JP2021067941A - Electrophotographic device, process cartridge, and cartridge set - Google Patents

Abstract

To provide an electrophotographic device that, even when a process speed is further accelerated, can prevent contamination of an electrifying member and stably form a high-quality electrophotographic image.SOLUTION: An electrophotographic device has an electrophotographic photoreceptor, an electrifying device, and a developing device. The electrifying device has a conductive member that is arranged to be contactable with the electrophotographic photoreceptor. A conductive layer of the conductive member has a matrix-domain structure. The domains form convex parts on an outer surface of the conductive member. The volume resistivity R1 of the matrix and the volume resistivity R2 of the domains are in a specific relationship. The developing device includes a toner having a specific number average particle diameter. The toner includes toner particles each having a toner base particle and a specific organic silicon polymer on the surface of the toner base particle. The organic silicon polymer forms convex parts 4 in a specific size on an outer surface of the toner particle. The adhesion ratio of the organic silicon polymer is 80 mass% or more.SELECTED DRAWING: Figure 2

Description

The present disclosure is directed to electrophotographic devices, process cartridges, and cartridge sets.

In recent years, further speeding up of the process speed of the electrophotographic image forming apparatus has been studied. At this time, in order to further increase the process speed while maintaining the quality of the electrophotographic image, the change over time in the charging performance of the charging member due to the so-called transfer residual toner adhering to the charging member is observed. We recognize that technological development is needed to prevent it.
That is, as the process speed of the printer is further increased, the transfer residual toner easily slips through the cleaning blade, so that the probability that the transfer residual toner comes into contact with the charging member also increases. Then, the transfer residual toner that has reached the charged member is pressurized between the charged member and the nip of the electrostatic latent image carrier, and is rubbed against the charged member to adhere to the outer surface of the charged member. Then, proper discharge to the electrostatic latent image carrier is unlikely to occur from the charged member to which the transfer residual toner is adhered, and as a result, white spots (white spots) may occur in the electrophotographic image.
We considered that it is effective to apply a negative charge to the transfer residual toner by using the charge member as one method of preventing the transfer residual toner from sticking to the outer surface of the charge member. Here, in Patent Document 1, in an electrophotographic apparatus adopting a so-called cleanerless system, a charging member having a conductive convex portion is used as a charging member, and a toner externally added with silica is used as a toner. Is described. It is disclosed that the transfer residual toner can be efficiently collected in the developing roller by injecting an electric charge into the transfer residual toner by the apparatus.

Japanese Unexamined Patent Publication No. 2016-102905

According to our study, the electrophotographic apparatus according to Patent Document 1 was found to have a certain effect in preventing the transfer residual toner from sticking to the charged member. However, I realized that there is still room for improvement in further increasing the process speed. Specifically, it has been found that when the process speed is further increased, it may not be possible to sufficiently prevent the transfer residual toner from sticking to the charged member.
The present disclosure discloses an electrophotographic apparatus, a process cartridge, and an electrophotographic apparatus capable of suppressing contamination of a charging member and stably forming a high-quality electrophotographic image even when the process speed is further increased. Provide a cartridge set.

According to the present disclosure, an electrophotographic photosensitive member, a charging device for charging the surface of the electrophotographic photosensitive member, and an electrostatic latent image formed on the surface of the electrophotographic photosensitive member are developed with toner to develop the electrons. An electrophotographic apparatus having a developing apparatus for forming a toner image on the surface of a photographic photosensitive member.
The charging device has a conductive member arranged so as to be in contact with the electrophotographic photosensitive member.
The conductive member has a support having a conductive outer surface and a conductive layer provided on the outer surface of the support.
The conductive layer has a matrix and a plurality of domains dispersed in the matrix.
The matrix contains the first rubber and
The domain contains a second rubber and an electronically conductive agent.
At least a portion of the domain is exposed to the outer surface of the conductive member.
The outer surface of the conductive member is composed of at least the matrix and the domain exposed on the outer surface of the conductive member.
The domain forms a protrusion on the outer surface of the conductive member.
The volume resistivity R1 of the matrix is ^{larger than 1.00 × 10 12} Ω · cm.
The volume resistivity R2 of the domain is smaller than the volume resistivity R1 of the matrix.
The developing device contains the toner and contains the toner.
The number average particle size of the toner is 4.0 μm or more and 10.0 μm or less.
The toner contains toner particles and toner particles having an organosilicon polymer on the surface of the toner mother particles.
The organosilicon polymer has a structure represented by the following formula (1) and has a structure represented by the following formula (1).
R-SiO _3/2 (1)
In the formula (1), R represents an alkyl group or a phenyl group having 1 or more and 6 or less carbon atoms.
The organosilicon polymer has convex portions formed on the outer surface of the toner particles.
The adhesion rate of the organosilicon polymer to the toner matrix particles is 80% by mass or more.
With respect to the cross-sectional image of the toner particles obtained by the scanning transmission electron microscope STEM, when the contour line of the toner mother particles is developed in a straight line to obtain a developed image of the cross-sectional image,
In the developed image,
Let L be the length of the straight line.
When the length of the line segment forming the boundary between the convex portion and the toner mother particle on the straight line is the convex width w, the ratio of the total sum Σw of the convex width w to the L (Σw / An electrophotographic apparatus in which L) is 0.30 or more and 0.95 or less is provided.
Further, according to the present disclosure, it is a process cartridge that can be attached to and detached from the main body of the electrophotographic apparatus.
The process cartridge develops a charging device for charging the surface of the electrophotographic photosensitive member and an electrostatic latent image formed on the surface of the electrophotographic photosensitive member with toner, and the toner image is displayed on the surface of the electrophotographic photosensitive member. Has a developing device for forming
The charging device has a conductive member arranged so as to be in contact with the electrophotographic photosensitive member.
The conductive member has a support having a conductive outer surface and a conductive layer provided on the outer surface of the support.
The conductive layer has a matrix and a plurality of domains dispersed in the matrix.
The matrix contains the first rubber and
The domain contains a second rubber and an electronically conductive agent.
At least a portion of the domain is exposed to the outer surface of the conductive member.
The outer surface of the conductive member is composed of at least the matrix and the domain exposed on the outer surface of the conductive member.
The domain forms a protrusion on the outer surface of the conductive member.
The volume resistivity R1 of the matrix is ^{larger than 1.00 × 10 12} Ω · cm.
The volume resistivity R2 of the domain is smaller than the volume resistivity R1 of the matrix.
The developing device contains the toner and contains the toner.
The number average particle size of the toner is 4.0 μm or more and 10.0 μm or less.
The toner contains toner particles and toner particles having an organosilicon polymer on the surface of the toner mother particles.
The organosilicon polymer has a structure represented by the following formula (1) and has a structure represented by the following formula (1).
R-SiO _3/2 (1)
In the formula (1), R represents an alkyl group or a phenyl group having 1 or more and 6 or less carbon atoms.
The organosilicon polymer has convex portions formed on the outer surface of the toner particles.
The adhesion rate of the organosilicon polymer to the toner matrix particles is 80% by mass or more.
With respect to the cross-sectional image of the toner particles obtained by the scanning transmission electron microscope STEM, when the contour line of the toner mother particles is developed in a straight line to obtain a developed image of the cross-sectional image,
In the developed image,
Let L be the length of the straight line.
When the length of the line segment forming the boundary between the convex portion and the toner mother particle on the straight line is the convex width w, the ratio of the total sum Σw of the convex width w to the L (Σw / A process cartridge in which L) is 0.30 or more and 0.95 or less is provided.
Further, according to the present disclosure, it is a cartridge set having a first cartridge and a second cartridge that can be attached to and detached from the main body of the electrophotographic apparatus.
The first cartridge has a charging device for charging the surface of the electrophotographic photosensitive member and a first frame for supporting the charging device.
The second cartridge has a toner container containing toner for developing an electrostatic latent image formed on the surface of the electrophotographic photosensitive member to form a toner image on the surface of the electrophotographic photosensitive member. ,
The charging device has a conductive member arranged so as to be in contact with the electrophotographic photosensitive member.
The conductive member has a support having a conductive outer surface and a conductive layer provided on the outer surface of the support.
The conductive layer has a matrix and a plurality of domains dispersed in the matrix.
The matrix contains the first rubber and
The domain contains a second rubber and an electronically conductive agent.
At least a portion of the domain is exposed to the outer surface of the conductive member.
The outer surface of the conductive member is composed of at least the matrix and the domain exposed on the outer surface of the conductive member.
The domain forms a protrusion on the outer surface of the conductive member.
The volume resistivity R1 of the matrix is ^{larger than 1.00 × 10 12} Ω · cm.
The volume resistivity R2 of the domain is smaller than the volume resistivity R1 of the matrix.
The number average particle size of the toner is 4.0 μm or more and 10.0 μm or less.
The toner contains toner particles and toner particles having an organosilicon polymer on the surface of the toner mother particles.
The organosilicon polymer has a structure represented by the following formula (1) and has a structure represented by the following formula (1).
R-SiO _3/2 (1)
In the formula (1), R represents an alkyl group or a phenyl group having 1 or more and 6 or less carbon atoms.
The organosilicon polymer has convex portions formed on the outer surface of the toner particles.
The adhesion rate of the organosilicon polymer to the toner matrix particles is 80% by mass or more.
With respect to the cross-sectional image of the toner particles obtained by the scanning transmission electron microscope STEM, when the contour line of the toner mother particles is developed in a straight line to obtain a developed image of the cross-sectional image,
In the developed image,
Let L be the length of the straight line.
When the length of the line segment forming the boundary between the convex portion and the toner mother particle on the straight line is the convex width w, the ratio of the total sum Σw of the convex width w to the L (Σw / A cartridge set in which L) is 0.30 or more and 0.95 or less is provided.

According to the present disclosure, even when the process speed is further increased, contamination of the charging member can be suppressed, and a high-quality electrophotographic image can be stably formed. , And a cartridge set can be provided.

Schematic diagram of cross-sectional observation of toner by STEM Schematic diagram showing how to measure a convex shape Schematic diagram showing how to measure a convex shape Schematic diagram showing how to measure a convex shape Sectional view perpendicular to the longitudinal direction of the charging roller Enlarged sectional view of the conductive layer Schematic diagram of the image for ghost image evaluation Explanatory drawing in the cross-sectional cutting direction from the conductive layer of the charging roller Schematic diagram of process cartridge Schematic diagram of electrophotographic equipment

Unless otherwise specified, the description of "XX or more and YY or less" or "XX to YY" indicating a numerical range means a numerical range including a lower limit and an upper limit which are end points.
When the numerical ranges are described step by step, the upper and lower limits of each numerical range can be arbitrarily combined.
In this disclosure, the following toner and conductive member are used.
The toner includes toner mother particles and toner particles having an organosilicon polymer on the surface of the toner mother particles.
The number average particle size of the toner is 4.0 μm or more and 10.0 μm or less.
The organosilicon polymer has a structure represented by the following formula (1) and has a structure represented by the following formula (1).
R-SiO _3/2 (1)
In the formula (1), R represents an alkyl group or a phenyl group having 1 or more and 6 or less carbon atoms.
The organosilicon polymer has convex portions formed on the outer surface of the toner particles.
The adhesion rate of the organosilicon polymer to the toner matrix particles is 80% by mass or more.
With respect to the cross-sectional image of the toner particles obtained by the scanning transmission electron microscope STEM, when the contour line of the toner mother particles is developed in a straight line to obtain a developed image of the cross-sectional image,
In the developed image,
Let L be the length of the straight line.
When the length of the line segment forming the boundary between the convex portion and the toner mother particle on the straight line is the convex width w, the ratio of the total sum Σw of the convex width w to the L (Σw / L) is 0.30 or more and 0.95 or less.
The conductive member has a support having a conductive outer surface and a conductive layer provided on the outer surface of the support, and the conductive layer is arranged so as to be in contact with the electrophotographic photosensitive member. , Matrix and multiple domains distributed within the matrix
The matrix contains the first rubber and
The domain contains a second rubber and an electronically conductive agent.
At least a portion of the domain is exposed to the outer surface of the conductive member.
The outer surface of the conductive member is composed of at least the matrix and the domain exposed on the outer surface of the conductive member.
The domain forms a protrusion on the outer surface of the conductive member.
The volume resistivity R1 of the matrix is ^{larger than 1.00 × 10 12} Ω · cm.
The volume resistivity R2 of the domain is smaller than the volume resistivity R1 of the matrix.
The outer surface of the conductive member is a surface of the conductive member that comes into contact with toner.

By combining such toner and a conductive member as a charging member, contamination of the charging member can be suppressed even when the process speed is further increased, and a high-quality electrophotographic image is stabilized. Can be formed The reason will be explained below.
The present inventors speculate the reason why the electrophotographic apparatus according to Patent Document 1 cannot sufficiently suppress the adhesion of toner to the charging member when the process speed is further increased as follows.

That is, the charging member according to Patent Document 1 has minute protrusions derived from conductive particles on its surface, and by bringing the minute protrusions into contact with the transfer residual toner, charge is injected into the transfer residual toner. ing. However, it is considered that it takes a certain time for the electric charge to be accumulated in the convex portion after the electric charge is injected into the transfer residual toner from the minute convex portion.
Therefore, when the process speed is increased, the transfer residual toner also reaches the charged member one after another at high speed. Then, even if the transfer residual toner comes into contact with the convex portion, the charge to be injected into the transfer residual toner is not sufficiently accumulated in the convex portion, so that the negative charge of the transfer residual toner is insufficient. Become. As a result, it is considered that the adhesion of the transfer residual toner to the charged member cannot be sufficiently suppressed.

Here, we consider that the conductive member as a charging member can accumulate a large amount of electric charge in the conductive layer, and the electric charge accumulated in the conductive layer is not consumed at once by one charge injection. It was considered that the transfer residual toner that reaches the conductive member one after another can be reliably negatively charged.
Further, in order to stably provide a high-quality electrophotographic image for a long period of time while responding to the high speed of the printer, the toner is transferred between the nip between the conductive member and the electrostatic latent image carrier. It is important to increase the motility in order to promote the negative charge of the transfer residual toner.
Here, we find that giving both the outer surface of the toner particles and the outer surface of the conductive member a convex shape is effective in improving the rolling property of the transfer residual toner and the conductive member in the nip portion. I considered that. It is considered that the rolling property of the toner is improved by engaging the convex portions of both the outer surface of the toner particles and the outer surface of the conductive member as if they were gears.

Further, as one method for giving the outer surface of the toner particles a convex shape, a method of externally adding the particles to the periphery of the toner mother particles can be considered. However, the external additive tends to move from the toner matrix particles to other members with long-term use. Therefore, in order to ensure good rolling properties of the toner over a long period of time, it is considered necessary to make the convex shape of the outer surface of the toner particles less likely to change even after long-term use. ..
As a result of repeated studies based on the above considerations, it has been found that the combination of the conductive member and the toner according to the present disclosure can well meet the above requirements.

In the conductive layer when a charging bias is applied between the support of the conductive member and the electrophotographic photosensitive member, the electric charge is applied from the support side to the opposite side of the conductive layer, that is, conductive as follows. It is considered that the member moves to the outer surface side. That is, the charge is accumulated near the interface between the matrix and the domain.
Then, the electric charge is sequentially transferred from the domain located on the conductive support side to the domain located on the side opposite to the conductive support side, and is opposite to the conductive support side of the conductive layer. It reaches the side surface (hereinafter also referred to as the "outer surface of the conductive layer"). At this time, if the charges of all the domains move to the outer surface side of the conductive layer in one charging step, it takes time to accumulate the charges in the conductive layer toward the next charging step. Then, it becomes difficult to achieve stable discharge in the high-speed electrophotographic image forming process.
Therefore, even when a charge bias is applied, it is preferable that charge transfer between domains does not occur at the same time. In addition, since the movement of electric charges is restricted in the high-speed electrophotographic image formation process, in order to discharge a sufficient amount of electric charges with one discharge, a sufficient amount of electric charges must be accumulated in each domain. Is preferable.

The conductive layer has a matrix and a plurality of domains dispersed in the matrix. The matrix then contains a first rubber and the domain contains a second rubber and an electronically conductive agent. Then, the matrix and the domain satisfy the following components (i) and (ii).
Component (i): The volume resistivity R1 of the matrix ^{is larger than 1.00 × 10 12} Ω · cm.
Component (ii): The volume resistivity R2 of the domain is smaller than the volume resistivity R1 of the matrix.

The conductive member provided with the conductive layer satisfying the components (i) and (ii) can accumulate a sufficient charge in each domain when a bias is applied between the conductive member and the photoconductor. Further, since the domains are separated by an electrically insulating matrix, simultaneous charge transfer between domains can be suppressed. As a result, it is possible to prevent most of the electric charges accumulated in the conductive layer from being released by one discharge.
As a result, even immediately after the end of one discharge, the electric charge for the next discharge can still be accumulated in the conductive layer. Therefore, it is possible to stably generate an electric discharge in a short cycle. In addition, such a discharge achieved by the conductive member according to the present disclosure is hereinafter also referred to as "fine discharge".

As described above, the conductive layer having the matrix domain structure satisfying the components (i) and (ii) suppresses the simultaneous generation of charge transfer between domains when a bias is applied, and also within the domains. Sufficient charge can be stored in the domain. Therefore, the conductive member can continuously and stably apply an electric charge to the charged body even when applied to an electrophotographic image forming apparatus having a high process speed.

Further, at least a part of the domain is exposed on the outer surface of the conductive member, and a convex portion of the domain is formed on the outer surface of the conductive member. As a result, a gear effect can be obtained between the conductive member and the toner particles, and the rolling property of the toner particles in the nip portion can be improved.
Further, since the domain in which the electric charge is accumulated is exposed as a convex portion on the outer surface of the conductive member, the electric charge can be injected into the transfer residual toner more efficiently.

