film made of resin, conductive fine powder, solid lubricant, or the like on the surface of a metal cylindrical tube and using the resin film in a developing device. It has been done.

By using this method, the above phenomenon is greatly reduced. However, in the above method,
Conductive fine powder, because the dispersibility of pigments such as solid lubricants is insufficient, it is likely to be unevenly distributed in the resin film, especially when the toner used is easy to charge up, a large amount of conductive fine powder,
A resin film containing a solid lubricant or the like in the resin must be formed on the surface of the metal cylindrical tube. As a result, the strength of the resin film on the sleeve surface is reduced. sometimes scraping or peeling, etc. of the film becomes liable problem occurs. In addition, when a resin coating containing a large amount of conductive fine powder, solid lubricant, etc. in a resin is formed on the surface of a metal cylindrical tube, the charge imparting property to the toner under a high temperature and high humidity environment becomes insufficient, The image density may be reduced.

In order to solve such a problem, a method of treating a pigment with a silane-based and titanium-based coupling agent disclosed in Japanese Patent Application Laid-Open No. 1-102485 has already been disclosed. However, they also use the conventional surface-treated pigment, since the dispersibility improvement of the resin to be film sleeve surface was still insufficient, giving more dispersibility of the pigment is improved, durability and electrification There has been a long-felt need for a developer carrier having excellent properties.

Accordingly, it is an object of the present invention to provide a highly durable developer carrier having stable image quality which does not cause deterioration of the film on the carrier surface due to repeated copying or durability and no peeling. Another object of the present invention is to provide a developer carrier capable of obtaining a high-quality image free from a decrease in density or a sleeve ghost over a long period of time even under different environmental conditions.

Another object of the present invention is to reduce the non-uniform charging of the toner layer on the surface of the developer carrier which occurs when a toner having a small particle diameter is used, and to provide a toner having an appropriate charge amount. It is to provide an agent carrier. Another object of the present invention is to provide a stable and high quality image by an electrophotographic apparatus using a developing device constituted by using the developer carrier of the present invention.

[0016]

The above object is achieved by the present invention described below. That is, the present invention is by at <br/> developer carrying member of a metal cylindrical tubular for use in a developing device for developing a latent image formed on the latent image holding member with a developer is carried and conveyed developer carrying member there are, on the metal cylindrical tube, pre-treated conductive fine powder in silicone oil having at least nitrogen-containing heterocyclic and / or a solid lubricant as a pigment, the
A resin film comprising a pigment dispersed and contained in a binder resin is formed , and the pigment in the resin film is formed.
The content of the (P) and該Ba Indah resin (B) (P /
B) is a developing device using characteristics and the developer carrying member to and it 1/20 to 5/1 der Rukoto.

[0017]

The present inventors have conducted intensive studies in order to solve the above-mentioned problems. As a result, the pigments such as conductive fine powder and solid lubricant contained in the resin film on the surface of the carrier were found. The inventors found out that this was one of the main causes of these problems, and examined pigments that could solve these problems.
As a result, it is easy to uniformly disperse in the resin film on the surface of the carrier, the strength of the resin film is not reduced, and the charge amount of the toner can be appropriately adjusted even when used for a long time in different environments. An excellent pigment was developed, and the object of the present invention was achieved by a development carrier using the pigment.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to preferred embodiments. First, the pigment treated with the silicone oil having at least a nitrogen-containing heterocycle used in the present invention will be described. In the present invention,
Conductive fine powder and / or a solid lubricant to use as a pigment
The conductive fine powder is aluminum,
Metal powders such as copper and silver, short metal fibers, carbon black,
Metal oxides such as titanium oxide, tin oxide, antimony oxide, and indium oxide; and the like , and as a solid lubricant
Is graphite, molybdenum disulfide, boron nitride, and zinc stearate.

