JP4324040B2 - Development method - Google Patents

Description

  The present invention relates to a developer carrier used for developing and developing a latent image formed on an image carrier such as an electrophotographic photosensitive member or an electrostatic recording dielectric in electrophotography and an electrophotographic method. The present invention relates to a developing method.

Conventionally, a number of methods are known as electrophotographic methods. Generally, a photoconductive material is used to form an electric latent image on an electrostatic latent image holding member (photosensitive drum) by various means. Then, a development bias is applied to the development area, and the electrostatic latent image is developed with a developer (toner) to be visualized, and if necessary, the toner image is transferred to a transfer material such as paper. The toner image is fixed on the transfer material by heat, pressure or the like to obtain a copy.
Although image formation by these electrophotographic methods has reached a satisfactory level for document copying, it will continue to be used for output images of full-color images required by the development of computers and the spread of high-resolution digital cameras. Further improvement in image quality and quality is desired.

  Development methods in electrophotography are mainly divided into a one-component development method and a two-component development method. Conventionally, two-component developers are used to output these full-color images. In the two-component development method, the carrier imparts electric charge to the toner by triboelectric charging, and carries the toner on its surface by electrostatic attraction due to this electric charge. A two-component developer having a toner and a carrier is coated on a developing sleeve containing a magnet as a developer carrier to a predetermined layer thickness by a developer layer thickness regulating member, so that magnetic force and friction resistance of the developing sleeve surface are coated. Is conveyed to a developing area formed between the electrostatic latent image carrier (photoconductor) and the developing sleeve and developed. However, in recent years, a developing device using a one-component developing system is often used for the purpose of reducing the weight and size of the electrophotographic apparatus.

  The one-component development method does not require carrier particles such as glass beads or iron powder unlike the two-component development method, and thus the development device itself can be reduced in size and weight. Furthermore, since the two-component developing method needs to keep the toner concentration in the two-component developer constant, a device for detecting the toner concentration and supplying a necessary amount of toner is required. For this reason, the developing device tends to be large and heavy. The one-component developing system is preferable because a replenishing device is not required, and the developing device can be made smaller and lighter.

In the one-component development system, a non-magnetic toner containing no magnetic material and a magnetic toner containing a magnetic material may be used in the toner, but when using for a full color image, the magnetic material is used from the viewpoint of color reproducibility. Non-magnetic one-component toner not included is often used.
As a developing device using a one-component developing system, an electrostatic latent image is formed on the surface of a photosensitive drum as an electrostatic latent image carrier, and friction between a developer carrier (developing sleeve) and toner, and / or The toner is positively or negatively charged by friction with the developer layer thickness regulating member for regulating the toner coat amount on the developing sleeve, and the toner is applied thinly on the developing sleeve, and the photosensitive drum and the developing sleeve Is transferred to the opposite development area, and a development bias is applied in the development area to develop the toner by causing the toner to fly and adhere to the electrostatic latent image on the surface of the photosensitive drum, thereby developing the electrostatic latent image as a toner image. Things are known. As the development bias, a blank pulse, a duty bias, a sawtooth wave, or the like is used. These biases are alternating biases in a broad sense, with the polarity of the electric field reversed within one period. By adjusting the magnitude and application time of the developing bias skipping voltage (development) and the magnitude and application time of the pull-back voltage, it has been used to prevent image blurring and to improve fog.

Recently, in order to digitize the electrophotographic apparatus and further increase the image quality, the toner has been reduced in particle size and particle size, and the waste toner has been used for the purpose of further reducing the weight and size of the electrophotographic apparatus. In order to alleviate this, toner transfer efficiency is improved. Further, for the purpose of shortening the first copy time and saving power, the toner fixing temperature tends to be lowered by a method such as increasing the ratio of the low softening point substance in the toner.
The above-described reduction in toner particle size and particle size, improvement in transfer efficiency, achievement of low-temperature fixing, and the like tend to be difficult only by a conventional pulverization method.

Therefore, a method for obtaining toner by a polymerization method has been studied. The polymerization method used for toner production is a monomer composition in which a polymerizable monomer, a colorant, a polymerization initiator and, if necessary, a crosslinking agent, a charge control agent, and other additives are uniformly dissolved or dispersed. After that, the monomer composition is dispersed in a continuous phase containing a dispersion stabilizer, for example, an aqueous phase using a suitable stirrer, and simultaneously undergoes a polymerization reaction to obtain a toner having a desired particle size. How to get.
Since this manufacturing method does not go through a pulverization step, it is not necessary to impart brittleness to the developer, and furthermore, a wide range of materials can be used, such as a large amount of low softening point substances that could not be used in conventional pulverization methods. Is preferable.

Further, the polymerization method has characteristics that the particle size distribution is sharp, and a spherical toner having a high transfer efficiency can be produced relatively easily.
However, even when a toner by polymerization is used, the formation of the toner layer on the developer carrying member depends on the environmental state, the physical properties of the toner, the surface state of the developer carrying member, etc., and is difficult to control. Especially at low temperatures and low humidity, the amount of charge per unit mass increases, so it is more likely to adhere electrostatically on the developer carrier. Also, under high temperatures and high humidity, external physical force is applied. Since the toner is made of a material that is easy to fluidize, the toner is easily deteriorated, and the developer carrier is contaminated by the toner (so-called “sleeve contamination”) or fused to the developer carrier (so-called “sleeve fusion”). Is likely to occur.

  As the copying is repeated, the toner is repeatedly rubbed against the developer carrier, so that additives for improving the fluidity of the toner are released from the toner, and these free substances are deposited on the developer carrier, or Since the low softening point substance in the toner forms a film on the developer carrier, there is a problem that the surface state of the developer carrier changes and the developability of the toner changes.

  Since the toner obtained by the polymerization method has extremely good fluidity compared to the toner obtained by the pulverization method, when the toner obtained by the polymerization method is used in a developing device using a conventional one-component development system, the toner However, there is a case where the phenomenon of slipping between the developer carrying member and the regulating member is likely to occur. For this reason, the charge amount between the developer particles is likely to be non-uniform, and the toner is likely to be in a non-uniform coating state on the developer carrying member, and as a result, a defective image with fog and unevenness is likely to occur. . Furthermore, since it is easy for toner to enter a bearing or the like during repeated image formation evaluation over a long period of time, and thus a toner fusion product is likely to occur, transfer defects are likely to occur during transfer.

In general, the toner obtained by the polymerization method is substantially spherical in order to improve transfer efficiency, so that it is easy to close-pack the toner in the developing device, and the toner is densely packed in the downstream portion of the regulating member in the developing device. Therefore, there is a case where the mechanical load force on the toner increases and the toner is fused on the developer carrying member, so-called sleeve contamination occurs. Sleeve contamination is undesirable because it causes a reduction in image density and fogging.
Since the toner obtained by the polymerization method has a high sphericity, the charge of the toner itself tends to be too high. Therefore, it is difficult to adjust the charge of the toner. However, problems relating to durability stability such as non-uniformity of toner charging and occurrence of fusion to the sleeve surface have not been completely solved.

  In addition, as the developing sleeve rotates repeatedly, the charge amount of the toner coated on the developing sleeve becomes too high due to contact with the developing sleeve, and the toner is attracted by the reflection force on the developing sleeve surface and developed. The so-called charge-up phenomenon that becomes stationary on the surface of the sleeve and does not move from the developing sleeve to the electrostatic latent image on the electrostatic latent image holding member (drum) is likely to occur particularly under low humidity. When such a charge-up phenomenon occurs, the toner in the upper layer becomes difficult to be charged and the development amount of the toner is reduced, which causes problems such as thin line images and thin image density of solid images. Furthermore, the toner that is not properly charged due to charge-up becomes poorly regulated and flows out onto the sleeve, so that a so-called blotch phenomenon in which spots and wavy irregularities occur. When a halftone image is developed, problems such as density unevenness are likely to occur.

  There has been proposed a method for improving the occurrence of fog and density unevenness by applying a blank pulse as a developing bias between the developing sleeve and the photosensitive drum (see, for example, Patent Document 1). By using this method, density unevenness and fogging in a halftone image are reduced. However, when toner obtained by a polymerization method having a small particle size and a spherical shape is used, the toner layer on the sleeve due to poor regulation such as slip-through. Since the layer thickness tends to increase and toner charge distribution tends to occur, the effect of improving fog and density unevenness is still insufficient.

  There has been proposed a method using a developing sleeve in which a coating layer in which conductive fine powder such as crystalline graphite and carbon is dispersed in a resin is provided on a substrate (see, for example, Patent Documents 2 and 3). Although this method is effective for preventing the charge-up phenomenon and improving the uniformity of charging, it is still insufficient. When a large amount of the above powder is added, the charge-up phenomenon is improved. However, in particular, when a non-magnetic one-component developer is used, the ability to impart charge to the toner becomes insufficient, and transportability is reduced and density unevenness is likely to occur. Furthermore, the coating layer becomes brittle and becomes easy to scrape, and the surface becomes non-uniform, resulting in problems such as a decrease in the durability of the coating layer. In addition, when the coating layer in which the crystalline graphite is dispersed is used, the surface of the coating layer has lubricity due to the scaly structure of the crystalline graphite, so the fusion to the sleeve is improved. However, since the shape of the crystalline graphite is scaly, the surface of the coating layer tends to be non-uniform due to partial wear due to durability, and there is a problem such as fluctuation in toner transportability. In particular, when the regulating force such as the contact pressure by the developer layer thickness regulating member is strengthened to regulate the toner layer on the developer carrying member, the regulating member is likely to be scratched. Lines are likely to occur. Furthermore, since the hardness of the crystalline graphite is low, wear and desorption of the crystalline graphite itself is likely to occur on the surface of the coating layer, and when the durability test was advanced, the surface roughness and surface composition of the coating layer changed, Toner conveyance failure and non-uniform charge application to the toner are likely to occur. On the other hand, when the addition amount is small, the effect of the conductive fine powder such as crystalline graphite and carbon is thin, and there remains a problem that it is insufficient for charge-up and fogging.

  There has also been proposed a method of preventing charge-up phenomenon of a toner and promptly imparting charging to the toner by using graphitized particles having a specific crystallinity instead of crystalline graphite (see, for example, Patent Document 4). ). However, using this method, although certain effects are observed in preventing charge-up phenomenon and improving charging uniformity, charging stability and transport for color non-magnetic toners prepared by spheronization or polymerization methods Stability is still insufficient.

In the toner resin, a quaternary ammonium salt compound, which is positively charged with respect to iron powder, is added to the spheroidized toner and the toner produced by the polymerization method is charged excessively such as charge-up. There has been proposed a method using a developing sleeve for preventing (see, for example, Patent Documents 5 and 6).
Although these methods are effective in preventing the charge-up phenomenon and improving the uniformity of charging, the charging stability and the conveyance stability for the toner are still insufficient.

In particular, when using a non-contact type developing device that uses a non-magnetic toner that does not have a magnetic material produced by a polymerization method and performs development in a non-contact state between the photosensitive drum and the developer carrier, it does not have a magnetic material. The charging stability and transport stability for non-magnetic toners have not been sufficiently solved.
Further, there has been proposed a developing sleeve in which a conductive coating layer in which conductive fine powders such as crystalline graphite and carbon and spherical particles are dispersed in a resin is provided on a metal substrate (see, for example, Patent Document 7). . In this developing sleeve, the wear resistance of the coating layer is improved to some extent, the shape of the coating layer surface is made uniform, and the change in surface roughness due to the durability test is relatively small, so that the toner coating on the sleeve is stabilized. Thus, the charge of the toner can be made uniform, there is little fog, image density, image density unevenness, etc., and the image quality tends to be stabilized. However, this developing sleeve is also insufficient for uniform charging to the spherical non-magnetic toner produced by the polymerization method and stabilization of the charge imparting ability to the toner, and the spherical particles and crystalline graphite of the coating layer are worn. Or, the coating layer surface roughness change or surface roughness non-uniformity caused by detachment, toner contamination and toner fusion of the coating layer, and the like occur. In such a case, toner charging is unstable. Tends to cause image defects.

  The spherical particles dispersed in the conductive coating layer of the developer carrier are low specific gravity and conductive spherical particles, and thereby the conductive spherical particles are uniformly dispersed in the conductive coating layer. A developing sleeve has been proposed in which the wear resistance of the coating layer and the shape of the surface of the coating layer are made uniform to improve uniform chargeability on the toner, and even when the coating layer is worn somewhat, toner contamination and toner fusion can be suppressed. (For example, refer to Patent Document 8). However, even in this developing sleeve, when a non-magnetic one-component toner is used, it is not complete in terms of uniform charging to the toner and the ability to impart charge to the toner. In addition, conductive particles such as crystalline graphite are likely to wear or drop off, and the wear of the coating layer is promoted from the worn and dropped parts, causing toner contamination and toner fusing, resulting in unstable toner charging and poor image quality. Cause.

There has been proposed a developing sleeve in which an inorganic compound having a different particle diameter is dispersed in a coating layer of a developer carrier to optimize the amount of toner transport and to impart frictional charge to the toner (for example, Patent Documents). 9). However, when a non-magnetic toner having a small particle size and a high sphericity produced by a polymerization method is used, the thickness of the toner layer on the sleeve tends to increase due to poor regulation of the toner layer thickness, such as slipping through. It is insufficient for stabilizing the uniform charging of the toner and the ability to impart charge to the toner, and has not yet reached a sufficient solution, such as being liable to cause image defects such as fogging and sweeping.
JP 09-311539 A Japanese Patent Laid-Open No. 02-105181 Japanese Unexamined Patent Publication No. 03-036570 Japanese Patent Laid-Open No. 2003-323042 JP 2003-057951 A JP 2002-311636 A Japanese Patent Laid-Open No. 03-200986 Japanese Patent Laid-Open No. 08-240981 Japanese Patent Application Laid-Open No. 07-306586

It is an object of the present invention to have high durability with little wear of the resin coating layer of the developer carrying member even after long-term use, less variation in wear of the resin coating layer, and destabilization of developer transportability provides non-uniform charging of the developer, further lowering of image density, image density unevenness, fogging, without problems such as swept occurs, the current image how high quality images to enable you be stably obtained That is.

Another object of the present invention is to impart a uniform and high charge to the developer on the developer carrying member even when used for a long period of time, to prevent overcharging of the developer, and to stabilize the charging of the developer. holding, image density decrease, fog, hardly occurs such scattering is to provide a current image how to obtain a stable image quality.

Another object of the present invention is to stably obtain a high-quality image without causing problems such as density reduction, image density unevenness, sweeping, fogging, developer fusion, and blotch even under different environmental conditions. to enable you be to provide a current image method.

The object of the present invention is to control the uneven charging of the developer that appears when a developer having a small particle diameter or a developer having a high spheroidization degree is used, and to provide sufficient charge to the developer. it is to provide a current image method is Ru can be a developer layer stably formed transported on-carrying member.

An object of the present invention, scratches and less likely to occur in fusion of the restriction member, which due to less likely to occur streaky image defect is to provide a current image how stable image quality can be obtained.
An object of the present invention is to apply a voltage in which an alternating current component that intermittently pauses as a developing bias is applied to a direct current component, and to develop the developer used in a developing method for visualizing a latent image on an electrostatic latent image carrier Even when a non-magnetic developer having a high degree of circularity produced by a polymerization method is used as a one-component developer in the carrier, the developer layer thickness on the developer carrier is prevented from being increased, and the developer to equalize the charge of, it is to provide a density unevenness, fogging developer fusion or blotches and sweeping like current image how a high-quality image free from image defects to enable you be stably obtained for.

As a result of diligent investigations on the above problems, the present invention and the like are based on a resin coating on the surface of a developer carrying member in a developing method using a voltage in which an alternating current component that intermittently pauses as a developing bias is superimposed on a direct current component. By including in the layer, the unevenness of the surface of the developer carrying member (hereinafter also referred to as “surface roughness”) and the variation in the material composition can be reduced, thereby the developer layer on the developer carrying member. the thickness found that charging of the developer can be uniformly performed with can be formed stably, and completed the present invention.
Since the developer layer thickness on the developer carrying member can be stably kept low and the developer can be charged uniformly, the effect of improving density uniformity, sweeping and fogging can be obtained when a blank pulse is used as a developing bias. I found that it appears synergistically. It has also been found that when a non-magnetic developer having a high degree of circularity produced by a polymerization method is used as a one-component developer, the effect can be exhibited particularly.
In other words, it is difficult to form a stable thin toner layer on the developer carrier due to high fluidity and slipping from the regulating member, etc. It has been found that the developing method of the present invention can stably form the toner layer thickness on the developer carrying member and can uniformly charge the developer with respect to the spherical developer that has been used.

