JP2001099137A - Conductive member, process cartridge and electrophotographic apparatus - Google Patents

Abstract

(57) Abstract: In a high-resolution and high-speed electrophotographic apparatus, a conductive member having stable conductive properties even in various environments (from high temperature and high humidity to low temperature and low humidity), a process cartridge and an electronic device using the same. A photographic device is provided. SOLUTION: In a conductive member comprising a support and a functional layer mainly composed of a polymer compound, a physical property of the conductive member is such that a volume resistance value is 1 × 10 ³ to 1 × 10 ¹² Ωcm,
A conductive member having a hardness (ASKER-C) of 10 ° to 90 °, a static friction coefficient of 1.0 or less, and a dynamic friction coefficient of 0.5 or less, wherein the conductive member is in an atmosphere at 180 ° C. Loss after heating for 6 hours is calculated as the standard heating loss (Δ
K), the solvent extraction rate when immersed in a solvent in which acetone and chloroform were mixed at a volume ratio of 1: 1 and left in an atmosphere at 23 ° C. for 120 hours was defined as a standard AC extraction rate (ΔC). A conductive member having 1% by weight or less and ΔC of 5% by weight or less, a process cartridge and an electrophotographic apparatus using the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive member used in an electrophotographic apparatus such as a copying machine, a printer and a facsimile, and an electrophotographic apparatus using the same.
The present invention relates to a conductive member that is required to have uniform conductivity, such as charging and developing applications, and an electrophotographic apparatus using the same.

[0002]

2. Description of the Related Art Conventionally, many methods have been known as an electrophotographic method. In general, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means. (Charging step), the latent image is developed with toner to form a visible image (development step), and if necessary, a toner image is transferred to a transfer material such as paper (transfer step). To fix a toner image on a transfer material (fixing step) to obtain a copy. Further, toner particles remaining on the photoconductor without being transferred onto the transfer material are mainly removed from the photoconductor by various means (cleaning step).

[0003] In such electrophotography, various conductive members are used for various purposes. For example, in the charging step, a charging member for bringing the photoconductor to a predetermined polarity and potential, and for example, in the developing step, a developing member may be mentioned as a representative, such as a roller, a blade, a brush, a belt, a film, a sheet, a chip, and the like. Opposite (contact or close) the photosensitive member surface
In this case, a DC voltage or a superimposed voltage of a DC voltage and an AC voltage is applied and used.

In particular, in a charging member used in contact with a photoreceptor, image defects caused by additives such as oily substances and low molecular substances in the charging member being transferred to and adhere to the surface of the photoreceptor. Occurred. In order to improve this, it is common to adopt a configuration in which the charging member is configured to have two or more layers so that a migration material from the lower layer is blocked by the surface layer.

However, even in this case, the low molecular weight resin component in the resin used as the surface layer may adhere to the surface of the photoreceptor in an atmosphere such as high temperature and high humidity. As disclosed in JP-A-89057, studies have been made to reduce the low-molecular-weight resin component, and a desired effect has been obtained. Further, as the life of the electrophotographic apparatus is extended, the life of the conductive member used therein is required to be extended. For example, as shown in Japanese Patent Application Laid-Open No. 9-31331, at 200 ° C. for 4 hours. It is disclosed that when a hydrocarbon-based oil having a heat loss (volatile content) of 30% or less is added to a silicone rubber, a change in resistance value is improved and a long-term use can be endured.

[0006] With the recent spread of computers and their peripheral devices, the flow of colorization and the increase of graphic images due to diversification of values has been remarkable. As a result, electrophotographic apparatuses such as printers, copiers, and faxes as information output means are required to have higher image quality, and faithful reproducibility of images is important. One of the means to cope with this is a flow of higher resolution. That is, how to recognize and reproduce the original image in detail, from 600 dpi to 1200d
One example is the development of technology to pi or higher.

When such a conventional conductive member as described above is used in such an electrophotographic apparatus requiring even higher image quality (or higher resolution), an environment for outputting an applied voltage or an image, or Under certain conditions or combinations of conditions, such as the image pattern to be output and the electrophotographic device to be used, fine white or black streaks or spots may occur, or foreign or partial foreign matter adheres to the conductive member surface. Density unevenness was sometimes caused by unevenness. In particular,
This tends to occur when an image is output after the conductive member has been sealed and stored for a long period of time, and there has been a problem that the quality of the image may be deteriorated before the number of durable sheets originally reached is reached.

Further, after using an electrophotographic apparatus having a high resolution (about 600 dpi or more, particularly 1200 dpi or more) and alternately standing in a high-temperature high-humidity environment and a low-temperature low-humidity environment,
This is likely to occur when only a DC voltage is applied to the charging device and an image or graphic image formed in a fine black-and-white repetitive pattern is output in a low-temperature and low-humidity environment. In addition, the process speed is high (the process speed is generally 100 m).
m / sec. As described above, in particular, 120 mm / sec. This is particularly likely to occur in the case of the above.

Although this development is at a level that hardly causes a problem in a conventional electrophotographic apparatus, by improving the performance of the electrophotographic apparatus in terms of hardware, it is possible to faithfully develop even a minute unevenness of a latent image to thereby develop an image. It is due to the minute appearance on the top. In other words, as described above, this is a new problem that has emerged with the improvement in hardware performance of the electrophotographic apparatus to cope with higher image quality, and is more likely to occur as the tendency for higher image quality increases. It is a phenomenon.

As described above, especially in an electrophotographic apparatus that requires high image quality and high speed, even under various conditions,
Technology relating to a conductive member having good characteristics and having no characteristic unevenness such as minute streaks or spots of black or white or foreign matter adhering to the surface of the conductive member or partial unevenness of foreign matter adhering thereto, and an apparatus using the same. Development was needed.

[0011]

SUMMARY OF THE INVENTION The object of the present invention has been made in view of the above-mentioned problems, and is suitable for high image quality and can be suitably used for a more sophisticated electrophotographic apparatus. An object of the present invention is to provide a conductive member, a process cartridge using the same, and an electrophotographic apparatus.

Another object of the present invention is to provide a high resolution (approximately 60
In electrophotographic apparatuses of 0 dpi or more, especially 1200 dpi or more, and high speed (process speed is about 100 mm / sec. Or more, especially 120 mm / sec. Or more), even in various environments (from high temperature and high humidity to low temperature and low humidity). An object of the present invention is to provide a conductive member having stable conductive characteristics, a process cartridge using the same, and an electrophotographic apparatus.

Another object of the present invention is to reduce foreign matter adhesion and partial foreign matter adhesion unevenness on the surface of a conductive member, and to reduce
Even when images of various patterns are output and used by applying only the C voltage, fine white or black streaks or spots,
Another object of the present invention is to provide a conductive member which has solved density unevenness and the like, a process cartridge and an electrophotographic apparatus using the conductive member.

Further, another object of the present invention is to provide a conductive member which is optimal for a so-called cleanerless process which does not have an independent cleaning device, as represented by a simultaneous developing cleaning mechanism, a process cartridge using the same, and a process cartridge. An object of the present invention is to provide an electrophotographic apparatus.

[0015]

Means for Solving the Problems In order to solve these problems, the present inventors have conducted intensive studies, and as a result, even if a conductive member obtained by the same manufacturing method is used after manufacturing. Due to differences in storage conditions until the service is provided,
When an image is output using a high-resolution or high-speed electrophotographic apparatus, it has been found that there is a considerable difference in the number of output sheets from the start of image output to the occurrence of image defects such as density unevenness. It has been reached.

According to the present invention, there is provided a conductive member comprising a support and a functional layer mainly composed of a polymer compound,
The physical property of the conductive member is such that the volume resistance value is 1 × 10 ³ Ωcm
A conductive member having a hardness of not less than 1 × 10 ¹² Ωcm, a hardness (ASKER-C) of not less than 10 ° and not more than 90 °, a coefficient of static friction of not more than 1.0 and a coefficient of dynamic friction of not more than 0.5; The non-conductive member is immersed in a solvent in which acetone and chloroform are mixed at a weight ratio of 1: 1 by setting a weight loss rate of heating when left in an atmosphere of 180 ° C. for 6 hours as a standard weight loss rate of heating (ΔK). When the solvent extraction rate when left in the atmosphere for 120 hours is the standard AC extraction rate (ΔC), ΔK is 1% by weight.
And a conductive member having ΔC of 5% by weight or less.

Since the conductive member having the structure of the present invention has very stable conductive characteristics, specific conditions such as an applied voltage, an environment for outputting an image, an image pattern to be output, and an electrophotographic apparatus to be used, etc. Because a good image can be obtained below or in a combination of conditions,
It is possible to provide a conductive member, a process cartridge and an electrophotographic apparatus using the same, which are suitable for high image quality and can be suitably used for a higher-speed electrophotographic apparatus.

[0018]

Embodiments of the present invention will be described below in detail.

The conductive member of the present invention can be suitably used for various applications requiring conductivity, such as charging, static elimination, and development. However, the conductive member is 600 dpi or more (preferably 1200 dpi).
i) or higher resolution and process speed of 1
00 mm / sec. Or more (preferably 120 mm / se
c. This is particularly effective in the high-speed electrophotographic apparatus described above. Of these, the present invention is particularly suitable for use in opposition to a photoreceptor, and its effect is remarkable in charging of a photoreceptor. Therefore, the present invention will be described below with reference to charging of a photoreceptor.

As a typical example of a conductive member used for charging, a conductive member to which a voltage is applied is brought into contact with a photoreceptor at a predetermined pressure, and a discharge in a minute gap between the conductive member and the photoreceptor is used. Then, the surface of the photoreceptor is charged to a predetermined potential.

In order to uniformly charge the surface of a photosensitive member used in a high-performance electrophotographic apparatus to a predetermined potential by such a method, first, a minute gap between the photosensitive member surface and the conductive member surface is required. It is very important that the discharge between them is more uniform and stable than before. For that purpose, it is needless to say that the dimensional stability of the conductive member is high, and at least a predetermined dimension (diameter, length, film thickness) and a predetermined physical property (volume resistance, surface resistance, , Hardness, modulus, etc.) is as small as possible (within ± 5% of the target value or center value if possible). In particular, the volume resistance of the conductive member may be 1 × 10 ³ Ωc depending on the process conditions of the electrophotographic apparatus used.
m or more and 1 × 10 ¹² Ωcm or less, of course, it is preferable that the variation of the volume resistance value in one conductive member is small, and it is ideal that there is no variation at all. It is desirable that the ratio between the value and the minimum value be within 5 times. Further, although the environment dependency of the volume resistance value is preferably as small as possible, it is more preferable if the ratio of the volume resistance value in the environment exhibiting the maximum resistance to the volume resistance value in the environment exhibiting the minimum resistance is within 10 times. Further, it is preferable that the dependency of the volume resistance value on the applied voltage or the applied time is small.

Next, physical uniformity when the photosensitive member and the conductive member are assembled is strongly required. That is, in the case of contact with a predetermined load, the nip width and shape should be uniform under the applicable contact conditions (the state of being incorporated in the electrophotographic apparatus but not moving is referred to as stationary) (if possible). (Within ± 5% of the ideal value or the calculated value) is desirable. Further, it is naturally preferable that the amount of deformation of the contact portion after the stationary state is continued for a long time is small, and that the volume resistance of the contact portion is smaller than the volume resistance of the portion other than the contact portion. After storage in the specified environment / time, before starting use, the deformation amount is within 5% of the maximum outer diameter or the maximum thickness of the conductive member, and the change in volume resistance of the abutting part is the part other than the abutting part. ± 20 compared
% Is desirable.

In addition, when the photosensitive member and the conductive member move relative to each other, the nip width and shape at the start of operation (hereinafter referred to as driving) and during continuous operation (hereinafter referred to as operating) are uniform (ideally, ideal values and Within ± 5% of the calculated value). Similarly, the change in volume resistance during operation is
It is preferable that the value falls within the range of ± 20%, but it goes without saying that the smaller the value, the better. The operation state is a state in which the operation is continuously performed, and is referred to herein as a “dynamic state”. The driving state is a state at the moment of transition from a stationary state to a dynamic state, and is referred to as a “static state”. Target state ".

In order to achieve these, it is preferable that the conductive member has moderate resistance to deformation (ie, shape stability). For this purpose, it is preferable that the hardness (ASKER-C) of the conductive member has an appropriate hardness (10 ° or more and 90 ° or less), and in particular, the surface thereof (that is, the functional layer provided at the uppermost position). (The outermost layer) is more preferably within this hardness range, and it is more preferable that the higher the functional layer, the higher the hardness is because the above-mentioned effect is easily obtained. These greatly contribute to stabilization of the stationary state, static and dynamic states, but are particularly effective in stabilizing the stationary state, and do not cause sagging even when stored for a long time in the stationary state. It is preferred.

In addition, if the upper functional layer has a higher tensile strength at break or a smaller elongation at break, the modulus at low elongation (generally, the elongation ratio is about 1% to 10%) tends to increase. As a result, even when a load is applied, the shape is hardly deformed, and the effect is further obtained. Therefore, there is an excellent effect in stabilizing the shape particularly in a static state in which a large load is momentarily applied. Therefore, as the static load and the dynamic load are not significantly different, the shape stabilization in the static and dynamic states is excellent. At this time, it is preferable that the loss tangent (physical tan δ) of the outermost layer is smaller because the time from when the load is applied to when the displacement occurs is shorter.

The coefficient of static friction on the surface of the conductive member is 1.
If it is 0 or less, the load in the static state is reduced. If the coefficient of kinetic friction is 0.50 or less, the load in the dynamic state is reduced. Therefore, the drive system (gear, shaft, other As a result, the torque to the power transmission member is reduced, so that wear and deterioration of the drive system members are reduced, contributing to high durability. In addition, since the frictional force is stable, pitch characteristics are hardly generated, so that images are also generated. It is easy to obtain a uniform product. Naturally, the closer the static friction coefficient and the dynamic friction coefficient are, the more preferable,
It is preferable that the temporal change of the dynamic friction coefficient is small because the effect of equalizing the nip state in the static and dynamic states can be obtained.

As described above, even in a conductive member that has achieved uniformity and stability one level higher than the conventional one,
Particularly when used in an electrophotographic apparatus having a high resolution of 600 dpi or more (preferably 1200 dpi or more), a considerable difference may occur in the number of output sheets from the start of image output to the occurrence of image defects such as density unevenness. It turned out to be. That is, despite the fact that the device is manufactured under the same manufacturing conditions, a large difference occurs in the durability as a result, and it tends to be remarkable particularly in a case where the uniformity of charging is disadvantageous. By carefully observing this development and conducting various verification experiments, it was discovered that the durability of the conductive member varied depending on the storage state during the period from manufacture to use. As a result of diligently analyzing the surface of different conductive members, there is a difference in the amount of substances present on the conductive member surface, and these substances are those in which components of the substance added to the conductive member migrated to the surface ( Surface transfer).

These surface transfer products are described in, for example,
Even if the low molecular weight resin component is reduced by using a solvent as disclosed in JP-A-89057, if there is a substance that is insoluble in the solvent, it remains, and is a component that volatilizes over a long period and migrates to the surface of the conductive member. In addition, even if the heat loss of a specific one of various additives (for example, hydrocarbon-based oil) is controlled to a predetermined range as disclosed in JP-A-9-31331, for example, It is presumed that components derived from additives other than the specific one (e.g., hydrocarbon-based oil) have migrated, or low molecular weight components of rubber and resin materials that cannot be completely removed by this method.

However, when the same material as the surface transfer material is intentionally applied to the surface, the initial image differs depending on the amount of application, but the durability is rather improved.
There is hardly any difference in the durability in the output after the number of sheets. This is presumed to be due to the fact that when applied to the surface, it was peeled off in the early stage of durability and there was no difference in durability thereafter. It is suggested that they are affected.

As a result of rationally interpreting these, the details are to be discussed in the future, but are generally estimated as follows. That is, the functional layer of the conductive member is mainly composed of a polymer compound,
For example, it is often a composite made by adding various additives such as a conductivity-imparting agent, a cross-linking agent, etc., and therefore has complex dielectric dispersion characteristics, causing polarization of individual materials and polarization at interfaces. Or applying a voltage means applying energy from the outside (regardless of AC voltage or DC voltage), so it is particularly easy to activate low molecular weight components, and as a result, phenomena such as bleeding, blooming or volatilization The effect is particularly large when using a discharge which tends to apply a high voltage, but it is considered that the same effect is exerted to a lesser extent even when no discharge is used, such as in developing applications.

The components which cause these phenomena include:
For example, low molecular weight high molecular compound components such as dimers and oligomers originally contained in the high molecular compound used as a raw material and derivatives and catalysts and residues thereof, or conductivity imparting agents and fillers, plasticizers and softening agents Additives such as agents themselves or decomposed products or water content, as well as reaction products such as gas generated by crosslinking or foaming, as well as residual solvents and impurities can be given as examples. The tendency is great. It is considered that these components are concentrated near the surface (outermost layer) of the conductive member, appear on the surface, or scatter or volatilize to the outside in some cases. In particular, when an organic compound component is contained, reaggregation or precipitation occurs. Is easy to occur,
When the conductive member is in contact with another member, the influence on the other member is large.

In general, the conductive member is often incorporated in a process cartridge (or in a single state) and stored in a highly airtight state in order to protect it from external moisture, dust and the like. For example, it is common to enclose in a bag made of a resin having a low gas permeability or a composite material obtained by evaporating a metal such as aluminum on the resin, or to store it in a tray made of these materials.
In such a highly airtight state, in particular, the volatile components are hard to diffuse to the outside, so that the volatile components are likely to have a high concentration in a bag or the like. Reattachment to the body surface is likely to occur.

When the volatile component is re-adhered to the surface of the conductive member, the bleed / bloom component is likely to agglomerate around the core. Furthermore, in a sealed state of a bag or the like, volatile components and the like do not completely transfer to the air, and the higher the concentration near the surface of the conductive member, the higher the concentration state continues, that is, the concentration distribution occurs. Conceivable. If this state is uniform over the entire surface of the conductive member, there is a possibility that the conductivity may be somewhat uniform, but the contact force is partially limited, as in the contact portion and its surroundings or the non-contact portion. Because they are different, the ease and degree of migration will also be different.

That is, as compared with the case where the volatile component and the bleed / bloom component are present alone, not only the transfer speed of the transfer substance from the inside to the surface of the conductive member is increased, but also the localization proceeds synergistically. When an image is output in this state, the transition of the bloom / bleed component is further promoted by the energy such as the applied voltage, and the localized state is further promoted. Since foreign matter adhesion (dirt) tends to be caused mainly by migrating substances on the conductive member surface, localization of foreign matter adhesion (dirt) on the conductive member surface also progresses dramatically, and image output starts. Therefore, it is estimated that the density unevenness of the image easily occurs in a short period of time. On the other hand, when the volatile component re-adheres to the surface of the photoconductor, a stable image cannot be obtained because the volatile component changes the photosensitive characteristics of the photoconductor.

Although this phenomenon is not a serious problem in an electrophotographic apparatus which is stored in a relatively airtight state or which is applied with an AC voltage having a very low resolution, a relatively low process speed and an excellent charging uniformity. , The higher the resolution, the faster the process speed,
The tendency is greater for an electrophotographic apparatus to which only the C voltage is applied, which is a new problem in such an electrophotographic apparatus.

Further, there is a trend toward miniaturization of recent electrophotographic apparatuses. In order to achieve this, a member having conventionally a single function is provided with a plurality of functions to reduce the number of members, and a phenomenon caused by eliminating a certain part is solved by improving the characteristics of the member. For example, it is necessary to improve the function of each member and to combine the members. In order to reduce the size, the number of fans occupying a large volume in the electrophotographic apparatus is often reduced. Since the fans are provided to dissipate the heat inside the electrophotographic apparatus to the outside, if the number of fans is reduced, the radiation efficiency is reduced. Furthermore, as a result of the miniaturization itself, the spatial volume inside the electrophotographic apparatus naturally decreases, so that the thermal conductivity is apparently improved, and as a result, internal heat is easily generated, and the temperature tends to be relatively high throughout. . In combination with these phenomena, heat is more likely to be trapped inside the electrophotographic apparatus than in the related art, so that the above-described phenomena is likely to occur, and it is necessary for the conductive member to have improved characteristics capable of coping with this phenomenon.

Therefore, in order to solve this problem, it is necessary to reduce both the standard heating weight loss rate (particularly the volatile component of the organic compound) and the bloom / bleed component from the conductive member. If it is a conductive member shown,
It has been found that the above-mentioned problems show good results.

In particular, the components (substances added to the rubber) that migrate from the elastic layer may dissolve the resin or photosensitive material used for the photosensitive member or cause a chemical reaction. And may change the characteristics of the photoconductor. Since these are mainly organic compounds in many cases, it is important from this viewpoint that volatile components of the organic compounds fall within the scope of the present invention. Further, it is preferable that the conductive member is made of a raw material that does not dissolve components contained in the photoconductor or has no reactivity.

In the conductive member of the present invention, the ratio of the volatile component of the organic compound to the standard heating loss rate (ΔK) is ΔΔ
Preferably, the hardness (Hn) (ASKER-C hardness) of the functional layer (hereinafter, the outermost layer) located at the uppermost or outer side of the conductive member is 10 ° or more and 90 ° or less. In addition, ΔK (ΔKn) of the outermost layer is 1% by weight or less, ΔC (ΔCn) of the outermost layer is 5% by weight or less, and the ratio of the volatile component of the organic compound in the ΔKn is 50% or less. It is very preferable that all of the materials constituting the outermost layer have a ΔK of 5% by weight or less, because not only the conductive member of the present invention can be easily obtained, but also the various characteristics of the conductive member are easily stabilized.

When a plurality of functional layers are provided, not only the ΔC and ΔK of the conductive member as a whole fall within the scope of the present invention, but also the standard AC extraction rate (ΔCi ) And the standard loss on heating (ΔKi) are ΔCi
≦ 50% by weight, ΔKi ≦ 2% by weight, more preferably at least the standard AC extraction rate (Δ) of the outermost layer (n-th layer).
Cn) and the standard heating loss rate (ΔKn) are more preferably ΔCn ≦ 5% by weight and ΔKn ≦ 1% by weight.

In particular, in the case of a roller-shaped conductive member having excellent static and dynamic shape stability (hereinafter referred to as a conductive roller),
A configuration including an elastic layer as a functional layer is generally used. In this case, the elastic layer is formed directly or through another layer around or above the support, and the outermost layer is formed directly or through another layer around or above the elastic layer. In the conductive member having such a configuration, when the hardness from the support to the elastic layer is represented by ΔHd, and the hardness when all the functional layers from the support to the outermost layer are represented by ΔHn, 1.1 × ΔHd ≦ ΔHn is suitable in view of the balance between the flexibility of the elastic layer and the shape retention of the outermost layer.

Further, the hardness (H) of any one (i-th layer) in the functional layer below the outermost layer is Hi, ΔK is ΔKi,
When ΔC is ΔCi, Hn> Hi, ΔKn <ΔKi,
ΔCn <ΔCi (i ≠ n, i is an integer and i = 1, 2,
3,..., N-1), or H of the elastic layer is Hd, Δ
K is ΔKd, ΔC is ΔCd, H of an arbitrary layer (j-th layer) in the functional layer above the elastic layer is Hj, and ΔK is ΔK.
When j and ΔC are ΔCj, Hd <Hj, ΔKd> ΔK
j, ΔCd> ΔCj, and ΔKj ≦ 2% by weight, ΔCj ≦ 50% by weight (d is an integer and d = 1, 2, 3, 3)
..., n-1 and j is an integer j = d + 1, d + 2,
d + 3,..., n−1, n. In addition, d <j) is preferable because it is easy to obtain a conductive member in which the effect of the present invention is very stable. In this range, the hardness of the upper functional layer is higher, or the tensile strength at break of the upper functional layer is higher, or the elongation at break of the upper functional layer is smaller, etc. It is preferable because shape stability is further improved.

Since the above-described phenomenon proceeds irreversibly and is easily promoted by external factors such as heat and stimulation, the temperature of the conductive member or a device using the same (for example, an electrophotographic device or a process cartridge) is as low as possible (generally). (50 ° C. or less). In particular, it is more preferable that the surrounding atmosphere in which the conductive member is used is designed so as not to exceed 50 ° C.

In order to sufficiently exhibit the effect of the conductive member of the present invention, ΔK and ΔC are preferably in the same range in a unit (for example, a process cartridge) in which the conductive member is incorporated. It is more preferable that the individual members and materials constituting the unit are in the same range.

Next, in order to make the static friction coefficient and the dynamic friction coefficient within the range of the present invention, the ten-point average roughness (R
z) is preferably 1 μm or more and less than 30 μm,
The smaller the variation between peaks in the chart, the more uniform the surface roughness is, which is more preferable.