In the present invention, when these pigments are contained in a resin according to the purpose, they are treated with a silicone oil having a nitrogen-containing heterocycle before use. The purpose of adding these pigments is, for example, when the conductive fine powder reduces the electrical resistance of the resin film , the solid lubricant is
It is added for the purpose of improving the lubricity of the coating surface. In the present invention, a silicone oil having a nitrogen-containing unsaturated heterocyclic ring and / or a nitrogen-containing saturated heterocyclic ring in a side chain is used for the treatment of the above-mentioned pigment. Silicone oils having the structure represented can be used.

[0020]

Embedded image

Examples of the nitrogen-containing unsaturated heterocycle are shown below.

Embedded image

[0022]

Embedded image

However, the present invention is not limited to the above compound examples, but preferably has a 5-membered or 6-membered heterocyclic ring. As the derivative, a known derivative having a hydrocarbon group, a halogen group, an amino group, a vinyl group, a mercapto group, a methacryl group, a glycidoxy group, a ureido group, or the like is used unless the charge control property is impaired. And their derivatives can be used.

The nitrogen equivalent of the silicone oil used in the present invention is preferably 25,000 or less, more preferably 5,000 or less. The nitrogen atom equivalent referred to herein means the equivalent (g / e) per nitrogen atom.
qiu) is the value obtained by dividing the molecular weight by the number of nitrogen atoms per molecule. These may be used alone or in a mixture of two or more.

[0025] is treated pigments described above in denatured <br/> silicone oil having a nitrogen-containing heterocycle in the following such methods. For example, the pigment is vigorously stirred with heating if necessary, and the modified silicone oil having a nitrogen-containing heterocyclic ring or a solution thereof as described above is sprayed or vaporized and sprayed. Alternatively, the pigment can be easily treated by slurrying the pigment and dropping a modified silicone oil having a nitrogen-containing heterocycle or a solution thereof into the slurry while stirring the pigment. Furthermore, it is also preferable to subsequently perform a heat treatment at a temperature of about 50 to 400 ° C.

In the present invention, the amount of the silicone oil having a nitrogen-containing heterocycle used for treating the pigment is preferably 0.2 to 70% by weight of the total amount of the treated pigment. Further, the appropriate treatment amount of the silicone oil having a nitrogen-containing heterocyclic ring is such that, with respect to 100 parts by weight of the pigment before being treated with the above silicone oil, the used weight part of the silicone oil is X, and the specific surface area of the pigment used is When the relationship represented by the following formula (I) is satisfied when bm ² / g and the nitrogen atom equivalent of the silicone oil having a nitrogen-containing heterocyclic ring in the side chain are a, particularly good results are obtained.

[0027]

(Equation 1) In the above formula, when X> b / 2, the silicone oil having a nitrogen-containing heterocycle becomes excessively large with respect to the pigment, which may cause problems such as oozing of the silicone oil having a nitrogen-containing heterocycle from the pigment. There is. Also, x <ab / 30,00
In the case of 0, the chargeability is insufficient and it is difficult to achieve the object of the present invention.

On the other hand, the viscosity of the silicone oil having a nitrogen-containing heterocycle at 25 ° C. is preferably 5,000 mPa or less, particularly preferably 3,000 mPa or less. Viscosity is 5,
If it is 000 mPa or more, the dispersion of the silicone oil having a nitrogen-containing heterocyclic ring in the pigment becomes insufficient, which tends to cause image defects such as fog.

The pigment used in the present invention may be treated with a silane coupling agent or a treating agent such as an organosilicon compound for the purpose of imparting hydrophobicity, if necessary. It can be treated with a treating agent that reacts with or physically adsorbs the pigment. Such treatment agents include, for example, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, diethylaminopropyltrimethoxysilane, aminophenyltrimethoxysilane,
Dimethylaminophenyltriethoxysilane, dimethylsilicone oil, hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchloro Silane, bromomethyldimethylchromesilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, Dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3 -Divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and 2 to 12 siloxane units per molecule, each of the terminal units containing one hydroxyl group bonded to Si Dimethylpolysiloxane. These are 1
It is used in the form of a species or a mixture of two or more species.