That is, the present invention is as follows.
(1) A non-contact developing method using a non-contact type developing device that performs development in a non-contact state between an electrostatic latent image carrier and a developer carrier,
A non-magnetic one-component developer is carried on a developer carrier, transported to a development area facing the electrostatic latent image carrier, and an alternating current component intermittently paused on the developer carrier is superimposed on the direct current component. applying a voltage as developing bias, and a step of a visible image of the latent image on the electrostatic latent image bearing member,
The developer carrier has at least a substrate and a resin coating layer formed on the substrate, and the resin coating layer includes:
Concavity and convexity imparting particles made of spherical carbon particles for imparting concavity and convexity to the surface of the resin coating layer having a volume average particle diameter of 3.2 to 8.7 μm, and a graphitization degree P (002) of 0.23 ≦ P (002) ≦ 0.92 and containing at least graphitized particles for imparting conductivity, having a volume average particle diameter of 0.49 to 3.78 μm, and
A developing method comprising: a developer carrying member having a volume particle size distribution of particles contained in the resin coating layer of 4.80 % or less.

(2) The developing method according to (1), wherein a volume average particle diameter of the graphitized particles is smaller than a volume average particle diameter of the unevenness imparting particles .
(3) The developing method according to (1) or (2), wherein the graphitized particles are obtained by graphitizing bulk mesophase pitch or mesocarbon microbeads. (4) The developing method according to any one of (1) to (3), wherein the nonmagnetic toner as the nonmagnetic one-component developer is produced by a polymerization method.

（式中、平均円形度をａ _ａｖｅ 、各粒子における円形度をａ _ｉ 、測定粒子数をｍとして示す。）。

（６）前記樹脂被覆層の層厚が４〜２０μｍである請求項１〜５の何れかに記載の現像方法。 (5) The developing method according to (4), wherein the non-magnetic one-component developer is a developer having an average circularity of 0.935 or more obtained from the following formulas (C) and (D): .
Circularity a = L ₀ / L (C)
(In the formula, L ₀ represents the circumference of a circle having the same projected area as the particle image, and L represents the circumference of the particle image.)

(In the formula, the average circularity is a _ave , the circularity of each particle is a _i , and the number of measured particles is m).

(6) The developing method according to any one of claims 1 to 5, wherein the resin coating layer has a thickness of 4 to 20 µm.

As described above, by incorporating specific irregularity-providing particles and graphitized particles in the resin coating layer of the developer carrier, the durability of the resin coating layer, which has been considered a problem in the past, can be improved, and the developer carrier It is possible to reduce the unevenness of the surface, the variation in wear and the variation in material composition, the developer layer thickness on the developer carrying member can be stably formed, and the developer can be charged uniformly . The further, by applying a voltage superimposed on the DC component of the AC component to pause intermittently to the developer carrying member as the developing bias, the image density decrease, image density unevenness, fogging, developer fused, sweeping It becomes possible to improve such problems.

Further, by appropriately selecting the volume average particle size and the degree of graphitization of the graphitized particles contained in the resin coating layer of the developer carrier, the abrasion resistance of the coating layer surface of the developer carrier, the machine of the resin coating layer it is possible to suppress the generation of suppression and blade scratches blotch and charge-up occurs with strength and improve the charge-providing performance to the developer.

By making the volume average particle size of the graphitized particles contained in the resin coating layer of the developer carrier smaller than the volume average particle size of the unevenness imparting particles, even if the coating layer surface wear due to durability occurs, the surface roughness Is less likely to change, and the developer transportability and the charge imparting property to the developer can be kept stable.

In addition, by using graphitized particles contained in the resin coating layer of the developer carrier obtained by graphitizing bulk mesophase pitch or mesocarbon microbeads, a uniform surface roughness can be obtained on the surface of the resin coating layer. At the same time, even when the surface of the coating layer is worn, there is little change in the surface roughness of the resin coating layer, and it is difficult for developer contamination and developer fusion to occur .

Further, the resin coating layer, by incorporating the quaternary ammonium salt compound, having stability and transport stability of the charge-providing to the developer.
In addition, by using a specific quaternary ammonium salt compound and containing a nitrogen-containing resin in the resin coating layer of the developer carrying member, it is possible to obtain more effects of charging stability and transport stability to the developer. can, fog or blotch, the occurrence of charge-up can be suppressed.

The developer carrying member of the present invention is a developing method in which a voltage obtained by superimposing an intermittently alternating AC component on a DC component is applied as a developing bias to visualize an electrostatic latent image on the electrostatic latent image carrier A developer carrier used for
The developer carrier has at least a substrate and a resin coating layer formed on the substrate,
The resin coating layer has a volume average particle size of 3.0 to 9.0 μm, and has irregularity-imparting particles for imparting irregularities to the resin coating layer surface, and the degree of graphitization P (002) is 0.20 ≦ P ( 002) ≦ 0.95 and containing graphitized particles for imparting electrical conductivity having a volume average particle size of 0.5 to 4.0 μm, and the resin coating layer is contained in the resin coating layer. In the volume particle size distribution of the contained particles, the abundance ratio of particles having a volume particle size of 10 μm or more is 5.0% or less.

The developer carrier of the present invention can reduce unevenness of the developer carrier and variations in material composition, and can stably form the developer layer thickness on the developer carrier, with the above-described configuration. Can be uniformly charged. In this way, the developer layer thickness on the developer carrier can be stably maintained at a low level and the developer can be charged uniformly, thereby improving density uniformity, sweeping and fogging when using a blank pulse as a developing bias. The effect of synergistically appears.
In addition, when used over a long period of time, the wear of the resin coating layer on the surface of the developer carrying member is caused by receiving a force from the developer layer thickness regulating member or an external additive such as an abrasive contained in the developer. However, the developer-carrying member of the present invention can suppress the change in surface roughness associated with the developer conveyance because the unevenness imparting particles are contained in the resin coating layer. In addition, the developer-carrying member of the present invention is such that the graphitized particles used in the resin coating layer are relatively hard and less likely to wear compared to crystalline graphite having a high degree of graphitization that has been used in the past. Because the difference in hardness from the binder resin such as phenol resin used in the layer is small, it is less likely to be unevenly scraped even if scraping due to durability or detachment of graphitized particles occurs. This has the effect of making it difficult for the uneven shape and material composition to change. In addition, the graphitized particles having a graphitization degree of 0.20 to 0.95 used for the developer carrier of the present invention have lubricity, so that it is difficult for the developer to adhere to the developer carrier. Have.
By including the graphitized particles according to the present invention in the resin coating layer, it is possible to obtain an effect of imparting a uniform and stable charge to the developer without causing developer contamination or developer charge-up. .

Hereinafter, the present invention will be described in detail with reference to preferred embodiments.
In the developer carrying member of the present invention, as a material constituting the resin coating layer formed on the substrate, in order to stably maintain the toner transportability through durability by imparting irregularities in the resin coating layer, In order to impart conductivity, the irregularity imparting particles having an average particle size of 3.0 to 9.0 μm, and the degree of graphitization P (002) is 0.20 ≦ P (002) ≦ 0.95 and the volume average Graphitized particles having a particle size of 0.5 to 4.0 μm are used.

Hereinafter, the unevenness imparting particles used in the present invention will be described.
As the irregularity-imparting particles used in the present invention, it is more preferable to use spherical particles than irregular particles because the irregularities on the surface of the resin coating layer are likely to be uniform and the developer transportability is stable. .
Here, the “spherical particles” mean particles having a major axis / minor axis ratio of about 1.0 to 1.5, and in the present invention, the ratio of major axis / minor axis is preferably 1.0. It is better to use particles of ~ 1.2. When the ratio of the major axis / minor axis of the spherical particles is 1.5 or less, the dispersibility of the particles in the resin coating layer becomes better, and it is easier to obtain a uniform coating layer surface shape and to obtain uniform frictional charge. It is preferable because non-uniform shaving of the resin coating layer hardly occurs.

  The unevenness imparting particles in the present invention preferably have a volume average particle size of 3.0 to 9.0 μm. If the volume average particle size of the unevenness imparting particles is less than 3.0 μm, the effect of forming unevenness on the surface of the coating layer is small, and it may be insufficient in terms of maintaining the developer transportability. If sufficient transportability cannot be obtained, uniform charging to the developer becomes insufficient, wear of the resin coating layer tends to increase, and charging unevenness such as developer charge-up and development Agent contamination, developer fusion, and the like occur, and image density lowering and density unevenness are likely to occur. When the volume average particle size exceeds 9.0 μm, the unevenness on the surface of the resin coating layer becomes too large, the developer is excessively conveyed or non-uniform, and the developer is not sufficiently charged. In such a case, image streaking, fading, fogging, and low density are likely to occur due to non-uniform frictional charging. In addition, since the convexity formed by the irregularity-imparting particles becomes too high, when the elastic blade is used as the developer layer thickness regulating member, the projections of the irregularity-imparting particles themselves may damage the blade. Streaks are likely to occur.

The developer carrying member of the present invention has an unevenness of the resin coating layer on the surface of the resin coating layer, that is, an arithmetic average roughness Ra (hereinafter referred to as “Ra”) of 0.2 to 1.5 μm. It is preferable that the thickness is 0.3 to 0.9 μm.
When Ra is less than 0.2 μm, particularly when an elastic blade and a developer having a high sphericity are used, the developer is likely to be fused or charged up, resulting in a decrease in image density, image streaking, and image density. Unevenness and sleeve ghosts may occur.
When Ra exceeds 1.5 μm, the amount of developer transported on the developer carrying member becomes too large, and it becomes difficult to uniformly charge the developer, and fog and sleeve ghost are likely to occur.

True density of unevenness imparting particles used in the present invention, 3 g / cm ³ or less, preferably 2.7 g / cm ³ or less, it is better and more preferably from 0.9~2.3g / cm ^3. When the true density of the unevenness imparting particles is 3 g / cm ³ or less, the dispersibility of the particles in the resin coating layer is better, and it is easier to obtain a uniform roughness on the surface of the resin coating layer, and the development is stable. The agent can be conveyed. Further, it is preferable because uniform charging and strength of the resin coating layer can be obtained. Furthermore, when the true density of the unevenness imparting particles is 0.9 g / cm ³ or more, the dispersibility of the unevenness imparting particles in the resin coating layer becomes better, which is preferable.

  Known particles can be used as the irregularity-imparting particles used in the present invention. For example, there are resin particles, metal oxide particles, carbonized particles and the like, and a preferable shape is spherical. As these spherical unevenness-imparting particles, for example, spherical resin particles obtained by suspension polymerization, dispersion polymerization or the like are used. The spherical resin particles can obtain a suitable surface roughness with a smaller addition amount, and can obtain a more uniform surface shape. Examples of such spherical unevenness-imparting particles include acrylic resin particles such as polyacrylate and polymethacrylate, polyamide resin particles such as nylon, polyolefin resin particles such as polyethylene and polypropylene, silicone resin particles, and phenol resin particles. , Polyurethane resin particles, styrene resin particles, benzoguanamine particles, and the like.

The resin particles obtained by the pulverization method may be used after thermally or physically spheroidizing. In this invention, it is preferable to use the uneven | corrugated particle | grains which have electroconductivity especially in the said uneven | corrugated particle | grains. That is, by imparting conductivity to the irregularity imparting particles, it is difficult to accumulate charges on the particle surface due to the conductivity, and it is possible to reduce the adhesion of the developer and improve the charge imparting property to the developer. In the present invention, the conductivity of the irregularity-imparting particles is preferably 10 ⁶ Ω · cm or less, more preferably 10 ⁻³ to 10 ⁶ Ω · cm. When the unevenness imparting particles have a volume resistance of 10 ⁶ Ω · cm or less, the particles exposed on the surface of the resin coating layer due to wear are less likely to cause contamination and fusion of the developer, and prompt and uniform charging is achieved. It is preferable because it is easy to perform. In particular, when conductive spherical unevenness-imparting particles as shown below are used, a better effect can be obtained.

  Particularly preferable conductive spherical unevenness-imparting particles include, for example, low density and highly conductive spherical carbon particles obtained by carbonizing and / or graphitizing by firing spherical resin particles and the like. Examples of spherical resin particles used for carbonization and / or graphitization include resins such as phenol resin, naphthalene resin, furan resin, xylene resin, divinylbenzene polymer, styrene-divinylbenzene copolymer, and polyacrylonitrile. And spherical particles.

  More preferable conductive spherical unevenness-imparting particles are formed on the surface of spherical resin particles made of phenol resin, naphthalene resin, furan resin, xylene resin, divinylbenzene polymer, styrene-divinylbenzene copolymer, polyacrylonitrile, etc. Conductive spherical unevenness obtained by coating carbon particles and / or graphitizing by coating bulk mesophase pitch by heat treatment of the coated particles in an oxidizing atmosphere followed by firing in an inert atmosphere or vacuum Particles.

In any of the above methods, the conductivity of the spherical irregularity-imparting particles obtained by changing the firing conditions can be controlled, so that the method is preferably used in the present invention. In addition, in some cases, the spherical irregularity-imparting particles obtained by the above-described method may have a conductive metal and / or metal oxidation within a range in which the true density of the conductive spherical irregularity-imparting particles does not become too high in order to further increase conductivity. An object may be plated.
The volume average particle diameter of the unevenness imparting resin particles can be adjusted by classification operation, the degree of sphericalness can be adjusted by thermal or mechanical treatment, and the true density can be adjusted by appropriately selecting the material and molecular weight or by plating treatment.

Next, the graphitized particles used in the present invention will be described.
The graphitized particles used in the present invention maintain a uniform surface roughness on the surface of the resin coating layer of the developer carrier, and at the same time, there is little change in the surface roughness of the coating layer even when the coating layer surface is worn. In addition, it is added to make it difficult to cause toner contamination and toner fusion. Further, the graphitized particles have an effect of enhancing the charge imparting property to the toner.

In the present invention, the graphitization degree P (002) of the graphitized particles dispersed in the coating layer of the developer carrier satisfies 0.20 ≦ P (002) ≦ 0.95. The degree of graphitization P (002) is said to be the Franklin P value. By measuring the lattice spacing d (002) obtained from the X-ray diffraction diagram of graphite, d (002) = 3.440-0. .086 (1-P ² ). This P value indicates the proportion of the disordered portion of the hexagonal mesh plane stack of carbon. The smaller the P value, the greater the degree of graphitization.
When the degree of graphitization P (002) of the graphitized particles dispersed in the resin coating layer exceeds 0.95, the wear resistance is excellent, but the conductivity and lubricity are deteriorated and the toner charge is reduced. Inhomogeneity and charge-up may occur, and image quality such as fogging, uneven density, and reduced image density tends to deteriorate. Further, when an elastic regulating blade is used as the developer layer thickness regulating member, blade scratches may occur, and streaks, density unevenness, etc. are likely to occur in the image. When P (002) is less than 0.20, the wear resistance of the surface of the resin coating layer, the mechanical strength of the resin coating layer, and the charge imparting property to the toner tend to decrease due to the deterioration of the wear resistance of the graphitized particles. There is.

  The graphitized particles used in the present invention are 1000 to 100000 after the aggregate such as coke, which has been used in the coating layer on the surface of the developer carrying member in Patent Document 2, Patent Document 3, etc., is solidified with tar pitch or the like. The raw materials and the manufacturing process are different from those of artificial graphite obtained by firing at about 1300 ° C. and then graphitizing at about 2500 to 3000 ° C. or crystalline graphite made of natural graphite. Therefore, although the graphitized particles according to the present invention have a slightly lower degree of graphitization than the conventionally used crystalline graphite, they have high conductivity and lubricity similarly to the conventionally used crystalline graphite. Unlike the crystalline graphite flakes or needles used in the past, it is characterized by being massive and having relatively high hardness.

  The graphitized particles in the present invention are different from the conductive spherical particles as the above-described unevenness-imparting particles used in the present invention in terms of the lubricity and charge imparting characteristics of the particles themselves due to the difference in raw materials and production methods.

