JP2010097133A - Developer carrier, method for producing the same, and developing device - Google Patents

Abstract

Provided is a developer carrier that can quickly and uniformly charge a developer, is effective in suppressing sleeve ghost (hereinafter referred to as ghost), and can provide a stable high-quality image through durability. To do. Further, the present invention provides a developer carrier capable of suppressing the frictional resistance between the developer carrier and the developing blade, and capable of suppressing blade turning and blade scratches that are likely to occur at the start of image formation.
A developer carrier that carries a developer carried on the outermost surface and carries the developer carried on a development region, which is used when a latent image formed on the latent image carrier is developed and visualized with a developer. And a substrate and a resin coating layer formed on the surface of the substrate, the resin coating layer containing a binder resin and graphite particles, and being easily scraped near the surface of the resin coating layer By using a configuration in which is present in a rich state, the vicinity of the outermost surface of the resin coating layer is very easily scraped.
[Selection figure] None

Description

  The present invention relates to a developer carrying member, a manufacturing method thereof, and a developing device using the same used in a copying machine, a printer, and the like of an image forming apparatus using electrophotography.

  Conventionally, many methods are known as electrophotographic methods. In general, an electric latent image is formed on an electrostatic latent image carrier (photosensitive drum) by various means using a photoconductive substance. Next, the electrostatic latent image is developed with a developer (toner) to be a visible image, and the toner image is transferred to a transfer material such as paper as necessary. Thereafter, the toner image is fixed on the transfer material by heat, pressure or the like to obtain a copy.

  As a developer carrier used in such an electrophotographic method, a resin coating layer formed by drying and curing a paint film containing a pigment and a resin component such as graphite or carbon is used. A developer carrier having a layer is widely used. It is because it is excellent in mass productivity. However, the pigment present in the vicinity of the surface of the developer carrier formed by such a method is often covered with a thin resin film. In other words, less pigment is exposed on the surface. This is considered to be because the pigment convects in the vicinity of the surface of the coating film in the process of drying the solvent from the coating film of the paint. In a copying machine or printer equipped with such a developer carrying member, the initial charge amount rises insufficiently and the charge amount distribution tends to be non-uniform. This is because the resin coating covering the pigment existing in the vicinity of the surface of the resin coating layer is gradually removed with repeated image formation, and the resin coating the pigment. There was a problem that the change in the charge amount of the developer was large until the coating was removed.

For such a problem, a method has been proposed in which the surface of the resin coating layer of the developer carrying body is polished to obtain a developer carrying body having a pigment exposed on the surface from a new time point. (Patent Document 1). The developer carrying member according to this method exhibits stable charge imparting performance to the developer from the start of use.
Japanese Patent No. 3323741

  However, in the polishing process according to Patent Document 1, it is necessary to pay particular attention not to cause scratches or cracks on the surface of the resin coating layer and to prevent the pigment from being excessively shaved. In addition, since the manufacturing process is increased, the advantage of forming the resin coating layer by the coating method is offset, and conversely, the manufacturing cost of the developer carrying member can be increased.

  Accordingly, an object of the present invention is to provide a developer carrying member that exhibits stable charge imparting performance with respect to the developer from the beginning of use and a method for producing the same.

  Another object of the present invention is to provide a developing device capable of forming a high-quality electrophotographic image stably from the start of use.

  Another object of the present invention is to suppress the frictional resistance between the developer carrier and the developing blade, and to suppress the blade turning and blade scratches that are likely to occur at the start of image output, the developer carrier, the developing device, and the developer carrier. It is to provide a body manufacturing method.