[0030] When the pigment treated with silicone oil having a nitrogen-containing heterocyclic ring in accordance with the present invention using a developer carrying member for chromatic <br/> the resin to be film contained triboelectrification of the developer becomes stable Thus, even under various environments, uniform chargeability can be provided. Therefore, when the developer carrier according to the present invention is used, a clear and high-density image without fog can be obtained, and the image does not deteriorate even when used continuously for a long period of time. Also, clear images can be obtained under high temperature and high humidity and under low temperature and low humidity.

Next, a binder resin material in which the pigment treated with the above-mentioned silicone oil having a nitrogen-containing heterocycle is dispersed and contained will be described. As the binder resin material used in the present invention, for example, styrene resin, vinyl resin, polyether sulfone resin, polycarbonate resin, polyphenylene oxide resin, polyamide resin, fluororesin, cellulose resin, acrylic resin and the like Thermosetting resins such as thermoplastic resins, epoxy resins, polyester resins, alkyd resins, phenol resins, melamine resins, polyurethane resins, urea resins, silicone resins, and polyimide resins, or photocurable resins can be used. Among them, silicone resins, those having a releasable property such as fluororesin, or polyether sulfone resin,
Those having excellent mechanical properties such as polycarbonate resin, polyphenylene oxide resin, polyamide resin, phenol resin, polyester resin, polyurethane resin, and styrene resin are more preferable.

[0032] according to the present invention the developer carrying member is comprised of a metal cylindrical tube, the resin to be film surrounding it. As the metal cylindrical tube, mainly stainless steel, aluminum or the like is suitably used. Resin to be film, the above conductive fine powder has been treated with a silicone oil having the above-mentioned such nitrogen-containing heterocyclic ring in the binder resin and / or solid lubricant
The agent is referred to as a pigment (hereinafter simply referred to as "pigment" or "pigment (P)").
(Also referred to as) .

At this time, the pigment (P) and the binder resin
As the ratio (P / B ratio) of (B) , P / B = 1/20
It is in the range of 5/1. The Vander amount exceeding 1/20, the effect of adding the pigments hardly observed, the amount of pigment exceeds 5/1 when the resin film becomes badly scraped and peeling of very brittle become resin film. The thickness of the resin film is usually preferably 20 μm or less for obtaining a uniform film thickness, but is not particularly limited to this thickness.

Next, a description will be given of a developing device in which the developer carrying member of the present invention having the above-described structure is incorporated. In FIG. 2, an image carrier that carries an electrostatic latent image formed by a known process, for example, an electrophotographic photosensitive drum 1, is rotated in the direction of arrow B. The sleeve 8 of the developing roller 11 carries the magnetic toner 4 as a one-component magnetic developer supplied by the hopper 3, and the developing sleeve 8 and the photosensitive drum 1 are opposed by rotating in the direction of arrow A. The toner 4 is transported to the developing unit D. A magnet 5 is provided in the developing sleeve 8 to magnetically attract and hold the magnetic toner 4 on the developing sleeve 8.
Is arranged. The developing sleeve 8 is placed on the metal cylindrical tube 6.
The resin layer 7 which is a specific resin film in the present invention (hereinafter referred to as “ resin layer 7” ).
Simply referred to as “resin layer”) . Reference numeral 9 denotes a gap indicating that the developing sleeve and the magnet are in a non-contact state.

The toner 4 obtains a triboelectric charge capable of developing the electrostatic latent image on the photosensitive drum 1 by friction with the resin layer 7 on the developing sleeve 8. In order to regulate the layer thickness of the magnetic toner 4 conveyed to the developing section D, a regulating blade 2 made of a ferromagnetic metal is moved from the surface of the developing sleeve to about 100 to 300 μm.
It is suspended from the hopper 3 so as to face the developing sleeve 8 with a gap width of m. When the lines of magnetic force from the magnetic pole N1 of the magnet 5 concentrate on the blade 2, a thin layer of the magnetic toner 4 is formed on the developing sleeve 8. Blade 2
For example, a non-magnetic blade can be used. The thickness of the thin layer of the magnetic toner 4 formed on the developing sleeve 8 is preferably smaller than the minimum gap between the developing sleeve 8 and the photosensitive drum 1 in the developing section D.