As described above, the conductive spherical unevenness-imparting particle is a spherical resin particle surface made of a resin such as phenol resin, naphthalene resin, furan resin, xylene resin, divinylbenzene polymer, styrene-divinylbenzene copolymer, polyacrylonitrile. In addition, a bulk mesophase pitch is coated by mechanochemical method, and the coated particles are heat-treated in an oxidizing atmosphere and then baked in an inert atmosphere or vacuum to be carbonized and / or graphitized. However, since the resin particles themselves are hard to graphitize, even if the surface is graphitized, the inside of the particles is carbonized, and the degree of graphitization P (002) of the particles themselves is not crystalline. The crystallinity is small. Therefore, when the conductive spherical unevenness imparting particles are dispersed in the resin coating layer, as described above, it has the effect of imparting a uniform surface roughness and improving the durability thereof, stable toner transportability and Has the effect of charging stability. However,
Addition of the irregularity-imparting particles alone cannot sufficiently exhibit uniform properties such as lubricity, conductivity, and chargeability on the resin coating layer surface.

Therefore, by using graphitized particles having the above characteristics together with the unevenness imparting particles in the resin coating layer, it is possible to impart wear resistance to the surface of the resin coating layer while maintaining excellent lubricity.
In addition to this, the graphitized particles used in the present invention are difficult to change in shape due to the degree of graphitization and the shape of the graphitized particles themselves. Even if the detachment occurs, the change in the surface shape of the resin coating layer can be kept small. In addition, the graphitized particles in the present invention have a small hardness difference from a binder resin such as a phenol resin used for the resin coating layer compared to the crystalline graphite that has been conventionally used, so that even if it is scraped, the resin is selectively used. The resin portion or graphitized particle portion of the coating layer is less likely to be scraped and is less likely to be shaved unevenly. Therefore, the change of the uneven shape on the surface of the resin coating layer can be suppressed small.

  When the graphitized particles are finely and uniformly dispersed in the resin coating layer, the transportability and wear resistance of the toner are improved, and therefore the dispersibility of the irregularity-imparting particles contained in the resin coating layer is also increased. As a result, the effect of preventing toner fusion is improved due to wear resistance and durability of the resin coating layer.

In the present invention, the graphitized particles dispersed in the resin coating layer of the developer carrying member preferably have a volume average particle size of 0.5 to 4.0 μm. Moreover, it is preferable that the volume average particle diameter of the graphitized particles dispersed in the resin coating layer is smaller than the volume average particle diameter of the unevenness imparting particles.
Since graphitized particles have a relatively low strength compared to the irregularity-providing particles, the smaller the volume average particle diameter of the irregularity-providing particles, the easier it is to disperse uniformly on the surface of the resin coating layer, and wear due to durability occurs. Even in this case, the surface of the resin coating layer is unlikely to become uneven, and the surface roughness is easily maintained.

  When the volume average particle diameter of the graphitized particles is less than 0.5 μm, the effect of imparting uniform surface roughness to the surface of the resin coating layer and the effect of enhancing the charge imparting performance are small, and the toner is insufficiently charged quickly and uniformly. In addition, toner charge-up due to abrasion of the resin coating layer, toner contamination, and toner fusion occur, which tends to cause fogging and a decrease in image density. When the volume average particle size exceeds 4.0 μm, the uniform dispersibility in the resin coating layer is reduced, the surface roughness tends to be non-uniform, and the wear of the resin coating layer varies during long-term use. It tends to occur, and image density unevenness and toner contamination / fusion due to the shaved portion are likely to occur.

  In the present invention, it is preferable that the relationship between the volume average particle diameter of the graphitized particles dispersed in the resin coating layer and the degree of graphitization P (002) satisfies the following formulas (A) and (B).

-0.0464Ln (x) + 0.3143≤Y≤-0.0464Ln (x) +0.7643 (A)
0.5 ≦ X ≦ 4.0 (B)
(In the formula, X represents the volume average particle diameter (μm) of the graphitized particles, and Y represents the degree of graphitization P (002) of the graphitized particles.)

It has been recognized that layered minerals such as graphite cause irregularity in layer stacking due to shear stress during grinding and pulverization, and change in interlayer distance. Also in the present invention, when the particle size is controlled in the pulverization / classification step in the manufacturing process of the graphitized particles, or when the graphitized particles are dispersed in the resin solution, the particle size of the graphitized particles is reduced. Accordingly, the degree of graphitization tends to decrease slightly. The above formulas (A) and (B) take into account the dispersion particle size dependence on the degree of graphitization of the graphitized particles after dispersion, and the volume average particle size of the graphitized particles dispersed in the resin coating layer is 0. -0.0464Ln (x) + 0.3143 ≦ Y ≦ when .5 to 4.0 μm
It is preferable to satisfy −0.0464Ln (x) +0.7643. In the case of Y <−0.0464Ln (x) +0.3143, the wear resistance of the graphitized particles tends to decrease, the wear resistance of the surface of the resin coating layer, the mechanical strength of the resin coating layer, and the charging of the toner. It tends to cause a decline in sex. Further, in the case of Y> −0.0464Ln (x) +0.7643, the wear resistance is excellent, but the conductivity and lubricity may be reduced, and the toner may be charged up. Image quality is likely to deteriorate, such as deterioration in image quality and image density reduction. In addition, when an elastic blade is used for the developer layer thickness regulating member, blade damage may occur. It tends to occur.

  The resin coating layer of the present invention requires that the abundance ratio of particles having a volume particle size of 10 μm or more in the volume particle size distribution is 5.0% or less in the entire particles contained in the resin coating layer. If particles existing in the resin coating layer have a volume particle size distribution of 10 μm or more in the volume particle size distribution of more than 5.0%, the surface roughness of the resin coating layer is difficult to be uniform, and the toner is rapidly and uniformly distributed. Inadequate charging is likely to occur, the toner coating is liable to be contaminated and fused on the convex portion of the resin coating layer, and the developer layer thickness regulating member is liable to be damaged due to durability.

The method for obtaining graphitized particles in the present invention is preferably the following method, but is not necessarily limited to these methods.
As a method for obtaining particularly preferred graphitized particles used in the present invention, graphitization is performed using optically anisotropic and single phase particles such as mesocarbon microbeads and bulk mesophase pitch as raw materials. It is preferable that the graphitized particles have a desired graphitization degree and can retain a lump shape.
The optical anisotropy of the above-mentioned raw materials is caused by the lamination of aromatic molecules, and the order is further developed by the graphitization treatment, and graphitized particles having a high degree of graphitization are obtained.

In the case of using the bulk mesophase pitch, it is preferable to use a material that is softened and melted by heating in order to obtain graphitized particles that are massive and have a high degree of graphitization.
The bulk mesophase pitch used in the present invention is obtained, for example, as follows. It can be obtained by extracting β-resin from a coal tar pitch or the like by solvent fractionation, and performing hydrogenation and heavy treatment. Moreover, you may use what was obtained by pulverizing after the said heavyening process, and then removing a solvent soluble part with benzene or toluene.

The bulk mesophase pitch in the present invention preferably has a quinoline soluble content of 95% by mass or more. When the amount less than 95% by mass is used, the inside of the particles is hardly liquid-phase carbonized, and solid-phase carbonization causes the particles to remain in a crushed state, making it difficult to obtain a spherical one. In order to make the quinoline soluble content 95% by mass or more, the temperature and the treatment time in the heavy processing are adjusted.
Examples of methods for graphitizing using the bulk mesophase pitch to obtain graphitized particles include the following methods. First, the bulk mesophase pitch is finely pulverized to 2 to 25 μm, and this is lightly oxidized by heat treatment at about 200 to 350 ° C. in air. By this oxidation treatment, only the surface of the bulk mesophase pitch is infusible, and internal melting and fusion are prevented during the graphitizing heat treatment in the next step. This oxidized bulk mesophase pitch preferably has an oxygen content of 5 to 15% by mass. If it is less than 5% by mass, fusion between the particles during the heat treatment is severe, which is not preferable. If it exceeds 15% by mass, the inside of the particle is oxidized, and it is difficult to obtain a spherical product in a crushed shape. . The oxygen content of the oxidized bulk mesophase pitch is adjusted by the temperature and time of the oxidation treatment.
Next, desired graphitized particles are obtained by firing the oxidized bulk mesophase pitch at about 2000 to 3500 ° C. in an inert atmosphere such as nitrogen or argon.

  Mesocarbon microbeads, which are preferred raw materials for graphitized particles, can be obtained by the following method. For example, coal-based heavy oil or petroleum-based heavy oil is heat-treated at a temperature of 300 to 500 ° C. and polycondensed to produce crude mesocarbon microbeads, which are subjected to processes such as filtration, stationary sedimentation, and centrifugation. In this method, the mesocarbon microbeads are separated, washed and purified with a solvent such as benzene, toluene, xylene and the like, and further dried.

As a method for obtaining graphitized particles by using the mesocarbon microbeads, firstly, the mesocarbon microbeads after drying are mechanically primarily dispersed with a mild force that does not cause destruction. This is preferable for preventing coalescence of the graphitized particles and obtaining a uniform particle size. Next, the mesocarbon microbeads after the primary dispersion are subjected to primary heat treatment at a temperature of 200 to 1500 ° C. in an inert atmosphere to be carbonized. In order to prevent the coalescence of the graphitized particles and to obtain a uniform particle size, it is preferable to mechanically disperse the carbide with a mild force that does not destroy the carbide.
The desired graphitized particles can be obtained by firing (secondary heat treatment) the carbide after the secondary dispersion treatment at about 2000 to 3500 ° C. in an inert atmosphere.

  Regardless of the production method, the graphitized particles obtained by the above method should have a volume average particle size of 0.5 to 4.0 μm by classification and a uniform particle size distribution to some extent. It is preferable for making the shape uniform.

Regardless of which raw material is used, the firing temperature for graphitization is preferably from 2000 to 3500 ° C, more preferably from 2300 to 3200 ° C.
When the calcination temperature is 2000 ° C. or lower, the graphitized particles have insufficient degree of graphitization, and the electrical conductivity and lubricity may be lowered to cause toner charge-up. As a result, image quality such as fogging and reduced image density is likely to deteriorate, and when an elastic blade is used for the developer layer thickness regulating member, blade damage may occur, causing streaks and uneven density in the image. It tends to be easy to do. When the firing temperature is 3500 ° C. or higher, the graphitized particles may have a too high graphitization degree. Therefore, the hardness of the graphitized particles is lowered, and the wear resistance of the graphitized particles is deteriorated. Abrasion, mechanical strength of the resin coating layer, and charge imparting property to the toner are likely to decrease.

  In addition to the above-described configuration, the developer carrier of the present invention further includes a quaternary ammonium salt compound that is uniformly dispersed in the binder resin of the resin coating layer by further adding a quaternary ammonium salt compound to the resin coating layer. With the salt compound, it is possible to exhibit good charge imparting stability and conveyance stability to a non-magnetic and highly spheroidized negatively charged toner manufactured by a spheroidizing toner or a polymerization method.

  In general, a toner manufactured by a polymerization method has a great advantage in that transferability of the toner is remarkably improved and transfer efficiency is improved as compared with a toner manufactured by a conventional jet milling method. On the other hand, the toner produced by the polymerization method is easy to charge up on the surface of the toner particles because the coloring material such as carbon is taken into the particles. For this reason, development unevenness, blotches, and density reduction due to toner contamination or fusion to the developer carrier are likely to occur. This is particularly noticeable in non-magnetic toners that do not have a magnetic material.

As the binder resin used for the resin coating layer of the developer carrying member, a nitrogen-containing resin having at least one of —NH ₂ group, ═NH group, and —NH— bond in the structure is used, and further shown below. By adding such a specific quaternary ammonium salt compound to the resin coating layer, it has a rapid and highly stable charge application and transport stability, and is also non-magnetic and spherical with a tendency to have excessive charge. The ability of the resin coating layer of the developer carrier to suppress the overall charging of negatively charged toners with a high degree of conversion can be suppressed, so that overcharging can be prevented and toner charge can be obtained quickly, properly and uniformly. Can do.

The exact reason why a quaternary ammonium salt compound, which has been known as a positive charge control agent for conventional toners, contributes to stabilizing the charge of negatively charged toners is not clear, but is presumed as follows. When a quaternary ammonium salt compound that is positively charged to iron powder is added to the resin coating layer on the developer carrier, it is uniformly dispersed in the binder resin in the resin coating layer to form a coating layer It is considered that the binder resin composition itself becomes negatively charged by being incorporated into the structure of the resin having —NH ₂ group, ═NH group, —NH— bond or the like in the binder resin. It is done. Therefore, for negatively chargeable toner, it acts in a direction that prevents the toner from having an excessive negative charge amount, and as a result, the charge amount can be stably controlled.

  From these facts, the inclusion of the quaternary ammonium salt compound in the resin coating layer of the developer carrier, in particular, combined with effects such as charge imparting to the resin coating layer by the graphitized particles, lubricity, etc. It is possible to obtain high charging stability and stable toner transportability in a thin layer with respect to non-magnetic toners obtained by a polymerization method, which are likely to occur. As a result, a synergistic effect with the improvement of fogging and sweeping by the blank pulse bias can be obtained, and a good image quality can be obtained with respect to the spherical non-magnetic one-component toner.

Examples of the quaternary ammonium salt compound having a positive chargeability with respect to iron powder that is more preferably used in the present invention include compounds represented by the following general formula.

_{(R 1, R 2, R} 3 and R ₄ in the formula are each an optionally substituted alkyl group, an optionally substituted aryl group, or an aralkyl group, R ₁ ~ R ₄ may be the same or different, and X ⁻ represents an anion of an acid.)

In the above general formula, X ^- Specific examples of the acid ions, organic sulfate ions, organic sulfonate ions, organic phosphate ions, molybdate ions, tungstate ions, such as heteropoly acid containing molybdenum atoms or tungsten atoms are preferred Used.

  Specific examples of the quaternary ammonium salt compound that is preferably used in the present invention and is positively charged with respect to iron powder include the following compounds (1) to (19). . Of course, the present invention is not limited to these.

The addition amount of the quaternary ammonium salt compound is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the binder resin used for the resin coating layer. If the amount is less than 1 part by mass, the effect of controlling the charge amount due to the addition is not observed. .
In addition, a resin containing at least one of —NH ₂ group, ═NH group or —NH— bond in the structure, preferably used in combination with the quaternary ammonium salt compound, is included as a catalyst in the production process. Examples thereof include a phenol resin, a polyamide resin, an epoxy resin using a polyamide as a curing agent, a urethane resin, or a copolymer of these resins. When these resins and a quaternary ammonium salt compound are mixed to form a resin coating layer, the quaternary ammonium salt compound is easily taken into the structure of the binder resin of the resin coating layer.

  In the resin coating layer of the developer carrying member of the present invention, the phenol resin that can be suitably used in combination with the quaternary ammonium salt compound is a phenol resin using a nitrogen-containing compound as a catalyst in the production process, The nitrogen-containing compound used may be either an acidic catalyst or a basic catalyst. For example, examples of the acidic catalyst include ammonium salts such as ammonium sulfate, ammonium phosphate, ammonium sulfamate, ammonium carbonate, ammonium acetate, and ammonium maleate, or amine salts. Basic catalysts include ammonia; dimethylamine, diethylamine, diisopropylamine, diisobutylamine, diamylamine, trimethylamine, triethylamine, tri-n-butylamine, triamylamine, dimethylbenzylamine, diethylbenzylamine, dimethylaniline, diethylaniline, N, N-di-n-butylaniline, N, N-diamilaniline, N, N-di-t-amylaniline, N-methylethanolamine, N-ethylethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, diethylethanol Amine, ethyldiethanolamine, n-butyldiethanolamine, di-n-butylethanolamine, triisopropanolamine, ethylenediamine, hexamethylenete Amino compounds such as lamin; pyridine and derivatives thereof such as pyridine, α-picoline, β-picoline, γ-picoline, 2,4-lutidine, 2,6-lutidine; quinoline compounds, imidazole, 2-methylimidazole, 2, Nitrogen-containing heterocyclic compounds such as imidazole such as 4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole and the like; Can be mentioned.

  Examples of the polyamide resin constituting the binder resin of the resin coating layer preferably used in the present invention include nylon 6, 66, 610, 11, 12, 9, 13, Q2 nylon, and the like, or these as a main component. Nylon copolymers, N-alkyl-modified nylon, N-alkoxylalkyl-modified nylon, and the like can be suitably used. Furthermore, various resins modified with polyamide, such as polyamide-modified phenol resin, or any resin containing a polyamide resin component such as an epoxy resin using a polyamide resin as a curing agent can be used. .