On the other hand, the toner is coated with an organosilicon polymer so that the surface of the toner matrix particles has a predetermined ratio. The toner particles have a convex portion of the organosilicon polymer on the outer surface thereof. As a result, the convex portion of the domain on the outer surface of the conductive member and the convex portion of the outer surface of the toner particles mesh with each other like a pair of gears, so that the rolling property of the toner particles is improved.
Further, the adhesion rate of the organosilicon polymer constituting the convex portion to the toner matrix particles is 80% or more. This means that the organosilicon polymer is firmly adhered to the toner mother particles, so that the shape of the convex portion on the surface of the toner particles is unlikely to change even after long-term use.
The conductive member toner will be described below.

<Conductive member>
As the conductive member, a conductive member having a roller shape (hereinafter, also referred to as “conductive roller”) will be described as an example with reference to FIG. FIG. 5 is a cross-sectional view perpendicular to the direction along the axis of the conductive roller (hereinafter, also referred to as “longitudinal direction”). The conductive roller 51 has a columnar conductive support 52 and a conductive layer 53 formed on the outer periphery of the support 52, that is, on the outer surface of the support.

<Support>
As the material constituting the support, materials known in the field of conductive members for electrophotographic and materials that can be used as conductive members can be appropriately selected and used. Examples include metals or alloys such as aluminum, stainless steel, conductive synthetic resins, iron and copper alloys.
Further, these may be subjected to an oxidation treatment or a plating treatment with chromium, nickel or the like. As the type of plating, either electroplating or electroless plating can be used. Electroless plating is preferable from the viewpoint of dimensional stability. Examples of the type of electroless plating used here include nickel plating, copper plating, gold plating, and various other alloy platings.
The plating thickness is preferably 0.05 μm or more, and the plating thickness is preferably 0.10 μm to 30.00 μm in consideration of the balance between work efficiency and rust prevention ability. The cylindrical shape of the support may be a solid cylindrical shape or a hollow cylindrical shape (cylindrical shape). The outer diameter of the support is preferably in the range of 3 mm to 10 mm.

If a medium resistance layer or an insulating layer is present between the support and the conductive layer, it may not be possible to quickly supply the electric charge after the electric charge is consumed by the discharge. Therefore, it is preferable that the conductive layer is provided directly on the support, or the conductive layer is provided on the outer periphery of the support only via an intermediate layer made of a thin film and a conductive resin layer such as a primer.
As the primer, a known primer can be selected and used depending on the rubber material for forming the conductive layer, the material of the support, and the like. Examples of the primer material include thermocurable resins and thermoplastic resins. Specific examples thereof include phenol-based resins, urethane-based resins, acrylic-based resins, polyester-based resins, and polyether-based resins. Known materials such as epoxy resins can be used.

<Conductive layer>
The conductive layer has a matrix and a plurality of domains dispersed in the matrix. The matrix then contains a first rubber and the domain contains a second rubber and an electronically conductive agent. Then, the matrix and the domain satisfy the following components (i) and (ii).
Component (i): The volume resistivity R1 of the matrix ^{is larger than 1.00 × 10 12} Ω · cm.
Component (ii): The volume resistivity R2 of the domain is smaller than the volume resistivity R1 of the matrix.

<Component (i); Matrix volume resistivity>
By making the volume resistivity R1 of the matrix ^{larger than 1.00 × 10 12} Ω · cm, it is possible to suppress the charge from moving around the domain and moving in the matrix. Then, it is possible to suppress the consumption of most of the electric charges accumulated in one discharge. Further, it is possible to prevent the electric charge accumulated in the domain from leaking to the matrix, so that the conductive path communicating in the conductive layer is formed.
Further, in the nip portion of the conductive member and the electrophotographic photosensitive member, the electric charge accumulated in the toner does not easily escape to the matrix side due to the engagement between the conductive member and the toner, and high rechargeability can be easily obtained.
The volume resistivity R1 is ^{preferably 2.00 × 10 12} Ω · cm or more. On the other hand, the upper limit of R1 is not particularly limited, but as a guide, ^{it is preferably 1.00 × 10 17} Ω · cm or less, and more preferably 8.00 × 10 ¹⁶ Ω · cm or less.

In order to transfer the charge through the domains in the conductive layer and achieve fine discharge, the region (domain) where the charge is sufficiently accumulated is divided by the electrically insulating region (matrix). We believe that the configuration is valid. By setting the volume resistivity of the matrix to the range of the high resistance region as described above, sufficient charges can be retained at the interface with each domain, and charge leakage from the domains can be suppressed.

Further, in order to achieve a fine discharge and a necessary and sufficient discharge amount, it is extremely effective to limit the charge transfer path to a domain-mediated path. By suppressing the leakage of charge from the domain to the matrix and limiting the charge transport path to the path through multiple domains, the density of the charge existing in the domain can be improved, so that the charge in each domain can be improved. The filling amount of can be further increased.
As a result, the total number of charges that can participate in the discharge can be improved on the surface of the domain as the conductive phase, which is the starting point of the discharge, and as a result, the ease of discharging from the surface of the conductive member can be improved. It is thought that it can be done.

<Component (ii); Domain resistivity>
The volume resistivity R2 of the domain is smaller than the volume resistivity R1 of the matrix. This makes it easier to limit the charge transport path to a path through multiple domains while suppressing the transfer of unintended charges in the matrix.
The volume resistivity R1 is preferably at 1.0 × 10 ⁵ times or more the volume resistivity R2. ^{R1 is more preferably 1.0 × 10 6} times to 1.0 × 10 ¹⁸ times that of R2, and further preferably 1.0 × 10 ⁷ times to 1.0 × 10 ¹⁷ times. It is even more preferable that the ratio is 0.0 × 10 ⁸ times to 1.0 × 10 ^{16 times.}
R2 is preferably 1.00 × 10 ¹ Ω · cm or more and 1.00 × 10 ⁴ Ω · cm or less, preferably 1.00 × 10 ¹ Ω · cm or more and 1.00 × 10 ² Ω · cm or less. Is more preferable.

By satisfying the above, the electric charge transport path in the conductive layer can be controlled, and it becomes easier to achieve fine discharge. Therefore, since the adhesion of the transfer residual toner to the surface of the conductive member can be further suppressed, it becomes easy to suppress ghosts, white spots, and uneven halftone density after durable use. ..
The volume resistivity of the domain is adjusted, for example, by changing the type and amount of the electronic conductive agent with respect to the rubber component of the domain so that the conductivity thereof is set to a predetermined value.

As the rubber material for the domain, a rubber composition containing a rubber component for the matrix can be used. In order to form the matrix domain structure, it is preferable that the difference in the solubility parameter (SP value) from the rubber material forming the matrix is within a certain range. That is, the absolute value of the difference between the SP value of the first rubber and the SP value of the second rubber is preferably 0.4 (J / cm ³ ) ^0.5 or more and 5.0 (J / cm ³ ) ^{0. It is .5} or less, more preferably 0.4 (J / cm ³ ) ^0.5 or more and 2.2 (J / cm ³ ) ^0.5 or less.
The volume resistivity of the domain can be adjusted by appropriately selecting the type of the electron conductive agent and the amount thereof added. As an electronically conductive agent used to control the volume resistivity of a domain to 1.00 × 10 ¹ Ωcm or more and 1.00 × 10 ⁴ Ωcm or less, the volume resistivity increases from high resistance to low resistance depending on the amount of dispersion. An electronically conductive agent that can be changed is preferable.

Examples of the electronic conductive agent blended in the domain include oxides such as carbon black, graphite, titanium oxide, and tin oxide; metals such as Cu and Ag; particles whose surface is coated with oxides or metals and made conductive. Is listed as. Further, if necessary, two or more kinds of these conductive agents may be blended in appropriate amounts and used.
Among the above-mentioned electronic conductive agents, it is preferable to use conductive carbon black, which has a high affinity with rubber and can easily control the distance between the electronic conductive agents. The type of carbon black blended in the domain is not particularly limited. Specific examples thereof include gas furnace black, oil furnace black, thermal black, lamp black, acetylene black, and Ketjen black.

Among them, can impart high conductivity to the domain, DBP oil absorption of 40 cm ^3/100 g or more 170cm ^3/100 g can be preferably used in which conductive carbon black below.
The content of the electronic conductive agent such as conductive carbon black is preferably 20 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the second rubber contained in the domain. More preferably, it is 50 parts by mass or more and 100 parts by mass or less.
It is preferable that a large amount of the conductive agent is blended as compared with the conductive member for general electrophotographic. Thereby, the volume resistivity of the domain can be easily controlled in the range of ^{1.00 × 10 1} Ωcm or more and 1.00 × 10 ^{4 Ω · cm or less.}
In addition, if necessary, fillers, processing aids, cross-linking aids, cross-linking accelerators, antiaging agents, cross-linking accelerators, cross-linking retarders, softeners, and dispersants commonly used as rubber compounding agents , Colorants and the like may be added to the rubber composition for the domain as long as the effects according to the present disclosure are not impaired.

<Component (iii); Distance between adjacent walls of the domain>
In order to transfer and transfer electric charges between domains, the arithmetic mean value Dm (hereinafter, also simply referred to as "interdomain distance Dm") of the distance between adjacent walls of domains in cross-sectional observation in the thickness direction of the conductive layer is determined. It is preferably 2.00 μm or less, and more preferably 1.00 μm or less.
Further, the inter-domain distance Dm is preferably 0.15 μm or more, more preferably 0.15 μm or more, because the domains can be reliably electrically separated by the insulating region (matrix) and the electric charge can be easily accumulated by the domains. It is 0.20 μm or more.

-Uniformity of the inter-domain distance Dm It is preferable that the distribution of the inter-domain distance Dm is uniform because fine discharge can be formed more stably. The uniform distribution of the inter-domain distance Dm creates a part of the conductive layer where the inter-domain distance is locally long, so that when there is a part where the charge supply is stagnant compared to the surroundings, the discharge is discharged. It is possible to reduce the phenomenon in which the ease of discharge is suppressed.
In the cross section in which the electric charge is transported, that is, in the cross section in the thickness direction of the conductive layer as shown in FIG. 8 (b), the depth from the outer surface of the conductive layer toward the support is 0.1 T to 0.9 T. Acquire a 50 μm square observation region at any three locations in the thickness region of. At this time, it is preferable that the coefficient of variation σm / Dm of the inter-domain distance is 0 or more and 0.40 or less by using the inter-domain distance Dm in the observation region and the standard deviation σm of the distribution of the inter-domain distance. It is more preferably 10 or more and 0.30 or less.
Within the above range, meshing with the toner particles is likely to occur efficiently, so that one toner particle is likely to be uniformly recharged. In addition, since the uniform distance between domains also suppresses discharge unevenness, a higher quality image is likely to be formed.

<Convex height of domain>
The domain is exposed on the outer surface of the conductive member. The outer surface of the conductive member is composed of at least a matrix and domains exposed on the outer surface of the conductive member. The outer surface of the conductive member has a convex portion of the domain.
Since the outer surface of the conductive member has a matrix domain structure and has a convex portion due to the domain containing the electron conductive agent, a gear effect is generated by increasing the contact frequency between the toner and the conductive member. Further, triboelectric charging generated between the toner and the matrix surface of the conductive member and injection charging from the electron conductive agent contained in the domain in contact with the toner occur at the same time.
When the domain is exposed on the outer surface of the conductive member and forms a convex portion, the toner that has reached the contact portion with the photosensitive drum is preferentially contacted on the surface of the conductive member. As a result, a negative charge can be suitably injected into the toner. As described above, the superposition of triboelectric charging and injection charging causes rapid charging of the toner adhering to the conductive member. As a result, contamination of the conductive member by toner is significantly suppressed.
Specifically, the average value of the heights of the protrusions formed by the domains is preferably 50 nm to 200 nm. More preferably, it is 80 nm to 150 nm. By setting the height to 50 nm or more, the chance of contact with the toner can be increased, and a sufficient injection charge can be imparted to the toner. On the other hand, when the nm is set to 200 nm or less, uneven discharge due to convexity can be suppressed.

<How to check the convex shape derived from the domain>
To confirm the convex shape of the surface according to the present invention, a thin piece including the surface can be taken out from the conductive layer, and the convex shape can be confirmed and the convex shape can be measured by a micro probe. The surface profile and electrical resistance profile of the flakes sampled from the conductive member are measured by SPM. From this, it can be confirmed that the convex portion is a convex derived from the domain. At the same time, it is possible to quantify and evaluate the height of the convex portion from the shape profile. The specific procedure will be described later.

<Method of forming a convex shape by domain>
The method of forming the convex shape by the domain is not particularly limited. For example, a convex shape can be obtained by grinding the surface of the conductive member. Further, the inventors believe that the conductive layer having a matrix domain structure can be suitably formed by a grinding step using a grindstone. Specifically, it is preferably formed by a method of grinding with a polishing grindstone with a plunge type polishing machine.

The mechanism by which the convex shape is formed by the domain by grinding wheel polishing is presumed as follows. First, the domains dispersed in the matrix are filled with an electron conductive agent, and have higher reinforcing properties than the matrix not filled with the electron conductive agent. Therefore, it is possible to form a convex shape derived from the domain by utilizing the difference in grindability caused by this difference in reinforcing property.
Specifically, when grinding with the same grindstone is performed, the domain is more difficult to grind than the matrix because of its high reinforcing property. Therefore, it is considered that a convex portion is formed by the domain.

Here, the polishing grindstone by the plunge type polishing machine will be described. The surface roughness of the polishing grindstone can be appropriately selected according to the polishing efficiency and the type of the constituent material of the rubber elastic layer. The roughness of the surface of the grindstone can be adjusted by the type of abrasive grains, the particle size, the degree of bonding, the binder, the structure (abrasive grain ratio), and the like.
The "particle size of the abrasive grains" indicates the size of the abrasive grains, and is expressed as, for example, # 80. The number in this case means how many stitches per inch (25.4 mm) of the mesh for selecting the abrasive grains, and the larger the number, the finer the abrasive grains.
"Coupling degree of abrasive grains" indicates hardness, and is represented by alphabets A to Z. The closer it is to A, the softer it is, and the closer it is to Z, the harder it is. The larger the amount of the binder contained in the abrasive grains, the harder the grindstone becomes.
The "abrasive grain structure (abrasive grain ratio)" represents the volume ratio of the abrasive grains to the total volume of the grindstone, and the size of the structure represents the density of the structure. The larger the number indicating the tissue, the coarser it is. A grindstone having a large number of structures and large pores is called a porous grindstone, and has advantages such as preventing clogging and burning of the grindstone.

Generally, this polishing grindstone can be manufactured by mixing raw materials (abrasive material, binder, pore agent, etc.), press molding, drying, firing, and finishing. As the abrasive grains, green carbide (GC), black carbide (C), white alumina (WA), brown alumina (A), zirconia alumina (Z) and the like can be used. These materials can be used alone or in combination of two or more.
Further, as the above-mentioned binder, vitrify (V), resinoid (B), resinoid reinforcement (BF), rubber (R), silicate (S), magnesia (Mg), shellac (E), etc. , Can be used.

Here, the outer diameter shape of the grinding wheel in the longitudinal direction is an inverted crown shape in which the outer diameter gradually decreases from the end to the center so that the conductive member (charged roller) can be polished into a crown shape. It is preferable to do so. The outer diameter shape of the grinding wheel is preferably an arc curve or a higher-order curve of a second order or higher with respect to the longitudinal direction.
In addition to this, the outer diameter shape of the polishing wheel may be a shape expressed by various mathematical formulas such as a quartic curve and a sine function. The outer shape of the grinding wheel is preferably one in which the change in outer diameter changes smoothly, but an arc curve or the like may be a shape similar to a polygonal shape formed by a straight line. The width in the direction corresponding to the axial direction of the polishing grindstone is preferably equal to or larger than the axial width of the conductive member.

The convex shape derived from the domain can be formed by appropriately selecting the grindstone in consideration of the above-mentioned factors and carrying out the grinding step under the conditions that promote the difference in grindability between the domain and the matrix.
Specifically, conditions in which polishing is suppressed and conditions in which abrasive grains with poor sharpness are used are preferable. For example, a processed grindstone (rubber containing abrasive grains) that shortens the time of the precision polishing process after rough cutting is performed. The abrasive grains can be abraded by polishing the surface of the grindstone dressed with the member. Polishing with a grindstone treated with a rubber member) can be taken.

<Relationship between inter-domain distance Dms and average particle size of toner>
In the present disclosure, when observing the outer surface of the conductive member, the arithmetic mean value Dms (μm) of the distance between adjacent wall surfaces of the domains in the conductive layer (hereinafter, also simply referred to as “interdomain distance Dms”) and the toner. The relationship with the number average particle size Dt (μm) is preferably Dt> Dms. More preferably, Dt-Dms is 0.1 to 10.0.
When Dt> Dms, the toner particles adhering to the surface of the conductive member are likely to come into contact with a plurality of domains existing on the surface of the conductive member, so that the toner is easily recharged uniformly.
The inter-domain distance Dms is preferably 0.20 μm or more and 2.50 μm or less, and more preferably 0.30 μm or more and 1.50 μm or less.