The present invention is particularly effective for a developing device of the type which develops an electrostatic latent image with such a thin toner layer, that is, a non-contact type developing device. However, the present invention can also be applied to a developing device in which the thickness of the toner layer in the developing section is equal to or greater than the minimum gap between the developing sleeve 8 and the photosensitive drum 1, that is, a contact type developing device. A power supply 10 applies a developing bias voltage to the developing sleeve 8 to fly the magnetic toner 4, which is a one-component magnetic developer, carried on the developing sleeve 8. When a DC voltage is used as the developing bias voltage, a voltage having a value between the potential of the image portion of the electrostatic latent image (the region where the toner 4 adheres and is visualized) and the potential of the background portion is used. 8 is preferably applied. On the other hand, an alternating bias voltage is applied to the developing sleeve 8 in order to increase the density of the developed image or to improve the gradation.
An oscillating electric field whose direction is alternately reversed may be formed in the developing unit D.

In this case, it is preferable to apply to the developing sleeve 8 an alternating bias voltage on which a DC voltage component having a value between the potential of the image portion and the potential of the background portion is superimposed.
Also, in so-called regular development in which toner is attached to a high potential portion of an electrostatic latent image having a high potential portion and a low potential portion to visualize the toner, a toner charged to a polarity opposite to the polarity of the electrostatic latent image is used. On the other hand, in so-called reversal development in which toner is attached to a low potential portion of an electrostatic latent image to make it visible, toner that is charged to the same polarity as the polarity of the electrostatic latent image is used. The high potential and the low potential are expressed by absolute values. In any case, the toner 4 is charged by friction with the developing sleeve 8.

FIG. 3 is a schematic structural view showing another embodiment of the developing device of the present invention, and FIG. 4 is a schematic structural diagram showing still another embodiment of the developing device of the present invention. In the developing device shown in FIGS. 3 and 4, as a member for regulating the layer thickness of the magnetic toner 4 on the developing sleeve 8, a material having rubber elasticity such as urethane rubber or silicone rubber, or a metal elastic material such as phosphor bronze or stainless steel is used. In FIG. 3, the elastic plate 20 is pressed against the rotation direction of the developing sleeve 8 in the forward direction, and in FIG. 4, the elastic plate 20 is developed. It is characterized in that the sleeve 8 is pressed against the rotating direction of the sleeve 8 in the opposite direction.

The developing device shown in FIGS. 3 and 4 and the other basic configuration are the same as those of the developing device shown in FIG. 2, and those having the same reference numerals are basically the same members. 2 to 4 are only schematic examples, and it goes without saying that there are various forms in the shape of the container, the presence or absence of the stirring member, the arrangement of the magnetic poles, and the like. Of course, it can also be used as a two-component developing device using carrier particles.

Next, the developer (toner) used for obtaining a visible image by the developer carrier or the developing device according to the present invention will be described. Toners are roughly classified into dry toners and wet toners. Dry toners are mainly used at present because wet toners have a large problem of solvent volatilization. Toners are mainly resins, release agents, charge control agents,
It is a fine powder in which a colorant and the like are melt-kneaded, solidified, pulverized, and then subjected to classification and the like to have a uniform particle size distribution. As the binder resin used for the toner, generally known resins can be used. For example, styrene such as styrene, α-methylstyrene, p-chlorostyrene and the like and monosubstituted styrene; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-ethyl acrylate copolymer, styrene -Butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer Polymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid Copolymer, styrene-maleic acid Styrene copolymers such as ether copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin,
Phenol resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, paraffin wax, carnauba wax and the like can be used alone or in combination.