  As the urethane resin constituting the resin coating layer suitably used in combination with the quaternary ammonium salt compound in the present invention, any resin containing a urethane bond can be used. The urethane bond is obtained by polymerization addition reaction of polyisocyanate and polyol. Polyisocyanates that are the main raw materials for polyurethane resins include TDI (tolylene diisocyanate), pure MDI (diphenylmethane diisocyanate), polymeric MDI (polymethylene polyphenyl polyisocyanate), TODI (tolidine diisocyanate), NDI (naphthalene diisocyanate), etc. Aromatic polyisocyanates; aliphatic systems such as HMDI (hexamethylene diisocyanate), IPDI (isophorone diisocyanate), XDI (xylylene diisocyanate), hydrogenated XDI (hydrogenated xylylene diisocyanate), hydrogenated MDI (dicyclohexylmethane diisocyanate) Polyisocyanate etc. are mentioned.

  Polyols that are the main raw materials for polyurethane resins include polyether polyols such as PPG (polyoxypropylene glycol), polymer polyol, and polytetramethylene glycol (PTMG); polyester polyols such as adipate, polycaprolactone, and polycarbonate polyol; PHD Examples thereof include polyether-based modified polyols such as polyols and polyether ester polyols; other epoxy-modified polyols; partially saponified polyols of ethylene-vinyl acetate copolymers (saponified EVA); flame retardant polyols and the like.

In the present invention, the volume resistance value of the resin coating layer of the developer carrying member is preferably 10 ⁻² to 10 ⁵ Ω · cm, more preferably 10 ⁻² to 10 ⁴ Ω · cm. When the volume resistance value of the resin coating layer exceeds 10 ⁵ Ω · cm, the toner is likely to be charged up, and toner contamination and fusion to the resin coating layer are likely to occur.
In the present invention, in order to adjust the volume resistance value of the resin coating layer to the above value, other conductive fine particles may be further dispersed in the resin coating layer.
Examples of the conductive fine particles 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, and potassium titanate. Metal oxide fine particles such as antimony oxide and indium oxide; metal fine particles such as aluminum, copper, silver and nickel; and inorganic fillers such as metal fibers and carbon fibers. The conductive fine particles preferably have a number average particle diameter of 1 μm or less, more preferably 0.01 to 0.8 μm. When the number average particle diameter of the conductive fine particles is 1 μm or less, the volume resistance value of the resin coating layer can be controlled to be satisfactorily low, toner charge-up can be prevented, and toner contamination can be suppressed.
Among these, as the conductive fine particles, conductive carbon black is preferable, and those having a number average particle diameter of 1 μm or less are preferably used.

  Next, the configuration of the developer carrier used in the present invention will be specifically described. The developer carrying member of the present invention comprises a substrate and a resin coating layer formed on the substrate. The base of the developer carrying member includes a cylindrical member, a columnar member, a belt-like member, etc., but a rigid cylindrical tube or a solid rod such as a metal is preferably used in a developing method that is not in contact with the photosensitive drum. It is done. As such a substrate, a non-magnetic metal or alloy such as aluminum, stainless steel, or brass, which is molded into a cylindrical shape or a cylindrical shape, and subjected to polishing, grinding, or the like is preferably used. The substrate is preferably used after being molded or processed with high accuracy in order to improve the uniformity of the image. For example, the straightness in the longitudinal direction is preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 10 μm or less, and the gap between the developer carrying member and the photosensitive drum is, for example, uniform with respect to the vertical plane. When the developer carrier is abutted through a spacer and the developer carrier is rotated, the fluctuation of the gap with the vertical surface is preferably 30 μm or less, more preferably 20 μm or less, and particularly preferably 10 μm or less. Aluminum is preferably used as the base material because of material cost and ease of processing.

Although the composition ratio of each component constituting the resin coating layer will be described below, this is a particularly preferable range in the present invention.
As for content of the unevenness | corrugation provision particle | grains disperse | distributed in a resin coating layer, 2-60 mass parts is preferable with respect to 100 mass parts of binder resin used for a resin coating layer, More preferably, it is the range of 2-40 mass parts. . When the content of the unevenness-imparting particles is less than 2 parts by mass, the effect of adding the unevenness-imparting particles is small and it is difficult to form necessary unevenness. When the amount exceeds 60 parts by mass, the adhesion between the unevenness imparting particles and the resin coating layer may become too low, and the wear resistance may deteriorate.
The content of the graphitized particles dispersed in the resin coating layer is preferably 2 to 200 parts by mass, more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the binder resin used for the resin coating layer. . Within this range, the effect of maintaining the surface shape of the developer carrying member, imparting electrification to the toner, and lubricity of the resin coating layer are further exhibited. When the content of the graphitized particles is less than 2 parts by mass, the effect of adding the graphitized particles is small. When the content of the graphitized particles exceeds 200 parts by mass, the adhesion of the resin coating layer becomes too low and the wear resistance deteriorates. May end up.

The content of conductive fine particles that can be contained in the resin coating layer together with the unevenness imparting particles and graphitized particles is preferably 40 parts by mass or less, more preferably 100 parts by mass of the binder resin used for the resin coating layer. 2 to 35 parts by mass. When the content of the conductive fine particles is within the above range, it is preferable because the volume resistance value and the like can be adjusted to a desired value without impairing other physical properties required for the resin coating layer.

The layer thickness of the resin coating layer having the above-described configuration is preferably 25 μm or less, more preferably 20 μm or less, and further preferably 4 to 20 μm, in order to obtain a uniform film thickness. However, it is not particularly limited to this layer thickness. Although these layer thicknesses are based also on the material used for a resin coating layer, they are obtained by making the adhesion mass into about 4000-20000 mg / m < ² >.

  For dispersing these particles in the binder resin, generally known dispersing devices such as a disperser using beads such as a paint shaker, a sand mill, an attritor, a dyno mill, a pearl mill and the like are preferably used. The method for forming the resin coating layer according to the present invention on the substrate is not particularly limited. For example, a coating liquid in which particles used for the resin coating layer of the developer carrier of the present invention are dispersed in a binder resin is applied to the developer carrier substrate by a method such as dipping, spraying, or brushing. The developer carrying member of the present invention can be obtained by coating on and drying. As an example of the method for forming the resin coating layer on the developer carrier, the distance between the substrate and the nozzle tip of the spray gun is constant while the substrate is rotated in the vertical direction parallel to the moving direction of the spray gun. And a coating solution in which the above materials are dispersed while applying a spray gun at a constant speed while keeping the spray gun at a constant speed. In general, in the air spray method, a coating liquid having a good particle dispersion can be obtained by stably forming a coating liquid into fine particle droplets.

  FIG. 1 schematically shows the basic structure of the resin coating layer of the developer carrying member of the present invention. Concavity and convexity imparting particles 13 and graphitized particles 14 are dispersed in the resin coating layer 12 on the aluminum cylindrical substrate 11. Note that conductive fine particles such as carbon black are not shown in FIG. 1 because they are very small compared to the unevenness imparting particles and graphitized particles.

Next, a developing device incorporating the developer carrying member of the present invention will be described. The developing method using the developer carrying member of the present invention is also within the scope of the present invention.
FIG. 2 schematically shows an example of the configuration of a non-contact type developing apparatus that performs development in a non-contact state between a photosensitive drum and a developer carrier used when a non-magnetic toner is used as a one-component developer. . In FIG. 2, an electrophotographic photosensitive drum 21 as an image carrier that carries an electrostatic latent image formed by a known process is rotated in the arrow B direction. The developing sleeve 24 as a developer carrier is composed of a metal cylindrical tube (base) 26 and a resin coating layer 25 formed thereon. Since a one-component developer (nonmagnetic toner) 23 is used, no magnet is provided inside the metal cylindrical tube 26. A columnar member can be used instead of the metal cylindrical tube.

  A stirring blade 28 for stirring the one-component developer 23 is provided in the hopper 22. Supply / peel as a developer supply / peeling member for supplying the monocomponent developer 23 to the developing sleeve 24 and stripping off the monocomponent developer 23 present on the surface of the developing sleeve 24 after development. The roller 20 is in contact with the developing sleeve 24. When the supply / peeling roller 20 as the developer supply / peeling member rotates in the same direction as the developing sleeve 24, the surface of the supply / peeling roller 20 moves in the counter direction with the surface of the developing sleeve 24. The one-component developer 23 supplied from the hopper 22 is supplied to the developer sleeve 24, and the developing sleeve 24 carries the one-component developer 23 and rotates in the direction of arrow A. The one-component developer 23 is transported to the developing portion D facing the photosensitive drum 21. The developer layer thickness of the one-component developer 23 carried on the developing sleeve 24 is regulated by a developer layer thickness regulating member 29 that presses the surface of the developing sleeve 24 via the developer layer. The one-component developer 23 obtains a triboelectric charge that can develop the electrostatic latent image on the photosensitive drum 21 by friction with the developing sleeve 24.

As the developer supply / peeling member supply / peeling roller 20, an elastic roller member such as resin, rubber or sponge is preferably used. As the developer supply / stripping member, a belt member or a brush member may be used instead of the roller member. The one-component developer 23 that has not been transferred to the photosensitive drum 21 is once peeled off from the surface of the developing sleeve 24 by the supply / peeling roller 20, thereby preventing the generation of a stationary developer on the developing sleeve and developing. It has the function of making the charge of the agent uniform.

When the supply / peeling roller 20 made of an elastic roller is used as the developer supply / peeling member, the peripheral speed of the supply / peeling roller 20 rotates in the counter direction at a portion facing the developing sleeve. It is preferably 20 to 120%, more preferably 30 to 100% with respect to 100% of the peripheral speed of the developing sleeve 24. When the peripheral speed of the supply / peeling roller 20 is less than 20%, the supply of the one-component developer is insufficient, the followability of the solid image is liable to deteriorate, and a ghost image is caused. If it exceeds 120%, the supply amount of the one-component developer is increased, which causes fogging due to poor regulation of the developer layer thickness and insufficient charge amount, and further easily damages the toner. Or toner fusing.
When the rotation direction of the supply / peeling roller 20 is the same (forward) direction at the portion facing the developing sleeve 24, the peripheral speed of the supplying / peeling roller is preferably 100 with respect to the peripheral speed of the developing sleeve. The toner supply amount may be in the range of ˜300%, more preferably 101 to 200%.
The rotation direction of the supply / peeling roller 20 is more preferably rotated in the counter direction at a position facing the developing sleeve in terms of stripping property and feeding property.

  The intrusion amount of the supply / peeling roller 20 with respect to the developing sleeve 24 is preferably 0.5 to 2.5 mm from the viewpoint of developer supply and stripping property. When the amount of penetration of the supply / peeling roller 20 is less than 0.5 mm, a ghost is likely to be generated due to insufficient peeling, and when the amount of penetration exceeds 2.5 mm, damage to the toner increases. The toner is likely to cause fusing and fogging due to toner deterioration.

A developing bias voltage is applied to the developing sleeve 24 by a power source 27 in order to develop the one-component developer 23 carried on the developing sleeve 24.
The developing bias used in the apparatus of the present invention will be described below. Conventionally, rectangular wave high frequency, sine high frequency, etc. have been used as the developing bias. However, a technique for faithfully developing a latent image in the trend of high image quality in recent years is desired, and the developer carrier is intermittently used. Application of a voltage obtained by superimposing a resting alternating current component on a direct current component as a developing bias has been performed. A developing bias (blank pulse bias) as shown in FIG. 3 is an example of the developing bias in which an alternating current component that intermittently pauses on the developer carrier is superimposed on the direct current component.

  The “blank pulse bias” of the development bias is a cycle in which an AC voltage and a DC voltage are superimposed and applied (amplitude part), and a subsequent period in which only the DC voltage is applied (blank part) is defined as one cycle. It is a bias that repeats this cycle. When this blank pulse bias is used as the developing bias, the toner does not reciprocate between the developing sleeve and the photosensitive drum in the blank portion, that is, the toner is attracted to either the developing sleeve or the photosensitive drum. The toner scattering level is improved. In addition, it is possible to obtain effects such as density uniformity, sweeping, and fogging.

However, in the conventional developing sleeve, as described above, when a highly spherical toner is used as the one-component developer, the thickness of the thin toner layer formed on the developing sleeve 24 due to poor regulation such as slipping through. Is likely to be large, and toner charge distribution is likely to occur, so that it is difficult to obtain an improvement effect such as fogging by a blank pulse.
On the other hand, the developing sleeve of the present invention can prevent the toner layer thickness on the developing sleeve from becoming thick even when toner having a high sphericity is used, and by uniformizing the toner charge, Improvement effects such as fogging can be obtained synergistically.

  In the developing device of FIG. 4, as a developer layer thickness regulating member that regulates the layer thickness of the one-component developer (nonmagnetic toner) 23 on the developing sleeve 24, a material having rubber elasticity such as urethane rubber, silicone rubber, Alternatively, an elastic regulation blade 29 made of a material having metal elasticity such as phosphor bronze or stainless copper can be used. In the developing device shown in FIG. 4, the elastic regulating blade 29 can be pressed against the developing sleeve 24 in the forward direction with the rotating direction of the developing sleeve 24 to form a thinner toner layer on the developing sleeve 24.

The elastic regulating blade 29 has a structure in which polyamide elastomer (PAE) is bonded to the surface of a phosphor bronze plate, which can obtain a stable pressurizing force, for stable regulating force and imparting (negative) charge to toner. It is preferable. Examples of the polyamide elastomer (PAE) include a copolymer of polyamide and polyether.
The contact pressure of the elastic regulating blade 29 against the developing sleeve 26 is preferably a linear pressure of 5 to 50 g / cm from the viewpoint of stabilizing the regulation of the toner and making the developer layer thickness suitable. If the contact pressure of the elastic regulating blade 29 is less than the linear pressure of 5 g / cm, the toner regulation becomes weak, causing fogging and toner leakage, and if the linear pressure exceeds 50 g / cm, Damage increases and tends to cause toner deterioration and fusion to the sleeve and blade.

  The developer carrier of the present invention is particularly effective when applied to an apparatus in which the supply / peeling roller 20 and the elastic regulating blade 29 are in pressure contact. That is, when the supply / peeling roller 20 and the elastic regulating blade 29 are in pressure contact with the developing sleeve 24, the surface of the developing sleeve 24 is more worn and the developer is fused by the members to be pressed. Since the environment is easy to use, the effect of the developer carrying member having the resin coating layer of the present invention is effectively expressed. FIG. 4 is merely a schematic illustration of the developing device of the present invention, and it goes without saying that there are various forms such as the shape of the developer container (hopper 22) and the presence or absence of the stirring blade 28.

Hereinafter, the developer used in the present invention will be described.
The developer used in the present invention is preferably a nonmagnetic toner as a nonmagnetic one-component developer. The non-magnetic toner can be manufactured using a pulverized toner manufacturing method and a polymerized toner manufacturing method. When the nonmagnetic toner according to the present invention is produced by a polymerization method, the toner can be produced by a specific production method described below.
First, in addition to monomers, a release agent, polar resin, colorant, charge control agent, polymerization initiator, cross-linking agent and other additives are added as appropriate, and uniformly dissolved or dispersed by a homogenizer, an ultrasonic disperser or the like. The monomer composition is dispersed in an aqueous phase containing a dispersion stabilizer by a usual stirrer, homomixer, homogenizer or the like. Preferably, granulation is performed by adjusting the stirring speed and time so that the droplets of the monomer composition have a desired toner particle size. Thereafter, stirring may be performed to such an extent that the particle state is maintained and the sedimentation of the particles is prevented by the action of the dispersion stabilizer. The polymerization is performed at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. In addition, the temperature may be raised in the latter half of the polymerization reaction, and in order to remove unreacted polymerizable monomers and by-products that cause odor during toner fixing, the latter half of the reaction, or the completion of the reaction. A part of the aqueous medium may be distilled off later. After completion of the reaction, the produced toner particles are collected by washing and filtration, dried, and then externally added with an external additive as necessary to obtain a toner. In the suspension polymerization method, it is usually preferable to use 300 to 3000 parts by weight of water as a dispersion medium with respect to 100 parts by weight of the monomer composition.