The conductive member can be formed, for example, by a method including the following steps (i) to (iv).
Step (i): Preparing a domain-forming rubber mixture (hereinafter, also referred to as “CMB”) containing carbon black and a second rubber;
Step (ii): A step of preparing a matrix-forming rubber mixture (hereinafter, also referred to as “MRC”) containing the first rubber;
Step (iii): A step of kneading CMB and MRC to prepare a rubber mixture having a matrix domain structure.
Step (iv): A layer of the rubber mixture prepared in step (iii) is formed on the conductive support directly or via another layer, and the layer of the rubber composition is cured to form a conductive layer. Process to do.

The components (i) to (iii) can be controlled, for example, by selecting the materials used in each of the above steps and adjusting the manufacturing conditions. This will be described below.
First, with respect to component (i), the volume resistivity of the matrix is determined by the composition of the MRC.

As the first rubber used for MRC, a rubber having low conductivity is preferable. Selected from the group consisting of natural rubber, butadiene rubber, butyl rubber, acrylonitrile butadiene rubber, urethane rubber, silicone rubber, fluororubber, isoprene rubber, chloroprene rubber, styrene butadiene rubber, ethylene propylene rubber, ethylene propylene diene rubber, and polynorbornene rubber. At least one is preferable.
More preferably, the first rubber is selected from the group consisting of butyl rubber, styrene-butadiene rubber, and ethylene propylene diene rubber.
Further, if the volume resistivity of the matrix is within the above range, the MRC may contain a filler, a processing aid, a cross-linking agent, a cross-linking aid, a cross-linking accelerator, a cross-linking accelerator, and a cross-linking retarder, if necessary. , Antioxidants, softeners, dispersants, colorants and the like may be added. On the other hand, it is preferable that the MRC does not contain an electron conductive agent such as carbon black in order to keep the volume resistivity of the matrix within the above range.

Further, with respect to the component (ii), the volume resistivity R2 of the domain can be adjusted by the amount of the electron conductive agent in the CMB. For example, as an electron conductive agent, DBP oil absorption ^amount, the case of using the conductive carbon black is not more than 40 cm 3/100 g or more 170cm ^3/100 g as an example. A desired range can be achieved by preparing the CMB so as to contain conductive carbon black of 40 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the second rubber of the CMB.

Further, regarding the distributed state of the domain related to the component (iii), it is effective to control the following four (a) to (d).
(A) Difference in interfacial tension σ between CMB and MRC;
(B) The ratio of the viscosity of CMB (ηd) to the viscosity of MRC (ηm) (ηm / ηd);
(C) The shear rate (γ) at the time of kneading the CMB and MRC and the amount of energy (EDK) at the time of shearing in the step (iii).
(D) Volume fraction of CMB with respect to MRC in step (iii).
Hereinafter, (a) to (d) will be described.

(A) Difference in interfacial tension between CMB and MRC Generally, when two kinds of incompatible rubbers are mixed, they are phase-separated. This is because the interaction between the same polymers is stronger than the interaction between different polymers, so that the same polymers aggregate to reduce the free energy and stabilize it.
Since the interface of the phase-separated structure comes into contact with different macromolecules, the free energy is higher than that of the inside stabilized by the interaction between the same molecules. As a result, in order to reduce the free energy of the interface, an interfacial tension is generated to reduce the area of contact with the dissimilar polymer. When this interfacial tension is small, even dissimilar polymers tend to be mixed more uniformly in order to increase entropy. The uniformly mixed state is dissolution, and the SP value (solubility parameter), which is a measure of solubility, tends to correlate with the interfacial tension.

That is, it is considered that the difference in interfacial tension between CMB and MRC correlates with the difference in SP value of the rubber contained therein. The difference between the absolute value of the solubility parameter SP value of the first rubber in MRC and the SP value of the second rubber in CMB is preferably 0.4 (J / cm ³ ) ^0.5 or more and 5.0 ( It is preferable to select a rubber having J / cm ³ ) ^0.5 or less, more preferably 0.4 (J / cm ³ ) ^0.5 or more and 2.2 (J / cm ³ ) ^{0.5 or less.} .. Within this range, a stable phase-separated structure can be formed, and the domain diameter of CMB can be reduced.

Here, specific examples of the second rubber that can be used for CMB include, for example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), acrylonitrile butadiene rubber (NBR), and styrene butadiene rubber (SBR). , Butyl rubber (IIR), ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPDM), kururuprene rubber (CR), nitrile rubber (NBR), hydrogenated nitrile rubber (H-NBR), silicone rubber, and urethane rubber. At least one selected from the group consisting of (U) is preferred.
The second rubber is more preferably selected from the group consisting of styrene butadiene rubber (SBR), butyl rubber (IIR), and acrylonitrile butadiene rubber (NBR), more preferably styrene butadiene rubber (SBR), and butyl rubber (IIR). At least one selected from the group consisting of is even more preferred.
The thickness of the conductive layer is not particularly limited as long as the desired function and effect of the conductive member can be obtained. The thickness of the conductive layer is preferably 1.0 mm or more and 4.5 mm or less.
The mass ratio of domain to matrix (domain: matrix) is preferably 5:95 to 40:60, more preferably 10:90 to 30:70, and even more preferably 13:87 to 25:75. is there.

(B) Viscosity ratio between CMB and MRC The closer the viscosity ratio between CMB and MRC (CMB / MRC) (ηd / ηm) is, the smaller the domain diameter can be. Specifically, the viscosity ratio is preferably 1.0 or more and 2.0 or less. The viscosity ratio of CMB and MRC can be adjusted by selecting the Mooney viscosity of the raw rubber used for CMB and MRC, and by blending the type and amount of the filler.
It is also possible to add a plasticizer such as paraffin oil to the extent that it does not interfere with the formation of the phase-separated structure. Further, the viscosity ratio can be adjusted by adjusting the temperature at the time of kneading.
The viscosity of the domain-forming rubber mixture or the matrix-forming rubber mixture can _{be obtained by measuring the Mooney viscosity ML (1 + 4)} at the rubber temperature at the time of kneading based on JIS K6300-1: 2013.

(C) Shear velocity during kneading between MRC and CMB and amount of energy during shearing The faster the shear rate during kneading between MRC and CMB and the greater the amount of energy during shearing, the more the inter-domain distance Dm and the amount of energy. Dms can be reduced.
The shear rate can be increased by increasing the inner diameter of the stirring member such as the blade or screw of the kneader, reducing the gap from the end face of the stirring member to the inner wall of the kneader, or increasing the rotation speed. Further, the energy at the time of shearing can be increased by increasing the rotation speed of the stirring member or increasing the viscosities of the first rubber in the CMB and the second rubber in the MRC.

(D) Volume Fraction of CMB with respect to MRC The volume fraction of CMB with respect to MRC correlates with the collision coalescence probability of the domain-forming rubber mixture with respect to the matrix-forming rubber mixture. Specifically, reducing the volume fraction of the domain-forming rubber mixture with respect to the matrix-forming rubber mixture reduces the collision-coalescence probability of the domain-forming rubber mixture and the matrix-forming rubber mixture. That is, the interdomain distances Dm and Dms can be reduced by reducing the volume fraction of the domains in the matrix within the range where the required conductivity can be obtained.
The volume fraction of CMB with respect to MRC (that is, the volume fraction with respect to the domain matrix) is preferably 15% or more and 40% or less.

<Domain diameter D>
The arithmetic mean value of the circle-equivalent diameter D (hereinafter, also simply referred to as “domain diameter D”) of the domain observed from the cross section of the conductive layer is preferably 0.10 μm or more and 5.00 μm or less.
Within this range, the outermost domain has a size smaller than that of the toner, so that fine discharge is possible and uniform discharge can be easily achieved.
By setting the average value of the domain diameter D to 0.10 μm or more, the path through which the charge moves can be effectively limited by the target path in the conductive layer. It is more preferably 0.15 μm or more, and further preferably 0.20 μm or more.
Further, by setting the average value of the domain diameter D to 5.00 μm or less, the ratio of the surface area to the total volume of the domains, that is, the specific surface area of the domains can be exponentially increased, and the charge is released from the domains. Efficiency can be dramatically improved. The average value of the domain diameter D is more preferably 2.00 μm or less, and further preferably 1.00 μm or less for the above reasons.
By setting the average value of the domain diameter D to 2.00 μm or less, the electrical resistance of the domain itself can be reduced, so that the amount of single discharge can be set to a necessary and sufficient amount, and fine discharge can be performed more efficiently.

<Circle-equivalent diameter Ds of the domain observed from the outer surface of the conductive layer>
The arithmetic mean value of the circle-equivalent diameter Ds (hereinafter, also simply referred to as “domain diameter Ds”) of the domain observed from the outer surface of the conductive layer is preferably 0.05 μm or more and 4.00 μm or less, preferably 0.10 μm. It is more preferably 2.00 μm or less.
When the domain diameter Ds is in the above range, meshing and contact with the toner particles occur efficiently, so that uniform recharging is likely to occur, and leakage to the matrix side is less likely to occur, so that a high amount of charge can be obtained. ..

In order to further reduce the concentration of electric fields between domains, it is preferable to make the outer shape of the domains closer to a sphere. For that purpose, it is preferable to make the domain diameter smaller within the above range. As a method, for example, in the step (iv), MRC and CMB are kneaded to cause phase separation between MRC and CMB. Then, in the step of preparing the rubber mixture in which the domain of CMB is formed in the matrix of MRC, a method of controlling so as to reduce the domain diameter of CMB can be mentioned.
By reducing the domain diameter of the CMB, the specific surface area of the CMB increases and the interface with the matrix increases. Therefore, a tension for reducing the tension acts on the interface of the domain of the CMB. As a result, the CMB domain has an outer shape closer to a sphere.

Here, with respect to the factors that determine the domain diameter in the matrix-domain structure formed when two incompatible polymers are melt-kneaded, Taylor's formula (formula (6)) and Wu's empirical formula (formula (formula) 7), (8)), and Tokita's formula (formula (9)) are known.
・ Taylor's formula D = [C ・ σ / ηm ・ γ] ・ f (ηm / ηd) (6)
・ Wu's empirical formula γ ・ D ・ ηm / σ = 4 (ηd / ηm) 0.84 ・ ηd / ηm> 1 (7)
γ ・ D ・ ηm / σ = 4 (ηd / ηm) −0.84 ・ ηd / ηm <1 (8)
・ Tokita's formula D = 12 ・ P ・ σ ・ φ / (π ・ η ・ γ) ・ (1 + 4 ・ P ・ φ ・ EDK / (π ・ η ・ γ))
(9)

In formulas (6) to (9), D is the maximum ferret diameter of the domain of CMB, C is a constant, σ is the interfacial tension, ηm is the viscosity of the matrix, ηd is the viscosity of the domain, and γ is the shear. Velocity, η is the viscosity of the mixed system, P is the collision coalescence probability, φ is the domain phase volume, and EDK is the domain phase breaking energy.
In order to make the inter-domain distance uniform in relation to the component (iii), it is effective to reduce the domain diameter according to the equations (6) to (9). Further, in the process of kneading MRC and CMB, the distance between domains changes depending on where the kneading process is stopped in the process of splitting the raw rubber of the domain and gradually reducing its particle size.
Therefore, the uniformity of the inter-domain distance can be controlled by the kneading time in the kneading process and the kneading rotation speed which is an index of the kneading strength, and the longer the kneading time, the higher the kneading rotation speed. The larger the value, the more uniform the distance between domains can be improved.

-Uniformity of domain diameter D;
It is preferable that the domain diameter D is uniform, that is, the particle size distribution is narrow. By making the distribution of the domain diameter D through which the electric charge passes in the conductive layer uniform, the concentration of the electric charge in the matrix domain structure is suppressed, and the ease of discharging is effectively increased over the entire surface of the conductive member. Can be done.
In the cross section in which the electric charge is transported, that is, in the cross section in the thickness direction of the conductive layer as shown in FIG. 8 (b), the depth from the outer surface of the conductive layer toward the support is 0.1 T to 0.9 T. The ratio σd / D (coefficient of variation σd / D) of the standard deviation σd of the domain diameter and the arithmetic average value D of the domain diameter is 0 when the observation region of 50 μm square is acquired at any three locations in the thickness region of. It is preferably 0.40 or more, and more preferably 0.10 or more and 0.30 or less.

In order to improve the uniformity of the domain diameter, it is the same as the above-mentioned method of improving the uniformity of the distance between domains, and if the domain diameter is reduced according to the equations (6) to (9), the uniformity of the domain diameter is also improved. To do. Furthermore, in the process of kneading MRC and CMB, in the process of splitting the raw rubber of the domain and gradually reducing its particle size, the uniformity of the domain diameter changes depending on where the kneading process is stopped. ..
Therefore, the uniformity of the domain diameter can be controlled by the kneading time in the kneading process and the kneading rotation speed which is an index of the kneading strength, and the longer the kneading time, the larger the kneading rotation speed. The more uniform the domain diameter can be, the better.

Of the cubic-shaped samples having a side of 9 μm sampled from any nine points of the conductive layer, at least eight samples preferably satisfy the following condition (1).
Condition (1): When one sample is divided into 27 unit cubes having a side of 3 μm and the volume Vd of the domain contained in each of the unit cubes is obtained, Vd is 2.7 μm ³ to 10. The number of unit cubes of .8 μm ^{3 is at least 20.}
By doing so, the electrical resistivity does not change easily even under a high-speed process, and the homogenization of the conductive path also suppresses uneven charging and uneven discharging, so that high-quality electrophotographic images can be stably produced. It becomes easy to form.

<Toner>
Next, the average particle size of the number of toners is 4.0 μm or more and 10.0 μm or less. When the number average particle diameter is in this range, the convex portion of the toner surface formed by the organosilicon polymer described later and the convex portion of the conductive member can be efficiently meshed with each other and uniformly recharged.
If it is smaller than 4.0 μm, the toner particles and the matrix come close to each other, and the toner particles easily adhere to each other, making it difficult to roll, so that rapid charging does not occur. If it is larger than 10.0 μm, it becomes difficult for one particle of the toner to have a uniform charge, and it becomes difficult for the toner to move toward the electrophotographic photosensitive member.
The average particle size of the number of toners is preferably 5.0 μm or more and 8.0 μm or less.

The toner includes toner mother particles and toner particles having an organosilicon polymer on the surface of the toner mother particles. The organosilicon polymer has a structure represented by the following formula (1).
R-SiO _3/2 (1)
In the formula, R is an alkyl group or a phenyl group having 1 or more and 6 or less carbon atoms.
The organosilicon polymer forms convex portions on the surface of the toner particles.
In the structure represented by the formula (1), R is preferably an alkyl group having 1 or more and 6 or less carbon atoms, and more preferably an alkyl group having 1 or more and 3 or less carbon atoms.
As the alkyl group having 1 or more and 3 or less carbon atoms, a methyl group, an ethyl group and a propyl group can be preferably exemplified. More preferably, R is a methyl group.

The organosilicon polymer is preferably in surface contact with the surface of the toner matrix particles. By surface contact, the movement, desorption, and burial of the convex portion due to the organosilicon polymer can be suppressed. As a result, maintenance of chargeability and fluidity can be achieved at a high level through long-term use. Even if the toner has passed through the cleaning blade after being used for a long period of time, the convex portion remains firmly on the surface of the toner particles, so that the gear effect between the toner and the conductive member can be maintained.
If the outer surface of the toner particles does not have a convex portion formed by the organosilicon polymer, the nip portion cannot sufficiently roll and the toner cannot be sufficiently charged.

Further, the adhesion rate of the organosilicon polymer to the toner matrix particles is 80% by mass or more.
If the sticking rate is less than 80% by mass, the detached protrusion contaminates the conductive member, and the charge applying ability is lowered. Further, after durability, convex portions are less likely to remain uniformly on the surface of the toner particles, and when the cleaning blade is passed through, it is difficult to roll, and toner fusion occurs.
The adhesion rate is preferably 85% by mass or more, and more preferably 90% by mass or more. On the other hand, the upper limit is not particularly limited, but is preferably 100% by mass or less, and more preferably 99% by mass or less.

With respect to the cross-sectional image of the toner particles obtained by the scanning transmission electron microscope STEM, when the contour line of the toner mother particles is developed in a straight line to obtain a developed image of the cross-sectional image,
In the developed image,
Let L be the length of the straight line.
When the length of the line segment forming the boundary between the convex portion and the toner mother particle on the straight line is the convex width w, the ratio of the total sum Σw of the convex width w to the L (Σw / L) needs to be 0.30 or more and 0.95 or less.

Σw / L is a value expressing how much the surface of the toner particles is covered with the organosilicon polymer. When Σw / L is small, the coating with the organosilicon polymer is small, and when Σw / L is large, the coating with the organosilicon polymer is large.
If Σw / L is less than 0.30, the meshing between the convex portion of the conductive member and the convex portion of the toner is insufficient and the rolling is insufficient, so that the member is contaminated. When Σw / L is larger than 0.95, the unevenness on the surface of the toner particles is reduced, so that a phenomenon such as slip occurs, the engagement between the toner and the conductive member is insufficient, and the member is contaminated.
Σw / L is preferably 0.45 or more and 0.80 or less.

These fixation rates and Σw / L can be controlled by a method for producing an organosilicon polymer, which will be described later, specifically, a hydrolysis temperature, the number of copies of alkoxysilane used as a raw material, a pH at the time of hydrolysis and polymerization, and the like.

Further, the maximum length of the convex portion is defined as the convex diameter D in the normal direction of the convex width w, and the length from the apex of the convex portion to the straight line in the line segment forming the convex diameter D is the convex height H. When
The convex portion includes a "specific height convex portion" having a convex height H of 40 nm or more and 300 nm or less.
Among the specific height convex portions, the ratio D / w of the convex diameter D to the convex width w is 0.33 or more and 0.80 or less, and the number ratio P (D / w) of the specific height convex portions is It is preferably 50% by number or more.