At this time, the effect can be further increased by controlling the minute shape of the surface which cannot be fully grasped by conventional index of surface roughness such as Rz, Ra, Rmax and Rk. That is, the surface of the conductive member has a fine uneven structure, and the difference between the height of the convex portion formed by the fine uneven structure and the depth of the concave portion is 0.01 μm or more and 10 μm
The following is preferred. These small irregularities do not allow solids to enter, but allow gas to enter, so an air layer is formed between the conductive member and the surface when it comes into contact with the photoreceptor, and the air layer acts as a barrier. This is because an additional effect of preventing intrusion and adhesion of a foreign substance can be obtained in a working form. At this time, a polymer material having particularly excellent release properties (for example, various fluorine-containing compounds and siloxane-containing compounds, or an olefin compound and a compound having a urethane bond, etc.) is used for the outermost layer of the conductive member. The effect can be obtained dramatically by increasing the surface area.

As a means for increasing the surface area, there is a method of increasing the number of minute irregularities. In particular, if the fractal shape or the self-similar shape is adopted, the releasability increasing effect by the surface area increasing effect is remarkably improved. In other words, it can be said that the surface having such a fine shape is difficult to be stained. Particularly, in the case of a conductive member or an electrophotographic apparatus in which only a DC voltage is applied without applying an AC voltage excellent in charging uniformity, the surface of the conductive member becomes dirty. This is preferable because adhesion and accumulation can be greatly reduced. Furthermore,
It is most suitable for an electrophotographic apparatus employing a cleaner-less system in which the transfer residual toner tends to remain.

Now, consider the characteristics required for the outermost layer of the conductive member of the present invention. In this case, the effect on the outermost layer itself can be considered first, but when there are two or more functional layers (especially having an elastic layer), it is necessary to consider the effect on the lower layer via the outermost layer. . First, high strength, high toughness, high wear resistance, and the like are required to maintain the initial surface shape for a long period of time. Second, consider the case where discharge occurs. Since discharge is dielectric breakdown of air, at the time of discharge, the influence of the energy of discharge on the surroundings, as well as by-products (hereinafter referred to as discharge products) and some ultraviolet rays are generated. The influence of the energy of discharge on the surroundings usually means that charge / discharge is repeated in small cycles. This means that high potential and low potential are repeated while high energy during discharge is high. It can be considered that the functional layer (particularly the outermost layer) is damaged. Examples of the discharge products include ions, electrons, and radicals generated by ionization of air, nitrogen oxides and the like generated as a by-product of these phenomena, and acidic substances generated by combining these with moisture in the air. And an oxidation reaction or a decomposition reaction exerted on the polymer material may occur. In some cases, not only the outermost layer but also a gas or liquid state may pass through the outermost layer and affect functional layers below the outermost layer. Furthermore, ultraviolet rays may be generated, albeit slightly, and the ultraviolet rays may excite ions in the outermost layer of the conductive member and change the molecular state, thereby causing a change in conductivity.

Since these phenomena occur around the outermost layer, at least the outermost layer has physical, chemical and electrical toughness, low permeability of discharge products, It is important that they are stable. In order to cope with these characteristics, it is preferable that at least the outermost layer has a three-dimensional structure, and a method such as crosslinking, vulcanization, network formation by introducing a trifunctional (or more) reactive group, or IPN is employed. be able to. Further, increasing the crystallinity of the resin used for the outermost layer is also an effective means.

More specifically, it is preferable that at least the outermost layer is formed of a polymer compound having high dielectric breakdown resistance and high binding energy, an additive, or the like. Low gas permeability (gas permeability coefficient is 5.0 × 10 ^-8 cm ³ · cm / cm ² · s
(ec · cmHg or less) is preferable because the influence on not only the outermost layer but also the lower layer can be reduced. Since the outermost layer has undergone a structural change such as addition of various additives to the polymer compound or crosslinking, the outermost layer is not simply determined by the type of the polymer compound, but changes variously depending on the additive, the structure, the manufacturing conditions, and the like. Therefore, it is important to actually measure using the outermost layer of the conductive member or using a sample formed under conditions close to the manufacturing conditions of the conductive member. In order to obtain a property having a small gas permeability (good gas permeation resistance), a polymer compound having a small gas permeability is used particularly for the outermost layer, and for example, mica, graphite, boron nitride (BN), etc. The addition of such a flat substance or a substance having a large aspect ratio has a great effect. These substances are effective when added in an amount of 1 part by weight or more based on 100 parts by weight of the binder of the polymer compound, and more preferably 5 parts by weight or more. Further, the effect is not limited to these substances, and the effect can be obtained by adding an inorganic substance or a crystalline substance so that the binder ratio is relatively reduced. Additives are preferred because the smaller the specific gravity, the larger the volume occupied in the binder.

Further, the ultraviolet rays generated may excite ions in the outermost layer of the conductive member and cause a change in conductivity due to a change in molecular state. In order to prevent such a phenomenon, it is preferable that the outermost layer has a work function at a level stable with respect to the energy of ultraviolet rays generated by discharge. Specifically, the outermost layer has a work function (Wf ) Is preferable. Further, it is preferable that the slope γ (cps / eV) of the work function measurement curve be 5 or more. As another method for improving the stability to ultraviolet light, it is also effective to add a material that absorbs ultraviolet light to the outermost layer of the conductive member.

As a matter of course, the higher the degree of the three-dimensional outermost layer, the more effective these properties are. In addition to the effect of improving various physical properties such as improvement and lowering of the contact angle, it is easy to maintain the initial surface shape. The method may be such that a compound having a three-dimensional structure is used as the outermost layer, or a three-dimensional reaction is caused by applying energy after forming the outermost layer. In this case, a further effect can be obtained by making the functional layers other than the outermost layer three-dimensional. However, in this case, the hardness may be too high. It is necessary to determine, but it is more preferable that the higher the three-dimensional degree, the higher the layer.

In addition, the addition of a substance (adsorbent) having a property of absorbing or adsorbing a gas or a liquid to at least the outermost layer can also affect the outermost layer or penetrate the outermost layer to the lower functional layer. It is effective in reducing the influence and the like. In the same sense, the smaller the water absorption of the outermost layer, the better.
Water absorption based on MD570 (conditions are 23 ° C / 60
% RH) is 1.5% or less (preferably 1.0% or less).

It is preferable that the outermost layer also has a small linear expansion coefficient because the shape stabilizing effect against environmental changes is excellent.
The coefficient of linear expansion when conforming to ASTM D696 is 1 × 1
The temperature is desirably 0 ^-2 ° C ^-1 or less (preferably 1 × 10 ^-4 ° C ^-1 or less).

On the other hand, in each functional layer of the conductive member,
Liquid substances may be added at room temperature to perform various functions. For example, in the case of an elastic layer, the hardness (ASKER-C) is required to be low hardness of 10 ° or more and 90 ° or less and at the same time to be conductive. It is common to add a softener, and a part of the plasticizer or the softener may migrate (bleed) to the surface of the elastic layer. At this time, if a lipophilic adsorbent is added to the elastic layer, the bleeding oil component is absorbed or adsorbed by the adsorbent, so that bleed can be reduced or prevented. If the liquid component has a hydrophilic property, the same effect can be obtained by adding a hydrophilic adsorbent.

When the adsorbent is added, the effect can be obtained in any layer, but it is preferable that the layer is above and close to the layer containing the most components to be absorbed or adsorbed. It is most desirable to add it to the layer containing the most components to be absorbed or adsorbed. In particular, when a lipophilic adsorbent is used, it is most preferable to add it to the elastic layer. The adsorbent absorbs and adsorbs the oily component, thereby making it difficult to bleed, and thereby preventing and reducing various problems caused by the adsorbent.

In this case, a larger amount of oil component is present (localized or unevenly distributed) in or around the adsorbent in the elastic layer than in other portions in the elastic layer. The plasticizing effect is slightly inferior to the uniformly dispersed state, but it does not cause a problem on the characteristics, and if a plasticizing effect equivalent to the uniformly dispersed state is absolutely necessary, if it is added a little more In this case, the bleeding property is not deteriorated by the absorption and absorption effects of the adsorbent. Of course, an adsorbent in a state where oil has been absorbed in advance may be added. That is, in the present invention, even when a plasticizer is added in a larger amount than usual, excellent bleeding resistance can be obtained, so that the most important surface property for the present conductive member is not changed, and low hardness is obtained. Elastic layer can be obtained. In addition, if a layer containing an adsorbent is provided above the elastic layer, even if an oily component bleeds from the elastic layer, it can be absorbed and adsorbed by that layer, so that a layer above it and other layers can be absorbed. The influence on the members can be prevented.

On the other hand, from the viewpoint of conductivity, the adsorbent is preferably contained in a low-resistance layer. The conductive member of the present invention is adjusted to a predetermined conductivity (volume resistance value). In particular, in the case of a laminated type, a predetermined conductivity as a conductive member is obtained by stacking layers having different resistances (may be the same). It is adjusted so as to have the property (volume resistance value). Therefore,
When a liquid component such as oil enters from the outside, swelling or the like occurs depending on the type of the polymer compound used in the layer, and the conductivity (resistance value) changes. Generally, the oil component is
Due to the insulating property, a decrease in conductivity (increase in resistance) occurs.
If the adsorbent is contained here, it is absorbed or adsorbed by the adsorbent rather than absorbed by the polymer compound, so that the influence on the polymer compound itself is small. If the adsorbent absorbs the liquid component, the adsorbent will swell, but if the adsorbent is originally high resistance, even if it contains a high-resistance liquid component, the change in resistance of the adsorbent will be small, and Is that the pressure on the surroundings (particularly, the high molecular compound mainly constituting the functional layer) due to the volume increase due to the swelling of the adsorbent is appropriately dispersed if the adsorbent is in a small powder form. Since the molecular compound can be suppressed to some extent by the viscoelastic properties and flexibility, the influence on the entire layer can be small. In addition, if the conductivity (resistance value) of the layer is in a high conductivity (low resistance) region, the influence thereof can be reduced.
The layer containing the adsorbent is preferably a low resistance layer,
More preferably, it is contained in the layer having the lowest resistance among the functional layers constituting the conductive member.

That is, it is preferable to include an adsorbent in the conductive member because it is possible to prevent the layer containing the adsorbent from penetrating from above and leaching from below, and thus it is preferable. It is very preferable to contain an adsorbent in the layer itself).

As the adsorbent of the present invention, powders having various molecular weights, surface shapes and surface characteristics can be used regardless of organic substances and inorganic substances, and are appropriately selected depending on the substance to be adsorbed. A fine powder having a diameter of 5 μm or less (preferably 3 μm or less) is preferable, and the sharper the particle size distribution, the more preferable.

Examples of the adsorbent include a substance which absorbs a liquid component, a substance having a fine pore structure on the surface, and the like. Examples of the substance that absorbs the liquid component include polynorbornene having excellent oil absorbing performance and a known water absorbing polymer having excellent water absorbing performance. On the other hand, examples of the substance having a fine pore structure on its surface include inorganic porous substances and organic porous substances, and include many materials such as ceramics and polymers. Depending on the pore size, sub-micropore material (pore size is 0.8 nm or less), micropore material (pore size is 0.8 to 2 nm), mesopore material (pore size is 2 to 50 nm), and macropore material (pore size is 50 nm) Microporous crystals and porous carbon typified by zeolite are well known.

In particular, carbon is lightweight, conductive, adsorbing, and heat resistant.
And various other excellent properties such as abrasion resistance.
Ultra-fine pores of sub-nanometer size equivalent to the molecular size of the body
From macroscopic to micron-order macropores
And highly developed porous porcelain
It is Bonn. These are submicroporous carbons (pore size
0.8 nm or less), microporous carbon (pore diameter of 0.8 to 2)
nm), mesoporous carbon (pore diameter 2-50 nm) and
It is classified into low carbon (pore diameter of 50 nm or more). representative
Activated carbon is one of the most popular products.
With a wider distribution from micropores to macropores
Is generated, and under appropriate conditions, 4000 m ^Two/ G
A product with a large specific surface area is always obtained,
Some conditions exhibit molecular sieve properties.

Research on porous silica (SiO ₂ ) is also active, and various pore sizes can be produced by examining materials and production conditions. Of these, mesoporous silica is preferred. Furthermore, synthesis from inorganic materials other than silica is also possible, for example, Al ₂ O ₃ , Nb ₂ O ₅ , Ta ₂ O ₅ , TiO ₂
And various non-silica-based mesoporous materials, including ZrO ₂ .

In particular, when a porous adsorbent is added to the outermost layer, even if the outermost layer surface is worn, the porous adsorbent appears on the surface from the inside, so that a fine surface shape and a large surface area can be easily secured. It is more preferable. In this case, the greater the adsorptive power, the more the amount of heat loss and the amount of solvent extraction can be reduced. For this purpose, compatibility between the adsorbent and the material to be adsorbed is important, and the larger the surface area of the adsorbent or the smaller the pore size of the adsorbent, the more preferable.

In the same sense, if the outermost layer is made porous, a fine surface shape and a large surface area can be maintained even when worn. Means for making the outermost layer porous include:
There are various methods without particular limitation. For example, (1) a method using various known porous polymer membranes as the outermost layer, (2) 2
A method in which a specific polymer compound is removed by a chemical and physical method to form a porous material after forming an outermost layer comprising at least one kind of polymer compound, and (3) a solvent or water is applied to a certain extent after the outermost layer is applied. A method of performing heating after quenching in a state of being contained (in this case, it is preferable to repeat exposure to a temperature lower than 10 ° C. or higher than the melting point of the solvent or water and exposure to a temperature higher than 10 ° C. or higher than the boiling point, It is preferable that the transfer be performed instantaneously, and if necessary, it is more preferable to reduce or increase the pressure in consideration of the vapor pressure of the solvent or water. be able to. At this time, if the pore size of the porous polymer membrane is sufficiently small, the liquid cannot pass through, so that the liquid barrier property is sufficient.

On the other hand, with respect to gas permeability, if the outermost layer contains an adsorbent, it can be adsorbed in the process of gas permeation through the pores, so that an increase in gas permeability can be suppressed as much as possible. More effect can be obtained by adding a large amount. Further, it is more preferable to add an adsorbent to a layer immediately below the outermost layer.

When the conductive member of the present invention has two or more functional layers, it may be difficult to obtain a sufficient adhesion or adhesion depending on the type of the polymer compound used for each layer. To solve such a problem, a primer or an adhesive may be used, but the process is inevitably complicated. As in the present invention, the two functional layers that are in direct contact with each other have a configuration in which the polymer compound that constitutes one of the functional layers is contained in the other functional layer. It is preferable because a good adhesion and adhesion can be obtained. The upper polymer compound may be mixed with the lower layer, or the lower polymer compound may be mixed with the upper layer.
In any case, it is necessary to use an amount that does not significantly affect the original properties of the specific layer, and it is generally preferable that the proportion of the high molecular weight compound to be added is less than 50% by weight of the whole. . In particular, in the two functional layers that are in direct contact with each other, the difference in the solubility parameter of the polymer compound mainly constituting each functional layer is 0.5 (J / cm ³ ) ^1/2.
In the case of the above, the above-mentioned means is particularly effective because problems such as peeling are likely to occur since the compatibility is weak. Also,
If two or more kinds of high-molecular compounds having poor compatibility are mixed, and a molding method is adopted in which the direction of the material flow is likely to be generated during molding such as injection molding or extrusion molding, for example, one of the polymer compounds has Since the same compounds tend to be localized in the vicinity, the same compounds come into direct contact with each other, which makes it easier to adhere.

Here, the electrical characteristics of the conductive member will be described in detail. Further, as described, the volume resistance value (ρc) is 1 × 1
It is preferably in the range from 0 ³ Ωcm to 1 × 10 ¹² Ωcm, more preferably from 1 × 10 ⁴ Ωcm to 1 × 10 ¹² Ωcm.
× 10 ¹¹ Ωcm or less. In the conductive member of the present invention, an optimum volume resistance value is selected within the above range of volume resistance value (1 × 10 ³ Ωcm or more and 1 × 10 ¹² Ωcm or less) depending on process conditions used. Normally, by controlling the process, if the volume resistance value is within the range of the optimum volume resistance value ± 1 digit (within two digits in the range), even if another conductive member having a different volume resistance value is supplied, it can be handled. However, it is needless to say that the variation of the volume resistance value between the conductive members is preferably small, and is preferably within one digit in the range.

FIG. 2 shows a method of measuring the volume resistance of the conductive member.
Shown in Conductive members in an environment of 23 ° C / 65% RH 12
After leaving it for more than an hour and allowing it to settle, apply a predetermined voltage while rotating it at a predetermined speed while pressing it against a metal drum under a predetermined load under the environment, and let the flowing current flow for a predetermined time with the passage of time. Record on chart. At this time, the outer diameter of the metal drum, the load, the applied voltage, the rotation speed of the metal drum and the conductive member, and the like are preferably performed under the conditions of the electrophotographic apparatus using the conductive member,
In the present invention, for simplicity, the metal drum is made of stainless steel (the surface has a ten-point average roughness Rz of 5 μm or less), the outer diameter is 30 mm, and the load W is 500 g per side (total 1 kg).
The rotation speed of the metal drum was 30 rpm, the rotation of the conductive member was driven by the metal drum, and the applied voltage was -500 V DC.

An example of the measurement chart at this time is shown in FIG. 3. In the present invention, the current value 30 seconds after the voltage application is read, and when the current value is I (A), the resistance value Rs ( Ω) is calculated as R = | V / I | = | −500 / I |.

Next, the nip area when the conductive member is pressed against the metal drum is measured by an appropriate means, and the volume resistance value of the conductive member is calculated from these values by the following equation.

Ρc = Rs × S / T ρc: Volume resistance value of conductive member (Ωcm), Rs: Resistance value of conductive member (Ω) S: Nip area (cm ² ), T: Effectiveness of conductive member Thickness (cm)

The effective thickness of the conductive member is defined as the thickness (or fiber length) of a layer (in the case of a plurality of layers, mainly) of a polymer material in a free state (a state in which no load is applied). In the case where the thickness is partially different, the load average is referred to as the effective thickness of the conductive member.

Further, it is preferable that the change in the volume resistance value is small with respect to temperature change, humidity change, temperature and humidity change, and the like.
Particularly, in the range from high temperature and high humidity (30 ° C./80% RH) to low temperature and low humidity (15 ° C./10% RH), the fluctuation of the volume resistance value is within 10 times (more preferably within 8 times, more preferably within 5 times). ) Is preferable, and the outermost layer is preferably made of a material having low hygroscopicity or water absorbency. Of course, even if the material has high hygroscopicity or water absorbency at the raw material stage, it is also possible to reduce the water absorbency or hygroscopicity as the outermost layer by involving a chemical reaction such as crosslinking or surface treatment.

Further, it is preferable that the applied voltage dependence of the volume resistance value is small. In general, the relationship between the applied voltage and the resistance (both volume resistance and surface resistance) of a polymer compound is such that the higher the voltage, the smaller the resistance (both volume resistance and surface resistance). Therefore, the same tendency is exhibited in a conductive member having a layer made of a polymer compound. However, these tendencies are affected by various factors such as the influence (the type and characteristics of the raw material or the type, characteristics and content of impurities) of the raw material used, the manufacturing conditions of the conductive member, and the layer structure. FIG. 6 shows an example of the dependency of the volume resistance value of the conductive member on the applied voltage. If the resistance dependence on the applied voltage is small, not only is it advantageous for leakage (especially DC voltage) even if there is a pinhole in the photoconductor, etc. Since the rotation of the conductive member is very smooth, the uniformity of the discharge and the conductivity is very good. Variations may occur.

Specifically, when the resistance of the conductive member changes with use or with the environment, in the case of a conductive member having a large resistance dependence on the applied voltage, the applied voltage greatly changes, As a result, there is a possibility that the contact state changes due to a change in the force of electrostatic attraction. Therefore, by reducing the applied voltage dependency, the influence due to these can be reduced.
At this time, the applied voltage dependency is 30 ° C./80% R
H, under each environment of 23 ° C./65% RH and 15 ° C./10% RH, the volume resistance value in each environment of the conductive member was determined from an applied voltage of 200 V (DC) to 1000 V (DC).
It is even more preferable that the ratio between the maximum value and the minimum value measured at every 100 V in the range of is within 10 times (preferably within 8 times, more preferably within 5 times). The measurement of the volume resistance value of the conductive member in these cases is performed by measuring the temperature,
After setting the humidity or the applied voltage to predetermined conditions, measurement and calculation are performed in the same manner as in the method shown in FIG.

In addition, the smaller the time dependency of the volume resistance value, the better. That is, the volume resistance value is calculated by a predetermined method by applying a voltage to the conductive member and measuring a current value after a predetermined time, but the current value measured immediately after the application changes (decreases or increases) with time. In many cases, the current value generally tends to decrease (the volume resistance value increases).
These tendencies vary depending on the material used (the type of binder or the conductivity-imparting material or a combination thereof), but the current value gradually changes over time, or the initial rate of change is large, but then becomes substantially constant. 3 shows various patterns such as: FIG. 7 shows the time dependence of the current value of the conductive member. In the case of the present invention, it is preferable that the above-mentioned time dependency of the volume resistance value is small, and according to the measurement method shown in FIG. In the meantime, the ratio of the maximum value to the minimum value is within 10 times (preferably within 8 times,
More preferably, it is within 5 times).

In addition, it is preferable that the partial variation of the volume resistance value within each of the conductive members is small, and the variation of the maximum value (ρc _MAX ) and the minimum value (ρc _MIN ) of the volume resistance value is reduced. When expressed as a ratio (ρc _MAX / ρc _MIN ), ρc _MAX / ρc _MIN is within 10 times (more preferably, 8 times).
(More preferably within 5 times, more preferably within 5 times). At this time, there are two types of ρc _MAX / ρc _MIN in the circumferential direction and the longitudinal direction, but the larger value is preferably in the above range.

The variation in the circumferential direction is measured according to the method shown in FIG. At this time, the current value chart a repetition period of the roller one round, because the minimum current value in the roller one round including a point after the application of a voltage 30 seconds and (I _MIN) the maximum current value (I _MAX), volume It is calculated by finding the maximum value (ρc _MAX ) and the minimum value (ρc _MIN ) of the resistance value, respectively.

The variation in the longitudinal direction is calculated by measuring and calculating the volume resistance value at each portion in the longitudinal direction of the conductive member by the method shown in FIG. 4, and calculating the ratio between the maximum value and the minimum value. FIG. 5 shows an example of the measurement result. In this measurement method, it is preferable to determine the width of the electrode in consideration of the outer diameter of the conductive member so as to be the same as the nip area when measuring the resistance in the circumferential direction, and the applied bias is also the same. However, in the case of the present invention, the electrode width is 10 mm and the applied bias is -500 V DC for simplicity.

Although these have been described in detail with respect to the volume resistance value of the conductive member, the same can be naturally applied to the surface resistance value.

The conductive member of the present invention has preferable electric characteristics other than the volume resistance value. That is, an alternating current (Iac) flowing by applying an AC voltage (peak-to-peak voltage Vpp) to the conductive member while relatively moving or rotating the conductive member and the photoconductor is measured, and Vpp (unit: kVpp) is calculated as x
Axis, Iac (unit: μA) is shown on the graph as the y-axis,
When the relationship between Iac and Vpp is expressed as y = f (x), 0 ≦
In the range of x ≦ 0.5, it is approximated by a linear expression of f (x) = ax (a is a positive number), and in the range of 1.0 ≦ x ≦ 3.0, as x increases, f (x) The inclination of the tangent becomes large, or any one point x in the range of 1.8 ≦ x ≦ 2.2
_{At 0} , 1.05 × ax ₀ ≦ f (x ₀ ) ≦ 1.50 ×
ax ₀ is preferable. If such electrical characteristics are provided, stable discharge characteristics are exhibited, so that a good image can be obtained for a long period of time.

Further, when the complex permittivity and the dielectric loss tangent (dielectric tan δ, which is expressed as tan δ ₀ in the present invention) when an AC voltage is applied to the conductive member are expressed by the following equations, 23 Under an environment of ° C./65% RH, the dielectric loss tangent is 2 or less, and the dielectric loss factor has a frequency of 1 × 10 ³ H
It is more preferable to have an inflection point or a shoulder in the range of z or more and 1 × 10 ⁵ Hz or less, and particularly preferable when only a DC voltage is applied.

Ε * = ε′−ε ″, tanδ _D = ε ″ / ε ′ (ε *: complex permittivity, ε ′: permittivity, ε ″: permittivity loss,
tanδ _D: dielectric loss tangent)

It is preferable that these electric properties are the same for the outermost layer. When there are a plurality of layers mainly composed of a polymer material, if all the layers are the same,
Very preferred.