Further, a pigment can be contained in the toner. For example, carbon black, nigrosine dye,
Lamp black, Sudan black SM, fast yellow G, Baie Njijin Yellow, Pigment Yellow,
India First Orange, Irgazine Red, Paranitroaniline Red, Toluidine Red, Carmine FB, Permanent Bordeaux FRR, Pigment Orange R, Risor Red 2G, Lake Red, Rhodamine FB, Rhodamine B Lake, Methyl Bio Red B Lake, Phthalocyanine Blue, Pigment Blue, Brilliant Green B, Phthalocyanine Green, Oil Yellow GG, Pomelo First Yellow CGG, Kaya Set Y963, Kaya Set Y
G, Pomelo First Orange RR, Oil Scarlet, Orazol Brown B, Savon First Scarlet CG, Oil Pink OP, etc. can be applied.

In order to use the toner as a magnetic toner, a magnetic powder may be contained in the toner. As such a magnetic powder, a substance magnetized in a magnetic field is used, and examples thereof include powder of a ferromagnetic metal such as iron, cobalt, and nickel, and alloys and compounds such as magnetite, hematite, and ferrite. The content of the magnetic powder is preferably 15 to 70% by weight based on the weight of the toner. Also, various release agents may be used in the toner, and such release agents include:
Polyfluoroethylene, fluororesin, silicone oil,
Low molecular weight polyethylene, low molecular weight polypropylene and the like can be mentioned. Further, if necessary, a charge control agent for facilitating positive or negative charging may be added.

[0043]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples. Example 1 Pigment component (A) • Graphite 100 parts Pigment component (B) • Phenol resin 100 parts • Methanol 90 parts • Isopropyl alcohol 160 parts The above pigment component (A) was slurried with isopropyl alcohol and stirred vigorously. A silicone oil having a nitrogen-containing heterocycle (having a viscosity of 10 at 25 ° C.)
0 mPa, a nitrogen atom equivalent of 850) was dropped,
After drying at 15 ° C. for 15 minutes, (B) was dispersed at room temperature for 5 hours using a sand mill. Measurement by a B-type viscometer showed a viscosity of 80 (mPa). Further, 100 parts of isopropyl alcohol was added, and the mixture was further dispersed for 1 hour.

A magnet-coated sleeve having a surface having an outer diameter of 20φ, which is subjected to blasting to form irregularities, is spray-coated to obtain a uniform coating film. Using the above dispersion, coating was performed so that the film thickness of the dried film was 10 μm. After coating, the coating was dried and cured to form a developer carrying member (sleeve). The center line average roughness Ra after coating was 1.3 μm. The silicone oil contains the structure of the formula (II) as a constituent unit.

[0045]

Embedded image

Next, this sleeve was incorporated into a developing device and an image output test was conducted. The following toner was used.・ Styrene-acrylic resin 100 parts ・ Magnetite 90 parts ・ 3,5-di-tert-butylsalicylate chromium complex 3 parts ・ Low molecular weight polypropylene 3 parts The above materials are kneaded, crushed, classified, etc. by a general dry toner production method. The average particle diameter is 8 μm, and the particle diameter of 4% or less is 10%, and the particle diameter of 12.7 μm or more is 0.9% by weight.
% Of the toner was obtained. The particle size distribution is based on the Coulter Counter TA-II. 0.9% of colloidal silica was externally added to this toner.

For image formation, GP55 manufactured by Canon was used. The distance between the developing sleeve and the blade is 200 μm,
An image endurance test for 10,000 sheets was performed. The environment for drawing is 25
C., 65% RH at normal temperature and normal humidity and 20.degree. C., 10% RH at low humidity. The change in image density at this time is shown in FIG. Measurement of image density is 5φ solid black image (5 ● density)
And the solid black density on the entire surface using a Macbeth reflection densitometer (Macbet)
h RD914).