In order to show the degree of surface contact between the surface of the toner particles and the convex portion, the cross section of the toner is observed by STEM. FIGS. 1 to 4 show a schematic view of the convex portion on the surface of the toner particles.
1 shown in FIG. 1 is a STEM image, which shows about 1/4 of the toner particles, 2 is a toner mother particle, 3 is a toner mother particle surface, and 4 is a convex portion. Further, in FIGS. 2 to 4, 5 is a convex width w, 6 is a convex diameter D, and 7 is a convex height H.
The cross-sectional image of the toner particles is observed, and the contour lines of the toner mother particles are developed in a straight line to obtain a developed image of the cross-sectional image. In the developed image, the length of the straight line is L. The length of the line segment of the portion forming the boundary between the convex portion and the toner mother particle on the straight line is defined as the convex width w. Further, the maximum length of the convex portion in the normal direction of the convex width w is defined as the convex diameter D, and the length from the apex of the convex portion to the straight line in the line segment forming the convex diameter D is defined as the convex height H.

In FIGS. 2 and 4, the convex diameter D and the convex height H are the same, and in FIG. 3, the convex diameter D is larger than the convex height H.
Further, FIG. 4 schematically shows a fixed state of particles similar to bowl-shaped particles in which the central portion of the hemispherical particles is recessed, which is obtained by crushing or breaking the hollow particles. In FIG. 4, the convex width w is the total length of the organosilicon polymer in contact with the surface of the toner matrix particles. That is, the convex width w in FIG. 4 is the sum of W1 and W2.
Based on the above conditions, if the ratio D / w of the convex diameter D to the convex width w of the convex portion of the organosilicon polymer is 0.33 or more and 0.80 or less, it is moved, desorbed, or desorbed. We found that it was difficult to bury.
Further, when the number ratio P (D / w) is 50% or more, the convex portion remains firmly in the toner that has passed through the cleaning, and it becomes easy to maintain the gear effect between the toner and the conductive member. As a result, it is easy to suppress contamination of the conductive member.

It is considered that a convex portion having a diameter of 40 nm or more is likely to cause a gear effect with the conductive member. On the other hand, it is considered that the effect of suppressing movement, desorption, and burial is remarkably exhibited through the durability evaluation because of the convex portion of 300 nm or less.
It was found that when the number ratio P (D / w) is 50% by number or more as the ratio of the convex portions of 40 nm or more and 300 nm or less, the toner adhering to the conductive member is likely to be uniformly recharged.
P (D / w) is preferably 75% by number or more, and more preferably 80% by number or more. On the other hand, the upper limit is not particularly limited, but is preferably 95% by number or less, and more preferably 90% by number or less.

Further, from the viewpoint of improving durability stability and gear effect, the convex height H is cumulatively distributed in the "specific height convex portion" having the convex height H of 40 nm or more and 300 nm or less, and the convex height H is taken. When the convex height, which is 80% by total from the smaller height H, is defined as H80, the H80 is preferably 65 nm or more. It is more preferably 70 nm or more, and further preferably 73 nm or more.
The upper limit is not particularly limited, but is preferably 120 nm or less, more preferably 100 nm or less, and further preferably 90 nm or less.

In the observation of the toner by the scanning electron microscope SEM, when the maximum diameter of the convex portion of the organosilicon polymer is the convex diameter R, the number average diameter of the convex diameter R is preferably 20 nm or more and 80 nm or less. More preferably, it is 35 nm or more and 60 nm or less.

The organosilicon polymer is preferably a polycondensation polymer of an organosilicon compound having a structure represented by the following formula (Z).

(In the formula (Z), R ₁ represents a hydrocarbon group (preferably an alkyl group) having 1 or more carbon atoms and 6 or less carbon atoms, and R ₂ , R ₃ and R ₄ are independent halogen atoms and hydroxy groups, respectively. , Acetoxy group, or alkoxy group.)
R ₁ is preferably an aliphatic hydrocarbon group having 1 or more and 3 or less carbon atoms, and more preferably a methyl group.

R ₂ , R ₃ and R ₄ are independently halogen atoms, hydroxy groups, acetoxy groups, or alkoxy groups (hereinafter, also referred to as reactive groups). These reactive groups are hydrolyzed, addition polymerized and polycondensed to form a crosslinked structure.
The hydrolyzability is mild at room temperature, and from the viewpoint of the precipitation property of the toner matrix particles on the surface, an alkoxy group having 1 to 3 carbon atoms is preferable, and a methoxy group or an ethoxy group is more preferable.
Further, _{the hydrolysis, addition polymerization and condensation polymerization of R 2} , R ₃ and R ₄ can be controlled by the reaction temperature, reaction time, reaction solvent and pH. In order to obtain the organosilicon polymer used in the present invention, an organosilicon compound having _three reactive groups (R ₂ , R 3 and R _{4 ) in one molecule other than R 1 in the above formula (Z) is obtained.} (Hereinafter, also referred to as trifunctional silane) may be used alone or in combination of two or more.

Examples of the compound represented by the above formula (Z) include the following.
Methyltrimethoxysilane, Methyltriethoxysilane, Methyldiethoxymethoxysilane, Methylethoxydimethoxysilane, Methyltrichlorosilane, Methylmethoxydichlorosilane, Methylethoxydichlorosilane, Methyldimethoxychlorosilane, Methylmethoxyethoxychlorosilane, Methyldiethoxychlorosilane, Methyl Triacetoxysilane, Methyldiacetoxymethoxysilane, Methyldiacetoxyethoxysilane, Methylacetoxydimethoxysilane, Methylacetoxymethoxyethoxysilane, Methylacetoxydiethoxysilane, Methyltrihydroxysilane, Methylmethoxydihydroxysilane, Methylethoxydihydroxysilane, Methyldimethoxy Trifunctional methylsilanes such as hydroxysilanes, methylethoxymethoxyhydroxysilanes and methyldiethoxyhydroxysilanes.
Ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltri Trifunctional such as methoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane. Sexual silane.
Trifunctional phenylsilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, and phenyltrihydroxysilane.

Further, an organosilicon polymer obtained by using the following in combination with an organosilicon compound having a structure represented by the formula (Z) may be used to the extent that the effect of the present invention is not impaired. Organosilicon compounds having four reactive groups in one molecule (tetrafunctional silane), organosilicon compounds having two reactive groups in one molecule (bifunctional silane) or organosilicon compounds having one reactive group (bifunctional silane) Monofunctional silane). For example, the following can be mentioned.
Dimethyldiethoxysilane, tetraethoxysilane, hexamethyldisilazane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriemethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-amino) Ethyl) Aminopropyltriethoxysilane, Vinyltriisocyanasilane, Vinyltrimethoxysilane, Vinyltriethoxysilane, Vinyldiethoxymethoxysilane, Vinylethoxydimethoxysilane, Vinylethoxydihydroxysilane, Vinyldimethoxyhydroxysilane, Vinylethoxymethoxyhydroxysilane, A trifunctional vinylsilane, such as vinyldiethoxyhydroxysilane.

Further, the content of the organosilicon polymer in the toner particles is preferably 1.0% by mass or more and 10.0% by mass or less, and more preferably 2.5% by mass or more and 6.0% by mass or less. ..

As a preferable method for forming the above-mentioned specific convex shape on the surface of the toner particles, an organosilicon compound is added to the place where the toner mother particles are dispersed in an aqueous medium to obtain a toner mother particle dispersion liquid to form a convex shape to disperse the toner particles. A method of obtaining a liquid can be mentioned.

The solid content concentration of the toner mother particle dispersion is preferably adjusted to 25% by mass or more and 50% by mass or less. The temperature of the toner mother particle dispersion is preferably adjusted to 35 ° C. or higher. Further, it is preferable to adjust the pH of the toner mother particle dispersion liquid to a pH at which condensation of the organosilicon compound does not easily proceed. Since the pH at which the condensation of the organosilicon polymer is difficult to proceed differs depending on the substance, the pH at which the reaction is most difficult to proceed is preferably within ± 0.5.

On the other hand, it is preferable to use an organosilicon compound that has been hydrolyzed. For example, it is hydrolyzed in a separate container as a pretreatment for the organosilicon compound. When the amount of the organosilicon compound is 100 parts by mass, the concentration of hydrolysis is preferably 40 parts by mass or more and 500 parts by mass or less of water from which ions have been removed such as ion-exchanged water and RO water, and 100 parts by mass or more and 400 parts by mass. The following is more preferable. The conditions for hydrolysis are preferably pH 2 to 7, temperature 15 to 80 ° C., and time 30 to 600 minutes.

The obtained hydrolysis liquid and the toner mother particle dispersion liquid are mixed to adjust the pH to a pH suitable for condensation (preferably 6 to 12, or 1 to 3, more preferably 8 to 12). By adjusting the amount of the hydrolysis liquid to 5.0 parts by mass or more and 30.0 parts by mass or less of the organosilicon compound with respect to 100 parts by mass of the toner mother particles, it becomes easy to form a convex shape. The temperature and time for the formation and condensation of the convex shape are preferably 35 ° C. to 99 ° C. and held for 60 minutes to 72 hours.

Further, in controlling the convex shape of the surface of the toner particles, it is preferable to adjust the pH in two steps. The convex shape on the surface of the toner particles can be controlled by appropriately adjusting the holding time before adjusting the pH and the holding time before adjusting the pH in the second step to condense the organosilicon compound. For example, it is preferable to hold the mixture at pH 4.0 to 6.0 for 0.5 hours to 1.5 hours and then at pH 8.0 to 11.0 for 3.0 hours to 5.0 hours. The convex shape can also be controlled by adjusting the condensation temperature of the organosilicon compound in the range of 35 ° C. to 80 ° C.
For example, the convex width w can be controlled by the amount of the organosilicon compound added, the reaction temperature, the reaction pH of the first step, the reaction time, and the like. For example, the longer the reaction time in the first stage, the larger the convex width tends to be.
The convex diameter D and the convex height H can be controlled by the hydrolysis temperature of the organosilicon compound, the amount of the organosilicon polymer added, the reaction temperature, the pH of the second step, and the like. For example, when the hydrolysis temperature is high, the convex height H tends to be large. Further, when the reaction pH in the second step is high, the convex diameter D and the convex height H tend to be large.

Hereinafter, specific methods for producing toner will be described, but the present invention is not limited to these.
It is preferable that the toner mother particles are produced in an aqueous medium to form convex portions containing an organosilicon polymer on the surface of the toner mother particles.
As a method for producing the toner matrix particles, a suspension polymerization method, a dissolution suspension method, and an emulsion aggregation method are preferable, and the suspension polymerization method is more preferable. In the suspension polymerization method, the organosilicon polymer is easily precipitated uniformly on the surface of the toner matrix particles, and the organosilicon polymer has excellent adhesiveness, environmental stability, charge amount reversal component suppressing effect, and durability and durability thereof. Become good. Hereinafter, the suspension polymerization method will be further described.

In the suspension polymerization method, a polymerizable monomer composition containing a polymerizable monomer capable of producing a binder resin and, if necessary, an additive such as a colorant is granulated in an aqueous medium, and the composition is granulated. This is a method for obtaining toner matrix particles by polymerizing the polymerizable monomer contained in the polymerizable monomer composition.
A mold release agent or other resin may be added to the polymerizable monomer composition, if necessary. Further, after the completion of the polymerization step, the produced particles can be recovered by washing and filtration by a known method. The temperature may be raised in the latter half of the polymerization step. Further, in order to remove the unreacted polymerizable monomer or by-product, it is also possible to distill off a part of the dispersion medium from the reaction system in the latter half of the polymerization step or after the completion of the polymerization step.
It is preferable to use the toner mother particles thus obtained to form convex portions of the organosilicon polymer by the above method.

A mold release agent may be used as the toner. Examples of the release agent include the following.
Paraffin wax, microcrystallin wax, petroleum wax and its derivatives such as petrolatum, Montan wax and its derivatives, hydrocarbon wax and its derivatives by the Fisher Tropsch method, polyolefin wax and its derivatives such as polyethylene and polypropylene, carnauba wax, Natural waxes and derivatives thereof such as candelilla wax, fatty acids such as higher aliphatic alcohols, stearic acids, palmitic acid, or acid amides, esters or ketones thereof, hardened castor oil and derivatives thereof, plant waxes, animal products. Wax, hydrocarbon resin.
Derivatives include oxides, block copolymers with vinyl-based monomers, and graft-modified products. The release agent may be used alone or in combination of two or more.
The content of the release agent is preferably 2.0 parts by mass or more and 30.0 parts by mass or less with respect to 100 parts by mass of the binder resin or the polymerizable monomer that produces the binder resin.

As other resins, for example, the following resins can be used.
Monopolymers of styrene and its substituents such as polystyrene and polyvinyltoluene; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalin copolymer, styrene-methylacrylate copolymer, styrene -Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-methacrylic acid Ethyl copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer Styrene-based copolymers such as coalesced, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethylmethacrylate, polybutylmethacrylate, poly Vinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic type Styrene. These may be used alone or in combination of two or more.

As the polymerizable monomer, the vinyl-based polymerizable monomer shown below can be preferably exemplified.
Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- Styrene derivatives such as n-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-phenylstyrene; methyl acrylate , Ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n -Acrylic polymerizable monomers such as nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate , N-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate. Methacrylic polymerizable monomers such as diethyl phosphate ethyl methacrylate and dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butylate, vinyl acrylate, etc. Vinyl ester; Vinyl ether such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropyl ketone.
Among these vinyl monomers, styrene, styrene derivatives, acrylic-based polymerizable monomers and methacrylic-based polymerizable monomers are preferable.

Further, a polymerization initiator may be added when the polymerizable monomer is polymerized. Examples of the polymerization initiator include the following.
2,2'-azobis- (2,4-divaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis Azo-based or diazo-based polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyloxycarbonate, cumene hydroperoxide, 2,4- Peroxide-based polymerization initiators such as dichlorobenzoyl peroxide and lauroyl peroxide.
These polymerization initiators are preferably added in an amount of 0.5 parts by mass to 30.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer, and may be used alone or in combination of two or more.

Further, in order to control the molecular weight of the binder resin constituting the toner matrix particles, a chain transfer agent may be added when the polymerizable monomer is polymerized. The preferable amount to be added is 0.001 part by mass to 15.000 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

On the other hand, in order to control the molecular weight of the binder resin constituting the toner matrix particles, a cross-linking agent may be added when the polymerizable monomer is polymerized. For example, the following can be mentioned.
Divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 -Hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene Glycol diacrylate, polyester type diacrylate (MANDA Nipponka), and the above acrylate converted to methacrylate.
Examples of the polyfunctional crosslinkable monomer include the following. Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis (4-methacryloxy-polyethoxyphenyl) propane, diacrylic phthalate, Triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl chlorendate.
The preferable amount to be added is 0.001 part by mass to 15.000 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

When the medium used in the suspension polymerization is an aqueous medium, the following can be used as the dispersion stabilizer for the particles of the polymerizable monomer composition.
Tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina ..
In addition, examples of the organic dispersant include the following. Polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, starch.
It is also possible to use commercially available nonionic, anionic and cationic surfactants. Examples of such a surfactant include the following. Sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate.

A colorant may be used as the toner, and a known toner may be used without particular limitation.
The content of the colorant is preferably 3.0 parts by mass to 15.0 parts by mass with respect to 100 parts by mass of the binder resin or the polymerizable monomer.

A charge control agent can be used during toner production, and known ones can be used. The amount of these charge control agents added is preferably 0.01 parts by mass to 10.00 parts by mass with respect to 100 parts by mass of the binder resin or the polymerizable monomer.

The toner particles may be used as they are as toner, or various organic or inorganic fine powders may be externally added to the toner particles, if necessary. The organic or inorganic fine powder preferably has a particle size of 1/10 or less of the weight average particle size of the toner particles from the viewpoint of durability when added to the toner particles.
As the organic or inorganic fine powder, for example, the following is used.
(1) Fluidity imparting agent: silica, alumina, titanium oxide, carbon black and carbon fluoride.
(2) Abrasive: Metal oxide (for example, strontium titanate, cerium oxide, alumina, magnesium oxide, chromium oxide), nitride (for example, silicon nitride), carbide (for example, silicon carbide), metal salt (for example, calcium sulfate, sulfuric acid) Barium, calcium carbonate).
(3) Lubricants: Fluorine-based resin powder (for example, vinylidene fluoride, polytetrafluoroethylene), fatty acid metal salt (for example, zinc stearate, calcium stearate).
(4) Charge control particles: metal oxides (for example, tin oxide, titanium oxide, zinc oxide, silica, alumina), carbon black.

Surface treatment of organic or inorganic fine powder may be performed in order to improve the fluidity of the toner and make the charge uniform. Examples of the treatment agent for hydrophobizing organic or inorganic fine powders include unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, and other organosilicon compounds. Includes organosilicon compounds. These treatment agents may be used alone or in combination of two or more.

<Process cartridge>
The process cartridge has the following aspects.
A process cartridge that can be attached to and detached from the main body of the electrophotographic device.
The process cartridge develops a charging device for charging the surface of the electrophotographic photosensitive member and an electrostatic latent image formed on the surface of the electrophotographic photosensitive member with toner, and the toner image is displayed on the surface of the electrophotographic photosensitive member. Has a developing device for forming
The developing device has toner and
The charging device has a conductive member arranged so as to be in contact with the electrophotographic photosensitive member.
The above-mentioned toner and conductive member can be applied to this process cartridge.
The process cartridge may have a frame for supporting the charging device and the developing device.