The developer carrier of the present invention is a developer carrier having a substrate and a resin coating layer formed on the surface of the substrate,
The resin coating layer contains a binder resin and graphite particles,
The binder resin comprises a Si atom-containing polymer having a siloxane bond and a Si atom-free polymer, and
The resin coating layer is
A (atomic%) is the existing ratio of silicon (Si) element on the surface of the resin coating layer measured by X-ray photoelectron spectroscopy,
The first abrasive tape having a ten-point average roughness Rzjis having a # 3000 alumina abrasive grain on the surface of the polyester film and provided with an abrasive layer of 9 μm or more and 16 μm or less is pressed against the surface of the developer carrier and a load of 0.5 kgf ( 4.9 N), and the developer carrying member is rotated 10 revolutions at 200 rpm while winding the first polishing tape at a speed of 15 mm / sec, and developed by rubbing and polishing with the first polishing tape. The abundance ratio of Si element measured by X-ray photoelectron spectroscopic analysis on the surface of the resin coating layer of the agent carrier is B (atomic%),
Development in which a second polishing tape provided with a polishing layer having a ten-point average roughness Rzjis of 26 μm or more and 34 μm or less having # 500 alumina abrasive grains on the surface of a polyester film is rubbed and polished with the first polishing tape The second abrasive tape is wound up at a speed of 15 mm / sec while being pressed against the surface of the agent carrier with a load of 2 kgf (19.6 N) and rotating the developer carrier 20 at 1000 rpm. When the Si element abundance ratio measured by X-ray photoelectron spectroscopic analysis on the surface of the resin coating layer of the developer carrying member that has been rubbed and polished with the polishing tape is C (atomic%),
A, B, and C satisfy the following formulas (1) and (2).

C <B ≦ 0.70A Formula (1)
0 <BC <AB Formula (2).

The developing device of the present invention is used for developing and visualizing a latent image formed on a latent image carrier with a developer, and carrying the developer carried on the outermost surface and carrying the developer carried on the development area. A developing device having an agent carrier,
The developer carrier is the developer carrier described above.

The method for producing a developer carrier of the present invention is a method for producing the developer carrier described above,
After forming a coating film of a paint containing a binder resin raw material and graphite particles on the surface of the substrate, the resin coating layer is formed by curing the coating film,
The raw material of the binder resin includes a precursor of a Si atom-containing polymer containing a siloxane bond and a precursor of a Si atom-free polymer.

  According to the present invention, a developer carrying member and a developing device that can quickly and uniformly charge a developer and can stably obtain a high-quality image from the beginning without density rising, fogging, and density unevenness. And a method for producing the developer carrier.

The developer carrying member according to the present invention is used when the latent image formed on the latent image carrying member is developed and visualized with the developer, and carries the developer on the outermost surface and transports the developer to the developing region. Is. As a basic configuration, it has a base and a resin coating layer. The resin coating layer contains a binder resin and graphite particles. The binder resin is composed of a Si atom-containing polymer having a siloxane bond and a Si atom-free polymer. The resin coating layer satisfies the following formulas (1) and (2):
C <B ≦ 0.70A Formula (1)
0 <BC <AB Formula (2).

In the above formulas (1) and (2),
A is the abundance ratio (atomic%) of silicon (Si) element on the surface of the resin coating layer measured by X-ray photoelectron spectroscopic analysis in a new developer carrier.

  B represents Si on the surface of the resin coating layer measured by X-ray photoelectron spectroscopic analysis after polishing the resin coating layer of a new developer carrier under predetermined conditions (hereinafter also referred to as “first condition”). The abundance ratio of elements (atomic%). Here, the first condition is specifically the first polishing in which a polishing layer having a ten-point average roughness Rzjis of 9 μm or more and 16 μm or less having # 3000 alumina abrasive grains is provided on the surface of the polyester film. Press the tape against the surface of the developer carrier. As the first polishing tape, for example, a band-shaped abrasive having a surface roughness Rzjis of 12 μm (trade name: LT-25AX3000, manufactured by Fuji Film Co., Ltd.) is used. Then, the first abrasive tape is wound up at a speed of 15 mm / sec while the developer carrier is rotated 10 times at 200 rpm in a state of being pressed with a load of 0.5 kgf (4.9 N). Thereafter, the abundance ratio of the Si element on the surface of the resin coating layer of the developer carrying member rubbed with the first polishing tape is measured by X-ray photoelectron spectroscopy.