Next, the friction coefficient will be described in detail. The conductive member of the present invention has a coefficient of static friction (μS) of 1.0 or less,
As described above, the dynamic friction coefficient (μD) is 0.5 or less. Further, when 1 ≦ μS / μD, and the maximum value of the dynamic friction coefficient (μD) is μD _max and the minimum value is μD _min , it is more preferable that 1 ≦ μD _max / μD _min ≦ 2.

It can be seen that the frictional force (or the coefficient of friction) shows various patterns of temporal changes depending on the surface properties and materials of the conductive member and the members in contact therewith, or on a combination thereof. FIG. 12 shows an example of a temporal change in the friction coefficient (load) of the conductive member.

As in the present invention, μS ≦ 1.0, μD ≦
If it is 0.5, it does not require too much force to start or continue rotation, so that an excessive load is not applied, and the surface of the conductive member or other contacting members, or damage to gears, etc. And change can be reduced, so that stable characteristics can be obtained for a long period of time.
Further, if 1 ≦ μS / μD, a large force is required at the beginning of starting rotation, but after that, a certain amount of inertial force is used once the rotation is started in order to require only a frictional force or less. As a result, smooth rotation can be obtained, so that chatter and stick-slip do not occur, and the load on the force transmission path can be reduced, so that the influence of wear of gears can be reduced. It is presumed that.

Further, in the range of 0 <t (second) ≦ 60, the maximum value of the dynamic friction coefficient (μD) obtained from the maximum value (arbitrary point) and the minimum value (arbitrary point) by the above equation is expressed by μD
_max , when the minimum value is μD _min , 1 ≦ μD _max / μD
_{If min} ≦ 2, variation in the partial dynamic frictional force is small and smooth rotation can be obtained, so that chatter and the like are less likely to occur, and the effects of long-term wear amount and wear variation are reduced. It is even more preferable from the viewpoint of high durability.

FIG. 9 shows an example (outline) of a method of measuring the static friction coefficient and the dynamic friction coefficient in the present invention. This measurement method is a method suitable for the case where the object to be measured is in the form of a roller, and is a method conforming to the Euler belt system. According to this method, the object and the conductive member as the object are measured at a predetermined angle (θ). Contacted belt (thickness 20μm, width 30mm, length 180m
In m), one end is connected to the measurement unit (load meter), and the other end is connected to the weight W. When the conductive member is rotated in a predetermined direction and speed in this state, the force measured by the measuring unit is
(G), when the weight of the weight is W (g), the friction coefficient (μ) is obtained by the following equation: μ = (1 / θ) In (F / W)

FIG. 10 shows an example of a chart obtained by this measuring method. Here, it is understood that the value immediately after rotating the conductive member is the force required to start rotation, and the value after that is the force required to continue rotation. The force at time t = 0 seconds) can be referred to as static friction force, and the force at any time 0 <t (seconds) ≦ 60 can be referred to as dynamic friction force at any time. The latter value was defined as the dynamic friction force.

Therefore, the static friction coefficient: μS = (1 / θ) In (F _{<t = 0>} / W) The dynamic friction coefficient: μD = (1 / θ) In (F _{<t = 30>} / W) Can be.

In this measuring method, the surface of the belt (the surface that comes into contact with the conductive member) is coated with a predetermined material (for example, the outermost layer of a photoreceptor, a developer coated by a suitable means, or a standard material such as stainless steel). ) Can determine the coefficient of friction for various substances.
In other words, it is more preferable to adjust the material of the contact surface, the rotation speed, the load, etc. to the process conditions of the actual machine, but it is necessary to measure the friction coefficient between the conductive member and the photoconductor and the friction coefficient between the conductive member and stainless steel. As a result of conducting a comparative study, it was found that the friction coefficient for stainless steel may be used. That is, the coefficient of friction between the conductive member and the photoreceptor = K × the coefficient of friction between the conductive member and stainless steel. Here, K is a numerical value determined by the material and state of the photoreceptor surface, and is a substantially constant value if the photoreceptor material and surface state are the same, but changes if they are slightly different.

Therefore, it is desirable that the material types, their compounding ratios, production conditions, surface physical properties, etc., match the actual system as much as possible. However, this requires a great deal of complexity and, as described above, the conductivity. Since the coefficient of friction between the member and the photoreceptor and the coefficient of friction between the conductive member and stainless steel tend to have regularity, in the present invention, for simplicity, the coefficient of friction is defined as Average roughness R
z is 5 μm or less), the rotation speed is 100 rpm, and the load is 5
It was measured under the condition of 0 g.

FIG. 11 shows another example (outline) of the method of measuring the static friction coefficient and the dynamic friction coefficient in the present invention.
This measurement method is a suitable method when the measurement object has a flat plate shape. According to this method, the conductive member to be measured is stably placed on the flat plate, and a load is applied from above, and the conductive member is connected to the measurement unit. In this state, the conductive member is pulled under the condition that the moving speed is constant, and when the conductive member starts moving in the lateral direction (or moves), the force measured by the measuring unit RR is F (g), and the load is W. (G), the coefficient of friction (μ) is obtained by the following equation; μ = F / W

In this case, the surface of the flat plate is made of a predetermined material (for example, the outermost layer of a photoreceptor, a developer in a sheet shape, or a standard material such as stainless steel) so that the coefficient of friction with respect to various materials is reduced. You can ask. In other words, the material of the contact surface, the relative moving speed,
It is more preferable to adjust the load and the like to the process conditions of the actual machine, but in the present invention, the friction coefficient was measured with respect to stainless steel, the moving speed was 100 mm / min, and the load was measured at 50 g. The chart obtained by this measuring method is the same as the method described above, and the same concept can be applied to the static friction coefficient and the dynamic friction coefficient.

It is more preferable that the coefficient of friction in the present invention is particularly μS ≦ 0.8 and μD ≦ 0.4 because the effect of the present invention can be further enhanced. Furthermore,
When 1 ≦ μS / μD ≦ 3 or when the maximum value of the dynamic friction coefficient (μD) is μD _max and the minimum value is μD _min , 1 ≦ μD
_max / μD _min ≦ 1.5 or μS ≧ μD ≧ μ
Even more preferred if D _60. In the present invention, μD
_max and μD _min are t = 30 ± 20 seconds (10 ≦ t (seconds))
≦ 50) represents the maximum dynamic friction coefficient and the minimum dynamic friction coefficient, and μD ₆₀ represents the dynamic friction coefficient at 60 seconds.

When measuring the dynamic friction coefficient, when the dynamic friction coefficient at time t1 is μD (t1) and the dynamic friction coefficient at time t2 is μD (t2), μD (t1) ≧ μD
If (t2) (where t1 <t2), the effect of the present invention can be obtained even more, and even if the conductive member is used once, the initial characteristics can be improved by a simple cleaning means or the like. It is even more preferable since further effects such as almost recovery can be obtained. Therefore, since the outermost layer can be repeatedly used without requiring a complicated process such as re-forming after the outermost layer is once peeled off, it is suitable for recycling and recycling, and is even more preferable.

As the material used for the outermost layer of the conductive member of the present invention, conventionally known thermosetting or thermoplastic resins,
Polymer compounds such as elastomers and rubbers can be used, but it is important that the outermost layer has characteristics such as high releasability and low dirt adhesion. From that viewpoint, the polymer compound used for the outermost layer is important. Particularly, a material having high releasability and low stain adhesion is particularly preferable. For example, polyamide-based polymer compounds (for example, nylon 6, nylon 66 and nylon 6
10 or a modified nylon such as a copolymerized nylon, a modified nylon such as an alkoxyalkylated nylon represented by methoxymethylated nylon or ethoxymethylated nylon), a fluorine-based polymer compound (fluorine-containing compound), or an imide-based polymer. Molecular compounds, urethane-based polymer compounds (ether- or ester-based urethane, or compounds having a urethane bond in the molecule, such as modified urethane modified with acryl or silicone), vinyl-based polymer compounds (for example, polyacetic acid) Vinyl, polyvinyl alcohol,
There are polyvinyl acetal, polyvinyl ether, N-vinyl polymer, vinylidene and the like, and modified products and derivatives thereof. More specifically, polyvinyl acetate is a homo- or copolymer of vinyl acetate. Polyvinyl alcohol is available in various degrees of saponification and further includes reactants such as acetalization, acetylation and dehydration. Polyvinyl acetal is a reaction product of polyvinyl alcohol and aldehyde, and has various structures depending on the type. Representative examples include polyvinyl butyral and polyvinyl formal. Examples of the polyvinyl ether include polyvinyl isobutyl ether, polyaryl vinyl ether, and polyvinyl thioether, and examples of the N-vinyl polymer include polyvinyl carbazole, polyvinyl pyrrolidone, poly-N-vinyl phthalimide, and polyvinyl amine. And a styrene-based polymer compound, a silicone-based polymer compound, an olefin-based polymer compound, and an epoxy-based polymer compound, and one or more of them can be used as a mixture or copolymer.

If necessary, a conductivity-imparting material, an insulating material, a charge adjusting material, a coloring material, a processing aid, a crosslinking (vulcanizing) agent, a crosslinking (vulcanizing) aid, an activator, a release agent , Lubricants, tackifiers, antioxidants, crosslinking (vulcanization) accelerators, foaming agents,
Foaming aids, fungicides, stabilizers, reinforcing agents, fillers, anti-aging agents, hydrolysis inhibitors, plasticizers, softeners, surface roughening materials,
What added a magnetic material and other various additives is used.

The outermost layer further has high releasability and low stain adhesion,
In addition, when it is necessary to reduce or control the friction coefficient, it is preferable to add a solid or liquid additive to the outermost layer so as to fall within the scope of the present invention. Examples of these additives include, for example, so-called solid lubricants, lubricants, fine resin particles,
Examples include inorganic powders and oils.

Typical examples of so-called solid lubricants are compounds whose basic structural units have a plate-like structure or a layered structure, for example, graphite, molybdenum disulfide, boron nitride, mica, clay, and the like, Hybridization with a molecule can be mentioned. As a hybrid product, for example, a hybrid product of clay and nylon 6 is particularly suitable for the present invention because it is particularly excellent in elastic modulus and gas barrier properties. As described above, in order to obtain a polymer and a hybrid material using a compound having a flat structure or a layered structure as a basic structural unit, (1)
Intra-layer polymerization initiation method, (2) polymer intercalation method, (3) common solvent method, (4) co-vulcanization method, (5) monomer modification method and the like.

Examples of the lubricant include aliphatic hydrocarbon compounds such as paraffin wax and polyolefin wax, higher fatty acids, aliphatic alcohols, fatty acid amides, fatty acid esters, and metallic soaps. it can. Further, for example, resin fine particles such as fluorine resin, silicone resin, acrylic resin, polyamide and olefin resin, inorganic powder such as silicon dioxide, titanium oxide, hydrotalcite and carbon powder, or silicone oil (unmodified Or various modifications) and oils such as ester plasticizers. By appropriately using one or more of these, a desired effect can be obtained.

In particular, when a conductive agent, a roughening agent, and other fillers are added to the outermost layer, the use of silicone oil acts as a leveling agent, so that coating defects can be eliminated, which is preferable. The type and amount of silicone oil are of course determined by the relationship with the binder and additives.
0000 ppm or less is preferable, and 10 ppm or more and 100
It is even more preferable that the content be 0 ppm or less. Further, the surface treatment of the conductive member surface is also effective for reducing the friction coefficient. As the surface treatment, for example, a coupling agent (titanium,
Silane-based and aluminum-based) treatment, halogenation treatment,
Oxidation treatment, carbonization treatment, plasma treatment, isocyanate treatment and the like can be mentioned.

As the thickness of the outermost layer, the average thickness is 100
0 μm or less (preferably 500 μm or less, more preferably 200 μm or less, more preferably 100 μm or less,
Above all, when the thickness is 50 μm or less, it is most preferable since a very excellent effect can be obtained.) Is more preferable. Further, when the thickness of the outermost layer is small to some extent, the outermost layer is required to have some high physical properties in order to stably maintain predetermined characteristics.
Particularly good results are obtained with the outermost layer having a 100% modulus of 4 × 10 ⁶ Pa or more, and more preferable if the wear resistance is good.

The material used for the elastic layer of the conductive member of the present invention is not particularly limited, and conventionally known resins, elastomers, rubbers and the like can be used.
A binder selected from a group of polymer compounds such as a resin, a thermoplastic elastomer (TPE) and a rubber may be added to a conductive material, an insulating material, a charge control material, a coloring material, a processing aid, a Vulcanization) agents, crosslinking (vulcanization) aids, activators, release agents, lubricants, tackifiers, antioxidants, crosslinking (vulcanization) accelerators, foaming agents, foaming aids, fungicides, stabilizers ,
A material to which a reinforcing agent, a filler, an antioxidant, a hydrolysis inhibitor, a plasticizer, a softener, a surface roughening material, a magnetic material, and other various additives are added is used.

As the resin, for example, a styrene resin,
Phenolic resins, epoxy resins, polyester resins, polyolefin resins such as polyethylene and polypropylene and their halides, ABS resins, ionomer resins, acrylic or methacrylic resins, urethane resins, silicone resins, vinyl chloride resins resin,
Vinyl acetate resin, polyvinyl alcohol (PVA),
Polyvinyl butyral, ethylene-vinyl alcohol copolymer (EVOH), saran resin, cellulose resin and derivatives thereof, rayon, polybutene, furan resin,
Diallyl phthalate resin, polyvinyl ether, polycarbonate, vinylidene chloride, polyethylene oxide, fluorine-based resin, polyamide-based resin and polyimide-based resin.
E, polyester TPE, olefin TPE, acrylic TPE, urethane TPE, silicone TP
E, fluorine TPE, polyamide TPE, butadiene TPE, acrylonitrile TPE and liquid crystal TPE
And further, as the rubber, for example, natural rubber (NR),
Isoprene rubber (IR) and its hydrogenated and modified products,
Ethylene propylene rubber (EPM in which ethylene and propylene are copolymerized at an arbitrary ratio or EPDM in which a diene such as ethylidene norbornene or dicyclopentadiene is added as a third component in addition to ethylene and propylene)
And its halide, butyl rubber (IIR) and its halide, butadiene rubber (cis-1,4 bond,
trans-1,4 bond, atactic or syndiotactic or isotactic-1,2 bond in any ratio between 0 and 100% by weight), transoctene rubber, nitrile rubber (NBR) and Carboxylated or hydrogenated product thereof, styrene-butadiene rubber (SBR) and its carboxylated or hydrogenated chloroprene rubber (such as sulfur-modified or mercaptan-modified type), chlorosulfonated polyethylene (CSM) and its alkylated product, urethane rubber ( Those having a -NHCOO- group obtained by the reaction of a polyester or polyether polyol with an isocyanate and modified products thereof), epichlorohydrin rubber (a homopolymer of epichlorohydrin, a copolymer of epichlorohydrin and ethylene oxide, and Binary or ternary copolymers to which unsaturated epoxides such as ruly glycidyl ether are added, and further, those in which alkylene oxides such as propylene oxide are used instead of ethylene oxide) and other halogens are introduced instead of chlorine , Silicone rubbers (having a siloxane structure in the main chain and containing alkyl groups such as methyl groups and substituents such as vinyl groups and phenyl groups in side chains) and their halides and organic polymer segment-introduced substances, fluorine Rubber (a monomer obtained by homopolymerizing or copolymerizing two or more monomers having various structures in which the main chain has a hydrocarbon skeleton and substituting fluorine, or a fluorine-containing monomer and an unsaturated hydrocarbon monomer such as propylene ), Acrylic rubber (monomer containing halogen active group as crosslinking site, epoxy A crosslinking monomer such as an active group-containing monomer, a diene monomer and a carboxyl group-containing monomer is introduced in an amount of 0.5 to 5% by mass), polynorbornene rubber, polysulfide rubber, polyether-based special rubber, propylene oxide rubber, ethylene·
Acrylic rubber and cyclized rubber (polyisoprene type, polybutadiene type, etc.) and the like can be mentioned.

These polymer compounds may be used singly or as a mixture (blended or alloyed) depending on the required properties, or the monomers constituting these polymer compounds may be used in an arbitrary manner. , Copolymerized (random, block and graft) at an arbitrary ratio, or a modified product obtained by, for example, introduction of a substituent or hydrogenation. The method for producing these polymer compounds is not particularly limited, but generally, a polymerization method such as solution polymerization, emulsion polymerization, or gas phase polymerization is used by adding a catalyst to the monomer, and the residue in the polymerized polymer compound is taken. From the viewpoint of reducing impurities and impurities, solution polymerization or gas phase polymerization is preferred. When two or more polymer compounds are used as a mixture, the properties (solid, liquid, latex, etc.), compatibility, size and shape of the dispersed particles, type, distribution and filling of the crosslinking agent It is important to appropriately select materials and processing conditions in consideration of the distribution of agents, co-crosslinkability between polymers, molecular weight, glass transition point, melting point, and the like, whereby, for example, NBR / ethylene propylene rubber, silicone rubber / Ethylene propylene rubber, silicone rubber /
Even in a combination such as acrylic rubber, which is usually not so good in compatibility, it is possible to form a fine domain composed of the other polymer compound in a matrix composed of the one polymer compound, and to form a polymer compound between the polymer compounds. Good dispersion state or sea / island structure.

The above-mentioned various additives may be added to these polymer compounds as needed, and sponges or solids may be used according to a predetermined processing method, and in some cases, may be used in a gel form, or may be formed into a fibrous form. It is possible. To carry out the operation of cross-linking or vulcanization, there are methods such as heating, hydrogenation, irradiation of moisture, ultraviolet rays, radiation and ultrasonic waves. As a result, high molecular weight, three-dimensionalization, IPN conversion and immobilization are obtained. And the like.

In the present invention, the elastic layer preferably has a thickness (or length) of 1 to 20 mm and a hardness of AS.
5 ° to 85 ° in KER-C hardness (preferably 10 to
° to 80 °) and a JISA hardness of 8
It is more preferable that the angle is 0 ° or less (preferably 70 ° or less). When a coating layer is formed above the elastic layer, the upper layer often has a higher hardness. In particular, when low hardness (ASKER-C hardness of 50 ° or less) is required, a blending device or a sponge may be used. When using a sponge, the foam diameter is 500
μm or less (more preferably 150 μm or less). The foamed surface may appear on the surface by polishing or the like, or may have a skin layer. The foamed state is either open cells or closed cells. However, when used in an electrophotographic apparatus to which an AC voltage is applied, it is preferable that a structure having a skin layer with closed cells can be provided from the viewpoint of reducing charging noise and the like. In addition, when used in an electrophotographic apparatus to which only a DC voltage is applied, it is preferable that the porosity is small in order to improve the precision of the conductive member, the withstand voltage, and the charging uniformity. Porosity per unit is 50%
The following is preferred.

The elastic layer thus obtained preferably has a large elasticity. Because, when a layer having elasticity is deformed when an external force is applied, a large elasticity means that the time required from the moment the force is applied to the time when the deformation is generated is short, In particular, when measuring the coefficient of friction, a force that instantaneously returns to the portion where the load is removed acts, but if the elasticity of the elastic layer is large, it acts in a direction to assist the force, and As a result, an unstable phenomenon such as stick-slip is unlikely to occur, so that there is a great advantage that stable characteristics are easily obtained. In this respect, the contribution of not only the surface (outermost layer) but also the layer below the surface (outermost layer) May not be ignored. Furthermore,
Although the details are unknown, further effects such as excellent stability of dimensions and shapes (for example, runout, roundness, changes due to heat shrinkage and expansion, and polishing properties, etc.) in various processing steps have been found, and are more desirable. There is a tendency.

By the way, as an index indicating elasticity, for example, a loss coefficient (dynamic tan δ,
In the present invention represents a tan [delta _T), the storage modulus,
Loss modulus, shear modulus, damping rate, mong modulus, spring constant, stress-load (SS) curve, permanent elongation, rebound resilience,
There are various types such as stress relaxation, creep, and compression set. For example, the rebound resilience is 30% or more (preferably 40% or more, more preferably 50% or more) or tan δ.
Is less than 0.4 (preferably less than 0.3, more preferably less than 0.25), and particularly preferably those having a so-called snappy property.

These characteristics depend on the type and amount of the vulcanizing agent,
Vulcanization conditions (temperature, time, etc.), vulcanization form (vulcanization density, reactivity, bonding mode, etc.), material properties (polymer molecular weight, unsaturation, cross-linking site, PH of raw materials, etc.) greatly depend on the conditions. Therefore, it is important to make appropriate selections so as to be optimal for each individual formulation.

When a conductivity-imparting material is used for each functional layer of the conductive member of the present invention, any of conventionally known electronic conductors and ionic conductors can be used.

The electronic conductor in the present invention refers to a substance having a volume resistivity of less than 1 × 10 ⁶ Ωcm.
Carbons (carbon black, graphite, carbon fiber, carbon particles, etc .; for example, grafted carbon black can control the compatibility with the binder polymer material depending on the polymer species introduced into the graft chain), metal powder (eg, Gold, silver, copper, nickel, aluminum and other alloys or pulverized and atomized into fine particles by atomization, etc., metal oxides (eg, zinc oxide, tin oxide, titanium oxide, iron oxide, ferrite, magnetite, etc.), and conductivity Examples include a treated double metal compound, an inorganic compound subjected to a conductive treatment, and a conductive polymer (for example, polyaniline, polypyrrole, polythiophene, polyacetylene, polypyridine, polyazulene, and the like).

Examples of the ionic conductor include metal salts, ammonium salts and ionic conductive polymers. Examples of positive ions constituting the metal salt include, for example,
Group I or II metal ions are mentioned, among which lithium, sodium and potassium metal salts having a relatively small cation radius are particularly preferable. As a positive ion constituting an ammonium salt, a quaternary ammonium ion is generally used. is there. On the other hand, as anions constituting these salts,
Examples include halogen, thiocyanate, perchlorate, sulfonate, trifluoromethanesulfonate, fluoroborate, carboxylate, phosphate and borate.
Examples of the ion conductive polymer include a compound having a polyether bond such as an alkylene oxide polymer and a complex thereof such as a salt thereof. These ionic conductors have a dissociation constant (the larger the conductivity, the better the conductivity) and the PH
(Because of interaction with other materials, 5-9, preferably 6-
8 is preferable), and can be used appropriately.

Furthermore, various surfactants can be used. Surfactants include cationic, anionic and nonionic surfactants, but generally have a tendency to easily migrate to the surface, so when using these, it is necessary to adjust them to fall within the scope of the present invention. Optimization is required. These conductivity-imparting materials may be used alone or in combination of two or more, and are not limited thereto.

In the present invention, it is preferable to use an electronic conductor for the outermost layer. This is because the outermost layer is in direct contact with the outside environment, and thus has the advantage that if it is an electronic conductor, it is less affected by heat and humidity, and it is difficult to transfer. In the present invention, it is preferable to use an ion conductor for the elastic layer. The elastic layer has a merit that the use of an ionic conductor has a merit that the uniformity of conductivity is easily obtained since it plays a main role with respect to the uniformity of conductivity. In addition, there is also an advantage that the addition of a small amount is sufficient, so that a decrease in the physical properties of the polymer compound is minimized.

When an ionic conductor is used for the elastic layer as one mode of the present invention, it is more preferable that the rubber used for the elastic layer has polarity in terms of compatibility, dispersibility, stability of dissociation state, and the like. . Here, the rubber having polarity is
It refers to one or more elements selected from nitrogen, oxygen and halogen in a rubber molecular structure, or a substance having a functional group or a bonding system containing these elements.

Examples of functional groups and bonding systems containing these elements include urethane bonds, ether bonds, ester bonds, halogen groups, halogenated alkyl groups, acrylonitrile groups, isocyanurate groups, isocyanate groups, and epoxy groups. , An amino group, a carboxyl group, a carbonyl group, an alkoxy group, a sulfone group and a substituted phenyl group. Typical examples thereof include urethane rubber, hydrin rubber, NBR, CR, chlorosulfonated polyethylene (CSM). ), Fluorine rubber and acrylic rubber. Among these examples, hydrin rubber and NBR are particularly preferable in terms of price and handling. In the case of hydrin rubber, as a particularly preferred composition,
A terpolymer of allyl glycidyl ether (AGE) / ethylene oxide (EO) / epicrol hydrin (ECH), preferably containing at least 5 mol% of AGE / 35 mol% of ethylene oxide.
In the case of NBR, the bound acrylonitrile content is 2
It is preferably at least 5% (particularly at least 30%), and hydrogenated ones are also preferably used.

The conductive member of the present invention may have two or more elastic layers. In this case, the rubber constituting each elastic layer may be of the above-mentioned type without any particular limitation, but is preferably of the same type, and more preferably of the same type. For example, epichlorohydrin, an elastic layer (lower elastic layer) on the side close to the conductive support having two elastic layers,
When a tertiary copolymer hydrin rubber composed of ethylene oxide and allyl glycidyl ether is used, the elastic layer (upper elastic layer) formed above the lower elastic layer is also preferably hydrin rubber. At this time, the hydrin rubber of the upper elastic layer may be a binary, ternary, or quaternary or higher copolymer or homopolymer, but it is a tertiary copolymer hydrin rubber composed of epichlorohydrin, ethylene oxide and allyl glycidyl ether. It is more preferable that the composition ratio and the like are the same or the same grade.
Of course, the present invention is not limited to the above-described example, and the same can be said for any case where rubber is used, or when there are three or more elastic layers.