FIG. 9 is a schematic cross-sectional view of a process cartridge for electrophotographic that includes a conductive member as a charging roller. This process cartridge integrates a developing device and a charging device, and is configured to be removable from the main body of the electrophotographic device.
The developing apparatus includes at least a developing roller 93 and a toner 99. The developing apparatus may integrate a toner supply roller 94, a toner container 96, a developing blade 98, and a stirring blade 910, if necessary.
The charging device may include at least a charging roller 92, and may include a cleaning blade 95 and a waste toner container 97. Since the conductive member may be arranged so as to be in contact with the electrophotographic photosensitive member, the electrophotographic photosensitive member (photosensitive drum 91) may be integrated with the charging device as a component of the process cartridge, or may be electronic. It may be fixed to the main body as a component of the photographic apparatus.
A voltage is applied to each of the charging roller 92, the developing roller 93, the toner supply roller 94, and the developing blade 98.

<Electrographer>
The electrophotographic apparatus has the following aspects.
Electrophotographic photosensitive member,
A charging device for charging the surface of the electrophotographic photosensitive member and an electrostatic latent image formed on the surface of the electrophotographic photosensitive member are developed with toner to form a toner image on the surface of the electrophotographic photosensitive member. An electrophotographic apparatus having a developing apparatus for
The charging device has a conductive member arranged so as to be in contact with the electrophotographic photosensitive member.
The above-mentioned toner and conductive member can be applied to this electrophotographic apparatus.
Electrographer
An image exposure apparatus for irradiating the surface of the electrophotographic photosensitive member with image exposure light to form an electrostatic latent image on the surface of the electrophotographic photosensitive member.
A transfer device for transferring a toner image formed on the surface of the electrophotographic photosensitive member to a recording medium, and a fixing device for fixing the toner image transferred to the recording medium on the recording medium.
May have.

FIG. 10 is a schematic configuration diagram of an electrophotographic apparatus using a conductive member as a charging roller. This electrophotographic apparatus is a color electrophotographic apparatus in which four process cartridges are detachably attached. Black, magenta, yellow, and cyan toners are used in each process cartridge.
The photosensitive drum 101 rotates in the direction of the arrow and is uniformly charged by the charging roller 102 to which a voltage is applied from the charging bias power supply, and an electrostatic latent image is formed on the surface by the exposure light 1011. On the other hand, the toner 109 stored in the toner container 106 is supplied to the toner supply roller 104 by the stirring blade 1010 and conveyed onto the developing roller 103.
Then, the developing blade 108 arranged in contact with the developing roller 103 uniformly coats the toner 109 on the surface of the developing roller 103, and the toner 109 is charged by triboelectric charging. The electrostatic latent image is developed by applying toner 109 conveyed by a developing roller 103 that is placed in contact with the photosensitive drum 101, and is visualized as a toner image.

The visualized toner image on the photosensitive drum is transferred to the intermediate transfer belt 1015 which is supported and driven by the tension roller 1013 and the intermediate transfer belt drive roller 1014 by the primary transfer roller 1012 to which a voltage is applied by the primary transfer bias power supply. Toner. Toner images of each color are sequentially superimposed, and a color image is formed on the intermediate transfer belt.
The transfer material 1019 is fed into the apparatus by the paper feed roller and conveyed between the intermediate transfer belt 1015 and the secondary transfer roller 1016. A voltage is applied to the secondary transfer roller 1016 from the secondary transfer bias power supply, and the color image on the intermediate transfer belt 1015 is transferred to the transfer material 1019. The transfer material 1019 on which the color image is transferred is fixed by the fixing device 1018, and is discarded outside the apparatus to complete the printing operation.
On the other hand, the toner remaining on the photosensitive drum without being transferred is scraped off by the cleaning blade 105 and stored in the waste toner storage container 107, and the cleaned photosensitive drum 101 repeats the above steps. Further, the toner remaining on the primary transfer belt without being transferred is also scraped off by the cleaning device 1017.

<Cartridge set>
The cartridge set has the following aspects.
A cartridge set having a first cartridge and a second cartridge that can be attached to and detached from the main body of the electrophotographic apparatus.
The first cartridge has a charging device for charging the surface of the electrophotographic photosensitive member and a first frame for supporting the charging device.
The second cartridge has a toner container containing toner for developing an electrostatic latent image formed on the surface of the electrophotographic photosensitive member to form a toner image on the surface of the electrophotographic photosensitive member. ,
The charging device has a conductive member arranged so as to be in contact with the electrophotographic photosensitive member.
The above-mentioned toner and conductive member can be applied to this cartridge set.

Since the conductive member may be arranged so as to be in contact with the electrophotographic photosensitive member, the first cartridge may include the electrophotographic photosensitive member, or the electrophotographic photosensitive member is fixed to the main body of the electrophotographic apparatus. You may. For example, the first cartridge comprises an electrophotographic photosensitive member, a charging device for charging the surface of the electrophotographic photosensitive member, and a first frame for supporting the electrophotographic photosensitive member and the charging device. You may be doing it. The second cartridge may include an electrophotographic photosensitive member.
The first cartridge or the second cartridge may include a developing device for forming a toner image on the surface of the electrophotographic photosensitive member. The developing device may be fixed to the main body of the electrophotographic device.

The methods for measuring various physical properties will be described below.
<Method of measuring domain volume>
The volume of the domain can be determined by measuring the conductive layer in three dimensions using FIB-SEM.
What is FIB-SEM? A sample is processed with a FIB (Focused Ion Beam) device, and the exposed cross section is SEM (scanning electron).
It is a method of observing using a microscope (scanning electron microscope). In order to investigate the three-dimensional structure, after repeating continuous processing and observation to acquire a large number of photographs, the SEM image is subjected to 3D reconstruction processing with computer software to obtain a three-dimensional sample structure. Build as a statue.
As a specific method for measuring the domain volume, a three-dimensional stereoscopic image is acquired using FIB-SEM (manufactured by FII) and confirmed from the image.
Sampling of the conductive layer is performed from any nine locations. In the case of a roller shape, when the length in the longitudinal direction is L, the circumference of the roller is 3 places each near (1/4) L, (2/4) L, and (3/4) L from the end. One sample is cut out from each of each 120 degrees in the direction.
Then, a three-dimensional measurement using FIB-SEM is performed, and an image of a cube shape having a side of 9 μm is measured at intervals of 60 nm. Here, the cross section of the conductive layer in each of the cross sections of (1/4) L, (2/4) L, and (3/4) L is set every 120 degrees in the circumferential direction of the roller from the core metal position to the surface of the conductive layer. Make measurements at the center of the distance.
In addition, in order to preferably observe the domain structure, pretreatment may be performed so that the contrast between the domain and the matrix can be preferably obtained. Here, the dyeing treatment can be preferably used.
Using the 3D visualization / analysis software Aviso (registered trademark, manufactured by FII), the images obtained thereafter are displayed on one side of 27 cubes having a side of 9 μm. Calculate the volume of the domain in the unit cube of 3 μm.
The distance between adjacent wall surfaces of the domain can also be measured in the same manner using the above 3D visualization / analysis software, and after obtaining the above measured values, it can be calculated by the arithmetic mean of the total of 27 samples. it can.

<Measurement method of SP value>
The SP value can be calculated accurately by creating a calibration curve using a material having a known SP value. As this known SP value, the catalog value of the material manufacturer can also be used. For example, for NBR and SBR, the SP value is almost determined by the content ratio of acrylonitrile and styrene regardless of the molecular weight.
Therefore, the rubber constituting the matrix and the domain is analyzed for the content ratio of acrylonitrile or styrene by using an analysis method such as pyrolysis gas chromatography (Py-GC) and solid-state NMR. Thereby, the SP value can be calculated from the calibration curve obtained from the material whose SP value is known.
The isoprene rubber is an isomer such as 1,2-polyisoprene, 1,3-polyisoprene, 3,4-polyisoprene, and cis-1,4-polyisoprene, trans-1,4-polyisoprene. The structure determines the SP value. Therefore, the isomer content ratio can be analyzed by Py-GC, solid-state NMR, or the like in the same manner as SBR and NBR, and the SP value can be calculated from a material having a known SP value.
The SP value of the material whose SP value is known is obtained by the Hansen sphere method.

<Method of observing the cross section of toner with a scanning transmission electron microscope (STEM)>
The cross section of the toner observed with a scanning transmission electron microscope (STEM) is prepared as follows.
Hereinafter, the procedure for producing the cross section of the toner will be described.
First, the toner is sprayed on a cover glass (Matsunami Glass Co., Ltd., square cover glass; square No. 1) so as to form a single layer, and an osmium plasma coater (filgen Co., Ltd., OPC80T) is used to apply Os to the toner as a protective film. A film (5 nm) and a naphthalene film (20 nm) are applied.
Next, a PTFE tube (inner diameter Φ1.5 mm × outer diameter Φ3 mm × 3 mm) is filled with a photocurable resin D800 (JEOL Ltd.), and the cover glass is placed on the tube with toner to make the photocurable resin D800. Place it quietly in a contacting orientation. After irradiating light in this state to cure the resin, the cover glass and the tube are removed to form a cylindrical resin in which toner is embedded on the outermost surface.
4 when the radius of the toner (for example, weight average particle size (D4)) from the outermost surface of the cylindrical resin is 8.0 μm at a cutting speed of 0.6 mm / s by an ultrasonic ultramicrotome (Leica, UC7). Cut by a length of .0 μm) to obtain a cross section of the central part of the toner.
Next, cutting is performed so that the film thickness is 100 nm, and a flaky sample of the cross section of the toner is prepared. By cutting by such a method, a cross section of the toner center portion can be obtained.
Images are acquired with a STEM probe size of 1 nm and an image size of 1024 x 1024 pixels. In addition, the controller of the Director Control panel of the bright field image
The image is acquired by adjusting ast to 1425, Brightness to 3750, Image Control panel Contrast to 0.0, Brightness to 0.5, and Gammma to 1.00. The image magnification is 100,000 times, and the image is acquired so as to fit in about one-fourth to one-half of the circumference of the cross section in one toner particle as shown in FIG.

The obtained image is subjected to image analysis using image processing software (image J (available from https://imagej.nih.gov/ij/)), and the convex portion containing the organosilicon polymer is measured. Image analysis is performed on 30 STEM images.
First, draw a line along the circumference of the toner matrix particle with the line drawing tool (select the Segmented line on the Line tab). The portion where the convex portion of the organosilicon polymer is buried in the toner mother particles is smoothly connected with the line assuming that the protrusion is not buried so as to maintain the curvature around the toner mother particles.
Convert the line to a straight line (select Selection on the Edit tab, change the line width to 500pixel in Properties, then select Selection on the Edit tab and perform Straightener).
As a result, a developed image in which the contour lines of the toner mother particles are developed in a straight line can be obtained. In the developed image, the convex width w, the convex diameter D, and the convex height H are measured for each convex portion containing the organosilicon polymer.
In the developed image, the length of the straight line is L. L corresponds to the length of the surface of the toner matrix particles in the STEM image. The length of the line segment of the portion forming the boundary between the convex portion and the toner mother particle on the straight line is defined as the convex width w. Further, the maximum length of the convex portion in the normal direction of the convex width w is defined as the convex diameter D, and the length from the apex of the convex portion (the apex outside the toner particle) to the straight line in the line segment forming the convex diameter D is defined. The convex height is H.

Let Σw be the total value of the convex width w of the “specific height convex portion” in which the convex height H existing in the developed image used for the image analysis is 40 nm or more and 300 nm or less. Σw / L is calculated from one image, and the arithmetic mean value of 30 STEM images is adopted.
Further, P (D / w) is calculated from the result of measuring 30 STEM images. H80 is calculated by taking the cumulative distribution of the convex height H.
The detailed measurement of the convex portion is as described above and FIGS. 2 to 4.
The measurement is performed after overlaying the scale on the image with Image J on the Straight Line of the Straight tab and setting the length of the scale on the image with the Set Scale of the Analyze tab. A line segment corresponding to the convex width w or the convex height H can be drawn with the Straight Line of the Straight tab and measured with the Measure of the Analyze tab.

<Calculation method of average particle size (convex diameter R) of convex parts in scanning electron microscope (SEM)>
The method of SEM observation is as follows. This is performed using images taken by the Hitachi ultra-high resolution field emission scanning electron microscope S-4800 (Hitachi High-Technologies Corporation). The image capturing conditions of S-4800 are as follows.
(1) Sample preparation A conductive paste (TED PELLA, Inc, Product No. 16053, PELCO Colloidal Graphite, Isopropanol base) is thinly applied to a sample table (aluminum sample table 15 mm × 6 mm), and toner is sprayed on the conductive paste. Further air blow is performed to remove excess toner from the sample table, and then platinum is vapor-deposited at 15 mA for 15 seconds. Set the sample table in the sample holder and adjust the sample table height to 30 mm with the sample height gauge.

(2) Setting of observation conditions for S-4800 Inject liquid nitrogen into the anti-contamination trap attached to the housing of S-4800 until it overflows, and leave it for 30 minutes. Start up "PC-SEM" of S-4800 and perform flushing (cleaning of FE chip which is an electron source). Click the acceleration voltage display part of the control panel on the screen and press the [Flushing] button to open the flushing execution dialog. Confirm that the flushing intensity is 2, and execute. Confirm that the emission current due to flushing is 20 to 40 μA. Insert the sample holder into the sample chamber of the S-4800 housing. Press [Origin] on the control panel to move the sample holder to the observation position.
Click the acceleration voltage display to open the HV setting dialog, and set the acceleration voltage to [2.0 kV] and the emission current to [10 μA]. In the [Basic] tab of the operation panel, set the signal selection to [SE] and select [Bottom (L)] for the SE detector to set the mode for observing the reflected electron image. Similarly, in the [Basic] tab of the operation panel, set the probe current of the electro-optical system condition block to [Normal], the focus mode to [UHR], and the WD to [8.0 mm]. Press the [ON] button on the acceleration voltage display of the control panel to apply the acceleration voltage.

(3) Focus adjustment Drag the inside of the magnification display section of the control panel to set the magnification to 5000 (5k) times. Rotate the focus knob [COARSE] on the operation panel and adjust the aperture alignment when the focus is reached to some extent. Click [Align] on the control panel to display the alignment dialog, and select [Beam]. Rotate the STIGMA / ALIGNMENT knobs (X, Y) on the operation panel to move the displayed beam to the center of the concentric circles.
Next, select [Aperture] and turn the STIGMA / ALIGNMENT knobs (X, Y) one by one to stop the movement of the image or adjust it to the minimum movement. Close the aperture dialog and focus with autofocus. This operation is repeated twice more to focus. With the midpoint of the maximum diameter of the observed particles aligned with the center of the measurement screen, drag the inside of the magnification display section of the control panel to set the magnification to 10000 (10k) times. Rotate the focus knob [COARSE] on the operation panel and adjust the aperture alignment when the focus is reached to some extent. Click [Align] on the control panel to display the alignment dialog, and select [Beam]. Rotate the STIGMA / ALIGNMENT knobs (X, Y) on the operation panel to move the displayed beam to the center of the concentric circles.
Next, select [Aperture] and turn the STIGMA / ALIGNMENT knobs (X, Y) one by one to stop the movement of the image or adjust it to the minimum movement. Close the aperture dialog and focus with autofocus. After that, the magnification is set to 50,000 (50k) times, the focus is adjusted using the focus knob and the STIGMA / ALIGNMENT knob in the same manner as above, and the focus is adjusted again by autofocus. Repeat this operation again to focus.

(4) Image saving Perform brightness adjustment in ABC mode, take a picture with a size of 640 x 480 pixels, and save it.
From the obtained SEM image, the number average diameter (D1) of the 500 convex portions having a diameter of 20 nm or more existing on the surface of the toner particles is calculated by the image processing software (image J). The measurement method is as follows.
-Measurement of the number average diameter of the convex parts of the organosilicon polymer The convex parts and the toner mother particles in the image are color-coded by binarization by particle analysis. Next, the maximum length of the selected shape is selected from the measurement commands, and the convex diameter R (maximum diameter) of one convex portion is measured. By performing this operation a plurality of times and obtaining the arithmetic mean value at 500 points, the number average diameter of the convex diameter R is calculated.

<Measurement method of fixation rate of organosilicon polymer>
160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water and dissolved in a water bath to prepare a sucrose concentrate. 31 g of the above sucrose concentrate in a centrifuge tube (capacity 50 ml), and 10 of a neutral detergent for cleaning a precision measuring instrument with a pH of 7 consisting of Contaminone N (nonionic surfactant, anionic surfactant, and organic builder). Add 6 mL of a mass% aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a dispersion. 1.0 g of toner is added to this dispersion, and the toner lumps are loosened with a spatula or the like.
The centrifuge tube is shaken on a shaker at 350 spm (strokes per min) for 20 minutes. After shaking, the solution is replaced with a glass tube for a swing rotor (capacity: 50 mL), and separated by a centrifuge (manufactured by Kokusan Co., Ltd., H-9R) at 3500 rpm for 30 minutes. Visually confirm that the toner and the aqueous solution are sufficiently separated, and collect the separated toner in the uppermost layer with a spatula or the like. The aqueous solution containing the collected toner is filtered through a vacuum filter and then dried in a dryer for 1 hour or more. The dried product is crushed with a spatula and the amount of silicon is measured by fluorescent X-ray. The adhesion rate (%) is calculated from the ratio of the amount of elements to be measured between the toner after washing with water and the initial toner.
The measurement of fluorescent X-rays of each element conforms to JIS K 0119-1969, but the specifics are as follows.