  C is the surface of the resin coating layer measured by X-ray photoelectron spectroscopic analysis after polishing the resin coating layer polished under the first condition under a predetermined condition (hereinafter also referred to as “second condition”) The Si element abundance ratio (atomic%). Here, specifically, the second condition is that polishing with the first polishing tape is performed in the same manner as described above. Next, the second polishing tape provided with a polishing layer having a ten-point average roughness Rzjis of 26 μm or more and 34 μm or less having # 500 alumina abrasive grains on the surface of the polyester film was rubbed and polished with the first polishing tape. Press against the surface of the developer carrier. As the second polishing tape, for example, a band-shaped abrasive (trade name: AX500, manufactured by Fuji Film Co., Ltd.) having a surface roughness Rzjis of 30 μm is used. Then, the second abrasive tape is wound up at a speed of 15 mm / sec while rotating the developer carrier 20 times at 1000 rpm in a state where it is brought into pressure contact with a load of 2 kgf (19.6 N). Thereafter, the abundance ratio of the Si element on the surface of the resin coating layer of the developer carrying member rubbed with the second polishing tape is measured by X-ray photoelectron spectroscopy.

  Next, the technical significance of the above formulas (1) and (2) will be described.

  Formula (1) shows that when the surface of the resin coating layer of the new developer carrier according to the present invention is polished with a weak force (first condition), 30 atomic% or more of Si element is reduced, This means that when polished with a stronger force (second condition), the Si element further decreases. That is, Formula (1) has shown that the surface vicinity of the resin coating layer is very easy to scrape.

  In formula (2), the polishing according to the second condition is more severe than the polishing according to the first condition. Nevertheless, the amount of Si element decrease means less than the polishing according to the first condition.

  Next, a method for polishing the surface of the developer carrying member with the polishing tape used as an index of the ease of scraping as described above will be described.

  FIG. 1 is a sectional view schematically showing an example of a polishing apparatus according to the present invention. The developer carrier 7 is rotated in the clockwise direction, and the belt-like abrasive 8 is brought into pressure contact with the developer carrier 7 while being fed from the feed roller 9, and moved toward the take-up roller 10 in the tape traveling direction 11 (arrow). Let At this time, the strip-shaped abrasive 8 rubs against the developer carrier 7 at a position where it contacts the developer carrier 7.

  The developer carrier of the present invention will be described.

  FIG. 2 shows a schematic partial cross-sectional view of an example of the developer carrying member of the present invention (magnetic one-component development method).

  As shown in FIG. 2A, in the developer carrying member of the present invention, a conductive resin coating layer 12 in which graphite particles b are dispersed in a binder resin a is formed on a cylindrical substrate 13. The developing sleeve 16 includes a magnet roller 14 accommodated in the developing sleeve 16. The conductivity of the resin coating layer 12 is adjusted by the graphite particles a dispersed in the binder resin b, and the unevenness (roughness) of the surface of the resin coating layer 12 is given by the graphite particles a. In addition, the resin coating layer 12 is formed with a portion where the Si atom-containing polymer that is easily shaved is concentrated in the vicinity of the surface. The Si atom-containing polymer that is easily scraped is more concentrated near the surface of the resin coating layer. As a result, the outermost surface of the resin coating layer of a new developer carrier is scraped by rotation of the developer carrier before printing at the initial use, and the pigment contained in the resin coating layer is coated with the resin. It will be exposed on the surface of the layer. As a result, a new developer carrier can be charged uniformly at an earlier time. Furthermore, since the resin coating layer in which more Si atom-containing polymer is present in the vicinity of the surface has high lubricity, it is possible to suppress blade turning and blade scratches that are likely to occur during the initial use of the developer bearing member.

  Further, in order to control the surface unevenness of the resin coating layer, as shown in FIG. 2B, a resin coating layer 15 in which an additive (solid particles) c is dispersed in a binder resin together with graphite particles a may be used. . As this additive, an agent that imparts conductivity, chargeability, lubricity, wear resistance and the like to the resin coating layer 15 is preferable. Also, a plurality of types of additives can be added.