In the case where a plurality of elastic layers are formed of the same type of rubber, the thickness of each elastic layer is determined in consideration of the balance between the resistance of the entire conductive member and the distribution of resistance to each layer. It is not necessary to add a conductive agent to each elastic layer because it is only necessary to determine the resistance, but from the viewpoint of conductive uniformity from a microscopic viewpoint, it is preferable to add a conductive agent to each elastic layer. Are preferably the same type of conductive agent, and more preferably the same conductive agent. The amount of the conductive agent added is preferably within ± 10% by weight in each elastic layer. The means for forming a plurality of elastic layers is not particularly limited, and the method of forming each elastic layer may be the same or different.For example, simultaneous formation of a plurality of layers by multilayer extrusion, forming the upper elastic layer after forming the lower elastic layer, There are various methods such as coating the tube and coating the upper elastic layer after forming the lower elastic layer. However, the upper elastic layer is coated after forming the lower elastic layer from the viewpoints of uniformity of film thickness and adhesion / familiarity of the interface. The method is preferred. in this case,
In general, a combination of a thick and low hardness lower elastic layer and a thin and hard upper elastic layer is often used.

When a liquid component is added to adjust the hardness of the elastic layer, a general plasticizer or softener can be used, but from the viewpoint of preventing migration, it reacts with rubber. Preferably, it is a liquid component having reactivity. These reactive liquid components include, for example, reactive plasticizers and low molecular weight liquid rubbers. Examples of the functional group of the reactive plasticizer include an unsaturated group, an epoxy group, an isocyanate group, a hydroxyl group, an amino group, a carboxyl group, a halogen and a phosphoric acid group. ) Or the main structure of the plasticizer in the side chain includes mineral processing oils such as paraffin oil, naphthenic oil and aromatic oil, rapeseed oil, cottonseed oil,
Vegetable oils such as soybean oil, beech flower oil, castor oil, linseed oil, palm oil, palm oil, fallen raw oil, wood wax, rosin, pine oil, dipentene and tall oil, or silicone oil, waxes, sub (factice) and Examples thereof include fatty acids and salts thereof. Commercially available reactive plasticizers include, for example, Lucant (Mitsui Chemicals) incorporating olefins, organic fatty acids such as stearic acid and lauric acid having a carboxyl group, and salts and esters thereof, and epoxy groups. (Kao), ADK Sizer (Adeka Argus), Epocyser (Dainippon Ink and Chemicals), and the like. Even in this case, it is preferable that the main structure has good compatibility with rubber.

Examples of the low molecular weight liquid rubber include, for example, liquid NBR, liquid CR, liquid IR, liquid polysulfide, liquid silicone rubber, liquid urethane rubber, and the like. Any liquid may be used as long as it has a functional group such as a carboxyl group or a modified one.
In this case, the liquid rubber is preferably a liquid rubber having good compatibility with the main rubber, and the closer the SP value, the more preferable.

When another layer is provided between the outermost layer and the elastic layer, the material to be used is not particularly limited. used. As a method for forming the other layer, it is common to form it in the same manner as the method for forming the outermost layer.
There is no particular limitation.

Incidentally, it is very preferable that each functional layer (especially, elastic layer) of the conductive member of the present invention has a shape memory property. This is because even a material deformed due to the influence of the compression state or the like can be restored to a level close to an almost initial shape by heating the glass to a glass transition temperature (Tg) or higher. Therefore, even a material deformed by being left or used can be reused, so that particularly excellent recyclability can be obtained.

The shape of the conductive member of the present invention is particularly limited, for example, a roller shape, a blade shape, a chip shape, a wire shape, a belt shape, a film shape, a brush shape, a sheet shape and a shape having a curved surface. However, it can be used either in a contact type or a non-contact type with respect to other members, but particularly excellent characteristics can be exhibited when used in a contact type. In this case, a roller-shaped conductive member (hereinafter referred to as a conductive roller) is preferable because it has excellent static and dynamic shape stability. When the conductive member has at least a conductive support and an outermost layer, the maximum diameter of the conductive member is preferable. (D)
And the maximum diameter (d) of the conductive support is 1.5 ≦ D / d ≦
A value of 4 is preferable because it has an advantage that stable characteristics can be easily produced with stable characteristics.

Further, the conductive member of the present invention is further improved.
To exhibit stable conductivity, the thickness must be 1 mm or more and 10 mm or more.
mm and an elastic layer containing an ion conductive agent and a thickness of 1μ
m or more and 1 mm or less and having an outermost layer containing an electronic conductive agent.
The thickness of the outermost layer is Y1 (mm) and the thickness of the elastic layer is Y0
(Mm), 1 × 10^-Five≦ Y1 / Y0 ≦ 5 × 10
^-1And an elastic layer is provided on the conductive support.
Resistance when exposed (ρ0) and conductivity formed up to the outermost layer
The ratio of the volume resistance value (ρ) of the member is 1 × 10^-2≤ρ0 / ρ
≦ 1 × 10^TwoIs preferable, and in particular, 1 ×
10^-Four≦ Y1 / Y0 ≦ 5 × 10^-2Relationship, and
Volume resistance (ρ) when an elastic layer is provided on a conductive support
0) and the volume resistance of the conductive member formed up to the outermost layer
(Ρ) is 1 × 10^-1≦ ρ0 / ρ ≦ 1 × 10¹Noseki
It is very preferable to be in charge. With such a configuration / characteristic
The conductive member has a small pinhole on the photoconductor.
Photoreceptor surface when it is produced or due to long-term use of electrophotographic equipment
Surface, wear on the conductive member surface, etc.
Good images without any problems such as leaks for a long time
And especially only DC voltage
It is suitable for an electrophotographic apparatus to apply.

When an ionic conductive agent is used for the elastic layer,
The outermost layer needs to function as a moisture barrier layer in order to reduce environmental fluctuations in various characteristics (particularly volume resistance value, etc.) of the elastic layer, and it is important to control the hydrophobicity of the outermost layer. To this end, the electron conductive agent added to the outermost layer is preferably one whose surface is made hydrophobic with a coupling agent (for example, a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, etc.) or a resin, and It is preferable that the polymer compound (resin, rubber, and elastomer) used for the outer layer has higher hydrophobicity and lower water absorption. Further, the smaller the particle size of the electronic conductive agent or the closer the conductivity between the electronic conductive agent and the polymer compound, the better the uniformity of conductivity when dispersed. In addition, particularly in the case of a conductive member accompanied by electric discharge, it is preferable that the outermost layer is a material stable to light or ultraviolet light in order to minimize the deterioration and property change of the material due to ultraviolet light generated at the time of electric discharge. . Also,
When the conductive member has a light color (especially white) and an unsaturated bond (especially an aromatic ring or a conjugated system) in the molecule, the color tone may be changed by a structural change that does not affect the physical properties. Be careful as there are.

In addition, the area where the innermost or lowermost functional layer is in contact with the conductive support (that is, the electrode area) is S0 (cm).
² ) The surface area formed by the outermost or upper surface is S1 (c
When m ² ), the relationship of S1 / S0> 2 is preferable because the withstand voltage can be further improved while ensuring the uniformity of conductivity. Generally, when a bias is applied to the conductive support, the conductive support is moved from the medium resistance layer (1 × 10 ³ to
A functional layer having a volume resistance of 1 × 10 ⁹ Ωcm)
The surface of the conductive member shows a predetermined surface potential, and at this time, the withstand voltage improves as the thickness of the middle resistance layer (the sum of a plurality of middle resistance layers) increases. That is, thickening the middle resistance layer is an effective means for improving the withstand voltage, but the same effect can be obtained by setting S1 / S0 ≧ 2.05 as in the present invention. It is.

The reason for this is not clear, and details will be discussed in the future, but it is presumed that the voltage distributed to the medium resistance layer per unit volume can be apparently reduced, and this effect appears. Is often 2.05 or more. Of course, a further effect can be obtained by combining the thickening of the middle resistance layer and the setting of S1 / S0 ≧ 2.05. That is, when the conductive member and the photosensitive member move relative to each other, the amount of current flowing from the conductive member to the photosensitive member can be easily controlled within a predetermined range. It is thought that it can be easily done.

However, if S1 / S0 is too large, although there is an effect on the improvement of the withstand voltage, the thickness of the medium resistance layer must be greatly increased in the end.
As a result, the effect of the present invention is sufficient, but the size of the conductive member increases, which is not suitable for miniaturizing the electrophotographic apparatus. Therefore, when miniaturization is particularly required, it is preferable that substantially 2.05 ≦ S1 / S0 ≦ 3.95. Further, since S1 / S0 is affected by the process speed, it is preferable to perform matching so as to meet the specifications (for example, process speed, resolution, bias conditions, and the like) of the electrophotographic apparatus main body so that optimum conditions are obtained.

In addition, when the conductive member is used in contact with another member (for example, a photoreceptor or the like), the nip area P (cm ² ) formed by the conductive member and the other member and the conductive member are determined. And the surface area S1 (cm ² ) of the conductive member. Although the reason is unknown, it is preferable that P / S1 ≧ 1/25 because stable conductive characteristics (particularly, discharge characteristics) can be obtained, and it is more preferable that P / S1 ≧ 1/16.

The use of the conductive member of the present invention in an electrophotographic apparatus is not particularly limited.
It is particularly suitable for an electrophotographic apparatus having a speed of 200 dpi or more (especially, a process speed of 160 mm / sec or more), an electrophotographic apparatus for outputting a color image or a graphic image, and a miniaturized electrophotographic apparatus. Further, it is more suitable for an electrophotographic apparatus requiring high durability (in particular, continuous output of 5000 sheets or more, and total output of 15,000 sheets or more). In addition, a so-called cleaner-less system having no independent cleaner mechanism. The present invention can be particularly usefully applied to an electrophotographic apparatus in which the developer component remaining after transfer becomes relatively large, such as an electrophotographic apparatus having the following.

In the case where the conductive member of the present invention is used as a charging member or a developing member, any one of a case where only a DC voltage is applied as an applied bias and a case where a voltage obtained by superimposing an AC voltage on a DC voltage is applied. Although it can be used in a photographic device, it is particularly suitable for an electrophotographic device that uses only a DC voltage as an applied bias that easily reflects conductive unevenness on an image.

In particular, when the photosensitive member is used as a charging member for the photosensitive member, the photosensitive member is located on the downstream side of the transfer step and the upstream side of the charging step opposite to the photosensitive member. (E.g., pre-exposure, exposure to the nip, pre-charging, etc.), or a device for removing foreign matter attached to the surface of the charging member may reduce the unevenness in conductivity. This is more preferable because it can be reduced.

Examples of an apparatus for removing foreign matter include brushes made of metal, rubber, resin, and composites thereof.
Means for mechanically stripping and removing foreign matter by bringing rollers, blades, sheets, films, belts, chips, etc. into contact with a charging member, or applying a bias in a contact or non-contact state to electrostatically attract and remove Means and the like can be mentioned. These foreign matter removing members are 1 × 10 ¹⁰ Ωc
m or less, and the surface is formed of a metal or a metal compound (oxide, sulfide, or the like) or a polymer compound (resin, rubber, and elastomer).
In the case of mechanically removing the foreign matter, a mechanical effect is not obtained if a function of adsorbing the foreign matter electrostatically is provided in consideration of the surface of the removing member and the triboelectric series of the foreign matter (such as toner). As a result, a better removal effect can be obtained. For that purpose, selection of the type of resin on the surface and addition of a charge control agent are effective means.

When a bias is applied to the removing member, it is preferable to use a DC bias having the same polarity as the charged polarity of the foreign matter. In this case, of course, from the above viewpoint, the selection of the material of the surface (metal, metal compound, resin, rubber, elastomer, etc.) and the study of the charge control agent are also effective. Further, in an electrophotographic apparatus in which the bias applied to the charging member is only a DC voltage, the DC bias applied to the foreign matter removing member is Vj (V), and the DC bias applied to the charging member is Vd (V). 0.8 ≦ Vj
/Vd≦1.2, and Vj / Vd = 1
Is more preferable.

The photoreceptor used in the electrophotographic apparatus of the present invention is not particularly limited, but has a preferable form and properties in relation to the conductive member.

If the relationship between the surface roughness of the photosensitive member and the surface roughness of the conductive member and the relationship between the two are within the range of the present invention, the coefficient of friction can be reduced and stabilized. preferable. That is, when the conductive member comes into contact with the photoreceptor, it forms a predetermined nip shape and is in contact with the photoreceptor, and the nip shape shows various shapes depending on the contact state, the contact pressure, and the like.

However, when the inside of the nip is observed in detail, it can be seen that the conductive member has a convex portion, and therefore, the conductive member is in direct contact with the photoreceptor at or near the top of the convex portion. Naturally, the deformation state changes depending on the contact state and contact pressure, etc.
Even for any one point convex part, the contact area may change, such as contact on a very small surface near the top, or crushing the top considerably, resulting in contact on a very large surface. When there are a plurality of convex portions in the nip portion, there are a plurality of directly contacting portions, and the area of direct contact is the sum of the contact areas of the individual convex portions. At this time, if the ratio (St / Sn) of the area (St) of the portion in direct contact with the nip portion (St) to the nip area (Sn) is more than 50% and 95% or less, a stable contact state is obtained. It is preferable because both the securing effect and the surface area reduction effect can be achieved. More preferably, it is 65% or more and 95% or less, and particularly preferably 80% or more and 95% or less.

In the case of the present invention, even if the area in direct contact is small, a conductive point and a discharge point are sufficiently secured around the area.
Of course, in various electrophotographic apparatuses, various conditions such as the material, shape, physical properties, dimensions, contact force, and contact state of the conductive member and the electrophotographic photoreceptor are different. Under such conditions and conditions, it is important that the relationship between the area of the portion in direct contact and the nip area be within the above range. These are particularly preferable because an effect of making the nip state uniform in the dynamic state can be obtained.

Furthermore, if the surface of the conductive member has a large number of minute uneven structures, and especially the surface of the conductive member has a fractal shape or a self-similar shape, if the surface of the conductive member has a fractal shape or a self-similar shape. Not only the contact area can be reduced and the effect is further enhanced, but also the charging efficiency (discharge amount contributing to charging / total discharge amount) is improved because a large number of discharge points can be secured. It is excellent when only a DC voltage that tends to be applied is applied.

The surface roughness of the photosensitive member and the conductive member is as follows:
It may be analyzed two-dimensionally or three-dimensionally using a contact type surface roughness meter or non-contact type surface roughness meter, etc., or may be expressed numerically from cross-sectional observation, Average roughness (R
Since z) is simple and excellent in reproducibility, the present invention uses a value measured under the same conditions using Rz as an index. Of course, R
Indices such as a, Rmax, Sm value, and Rk may be used. However, it should be noted that these values and Rz may not be completely correlated, but a similar tendency is generally observed.

Further, when the conductive member moves relative to the photosensitive member (for example, the photosensitive member rotates and the charging member is fixed, the photosensitive member and the charging member rotate, and the charging member moves in the longitudinal direction of the photosensitive member). In (2), it is preferable to have a drive device for performing one or both of the movement and rotation of the conductive member from the viewpoint of completely preventing idle rotation and slip. At this time, the charging potential of the photoreceptor (hereinafter referred to as frictional charging potential) in a state where a predetermined voltage is not applied to the conductive member is Vd.
₀ (V), and the charging potential (standard charging potential) of the photoconductor when a predetermined voltage is applied to the conductive member is Vd.
When (V) is satisfied, it is preferable that | Vd ₀ /Vd|≦0.1.

As the photoreceptor used in the electrophotographic apparatus using the conductive member of the present invention, a conventionally known photoreceptor can be used without any particular limitation. In addition, the basic structure is that a photosensitive layer is provided on a conductive support.

As the photosensitive layer, for example, an organic photoconductor,
A single layer containing a charge generation material and a charge transport material in the same layer, formed by applying a photoconductor such as amorphous silicon and selenium as a paint with a binder, if necessary, or by applying vacuum deposition. And a stacked type having a charge generating layer containing a charge generating material and a charge transporting layer containing a charge transporting material. The laminated type is further classified into a type having a conductive support, a charge generation layer and a charge transport layer in this order, and a type having a conductive support, a charge transport layer and a charge generation layer in this order. In the present invention, a laminate type using an organic photoconductor, particularly a type in which a charge transport layer is laminated on a charge generation layer is preferable.

Examples of the conductive support include metal (aluminum, aluminum alloys, stainless steel, chromium and titanium, etc.), conductive polymers and the like which have conductivity, metals, resins, fibers, paper and the like. Having a layer in which aluminum, an aluminum alloy, an indium oxide-tin oxide alloy, or the like is formed by vacuum evaporation on the surface of the polymer, or conductive particles (eg, carbon black, tin oxide, metal powder, etc.) in a polymer compound. Dispersed materials can be used. Examples of the shape include a drum shape, a sheet shape, and a belt shape, and a shape most suitable for the applied electrophotographic apparatus is preferable.

An undercoat layer having a barrier function and an adhesive function can be provided between the conductive support and the photosensitive layer.
The undercoat layer is, for example, casein, polyvinyl alcohol,
Nitrocellulose, ethylene-acrylic acid copolymer,
It can be formed of polyamide, polyurethane, gelatin, aluminum oxide and the like. The thickness of the undercoat layer is preferably 5 μm or less, more preferably 0.5 to 3 μm. The undercoat layer should be 1 × 10
It is desirable to be ⁷ Ωcm or more.

The charge generation layer is formed by vacuum-depositing the charge generation material on a conductive support, or dispersing the charge generation material in a binder resin using an appropriate solvent by coating a known solution on the conductive support. Coating by a method (for example, a coating method such as a dip coating method, a spray coating method, a Meyer bar coating method, a blade coating method, a roll coating method and a beam coating method),
It can be formed by drying. The film thickness is
5 μm or less, especially 0.1-1 μm
m is preferable.

Examples of the charge generating material include azo pigments such as monoazo, bisazo and trisazo; phthalocyanine pigments such as metal phthalocyanine and non-metal phthalocyanine; indigo pigments such as indigo and thioindigo; Cyclic quinone pigments; perylene pigments such as perylene anhydride and perylene imide; squarylium pigments; pyrylium and thiapyrylium salts; and triphenylmethane pigments.

The binder resin is selected from various insulating resins or organic photoconductive polymers. Examples thereof include polyvinyl butyral, polyvinyl benzal, polyarylate, polycarbonate, polyester, phenoxy resin, cellulose resin, acrylic resin, and polyurethane. Is preferred. These resins may have a substituent, and the substituent is preferably a halogen atom, an alkyl group, an alkoxy group, a nitro group, a trifluoromethyl group, a cyano group, or the like. Further, the content of the binder resin is preferably 80% by weight or less based on the total weight of the charge generation layer,
In particular, it is preferably at most 40% by weight.

The solvent is preferably selected from those that dissolve the resin and do not dissolve the charge transport layer and the intermediate layer described below. Specifically, ethers such as tetrahydrofuran and 1,4-dioxane; ketones such as cyclohexanone and methyl ethyl ketone; amides such as N, N-dimethylformamide; esters such as methyl acetate and ethyl acetate; toluene, xylene and Aromatic hydrocarbon compounds such as monochlorobenzene; alcohols such as methanol, ethanol and 2-propanol; and aliphatic hydrocarbon compounds such as chloroform and methylene chloride.

The charge transport layer is stacked on or below the charge generation layer, and has a function of receiving charge carriers from the charge generation layer and transporting the carriers in the presence of an electric field. The charge transport layer can be formed by applying a solution prepared by dissolving a charge transport material in a solvent together with an appropriate binder resin as required (for example, the same method as used for the charge generation layer), and drying the solution. it can. The thickness is preferably from 5 to 40 μm, particularly preferably from 15 to 30 μm.

The charge transporting material is roughly classified into an electron transporting material and a hole transporting material. Examples of the electron transporting material include 2,4,7-trinitrofluorenone, 2,4,5,7
-Electron-withdrawing materials such as tetranitrofluorenone, chloranil and tetracyanoquinodimethane, and those obtained by polymerizing these electron-withdrawing materials; and the hole transporting materials include polycyclic aromatic compounds such as pyrene and anthracene. Group compounds: carbazole, indole, imidazole, oxazole, thiazole, oxadiazole, pyrazole,
Heterocyclic compounds such as pyrazoline, thiadiazole and triazole; p-diethylaminobenzaldehyde-N,
Hydrazone-based compounds such as N-diphenylhydrazone and N, N-diphenylhydrazino-3-methylidene-9-ethylcarbazole; α-phenyl-4′-N, N-diphenylaminostilbene, 5- [4- (di- p-tolylamino) benzylidene] -5H-dibenzo [a, b]
Styryl compounds such as cycloheptene; benzidine compounds; triarylmethane compounds; triphenylamine compounds; or polymers having a group derived from these compounds in the main chain or side chain (eg, poly-N-vinylcarbazole) And polyvinyl anthracene). In addition to these organic charge transport materials, inorganic materials such as selenium, selenium-tellurium, amorphous silicon, and cadmium sulfide can be used. These charge transporting materials may be used alone or in combination of two or more.

When the charge transporting material does not have a film-forming property, an appropriate binder resin can be used. Specifically, insulating resins such as acrylic resin, polyarylate, polyester, polycarbonate, polystyrene, acrylonitrile-styrene copolymer, polyacrylamide, polyamide and chlorinated rubber, or organic photoconductive materials such as poly-N-vinylcarbazole and polyvinylanthracene Polymer and the like. The content of such a binder resin is preferably 20 to 90% by weight or less, more preferably 40 to 70% by weight, based on the total weight of the charge transport layer.
It is preferable that

As another specific example of the present invention, an electrophotographic photosensitive member having a photosensitive layer containing the above-described charge generation material and charge transport material in the same layer can be mentioned. In this case, a charge transfer complex composed of poly-N-vinylcarbazole and trinitrofluorenone can be used as the charge transport material. The electrophotographic photoreceptor can be prepared by applying a solution obtained by dispersing and dissolving the charge generation material and the charge transport material in an appropriate binder resin solution on a conductive support and drying the solution. The content of such a binder resin is from 20 to 9 with respect to the total weight of the photosensitive layer.
It is preferably 0% by weight, particularly preferably 40 to 70% by weight. The thickness is preferably from 5 to 40 μm, particularly preferably from 15 to 30 μm.

Further, in the present invention, a protective layer may be provided on the photosensitive layer for the purpose of protecting the photosensitive layer from external mechanical and chemical influences. As the protective layer, a resin layer or a resin layer containing conductive particles or a charge transport material is used. When an electrostatic latent image is formed on the protective layer, the volume resistance of the protective layer is 1 × 10 ¹⁰ Ωcm
Or more, more preferably 1 × 10 ¹¹ Ωcm or more.

For the protective layer, for example, acrylic resin, polyvinyl butyral, polyarylate (polycondensate of bisphenol A and phthalic acid), polyamide, polyimide, polycarbonate, polyester, urethane resin, methacrylic resin, styrene-butadiene copolymer A liquid in which a high molecular compound such as styrene-acrylonitrile copolymer and styrene-acrylic acid copolymer is dissolved in an appropriate organic solvent is applied on the photosensitive layer, and then dried. Line (for example,
Even better effects can be obtained by increasing the molecular weight such as cross-linking or polymerization by irradiation with ultraviolet rays, microwaves and γ rays. In the present invention, this protective layer is also a part of the photosensitive layer.

The photoreceptor thus prepared preferably has a surface roughness as small as possible (Rz of 5 μm or less) and has a capacitance of 5 per cm ² of the surface area of the photosensitive layer.
It is preferable that it is 0 pF or more and 500 pF or less. Further, the thickness of the outermost layer of the photoconductor is 0.1 μm or more and 50 μm or less, the volume resistance of the outermost layer of the photoconductor is 1 × 10 ¹⁰ Ωcm or more, the capacitance of the conductive member is C1, and the static When the capacitance is C2, C1 / C2 ≦ 0.2 and R of the conductive member
When z is Rz1 and Rz of the photoreceptor is Rz2, Rz1
If ≧ Rz2 and 3 ≦ Rz1 + Rz2 ≦ 30, the image quality is further improved, so that it is even more preferable.

The toner used in the electrophotographic apparatus of the present invention is not particularly limited, and either toner particles produced by a pulverization method or a polymerization method can be used, and either a magnetic toner or a non-magnetic toner can be used. Can be used, but there are preferable forms and properties in relation to the conductive member. The conductive member of the present invention can contain the amount of loss on heating and the amount of solvent extraction within a predetermined range, and thus can be suitably used as long as the Tg of the toner is 40 ° C. or more and 70 ° C. or less.