As the measuring device, the wavelength dispersive fluorescent X-ray analyzer "Axios" (manufactured by PANalytical) and the attached dedicated software "SuperQ ver.4.0F" (manufactured by PANalytical) for setting the measurement conditions and analyzing the measurement data. ) Is used. Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 10 mm, and the measurement time is 10 seconds. Further, when measuring a light element, it is detected by a proportional counter (PC), and when measuring a heavy element, it is detected by a scintillation counter (SC).
As a measurement sample, put about 1 g of toner after washing with water or initial toner in a dedicated press aluminum ring with a diameter of 10 mm and flatten it, and then flatten it with a tablet molding compressor "BRE-32" (manufactured by Maekawa Testing Machine Co., Ltd.). ) Is pressed at 20 MPa for 60 seconds, and pellets molded to a thickness of about 2 mm are used.
The measurement is performed under the above conditions, the element is identified based on the obtained peak position of X-rays, and the concentration is calculated from the counting rate (unit: cps) which is the number of X-ray photons per unit time.

As a quantification method in the toner, for example, the amount of silicon is added so that the amount of silicon is 0.5 parts by mass with respect to 100 parts by mass of toner particles, and for example, silica (SiO ₂ ) fine powder is sufficiently mixed using a coffee mill. To do. Similarly, the silica fine powder is mixed with the toner particles so as to be 2.0 parts by mass and 5.0 parts by mass, respectively, and these are used as a sample for the calibration curve.
For each sample, pellets of the sample for the calibration curve were prepared as described above using a tablet molding compressor, and when PET was used for the spectroscopic crystal, the diffraction angle (2θ) = 109.08 ° was observed. The count rate (unit: cps) of Si-Kα rays is measured. At this time, the acceleration voltage and current value of the X-ray generator are set to 24 kV and 100 mA, respectively. A calibration curve having a linear function is obtained with the obtained X-ray count rate on the vertical axis and the _{amount of SiO 2 added in each calibration curve sample on the horizontal axis.}
Next, the toner to be analyzed is pelletized as described above using a tablet molding compressor, and the count rate of Si—Kα rays is measured. Then, the content of the organosilicon polymer in the toner is determined from the above calibration curve. The ratio of the elemental amount of the toner after washing with water to the elemental amount of the initial toner calculated by the above method is calculated and used as the fixing rate (%).

<Measuring method of weight average particle size (D4) and number average particle size (D1) of toner>
The weight average particle size (D4) and the number average particle size (D1) of the toner are the precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, Beckman. Using Coulter) and the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (Beckman Coulter) for setting measurement conditions and analyzing measurement data, the number of effective measurement channels is 25,000. Measure with a channel, analyze the measurement data, and calculate.
As the electrolytic aqueous solution used for the measurement, a special grade sodium chloride dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter) can be used.
Before performing measurement and analysis, set the dedicated software as follows.
In the dedicated software "Change standard measurement method (SOM) screen", set the total count number in the control mode to 50,000 particles, measure once, and set the Kd value to "standard particles 10.0 μm" (Beckman Coulter). The value obtained using (manufactured by) is set. By pressing the threshold / noise level measurement button, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check the flash of the aperture tube after measurement.
On the "pulse to particle size conversion setting screen" of the dedicated software, the bin spacing is set to logarithmic particle size, the particle size bin is set to 256 particle size bins, and the particle size range is set from 2 μm to 60 μm.

The specific measurement method is as follows.
(1) Approximately 200 ml of the electrolytic aqueous solution is placed in a glass 250 ml round bottom beaker dedicated to Multisizer 3 and set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and air bubbles in the aperture tube are removed by the "flash of the aperture tube" function of the dedicated software.
(2) Approximately 30 ml of the electrolytic aqueous solution is placed in a 100 ml flat-bottomed beaker made of glass, and "Contaminone N" (nonionic surfactant, anionic surfactant, and organic builder) as a dispersant is used as a dispersant for precise measurement of pH 7. Add about 0.3 ml of a diluted solution obtained by diluting a 10% by mass aqueous solution of a neutral detergent for cleaning a vessel, manufactured by Wako Pure Chemical Industries, Ltd.) with ion-exchanged water 3 times by mass.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in with the phase shifted by 180 degrees, and are installed in the water tank of the ultrasonic disperser "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios) with an electrical output of 120 W. A predetermined amount of ion-exchanged water is added, and about 2 ml of the Contaminone N is added into the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner (particles) is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. In ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10 ° C. or higher and 40 ° C. or lower.
(6) Using a pipette, the electrolytic aqueous solution of (5) in which toner (particles) is dispersed is dropped onto the round bottom beaker of (1) installed in the sample stand so that the measured concentration becomes about 5%. Adjust to. Then, the measurement is performed until the number of measurement particles reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the device, and the weight average particle size (D4) or the number average particle size (D1) is calculated. In addition, when the graph / number% and graph / volume% are set by the dedicated software, the "arithmetic diameter" on the analysis / number statistic (arithmetic mean) and analysis / volume statistic (arithmetic mean) screens is the number average. The particle size (D1) and the weight average particle size (D4).

Hereinafter, the configuration according to the present disclosure will be described in more detail with reference to Examples and Comparative Examples, but the configuration according to the present disclosure is not limited to the configuration embodied in the Examples. In addition, "parts" used in Examples and Comparative Examples are based on mass unless otherwise specified.

[Manufacturing example of toner 1]
(Preparation step of aqueous medium 1)
14.0 parts of sodium phosphate (12-hydrate manufactured by Rasa Industries, Ltd.) was put into 650.0 parts of ion-exchanged water in a reaction vessel equipped with a stirrer, a thermometer, and a return pipe, and nitrogen was purged. However, the temperature was kept at 65 ° C. for 1.0 hour.
T. K. Using a homomixer (manufactured by Tokushu Kagaku Kogyo Co., Ltd.), a calcium chloride aqueous solution in which 9.2 parts of calcium chloride (dihydrate) is dissolved in 10.0 parts of ion-exchanged water is batched while stirring at 15,000 rpm. The mixture was charged to prepare an aqueous medium containing a dispersion stabilizer. Further, 10% by mass hydrochloric acid was added to the aqueous medium to adjust the pH to 5.0 to obtain the aqueous medium 1.

(Preparation step of polymerizable monomer composition)
・ Styrene: 60.0 parts ・ C.I. I. Pigment Blue 15: 3: 6.5 parts The material was put into an attritor (manufactured by Mitsui Miike Machinery Co., Ltd.), and further dispersed with zirconia particles having a diameter of 1.7 mm at 220 rpm for 5.0 hours to obtain a pigment. A dispersion was prepared. The following materials were added to the pigment dispersion.
-Styrene: 20.0 parts-n-butyl acrylate: 20.0 parts-Crosslinking agent (divinylbenzene): 0.3 parts-Saturated polyester resin: 5.0 parts (propylene oxide-modified bisphenol A (2 mol adduct) Polycondensate of terephthalic acid (molar ratio 10:12), glass transition temperature Tg = 68 ° C., weight average molecular weight Mw = 10000, molecular weight distribution Mw / Mn = 5.12)
-Fischer-Tropsch wax (melting point 78 ° C): 7.0 parts This was kept warm at 65 ° C, and T.I. K. A polymerizable monomer composition was prepared by uniformly dissolving and dispersing at 500 rpm using a homomixer (manufactured by Tokushu Kagaku Kogyo Co., Ltd.).

(Granulation process)
The temperature of the aqueous medium 1 was set to 70 ° C., and T.I. K. While maintaining the rotation speed of the homomixer at 15,000 rpm, the polymerizable monomer composition was put into the aqueous medium 1 and 10.0 parts of t-butylperoxypivalate as a polymerization initiator was added. Granulation was carried out for 10 minutes while maintaining 15,000 rpm with the stirring device as it was.

(Polymerization / distillation process)
After the granulation step, the stirrer is replaced with a propeller stirring blade, and while stirring at 150 rpm, polymerization is carried out at 70 ° C. for 5.0 hours, and the temperature is raised to 85 ° C. and heated for 2.0 hours to carry out the polymerization reaction. went.
After that, the return pipe of the reaction vessel was replaced with a cooling pipe, and the slurry was heated to 100 ° C. to carry out distillation for 6 hours to distill off the unreacted polymerizable monomer to obtain a toner mother particle dispersion. ..

(Polymerization of organosilicon compounds)
60.0 parts of ion-exchanged water was weighed in a reaction vessel equipped with a stirrer and a thermometer, and the pH was adjusted to 4.0 with 10% by mass of hydrochloric acid. This was heated with stirring to bring the temperature to 10 ° C. Then, 40.0 parts of methyltriethoxysilane, which is an organosilicon compound, was added and stirred for 2 hours or more for hydrolysis. The end point of the hydrolysis was visually confirmed that the oil and water did not separate and became one layer, and the mixture was cooled to obtain a hydrolyzed solution of an organosilicon compound.
After cooling the temperature of the obtained toner mother particle dispersion to 55 ° C., 25.0 parts of a hydrolyzate of the organosilicon compound was added to start the polymerization of the organosilicon compound. After holding for 15 minutes as it was, the pH was adjusted to 5.5 with a 3.0% aqueous sodium hydrogen carbonate solution. After holding for 60 minutes while continuing stirring at 55 ° C., the pH was adjusted to 9.5 with a 3.0% aqueous sodium hydrogen carbonate solution, and the mixture was further held for 240 minutes to obtain a toner particle dispersion.

(Washing and drying process)
After the polymerization step is completed, the toner particle dispersion is cooled, hydrochloric acid is added to the toner particle dispersion to adjust the pH to 1.5 or less, the mixture is left to stir for 1 hour, and then solid-liquid separated with a pressure filter to separate the toner cake. Got This was reslurried with ion-exchanged water to form a dispersion liquid again, and then solid-liquid separated with the above-mentioned filter to obtain a toner cake.
The obtained toner cake was dried and classified in a constant temperature bath at 40 ° C. for 72 hours to obtain toner particles 1. Table 1 shows the conditions for producing the toner particles 1.

[Manufacturing method of toner particles 2 to 8]
Toner particles 2 to 8 were obtained in the same manner as the toner particles 1 except that the conditions shown in Table 1 were changed.

[Manufacturing method of comparative toner particles (toner particles 9)]
Toner particles 9 which are comparative toner particles were obtained in the same manner as the toner particles 1 except that the polymerization of the organosilicon compound was changed as shown below.
(Polymerization of organosilicon compounds)
A mixed solvent prepared by dissolving 1.0 part of polyvinyl alcohol in 20 parts of a mixed solution of ethanol / water = 1: 1 (mass ratio) was dispersed in a toner mother particle dispersion, and then 3- (methacryloxy) as a silicon compound. Twenty parts of propyltrimethoxysilane was dissolved, and the mixture was further stirred for 5 hours to swell and internalize 3- (methacryloxy) propyltrimethoxysilane in the toner particles.
Then, after the temperature was adjusted to 70 ° C., the pH was adjusted to 9.5 with a 3.0% aqueous sodium hydrogen carbonate solution. By stirring at room temperature for 10 hours, the sol-gel reaction was allowed to proceed on the surface of the toner particles to obtain toner particles 9.

[Manufacturing method of comparative toner particles (toner particles 10)]
By not performing the polymerization of the organosilicon compound in the production example of the toner particles 1, the toner particles 10 which are the comparative toner particles were obtained.

表中、保持時間及び時間の単位はｈである。「添加量」は有機ケイ素化合物の重合工程における有機ケイ素化合物の添加量（部）である。

In the table, the holding time and the unit of time are h. The "addition amount" is the addition amount (part) of the organosilicon compound in the polymerization step of the organosilicon compound.

<Manufacturing example of conductive member 1>
[1-1. Preparation of domain-forming rubber mixture (CMB)]
Each material shown in Table 2 was mixed with a 6-liter pressurized kneader (trade name: TD6-15MDX, manufactured by Toshin Co., Ltd.) in the blending amount shown in Table 2 to obtain CMB. The mixing conditions were a filling rate of 70% by volume, a blade rotation speed of 30 rpm, and 30 minutes.

[1-2. Preparation of rubber mixture for matrix formation (MRC)]
Each material shown in Table 3 was mixed with a 6-liter pressurized kneader (trade name: TD6-15MDX, manufactured by Toshin Co., Ltd.) at the blending amount shown in Table 3 to obtain MRC. The rate was 70% by volume, the blade rotation speed was 30 rpm, and the ratio was 16 minutes.

[1-3. Preparation of unvulcanized rubber mixture for forming conductive layer]
The CMB and MRC obtained above were mixed in the blending amounts shown in Table 4 using a 6-liter pressurized kneader (trade name: TD6-15MDX, manufactured by Toshin Co., Ltd.). The mixing conditions were a filling rate of 70% by volume, a blade rotation speed of 30 rpm, and 20 minutes.

Next, the vulcanizing agent and the vulcanization accelerator shown in Table 5 were added to 100 parts of the mixture of CMB and MRC in the blending amounts shown in Table 5, and an open roll having a roll diameter of 12 inches (0.30 m) was used. It was mixed to prepare a rubber mixture for forming a conductive layer.
The mixing conditions were a front roll rotation speed of 10 rpm and a rear roll rotation speed of 8 rpm, and after turning left and right 20 times in total with a roll gap of 2 mm, thinning was performed 10 times with a roll gap of 0.5 mm.

(2. Fabrication of conductive member)
[2-1. Preparation of a support with a conductive outer surface]
As a support having a conductive outer surface, a round bar having a total length of 252 mm and an outer diameter of 6 mm was prepared by subjecting the surface of stainless steel (SUS) to electroless nickel plating.

[2-2. Molding of conductive layer]
A die with an inner diameter of 12.5 mm is attached to the tip of a crosshead extruder that has a support mechanism for supplying and a mechanism for discharging unvulcanized rubber rollers. Was adjusted to 60 mm / sec. Under these conditions, a rubber mixture for forming a conductive layer was supplied from the extruder, and the outer peripheral portion of the support was covered with the rubber mixture for forming a conductive layer in the crosshead to obtain an unvulcanized rubber roller.
Next, the unvulcanized rubber roller was put into a hot air vulcanizer at 160 ° C. and heated for 60 minutes to vulcanize the rubber mixture for forming a conductive layer, and a conductive layer was formed on the outer peripheral portion of the support. Got a roller. After that, both ends of the conductive layer were cut off by 10 mm to make the length of the conductive layer in the longitudinal direction 231 mm.

[2-3. Polishing of conductive layer]
Next, by polishing the surface of the conductive layer under the polishing conditions described in the following polishing condition 1, the diameter of the central portion is 8.5 mm, and each diameter at a position of 90 mm from the central portion to both ends is 8 A conductive member 1 having a crown shape and having a diameter of .44 mm was obtained.

(Polishing condition 1)
As a grindstone, a cylindrical grindstone (manufactured by Teiken Co., Ltd.) having a diameter of 305 mm and a length of 235 mm was prepared. The types of abrasive grains, particle size, degree of coupling, binder, and structure (abrasive grain ratio) abrasive grains are as follows.
-Abrasive grain material: GC (green silicon carbide), (JIS R6111-2002)
-Abrasive grain size: # 80 (average particle size 177 μm JIS B4130)
・ Coupling degree of abrasive grains: HH (JIS R6210)
-Binder: V4PO (Vitrified)
-Abrasive grain structure (abrasive grain ratio): 23 (abrasive grain content 16% JIS R6242)
Using the above grindstone, the surface of the conductive layer was polished under the following polishing conditions.
First, the rotation speed of the grindstone is 2100 rpm, the rotation speed of the conductive member is 250 rpm, and as a rough cutting process, the grindstone penetrates the conductive member at a speed of 20 mm / sec and then contacts the outer peripheral surface of the conductive member by 0.24 mm. Let me.
As a precision polishing step, the penetration speed is changed to 0.5 mm / sec, and after 0.01 mm penetration, the grindstone is separated from the conductive member to complete the polishing.
As the polishing method, an upper cut method is adopted in which the rotation directions of the grindstone and the conductive member are the same.

The method for measuring the physical properties of the conductive member is as follows.
[Confirmation of matrix domain structure]
The presence or absence of the formation of the matrix domain structure in the conductive layer is confirmed by the following method.
A section (thickness 500 μm) is cut out using a razor so that a cross section perpendicular to the longitudinal direction of the conductive layer of the conductive member can be observed. Next, platinum vapor deposition is performed, and a scanning electron microscope (SEM) (trade name: S-4800, manufactured by Hitachi High-Technologies Corporation) is used to take an image at 1000 times to obtain a cross-sectional image.
In the cross-sectional image, the matrix domain structure observed in the section from the conductive layer has a plurality of domains 6b dispersed in the matrix 6a and exists in an independent state without connecting the domains. Indicates the form to be used. 6c is an electron conductive agent. On the other hand, the matrix is in a state of being communicated in the image and the domain is divided by the matrix.

Further, in order to quantify the obtained captured image, an 8-bit image processing software (trade name: ImageProPlus, manufactured by Media Cybernetics) was used on the fracture surface image obtained by observation with SEM. Grayscale is performed to obtain a monochrome image with 256 gradations. Next, after inverting the black and white of the image so that the domain in the fracture surface becomes white, the binarization threshold is set for the brightness distribution of the image based on the algorithm of Otsu's discriminant analysis method. Obtain a valued image.
With the counting function for the binarized image, the domains are different from each other as described above with respect to the total number of domains existing in the area of 50 μm square and having no contact with the border of the binarized image. Calculate the number percent K of domains that are isolated without connection.
Specifically, the counting function of the image processing software is set so that domains having contacts at the borders at the ends of the binarized images in the four directions are not counted.
The conductive layer of the conductive member is evenly divided into five equal parts in the longitudinal direction, and the section is prepared from a total of 20 points, one point at an arbitrary point from each of the regions obtained by evenly dividing into four equal parts in the circumferential direction. The arithmetic mean value (number%) of K when the above measurement is performed is calculated.
When the arithmetic mean value (number%) of K is 80 or more, the matrix domain structure is evaluated as "yes", and when the arithmetic mean value (number%) of K is less than 80, it is evaluated as "none".