Example 2 Pigment component (A) 40 parts of tin oxide Pigment component (B) 100 parts of phenolic resin 90 parts of methanol 160 parts of isopropyl alcohol Silicone oil having a nitrogen-containing heterocyclic ring (viscosity at 25 ° C. 3300 mPa, (A) and (B) treated in the same manner as in Example 1 with a nitrogen atom equivalent of 4,000) were dispersed at room temperature for 5 hours using a sand mill. Measurement by a B-type viscometer showed a viscosity of 130 (mPa). Further, 100 parts of isopropyl alcohol was added, and the mixture was further dispersed for 1 hour (the pigment treatment with the nitrogen-containing heterocyclic silicone oil of Examples 3 to 8 described below was also performed in the same manner as in Example 1).

In the same manner as in Example 1, spray coating is performed on the magnet-containing sleeve having an outer diameter of 20φ to obtain a uniform coating film. Using the above dispersion, coating was performed so that the film thickness of the dried film was 10 μm. After coating, the coating was dried and cured to form a developer carrying member (sleeve). Thereafter, the same image output as in Example 1 was performed. The change in image density at this time is shown in FIG.
The silicone oil contains the structure of the formula (III) as a constituent unit.

[0050]

Embedded image

Example 3 Pigment component (A) 100 parts of graphite Pigment component (B) 100 parts of phenol resin 90 parts of methanol 160 parts of isopropyl alcohol Silicone oil having a nitrogen-containing heterocycle (viscosity at 25 ° C. 90 mPa, nitrogen (A) and (B) were treated with a sand mill at room temperature for 5 hours. 120 (m
Pa). Further isopropyl alcohol 1
00 parts were added, and the mixture was further dispersed for 1 hour.

A uniform coating film is obtained by spray-coating the magnet-containing sleeve having an outer diameter of 32φ, on which the surface is subjected to blast treatment to form irregularities. Using the above dispersion liquid, coating was performed so that the coating film thickness after drying was 15 μm. After coating, the coating was dried and cured to form a developer carrying member (sleeve). The following toner was used.・ Styrene-acrylic resin 100 parts ・ Magnetite 90 parts ・ Chromium complex of monoazo dye 4 parts ・ Low molecular weight polypropylene 4 parts

The above materials are kneaded, crushed, classified and the like by a general dry toner production method, and have an average particle size of 8 μm and a particle size of 4 μm.
A toner containing 9% of those having a particle size of 1 μm or less and 0.9% by weight of those having a particle size of 12.7 μm or more was obtained. The particle size distribution is measured using a Coulter counter TA-II. 0.9% of colloidal silica was externally added to this toner. For image formation, NP6060 manufactured by Canon was used. When the distance between the developing sleeve and the blade is 200 μm,
An image endurance test for 10,000 sheets was performed. The environment for drawing is 24
C., 65% RH at normal temperature and normal humidity and 20.degree. C., 10% RH at low humidity. The change in image density at this time is shown in FIG. Measurement of image density is 5φ solid black image (5 ● density)
And the solid black density on the entire surface using a Macbeth reflection densitometer (Macbet)
h RD914).

Example 4 Pigment component (A) 10 parts of carbon black 70 parts of graphite Pigment component (B) 100 parts of phenol resin 90 parts of methanol 160 parts of isopropyl alcohol Silicone oil having a nitrogen-containing heterocycle (at 25 ° C.) (A) and (B) treated with a viscosity of 90 mPa and a nitrogen atom equivalent of 1,200) were dispersed at room temperature for 5 hours using a sand mill. 100 (m
Pa). Further isopropyl alcohol 1
00 parts were added, and the mixture was further dispersed for 1 hour.

In the same manner as in Example 3, a uniform coating film is obtained by spray coating on the sleeve containing the magnet having an outer diameter of 32φ. Using the above dispersion liquid, coating was performed so that the coating film thickness after drying was 15 μm. After coating, the coating was dried and cured to form a developer carrying member (sleeve). The same image output durability test as in Example 3 was performed. The change in image density at this time is shown in FIG.