That is, the loss on heating and the amount of solvent extracted in the conductive member tend to migrate to the surface of the conductive member for a long period of time. Generally, the toner component adheres to the surface of the conductive member as the toner is used. This tendency increases as the Tg of the toner decreases, and in particular, in a toner having improved melting properties such as recent toners, the toner tends to adhere. There is a large tendency to stick to the surface of the conductive member. However, in the present invention, since the above-mentioned components which cause the fixing phenomenon could be reduced, the fixing property of the toner on the surface of the conductive member was improved (it is difficult to fix or the amount of fixing is reduced). It is also possible to use a toner having a Tg that cannot be used under the related art.

The toner particles used in the present invention are:
It is particularly preferably substantially spherical, and the shape factor SF-1 represented by the following formula is 100 to 160, and the shape factor SF-2
Is preferably from 100 to 140. Where SF
-1 and SF-2 are measured as follows. That is, for example, FE-SEM (S-80 manufactured by Hitachi, Ltd.)
0), 100 toner images of 2 μm or more enlarged 1000 times are sampled at random, and the image information is introduced into an image analyzer (Luzex III, manufactured by Nicolet) via an interface, and analyzed, and the following formula is used. The value obtained is defined.

SF-1 = ｛(MXLNG) ² × π / (A
REA) × 4｝ × 100 SF-2 = ((PERIME) ² / (AREA) × 4
π) × 100 where MXLNG is the absolute maximum length of the particle, PERI
ME indicates the perimeter of the particle, and AREA indicates the projection surface of the particle.

When the shape factor SF-1 exceeds 160, the toner particles deviate from a spherical shape, or when SF-2 is 140
In the case where the ratio is more than 3, the surface irregularities of the toner particles become remarkable. Toner particles that are non-spherical or have irregularities on the surface are scraped off by friction due to the carrier or toner particles coming into contact with each other and gradually become closer to a spherical shape. Since it is large, the change in the bulk density is large, and the toner density detection sensor tends to output an inappropriate output.

Recently, as a method of measuring the shape of a toner simply and with good reproducibility, a nonionic surfactant 0.1
5 mg of toner is dispersed in 10 ml of water in which a dispersion is prepared, and a dispersion is prepared by irradiating the dispersion with ultrasonic waves of 20 kHz and 50 W / 10 cm ³ for 5 minutes (Flow Particle Image A).
analyzer (hereinafter referred to as FPIA)
Method), and the measured value C1 of particles having a particle size of 0.6 to 2.0 μm in the FPIA method is preferably 3 to 50% by number. Furthermore, 20kHz, 50W
Particle size of 0.6 to 2.0 μm measured by a flow type particle image analyzer when the dispersion liquid is irradiated with ultrasonic waves of / 10 cm ³ for 1 minute
It is more preferable that the measured value C2 of the particles is 2 to 40% by number, and the value C of (C1 / C2) × 100 is 105 to 150
Is more preferable.

The method of producing the substantially spherical toner preferably used in the present invention is not particularly limited, and the irregular toner produced by the pulverization method may be stirred by applying energy such as mechanical force or heat to the irregular toner. Either a spherical toner or a toner particle produced by a polymerization method can be used, but a polymerization method is preferred when it is necessary to impart shape stability or impart high functionality. The polymerization method can obtain a substantially spherical toner having various characteristics by optimizing various conditions and weight loss, but it is particularly preferable that the toner is produced by a suspension polymerization method. 2
A seed polymerization method in which a monomer is further adsorbed to the polymer particles once obtained, which is more preferably composed of layers or more, and then polymerized using a polymerization initiator can also be suitably used in the present invention.

The toner used in the present invention has a preferable tribo value in a preferable range. That is, in the electrophotographic apparatus using the conductive member of the present invention, if the tribo value of the toner on the surface of the developer carrying member is the same as the charging polarity of the photosensitive member and is in the range of 10 to 40 mC / kg, it is stable. It is possible and preferable.

In the production of toner particles by the pulverization method used in the present invention, constituent materials such as a binder resin, a colorant and a charge control agent are sufficiently mixed by a ball mill or other mixer, and then heated roll kneader or extruder. The toner particles are obtained by kneading well using a heat kneader as described above, solidifying by cooling, mechanically pulverizing and classifying. Further, after classification, toner particles subjected to a hot air treatment or a spheroidization treatment by applying a mechanical impact are more preferable.

Examples of the type of the binder resin used in the production of the toner particles by the pulverization method include, for example, styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, and a homopolymer of a substituted product thereof; styrene-p
-Chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer Polymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer And styrene-based copolymers such as styrene-acrylonitrile-indene copolymer; polyvinyl chloride, phenolic resin, natural modified phenolic resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester Fat, polyurethane, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, bear Roman indene resin and petroleum resins. Further, a crosslinked styrene resin is also a preferable binder resin.

Examples of comonomers for the styrene monomer of the styrene copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and the like.
Double such as dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile and acrylamide A monocarboxylic acid having a bond or a substituted product thereof;
For example, dicarboxylic acids having a double bond such as maleic acid, butyl maleate, methyl maleate and dimethyl maleate and their substituted products; for example, vinyl esters such as vinyl chloride, vinyl acetate and vinyl benzoate; Olefins such as ethylene, propylene and butylene; vinyl ketones such as vinyl methyl ketone and vinyl hexyl ketone;
For example, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether are used alone or in combination, and as a crosslinking agent, a compound having two or more polymerizable double bonds is mainly used. . Aromatic divinyl compounds such as, for example, divinylbenzene and divinylnaphthalene;
For example, carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate and 1,3-butanediol dimethacrylate; divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide and divinyl sulfone And a compound having three or more vinyl groups; can be used alone or as a mixture. In particular, it is preferable to add a polar resin such as a copolymer of styrene and (meth) acrylic acid, a maleic acid copolymer, and a saturated polyester resin.

Further, the toner particles produced by the polymerization method used in the present invention have a sharp particle size distribution as compared with the pulverized toner particles, and have a shape close to a true sphere, so that the change in shape due to durability is small. The change in bulk density is also small. In the case of pulverized toner, the uneven surface is scraped off due to friction caused by the carrier or toner contact due to agitation and approaches a spherical shape, so the shape change is large, whereas polymerized toner particles that are originally a true sphere have few factors that change the shape. Since the shape change is small, the change in bulk density is small.

In the case where a polymerization method is used for the production of toner particles, it is possible to specifically produce the toner particles by the following production method. A monomer obtained by adding a release agent, a colorant, a charge control agent, a polymerization initiator, and other additives composed of a low softening point substance to a monomer and uniformly dissolving or dispersing the mixture using a homogenizer, an ultrasonic disperser, or the like. The body composition is dispersed in an aqueous phase containing a dispersant using a conventional stirrer, homomixer, homogenizer, or the like. Preferably, the granulation is performed by adjusting the stirring speed and time so that the droplets of the monomer composition have the desired size of the toner particles. Thereafter, stirring may be performed by the action of the dispersant to such an extent that the particle state is maintained and the sedimentation of the particles is prevented. The polymerization is performed at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. Further, the temperature may be raised in the second half of the polymerization reaction, and further, for the purpose of improving the durability characteristics in the image forming method of the present invention, the second half of the reaction for removing unreacted polymerizable monomers, by-products, and the like, Alternatively, a part of the aqueous medium may be distilled off after the completion of the reaction. After the reaction, the generated toner particles are collected by washing and filtration, and dried. In the suspension polymerization method, water 3 is usually added to 100 parts by weight of the monomer system.
It is preferable to use 00 to 3000 parts by weight as the dispersion medium.

In the present invention, a toner having a core / shell structure in which a material having a low softening point is coated with a shell resin is preferably used. The function of the core / shell structure is that the anti-blocking property can be imparted without deteriorating the excellent fixability of the toner, and the polymerization of only the shell portion is more effective than the polymerization of a bulk toner having no core. This is because the residual monomer can be easily removed in the post-treatment step after the step.

In the toner having a core / shell structure, a low softening point substance is preferable as a main component of the core portion, and a compound having a main peak maximum value of 40 to 90 ° C. measured according to ASTM D3418-8 is preferred. Preferably, specifically, paraffin wax, microcrystalline wax, polyolefin wax, Fischer-Tropsch wax, carnauba wax, amide wax, alcohol, higher fatty acid, acid amide wax, ester wax, ketone, hydrogenated castor oil, plant, animal , Minerals, petrolactam and their derivatives or their graft / block compounds can be used.

In the toner having a core / shell structure, the shell resin forming the shell portion may be a generally used styrene- (meth) acrylic copolymer, polyester resin, epoxy resin or styrene-butadiene copolymer. Coalescence is preferred. The following monomers are preferably used as a monomer for obtaining a styrene-based copolymer. Styrene, o- (m-, p-) methylstyrene, m
A styrene monomer such as-(p-) ethylstyrene;
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, ( (Meth) acrylate monomers such as behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and diethylaminoethyl (meth) acrylate; butadiene, isoprene, cyclohexene, Ene monomers such as (meth) acrylonitrile and acrylamide are preferably used.

When producing a toner having a core / shell structure, it is particularly preferable to add a polar resin in addition to the outer shell resin in order to make the outer shell resin contain a substance having a low softening point. As the polar resin used in the present invention, a copolymer of styrene and (meth) acrylic acid, a maleic acid copolymer, a saturated polyester resin and an epoxy resin are preferably used. It is particularly preferable that the polar resin does not contain an unsaturated group capable of reacting with a shell resin or a monomer in the molecule. If a polar resin having an unsaturated group is included, a cross-linking reaction occurs with a monomer forming the outer shell resin layer,
In particular, a full-color toner has an extremely high molecular weight and is disadvantageous for color mixing of four-color toner, which is not preferable. In the present invention, an outermost resin layer may be further provided on the surface of the toner particles.

When a polymerization method is used in the present invention, for example, 2,2′-azobis- (2,4
-Dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvalero Azo polymerization initiators such as nitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide,
A peroxide polymerization initiator such as diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide is used. The amount of the polymerization initiator varies depending on the desired degree of polymerization, but is generally used in an amount of 0.5 to 20% by weight based on the monomer. Although the type of the initiator slightly varies depending on the polymerization method, it is used alone or in combination with reference to the 10-hour half-life temperature.

Examples of the external additives of the toner usable in the present invention include oxides such as alumina, titanium oxide, silica, zirconium oxide and magnesium oxide, as well as silicon carbide, silicon nitride, boron nitride, and aluminum nitride. , Magnesium carbonate and organosilicon compounds. Among them, as the inorganic oxide fine particles (A), alumina, titanium oxide, zirconium oxide, magnesium oxide or silica-treated fine particles of these are preferable for stabilizing the charging of the toner regardless of temperature and humidity.
Further, alumina or titanium oxide fine particles or silica surface-treated fine particles thereof are preferable for improving the fluidity of the toner. Further, it is preferable that the inorganic oxide fine particles (A) have been subjected to a hydrophobic treatment in order to reduce the dependence of the charge amount of the toner on the environment such as temperature and humidity and to prevent the toner from being released from the toner surface.

Examples of the hydrophobizing agent include coupling agents such as a silane coupling agent, a titanium coupling agent and an aluminum coupling agent, and oils such as silicone oil, fluorine-based oil and various modified oils. Among the above-mentioned hydrophobizing agents, a coupling agent is particularly preferable in terms of reacting with residual groups on the inorganic oxide fine particles or adsorbed water to achieve uniform treatment, stabilizing charging of the toner, and imparting fluidity. As the inorganic oxide fine particles (A) used in the present invention, alumina or titanium oxide fine particles that have been subjected to a surface treatment while hydrolyzing a silane coupling agent are particularly preferable, from the viewpoints of stabilizing charging and imparting fluidity. Extremely effective.

The coupling agent may be any of a silane coupling agent and a titanium coupling agent. Particularly preferably used are silane coupling agents, for example, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, isobutyl Trimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane,
Examples thereof include hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, and n-octadecyltrimethoxysilane.

In order to improve the transferability and / or the cleaning property, it is also preferable to further add inorganic or organic particles having a primary particle diameter of at least 50 nm (preferably having a specific surface area of less than 50 m ² / g), which are nearly spherical. It is one of the forms.
For example, spherical silica particles, spherical polymethylsilsesquioxane particles, and spherical resin particles are preferably used.

In the toner of the present invention, other additives such as lubricant powders such as Teflon powder, zinc stearate powder and polyvinylidene fluoride powder; cerium oxide powder, Abrasives such as silicon powder and strontium titanate powder; anti-caking agents such as titanium oxide powder and aluminum oxide powder; or conductivity-imparting agents such as carbon black powder, zinc oxide powder and tin oxide powder, and vice versa. Polar organic fine particles and inorganic fine particles can be used in small amounts as a developing property improver.

The volume of the developer thus obtained was 50
% When the average particle diameter is _{Dv 50, 0.2 ≦ Rz1 / Dv} 50
A range of ≦ 5 is preferable because the adhesion of the developer component to the surface of the conductive member is unlikely to be partially uneven, and is particularly preferable when a non-magnetic one-component developer is used.

When the conductive member of the present invention is used for the charging means and the developing means, the ten-point average roughness of the surface of the conductive member (hereinafter, charging member) used for the charging means is such that the developer of the developing means is It is preferable that the surface is smaller than the ten-point average roughness of the surface of the conductive member (hereinafter referred to as "developer-carrying member") used for carrying and transporting, since a good result in image quality can be obtained.

The outermost layer of the conductive member of the present invention preferably contains a charge control agent for controlling the charge of the toner. This is because the electrostatic charge due to friction between the conductive member surface and the toner can be controlled, so that the adhesion and fixation of the developer component to the conductive member surface can be reduced, and This is because even if it has been removed, the detachability from the surface of the conductive member can be improved.
From this viewpoint, it is particularly suitable for an electrophotographic apparatus having a simultaneous development cleaning mechanism (that is, a so-called cleaner-less system) that requires control of the polarity of the toner remaining on the photoconductor. Can be used.

The conductive member of the present invention is suitably used for a process cartridge detachably mountable to an electrophotographic apparatus integrally supporting at least one selected from the group consisting of a charging device, an electrophotographic photosensitive member and a developing device. Is done. Furthermore, the conductive member of the present invention has excellent recyclability and is therefore very suitable for reuse.

The charging member of the present invention can be used for applications requiring conductivity, such as charging and erasing of a photoreceptor, and a developing member such as a member for applying a charge to a developer carrier or a developer or a regulating member. It can be used very preferably, for example, fixing,
It can be used for other purposes such as static elimination and cleaning under predetermined conditions.

Examples of the present invention will be described below, but it is needless to say that the present invention is not limited to these.

[0190]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the structure, material, manufacturing method and the like of members and an evaluation machine used in the present invention will be described.

[Electrophotographic Apparatus 1] FIG. 15 shows a color electrophotographic apparatus (copier or laser beam printer) using an electrophotographic process, and shows a main configuration of an image forming section arranged in a tandem type used in the electrophotographic apparatus. As shown in FIG.

In FIG. 16, the color image forming apparatus has first to fourth image forming units I, II, III and IV which can form visible images of, for example, yellow, cyan, magenta and black in the main body of the apparatus. Each of the image forming units I to IV has a configuration arranged in tandem, and each of the image forming units I to IV has a dedicated photoconductive layer.
3a and 104a. Each image carrier 101a-
Reference numeral 104a denotes dedicated image forming means around the periphery, for example, primary chargers 101b, 102b, 103b
And 104b, transfer units 101c, 102c, 103c and 104c, developing units 101d, 102d, 103d and 104d, and exposure units 101e, 102e, 103e and 1
04e, cleaners 101f, 102f, 103f and 1
04f and the like are provided.

The image carrier 1 of each of the image forming units I to IV
01a to 104a, a transfer belt driving pulley 9
Further, a transfer belt 8 which is stretched and driven by a transfer belt driven pulley 10 is provided. Further, in FIG.
A paper feed unit (not shown) is disposed on the right side of the first image forming unit I, and a fixing unit (not shown) is disposed on the left side of the fourth image forming unit IV.

In FIG. 16, in order to form a color image, first, in the first image forming section I, a charge is uniformly applied to a rotating image carrier 101a having a photoconductive layer by a charger 101b. Exposure unit 101e indicated by
Exposure is performed to form a latent image on the photoconductive layer on the image carrier 101a. Next, the latent image is developed by, for example, the yellow toner developing device 101d to form a visible image.

On the other hand, a transfer material (not shown) is conveyed to the first image forming unit I from the paper feeding unit by the transfer belt 8 driven by the transfer belt driving pulley 109 and the transfer belt driven pulley 110. Further, the rotating image carrier 10
1a is a case where the toner remaining on the photoconductive layer is the cleaner 1
01f and ready for the formation of a new latent image.

The same process is performed in the second image forming section II, and another color, for example, cyan toner is transferred to the transfer material. And after that, such a process is continuously performed,
The multicolor toner is transferred to the transfer material by performing the same in the third and fourth image forming units III and IV,
A desired color image can be formed.

The digital copying machine was modified as follows to obtain an electrophotographic apparatus 1. First, set the resolution to 1200 dp
i, the process speed is 120 mm / sec, and the charging means of the photoconductor is a contact-type conductive roller (charging roller);
DC voltage -1300 is used as a charging bias for the charging roller.
V was applied. The pre-exposure device before charging was removed.

Further, the development portion was modified from one-component jumping development to use of a two-component developer. The developing bias was DC-500V. Further, the transfer means using the corona charger was changed to a roller transfer method.

[Electrophotographic Apparatus 2] An electrophotographic apparatus 1 was equipped with a pre-exposure apparatus.

[Electrophotographic Apparatus 3] A superimposed voltage of a DC voltage and an AC voltage (the DC voltage is -700 V,
The electrophotographic apparatus 1 was modified so as to apply an AC voltage of 2 kVpp, a frequency of 1 kHz, and a sine wave, thereby obtaining an electrophotographic apparatus 3.

[Electrophotographic Apparatus 4] The developing section of the electrophotographic apparatus 1 was changed to a contact developing system using a conductive roller (developing roller) to obtain an electrophotographic apparatus 4. The charging bias of the developing roller was such that a DC voltage of -500 V was applied.

[Electrophotographic Apparatus 5] An electrophotographic apparatus 5 was obtained by removing the cleaner means independent of the electrophotographic apparatus 4 and remodeling it into a cleanerless system.

[Electrophotographic Apparatus 6] Electrophotographic apparatus 5 was further modified as follows to obtain electrophotographic apparatus 6. A roller made of a conductive fur brush was brought into contact with the surface of the conductive member to form a foreign matter removing roller. The conductive fur brush is obtained by adding carbon black to a fluororesin, kneading the mixture, and then molding the mixture into a fibrous shape to form a fur brush. Since the fluororesin has particularly low hygroscopicity and water absorption, the fur brush has a feature that the change in resistance to environmental fluctuation is very small. In this embodiment, the foreign matter removing roller is made of a fur brush, but may be made of another material such as a metal. Further, a rotation driving device for the foreign matter removing roller was attached, and the rotating direction of the foreign matter removing roller was a direction following the rotating direction of the conductive member, and was 1.2 times the rotation speed of the conductive member. DC-13 is used as a bias for the foreign matter removing roller.
00V can be applied.

[Electrophotographic Apparatus 7] The process speed of the electrophotographic apparatus 1 was set to 160 mm / sec, and the electrophotographic apparatus 7 was obtained.

[Photoreceptor Production Example 1] A photoreceptor 1 was prepared by providing a subbing layer, a positive charge injection preventing layer, a charge generation layer and a charge transport layer in this order on a 30 mm-diameter aluminum cylinder.

The undercoat layer is a conductive layer having a thickness of about 20 μm provided for leveling defects and the like of the aluminum drum and preventing occurrence of moire due to reflection of light exposure.

The positive charge injection preventing layer is provided to prevent the positive charges injected from the aluminum support from canceling the negative charges charged on the surface of the photosensitive member, and has a thickness of about 1 μm.
The resistance is adjusted to about 10 ⁶ Ωcm by the polyamide resin.

The charge generation layer is a layer provided to generate positive and negative charge pairs by receiving laser exposure, and is a layer having a thickness of about 0.3 μm in which a titanyl phthalocyanine pigment is dispersed in a resin. .

The charge transport layer is a 17 μm-thick layer in which hydrazone is dispersed in a polycarbonate resin, and is a P-type semiconductor. Therefore, the negative charges charged on the photoreceptor surface cannot move through this layer, and only the positive charges generated in the charge generation layer can be transported to the photoreceptor surface.

When the characteristics of this photoreceptor were measured, the volume resistivity of the surface (in the case of the charge transport layer alone) was 5 × 10 ¹⁵ Ω.
cm, Rz (Rz2) of the photoreceptor surface = 2.0 μm, and capacitance C2 (expressed per 1 cm ² of surface area of the photoreceptor) was 100 pF / cm ² .

The capacitance was measured as follows.
That is, an aluminum sheet was wrapped around an aluminum cylinder, and the photosensitive layer was applied on the aluminum sheet under the same conditions as when the photosensitive layer was applied on the aluminum cylinder to prepare a sample for measuring capacitance. The capacitance was measured with an impedance measuring device (YHP 4192A), and the capacitance per 1 cm ² of the photoconductor was determined.

[Photoreceptor Production Examples 2 and 3] In the photoreceptor production example 1, the thickness of the photosensitive layer was changed by changing the viscosity of the coating material and the coating conditions, thereby producing photoreceptors 2 and 3. The volume resistance value of the surface of the photoreceptor 2 (in the case of the charge transport layer alone) is 5 × 10 ¹⁵ Ωcm, and Rz (Rz2) = 2.0 μm
m, the capacitance C2 (expressed per 1 cm ² of the surface area of the photoconductor) is 60 pF / cm ² , and the volume resistance value of the surface of the photoconductor 3 (in the case of the charge transport layer alone) is 5 × 10 ¹⁵ Ωc.
m, Rz (Rz2) = 2.1 μm, capacitance C2 (expressed per 1 cm ² of surface area of the photoconductor) is 400 pF / c
m ² .

[Toner Production Example 1] In ion-exchanged water, 0.1%
Adding a predetermined amount of 1M-Na ₃ PO ₄ aqueous solution and 1.0 M-CaCl ₂ aqueous solution, and stirred to obtain an aqueous medium containing a calcium phosphate salt.

Next, the following materials were heated and uniformly dissolved and dispersed using a granulator.

C. Styrene (polymerizable monomer) 100 parts by weight n-butyl acrylate (polymerizable monomer) 15 parts by weight I. Pigment Blue 15: 3 (cyan colorant) 5 parts by weight Metal compound of di-alkyl-salicylic acid (charge control agent) 1 part by weight Saturated polyester resin 10 parts by weight Ester wax (release agent) 20 parts by weight Polymerization 4 parts by weight of an initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

The polymerizable monomer composition was charged into the aqueous medium, heated and stirred under a nitrogen atmosphere to granulate the polymerizable monomer composition, and then polymerized. Thereafter, the residual monomer was distilled off, and after cooling, hydrochloric acid was added to dissolve the calcium phosphate, followed by filtration, washing and drying to obtain cyan toner particles (A). Obtained cyan toner particles (A)
The measured value C1 by the FPIA method was 55% by number, the measured value C2 was 25% by number, and the value C was 240.

Next, the amounts of the resin fine particles and the resin ultrafine particles were adjusted by air classification of the cyan toner particles (A). After the classification of the cyan toner particles (A), the measured value C1 of the cyan toner particles (B) by the FPIA method was 20% by number, the measured value C2 was 18% by number, the value C was 120, and SF
-1 and SF-2 were measured, SF-1 = 12
0, SF-2 = 110, indicating a substantially spherical shape. The weight average particle size of the cyan toner particles (B) determined by the Coulter counter method was 7.5 μm.

100 parts by weight of cyan toner particles (B),
Toner 1 was prepared by mixing 1.3 parts by weight of a hydrophobic silica fine powder having a BET specific surface area of 200 m ² / g (primary average particle size: 0.01 μm). The measured value C1 of the toner 1 by the FPIA method is 20% by number, the measured value C2 is 18% by number, and the value C
Is 120, SF-1 = 120 and SF-2 = 110, and the weight average particle size by the Coulter counter method is 7.
It was 5 μm. Further, the glass transition point (T
g) was measured and found to be 60 ° C.

[Toner Production Examples 2 and 3] Cyan toner particles (A) -2 and cyan toner particles (A) -2 having different polymerization degrees and reactivity by changing the ratio of the polymerizable monomer composition and the polymerization conditions in Toner Production Example 1. A) -3 was created.

Toner particles (A) -2 and (A) -3 were prepared in the same manner as in toner production example 1 to prepare toners 2 and 3, respectively.