[Measurement of matrix volume resistivity R1]
For the volume resistivity R1 of the matrix, for example, a thin piece having a predetermined thickness (for example, 1 μm) containing the matrix domain structure is cut out from the conductive layer, and a scanning probe microscope (SPM) or a scanning probe microscope (SPM) or It can be measured by contacting a micro probe of an atomic force microscope (AFM).
The slices are cut out from the elastic layer when, for example, as shown in FIG. 3B, the longitudinal direction of the conductive member is the X-axis, the thickness direction of the conductive layer is the Z-axis, and the circumferential direction is the Y-axis. The flakes are cut out to include at least a portion of a plane parallel to the YZ plane (eg, 83a, 83b, 83c) perpendicular to the axial direction of the conductive member. Cutting can be performed using, for example, a sharp razor, a microtome, or a focused ion beam method (FIB).
For the measurement of volume resistivity, one side of the thin section cut out from the conductive layer is grounded. Next, a scanning probe microscope (SPM) or an atomic force microscope (AFM) microprobe was brought into contact with the matrix portion of the surface opposite to the ground surface of the thin section, and a DC voltage of 50 V was applied for 5 seconds. , The arithmetic average value is calculated from the value obtained by measuring the ground current value for 5 seconds, and the electric resistance value is calculated by dividing the applied voltage by the calculated value. Finally, the film thickness of the flakes is used to convert the resistance value into volume resistivity. At this time, the SPM or AFM can measure the film thickness of the thin section at the same time as the resistance value.
The value of the volume resistivity R1 of the matrix in the columnar charging member is, for example, the above-mentioned measured value obtained by cutting out one thin sample from each of the regions in which the conductive layer is divided into four in the circumferential direction and five in the longitudinal direction. After obtaining the above, it is obtained by calculating the arithmetic mean value of the volume resistivity of a total of 20 samples.
In this embodiment, first, a thin section having a thickness of 1 μm was cut out from the conductive layer of the conductive member using a microtome (trade name: Leica EM FCS, manufactured by Leica Microsystems) at a cutting temperature of -100 ° C. .. As shown in FIG. 3B, the flakes are in the axial direction of the conductive member when the longitudinal direction of the conductive member is the X-axis, the thickness direction of the conductive layer is the Z-axis, and the circumferential direction is the Y-axis. It was cut out so as to include at least a part of the YZ plane (for example, 83a, 83b, 83c) perpendicular to the YZ plane.
In an environment where the temperature is 23 ° C. and the humidity is 50% RH, one surface of the flakes (hereinafter, also referred to as “grounding surface”) is grounded on a metal plate, and the surface opposite to the grounding surface of the flakes (hereinafter, “grounding surface”). Scanning probe microscope (SPM) (trade name: Q-Scope250, manufactured by Quant Instrument Corporation), which corresponds to the matrix of the measurement surface) and where the domain does not exist between the measurement surface and the ground surface. ) Cantilever was brought into contact. Subsequently, a voltage of 50 V was applied to the cantilever for 5 seconds, the current value was measured, and the arithmetic mean value for 5 seconds was calculated.
The surface shape of the measurement section was observed by SPM, and the thickness of the measurement point was calculated from the obtained height profile. Furthermore, the concave area of the contact portion of the cantilever was calculated from the observation result of the surface shape. The volume resistivity was calculated from the thickness and the recessed area.
For the flakes, the conductive layer was divided into 5 equal parts in the longitudinal direction, and the conductive layer was divided into 4 equal parts in the circumferential direction. It was. The average value was taken as the volume resistivity R1 of the matrix.
The scanning probe microscope (SPM) (trade name: Q-Scope250, manufactured by Quant Instrument Corporation) was operated in the contact mode.

[Measurement of domain resistivity R2]
In the measurement of the volume resistivity R1 of the above matrix, the volume resistivity R2 of the domain is measured by the same method except that the measurement is performed at the location corresponding to the domain of the ultrathin section and the measurement voltage is set to 1 V. ..
In this embodiment, in the above (measurement of the volume resistivity R1 of the matrix), the place where the cantilever of the measurement surface is brought into contact corresponds to the domain and the place where the matrix does not exist between the measurement surface and the ground surface. R2 was calculated by carrying out the same method except that the voltage applied at the time of measuring the current value was changed to 1V.

[Measurement of the height of the convex part of the outer surface by the domain]
A thin section having a thickness of 1 μm is cut out from the conductive layer of the conductive member using a microtome (trade name: Leica EM FCS, manufactured by Leica Microsystems, Inc.) at a cutting temperature of -100 ° C. At this time, the flakes are made to be a plane perpendicular to the axis of the conductive support.
The cutout position from the conductive layer is L at the length in the longitudinal direction of the conductive layer, and L / 4 from both ends of the conductive layer toward the center in the longitudinal direction.
At this time, in order to confirm the convex shape derived from the domain, care should be taken not to apply any processing to the surface of the conductive member. Next, a scanning probe microscope (SPM) (trade name: MFP-3D-Origin; manufactured by Oxford Instruments) was used on the section including the surface of the conductive member obtained as described above. By measuring the surface of the conductive member under the following conditions, the profile of the electric resistance value and the shape profile are measured. -Measurement mode: AM-FM mode-Explorer: OMCL-AC160TS (trade name: manufactured by Olympus)
-Resonance frequency: 251.825-261.08 kHz
-Spring constant: 23.59 to 25.18 N / m
・ Scan speed: 0.8 to 1.5Hz
-Scan size: 10 μm, 5 μm, 3 μm
-Target April: 3V and 4V
・ Set Point: All 2V
Next, it is confirmed that the convex portion in the surface shape profile obtained by the above measurement is derived from the domain having higher conductivity than the surroundings in the electrical resistance value profile. Further, the height of the convex shape is calculated from the profile.
The calculation method is obtained by taking the difference between the arithmetic mean value of the profile of the shape derived from the domain and the arithmetic mean value of the shape profile of the adjacent matrix. The arithmetic mean value is calculated from the measured values of 50 randomly selected convex portions in each of the sections cut out from the above three locations.

[Measurement of the equivalent circle diameter D of the domain observed from the cross section of the conductive layer]
The circle-equivalent diameter D of the domain is calculated as follows.
When the length of the conductive layer in the longitudinal direction is L and the thickness of the conductive layer is T, the drawings are taken from three locations: the center of the conductive layer in the longitudinal direction and L / 4 from both ends of the conductive layer toward the center. A sample having a thickness of 1 μm having a surface showing a cross section (83a, 83b, 83c) in the thickness direction of the conductive layer as shown in 8 (b) was used as a microtom (trade name: Leica EM FCS, Leica Micro). Cut out using (manufactured by Systems).
Platinum is deposited on the cross section of the conductive layer in the thickness direction of each of the three obtained samples. Next, of the platinum-deposited surfaces of each sample, three arbitrarily selected locations within a thickness region from the outer surface of the conductive layer to a depth of 0.1 T to 0.9 T were subjected to a scanning electron microscope (SEM) (trade name). : Photographed at 5000x using S-4800, manufactured by Hitachi High-Technologies Corporation.
Each of the obtained nine captured images is binarized by image processing software (product name: ImageProPlus; manufactured by Media Cybernetics) and quantified by the counting function, and the area of the domain included in each captured image. The arithmetic mean value S of is calculated.
Next, the circle-equivalent diameter of the domain (= (4S / π) ^0.5 ) is calculated from the arithmetic mean value S of the domain area calculated for each captured image. Next, the arithmetic mean value of the circle-equivalent diameter of the domain of each photographed image is calculated to obtain the circle-equivalent diameter D of the domain observed from the cross section of the conductive layer of the conductive member to be measured.

[Measurement of domain particle size distribution]
The particle size distribution of the domain is measured as follows in order to evaluate the uniformity of the circle equivalent diameter D of the domain. First, image processing software (trade name) for a 5000x observation image obtained by measuring the circle-equivalent diameter D of the above domain with a scanning electron microscope (trade name: S-4800, manufactured by Hitachi High-Technologies Corporation). : ImageProPlus; manufactured by Media Cybernetics) to obtain a binarized image. Next, for the domain group in the binarized image, the average value D and the standard deviation σd are calculated by the counting function of the image processing software.
Next, σd / D, which is an index of the particle size distribution, is calculated.
In the measurement of the σd / D particle size distribution of the domain diameter, when the length of the conductive layer in the longitudinal direction is L and the thickness of the conductive layer is T, the center of the conductive layer in the longitudinal direction and the center from both ends of the conductive layer. The cross section in the thickness direction of the conductive layer as shown in FIG. 8 (b) is acquired at three points of L / 4 toward. Each of the three sections obtained from the above three measurement positions is 50 μm square at any three locations in the thickness region from the outer surface of the conductive layer to a depth of 0.1 T to 0.9 T, for a total of nine locations. Area is extracted as an analysis image, measurement is performed, and the arithmetic mean value of 9 places is calculated.

[Measurement of inter-domain distance Dm observed from the cross section of the conductive layer]
When the length of the conductive layer in the longitudinal direction is L and the thickness of the conductive layer is T, the figure is taken from three locations of L / 4 from the center of the conductive layer in the longitudinal direction and from both ends of the conductive layer toward the center. A sample having a surface showing a cross section (83a, 83b, 83c) in the thickness direction of the conductive layer as shown in 8 (b) is obtained.
For each of the three obtained samples, 50 μm at any three locations in the thickness region from the outer surface of the conductive layer to a depth of 0.1 T to 0.9 T on the surface where the cross section of the conductive layer in the thickness direction appears. Place analysis areas on all sides. The three analysis areas are photographed with a scanning electron microscope (trade name: S-4800, manufactured by Hitachi High-Technologies Corporation) at a magnification of 5000 times. Each of the obtained nine captured images is binarized using image processing software (trade name: LUZEX; manufactured by NIRECO CORPORATION).
The procedure for binarization is as follows. The captured image is grayscaled with 8 bits to obtain a monochrome image with 256 gradations. Then, the black and white of the image is inverted and binarized so that the domain in the captured image becomes white, and a binarized image of the captured image is obtained. Next, for each of the nine binarized images, the distance between the walls of the domain is calculated, and the arithmetic mean value thereof is calculated. Let this value be Dm. The distance between walls is the distance (shortest distance) between the walls of the closest domains, and can be obtained by setting the measurement parameter as the distance between adjacent walls in the above image processing software.

[Measurement of uniformity of inter-domain distance Dm]
From the distribution of the inter-wall distance of the domains obtained in the process of measuring the inter-domain distance Dm, the standard deviation σm of the inter-domain distance is calculated, and the coefficient of variation σm / Dm, which is an index of the uniformity of the inter-domain distance, is calculated.

[Circle-equivalent diameter Ds of the domain observed from the outer surface of the conductive layer]
The circle-equivalent diameter Ds of the domain observed from the outer surface of the conductive layer is measured as follows.
When the length of the conductive layer in the longitudinal direction is L, the microtome (trade name: Leica EM FCS, trade name: Leica EM FCS, A sample containing the outer surface of the conductive layer is cut out using a Leica Microsystems (manufactured by Leica Microsystems). The thickness of the sample is 1 μm.
Platinum is deposited on the outer surface of the conductive layer of the sample. Arbitrary three locations on the platinum-deposited surface of the sample are selected and photographed at a magnification of 5000 using a scanning electron microscope (SEM) (trade name: S-4800, manufactured by Hitachi High-Technologies Corporation). Each of the obtained 9 captured images is binarized using image processing software (trade name: ImageProPlus; manufactured by Media Cybernetics) and quantified by the counting function, and the domains included in each of the captured images. Calculate the arithmetic mean value Ss of the flat area of.
^{Next, the circle-equivalent diameter of the domain (= (4S / π) 0.5} ) is calculated from the arithmetic mean value Ss of the flat area of the domain calculated for each captured image. Next, the arithmetic mean value of the domain equivalent diameter of each captured image is calculated to obtain the domain equivalent circle diameter Ds when the conductive member to be measured is observed from the outer surface. The calculation results are shown in Table 7 as "circle equivalent diameter Ds".

[Distance between adjacent walls of the domain observed from the outer surface of the conductive member Dms]
When the length of the conductive layer in the longitudinal direction is L and the thickness of the conductive layer is T, razors are sewn from three places, the center of the conductive layer in the longitudinal direction and L / 4 from both ends of the conductive layer toward the center. Is used to cut out a sample so that the outer surface of the conductive member is included. The size of the sample is 2 mm in each of the circumferential direction and the longitudinal direction of the conductive member, and the thickness is the thickness T of the conductive member.
For each of the three obtained samples, 50 μm square analysis regions were placed at arbitrary three locations on the surface corresponding to the outer surface of the conductive member, and the three analysis regions were used as scanning electron microscopes (trade name: S). -4800, manufactured by Hitachi High-Technologies Corporation) is used to shoot at a magnification of 5000 times. Each of the obtained nine captured images is binarized using image processing software (trade name: LUZEX; manufactured by NIRECO CORPORATION).
The procedure for binarization is the same as the procedure for binarization when determining the interdomain distance Dm described above. Next, for each of the binary images of the nine captured images, the distance between the wall surfaces of the domain is obtained, and the arithmetic mean value thereof is calculated. Let this value be Dms.

<Manufacturing example of conductive members 2 to 12>
The conductive members 2 to 12 were formed in the same manner as the conductive member 1 except that the materials and conditions shown in Tables 6A-1 to 6A-4 were used for the raw rubber, the conductive agent, the vulcanizing agent, and the vulcanization accelerator. Manufactured. The details of the materials shown in Tables 6A-1 to 6A-4 are shown in Table 6B-1 for the rubber material, 6B-2 for the conductive agent, and 6B-3 for the vulcanizing agent and the vulcanization accelerator. .. Further, the polishing conditions 2 to 5 shown in Table 6A-2 are as follows.

(Polishing condition 2)
It is the same as the polishing condition 1 except that the penetration speed in the precision polishing step is set to 0.2 mm / sec.

(Polishing condition 3)
It is the same as the polishing condition 1 except that the penetration speed in the precision polishing step is 0.15 mm / sec.

(Polishing condition 4)
It is the same as the polishing condition 1 except that the penetration speed in the precision polishing step is 1.0 mm / sec.

(Polishing condition 5)
It is the same as the polishing condition 1 except that the penetration speed in the precision polishing step is 1.5 mm / sec.
Table 7 shows the measurement results and evaluation results of the obtained conductive members 1 to 12.

Regarding the Mooney viscosity in the table, the value of the raw rubber is the catalog value of each company. The value of the domain-forming rubber mixture is the Mooney viscosity ML ( _{1 + 4)} based on JIS K6300-1: 2013, and is measured at the rubber temperature when all the materials constituting the domain-forming rubber mixture are kneaded. Is.
Units of SP values, ^{(J /} cm ³⁾ is ^0.5, DBP represents a DBP oil absorption amount ^(cm 3 / 100g). Each material is shown in Tables 6B-1 to 6B-3.

表中のムーニー粘度に関し、原料ゴムの値は各社のカタログ値である。マトリックス形成用ゴム混合物のムーニー粘度の値は、ＪＩＳ Ｋ６３００−１：２０１３に基づくムーニー粘度ＭＬ_{（１＋４）}であり、マトリックス形成用ゴム混合物を構成するすべての材料を混練している時のゴム温度で測定されたものである。

Regarding the Mooney viscosity in the table, the value of the raw rubber is the catalog value of each company. The Mooney viscosity value of the matrix-forming rubber mixture is the Mooney viscosity ML _{(1 + 4)} based on JIS K6300-1: 2013, which is the rubber temperature when all the materials constituting the matrix-forming rubber mixture are kneaded. It was measured.

<Manufacturing method of conductive member 13>
As the material of the unvulcanized rubber composition, the material shown in Table 6-C1 was used, and the conductive base material C13 was produced in the same manner as in Example 1 except that the material was polished under the polishing condition 2.
Next, according to the following method, a conductive resin layer was further provided on the conductive layer base material C13 to manufacture the conductive member 13, and the same measurement as in Example 1 was performed. The results are shown in Table 7.

First, methyl isobutyl ketone was added to a caprolactone-modified acrylic polyol solution "Plaxel DC2016" (trade name, manufactured by Daicel Corporation) to adjust the solid content to 12% by mass. To 834 parts of this solution (100 parts of acrylic polyol solid content), the other five kinds of materials shown in Table 6-C2 below were added to prepare a mixed solution.

Next, 188.5 g of the mixed solution was placed in a glass bottle having an internal volume of 450 mL together with 200 g of glass beads having an average particle size of 0.8 mm as a medium, and dispersed for 48 hours using a paint shaker disperser. After dispersion, 7.2 g of porous resin particles "Techpolymer MPB-20" (trade name, manufactured by Sekisui Plastics Co., Ltd.) was added.
This is an amount equivalent to 40 parts of the porous resin particles with respect to 100 parts of the acrylic polyol solid content. Then, it was dispersed for 5 minutes, and the glass beads were removed to prepare a coating liquid for the surface layer.