Example 5 Pigment component (A) 25 parts of carbon black Pigment component (B) 100 parts of phenol resin 90 parts of methanol 160 parts of isopropyl alcohol Silicone oil having a nitrogen-containing heterocycle (viscosity 70 mPa at 25 ° C., (A) treated with nitrogen atom equivalent 830) and (B) were dispersed at room temperature for 5 hours using a sand mill. 100 (mP
The viscosity of a) was shown. Further isopropyl alcohol 10
0 parts were added and the dispersion was further performed for 1 hour.

In the same manner as in Example 3, a uniform coating film is obtained by spray coating on the sleeve containing the magnet having an outer diameter of 32φ. Using the above dispersion liquid, coating was performed so that the coating film thickness after drying was 15 μm. After coating, the coating was dried and cured to form a developer carrying member (sleeve). In Example 5 , a comparison was made by mounting the developing sleeve of 32φ on the developing device of NP6060, and adding the toner of Example 3 and performing idle rotation.

Comparative Example 1 100 parts of phenolic resin 90 parts of methanol 160 parts of isopropyl alcohol 100 parts of graphite The above materials were dispersed at room temperature for 5 hours using a sand mill. Measurement with a B-type viscometer showed a viscosity of 75 mPa. Further, 100 parts of isopropyl alcohol was added, and the mixture was further dispersed for 1 hour. In the same manner as in Example 1, coating was performed using this dispersion liquid so that the coating film thickness after drying was 10 μm. At this time, coating was performed so that the center line average roughness Ra was the same as that in Example 1. This was similarly dried and cured to produce a development carrier, and an image output test was performed. The change in image density at this time is shown in FIG.

Comparative Example 2 100 parts of phenolic resin 90 parts of methanol 160 parts of isopropyl alcohol 100 parts of tin oxide The above materials were dispersed at room temperature for 5 hours using a sand mill. Measurement with a B-type viscometer showed a viscosity of 85 mPa. Further, 100 parts of isopropyl alcohol was added, and the mixture was further dispersed for 1 hour. In the same manner as in Example 2, coating was performed using this dispersion liquid so that the coating film thickness after drying was 10 μm. Similarly, a dried and cured development carrier was prepared and subjected to an image output test. The image density change at this time is shown in FIG.

Comparative Example 3 100 parts of phenolic resin 90 parts of methanol 160 parts of isopropyl alcohol 100 parts of graphite The above materials were dispersed at room temperature for 5 hours using a sand mill. Measurement with a B-type viscometer showed a viscosity of 100 mPa. Further, 100 parts of isopropyl alcohol was added, and the mixture was further dispersed for 1 hour. In the same manner as in Example 3, coating was performed using this dispersion liquid so that the film thickness after drying was 15 μm. Similarly, a dried and cured development carrier was prepared and subjected to an image output test. The change in image density at this time is shown in FIG.

Comparative Example 4 100 parts of phenolic resin 90 parts of methanol 160 parts of isopropyl alcohol 5 parts of carbon black 100 parts of graphite The above materials were dispersed at room temperature for 5 hours using a sand mill. Measurement with a B-type viscometer showed a viscosity of 120 mPa. Further, 100 parts of isopropyl alcohol was added, and the mixture was further dispersed for 1 hour. In the same manner as in Example 4, coating was performed using this dispersion so that the film thickness after drying was 15 μm. Similarly, a dried and cured development carrier was prepared and subjected to an image output test. The change in image density at this time is shown in FIG.

Comparative Example 5 A developing sleeve was prepared and idling was performed without performing the treatment with the silicone oil having a nitrogen-containing heterocyclic ring in Example 5.

For Examples 1 to 5 and Comparative Examples 1 to 5 ,
The film thickness before and after endurance and the center line average roughness Ra before and after endurance were measured and are shown in Table 1. As a result, in the samples of Examples 1 to 5 , the changes in the film thickness and Ra were small, but in the samples of Comparative Examples 1 to 5 , both decreased greatly. Further, when the developing sleeve after the durability test was observed, the sample of the comparative example showed deposits and fusion of fine powder toner on the coating layer and peeling off of the film, while the sample of the example showed these fusions. No peeling of the kimono and the film was observed.