The measured value C1 of the toner 2 by the FPIA method was 22% by number, the measured value C2 was 17% by number, and the value C was 125%.
SF-1 = 125, SF-2 = 115, and the weight average particle size by a Coulter counter method was 7.5 μm, Tg.
Is 45 ° C., and the measured value C of the toner 3 by the FPIA method is
1 is 23% by number, measured value C2 is 18% by number, and value C is 12%.
7, SF-1 = 125, SF-2 = 110, and the weight average particle diameter by a Coulter counter method was 7.5 μm.
Tg was 70 ° C.

[Toner Production Example 4] Polyester resin 100 parts by weight Metal-containing azo dye 3.3 parts by weight Low molecular weight polypropylene 6.6 parts by weight Carbon black 6.0 parts by weight After the above materials were dry-mixed, set to 160 ° C. The mixture was kneaded with a twin-screw kneading extruder. The obtained kneaded material was cooled, finely pulverized by an air-flow type pulverizer, and then subjected to air classification to obtain a toner composition having an adjusted particle size distribution. When this toner composition was observed with an electron microscope, it was found that the toner composition had an irregular shape peculiar to the pulverized toner. 1.3% by weight of hydrophobically treated titanium oxide was externally added to the toner composition to prepare a toner 4 having an average particle size of 7.7 μm.

[Developer Production Examples 1-4] Nickel zinc ferrite having an average diameter of 60 μm coated with an acryl-modified silicone resin was added to 100 parts by weight of toner 1,
6 parts by weight of 2, 3 and 4 were mixed, and
2, 3, and 4.

Here, the conductive members used in Examples and Comparative Examples of the present invention will be described in detail below.

Table 1 shows the main structure of the conductive member described above, Table 2 shows the characteristics of the conductive rubber roller, and Tables 3 and 4 collectively show the characteristics of the conductive member.

[Production Example 1 of Conductive Member] <1-1 Preparation of Elastic Layer> 100 parts by weight of epichlorohydrin rubber (Epichromer CG, manufactured by Daiso), 1 part by weight of stearic acid, 5.5 parts by weight of calcium carbonate, and hydroxide 4.4 parts by weight of calcium, hydrous silicic acid (Nipsil VN
3, 9 parts by weight of Nippon Silica Co., 0.9 parts by weight of diethylene glycol, 5 parts by weight of naphthenic process oil (Diana Process Oil NM-280, manufactured by Idemitsu Kosan Co., Ltd.)
15 parts by weight of liquid NBR (N280, manufactured by JSR) and dimethyldidodecyl ammonium chloride (conductive agent) 2
The parts by weight were kneaded with a sufficiently cooled kneader to obtain a hydrin rubber batch. The liquid NBR used here was NBR
As well as a role as a reactive plasticizer. This was aged overnight in a cool and dark place kept at 20 ° C. or lower, and 1 part by weight of pentalit and 2.3 parts by weight of a polythiol vulcanizing agent were added and kneaded with an open roll to obtain a rubber compound 1.

Next, a stainless steel cored bar having a length of 450 mm and a diameter of 7.95 mm coated with a conductive adhesive in advance is set as a conductive support at the center of a cylindrical mold having a smooth inner surface, and the periphery thereof is set. After the conductive rubber compound 1 is poured by injection, the mixture is vulcanized by leaving it in an atmosphere at 170 ° C. for 20 minutes to form an elastic layer around a stainless steel core serving as a conductive support. A crown-shaped conductive rubber roller 1 was obtained by preparing a solid rubber roller having no running line and precisely polishing the surface.

<1-2 Preparation of Coating for Outermost Layer> Two-part curable acrylic-modified urethane (Olester Q161-4)
5, 10 parts by weight of surface-treated tin oxide A (described later), 1 part by weight of roughener resin particles 1 (described later), and roughener resin particles 2 (trefil) R-902, manufactured by Toray Dow Corning Silicone Co., Ltd.) 1
Parts by weight, 100 ppm of silicone oil (SH28PA, manufactured by Toray Dow Corning Silicone Co., Ltd.), 1 part by weight of mica (Szolite Mica, manufactured by Kuraray Co., Ltd.), 0.5 part by weight of mesoporous silica (pore diameter: 20 nm), and dialkyl-salicylic acid 0.5 parts by weight of a metal compound (load control agent) was dispersed for 12 hours by a paint shaker using a medium. Thereafter, the media is separated, and hexamethylene diisocyanate (HMDI) is used as a curing agent in OH / NCO = 1.
/ 1 and then mixed with toluene to adjust the solid content to 5% by weight to prepare the outermost layer coating material 1.

The surface treated tin oxide A was prepared as follows. In methanol containing a small amount of water and a hydrolysis catalyst, γ-methacryloxypropyltrimethoxysilane (KBM
502, manufactured by Shin-Etsu Chemical Co., Ltd.) to a concentration of 0.5% by weight to prepare a surface treatment liquid. Conductive tin oxide (a transparent conductive powder whose surface was doped with antimony oxide, primary particle size 0.02 μm) was immersed in this surface treatment solution for 3 hours while stirring, and then filtered to remove the solvent. The conductive tin oxide from which the solvent had been removed was dried at 80 ° C. for 6 hours with stirring, and further heated at 135 ° C. for 6 hours with stirring to obtain surface-treated conductive tin oxide A.

Further, the roughening agent resin particles 1 were prepared as follows. After dry mixing 100 parts by weight of acrylic resin, 2 parts by weight of calcium stearate, 3 parts by weight of low molecular weight polypropylene and 6 parts by weight of conductive carbon black, 1
The mixture was kneaded with a twin-screw kneading extruder set at 60 ° C. The obtained kneaded material was cooled, coarsely pulverized by an air-flow type pulverizer, finely pulverized by a mechanical pulverizer, and then subjected to air classification to adjust the particle size distribution.
Thereafter, the surface was polished to obtain roughly spherical roughening agent resin particles 1. The powder resistance of the roughening agent resin particles 1 is 2.3 × 10 ² Ωc.
m, the average particle size was 8.0 μm, and the particle size distribution had a peak near the average particle size.

<1-3 Preparation of Conductive Member> The surface of the conductive rubber roller 1 was washed with 2-butanone, and then subjected to a primer treatment with γ-mercaptopropyltrimethoxysilane to improve the adhesive strength. 1 was used for dip coating. The coating conditions were a pulling speed of 50 mm / sec.
c. And the coating was repeated. After coating,
Air-dry for 8 hours in an atmosphere of 20 ° C./70% RH.
The outermost layer was formed by heating in a hot-air drying oven at 35 ° C. for 30 minutes to form a conductive member 1, and the following characteristics were measured.

<1-4 Measurement of Physical Properties> The following items were measured for the conductive member 1 and the conductive rubber roller 1 (however, for the conductive rubber roller 1, (1) and (2)
(4) and (7) were not measured).

(1) ΔK ΔK of the conductive member 1 was obtained as follows.

First, the prepared conductive member was heated at 23 ° C./65.
After being left for one day in an environment of% RH, the weight of the conductive member 1 was accurately weighed to the unit of 0.1 mg in the same environment (WB). Next, the conductive member 1 was placed in an oven maintained at 180 ° C. in advance and left in the atmosphere for 6 hours. At this time, care is taken so that the functional layer portion of the conductive member 1 does not directly contact the floor on the dedicated table. Six hours later, the conductive member 1 was taken out of the oven, cooled in a desiccator overnight, and then accurately weighed to the unit of 0.1 mg (W
A). The weight of the support was measured after completely removing rubber, resin and the like (SB). When the support clearly has a volatile component such as a resin, two or more samples are prepared, and one of them is completely removed of rubber, resin, etc., and only the support is taken out. Although it is necessary to measure the change in weight of the support before and after heating, SB = SA may be used for a metal as in this embodiment. Of course, the smaller the volatile component from the support, the better.

ΔK = [｛(WB−SB) − (WA−S
A)｝ / (WB-SB)] × 100 where ΔK: standard heating weight loss rate (unit: weight%), WB: weight of sample before heating (in this case, conductive member 1) (unit: g) SB: Weight of support before heating (unit: g) WA: Weight of sample after heating (in this case, conductive member 1) (unit: g) SA: Weight of support after heating (unit: g) : G), ΔK of the conductive member 1 was 0.81% by weight.

(2) ΔC The ΔC of the conductive member 1 was obtained by measuring the amount of extraction by the solvent and using the measured value to calculate from the following equation. First, 500 ml of acetone and 500 ml of chloroform were mixed well to prepare a solvent in which acetone and chloroform were mixed at a volume ratio of 1: 1. The conductive member 1 whose weight (Wb) was accurately measured to the unit of 0.1 mg in advance was mixed with the mixed solvent 500 m
After being completely immersed in 1 L and left in an atmosphere of 23 ° C. for 120 hours, the conductive member 1 was taken out and the solvent was separated (in the embodiment of the present invention, the mixed solvent was 500 ml, but the mixed solvent was the volume of the conductive member. It is sufficient that the conductive member is completely immersed in the solvent. The solvent from which the conductive member 1 has been separated is filtered through a filter paper, and then concentrated by a reduced-pressure / heated evaporator. 60 ° C, 90 ° C
And at 120 ° C. for 1 hour each to completely remove the solvent, is referred to as an extraction amount (AC extraction amount) Wt.

The weight of the support was measured after completely removing rubber, resin and the like (Sb). In the case where the support clearly has an extractable component such as a resin, two or more samples are prepared, one of them is completely removed of rubber, resin, etc., and only the support is taken out. It is necessary to measure the change in weight of the support before and after immersion in the solvent, and it is preferable that the components extracted from the support be small.

ΔC = {Wt / (Wb−Sb)} × 100 where ΔC: standard AC extraction rate (unit: weight%), Wt: extraction amount (unit: g), Wb: sample before immersion In this case, the weight (unit: g) of the conductive member), Sb: the weight (unit: g) of the support before immersion, and the ΔC of the conductive member 1 was determined to be 3.7% by weight. there were.

(3) Hardness (ASKER-C hardness) In the present invention, ASKER-C hardness was adopted as an index indicating the hardness of the conductive member 1, and measured by the method shown in FIG. That is, the conductive member 1 is set at a predetermined position using a V block to support both ends, and the conductive member 1
ASKER-C hardness tester is pressed against a predetermined measuring point with a predetermined load, and a value after a predetermined time is measured therefrom.
KER-C hardness was used.

As a precaution in measurement, the hardness changes depending on the load, the time from pressing to reading the value, and the pressing speed, and the like. In this embodiment, the load is 1 kgf (the hardness meter itself). And the weight added from the outside was adjusted to be 1 kg in weight), and the pressing speed was 50 mm / sec.

The measurement points are a total of three places at both ends (arbitrary places within 30 mm from the end) and at the center, and the simple (arithmetic) average of the conductive member 1 (or the conductive roller 1) is obtained. ASKER-C hardness was used.

The ASKER-C hardness of the conductive member 1 is 70 ° at the left end, 68 ° at the center, and 72 ° at the right end, and the simple average of 70 ° is the ASKE-C hardness of the conductive member 1.
It was set to RC hardness.

The hardness of the conductive roller 1 was measured in the same manner. As a result, the left end was 69 °, the center was 67 °, and the right end was 71 °. ASKER-C hardness.

In this embodiment, the hardness is ASKER-C, but other hardness (for example, JIS-A, ASTM
-D, micro hardness, Wallace hardness, etc.), an optimum load may be selected and a similar measurement method may be employed.

In this embodiment, the conductive member has a roller shape. However, regardless of the shape of the conductive member, it is possible to select and measure a place where the thickness of the functional layer mainly composed of a polymer compound is the largest. It is preferable (as long as the wall thickness is almost constant as in the present embodiment, the measuring point may be anywhere).

(4) Friction Coefficient The static friction coefficient and the dynamic friction coefficient of the conductive member 1 were measured by the method described above using the means shown in FIG. FIG.
The static friction coefficient and the dynamic friction coefficient were calculated and obtained from the chart obtained by using the following equation.

ΜS = (1 / θ) In (F _{<t = 0>} / W), where μS: coefficient of static friction, θ: angle (rad) between the conductive member and the belt F _{<t = 0>} : The force (g) at 0 seconds on the chart and the weight of the weight are W (g) μD = (1 / θ) In (F _{<t = 30>} / W) where μD: dynamic friction coefficient, θ: conductivity Angle (rad) between the conductive member and the belt F _{<t = 30>} : Force (g) at 30 seconds on the chart, W (g) The weight of the weight was measured by this method, and μS = 0.80 , ΜD =
0.40. For reference, μD _max = 0.45,
μD _min = 0.35.

(5) Electric properties Volume resistance value 30 ° C./° C. of conductive member 1 (or conductive rubber roller 1)
80% RH, 23 ° C / 65% RH and 15 ° C / 10% R
The volume resistance value in each environment of H was determined using the apparatus of FIG.
It was measured and calculated according to the method described above.

30 ° C./80% RH of conductive member 1, 23
The volume resistivity values in each environment of 1.3 ° C./65% RH and 15 ° C./10% RH were 1.3 × 10 ⁵ Ωcm, 2.1
× 10 ⁵ Ωcm and 7.7 × 10 ⁵ Ωcm.

The conductive rubber roller 1 was heated at 30 ° C./8
0% RH, 23 ° C / 65% RH and 15 ° C / 10% RH
The volume resistance value in each environment is 1.1 × 10 ⁵
Ωcm, 2.0 × 10 ⁵ Ωcm and 9.5 × 10 ⁵ Ωcm
Met.

Resistance unevenness The temperature of the conductive member 1 (or the conductive rubber roller 1) was 23 ° C. /
The circumferential resistance unevenness and the longitudinal resistance unevenness in an environment of 65% RH were measured according to the methods shown in FIGS. The circumferential resistance unevenness refers to the ratio of the maximum resistance value / minimum resistance value in the circumferential direction, and the longitudinal resistance unevenness refers to the ratio of the maximum resistance value / minimum resistance value in the longitudinal direction.

As a result, in the conductive member 1, the circumferential resistance unevenness was 1.4 and the longitudinal resistance unevenness was 1.9, and in the conductive rubber roller 1, the circumferential resistance unevenness was 1.5 and the longitudinal resistance unevenness was 1.5. Was 1.9.

Dependence of Volume Resistance Value on Applied Voltage The temperature of the conductive member 1 (or the conductive rubber roller 1) was 30 ° C. /
80% RH, 23 ° C / 65% RH and 15 ° C / 10% R
The applied voltage dependency of the volume resistance under each environment of H is
Using the apparatus shown in FIG. 2, an applied voltage (direct current) was applied at an interval of 100 V from -200 V to -1000 V and measured.

When the conductive member 1 was measured, the volume resistance decreased as the applied voltage increased in any environment (the maximum value at -200 V, -1000 V).
V shows the minimum value). At this time, the ratio between the maximum value and the minimum value is 2.6 times in an environment of 30 ° C./80% RH and 23 ° C./6
It was 2.8 times in the environment of 5% RH and 3.3 times in the environment of 15 ° C./10% RH.

When the conductive rubber roller 1 was measured, the tendency was the same as that of the conductive member 1. The ratio between the maximum value and the minimum value was 2.4 times in an environment of 30 ° C./80% RH and 23 ° C.
The ratio was 2.8 times in an environment of / 65% RH and 3.6 times in an environment of 15 ° C./10% RH.

Time Dependence of Volume Resistance Value The temperature of the conductive member 1 (or the conductive rubber roller 1) was 30 ° C. /
80% RH, 23 ° C / 65% RH and 15 ° C / 10% R
The time dependence of the volume resistance under each environment of H is shown in FIG.
The time change of the volume resistance value was measured for 60 seconds immediately after the voltage was applied (0 seconds) using the apparatus described in (1).

When the conductive member 1 was measured, the volume resistance value tended to increase (current value decreased) with the passage of time in any environment. Decreased, showing almost constant value. The ratio of the maximum current value / minimum current value at this time was found to be 3.2 times in an environment of 30 ° C./80% RH and 23 ° C./6
It was 3.1 times in an environment of 5% RH and 3.8 times in an environment of 15 ° C./10% RH.

When the conductive rubber roller 1 was measured, the same tendency as that of the conductive member 1 was obtained.
It was 3.0 times in the environment of RH, 3.0 times in the environment of 23 ° C./65% RH, and 3.7 times in the environment of 15 ° C./10% RH.

Capacitance (C1) The conductive member was brought into contact with the metal drum and rotated (10 rpm), and a voltage of 2 kVpp and a frequency of 100 Hz was applied to determine the capacitance C0. Note that the capacitance C1 in this embodiment is
Is a value obtained by dividing C0 by the surface area S1. That is, C1 = C
0 / S1, which is a value per unit area. The value determined in this way was 7.5 pF / cm ² .

(6) Rz The Rz of the conductive member 1 and the conductive rubber roller 1 was measured in accordance with JIS B0601, and manufactured by Kosaka Laboratory Co., Ltd.
Using rfcoder SE-3400, feed rate 0.5 mm / s, cutoff 0.8 mm, measurement length 2.5
mm. The measurement was performed in the generatrix (longitudinal) direction at any three places of the conductive member (or the conductive roller), and a simple average of the three values was defined as Rz of the conductive member (or the conductive roller).

The conductive member 1 has a right end, a center,
When measured at three locations at the left end, they were 4.5 and 4, respectively.
Since it was 0 and 5.0 μm, the simple average of 4.5 μm was defined as Rz (Rz1) of the conductive member 1.

Similarly, the Rz of the conductive roller 1
Was 6.3 μm.

(7) Film thickness The cross section of the conductive member 1 was observed with an electron microscope of 100 times,
The film thickness was determined from a simple average of 10 arbitrary locations. When the surface irregularities were relatively large, five concave portions and five convex portions were arbitrarily selected and determined by a simple average thereof.

In the conductive member 1, slight irregularities were observed. Five concave portions were selected and the film thickness was measured.
1, 20, 21, 23 and 20 μm. Further, five convex portions were selected and the film thickness was measured.
0, 30, 29, and 29 μm, and the simple average of these was determined as the film thickness. Therefore, the film thickness (average film thickness) 2
5 μm, minimum film thickness 18 μm, maximum film thickness 31 μm,
It can be seen that the film thickness variation is within ± 20% of the average value.

(8) Outer Diameter The outer diameter of the conductive member 1 (or the conductive roller 1) was measured and calculated as follows. First, using a laser outer diameter measuring machine, three points near the both ends (left end, right end) and in the center were measured.
The outer diameter of four points was measured at each point at every 45 °, and the simple average of the measured values at each point was defined as the outer diameter of that point. That is, the outer diameter of each location (left end, right end, center) =
(D1 + d2 + d3 + d4) / 4.

Next, the outer diameter (average outer diameter) of the conductive member 1 was determined by substituting the outer diameter of each part into the following equation and calculating. That is, the outer diameter of the conductive member 1 (or the conductive roller 1) = (right end outer diameter + left end diameter + center outer diameter × 2) / 4.

As a result, the outer diameter of the conductive member 1 is 16.30.
mm, and the outer diameter of the conductive rubber roller 1 is 16.25.
mm. Also, the outer diameter difference (crown amount) from the center part was 96 μm in the conductive member 1 by measuring the outer diameter of each part.
m, 100 μm for the conductive rubber roller 1. The rubber length of the conductive member 1 (or the conductive rubber roller 1) is 350 mm. Here, when the area (ie, electrode area) S0 (cm ² ) where the innermost or lower functional layer contacts the conductive support and the surface area S1 (cm ² ) formed by the outermost or upper surface are obtained, S0 = 35 × 0.7
95π = 87.4 cm ² , S = 35 × 1.630π = 1
Since it is 79.2 cm ² , S1 / S0 = 179.2 /
88.5 = 2.05.

(9) Gas Permeability of Outermost Layer A stainless steel roller having an outer diameter of 16 mm was prepared, a 50 μm-thick fluororesin film was wound therearound, and dip coating was performed using the outermost layer coating material 1. The coating conditions were a lifting speed of 50 mm / sec. And the coating was repeated. After coating, the resultant was air-dried in an atmosphere of 20 ° C./70% RH for 8 hours, and further heated in a hot-air drying oven at 135 ° C. for 30 minutes. After cooling, it was separated from the fluororesin film to form an outermost layer 1 film having a thickness of 45 μm.

The oxygen gas permeability coefficient (P (O ₂ )) and nitrogen gas permeability coefficient (P (N ₂ )) of the obtained outermost layer 1 film
Was measured by a known high vacuum method, and P (O ₂ ) = 5.
8 × 10 ^-9 cm ³ · cm / cm ² · sec · cmHg, P
(N ₂ ) = 2.0 × 10 ⁻⁹ cm ³ · cm / cm ² · sec
-CmHg. Therefore, P (O ₂ ) / P (N ₂ ) =
2.90.

(10) The work function of the outermost layer The work function is defined as the minimum energy required to extract one electron from the surface of a substance to just outside the surface. A photoelectron measuring device AC-1 manufactured by Riken Keiki Co., Ltd. can be used for measurement of work-related. This measuring instrument AC-1
Is that the work function of the surface of the current conductive member 1 can be easily measured in the atmosphere.

FIG. 14 shows a work function measurement curve obtained by measurement with the measuring instrument AC-1. In FIG. 14, the horizontal axis indicates the excitation energy (eV), and the vertical axis indicates the number (yield) (cps) (counts per second) of emitted photoelectrons. In general, the measurement curve rapidly rises due to a sudden increase in photoelectron emission from a certain value, and the rising point is defined as a work function value Wf. The degree of photoelectron emission thereafter (to the right of the point Wf) is defined by the slope γ (cps / eV) of the measurement curve approximated by the straight line 1. In the above measurement, a sodium lamp was used as a measurement light source, and the light emission intensity was 500 nW.

As a result of measuring the work function of the conductive member 1, Wf = 5.2 (eV) and γ = 11.0
(Cps / eV).

[Production Example 2 of Conductive Member] <2-1 Preparation of Lower Elastic Layer> 100 parts by weight of epichlorohydrin rubber (Epichromer CG, manufactured by Daiso), 1 part by weight of stearic acid, 3 parts by weight of clay, Ca (OH) _Two
4.4 parts by weight, CaO3 parts by weight, hydrous silicic acid (Nipsil VN3, manufactured by Nippon Silica Co., Ltd.) 9 parts by weight, diethylene glycol 0.9 parts by weight, naphthenic process oil (Diana Process Oil NM-280, manufactured by Idemitsu Kosan Co., Ltd.) 1
5 parts by weight, 15 parts by weight of liquid NBR (N280, manufactured by JSR) and 2.2 parts by weight of potassium trifluoromethanesulfonate (conductive agent) were kneaded with a sufficiently cooled kneader to obtain a hydrin rubber batch. The liquid NBR used here
Has a role as a reactive plasticizer as well as a property as an NBR. This was aged overnight in a cool and dark place kept at 20 ° C. or lower, and then 1.2 parts by weight of pentalit and 2.3 parts by weight of a polythiol vulcanizing agent were added and kneaded with an open roll to obtain a rubber compound 2-1. .

While extruding the rubber compound 2-1 at an outer diameter of 17 mm with an extruder, a 450 mm long, 8.05 mm diameter stainless steel mandrel to which a conductive adhesive was applied in advance was supplied. An unvulcanized roller having a rubber compound 2 around the support was obtained. A nylon tape is tightly wound around an unvulcanized rubber roller and wetted with water, and then vulcanized (vapor pressure: 6.0 kg / c)
(m ² , 60 minutes), vulcanized and peeled off the tape. The surface was precisely polished using a computer-controlled polishing machine to form a lower elastic layer roller.

<2-2 Preparation of Upper Elastic Layer> Epichlorohydrin Rubber (Epichromer CG, manufactured by Daiso) 100
Parts by weight, stearic acid 1 part by weight, clay 3 parts by weight, Ca
(OH) ₂ 4.4 parts by weight, hydrous silicic acid (Nipsil V
N3, manufactured by Nippon Silica Co., Ltd.) 9 parts by weight, diethylene glycol 0.9 parts by weight, liquid NBR (N280, manufactured by JSR)
18 parts by weight, 2.0 parts by weight of potassium trifluoromethanesulfonate, 1.5 parts by weight of pentalit and 2.5 parts by weight of a polythiol vulcanizing agent were kneaded with a sufficiently cooled open roll to obtain a hydrin rubber batch. It was dissolved in toluene and adjusted to have a solid content of 5% by weight to obtain a hydrin rubber coating for the upper elastic layer.

After the surface of the lower elastic roller 1 was washed with 2-butanone, dip coating was performed using a hydrin rubber coating for the upper elastic layer. The coating conditions were a pulling speed of 60 mm / sec.
c. And the coating was repeated. After coating,
Air dry for 8 hours in an atmosphere of 20 ° C./70% RH.
The upper elastic layer was formed by heating in a hot air drying oven at 0 ° C. for 30 minutes to obtain a conductive rubber roller 2 composed of two elastic layers.