Examples of polymerizable monomers that can be used in the above polymerized toner include styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and p-ethylstyrene; acrylic Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, acrylic Acrylic acid esters such as phenyl acid; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, methacryl Acid steer Le, phenyl methacrylate, dimethylaminoethyl methacrylate, methacrylic acid esters other acrylonitrile such as diethylaminoethyl methacrylate, methacrylonitrile, and the like monomers acrylamide.
These monomers can be used alone or in admixture of two or more. Among the above-mentioned monomers, styrene or a styrene derivative is preferably used alone or mixed with other monomers from the viewpoint of toner development characteristics and durability.

  Examples of the crosslinking agent used in the polymerization method include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxyls having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate. Acid esters; divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone; and compounds having three or more vinyl groups. Particularly preferable cross-linking agents include divinylbenzene.

  As a preferable addition amount of the crosslinking agent, the crosslinking agent is preferably 0.01 to 1.0 part by mass per 100 parts by mass of the vinyl polymer or vinyl copolymer. More preferably, it is 0.1-0.9 mass part.

  The yellow toner, magenta toner and cyan toner used in the present invention preferably contain a wax as a release agent. The wax is preferably a solid wax that is solid at room temperature. The wax contained in the toner is not limited by the polymerized toner and the pulverized toner. Specific examples include paraffin wax, polyolefin wax, Fischer-Tropsch wax, amide wax, higher fatty acid, ester wax, and derivatives such as graft compounds and block compounds.

  In the present invention, it is preferable to add 5 to 30% by mass of wax in the toner particles. When the addition amount is less than 5% by mass, the high-temperature offset resistance is deteriorated, and further, the image on the back surface may show an offset phenomenon when fixing a double-sided image. When the amount is more than 30% by mass, when toner is produced by a polymerization method, toner particles are easily coalesced during granulation, and a product having a wide particle size distribution is easily generated. Furthermore, from this, the encapsulation of the wax becomes insufficient, and the developability, transferability, and blocking resistance tend to deteriorate. Therefore, the uniformity of the image is also inferior.

  For the purpose of controlling the chargeability of the toner, it is preferable to add a charge control agent to the toner particles. Of these known charge control agents, those having little polymerization inhibition and aqueous phase transfer are preferred. Examples of the positive charge control agent include nigrosine dyes, triphenylmethane dyes, quaternary ammonium salts, guanidine derivatives, imidazole derivatives, amine compounds, and the like. Examples of negative charge control agents include metal-containing salicylic acid copolymers, metal-containing monoazo dye compounds, urea derivatives, styrene-acrylic acid copolymers, and styrene-methacrylic acid copolymers. As addition amount of these charge control agents, 0.1-10 mass parts is preferable with respect to 100 mass parts of binder resin or a polymer monomer. The developer carrier of the present invention is particularly effective in combination with a negatively charged toner when a quaternary ammonium salt compound is dispersed in a resin coating layer. Is preferably a negative charge control agent.

In the present invention, known colorants can be used for the toner. For example, examples of the black pigment include carbon black, aniline black, nonmagnetic ferrite, and magnetite.
Examples of the yellow pigment include yellow iron oxide, navel yellow, naphthol yellow S, Hansa yellow G, Hansa yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, tartrazine lake and the like.

Examples of the orange pigment include permanent orange GTR, pyrazolone orange, vulcan orange, benzidine orange G, indanthrene brilliant orange RK, and indanthrene brilliant orange GK.
Examples of red pigments include Bengala, Permanent Red 4R, Risor Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red C, Lake Red D, Brilliant Carmine 6B, Brilliant Carmine 3B, Eoxin Lake, Rhodamine Lake B, Alizarin Lake, etc. Can be mentioned.

Examples of the blue pigment include alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, first sky blue, and indanthrene blue BG.
Examples of purple pigments include Fast Violet B and Methyl Violet Lake.
Examples of the green pigment include Pigment Green B, Malachite Green Lake, Final Yellow Green G, and the like.
Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.

These colorants can be used alone or in combination, and further in a solid solution state.
The colorant used in the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. The addition amount of the colorant is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

As the colorant when the toner of the present invention is used as a translucent color toner, various types and pigments of various colors as shown below can be used.
For example, C.I. I. 10316 (Naphthol Yellow S), C.I. I. 11710 (Hansa Yellow 10G), C.I. I. 11660 (Hanza Yellow 5G), C.I. I. 11670 (Hanza Yellow 3G), C.I. I. 11680 (Hansa Yellow G), C.I. I. 11730 (Hansa Yellow GR), C.I. I. 11735 (Hansa Yellow A), C.I. I. 117408 (Hansa Yellow RN), C.I. I. 12710 (Hansa Yellow R), C.I. I. 12720 (Pigment Yellow L), C.I. I. 21090 (benzidine yellow), C.I. I. 21095 (Benzidine Yellow G), C.I. I. 21100 (Benzidine Yellow GR), C.I. I. 20040 (Permanent Yellow NCR), C.I. I. 21220 (Vulcan Fast Yellow 5), C.I. I. 21135 (Vulcan Fast Yellow R) and the like.

Examples of red pigments include C.I. I. 12055 (Starlin I), C.I. I. 12075 (permanent orange), C.I. I. 12175 (Risor Fast Orange 3GL), C.I. I. 12305 (permanent orange GTR), C.I. I. 11725 (Hansa Yellow 3R), C.I. I. 21165 (Vulcan Fast Orange GG), C.I. I. 21110 (Benzidine Orange G), C.I. I. 12120 (Permanent Red 4R), C.I. I. 1270 (Para Red), C.I. I. 12085 (Fire Red), C.I. I. 12315 (Brilliant Fast Scarlet), C.I. I. 12310 (Permanent Red F2R
), C.I. I. 12335 (Permanent Red F4R), C.I. I. 12440 (Permanent Red FRL), C.I. I. 12460 (Permanent Red FRLL), C.I. I. 12420 (Permanent Red F4RH), C.I. I. 12450 (Light Fast Red Toner B), C.I. I. 12490 (Permanent Carmine FB), C.I. I. 15850 (brilliant carmine 6B) and the like.

  Examples of blue pigments include C.I. I. 74100 (metal-free phthalocyanine blue), C.I. I. 74160 (phthalocyanine blue), C.I. I. 74180 (Fast Sky Blue).

  Examples of the polymerization initiator used in the polymerization method include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane). -1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azo or diazo polymerization initiators such as azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide, di Isopropylpyrooxycarbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicyl peroxide, 2,4-dichlorobenzoyl peroxide, lauryl peroxide, 2,2-bis'4,4-t -Butylperoxycyclohexyl) propane, tris (t-butyl) Ruperuokishi) or peroxide initiators such as triazine, polymeric initiators having a peroxide in the side chain, potassium persulfate, persulfates such as ammonium persulfate, hydrogen peroxide or the like is used. The polymerization initiator is preferably added in an amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer, and may be used alone or in combination.

  As a polar resin used in the polymerization method, a cationic polymer such as a polymer of a nitrogen-containing monomer such as dimethylaminoethyl methacrylate or diethylaminoethyl methacrylate or a copolymer with styrene or an unsaturated carboxylic acid ester; Nitrile monomers such as acrylonitrile, halogen-containing monomers such as vinyl chloride, unsaturated carboxylic acids such as acrylic acid and methacrylic acid, other unsaturated dibasic acids and unsaturated dibasic acid anhydrides, nitro-based monomers An anionic polymer such as a polymer with a monomer or a copolymer with a styrene monomer or the like can be used.

  An external additive may be added to the toner particles in the present invention for the purpose of imparting various properties. The external additive preferably has a particle size of 1/10 or less of the weight average particle size of the toner particles from the viewpoint of durability when added to the toner. The particle diameter of the external additive means the volume average particle diameter obtained by observing the surface of the toner particles with an electron microscope. As external additives for the purpose of imparting these characteristics, for example, the following are used.

(1) Fluidity imparting agent: metal oxide (silicon oxide, aluminum oxide, titanium oxide), carbon black and carbon fluoride. Those subjected to hydrophobic treatment are more preferred.
(2) Abrasive: Metal oxide (strontium titanate, cerium oxide, aluminum oxide,
Magnesium oxide, chromium oxide), nitride (silicon nitride), carbide (silicon carbide) and metal salts (calcium sulfate, barium sulfate, calcium carbonate).
(3) Lubricant: fluororesin powder (vinylidene fluoride, polytetrafluoroethylene) and fatty acid metal salt (zinc stearate, calcium stearate).
(4) Charge controllable particles: metal oxides (tin oxide, titanium oxide, zinc oxide, silicon oxide, aluminum oxide) and carbon black.

  These external additives may be used preferably in the range of 0.1 to 10 parts by mass, more preferably in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the toner particles. These external additives may be used alone or in combination.

In order to improve the image quality, the toner preferably has a weight average particle diameter of 4 to 8 μm. A toner having a weight average particle size of less than 4 μm is not preferable because it tends to cause uneven image unevenness due to fogging or transfer failure. If the toner has a weight average particle size exceeding 8 μm, fusion or the like is likely to occur. .
Further, in the circularity (frequency distribution) based on the number of toners measured by the flow type particle image measuring device, the average circularity is preferably 0.935 or more from the viewpoint of transfer rate.

Toner particle size distribution control and particle size control can be done by changing the type and amount of a poorly water-soluble inorganic salt or protective colloid dispersant and mechanical device conditions such as rotor peripheral speed, number of passes, and stirring blades. A predetermined toner can be obtained by controlling stirring conditions such as shape, container shape, solid content concentration in an aqueous solution, and the like.
The degree of circularity can be adjusted by the type and amount of the polymerization initiator used in the production by suspension polymerization, the stirring speed, time, temperature, etc. in the production.

  In the present invention, any appropriate stabilizer is used as a dispersion medium used when a toner is produced by a polymerization method. For example, as an inorganic compound, tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate And fine powders of inorganic compounds such as bentonite, silica and alumina. Organic compounds such as polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and salts thereof, polymethacrylic acid and salts thereof, and starch may be used.

  In the present invention, as a colorant used in producing a toner by a polymerization method, it is necessary to pay attention to the polymerization inhibitory property and water phase migration property of the colorant, and the colorant is preferably surface-modified. For example, it is better to perform a hydrophobic treatment without polymerization inhibition. In particular, dyes and carbon blacks have a polymerization inhibition property, so care must be taken when using them. A preferable method for surface-treating the dye system includes a method in which a polymerizable monomer is previously polymerized in the presence of these dyes, and the obtained colored polymer is added to the monomer composition. Carbon black may be treated with a substance that reacts with the surface functional group of carbon black, such as polyorganosiloxane, in addition to the same treatment as the above dye.

  In the case of a pulverized toner, a known method is used. For example, a binder resin, a charge control agent, and if necessary, a wax, a magnetic material, a colorant, and other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill, and then heated rolls, kneaders, and extruders. The toner particles having a desired particle diameter are obtained by melt-kneading using a heat kneader, etc., cooling and solidifying and pulverizing, followed by classification. The obtained toner particles may be subjected to a surface treatment as necessary. Thereafter, the toner is obtained by adding and mixing the external additive. Either the classification or the surface treatment may be performed first. In the classification process, it is preferable to use a multi-division classifier utilizing the Coanda effect in terms of production efficiency.

  Spheroidization treatment and surface smoothening treatment for the purpose of improving transferability of toner particles obtained by the pulverization method include a warm bath method in which pulverized toner particles are dispersed in water and heated, a heat treatment method in which the toner particles pass through a hot air stream, Examples include a mechanical impact method in which mechanical energy is applied and processed. Among them, the thermomechanical impact in which the processing temperature is a temperature in the vicinity of the glass transition point Tg of toner particles (Tg ± 10 ° C.) in the mechanical impact method is preferable from the viewpoint of preventing aggregation and productivity.

The binder resin used in the pulverized toner includes polystyrene, poly-p-chlorostyrene, polyvinyltoluene, styrene-p-chlorostyrene copolymer, styrene vinyltoluene copolymer and other homopolymers of styrene and its derivatives, and Copolymers thereof; Styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-n-butyl acrylate copolymer, etc., styrene-acrylic acid ester copolymer; styrene-methacrylic acid Copolymers of styrene and methacrylic esters such as methyl copolymers, styrene-ethyl methacrylate copolymers, styrene-n-butyl methacrylate copolymers; multi-component copolymers of styrene, acrylate esters and methacrylate esters Styrene-acrylonitrile copolymer, styrene-vinyl Styrenes of styrene and other vinyl monomers such as ruether copolymer, styrene-butadiene copolymer, styrene-vinyl methyl ketone copolymer, styrene-acrylonitrile indene copolymer, styrene-maleic acid ester copolymer Copolymer: Polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyester, polyamide, epoxy resin, polyvinyl butyral, polyacrylic acid, phenol resin, aliphatic or alicyclic hydrocarbon resin, petroleum resin, chlorinated paraffin, etc. Is exemplified. These can be used alone or in combination.

  When used in the pressure fixing system, the binder resin for toner includes low molecular weight polyethylene, low molecular weight polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, higher fatty acid, polyamide resin, polyester resin. Can be used alone or in combination. As comonomer for constituting the styrene copolymer, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid , Methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide and other monocarboxylic acids or derivatives thereof, maleic acid, butyl maleate, methyl maleate, maleic And dicarboxylic acids having a double bond such as dimethyl acid and derivatives thereof.

  Particularly preferred binder resins for non-magnetic toners (yellow, magenta, cyan, black) obtained by the pulverization method include styrene-acrylate resins and polyester resins. As the colorant, the same colorant as that for the polymerized toner can be used. The content is 12 parts by mass or less, preferably 0.5 to 9 parts by mass with respect to 100 parts by mass of the binder resin.

The physical property measurement method according to the present invention will be described below.
(1) Graphitization degree of graphitized particles P (002)
The degree of graphitization P (002) is determined by measuring the lattice spacing d (002) obtained from the X-ray diffraction spectrum of graphite using a powerful fully automatic X-ray diffractometer “MXP18” system manufactured by Mac Science Co., Ltd. (002) = 3.440−0.086 (1-P (002) ² ) The degree of graphitization of the graphitized particles in the coating solution intermediate is measured by washing and separating the graphitized particles from the coating solution intermediate.
Note that the lattice interval d (002) is CuKα as an X-ray source, and the CuKβ line is removed by a nickel filter. High-purity silicon is used as the standard substance, and the calculation is performed from the peak positions of the C (002) and Si (111) diffraction patterns. The main measurement conditions are as follows. X-ray generator: 18 kW
Goniometer: Horizontal goniometer Monochromator: Working tube voltage: 30.0kV
Tube current: 10.0mA
Measurement method: Continuous method Scan axis: 2θ / θ
Sampling interval: 0.020 deg
Scan speed: 6.000 deg / min
Divergence slit: 0.50deg
Scattering slit: 0.50deg
Receiving slit: 0.30mm

(2) Measurement of toner particle size For the average particle size and particle size distribution of toner, Coulter Multisizer (manufactured by Beckman Coulter, Inc.) is used, and the number distribution and volume distribution are output. As the electrolytic solution, a 1% NaCl aqueous solution is prepared using first grade sodium chloride. As a measuring method, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the aqueous electrolytic solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion process for about 1 to 3 minutes with an ultrasonic disperser, and the volume distribution is calculated by measuring the volume and number of toners of 2 μm or more using the Coulter Multisizer with a 100 μm aperture. From this, the volume-based weight average particle diameter obtained from the volume distribution is obtained.

(3) Toner circularity The toner circularity a in the present invention is used as a simple method for quantitatively expressing the shape of toner particles. In the present invention, the flow type particle image measuring device “FPIA-2100” is used. Measurement is performed using “type” (manufactured by Sysmex Corporation), and calculation is performed using the following formula (C).
Circularity a = L ₀ / L (C)
(In the formula, L ₀ represents the circumference of a circle having the same projected area as the particle image, and L represents the circumference of the particle image.)
Here, “the same projected area as the particle image” is the area of the binarized toner particle image, and “peripheral length of the particle image” is the contour line obtained by connecting the edge points of the toner particle image. Define length. The measurement uses the perimeter of the particle image when image processing is performed at an image processing resolution of 512 × 512 (pixels of 0.3 μm × 0.3 μm).
In the present invention, the degree of circularity a is an index indicating the degree of unevenness of the toner, and is 1.000 when the toner is a perfect sphere. The more complicated the surface shape, the smaller the degree of circularity. The average circularity a _ave , which means the average value of the circularity frequency distribution, is expressed by the following equation (D) where the circularity (center value) at the dividing point i of the particle size distribution is ai and the number of measured particles is m. Calculated.