<Graphite particles>
The graphite particles used in the present invention have high conductivity and lubricity similar to crystalline graphite, although the degree of graphitization is slightly lower than that of conventionally used crystalline graphite. Further, the shape of the particles is generally spherical and the hardness of the particles themselves is relatively high, whereas the crystalline graphite conventionally used is flake shaped or needle shaped. A developer carrier in which crystalline graphite is arranged in a resin coating layer is disclosed in Japanese Patent Application Laid-Open Nos. 02-105181, 03-036570, and the like. Crystalline graphite is artificial graphite or natural graphite obtained by molding an aggregate such as coke with tar pitch or the like, then firing it at 1000 ° C. to 1300 ° C. and then graphitizing at 2500 ° C. to 3000 ° C. It has been known. However, the graphite particles used in the present invention are different from crystalline graphite in the interplanar spacing of the graphite (002) plane (hereinafter abbreviated as “graphite d (002)”) measured by X-ray diffraction.

  Therefore, the graphite particles having the above characteristics are easily dispersed uniformly in the resin coating layer, and give a uniform surface shape and wear resistance to the surface of the coating layer. In addition, since the shape of the particle itself is difficult to change, even if the resin part of the coating layer is selectively scraped or the particle itself falls off due to the influence, the particle protrudes or is exposed again from the resin layer. In some cases, the change in the surface shape can be kept small.

  Furthermore, in the resin coating layer containing graphite particles, it is possible to improve the triboelectric charge-providing property to the toner, compared with the case where conventional crystalline graphite is used, without causing toner charge-up.

  The graphite particles preferably have a volume average particle size in the range of 1.0 μm to 13.0 μm. When the volume average particle size of the graphite particles is 1.0 μm or more, there are not many graphite particles with a small particle size that have little effect of enhancing the charging performance, and quick and uniform charging to the developer is sufficient. At the same time, graphite particles are less likely to be lost from the resin coating layer, and toner charge-up suppression, ghost suppression, and image density are easily stabilized. On the other hand, when the volume average particle size of the graphite particles is 13.0 μm or less, there are not too many coarse graphite particles that increase the surface roughness of the resin coating layer, and charging to a uniform toner is easy. This stabilizes the image quality. At the same time, the toner is quickly and uniformly charged, and the mechanical strength of the resin coating layer does not decrease.

  It is also possible to contain crystalline GF in the resin coating layer as graphite particles.

  As content of the graphite particle in a resin coating layer, 2 to 150 mass parts is preferable with respect to 100 mass parts of binder resin, and 4 to 100 mass parts is more preferable. When the content of the graphite particles is 2 parts by mass or more, the effect of increasing the hardness of the resin coating layer by the addition of the graphite particles is exhibited, and the wear resistance of the developer carrier is improved. Further, when the content of the graphite particles is 150 parts by mass or less, the adhesiveness of the resin coating layer is sufficiently ensured and the wear resistance can be maintained.

<Conductive fine particles>
The resin coating layer may further contain the following conductive fine particles. Metal powders such as aluminum, copper, nickel and silver; metal oxides such as antimony oxide, indium oxide and tin oxide; carbon materials such as carbon fiber, carbon black and graphite. The conductive fine particles control the viscosity of the paint used for forming the resin coating layer, control the conductivity of the resin coating layer, and the like. The finer particle size of the conductive fine particles is desirable, and the particle size is preferably 1 μm or less. Among these, fine carbon black having a primary particle size of 1 μm or less can be suitably used. In particular, conductive amorphous carbon is particularly excellent in electrical conductivity, and is preferable in order to obtain a certain degree of conductivity by simply filling a polymer material to impart conductivity and controlling the amount of addition.

The resin coating layer is electrically conductive to prevent the developer from sticking to the developer carrier due to charge-up, or from poor charging of the developer from the surface of the developer carrier caused by charge-up of the developer. It is desirable that The volume resistance value of the resin coating layer is preferably 10 ⁴ Ω · cm or less, more preferably 10 ³ Ω · cm or more and 10 ⁻³ Ω · cm or less. When the volume resistance value of the conductive coating layer on the surface of the developer carrying member exceeds 10 ⁴ Ω · cm, poor charge application to the developer is likely to occur, and as a result, so-called blotch is likely to occur.