<2-2 Preparation of Outer Layer Coating> Vinyl butyral-vinyl acetate-vinyl alcohol copolymer (T
g = 90 ° C.) in a solution of butyral resin in ethanol, mixed alcohol (methanol / ethanol = weight ratio:
1/1) was added to adjust the solid content to 5% by weight. Based on 100 parts by weight of the solid content, 3 parts by weight of graphite, 2 parts by weight of boron nitride, and surface-treated tin oxide (for the outermost layer paint 1) 10 parts by weight, silicone oil (SH28)
PA, manufactured by Dow Corning Toray Silicone Co., Ltd.) 150pp
m, mesoporous activated carbon (pore diameter 40 nm) 0.5 part by weight and di-alkyl-salicylic acid metal compound (charge control agent)
After adding 0.5 parts by weight and dispersing for 12 hours using a medium with a paint shaker, the medium was separated, and then 4 parts by weight of hexamethylene diisocyanate (HMDI) was added to prepare a coating 2 for the outermost layer.

<2-3 Preparation of Conductive Member> After the surface of the conductive rubber roller 2 was washed with 2-butanone, dip coating was performed using the outermost layer paint 2. The coating conditions were a lifting speed of 40 mm / sec. And the coating was repeated. After coating, air-dry in an atmosphere of 20 ° C./70% RH for 8 hours, and further heat for 30 minutes in a hot-air drying oven at 160 ° C. to form an outermost layer, thereby forming a conductive member 2. Was measured.

<2-4 Characteristics> Conduction was performed in the same manner as in Production Example 1 of the conductive member.

[Production Example 3 of Conductive Member] <3-1 Preparation of Elastic Layer> NBR (N220S, JSR
100 parts by weight, liquid NBR (N280, manufactured by JSR) 25 parts by weight, zinc oxide 5 parts by weight, stearic acid 1 part by weight, hydrous silicic acid (Nipsil VN3, manufactured by Nippon Silica Co., Ltd.) 9 parts by weight, hard clay 3 parts by weight, 1 part by weight of diethylene glycol, 0.2 parts by weight of polyethylene glycol, 3 parts by weight of potassium perchlorate, 0.5 part by weight of 2-mercaptobenzimidazole (Nocrack MB, manufactured by Ouchi Shinko Chemical Co., Ltd.), N- 0.5 parts by weight of isopropyl-N'-phenyl-p-phenylenediamine (Ozonone 3C, manufactured by Seiko Chemical Co., Ltd.), wax (SnmproofExt)
ra, Uniroyal Chem. 0.5 parts by weight, 20 parts by weight of DOP and 10 parts by weight of naphthenic oil were kneaded with a sufficiently cooled kneader to obtain a conductive NBR rubber batch. Note that potassium perchlorate was used in a state where it was previously added to and mixed with diethylene glycol.

After aging this NBR rubber batch overnight, 0.5 parts by weight of sulfur was used as a vulcanizing agent, and N-cyclohexyl 2-benzothiazylsulfenamide (Sancellar CM, manufactured by Sanshin Chemical Co., Ltd.) was used as a vulcanization accelerator. 0.0 parts by weight, zinc diethyldithiocarbamate (Axel EZ, manufactured by Kawaguchi Chemical Co., Ltd.)
1.5 parts by weight of tetrabutyl thiuram disulfide (Noxeller TBT, manufactured by Ouchi Shinko Chemical Co., Ltd.) were added and kneaded with an open roll to obtain a rubber compound 3.

A conductive rubber roller 3 was prepared in the same manner as in the production of the conductive member 1 except that the rubber compound 3 was used instead of the rubber compound 1.

<3-2 Preparation of Outer Layer Coating> Fluorine-based resin coating containing ethylene tetrafluoride-vinyl ether-vinyl ester copolymer as a main component (B-type viscosity (25 ° C.) =
650 cp, solid content hydroxyl value = 60 mg KOH / g, number of colors = 5 or less by Gardner, Tg = 25 ° C., pencil hardness = B
Above) was adjusted to a solid content of 5% by weight using ethyl acetate. 8% by weight of surface-treated conductive carbon black A (described later), 1 part by weight of roughening agent resin particles 2 (Trefil R-902, manufactured by Dow Corning Toray Silicone Co., Ltd.), 100 parts by weight of the solid content of the paint, silicone 100 ppm of oil (SH28PA, manufactured by Dow Corning Toray Silicone Co., Ltd.), 1 part by weight of mica (manufactured by Szolite Mica, manufactured by Kuraray Co., Ltd.), 0. Mesoporous silica (pore diameter: 20 nm)
5 parts by weight and 0.5 parts by weight of a metal compound of di-alkyl-salicylic acid (charge controlling agent) were dispersed in a paint shaker for 12 hours using a medium, followed by separation of the media and diphenylmethane diisocyanate (MD) as a curing agent.
I) was added and mixed so that OH / NCO = 1/1 to prepare a paint 3 for the outermost layer.

The surface-treated conductive carbon black A
Was created as follows. Γ-glycidoxypropyltrimethoxysilane (SH6040, manufactured by Toray Dow Corning Silicone Co., Ltd.) is dissolved in a small amount of water and methanol containing a hydrolysis catalyst to a concentration of 0.5% by weight to prepare a surface treatment liquid. I do. A conductive carbon black (Ketjen Black EC-P, manufactured by Lion Corporation) was immersed in this surface treatment solution for 1 hour with stirring, and then filtered to remove the solvent. 80 with stirring the conductive tin oxide from which the solvent has been removed.
C. for 1 hour and further heated at 135.degree. C. for 2 hours with stirring to obtain surface-treated conductive carbon black A.

<3-3 Preparation of Conductive Member> A conductive rubber roller 3 was used in place of the conductive rubber roller 1 and an outermost layer paint 3 was used in place of the outermost layer paint 1. The conductive member 3 was produced in the same manner as in the member production example.

<3-4 Characteristics> Conduction was performed in the same manner as in Production Example 1 of the conductive member.

[Production Example 4 of Conductive Member] <4-1 Preparation of Elastic Layer> 100 parts by weight of chlorosulfonated polyethylene rubber (hereinafter CSM; Hypalon 40, manufactured by DuPont), potassium trifluoromethanesulfonate (conductive agent) 3 Parts by weight, hydrous silicic acid (Nipsil VN
3, 6 parts by weight of Nippon Silica Co., 1 part by weight of diethylene glycol, 5 parts by weight of naphthenic process oil (Diana Process Oil NM-280, manufactured by Idemitsu Kosan Co., Ltd.), DO
P5 parts by weight, sub part (candy sub, manufactured by Tenma Sub Kako Co., Ltd.) 1 part by weight, stearic acid 1 part by weight, magnesium oxide 6 parts by weight, pentaerythritol 3 parts by weight, and dipentamethylenethiuram tetrasulfide (Succinol TRA, Sumitomo Chemical Co., Ltd.) 2 parts by weight) and kneaded with a sufficiently cooled open roll to prepare a rubber compound 4.

A conductive rubber roller 4 was produced in the same manner as in the production of the conductive member 1 except that the rubber compound 4 was used instead of the rubber compound 1.

<4-2 Preparation of Coating for Outermost Layer> Polyetherimide was dissolved in methylene chloride to adjust the solid content to 5% by weight. (Described later) 10 parts by weight, roughener resin particles 2
(Trefil R-902, manufactured by Toray Dow Corning Silicone Co., Ltd.) 1.8 parts by weight, silicone oil (SH28P
A, manufactured by Dow Corning Toray Silicone Co.) 100pp
m, 1 part by weight of mica (manufactured by Kuraray Co., Ltd.) and 0.5 part by weight of a metal compound of di-alkyl-salicylic acid (charge control agent) were dispersed in a paint shaker for 12 hours using a medium. By filtering and separating, the paint 4 for the outermost layer was prepared.

<4-3 Preparation of Conductive Member> The conductive rubber roller 4 was set in a dedicated rotating device and rotated at 400 rpm. Next, the outermost layer paint 4 was sprayed from the discharge port onto the surface of the conductive rubber roller 4 using a spray coater whose air pressure was adjusted to 2.5 kgf / cm ² . The moving speed of the discharge port is 200 mm / min. The distance between the discharge port and the substrate 9 was 60 mm. Thereafter, the conductive member 4 was formed by heating and drying at 120 ° C. for 60 minutes.

<4-4 Characteristics> Conduction was performed in the same manner as in Production Example 1 of the conductive member.

[Production Example 5 of Conductive Member] <5-1 Preparation of Elastic Layer> EPDM (EP33, JSR
100 parts by weight, conductive carbon black 15 parts by weight, silica 3 parts by weight, paraffin oil 50 parts by weight, stearic acid 1 part by weight, zinc oxide 5 parts by weight, and diethylene glycol 3 parts by weight are kneaded with a sufficiently cooled kneader. Thus, a conductive EPDM rubber batch was obtained. After aging this overnight, 0.3 parts by weight of sulfur as a vulcanizing agent, 1.6 parts by weight of N-cyclohexyl-2-benzothiazylsulfenamide as a vulcanization accelerator, and 1.0 part of zinc diethyldithiocarbamate were used.
Parts by weight, 1.4 parts by weight of tetrabutylthiuram disulfide, 5 parts by weight of azodicarbonamide and 5 parts by weight of p, p'-oxybis (benzenesulfonylhydrazide) as a foaming agent were added and kneaded to obtain a rubber compound 5.

The rubber compound 5 is extruded into a tube having an inner diameter of 9 mm and an outer diameter of 15.3 mm using an extruder, and cut into a predetermined length. Next, it is preferable to insert the material into a cylindrical mold having an inner diameter of 16 mm (at this time, it is preferable to apply a small amount of powder such as mica, talc, charcoal, etc. on the surface and then insert it. In consideration of the properties, graphite was used) and the center was 450 m long.
m, and a core metal having a diameter of 7.95 mm (iron plated with nickel chrome). In this state, the mixture was left standing in an atmosphere at 170 ° C. for 60 minutes to perform crosslinking and foaming, and then taken out of the mold to prepare a conductive rubber roller 5 having a skin layer on the surface and made of a foam.

The state of the cross section was taken into a computer and subjected to image processing to examine the foaming diameter and porosity. The foaming diameter (average diameter based on a simple average of arbitrary 10 locations) was 56%.
At μm, the porosity was 47%.

<5-2 Preparation of paint for outermost layer> Paint 1 for the outermost layer was used.

<5-3 Preparation of Conductive Member> A conductive member 5 was prepared in the same manner as in the conductive member production example 1 except that the conductive rubber roller 5 was used instead of the conductive rubber roller 1. .

<5-4 Characteristics> Conduction was performed in the same manner as in Production Example 1 of the conductive member.

[Production Example 6 of Conductive Member] <6-1 Preparation of Elastic Layer> EPDM (EP33, JSR
100 parts by weight), 17 parts by weight of conductive carbon black, 3 parts by weight of silica, 55 parts by weight of paraffin oil, 1 part by weight of stearic acid, 5 parts by weight of zinc oxide and 3 parts by weight of diethylene glycol are kneaded with a sufficiently cooled kneader. Thus, a conductive EPDM rubber batch was obtained. After aging this overnight, 0.3 parts by weight of sulfur as a vulcanizing agent, 1.6 parts by weight of N-cyclohexyl-2-benzothiazylsulfenamide as a vulcanization accelerator, and 1.0 part of zinc diethyldithiocarbamate were used.
Parts by weight, 1.4 parts by weight of tetrabutylthiuram disulfide, 7.5 parts by weight of azodicarbonamide and 7.5 parts by weight of p, p'-oxybis (benzenesulfonylhydrazide) as a foaming agent were added and kneaded.
I got

The rubber compound 6 is extruded into a tube having an inner diameter of 8 mm and an outer diameter of 14.5 mm using an extruder and cut into a predetermined length. This was put into a vulcanization can and subjected to primary vulcanization by steam vulcanization (direct steam) at a steam pressure of 6 kg / cm ² for 1 hour to obtain a foam tube. In order to achieve uniform vulcanization and foaming, the foam tube was further subjected to secondary vulcanization (oven) at 130 ° C. for 45 minutes, and then a conductive adhesive was applied in advance to a length of 450 mm and a diameter of 8. A 05 mm core (iron-nickel-plated iron) is coated and heated at 130 ° C. for 30 minutes for bonding. After sufficient cooling, the outer diameter was precisely polished to produce a sponge-type conductive roller 6 having a foamed surface on the surface.

[0300] The state of the cross section was taken into a computer and subjected to image processing to examine the foaming diameter and porosity. The foaming diameter (average diameter based on a simple average of arbitrary 10 locations) was 10
At 2 μm, the porosity was 60%.

<6-2 Preparation of Outer Layer Coating Material> Outer layer coating material 1 was used.

<6-3 Preparation of Conductive Member> A conductive member 6 was prepared in the same manner as in the conductive member production example 1 except that the conductive rubber roller 6 was used instead of the conductive rubber roller 1. .

<6-4 Characteristics> Conduction was performed in the same manner as in Production Example 1 of the conductive member.

[Production Example 7 of Conductive Member] <7-1 Preparation of Elastic Layer> 15 parts by weight of naphthenic process oil (Diana Process Oil NM-280, manufactured by Idemitsu Kosan Co., Ltd.), liquid NBR (N280, manufactured by JSR)
A conductive rubber roller 7 was prepared in the same manner as in the conductive member production example 1 except that the amount was 5 parts by weight.

<7-2 Preparation of Outer Layer Coating> N-methoxymethylated nylon (Toresin EF-30T, manufactured by Teikoku Chemical Industry Co., Ltd.) was dissolved in methanol and adjusted to have a solid content of 15% by weight. . Add 10 parts by weight of conductive tin oxide not surface-treated to 100 parts by weight of N-methoxymethylated nylon in the solution, media (glass beads)
Was added and dispersed with a paint shaker for 12 hours. Thereafter, Methia was separated by filtration to prepare paint 7 for the outermost layer.

<7-3 Preparation of Conductive Member> The same as in the conductive member production example 1 except that the conductive roller 7 is used instead of the conductive roller 1 and the outermost layer paint 7 is used instead of the outermost layer paint 1. After coating, the conductive member 7 was formed by heating at 70 ° C. for 30 minutes.

<7-4 Characteristics> Conduction was performed in the same manner as in Production Example 1 of the conductive member.

[Production Examples 8-12 of Conductive Member] In the preparation of the paint for the outermost layer of Production Example 1 of the conductive member, the roughening agent resin particles 1 (coarse 1) and the roughening agent resin particles 2 (coarse 2) were used. The conductive members 8 to 12 were prepared in the same manner as in the conductive member production example 1 except that the following changes were made.

The paint 8 for the outermost layer was prepared based on the paint 1 for the outermost layer and without adding (coarse 1) and (coarse 2).

[0310] The outermost layer paint 9 was prepared by using 1.5 parts by weight of each of (Coarse 1) and (Coarse 2).

[0311] The outermost layer paint 10 was obtained by using each of 2 parts by weight for (Coarse 1) and (Coarse 2).

[0312] The outermost layer paint 11 was prepared by using each of (Rough 1) and (Coarse 2) in 3 parts by weight.

[0313] The outermost layer paint 12 was prepared by using each of 5 parts by weight for (Coarse 1) and (Coarse 2).

The conductive members 8, 9, 1 and 12 were prepared in the same manner as in the conductive member production example 1 except that the outermost layer paint 1 was replaced with the outermost layer paints 8, 9, 10, 11 and 12.
0, 11 and 12.

[Production Example 13 of Conductive Member] The core used in Production Example 1 of the conductive member was ground only at the portion in contact with the elastic layer to have an outer diameter of 4.5 mm. Except that this cored bar was used, the conductive member 13 was produced in the same manner as in the conductive member production example 1.
It was created. The characteristics were the same as in the conductive member production example 1.

[Production Example 14 of Conductive Member] <14-1 Preparation of Elastic Layer> 100 parts by weight of epichlorohydrin rubber (Epichromer CG, manufactured by Daiso), 1 part by weight of stearic acid, 5.5 parts by weight of calcium carbonate, and hydroxide 4.4 parts by weight of calcium, 9 parts by weight of hydrous silicic acid (Nipsil VN3, manufactured by Nippon Silica), 0.9 parts by weight of diethylene glycol, 5 parts by weight of naphthenic process oil (Diana Process Oil NM-280, manufactured by Idemitsu Kosan Co., Ltd.) 15 parts by weight of liquid NBR (N280, manufactured by JSR)
Dimethyldidodecyl ammonium chloride (conductive agent)
3 parts by weight and 1 part by weight of the conductive carbon black were kneaded with a sufficiently cooled kneader to obtain a hydrin rubber batch. After aging overnight in a cool and dark place kept at 20 ° C. or lower, 1 part by weight of pentalit, 2.3 parts by weight of a polythiol vulcanizing agent, 5 parts by weight of azodicarbonamide as a foaming agent and p, p ′.
-Oxybis (benzenesulfonyl hydrazide) (5 parts by weight) was added and kneaded with an open roll to obtain a rubber compound 14.

The rubber compound 14 is extruded into a tube having an inner diameter of 9 mm and an outer diameter of 15.3 mm by using an extruder, and cut into a predetermined length. Next, it is preferable to insert the material into a cylindrical mold having an inner diameter of 16 mm (at this time, it is preferable to apply a small amount of powder such as mica, talc, charcoal, etc. to the surface and then insert it. Was taken into account, and graphite was 450m long at the center.
m, and a core metal having a diameter of 7.95 mm (iron plated with nickel chrome). In this state, the substrate was left to stand in an atmosphere at 170 ° C. for 60 minutes to perform crosslinking and foaming, and then taken out of the mold to prepare a conductive rubber roller 14 having a skin layer on the surface and made of a foam.

The cross section was taken into a computer and subjected to image processing to examine the foam diameter and porosity. The foam diameter (average diameter based on a simple average of arbitrary 10 locations) was 50%.
At μm, the porosity was 37%.

<14-2 Preparation of Coating for Outermost Layer> A coating for outermost layer 14 was prepared in the same manner as in Production Example 1 of the conductive member except that the surface-treated tin oxide A was used in an amount of 5 parts by weight.

<14-3 Preparation of Conductive Member> A conductive member was produced except that the conductive rubber roller 14 was used instead of the conductive rubber roller 1 and the outermost layer paint 14 was used instead of the outermost layer paint 1. Conductive member 14 as in Example 1
It was created.

<14-4 Characteristics> Conduction was performed in the same manner as in Production Example 1 of the conductive member.

[Production Example 15 of Conductive Member] <15-1 Preparation of Elastic Layer> Except that 1.7 parts by weight of dimethyldidodecylammonium chloride (conductive agent) and conductive carbon black were not added, A conductive rubber roller 15 was produced in the same manner as in the production example 14 of the conductive member. The foaming diameter (average diameter based on a simple average of 10 arbitrary locations) was 60 μm, and the porosity was 42%.

<15-2 Preparation of paint for outermost layer> A paint 15 for the outermost layer was prepared in the same manner as in Production Example 14 of the conductive member except that the surface-treated tin oxide A was used at 17.5 parts by weight.

<15-3 Preparation of Conductive Member> A conductive member was produced except that the conductive rubber roller 15 was used instead of the conductive rubber roller 14 and the outermost layer paint 15 was used instead of the outermost layer paint 14. A conductive member 15 was formed in the same manner as in Example 14.

<15-4 Properties> Conduction was performed in the same manner as in Production Example 1 of the conductive member.

[Production Example 16 of Conductive Member] <16-1 Preparation of Elastic Layer> A liquid NBR (N280, manufactured by JSR) without adding a naphthenic process oil (Diana Process Oil NM-280, manufactured by Idemitsu Kosan Co., Ltd.) ) Was changed to 20 parts by weight, and a conductive roller 16 was prepared in the same manner as in the conductive member production example 1.

<16-2 Preparation of Outer Layer Coating> N-methoxymethylated nylon (Toresin EF-30T, manufactured by Teikoku Chemical Industry Co., Ltd.) was dissolved in methanol and adjusted to have a solid content of 15% by weight. . 10 parts by weight of surface-treated conductive tin oxide A was added to 100 parts by weight of N-methoxymethylated nylon in the solution, and media (Gas beads) was added.
Was added and dispersed with a paint shaker for 12 hours. Thereafter, Methia was separated by filtration, and 1.5% of paratoluenesulfonic acid was added to 100% by weight of N-methoxymethylated nylon.
The outermost layer coating material 16 was prepared by adding the parts by weight and sufficiently dissolving and mixing.

<16-3 Preparation of Conductive Member> After coating in the same manner as in Conductive Member Production Example 7, heating at 120 ° C. for 30 minutes, and further heating at 135 ° C. for 24 hours to form conductive member 16 Created. In the present embodiment, since the elastic layer is also heated for a long time when the surface layer is formed, the rubber used for the elastic layer is preferably a rubber having good heat resistance. When hydrin rubber is used, it tends to be softened and deteriorated. Therefore, a type containing a large amount of AGE is preferable.

<16-4 Characteristics> Conduction was performed in the same manner as in Production Example 1 of the conductive member.

A major feature of the conductive member 16 is that it has very good gas permeability resistance (small gas permeability coefficient). Confirmation using an analytical technique such as thermal analysis or IR revealed that N-methoxymethylated nylon was crystallized as well as crosslinked.

[Production Example 17 of Conductive Member] <17-1 Preparation of Elastic Layer> Liquid NBR (N280, J
No. SR No.) and Diana Process Oil NM-2 as a naphthenic process oil
The conductive roller 17 was formed in the same manner as in the production example 1 of the conductive member except that Diana Process Oil NS-24 (manufactured by Idemitsu Kosan) was changed to 20 parts by weight instead of 5 parts by weight of 80 (manufactured by Idemitsu Kosan). Created.

<17-2 Preparation of Paint for Outermost Layer> Paint 7 for the outermost layer was used.

<17-3 Preparation of Conductive Member> Instead of the conductive roller 1, the conductive roller 17 is
The conductive member 17 was prepared in the same manner as in the conductive member production example 1 except that the outermost layer paint 7 was used instead of the above.

<17-4 Characteristics> Conduction was performed in the same manner as in Production Example 1 of the conductive member.

[Production Example 18 of Conductive Member] <18-1 Preparation of Elastic Layer> A stainless steel cored bar having a length of 450 mm and a diameter of 15 mm to which a conductive adhesive was previously applied (the outer diameter of a portion of 50 mm from both ends). Is 7.95 mm and the other part has an outer diameter of 15 mm) as a conductive support, and a cylindrical mold having an inner diameter of 18 mm is used as a mold in the same manner as in the conductive member production example 1. To make a solid rubber roller. Further, the surface is precisely polished to obtain a crown-shaped conductive rubber roller 18 (average outer diameter of 16.
25 mm).

<18-2 Preparation of Outer Layer Coating Material> Outer layer coating material 1 was used.

<18-3 Preparation of Conductive Member> A conductive member 18 was obtained in the same manner as in the production example 1 of the conductive member except that the conductive rubber roller 18 was used.

<18-4 Characteristics> Conduction was performed in the same manner as in Production Example 1 of the conductive member.

[Manufacturing Example 19 of Conductive Member] <19-1 Preparation of Elastic Layer> A conductive rubber roller 3 was used. <19-2 Preparation for outermost layer> Chlorosulfonated polyethylene rubber (hereinafter CSM; Hypalon 40, DuPon)
100 parts by weight, conductive carbon black 5 parts by weight, potassium trifluoromethanesulfonate (conductive agent)
1.5 parts by weight, 1 part by weight of hydrous silicic acid (Nipsil VN3, manufactured by Nippon Silica), 1 part by weight of diethylene glycol,
1 part by weight of stearic acid, 6 parts by weight of magnesium oxide, 3 parts by weight of pentaerythritol and 2 parts by weight of dipentamethylenethiuram tetrasulfide (Socinol TRA, manufactured by Sumitomo Chemical Co., Ltd.) are added, kneaded with a sufficiently cooled open roll, and extruded. 16.1 mm inside diameter, 75 μm wall thickness
While being extruded into a tube shape, continuous vulcanization was performed with UHF to obtain an outermost layer tube 19.

<19-3 Preparation of Conductive Member> In a state where air is blown into the inner surface of the outermost layer tube 19 and the inner diameter is slightly expanded, the conductive rubber roller 3 coated with a thin conductive primer in advance is applied to the outermost layer tube 19. Inserted and mated 19 inside. Then, it was left in an oven at 135 ° C. for 30 minutes to be adhered to obtain a conductive member 19.

<19-4 Characteristics> Conduction was performed in the same manner as in Production Example 1 of the conductive member.