  As a specific measurement method, 10 ml of ion-exchanged water from which impure solids and the like are previously removed is prepared in a container, and after adding a surfactant, preferably an alkylbenzene sulfonate as a dispersant, a measurement sample 0.02 g is added and dispersed uniformly. As a means to disperse, an ultrasonic disperser “UH-50 type” (manufactured by SMT Co., Ltd.) equipped with a titanium alloy chip having a diameter of 5 mm as a vibrator is used. A dispersion is obtained. In that case, it cools suitably so that the temperature of this dispersion may not be 40 degreeC or more. The dispersion concentration is adjusted so that the toner particle concentration at the time of measurement is 3000 to 10,000 / μl, and 1000 or more toner particles are measured. After the measurement, the average circularity of the toner is obtained using this data.

(4) Measurement of the arithmetic average roughness Ra of the surface of the developer carrier The arithmetic average roughness of the surface of the developer carrier is based on JIS B0601 (2001), according to Surfcorder SE-3500 manufactured by Kosaka Laboratory. To do. As measurement conditions, each of 3 points in the axial direction × 3 points in the circumferential direction = 9 points was measured at a cutoff of 0.8 mm, an evaluation length of 4 mm, and a feed rate of 0.5 mm / s, and an average value thereof was taken.

(5) Measurement of Volume Resistance Value of Resin Coating Layer The volume resistance value of the resin coating layer is determined by using the same coating liquid that constitutes the resin coating layer of the developer carrier on a PET sheet having a thickness of 100 μm. A coating layer having a thickness of 20 μm is formed, and measurement is performed by attaching a 4-terminal probe to Lorester AP (manufactured by Mitsubishi Yuka Co., Ltd.). In addition, a measurement environment shall be 20-25 degreeC and 50-60RH%.

(6) Measurement of particle size of irregularity imparting particles and graphitized particles and measurement of abundance ratio of particles in resin coating layer Volume average particle size of irregularity imparting particles and graphitized particles and abundance ratio of particles in resin coating layer are: It can be measured using a Coulter LS-230 particle size distribution meter (manufactured by Beckman Coulter, Inc.) of a laser diffraction type particle size distribution meter. As a measuring method, a small amount module is used, and isopropyl alcohol (IPA) is used as a measuring solvent. Wash the measurement system of the particle size distribution analyzer with IPA for about 5 minutes, and execute the background function after washing. Next, 1 to 25 mg of a measurement sample is added to 50 ml of IPA. The solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes to obtain a sample solution, and the sample solution is gradually added into the measurement system of the measurement device, and the sample solution is displayed on the screen of the device. Particles calculated from the volume average particle diameter and volume distribution by PIDS (polarized scattering intensity difference measurement method), adjusting the sample concentration in the measurement system so that the sample concentration in the sample cell is 45 to 55%. Can be obtained.
(7) Measuring the degree of spherical shape of the irregularity-imparting particles The major axis / minor axis ratio of the irregularity-forming particles was photographed at about 6000 times using an electron microscope, and the major axis and minor axis of the particles were measured on the photograph, calculate. This is measured for 100 samples, and the average value is taken as the ratio of major axis / minor axis.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example and a comparative example, a present Example does not limit this invention at all. In the examples and comparative examples, “%” and “part” are all based on mass unless otherwise specified.

<Method for producing graphitized particles>
Graphitized particles used for the resin coating layer of the developer carrying member were prepared as follows.
(Production Example of Graphitized Particle A-1)
The manufacturing method of graphitized particle A-1 is demonstrated.
First, as a raw material for graphitized particles, heat-treat heavy coal oil, centrifuge the generated crude mesocarbon microbeads, wash with benzene, dry, and then mechanically disperse with an atomizer mill To obtain mesocarbon microbeads. The mesocarbon microbeads were subjected to primary firing at 1200 ° C. in a nitrogen atmosphere and carbonized, followed by secondary dispersion in an atomizer mill, followed by secondary firing at 3000 ° C. in a nitrogen atmosphere, followed by graphitization. Thus, graphitized particles A-1 (degree of graphitization 0.42, volume average particle size 1.86 μm) were obtained. Table 1 shows the physical properties of the graphitized particles A-1.
(Production Example of Graphitized Particle A-2)
The graphitized particle A-2 was prepared in the same manner as the graphitized particle A-1 except that the classification conditions of the graphitized particle A-1 were changed. Obtained. Table 1 shows the physical properties of the graphitized particles A-2.
(Production Example of Graphitized Particle A-3)
The graphitized particles A-3 were prepared in the same manner as the graphitized particles A-1, except that the classification conditions of the graphitized particles A-1 were changed. Obtained. Table 1 shows the physical properties of the graphitized particles A-3.

(Production Example of Graphitized Particle A-4)
A method for producing the graphitized particles A-4 will be described.
After heat treating coal-based heavy oil similar to that used in graphitized particle A-1 as a raw material for graphitized particles, the resulting crude mesocarbon microbeads are centrifuged, washed and purified with benzene, and dried. Then, mesocarbon microbeads were obtained by mechanically dispersing with an atomizer mill. The mesocarbon microbeads were first baked at 1200 ° C. in a nitrogen atmosphere to be carbonized, followed by secondary dispersion in an atomizer mill, followed by secondary calcination at 2200 ° C. in a nitrogen atmosphere, followed by classification. As a result, graphitized particles A-4 (degree of graphitization: 0.93, volume average particle size: 3.82 μm) were obtained. Table 1 shows the physical properties of the graphitized particles A-4.
(Production example of graphitized particles A-5)
The graphitized particle A-5 was prepared in the same manner as the graphitized particle A-4 except that the classification conditions of the graphitized particle A-4 were changed, and the graphitized particle A-5 (graphitization degree 0.93, volume average particle size 0.55 μm) was obtained. Obtained. Table 1 shows the physical properties of the graphitized particles A-5.

(Production Example of Graphitized Particle A-6)
A method for producing the graphitized particles A-6 will be described.
After heat treating coal-based heavy oil similar to that used in graphitized particle A-1 as a raw material for graphitized particles, the resulting crude mesocarbon microbeads are centrifuged, washed and purified with benzene, and dried. Then, mesocarbon microbeads were obtained by mechanically dispersing with an atomizer mill. The mesocarbon microbeads were subjected to primary firing at 1200 ° C. in a nitrogen atmosphere and carbonized, followed by secondary dispersion with an atomizer mill, followed by secondary firing at 3300 ° C. in a nitrogen atmosphere for further graphitization. As a result, graphitized particles A-6 (degree of graphitization 0.23, volume average particle size 3.92 μm) were obtained. Table 1 shows the physical properties of the graphitized particles A-6.
(Production Example of Graphitized Particle A-7)
A graphitized particle (degree of graphitization 0.23, volume average particle size 0.52 μm) A-7 was prepared in the same manner as graphitized particle A-6 except that the classification conditions of graphitized particle A-6 were changed. Obtained. Table 1 shows the physical properties of the graphitized particles A-7.

(Production Example of Graphitized Particle A-8)
A method for producing the graphitized particles A-8 will be described.
As a raw material for graphitized particles, β-resin is extracted from coal tar pitch by solvent fractionation, hydrogenated and heavyized, and then the solvent-soluble component is removed with toluene to remove bulk mesophase pitch. Got. The bulk mesophase pitch powder was finely pulverized, oxidized in air at about 300 ° C., heat-treated at 2300 ° C. in a nitrogen atmosphere, further classified, and graphitized particles A-8 (degree of graphitization 0) .39, volume average particle size 1.92 μm). Table 1 shows the physical properties of the graphitized particles A-8.
(Production Example of Graphitized Particle A-9)
A method for producing the graphitized particles A-9 will be described.
As a raw material for graphitized particles, β-resin was extracted from the same coal tar pitch as that used for graphitized particles A-8 by solvent fractionation, hydrogenated and heavyized, and then toluene. The bulk mesophase pitch was obtained by removing the solvent-soluble component. The bulk mesophase pitch powder was finely pulverized, oxidized in air at about 300 ° C., then heat-treated at 2000 ° C. in a nitrogen atmosphere, further classified, and graphitized particles A-9 (zero graphitization degree). 0.65 and a volume average particle size of 3.89 μm). Table 1 shows the physical properties of the graphitized particles A-9.

(Production Example of Graphitized Particle A-10)
A method for producing the graphitized particles A-10 will be described.
As a raw material for graphitized particles, β-resin was extracted from the same coal tar pitch as that used for graphitized particles A-8 by solvent fractionation, hydrogenated and heavyized, and then toluene. The bulk mesophase pitch was obtained by removing the solvent-soluble component. The bulk mesophase pitch powder was finely pulverized, oxidized in air at about 300 ° C., then heat treated at 3200 ° C. in a nitrogen atmosphere, and further classified to graphitized particles A-10 (zero graphitization degree). .25, volume average particle size 0.62 μm). Table 1 shows the physical properties of the graphitized particles A-10.
(Production example of graphitized particles a-1)
A graphitized particle a-1 (degree of graphitization 0.39, volume average particle size 7.18 μm) was prepared in the same manner as graphitized particle A-8 except that the classification conditions of graphitized particle A-8 were changed. Obtained. Table 1 shows the physical properties of the graphitized particles a-1.
(Production example of graphitized particles a-2)
A method for producing the graphitized particles a-2 will be described.
After heat treating coal-based heavy oil similar to that used in graphitized particle A-1 as a raw material for graphitized particles, the resulting crude mesocarbon microbeads are centrifuged, washed and purified with benzene, and dried. Then, mesocarbon microbeads were obtained by mechanically dispersing with an atomizer mill. The mesocarbon microbeads were subjected to primary firing at 1200 ° C. in a nitrogen atmosphere and carbonized, followed by secondary dispersion in an atomizer mill, followed by secondary firing at 1800 ° C. in a nitrogen atmosphere, followed by classification. Thus, graphitized particles a-2 (degree of graphitization 0.98, volume average particle size 3.64 μm) were obtained. Table 1 shows the physical properties of the graphitized particles a-2.

(Production example of graphitized particles a-3)
A method for producing the graphitized particles a-3 will be described.
Spherical phenol resin particles (volume average particle diameter 3.91 μm) are used as raw materials for graphitized particles, and the spherical phenol resin particles are graphitized by firing at 2200 ° C. in a nitrogen atmosphere, and further classified to graphitized particles. a-3 (degree of graphitization cannot be measured, volume average particle size 3.89 μm) was obtained. Table 1 shows the physical properties of the graphitized particles a-3.
(Production example of graphitized particles a-4)
Next, the manufacturing method of graphitized particle a-4 is demonstrated.
Coke and tar pitch are used as raw materials for the graphitized particles. The coke and tar pitch are graphitized by firing at 2800 ° C. in a nitrogen atmosphere, and further classified to graphitized particles a-4 (degree of graphitization 0. 07, volume average particle size 7.38 μm). Table 1 shows the physical properties of graphitized particles a-4.

<Method for producing irregularity imparting particles>
(Production example of irregularity imparting particles B-1)
Concavity and convexity imparted particles are obtained by using a coal-based bulk mesophase pitch powder 14 having a number average particle diameter of 2 μm or less using a raikai machine (automatic mortar, manufactured by Ishikawa Factory) on 100 parts of spherical phenol resin particles having a volume average particle diameter of 6.1 μm. The coating was uniformly coated, thermally stabilized at 280 ° C. in air, then graphitized by firing at 2000 ° C. in a nitrogen atmosphere, and further classified to obtain unevenness imparting particles B-1. The obtained unevenness imparting particles B-1 were spherical conductive carbon particles having a volume average particle size of 6.3 μm. The true density of the unevenness imparting particles B-1 was 1.48 g / cm ³ , the volume resistance value was 8.1 × 10 ⁻² Ω · cm, and the ratio of major axis / minor axis of the particles was 1.05. Table 2 shows the physical properties of the irregularity-providing particles B-1.
(Production example of irregularity imparting particles B-2)
Except having changed the classification conditions of uneven | corrugated particle | grains B-1, it produced similarly to the uneven | corrugated particle | grains B-1, and obtained uneven | corrugated particle | grains B-2 with a volume average particle diameter of 3.2 micrometers. Table 2 shows the physical properties of the uneven particle B-2.

(Production example of irregularity imparting particles B-3)
Except for using spherical phenol resin particles having a volume average particle size of 8.6 μm instead of spherical phenol resin particles having a volume average particle size of 6.1 μm used for producing the uneven particle providing particle B-1, providing irregularities. Produced in the same manner as the particle B-1, an unevenness imparting particle B-3 having a volume average particle size of 8.7 μm was obtained. Table 2 shows the physical properties of the uneven particle B-3.
(Manufacturing example of irregularity imparting particles b-1)
Except having changed the classification conditions of uneven | corrugated particle | grains B-1, it produced similarly to the uneven | corrugated particle | grains B-1, and obtained uneven | corrugated particle | grains b-1 with a volume average particle diameter of 2.1 micrometers. Table 2 shows the physical properties of the unevenness imparting particles b-1.
(Production example of unevenness imparting particles b-2)
Except having changed the classification conditions of uneven | corrugated particle | grains B-1, it produced similarly to the uneven | corrugated particle | grains B-1, and obtained uneven | corrugated particle | grains b-2 with a volume average particle diameter of 9.5 micrometers. Table 2 shows the physical properties of the unevenness imparting particles b-2.

[Example 1]
<Manufacture of developer carrier>
A coating solution for the resin coating layer provided on the surface of the developing sleeve was prepared at the following mixing ratio.
-300 parts of resol-type phenolic resin (50% methanol solution) produced using ammonia as a catalyst-70 parts of graphitized particles A-1-30 parts of carbon black-12 parts of irregularities imparted particles B-1-500 parts of isopropyl alcohol Is dispersed in a sand mill using glass beads. As a dispersion method, 70 parts of graphitized particles A-1 and 200 parts of isopropyl alcohol are added to 200 parts of a resol-type phenol resin solution (containing 50% methanol) prepared using ammonia as a catalyst, and glass beads having a diameter of 1 mm are added. Was dispersed in a sand mill using media particles to obtain a coating liquid intermediate I-1. The volume average particle diameter of graphitized particles in this coating liquid intermediate I-1 was 1.73 μm, and the degree of graphitization P (002) was 0.41.

  100 parts of isopropyl alcohol, 30 parts of carbon black, and 12 parts of irregularity-providing particles B-1 were added to 100 parts of the remaining resol type phenol resin solution (containing 50% methanol), and glass beads having a diameter of 1.5 mm were used as media particles. Sand mill dispersion was performed to obtain a coating liquid intermediate J-1. The coating liquid intermediate I-1, the coating liquid intermediate J-1, and 200 parts of isopropyl alcohol were mixed and stirred to obtain a coating liquid K-1. The abundance ratio of particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquid K-1 was 0.15%. Table 3 shows the physical properties of the coating solution.

  A resin coating layer is formed on an aluminum cylindrical tube having an outer diameter of 16 mm by the spray method using the coating solution K-1, and then heated at 150 ° C. for 30 minutes in a hot air drying furnace to cure the resin coating layer. Developer carrier S-1 was obtained.

<Toner Production Example 1>
A polymerized toner was prepared by a polymerization method according to the following procedure. First, 3 parts of tricalcium phosphate is added to 900 g of ion-exchanged water heated to 60 ° C., and stirred at 10,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). An aqueous medium was prepared.
Further, the following formulation was put into a homogenizer (manufactured by Nippon Seiki Co., Ltd.), heated to 60 ° C., stirred at 9,000 rpm, dissolved and dispersed.
-Styrene 150 parts-n-butyl acrylate 50 parts-C.I. I. Pigment Blue 15: 3 18 parts, Aluminum salicylate compound 2 parts (Bontron E-88: manufactured by Orient Chemical Co., Ltd.)
Polyester resin 15 parts (polycondensation product of propylene oxide modified bisphenol A and isophthalic acid, Tg = 65 ° C., Mw = 10000, Mn = 6000)
-Stearyl stearate 30 parts (DSC main peak 60 ° C)
・ Divinylbenzene 0.6 parts

In this, 5 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition. The polymerizable monomer composition was put into the aqueous medium, and granulated by stirring at 8,000 rpm using a TK homomixer at 60 ° C. in a nitrogen atmosphere. Then, the temperature was raised to 70 ° C. over 2 hours while being transferred to a propeller type agitator and further heated up to 80 ° C. at a temperature raising rate of 40 ° C./Hr after 4 hours, and reacted at 80 ° C. for 5 hours. To produce polymer particles. After the completion of the polymerization reaction, the slurry containing the particles is cooled, washed with 10 times the amount of water as the slurry, filtered and dried, and the particle size is adjusted by classification to obtain cyan toner particles (weight average particle size 6.8 μm). The average circularity was 0.976).
To 100 parts of the cyan toner particles, 1.3 parts of silica (R812, manufactured by Nippon Aerosil Co., Ltd.) was mixed with a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.) to obtain the toner A of the present invention. .