  As described above, the resin coating layer of the present invention is characterized by containing graphite particles. In the developer carrier of the present invention, the graphite particles are exposed on the surface of the resin coating layer during the initial use, so that the work function gradient γ increases. The work function representing the slope γ is defined as the minimum energy required to extract one electron from the surface of a substance just outside the surface. In the work function measurement curve, the horizontal axis represents excitation energy [eV], and the vertical axis represents the number of emitted photoelectrons (yield) [cps] (counts per second). In general, the emission of photoelectrons suddenly increases from a certain value, the measurement curve rises rapidly, and the rising point is defined as the work function value Wf. Further, the degree of photoelectron emission after that (on the right side of the Wf point) is defined by the slope γ of the measurement curve that is close to a straight line. If many graphite particles are exposed on the surface of the resin coating layer of the developer carrying member, the work function gradient γ increases. If the exposure is small, the work function gradient γ decreases.

As the developer carrying member, the slope γ is ^preferably 10 (cps ^0.5 / eV) or more and 70 (cps ^0.5 / eV) or less, but in order to impart quick and uniform charging to the developer, More preferably, it is 20 or more and 50 or less. When γ is 10 (cps ^0.5 / eV) or more, the developer particles are appropriately slippery on the surface of the developer carrying member, so that the developer is prevented from being charged up, and the developer is uniformly and quickly charged. It becomes easy to give. If γ is 70 (cps ^0.5 / eV) or less, it is possible to suppress the wear of the graphite particles on the surface of the coating layer because the exposed amount of the graphite particles on the surface of the resin coating layer is too large.

  The developer carrier of the present invention will be described in more detail.

  The developer carrying member of the present invention has a developing sleeve in which a conductive resin coating layer is formed on the surface of a cylindrical substrate, and a magnetic roller is accommodated in the developing sleeve. In the non-magnetic one-component developing method, a magnetic roller is not required, so that the substrate may be a cylindrical sleeve type or a solid solid column.

<Substrate>
The base of the developer carrying member includes a cylindrical member, a columnar member, a belt-like member, etc., depending on the developing method. In a developing method that does not contact the photosensitive drum, a rigid cylindrical tube such as metal is used. Alternatively, a solid bar is preferably used. That is, as the substrate, a non-magnetic metal or alloy such as aluminum, stainless steel, brass or the like formed into a cylindrical shape or a columnar shape, and subjected to polishing, grinding, or the like is preferably used. These substrates are preferably molded or processed with high accuracy in order to achieve image uniformity. For example, the straightness in the longitudinal direction is preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 10 μm or less. Deflection of the gap between the developer carrying member and the photosensitive drum, for example, the deviation of the gap between the vertical surface when the developer carrying member is rotated by abutting the vertical surface with a uniform spacer is preferably 30 μm or less. More preferably, it is 20 micrometers or less, More preferably, it is 10 micrometers or less. Aluminum is preferably used because of material cost and ease of processing.

  In addition, as a base in the case of using a developing method in which the photosensitive drum is brought into direct contact, a cylindrical member having a layer configuration including a metal cored bar and rubber such as urethane, EPDM, silicone, or elastomer is preferably used. In a developing method using a magnetic developer, a magnet roller or the like in which a magnet is provided is disposed in the developer carrying body in order to magnetically attract and hold the developer on the developer carrying body. In that case, the substrate may be cylindrical and a magnet roller may be disposed inside the substrate.

<Resin coating layer>
The resin coating layer is formed so as to satisfy the above formulas (1) and (2).

  The resin coating layer contains a binder resin and graphite particles.

  The binder resin is composed of a Si atom-containing polymer and a Si atom-free polymer.