[5. Surface layer formation]
The conductive base material C13 was immersed in a coating liquid with its longitudinal direction in the vertical direction, and the conductive resin layer was coated by a dipping method. The immersion time was 9 seconds, the pull-up speed was 20 mm / s at the initial speed, and the final speed was 2 mm / s, during which the speed was changed linearly with time. The obtained coated product was air-dried at 23 ° C. for 30 minutes, then dried in a hot air circulation drying oven at a temperature of 80 ° C. for 30 minutes and further at a temperature of 160 ° C. for 1 hour to cure the coating film and conduct it. A conductive member 13 having a conductive resin layer formed on the outer peripheral portion of the conductive base material was obtained.

表７中、例えば「７．１３Ｅ＋１６」は、「７．１３×１０^１６」であることを示す。また、ＭＤ構造は、マトリックスドメイン構造の有無を示す。

In Table 7, for example, "7.13E + 16" indicates that it is ^{"7.13 × 10 16".} The MD structure indicates the presence or absence of a matrix domain structure.

<Example 1>
<Manufacturing example of toner 1>
The following actual machine evaluation was performed using the toner particles 1 as the toner 1 as it is. Tables 8 and 9 show the physical characteristics of the toner and the evaluation results of the actual machine.
First, as an electrophotographic apparatus, an electrophotographic laser printer (trade name: LBP9950Ci, manufactured by Canon Inc.) was prepared. Next, the conductive member 1, the electrophotographic apparatus, and the process cartridge were left in an environment of 15 ° C. and 10% RH for 48 hours for the purpose of acclimatizing to the measurement environment.
The electrophotographic apparatus corresponds to the configuration shown in FIG.
In addition, in order to evaluate in a high-speed process, it was modified as follows. The modification points were that the rotation speed of the developing roller was set to rotate at twice the peripheral speed of the drum by changing the gear and software of the evaluation machine body, and the process speed was changed to 330 mm / sec. It is a thing. The toner contained in the toner cartridge of LBP9950Ci was extracted, the inside was cleaned by an air blow, and then 180 g of toner 1 to be evaluated was loaded. Further, the conductive member 1 was set as a charging roller of the process cartridge, incorporated into the laser printer, and the pre-exposure device in the laser printer was removed.
By making the above modifications, the toner and the organosilicon polymer pass through the cleaning blade, and the mode becomes stricter in evaluating the contamination level and the ghost level of the charged member.
Next, in the same environment, leave 50 mm on each side and print out an image with a print rate of 4.0% up to 20000 sheets in the horizontal direction of A4 paper in the center, and evaluate after outputting the initial image and 20000 sheets. Was done.

<Ghost image evaluation>
The above laser printer was used as it was for forming the evaluation image.
The evaluation image has an "E" character in the upper part of the image and a halftone image from the center to the lower part of the image.
Specifically, the upper end 10 cm of the image is an image in which the letter "E" of the alphabet having a size of 4 points is printed so that the printing rate is 4.0%. As a result, the surface potential of the photosensitive drum after the transfer process, that is, before the charging process, can form unevenness along the surface potential corresponding to the first letter "E" in a region of about one circumference of the photosensitive drum. FIG. 7 shows an example of the evaluation image.
Further, a halftone image (an image in which a horizontal line having a width of 1 dot and an interval of 2 dots is drawn in the direction perpendicular to the rotation direction of the photosensitive drum) was output below 10 cm. This halftone image was visually observed and evaluated according to the following criteria. C or higher was judged to be good.
[Evaluation of letter "E" on halftone image]
A: Even when observed with a microscope, no image unevenness due to the letter "E" can be seen on the halftone image.
B: Visually, there is no image unevenness due to "E" in a part of the halftone image, but when observed with a microscope, image unevenness due to the letter "E" is observed.
C: The image of the letter "E" can be visually seen in a part of the halftone image.
D: The image of the letter "E" can be visually seen on the entire surface of the halftone image.

<Evaluation of member contamination>
The evaluation of the detachment of the convex portion and the contamination of the member by the external additive (halftone gradation stability) was performed as follows.
A new conductive member 1 was newly attached to the drum unit, and an image was output. As the image, an image in which halftone was printed on the entire surface was prepared. The densities of the left and right 30 mm margins and the center of the halftone image were measured, respectively, and evaluation was performed from the difference in density between the margins and the center.
It is known that when the charged member is contaminated, uneven charging occurs on the photoconductor, and uneven density of the halftone image occurs.
The density is X-Rite color reflection densitometer (X-rite 50 manufactured by X-rite).
It was measured in 0 Series). C or higher was judged to be good.
(Evaluation criteria)
A: Halftone density difference after durability evaluation is less than 0.030 B: Halftone density difference after durability evaluation is 0.030 or more and less than 0.050 C: Halftone density difference after durability evaluation is 0. 050 or more and less than 0.100 D: Halftone density difference after durability evaluation is 0.100 or more

<Evaluation of white spots>
The toner fusion level to the charged member and the photoconductor caused by the contamination of the charged member by the toner is the toner fusion state on the surface of the photoconductor and the effect on the image caused by it after the durable use of 20000 sheets (white spots). Was visually evaluated. C or higher was judged to be good.
(Evaluation criteria)
A: Not generated B: Toner fusion is slight but inconspicuous C: Toner fusion is large and spot-like white spots are slightly seen in a solid black image D: Large toner fusion occurs and is several mm Conspicuous linear white-out image defects

ケイ素量は、トナー粒子中の有機ケイ素重合体の含有量である。凸径Ｒは、個数平均径である。

The amount of silicon is the content of the organosilicon polymer in the toner particles. The convex diameter R is the number average diameter.

<Examples 2 to 19 and Comparative Examples 1 to 5>
<Manufacturing example of toners 2 to 11>
The toner particles 2 to 9 were used as they were as toners 2 to 9 for evaluation. The toner 10 and the toner 11 were manufactured as follows using the toner particles 10 for comparison, and evaluated in the same manner as in Example 1. The physical properties are shown in Table 8 and the evaluation results are shown in Table 9.
Each toner and conductive member were evaluated using the combination shown in Table 9.

-Preparation of Comparative Toner 10 First, organosilicon fine particles A were synthesized as shown below.
500 g of ion-exchanged water was charged into the reaction vessel, and 0.2 g of a 48% sodium hydroxide aqueous solution was added to prepare an aqueous solution. To this aqueous solution, 65 g of methyltrimethoxylane and 50 g of tetraethoxylane were added, a hydrolysis reaction was carried out for 1 hour while keeping the temperature at 13 to 15 ° C., and 2.5 g of a 20% sodium dodecylbenzene sulfonate aqueous solution was further added. The hydrolysis reaction was carried out at the same temperature for 3 hours. A transparent reaction containing a silanol compound was obtained in about 4 hours.
Next, a condensation reaction was carried out for 5 hours while maintaining the temperature of the obtained reaction product at 70 ° C. to obtain an aqueous suspension containing fine particles composed of an organosilicon compound. This aqueous suspension was filtered through a membrane filter, and the passing liquid portion was subjected to a centrifuge to separate white fine particles. The separated white fine particles were washed with water and dried with hot air at 150 ° C. for 5 hours to obtain organosilicon fine particles A.
When the organosilicon fine particles A were observed with a scanning electron microscope, the organosilicon fine particles A were hollow hemispheres, and image analysis was performed to calculate the number average particle diameter (μm) of the major and minor diameters of the hemisphere. The major axis was 180 nm and the minor axis was 80 nm.
To 10: 100 parts of toner particles for comparison, 3.0 parts of organosilicon fine particles A were added, mixed with a Henschel mixer at a peripheral speed of 20 m / s of a stirring blade, and then hexamethyldi having an average particle diameter of 12 nm. 1.5 parts of the silazane-treated hydrophobic silica were mixed with a Henschel mixer at a peripheral speed of 20 m / s of the stirring blade to prepare a comparative toner 10.

-Preparation of Comparative Toner 11 In the production of Comparative Toner 10, the organosilicon fine particles A were changed to hydrophobic sol-gel silica (manufactured by Nippon Aerosil Co., Ltd .: number average diameter 80 nm), and the peripheral speed of the Henschel mixer stirring blade was changed from 20 m / s to 40 m. The comparative toner 11 was produced in the same manner except that it was changed to / s.

1 STEM image, 2 toner particles, 3 toner particle surface, 4 convex organosilicon compound, 5 convex width W of organosilicon compound, 6 convex diameter D of organosilicon compound, 7 convex height H of organosilicon compound,
51 Outer surface of conductive member, 52 Conductive support, 53 Conductive layer,
6a matrix, 6b domain, 6c electron conductive agent,
81 Conductive member, 82 XZ plane, 82a XZ plane parallel to 82, 83 YZ plane perpendicular to the axial direction of the conductive member, 83a Cross section at L / 4 from one end of the conductive layer toward the center, 83b Cross section at the center of the conductive layer in the longitudinal direction, 83c Cross section at L / 4 from one end of the conductive layer toward the center
91 electrophotographic photosensitive member, 92 conductive member (charging roller), 93 developing roller, 94 toner supply roller, 95 cleaning blade, 96 toner container, 97 waste toner container, 98 developing blade, 99 toner, 910 stirring blade,
101 Photosensitive drum, 102 Charging roller, 103 Development roller, 104 Toner supply roller, 105 Cleaning blade, 106 Toner container, 107 Waste toner storage container, 108 Development blade, 109 Toner, 1010 Stirring blade, 1011 Exposure light, 1012 Primary transfer roller 1013 Tension roller, 1014 Intermediate transfer belt drive roller, 1015 Intermediate transfer belt, 1016 Secondary transfer roller, 1017 Cleaning device, 1018 Fixer, 1019 Transfer material

Claims (10)

An electrophotographic photosensitive member, a charging device for charging the surface of the electrophotographic photosensitive member, and an electrostatic latent image formed on the surface of the electrophotographic photosensitive member are developed with toner and formed on the surface of the electrophotographic photosensitive member. An electrophotographic apparatus having a developing apparatus for forming a toner image.
The charging device has a conductive member arranged so as to be in contact with the electrophotographic photosensitive member.
The conductive member has a support having a conductive outer surface and a conductive layer provided on the outer surface of the support.
The conductive layer has a matrix and a plurality of domains dispersed in the matrix.
The matrix contains the first rubber and
The domain contains a second rubber and an electronically conductive agent.
At least a portion of the domain is exposed to the outer surface of the conductive member.
The outer surface of the conductive member is composed of at least the matrix and the domain exposed on the outer surface of the conductive member.
The domain forms a protrusion on the outer surface of the conductive member.
The volume resistivity R1 of the matrix is ^{larger than 1.00 × 10 12} Ω · cm.
The volume resistivity R2 of the domain is smaller than the volume resistivity R1 of the matrix.
The developing device contains the toner and contains the toner.
The number average particle size of the toner is 4.0 μm or more and 10.0 μm or less.
The toner contains toner particles and toner particles having an organosilicon polymer on the surface of the toner mother particles.
The organosilicon polymer has a structure represented by the following formula (1) and has a structure represented by the following formula (1).
R-SiO _3/2 (1)
In the formula (1), R represents an alkyl group or a phenyl group having 1 or more and 6 or less carbon atoms.
The organosilicon polymer has convex portions formed on the outer surface of the toner particles.
The adhesion rate of the organosilicon polymer to the toner matrix particles is 80% by mass or more.
With respect to the cross-sectional image of the toner particles obtained by the scanning transmission electron microscope STEM, when the contour line of the toner mother particles is developed in a straight line to obtain a developed image of the cross-sectional image,
In the developed image,
Let L be the length of the straight line.
When the length of the line segment forming the boundary between the convex portion and the toner mother particle on the straight line is the convex width w, the ratio of the total sum Σw of the convex width w to the L (Σw / An electrophotographic apparatus in which L) is 0.30 or more and 0.95 or less. The electrophotographic apparatus according to claim 1, wherein the arithmetic mean value Dm of the distance between adjacent wall surfaces of the domain in the conductive layer in the cross-sectional observation of the conductive member is 0.15 μm or more and 2.00 μm or less. The electrophotographic apparatus according to claim 2, wherein the coefficient of variation σm / Dm of the distance between adjacent wall surfaces of the domain is 0 or more and 0.40 or less, where σm is the standard deviation of the distribution of Dm. Any of claims 1 to 3 in which the arithmetic mean value Dms of the distance between adjacent walls of the domain in the conductive layer when observing the outer surface of the conductive member is 0.20 μm or more and 2.50 μm or less. The electrophotographic apparatus according to paragraph 1. The electrophotographic apparatus according to any one of claims 1 to 4, wherein R1 is ^{larger than 1.0 × 10 12} Ω · cm and not more than 1.0 × 10 ^{17 Ω · cm.} In the developed image, the maximum length of the convex portion is defined as the convex diameter D in the normal direction of the convex width w, and the length from the apex of the convex portion to the straight line in the line segment forming the convex diameter D is convex. Height H
When
The convex portion includes a "specific height convex portion" having a convex height H of 40 nm or more and 300 nm or less.
Among the specific height convex portions, the ratio (D / w) of the convex diameter D to the convex width w is 0.33 or more and 0.80 or less, and the number ratio P (D / w) of the specific height convex portions. ) Is 50% by number or more, according to any one of claims 1 to 5. The volume resistivity R1 is an electrophotographic apparatus according to any one of claims 1 to 6 wherein it is 1.0 × 10 ⁵ times or more the volume resistivity R2. The electrophotographic apparatus according to any one of claims 1 to 7, wherein the average value of the heights of the convex portions formed by the domains is 50 nm to 200 nm. A process cartridge that can be attached to and detached from the main body of the electrophotographic device.
The process cartridge develops a charging device for charging the surface of the electrophotographic photosensitive member and an electrostatic latent image formed on the surface of the electrophotographic photosensitive member with toner, and the toner image is displayed on the surface of the electrophotographic photosensitive member. Has a developing device for forming
The charging device has a conductive member arranged so as to be in contact with the electrophotographic photosensitive member.
The conductive member has a support having a conductive outer surface and a conductive layer provided on the outer surface of the support.
The conductive layer has a matrix and a plurality of domains dispersed in the matrix.
The matrix contains the first rubber and
The domain contains a second rubber and an electronically conductive agent.
At least a portion of the domain is exposed to the outer surface of the conductive member.
The outer surface of the conductive member is composed of at least the matrix and the domain exposed on the outer surface of the conductive member.
The domain forms a protrusion on the outer surface of the conductive member.
The volume resistivity R1 of the matrix is ^{larger than 1.00 × 10 12} Ω · cm.
The volume resistivity R2 of the domain is smaller than the volume resistivity R1 of the matrix.
The developing device contains the toner and contains the toner.
The number average particle size of the toner is 4.0 μm or more and 10.0 μm or less.
The toner contains toner particles and toner particles having an organosilicon polymer on the surface of the toner mother particles.
The organosilicon polymer has a structure represented by the following formula (1) and has a structure represented by the following formula (1).
R-SiO _3/2 (1)
In the formula (1), R represents an alkyl group or a phenyl group having 1 or more and 6 or less carbon atoms.
The organosilicon polymer has convex portions formed on the outer surface of the toner particles.
The adhesion rate of the organosilicon polymer to the toner matrix particles is 80% by mass or more.
With respect to the cross-sectional image of the toner particles obtained by the scanning transmission electron microscope STEM, when the contour line of the toner mother particles is developed in a straight line to obtain a developed image of the cross-sectional image,
In the developed image,
Let L be the length of the straight line.
When the length of the line segment forming the boundary between the convex portion and the toner mother particle on the straight line is the convex width w, the ratio of the total sum Σw of the convex width w to the L (Σw / A process cartridge in which L) is 0.30 or more and 0.95 or less. A cartridge set having a first cartridge and a second cartridge that can be attached to and detached from the main body of the electrophotographic apparatus.
The first cartridge has a charging device for charging the surface of the electrophotographic photosensitive member and a first frame for supporting the charging device.
The second cartridge has a toner container containing toner for developing an electrostatic latent image formed on the surface of the electrophotographic photosensitive member to form a toner image on the surface of the electrophotographic photosensitive member. ,
The charging device has a conductive member arranged so as to be in contact with the electrophotographic photosensitive member.
The conductive member has a support having a conductive outer surface and a conductive layer provided on the outer surface of the support.
The conductive layer has a matrix and a plurality of domains dispersed in the matrix.
The matrix contains the first rubber and
The domain contains a second rubber and an electronically conductive agent.
At least a portion of the domain is exposed to the outer surface of the conductive member.
The outer surface of the conductive member is composed of at least the matrix and the domain exposed on the outer surface of the conductive member.
The domain forms a protrusion on the outer surface of the conductive member.
The volume resistivity R1 of the matrix is ^{larger than 1.00 × 10 12} Ω · cm.
The volume resistivity R2 of the domain is smaller than the volume resistivity R1 of the matrix.
The number average particle size of the toner is 4.0 μm or more and 10.0 μm or less.
The toner contains toner particles and toner particles having an organosilicon polymer on the surface of the toner mother particles.
The organosilicon polymer has a structure represented by the following formula (1) and has a structure represented by the following formula (1).
R-SiO _3/2 (1)
In the formula (1), R represents an alkyl group or a phenyl group having 1 or more and 6 or less carbon atoms.
The organosilicon polymer has convex portions formed on the outer surface of the toner particles.
The adhesion rate of the organosilicon polymer to the toner matrix particles is 80% by mass or more.
With respect to the cross-sectional image of the toner particles obtained by the scanning transmission electron microscope STEM, when the contour line of the toner mother particles is developed in a straight line to obtain a developed image of the cross-sectional image,
In the developed image,
Let L be the length of the straight line.
When the length of the line segment forming the boundary between the convex portion and the toner mother particle on the straight line is the convex width w, the ratio of the total sum Σw of the convex width w to the L (Σw / A cartridge set in which L) is 0.30 or more and 0.95 or less.

Images