<Evaluation>
Remodeling of the developing device configuration of the evaluation machine is based on the EP-85 cyan cartridge used in a commercially available color laser beam printer (LBP2510 manufactured by Canon Inc.) and the developer carrier and the developer carrier mounted on the developer carrier. The auxiliary roller was removed, the toner cartridge A was filled with the toner A, and the developer carrier S-1 was further incorporated. Further, the diameter of the roller on the left and right of the developer carrying member was changed to a larger one, and the SD gap between the developer carrying member and the photosensitive member was set to 250 μm. An elastic blade (in which a polyamide polyether elastomer having a Shore D hardness of 40 degrees was injection-molded on a phosphor bronze thin plate) as a developer layer thickness regulating member was used, and a modified one was used. As the developing bias, those shown in FIG. 3 having Vpp: 2 kV, Vdc: 250 V, frequency f = 3 kHz, and blank portion 100 Hz were used. A modified EP-85 cyan cartridge was installed in the cyan station, and dummy cartridges were installed in the other stations, and a single color evaluation was performed as a durability test of 15,000 sheets.

An evaluation test was conducted on the following items. Table 4 shows the evaluation results. Endurance environment: 15 ° C / 10% RH low temperature / low humidity environment (L / L), 23 ° C / 60% RH normal temperature / normal humidity environment (N / N) and 30 ° C / 85% RH high temperature / An evaluation test was conducted on three durability environments of high humidity environment (H / H).
<Evaluation method>
(1) Image Density For the image density, a reflection densitometer RD918 (manufactured by Macbeth Co., Ltd.) was used.

(2) Fog Measure the reflectance of a solid white image, further measure the reflectance of an unused transfer paper, and subtract the highest value of the reflectance of the unused transfer paper from the worst value of the reflectance of the solid white image. The thing was made into fog density and evaluated according to the following evaluation criteria. The reflectance was measured with TC-6DS (manufactured by Tokyo Denshoku Co., Ltd.).
A: The level is 1.5% or less and is hardly observable visually.
B: A level that is about 1.5 to 2.0% and can be confirmed by looking closely.
C: About 2.0 to 3.0%, practically lower limit level.
D: When it exceeds 4.0%, it is a level where fog can be confirmed at first glance (impractical).

(3) Density uniformity The density uniformity in the halftone images was mainly compared visually. The evaluation results were displayed with the following indices.
A: No difference in shading is observed.
B: A slight shading difference is observed.
C: A considerable difference in shading is observed.
D: A light and shade difference which is a practical problem is observed.

(4) Abrasion resistance of resin coating layer The arithmetic average roughness (Ra) of the resin coating layer surface of the developer carrier was measured before and after durability. Further, a laser dimension measuring device manufactured by Keyence Co., Ltd. was used for measuring the amount of abrasion (film abrasion) of the resin coating layer. Using a controller LS-5500 and a sensor head LS-5040T, a sensor unit was separately fixed to an apparatus equipped with a developing sleeve fixing jig and a developing sleeve feed mechanism, and measurement was performed from an average value of the outer diameter dimensions of the developing sleeve. The development measurement was divided into 30 parts in the longitudinal direction of the sleeve and measured at 30 points. Further, after the development sleeve was rotated 90 ° in the circumferential direction, measurements were further made at 30 points, a total of 60 points, and the average value was taken. The outer diameter of the sleeve before application of the resin coating layer is measured in advance, the outer diameter after the resin coating layer is formed, and further the outer diameter after durable use is measured. did.

(5) Contamination resistance of the resin coating layer The surface of the developer carrying member after the durability test was observed at about 200 times using an ultra-deep shape measuring microscope manufactured by Keyence Co., Ltd. The degree was evaluated based on the following criteria.
A: Only minor contamination is observed.
B: Some contamination is observed.
C: Contamination is partially observed.
D: Significant contamination is observed (impractical level).

(6) Image streaks / unevenness Linear and striped streaks that occur in the halftone and run in the image traveling direction were evaluated according to the following criteria.
A: Neither image nor sleeve can be confirmed at all.
B: At halftone, streaks can be confirmed, but with solid black, minor levels can be confirmed.
C: Although a difference in shading can be confirmed even in a solid black image, it can be used.
D: The density difference which is a practical problem in the whole solid black image is conspicuous.

(7) Sweeping An image in which a solid white image followed by a solid image having a length × width of 30 mm × 20 mm was output, and the darkened portion was visually evaluated according to the following criteria.
A: Almost no confirmation on the image.
B: A slight difference in density can be confirmed.
C: Level at which density difference can be confirmed, but there is no practical problem.
D: Unusable level.

(8) Blade Scratch After the evaluation test, the blade surface was visually evaluated and sampled images were evaluated according to the following criteria.
Blade scratch A: Minor and no effect on image.
Blade scratch B: Slightly conspicuous, but no effect on image.
Blade scratch C: Conspicuous scratches occur in several places and appear as slight streaks on the image.
Blade scratch D: A lot of very conspicuous scratches are generated and appear as remarkable streaks on the image (impractical level).

[Example 2]
As the unevenness imparting particles, the unevenness imparting particles B-2 having a volume average particle diameter of 3.2 μm were used instead of the unevenness imparting particles B-1 used in Example 1.
The addition amount of the irregularity imparting particles B-2 was adjusted so that the developer carrying body S-1 prepared in Example 1 and the surface arithmetic average roughness Ra were substantially equal (described in Table 3). In addition, in order to adjust the arithmetic average roughness Ra of the surface of the developer carrying member to be equal, the addition amount of the unevenness imparting particles was adjusted in advance by several points. The same applies to the following embodiments. The coating liquid intermediate I-1 used in Example 1 was mixed and stirred with the coating liquid intermediate J-2 using the unevenness imparting particles B-2 instead of the coating liquid intermediate J-1, and the coating liquid K was mixed. -2 was obtained. The abundance ratio of the particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquid K-2 was 0.07%. A developer carrier S-2 was produced in the same manner as in Example 1 except that the coating liquid K-2 was used, and the same evaluation was performed. The results are shown in Table 4.

[Example 3]
As the unevenness imparting particles, the unevenness imparting particles B-3 having a volume average particle size of 8.7 μm were used instead of the unevenness imparting particles B-1 used in Example 1.
The addition amount of the unevenness imparting particles B-3 was adjusted so that the developer carrying body S-1 prepared in Example 1 and the surface arithmetic average roughness Ra were substantially equivalent (described in Table 3). The coating liquid intermediate I-1 used in Example 1 was mixed and stirred with the coating liquid intermediate J-3 using the unevenness imparting particles B-3 instead of the coating liquid intermediate J-1, and the coating liquid K was mixed. -3 was obtained. The ratio of particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquid K-3 was 4.20%. A developer carrier S-3 was prepared in the same manner as in Example 1 except that the coating liquid K-3 was used, and the same evaluation was performed. The results are shown in Table 4.

[Comparative Example 1]
As the unevenness imparting particles, the unevenness imparting particles b-1 having a volume average particle size of 2.1 μm were used instead of the unevenness imparting particles B-1 used in Example 1.
The addition amount of the unevenness imparting particles b-1 was adjusted so that the developer carrying member S-1 prepared in Example 1 and the surface arithmetic average roughness Ra were substantially equal (described in Table 3). The coating liquid intermediate I-1 used in Example 1 was mixed and stirred with the coating liquid intermediate J-4 using the unevenness imparting particles b-1 instead of the coating liquid intermediate J-1, and the coating liquid K was mixed. -4 was obtained. The abundance ratio of particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquid K-4 was 0.04%. A developer carrier S-4 was prepared in the same manner as in Example 1 except that the coating liquid K-4 was used, and the same evaluation was performed. The results are shown in Table 4.

[Comparative Example 2]
As the unevenness imparting particles, the unevenness imparting particles b-2 having a volume average particle size of 9.5 μm were used instead of the unevenness imparting particles B-1 used in Example 1.
The addition amount of the irregularity imparting particles b-2 was adjusted so that the developer carrying body S-1 prepared in Example 1 and the surface roughness Ra were substantially equal (described in Table 3). The coating liquid intermediate I-1 used in Example 1 was mixed and stirred with the coating liquid intermediate J-5 using the unevenness imparting particles b-2 instead of the coating liquid intermediate J-1, and the coating liquid K was mixed. -5 was obtained. The abundance ratio of the particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquid K-5 was 5.40%. A developer carrier S-5 was prepared in the same manner as in Example 1 except that the coating liquid K-5 was used, and the same evaluation was performed. The results are shown in Table 4.

[Example 4]
Using the graphitized particle A-2 (degree of graphitization 0.42 and volume average particle size 3.95 μm) instead of the graphitized particle A-1 used in Example 1, a coating liquid intermediate I-2 is obtained. It was. The volume average particle diameter of the graphitized particles in this coating liquid intermediate I-2 was 3.78 μm, and the degree of graphitization P (002) was 0.41. The addition amount of the unevenness imparting particles B-1 was adjusted so that the developer carrying body S-1 prepared in Example 1 and the surface arithmetic average roughness Ra were substantially equal (described in Table 3). In the same manner as in Example 1, the coating liquid intermediate I-2 was mixed and stirred with the coating liquid intermediate J-2 in which the addition amount of the unevenness imparting particles B-1 was adjusted instead of the coating liquid intermediate J-1. Thus, a coating solution K-6 was obtained. The abundance ratio of particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquid K-6 was 0.13%. A developer carrier S-6 was produced in the same manner as in Example 1 except that the coating liquid K-5 was used, and the same evaluation was performed. The results are shown in Table 4.

[Example 5]
The coating liquid intermediate I-2 used in Example 4 was mixed and stirred with the coating liquid intermediate J-7 using the unevenness imparting particles B-2 to obtain a coating liquid K-7. The addition amount of the unevenness imparting particles B-2 was adjusted so that the developer carrying body S-1 prepared in Example 1 and the surface roughness Ra were substantially equal (described in Table 3). The abundance ratio of particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquid K-7 was 0.12%. A developer carrier S-7 was produced in the same manner as in Example 1 except that the coating liquid K-7 was used, and the same evaluation was performed. The results are shown in Table 4.

[Example 6]
The coating liquid intermediate I-2 used in Example 4 was mixed and stirred with the coating liquid intermediate J-8 using the unevenness imparting particles B-3 to obtain a coating liquid K-8. The addition amount of the unevenness imparting particles B-3 was adjusted so that the developer carrying member S-1 prepared in Example 1 and the surface roughness Ra were substantially equal (described in Table 3). The abundance ratio of particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquid K-8 was 2.70%. A developer carrier S-8 was produced in the same manner as in Example 1 except that the coating liquid K-8 was used, and the same evaluation was performed. The results are shown in Table 4.

[Comparative Example 3]
The coating liquid intermediate J-2 used in Example 4 was mixed and stirred with the coating liquid intermediate J-9 using the unevenness imparting particles b-1 to obtain a coating liquid K-9. The addition amount of the unevenness imparting particles b-1 was adjusted so that the developer carrying body S-1 prepared in Example 1 and the surface roughness Ra were substantially equal (described in Table 3). The abundance ratio of the particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquid K-9 was 0.09%. A developer carrier S-9 was produced in the same manner as in Example 1 except that the coating liquid K-9 was used, and the same evaluation was performed. The results are shown in Table 4.

[Comparative Example 4]
The coating liquid intermediate J-2 used in Example 4 was mixed and stirred with the coating liquid intermediate J-10 using the unevenness imparting particles b-2 to obtain a coating liquid K-10. The addition amount of the irregularity imparting particles b-2 was adjusted so that the developer carrying body S-1 prepared in Example 1 and the surface roughness Ra were substantially equal (described in Table 3). The abundance ratio of particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating solution K-10 was 4.20%. A developer carrier S-10 was produced in the same manner as in Example 1 except that the coating liquid K-10 was used, and the same evaluation was performed. The results are shown in Table 4.

[Example 7]
Using the graphitized particles A-3 (degree of graphitization 0.42 and volume average particle size 0.53 μm) instead of the graphitized particles A-1 used in Example 1, a coating liquid intermediate I-3 is obtained. It was. The volume average particle diameter of the graphitized particles in this coating liquid intermediate I-3 was 0.49 μm, and the degree of graphitization P (002) was 0.41. The addition amount of the unevenness imparting particles B-1 was adjusted so that the developer carrying body S-1 prepared in Example 1 and the surface roughness Ra were substantially equivalent (described in Table 3). In the same manner as in Example 1, the coating liquid intermediate I-3 was mixed and stirred with the coating liquid intermediate J-3 in which the addition amount of the unevenness imparting particles B-1 was adjusted instead of the coating liquid intermediate J-1. Thus, a coating liquid K-11 was obtained. The abundance ratio of the particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquid K-11 was 0.22%. A developer carrier S-11 was produced in the same manner as in Example 1 except that the coating liquid K-11 was used, and the same evaluation was performed. The results are shown in Table 4.

[Examples 8 and 9]
The coating liquid intermediate I-3 used in Example 7 was mixed and stirred with the coating liquid intermediate J-12, 13 using the unevenness imparting particles B-2 or B-3, and the coating liquid K-12, 13 was mixed. Got. The addition amount of the unevenness imparting particles B-2 or B-3 was adjusted so that the developer carrying member S-1 prepared in Example 1 and the surface roughness Ra were substantially equivalent (described in Table 3). The abundance ratio of particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquids K-12 and 13 was 0.08% and 4.80%, respectively. Developer carrying bodies S-12 and 13 were produced in the same manner as in Example 1 except that the coating liquids K-12 and 13 were used, and the same evaluation was performed. The results are shown in Table 4.

[Comparative Examples 5 and 6]
The coating liquid intermediates J-14 and 15 using the unevenness imparting particles b-1 and b-2 were mixed and stirred into the coating liquid intermediate I-3 used in Example 7, and the coating liquids K-14 and 15 were mixed. Got. The addition amount of the unevenness imparting particles b-1 and b-2 was adjusted so that the developer carrying member S-1 prepared in Example 1 and the surface roughness Ra were substantially equal (described in Table 3). The abundance ratio of particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquids K-14 and 15 was 0.13% and 6.30%, respectively. Developer carrying bodies S-14 and 15 were produced in the same manner as in Example 1 except that the coating liquids K-14 and 15 were used, and the same evaluation was performed. The results are shown in Table 4.

[Example 10]
Instead of graphitized particle A-1 used in Example 1, graphitized particle A-4 (degree of graphitization 0.93, volume average particle size 3.82 μm) was used.
A coating liquid intermediate I-4 was prepared in the same manner as in Example 1 using the graphitized particles A-4. The volume average particle diameter of the graphitized particles in this coating liquid intermediate I-4 was 3.71 μm, and the degree of graphitization P (002) was 0.92. The coating liquid intermediate J-16 in which the addition amount of the unevenness imparting particles B-2 was adjusted was mixed and stirred to obtain a coating liquid K-16. The addition amount of the unevenness imparting particles B-2 was adjusted so that the developer carrying body S-1 prepared in Example 1 and the surface roughness Ra were substantially equal (described in Table 3). The abundance ratio of particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquid K-16 was 0.14%. A developer carrier S-16 was produced in the same manner as in Example 1 except that the coating liquid K-16 was used, and the same evaluation was performed. The results are shown in Table 5.

[Example 11]
A coating liquid intermediate J-17 in which the addition amount of the unevenness imparting particles B-3 was adjusted to the coating liquid intermediate I-4 using the graphitized particles A-4 was prepared, and the coating liquid was mixed and stirred. K-17 was obtained. The addition amount of the unevenness imparting particles B-3 was adjusted so that the developer carrying member S-1 prepared in Example 1 and the surface roughness Ra were substantially equal (described in Table 3). The abundance ratio of the particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquid K-17 was 2.60%. A developer carrier S-17 was produced in the same manner as in Example 1 except that the coating liquid K-17 was used, and the same evaluation was performed. The results are shown in Table 5.