[Production Example 20 of Conductive Member] <20-1 Preparation of Elastic Layer> Silicone rubber (dimethylsiloxane unit 97.0 mol%, methylvinylsiloxane unit 2.5 mol%, methylphenylsiloxane unit 0.47 mol%, molecule Both ends of the chain are methylvinylsilyl groups (0.03 mol%) 100 parts by weight, hydrous silica 7 parts by weight, mica 3 parts by weight, quartz powder 5 parts by weight, dimethyl silicone oil 5 parts by weight, zinc stearate 1 part by weight, oxidation 5 parts by weight of zinc and 1 part by weight of polyethylene glycol were kneaded with a heated open roll to obtain a silicone rubber batch.

Next, 100 parts by weight of an acrylic rubber (mainly a copolymer of ethyl acrylate, butyl acrylate, methoxyethyl acrylate and vinyl chloroacetate as a crosslinking point monomer and containing 4% by weight of a crosslinking monomer), conductive carbon 10 parts by weight of black, thermal black 5
Parts by weight, zinc stearate 1 part by weight, zinc oxide 5 parts by weight, hydrous silicic acid 5 parts by weight, mica 3 parts by weight, polyethylene glycol 1 part by weight and liquid NBR (N280, JS
R company) 5 parts by weight kneaded with a cooled open roll,
An acrylic rubber batch was obtained.

30 parts by weight of the silicone rubber batch was gradually added to 70 parts by weight of the obtained acrylic rubber batch.
After sufficient mixing and kneading, 5 parts by weight of dicumyl peroxide and 5 parts by weight of triallyl isocyanurate were added (based on 100 parts by weight of the total rubber), and the mixture was further kneaded to obtain an acrylic silicone rubber.

[0345] Further, except that a core metal having a length of 450 mm and an outer diameter of 8 mm, which was previously coated with a conductive adhesive, was used as a conductive support, and a cylindrical mold having an inner diameter of 18 mm was used as a mold. Then, a solid rubber roller was produced in the same manner as in Production Example 1 of the conductive member. Further, the surface is precisely polished to obtain a straight conductive roller 20 (average outer diameter of 17.2).
0 mm).

<20-2 Preparation of Outer Layer Coating Material> Ternary copolymer nylon (Platabond MX-1178, manufactured by Nippon Rilsan Co., Ltd.) was dissolved in methanol to prepare a 10% by weight solution. 6 parts by weight of the surface-treated tin oxide A, 2.5 parts by weight of the roughening agent resin particles 1, 2.5 parts by weight of the roughening agent resin particles 2 and 100 parts by weight of the silicone oil (100 parts by weight of the resin component in the solution) SH28PA, 100 ppm, mica (Szolite mica, Kuraray) 1 part by weight and mesoporous silica (pore diameter 20 nm)
After dispersing 0.5 part by weight of the medium using a paint shaker for 12 hours, the medium was separated to prepare a paint 20 for the outermost layer.

<20-3 Preparation of Conductive Member> The surface of the conductive rubber roller 20 was washed with 2-butanone, and then treated with a primer with γ-mercaptopropyltrimethoxysilane to improve the adhesive strength. Using the paint 20, spray coating was performed with an air gun. After coating, 20 ℃ /
The resultant was air-dried in an atmosphere of 70% RH for 8 hours, and further heated in a hot-air drying oven at 135 ° C. for 30 minutes to form an outermost layer, thereby obtaining a conductive member 20.

<20-4 Characteristics> Conduction was performed in the same manner as in Production Example 1 of the conductive member.

[Production Example 21 of Conductive Member] <21-1 Preparation of Elastic Layer> The same procedure as in Production Example 1 of conductive member was carried out except that dimethyldidodecyl ammonium chloride (conductive agent) was used in an amount of 1.2 parts by weight. Thus, a rubber compound 21 was obtained. In addition, a conductive rubber roller 21 was obtained in the same manner as in the conductive member production example 20 except that the rubber compound 21 was used.

<21-2 Preparation of Outer Layer Coating> 2.5 parts by weight of roughening agent resin particles 1 and 2.5 parts of roughening agent resin particles 2
An outermost layer paint 21 was prepared in the same manner as in the conductive member production example 1 except that the amount was changed to parts by weight.

<21-3 Preparation of Conductive Member> A conductive rubber roller 21 was used in place of the conductive rubber roller 20, and the outermost layer paint 21 was used instead of the outermost layer paint 20. The conductive member 21 was obtained in the same manner as in the production example 20 of the conductive member.

<21-4 Characteristics> Conducted in the same manner as in Production Example 1 of the conductive member.

[Production Example 22 of Conductive Member] <22-1 Preparation of Elastic Layer> 100 parts by weight of epichlorohydrin rubber (Epichromer CG, manufactured by Daiso), 1 part by weight of stearic acid, 5 parts by weight of calcium carbonate, 4 parts by weight of calcium hydroxide Parts by weight, hydrous silicic acid (Nipsil VN3,
6 parts by weight of Nippon Silica Co., 1 part by weight of diethylene glycol, di-n-octyl phthalate (Sansoizer n
DOP, manufactured by Shin Nippon Rika Co., Ltd.) 5 parts by weight, polyester plasticizer A (ADK Sizer PN-350, manufactured by Adeka Agers Chemical Co., Ltd.) 10 parts by weight, polyester plasticizer B (P
araplex G-25, C.I. PHall Corporation (5 parts by weight) and dimethyloctylhydroxyethylammonium perchlorate (conductive agent) (3 parts by weight) were kneaded with a sufficiently cooled kneader to obtain a hydrin rubber batch. 20 ℃
After aging overnight in a cool and dark place maintained below, 1 part by weight of pentalit and 2.3 parts by weight of a polythiol vulcanizing agent were added and kneaded with an open roll to obtain a rubber compound 22.

The rubber compound 22 was extruded by an extruder to an outer diameter of 17 m.
While extruding with m, the conductive compound was previously applied, and a stainless steel core bar having a length of 450 mm and a diameter of 8.05 mm was supplied to the conductive support, and the rubber compound 22 was wound around the conductive support by simultaneous extrusion. An unvulcanized roller was obtained.

A nylon tape is tightly wound around an unvulcanized rubber roller, wetted with water, and then vulcanized (vapour pressure 6.
(0 kg / cm ² , 60 minutes), vulcanized and peeled off the tape. The surface was precisely polished using a computer-controlled polishing machine to obtain a conductive rubber roller 22.

<22-2 Preparation of Paint for Intermediate Layer> Copolymer nylon (6/66 / alicyclic polyamide, Mw = 4 ×
10 ⁴ , heat deformation temperature 60 ° C) with methanol / toluene /
It was dissolved in a mixed solvent of water = 7 / 2.5 / 0.5 (weight ratio) and adjusted so that the solid content became 10% by weight. 6 parts by weight of surface conductive carbon black was added to 100 parts by weight of copolymerized nylon in the solution, and media (glass beads) were added.
The mixture was dispersed for 12 hours with a paint shaker to which water was added. Thereafter, the medium was separated by filtration to prepare a coating material 22 for an intermediate layer.

<22-3 Preparation of Paint for Outermost Layer> Paint 8 for the outermost layer was used.

<22-4 Preparation of Conductive Member> The surface of the conductive rubber roller 22 was washed with 2-butanone, and then treated with a primer with γ-mercaptopropyltrimethoxysilane to improve the adhesive strength. Dip coating was performed using the paint 22. Coating conditions are 150m lifting speed
The coating was repeatedly performed with the top and bottom inverted at m / sec. After coating, air-dry for 8 hours in an atmosphere of 20 ° C./70% RH,
Further, the mixture was heated in a hot air drying furnace at 120 ° C. for 30 minutes to form an intermediate layer.

Further, dip coating was performed thereon using the paint 8 for the outermost layer. Coating conditions are 100mm lifting speed
The coating was repeated with the top and bottom inverted at / sec. After the coating, the resultant was air-dried in an atmosphere of 20 ° C./70% RH for 8 hours, and further heated in a hot-air drying oven at 135 ° C. for 30 minutes to form an outermost layer. Thus, a conductive member 22 was obtained.

<22-5 Properties> Conduction was performed in the same manner as in Production Example 1 of the conductive member.

[Production Example 23 of Conductive Member] <23-1 Preparation of Elastic Layer> A conductive rubber roller 22 was used.

<23-2 Preparation of Intermediate Layer Coating> A polyester urethane resin coating (butyl acetate, caprolactam, heat deformation temperature of 70 ° C.) was adjusted to a solid content of 10% by weight using butyl acetate. did. 5 parts by weight of the surface conductive carbon black was added to 100 parts by weight of the solid content in the solution, and the mixture was dispersed for 12 hours using a paint shaker to which media (glass beads) was added. Thereafter, the medium was separated by filtration to prepare a coating material 23 for an intermediate layer.

<23-3 Preparation of Paint for Outermost Layer> Paint 8 for the outermost layer was used.

<23-4 Preparation of Conductive Member> Except that the intermediate layer paint 23 was used instead of the intermediate layer paint 22,
A conductive member 23 was prepared in the same manner as in the conductive member production example 22.

<23-5 Characteristics> Conducted in the same manner as in Production Example 1 of the conductive member.

[0366]

[Table 1]

[0367]

[Table 2]

[0368]

[Table 3]

[0369]

[Table 4]

[0370] Examples using these conductive members, photoreceptors, developers and electrophotographic devices will be described below.

Example 1 Evaluation was performed using various conductive members. (Example 1-1) In the combinations shown in Table 5, 10000
Endurance was performed on the sheets, and the state of the image was checked every 2000 sheets from the beginning. The durability conditions were as follows: evaluation mode: 3% character original, A4 landscape feed, continuous paper feed, 23 ° C / 65% R
H environment.

In the image evaluation, a halftone image (1 dot 2 spaces) is imaged every 2000 sheets from the beginning to evaluate the charging uniformity (image pattern: A), and to evaluate the other image properties (image pattern: Was evaluated. At this time, the volume resistance of the charging roller was measured at the initial stage and after 10,000 sheets had passed, and the change in roller resistance due to durability was determined.

[0373] In addition, when the
After leaving for 30 days in an environment of 0 ° C./95% RH, 1 night or more 2
After adapting to an environment of 3 ° C./65% RH, an initial image was confirmed in the same environment.

The ranking of the evaluation of images and characteristics is A, B,
Expressed as C, D and E. A indicates the best condition,
E means the worst condition.

As a result, a good image can be obtained through the initial and endurance periods, and the change in volume resistance is small (generally, about 7 times the initial state when the dirt arrives after the endurance, and within 2 times the initial state when the dirt is removed). It turned out to be a characteristic. Table 5 shows the results.

(Examples 1-2 to 18) The combinations shown in Tables 5 to 7 were evaluated in the same manner as in Example 1-1. The results are shown in Tables 5 to 7.

(Comparative Examples 1 to 3) The combinations shown in Table 7 were evaluated in the same manner as in Example 1-1. Table 7 shows the results.

[0378]

[Table 5]

[0379]

[Table 6]

[0380]

[Table 7]

(Example 2) Here, evaluation was performed using various electrophotographic apparatuses (Examples 2-1 to 11). Table 8 shows combinations of the conductive member, the photoconductor, the developer, and the electrophotographic apparatus and the evaluation results.

[0382]

[Table 8]

(Embodiment 3) Here, the evaluation was performed by changing the photosensitive member and the developer (Examples 3-1 to 6). Table 9 shows combinations of the conductive member, the photoconductor, the developer, and the electrophotographic apparatus and the evaluation results.

[0384]

[Table 9]

Example 4 Here, the recyclability when the conductive member was used for charging was evaluated (Examples 4-1 to 5). As can be seen from these results, the conductive member of the present invention can be further used as it is without cleaning because the amount of dirt attached is small. However, under these conditions, the level of the image in the initial stage (the initial meaning of the second use) cannot be denied.

Further, the conductive member of the present invention can easily remove attached dirt. The cleaning can be performed by a simple means such as dry wiping or air blowing without the need for a complicated step of generally performing washing with water or a solvent or removing the entire surface layer to re-form the surface layer.

The charging roller thus cleaned is
The original function is almost restored, and a good image is obtained. However, the level seems to be slightly inferior to the first use. In this embodiment, the cleaning is performed by 3
Although it was confirmed until the last use, there is also the possibility of further use.
Table 10 shows combinations of the conductive member, the photoconductor, the developer, and the electrophotographic apparatus, and the evaluation results.

[0388]

[Table 10]

[0389]

As described above, according to the present invention, it is possible to provide a conductive member having extremely excellent conductive characteristics stably for a long period of time, a process cartridge and an electrophotographic apparatus using the same.

Since the conductive member of the present invention has very stable characteristics, the conductive member can be used simply by using a low-Tg toner or a high-Tg toner, which was conventionally difficult to use in the contact charging system. In addition to the excellent characteristics as described above, the usable characteristic range of the toner used therearound can be expanded, and the merits as an electrophotographic apparatus and a process cartridge are great.

Also, the present invention provides a particularly high image quality (600 dpi).
An electrophotographic apparatus having the above resolution, especially 1200 dpi or more, or a high-speed electrophotographic apparatus (process speed of 1
The present invention can be particularly suitably used in electrophotographic devices requiring various advanced functions, such as electrophotographic devices having 20 mm / sec or more, particularly 160 mm / sec or more, and high durability (10000 sheets).

Further, the present invention can be favorably used in a color machine or a cleanerless system electrophotographic apparatus in which foreign matter is likely to adhere to the surface of the conductive member.

In addition, since the conductive member of the present invention is very excellent in recyclability, it has an excellent advantage that a conductive member that can be used repeatedly can be supplied by a simple cleaning method.

[Brief description of the drawings]

FIG. 1 is a sectional view (circumferential direction) showing an example of a conductive member of the present invention.

FIG. 2 is a schematic view of a conductive member volume resistance measuring instrument according to the present invention.

FIG. 3 is an example of a measurement result using a volume resistance measuring device.

FIG. 4 is a schematic view of a volume resistance measuring device in the longitudinal direction of the conductive member of the present invention.

FIG. 5 is an example of a measurement result using a volume resistance measuring device in a longitudinal direction of a conductive member.

FIG. 6 is an example showing an applied voltage dependency of a volume resistivity of a conductive member.

FIG. 7 is an example showing time dependence of a current value of a conductive member.

FIG. 8 is an example showing the dielectric properties of a conductive member.

FIG. 9 is an example of an apparatus for measuring the coefficient of friction of a conductive member according to the present invention.

FIG. 10 is an example of a chart when measured using a friction coefficient measuring device.

FIG. 11 is another example of the friction coefficient measuring device for a conductive member of the present invention.

FIG. 12 is an example showing a temporal change of a friction coefficient (here, load) of a conductive member.

FIG. 13 shows a powder (roughening agent) used for the conductive member of the present invention.
It is a schematic diagram of a resistance value measuring instrument.

FIG. 14 is an example of a measurement result of a work function of a conductive member.

FIG. 15 is a schematic view showing an example of a tandem type color electrophotographic apparatus using the conductive member of the present invention.

16 is an enlarged view of an image forming section of the tandem type color electrophotographic apparatus of FIG.

FIG. 17 is an enlarged view of the I station in FIG. 16;

FIG. 18 is a schematic view showing an example of a belt-shaped intermediate transfer type color electrophotographic apparatus using the conductive member of the present invention.

FIG. 19 is a schematic view showing an example of a drum-shaped intermediate transfer type color electrophotographic apparatus using the conductive member of the present invention.

FIG. 20 is a schematic view showing another example of an electrophotographic apparatus using the conductive member of the present invention.

FIG. 21 is a schematic view showing another example of an electrophotographic apparatus using the conductive member of the present invention.

FIG. 22 is a schematic view showing another example of an electrophotographic apparatus using the conductive member of the present invention.

FIG. 23 is a schematic view showing another example of an electrophotographic apparatus using the conductive member of the present invention.

FIG. 24 is a schematic view showing another example of an electrophotographic apparatus using the conductive member of the present invention.

FIG. 25 is a schematic view showing another example of an electrophotographic apparatus using the conductive member of the present invention.

FIG. 26 is a schematic view showing another example of an electrophotographic apparatus using the conductive member of the present invention.

FIG. 27 is a schematic view showing another example of an electrophotographic apparatus using the conductive member of the present invention.

FIG. 28 is a schematic view showing a method for measuring ASKER-C hardness.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Photoreceptor 2 Charger 2a Support 2b Elastic layer 2c Coating layer 2z Outermost layer 3 Image exposure 4 Developing unit 5 Transfer paper 6 Transfer device 7 Fixing device 8, 13 Cleaning device 9 Conductive member foreign material removing member 10 Transfer paper guide 11 Paper feed roller 15 Fixing device 20 Intermediate transfer member 26, 28, 29 Bias power supply 37, 38, 39 Cleaning charging member 41 Yellow developing device 42 Magenta developing device 43 Cyan developing device 44 Black developing device 61 Drive roller 62 Primary transfer roller 63 Secondary transfer roller 64 Secondary transfer facing roller 600 Metal drum 601, 801 Power supply 602, 802, 1004 Ammeter 800, 1001, 1002 Electrode 1000 Measurement cell 1003 Guide ring 1005 Voltmeter 1006 Constant voltage device 1007 Measurement sample 1008 Insulator Load N effective length

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hiroshi Inoue 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term in Canon Inc. (reference) 2H003 BB11 CC05 EE11 2H077 AD02 AD06 AD13 FA11 FA21 FA25 GA02 GA13 3J103 AA02 AA14 AA15 AA51 FA01 FA30 GA02 GA52 GA57 GA58 GA60 HA03 HA12 HA20 HA22 HA53

Claims (39)

[Claims] At least a support and a polymer compound are mainly used.
A conductive member comprising a functional layer as a body,
The physical properties of the conductive member are such that the volume resistance value is 1 × 10 ^ThreeΩcm or less
Top 1 × 10¹²Ωcm or less, hardness (ASKER-C) is 1
0 ° or more and 90 ° or less, and the static friction coefficient is 1.0 or more
Bottom, a conductive member having a dynamic friction coefficient of 0.5 or less,
When the conductive member is left in an atmosphere of 180 ° C. for 6 hours
The heating loss rate is defined as the standard heating loss rate (ΔK), and acetone
Immersed in a mixed solvent of chloroform and chloroform at a volume ratio of 1: 1
Extraction when left in a 23 ° C atmosphere for 120 hours
When the rate is defined as a standard AC extraction rate (ΔC), ΔK is 1% by weight.
And ΔC is 5% by weight or less.
Electrical members. 2. Ten-point average roughness (Rz) of a conductive member surface
2. The conductive member according to claim 1, wherein is less than or equal to 1 μm and less than 30 μm. 3. The oxygen or nitrogen gas permeability coefficient of the outermost layer is 5.0 × 10 ⁻⁸ cm ³ · cm / cm ² · sec · cm.
The conductive member according to claim 1, wherein Hg is not more than Hg. 4. An outermost layer containing a substance having a property of absorbing or adsorbing a gas or liquid (hereinafter referred to as an adsorbent).
4. The conductive member according to any one of 3. 5. The conductive member according to claim 1, wherein the outermost layer contains a charge control agent for controlling the charge of the toner. 6. The conductive member according to claim 1, which has two or more functional layers. 7. As a functional layer, at least a functional layer having rubber elasticity (hereinafter referred to as an elastic layer) provided directly or through another layer above or around the support and directly or above or around the elastic layer. Having an outermost layer provided via another layer,
The conductive member according to claim 6, wherein the elastic layer has a hardness (ASKER-C) of 5 ° or more and 85 ° or less. 8. The conductive member according to claim 7, wherein the elastic layer is made of a rubber containing an ether bond. 9. The conductive member according to claim 7, wherein the elastic layer is made of a rubber containing halogen. 10. The conductive member according to claim 7, wherein said elastic layer is made of epichlorohydrin rubber. 11. The conductive member according to claim 7, wherein the elastic layer contains a reactive liquid component. 12. The conductive member according to claim 11, wherein the reactive liquid component is one or both of a reactive plasticizer and a liquid rubber. 13. The conductive member according to claim 7, wherein the elastic layer contains an ion conductive agent. 14. An elastic layer having a thickness of 1 mm or more and 10 mm or less and containing an ionic conductive agent and an outermost layer having a thickness of 1 μm or more and 1 mm or less and containing an electronic conductive agent, wherein 1 × 10 ⁻⁵ ≦ Thickness of outer layer / thickness of elastic layer ≦ 5 × 10 ⁻¹ , and the volume resistivity (ρ0) when the elastic layer is provided on the conductive support and the conductivity formed up to the outermost layer The ratio of the volume resistance value (ρ) of the member is 1 × 10 ⁻² ≦ ρ0 / ρ ≦
The conductive member according to claim 7, wherein the conductive member has a relationship of 1 × 10 ² . 15. The relationship of S1 / S0> 2, where S0 is the area of the innermost or lower functional layer in contact with the conductive support, and S1 is the surface area of the outermost or upper surface. Item 15. The conductive member according to any one of Items 7 to 14. 16. The conductive member according to claim 1, which has a roller shape. 17. At least a charging unit for charging a photosensitive member by a charging unit to which a voltage is applied, an exposure unit for forming an electrostatic latent image by exposure, and a developing unit for visualizing the electrostatic latent image with toner. An electrophotographic apparatus having
An electrophotographic apparatus using the conductive member according to claim 1. 18. The electrophotographic apparatus according to claim 17, wherein the conductive member charges the photosensitive member to a predetermined polarity and potential. 19. The electrophotographic apparatus according to claim 17, further comprising an apparatus for removing foreign matter attached to the surface of the conductive member. 20. A member positioned opposite to the photosensitive member and downstream of the transfer means and upstream of the charging means for leveling the potential of the surface of the photosensitive member before the end of the charging means.
20. The electrophotographic apparatus according to any one of 7 to 19. 21. The electrophotographic apparatus according to claim 17, wherein the conductive member carries a developer charged to a predetermined polarity and potential. 22. The electrophotographic apparatus according to claim 17, wherein the conductive member is used to face the photosensitive member. 23. The electrophotographic apparatus according to claim 22, wherein the conductive member contacts the photosensitive member. 24. The electrophotographic apparatus according to claim 17, wherein the conductive member charges the developer to a predetermined polarity and potential. 25. The electrophotographic apparatus according to claim 17, wherein the applied voltage is a DC voltage. 26. The electrophotographic apparatus according to claim 17, wherein the electrostatic capacity of the photoconductor is 50 pF or more and 500 pF or less per 1 cm ² of the surface area of the photosensitive layer. 27. The electrophotographic apparatus according to claim 17, wherein the outermost layer of the photosensitive member has a thickness of 0.1 μm or more and 50 μm or less. 28. The outermost layer of the photoconductor has a volume resistance of 1 × 1.
Is 0 ¹⁰ [Omega] cm or more electrophotographic apparatus according to any one of claims 17 to 27. 29. The electrophotographic apparatus according to claim 17, wherein C1 / C2 ≦ 0.2, where C1 is the capacitance of the conductive member and C2 is the capacitance of the photosensitive member. . 30. The electrophotograph according to claim 17, wherein, when Rz of the conductive member is Rz1 and Rz of the photosensitive member is Rz2, Rz1 ≧ Rz2 and 3 ≦ Rz1 + Rz2 ≦ 30. apparatus. 31. The electrophotographic apparatus according to claim 17, wherein the Tg of the toner in the developer is from 40 ° C. to 70 ° C. 32. The electrophotographic apparatus according to claim 17, wherein the toner in the developer is substantially spherical. 33. A dispersion liquid is prepared by dispersing 5 mg of toner in 10 ml of water in which 0.1 mg of nonionic surfactant is dissolved, and prepares a dispersion at 20 kHz and 50 W / 10 c.
flow particle image analyzer (Flow Particle Ima) when ultrasonic waves of m ³ are applied to the dispersion for 5 minutes.
Ge Analyzer) (hereinafter referred to as F
33. The electrophotographic apparatus according to claim 32, wherein a measured value C1 of particles having a particle size of 0.6 to 2.0 [mu] m in the PIA method is 3 to 50% by number. 34. The electrophotographic apparatus according to claim 32, wherein the toner in the developer is formed by a polymerization method. 35. The electrophotographic apparatus according to claim 32, wherein the toner in the developer has a structure of two or more layers. 36. The electrophotographic apparatus according to claim 17, wherein a non-magnetic one-component developer is used as the developer. 37. The charging device and the developing device according to claim 1, wherein
7. The conductive member according to claim 6, wherein the ten-point average roughness of the surface of the conductive member used for the charging means is smaller than the ten-point average roughness of the surface of the conductive member used for the developing means.
The electrophotographic apparatus according to any one of 7 to 36. 38. The conductive member according to claim 1, wherein at least one selected from the group consisting of a charging device, an electrophotographic photosensitive member, and a developing device is integrally supported, and at least a conductive member used for the charging device. A process cartridge detachable from an electrophotographic apparatus using the conductive member. 39. The process cartridge according to claim 38, wherein the conductive member according to claim 1 is reused after being recycled.