[0064]

[Table 1]

[0065]

As described above, according to the present invention, there is provided a developing carrier capable of obtaining a high-density and uniform image through durable image formation, and a developing apparatus using the same.
Further, according to the present invention, it is possible to prevent the deterioration of the film on the development carrier and the peeling of the film caused by repeated copying and durable image formation, which are seen in the conventional development carrier. or,
According to the present invention, accumulation of fine toner on the development carrier,
Since a proper charging failure due to fusion does not occur, it is possible to obtain a clear image without a decrease in image density, density unevenness, and thick and thin characters. Further, according to the present invention, it is possible to obtain a stable image which is not affected by environmental changes.

[Brief description of the drawings]

FIG. 1 is a schematic view of a conventional developing device having a developing roller on which a resin film is not formed.

FIG. 2 is a schematic view of a developing device having a developer carrier having a resin film formed thereon according to the present invention.

FIG. 3 is a view showing a developing device having a developer carrier on which a resin film according to the present invention is formed, and having a different type of developer layer regulating member.

FIG. 4 is a view showing a developing device having a developer carrier on which a resin film according to the present invention is formed, wherein the type of regulating member for the developer layer is different.

FIG. 5 is a drawing-out test result A in Example 1.

FIG. 6 is a drawing test result B in Example 2.

FIG. 7 is a drawing-out test result C in Example 3.

FIG. 8 is an image-drawing test result D in Example 4.

FIG. 9 is a drawing test result E in Comparative Example 1.

FIG. 10 is a drawing test result F in Comparative Example 2.

FIG. 11 is a drawing test result G in Comparative Example 3.

FIG. 12 is a drawing test result H in Comparative Example 4.

[Explanation of symbols]

 1: photosensitive drum (electrostatic latent image carrier) 2: magnetic regulating blade 3: container 4: developer (toner) 5: magnet roll 6: metal cylindrical tube 7: resin coating 8: developing sleeve 9: void 10: development Bias power supply 11: developing roller 12: developing roller 13: developing sleeve 20: elastic regulating blade 21: elastic regulating blade N1, S1, N2, S2: magnetic pole

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazuki Saiki 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Yasuhide Goseki 3-30-2 Shimomaruko, Ota-ku, Tokyo (56) References JP-A-3-279982 (JP, A) JP-A-61-277965 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 15 / 08-15/09

Claims (4)

(57) [Claims] 1. A met developer carrying member of a metal cylindrical tubular for use in a developing device for developing a latent image formed on the latent image holding member with a developer is carried and conveyed by the developer bearing member,
A conductive fine powder previously treated with a silicone oil having at least a nitrogen-containing heterocycle on a metal cylindrical tube and / or
Represents a solid lubricant as a pigment, and the pigment is contained in a binder resin.
A resin film that is dispersed and contained in is formed ,
The pigment (P) in the resin film and the binder resin
A developer carrier , wherein the content ratio (P / B) with (B) is 1/20 to 5/1 . 2. The method according to claim 1, wherein the resin film has a thickness of 20 μm or less.
The developer carrier according to claim 1. 3. A developer carrying a one-component developer accommodated in a developing container on a developer carrier and forming a thin film of the developer on the developer carrier by a developer layer regulating member. A developing device that transports the developer by a carrier to a developing unit facing the latent image carrier and develops a latent image formed on the latent image carrier; The agent carrier is at least nitrogen-containing on a metal cylindrical tube.
A guide pre-treated with a silicone oil having a heterocyclic ring
A pigment comprising an electric fine powder and / or a solid lubricant;
Of resin dispersed in binder resin is formed
And the pigment (P) in the resin film and
The content ratio (P / B) with the binder resin (B) is 1 /
20 to 5/1 . 4. The resin film having a thickness of 20 μm or less.
The developing device according to claim 3.