[Examples 12 and 13]
A coating solution was used in the same manner as in Example 1 except that graphitized particles A-5 (degree of graphitization: 0.93, volume average particle size: 0.55 μm) were used instead of the graphitized particles A-4 used in Example 10. Intermediate I-5 was made. The volume average particle diameter of the graphitized particles in this coating liquid intermediate I-5 was 0.53 μm, and the degree of graphitization P (002) was 0.92. Coating liquid intermediates J-18 and 19 in which the addition amounts of the unevenness imparting particles B-2 and B-3 were adjusted were obtained, and these were mixed and stirred to obtain coating liquids K-18 and 19. The addition amount of the unevenness imparting particles B-2 and B-3 was adjusted so that the developer carrying member S-1 prepared in Example 1 and the surface roughness Ra were substantially equal (described in Table 3). The abundance ratio of particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquids K-18 and 19 was 0.07% and 4.80%, respectively. Developer carrying bodies S-18 and 19 were produced in the same manner as in Example 1 except that the coating liquids K-18 and 19 were used, and the same evaluation was performed. The results are shown in Table 5.

[Example 14]
Instead of graphitized particle A-1 used in Example 1, graphitized particle A-6 (degree of graphitization 0.23, volume average particle size 3.92 μm) was used.
A coating liquid intermediate I-6 was produced using the graphitized particles A-6. The volume average particle diameter of the graphitized particles in this coating liquid intermediate I-6 was 3.75 μm, and the degree of graphitization P (002) was 0.23. A coating liquid intermediate J-20 with an adjusted amount of the irregularity imparting particles B-2 was obtained, and these were mixed and stirred to obtain a coating liquid K-20. The addition amount of the unevenness imparting particles B-2 was adjusted so that the developer carrying body S-1 prepared in Example 1 and the surface roughness Ra were substantially equal (described in Table 3). The abundance ratio of particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquid K-20 was 0.14%. A developer carrier S-16 was produced in the same manner as in Example 1 except that the coating liquid K-20 was used, and the same evaluation was performed. The results are shown in Table 5.

[Example 15]
Coating solution in the same manner as in Example 1 except that graphitized particle A-7 (degree of graphitization 0.23, volume average particle size 0.52 μm) was used instead of graphitized particle A-6 used in Example 14. Intermediate I-7 was made. The volume average particle diameter of the graphitized particles in this coating liquid intermediate I-7 was 0.52 μm, and the degree of graphitization P (002) was 0.23. A coating liquid intermediate J-21 with an adjusted addition amount of the unevenness imparting particles B-2 was obtained, and these were mixed and stirred to obtain a coating liquid K-21. The addition amount of the unevenness imparting particles B-2 was adjusted so that the developer carrying body S-1 prepared in Example 1 and the surface roughness Ra were substantially equal (described in Table 3). The ratio of particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquid K-21 was 0.07%. A developer carrier S-21 was produced in the same manner as in Example 1 except that the coating liquid K-21 was used, and the same evaluation was performed. The results are shown in Table 5.

[Example 16]
Instead of the graphitized particles A-1, graphitized particles A-8 (degree of graphitization 0.39, volume average particle size 1.92 μm) were used. Other than that, the coating liquid intermediate I-8 was prepared with the same material and blending ratio as in Example 1, and the surface roughness Ra was almost the same as that of the developer carrier S-1 prepared in Example 1. Thus, the coating liquid intermediate J-22 in which the addition amount of the unevenness imparting particles B-1 was adjusted was obtained (described in Table 3), and these were mixed and stirred to obtain a coating liquid K-22. In addition, the volume average particle diameter of the graphitized particles in the coating liquid intermediate I-8 was 1.87 μm, and the degree of graphitization P (002) was 0.38. The abundance ratio of particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquid K-22 was 0.14%. A developer carrier S-22 was produced in the same manner as in Example 1 except that the coating liquid K-22 was used, and the same evaluation was performed. The results are shown in Table 5.

[Example 17]
Instead of graphitized particle A-1, graphitized particle A-9 (degree of graphitization 0.65, volume average particle size 3.89 μm) was used. Others were the same materials and blending ratio as in Example 1, and a coating liquid intermediate I-9 was produced. The volume average particle diameter of the graphitized particles in this coating liquid intermediate I-9 was 3.76 μm, and the degree of graphitization P (002) was 0.63. Further, the amount of the irregularity imparting particle B-1 added was adjusted so that the developer carrying body S-1 produced in Example 1 and the surface roughness Ra were substantially equal to obtain a coating liquid intermediate J-23. (Described in Table 3), and they were mixed and stirred to obtain a coating solution K-23. The abundance ratio of particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquid K-23 was 0.12%. A developer carrier S-23 was produced in the same manner as in Example 1 except that the coating liquid K-23 was used, and the same evaluation was performed. The results are shown in Table 5.

[Example 18]
Instead of graphitized particles A-9, graphitized particles A-10 (degree of graphitization 0.25, volume average particle size 0.62 μm) were used. The other materials and blending ratios are the same as those in Example 1, and the coating liquid intermediate I-10 is prepared so that the surface roughness Ra is substantially the same as that of the developer carrier S-1 prepared in Example 1. Coating liquid intermediate J-24 was obtained by adjusting the amount of addition of irregularity imparting particles B-1 (described in Table 3), and mixed and stirred to obtain coating liquid K-24. In addition, the volume average particle diameter of the graphitized particles in the coating liquid intermediate I-10 was 0.62 μm, and the degree of graphitization P (002) was 0.25. The abundance ratio of particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquid K-24 was 0.21%. A developer carrier S-24 was produced in the same manner as in Example 1 except that the coating liquid K-24 was used, and the same evaluation was performed. The results are shown in Table 5.

[Comparative Example 7]
Instead of graphitized particle A-1, graphitized particle a-1 (degree of graphitization: 0.72, volume average particle size: 7.18 μm) was used. The other materials and blending ratios are the same as in Example 1, and the coating liquid intermediate I-11 is prepared so that the surface roughness Ra is substantially equal to the developer carrier S-1 prepared in Example 1. A coating liquid intermediate J-25 was obtained by adjusting the amount of addition of the unevenness imparting particles B-1 (described in Table 3), and mixed and stirred to obtain a coating liquid K-25. The volume average particle diameter of the graphitized particles in the coating liquid intermediate I-11 was 6.97 μm, and the degree of graphitization P (002) was 0.72. The abundance ratio of particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquid K-25 was 7.10%. A developer carrier S-25 was produced in the same manner as in Example 1 except that the coating liquid K-25 was used, and the same evaluation was performed. The results are shown in Table 5.

[Comparative Example 8]
Instead of graphitized particle A-1, graphitized particle a-2 (graphitization degree 0.98, volume average particle size 3.64 μm) was used. The other materials and blending ratios are the same as in Example 1, and the coating liquid intermediate I-12 is prepared so that the surface roughness Ra is substantially equal to the developer carrier S-1 prepared in Example 1. The addition amount of the unevenness imparting particles B-1 was adjusted to obtain a coating liquid intermediate J-26 (described in Table 3), which was mixed and stirred to obtain a coating liquid K-26. In addition, the volume average particle diameter of the graphitized particles in the coating liquid intermediate I-12 was 3.51 μm, and the degree of graphitization P (002) was 0.97. The abundance ratio of particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquid K-26 was 0.14%. A developer carrier S-26 was produced in the same manner as in Example 1 except that the coating liquid K-26 was used, and the same evaluation was performed. The results are shown in Table 5.

[Example 19]
A coating solution for a resin coating layer provided on the surface of the developing sleeve was prepared at the following mixing ratio.
-300 parts of a resol type phenolic resin (50% methanol solution) (Ammonia was used as a catalyst during phenol synthesis)
-Graphitized particles A-1 70 parts-Carbon black 30 parts-Concavity and convexity imparting particles B-1 12 parts-Methanol 500 parts-Quaternary ammonium salt compound represented by the following formula 50 parts

For the quaternary ammonium salt compound represented by the above formula, the triboelectric charge amount with the iron powder was measured by a blow-off method using a triboelectric charge meter TB-200 type (manufactured by Toshiba Chemical Co., Ltd.). It was sex.
A coating liquid intermediate I-13 was obtained in the same manner as in Example 1 except that methanol was used instead of isopropyl alcohol. The volume average particle diameter of the graphitized particles in the coating liquid intermediate I-13 was 1.77 μm, and the degree of graphitization P (002) was 0.41. Next, 100 parts of the remaining resol type phenolic resin solution (containing 50% methanol), 30 parts of carbon black, irregularity-providing particles B-1, and the above quaternary ammonium salt compound were used as media particles. Then, a coating liquid intermediate J-27 was obtained. The coating liquid intermediate I-13, the coating liquid intermediate J-27, and 200 parts of methanol were mixed and stirred to obtain a coating liquid K-27. The abundance ratio of particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquid K-27 was 0.18%. A developer carrier S-27 was produced in the same manner as in Example 1 except that the coating liquid K-27 was used, and the same evaluation was performed. The results are shown in Table 5.

[Example 20]
A coating solution K-28 was obtained in the same manner as in Example 19 except that the quaternary ammonium salt compound represented by the following formula was used instead of the quaternary ammonium salt compound used in Example 19. The abundance ratio of particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquid K-28 was 0.18%. A developer carrier S-28 was produced in the same manner as in Example 1 except that the coating liquid K-28 was used, and the same evaluation was performed. The results are shown in Table 5.

For the quaternary ammonium salt compound represented by the above formula, the triboelectric charge amount with the iron powder was measured by the blow-off method using a triboelectric charge meter TB-200 type (manufactured by Toshiba Chemical Corporation). It was sex.
[Comparative Example 9]
Instead of graphitized particle A-1, graphitized particle a-3 (the degree of graphitization cannot be measured and the volume average particle size is 3.89 μm) was used. The other materials and blending ratios are the same as in Example 1, and the coating liquid intermediate I-14 is prepared so that the surface roughness Ra is substantially the same as that of the developer carrier S-1 prepared in Example 1. Coating liquid intermediate J-29 was obtained by adjusting the amount of addition of irregularity imparting particles B-1 (described in Table 3), and mixed and stirred to obtain coating liquid K-29. In addition, the volume average particle diameter of the graphitized particles in the coating liquid intermediate I-14 was 3.86 μm, and the degree of graphitization P (002) was not measurable. The abundance ratio of particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquid K-29 was 0.16%. A developer carrier S-29 was produced in the same manner as in Example 1 except that the coating liquid K-29 was used, and the same evaluation was performed. The results are shown in Table 5.

[Comparative Example 10]
Instead of graphitized particle A-1, graphitized particle a-4 (degree of graphitization 0.07, volume average particle size 7.38 μm) was used. The other materials and blending ratios are the same as in Example 1, and the coating liquid intermediate I-15 is prepared so that the surface roughness Ra is substantially the same as that of the developer carrier S-1 prepared in Example 1. The coating liquid intermediate | middle J-30 was obtained by adjusting the addition amount of uneven | corrugated provision particle | grains B-1 (it describes in Table 3), they were mixed and stirred and the coating liquid K-30 was obtained. In addition, the volume average particle diameter of the graphitized particles in the coating liquid intermediate I-15 was 7.16 μm, and the degree of graphitization P (002) was 0.07. The abundance ratio of particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquid K-30 was 6.80%. A developer carrier S-30 was produced in the same manner as in Example 1 except that the coating liquid K-30 was used, and the same evaluation was performed. The results are shown in Table 5.

[Example 21]
A coating solution for a resin coating layer provided on the surface of the developing sleeve was prepared at the following mixing ratio.
・ Nylon copolymer consisting mainly of 66 nylon 500 parts (solid content 30%)
-Graphitized particles A-1 70 parts-Carbon black 30 parts-Concavity and convexity imparting particles B-1 12 parts-Methanol 300 parts-Quaternary ammonium salt compound represented by the following formula 50 parts

  For the quaternary ammonium salt compound represented by the above formula, the triboelectric charge amount with the iron powder was measured by the blow-off method using a triboelectric charge meter TB-200 type (manufactured by Toshiba Chemical Co., Ltd.). It was sex.

The above material was dispersed in a sand mill using glass beads. As a dispersion method, a sand mill in which 70 parts of graphitized particles A-1 and 100 parts of methanol are added to 300 parts of a nylon copolymer mainly composed of 66 nylon, and glass beads having a diameter of 1 mm are used as media particles. To obtain a coating liquid intermediate I-16. The volume average particle diameter of the graphitized particles in the coating liquid intermediate I-16 was 1.75 μm, and the degree of graphitization P (002) was 0.41. In addition, 100 parts of methanol, 30 parts of carbon black, 12 parts of unevenness imparting particles B-1 and 50 parts of the quaternary ammonium salt compound were added to the remaining 200 parts of nylon copolymer consisting mainly of 66 nylon, A sand mill dispersion using glass beads having a diameter of 1.5 mm as media particles was dispersed to obtain a coating liquid intermediate J-31. The coating liquid intermediate I-16, the coating liquid intermediate J-31, and 100 parts of methanol were mixed and stirred to obtain a coating liquid K-31. The abundance ratio of particles having a volume particle size of 10 μm or more in the volume particle size distribution in the coating liquid K-31 was 0.13%. Table 3 shows the physical properties of the coating solution. A developer carrier S-31 was produced in the same manner as in Example 1 except that the coating liquid K-31 was used, and the same evaluation was performed. The results are shown in Table 5.

It is a schematic diagram which shows an example of a structure of the resin coating layer of the developing agent carrier of this invention. 1 is a schematic configuration diagram showing one embodiment of a developing device using a developer carrying member of the present invention. An example of a developing bias (blank pulse bias) used in the developing method of the present invention is shown. 1 is a schematic configuration diagram showing one embodiment of a developing device using a developer carrying member of the present invention.

Explanation of symbols

11: Cylindrical substrate 12: Resin coating layer 13: Concavity / convexity imparting particles 14: Graphitized particles 20: Feeding / peeling roller 21: Electrophotographic photosensitive drum 22: Hopper 23: Nonmagnetic one-component developer 24: Development sleeve 25: Resin coating layer 26: Metal cylindrical tube (base)
27: Power supply 28: Stirring blade 29: Developer layer thickness regulating member

Claims (6)

A non-contact developing method using a non-contact type developing device that performs development in a non-contact state between an electrostatic latent image carrier and a developer carrier,
A non-magnetic one-component developer is carried on a developer carrier, transported to a development area facing the electrostatic latent image carrier, and an alternating current component intermittently paused on the developer carrier is superimposed on the direct current component. applying a voltage as developing bias, and a step of a visible image of the latent image on the electrostatic latent image bearing member,
The developer carrier has at least a substrate and a resin coating layer formed on the substrate, and the resin coating layer includes:
Concavity and convexity imparting particles made of spherical carbon particles for imparting concavity and convexity to the surface of the resin coating layer having a volume average particle diameter of 3.2 to 8.7 μm, and a graphitization degree P (002) of 0.23 ≦ P (002) ≦ 0.92 and containing at least graphitized particles for imparting conductivity, having a volume average particle diameter of 0.49 to 3.78 μm, and
A developing method comprising: a developer carrying member having a volume particle size distribution of particles contained in the resin coating layer of 4.80 % or less. The volume average particle diameter of the graphitized particles, a developing method according to claim 1, wherein the smaller than the volume average particle size of the concavo-convex imparting particles. 3. The developing method according to claim 1, wherein the graphitized particles are obtained by graphitizing bulk mesophase pitch or mesocarbon microbeads . 4. The developing method according to claim 1, wherein the nonmagnetic toner as the nonmagnetic one-component developer is produced by a polymerization method. Before Kihi magnetic one-component developer the following formula (C), the developing method according to claim 4, characterized in that an average circularity of 0.935 or more developer obtained from (D).
Circularity a = L ₀ / L (C)
(In the formula, L ₀ represents the circumference of a circle having the same projected area as the particle image, and L represents the circumference of the particle image.)

(In the formula, the average circularity is a _ave , the circularity of each particle is a _i , and the number of measured particles is m) .
The developing method according to claim 1, wherein the resin coating layer has a thickness of 4 to 20 μm.

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