  Thus, by using the Si atom-containing polymer and the Si atom-free polymer as the binder resin, more Si atom-containing polymer can be present in the vicinity of the surface of the resin coating layer. One of the reasons why the Si atom-containing polymer is present more in the vicinity of the surface of the resin coating layer of the developer carrier is that the Si atom-containing polymer has a smaller surface free energy than the Si atom-free polymer. Can be mentioned. That is, the resin coating layer according to the present invention is formed by drying and curing a coating film of a resin coating layer forming coating material containing a raw material of a Si atom-containing polymer and a raw material of a Si atom-free polymer. . Then, Si atoms having a relatively small surface free energy due to a convection phenomenon generated in the coating film in the process of drying and curing of the coating film in which the Si atom-containing polymer and the Si atom-free polymer are formed. The contained polymer tends to be raised on the surface side of the coating film. As a result, it is considered that the resin coating layer has a larger amount of Si atom-containing polymer in the vicinity of the surface.

  Here, the Si atom-containing polymer preferably has more methyl groups bonded to Si atoms, and preferably has a smaller molecular weight than the Si atom-free polymer. Having the methyl group bonded to the Si atom increases the degree of freedom of the Si atom-containing polymer, and therefore the Si atom-containing polymer is more likely to be unevenly distributed near the surface of the coating film. In addition, since the molecular weight of the Si atom-containing polymer is relatively small compared to the Si atom-free polymer, the Si atom-containing polymer can be raised on the surface of the coating film during drying and curing of the coating film. It becomes easier.

  Further, it is preferable that the difference in SP value between the Si atom-containing polymer and the Si atom-free polymer is 3 or more and 8 or less. By setting the SP value within this range, excessive separation between the Si atom-containing polymer and the Si atom-free polymer in the coating film can be suppressed.

<< Si atom-containing polymer >>
The Si atom-containing polymer according to the present invention has a siloxane bond.

  The Si atom-containing polymer is preferably a siloxane-modified polycarbonate polymer. By having a polysiloxane part at the end, the degree of freedom of the siloxane part is increased, and the local concentration is more concentrated in the vicinity of the surface. At this time, the longer siloxane chain works effectively to improve lubricity. The polysiloxane group in the present invention is derived from polyalkylsiloxane, polyarylsiloxane, polyalkylarylsiloxane or the like. Specific examples include polydimethylsiloxane, polydiethylsiloxane, polydiphenylsiloxane, and polymethylphenylsiloxane. Two or more of these may be used in combination. In addition, the siloxane site | part in this invention points out the repeating unit of Si-O bond, and also includes the substituent directly couple | bonded with Si.

  The siloxane-modified polycarbonate polymer has a repeating structural unit represented by the following formula (3) and a repeating unit represented by the following formula (4), and either one or both of the terminals have the following formula ( 5) is preferable. By satisfying the above conditions, the siloxane-modified polycarbonate polymer is more likely to be concentrated in the vicinity of the surface of the developer carrier, and the lubricity of the surface of the developer carrier is improved.

In formula (3), X represents a single bond, —O—, —S—, or a substituted or unsubstituted alkylidene group. R _{11 to} R ₁₈ are the same or different and each represents a hydrogen atom, a halogen atom, an alkoxy group, a nitro group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and an astatine atom. The alkylidene group preferably has 2 to 16 carbon atoms. The alkoxy group preferably has 1 to 16 carbon atoms. The alkyl group preferably has 1 to 16 carbon atoms. The aryl group preferably has 6 to 20 carbon atoms.

In formula (4), R ₂₁ and R ₂₂ are the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R _{23 to} R ₂₆ are the same or different and each represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. a is the same or different and represents an integer of 1 to 30, and m represents an integer of 1 to 500. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and an astatine atom. The alkyl group preferably has 1 to 16 carbon atoms. The aryl group preferably has 6 to 20 carbon atoms.

a is an integer of 1 to 30, and preferably an integer of 1 to 3. If a is 1 or more, it is possible to have a material that tends to be concentrated near the surface, such as a methyl group. If a is 30 or less, the lubricity effect of the siloxane part in the compound can be extracted, and if a is 3 or less, the lubricity effect of the siloxane part in the compound can be sufficiently extracted. It is. R _{23 to} R ₂₆ are preferably methyl groups.

  m is an integer of 1 to 500, and preferably an integer of 10 to 100. In order to obtain sufficient siloxane lubricity, a longer siloxane chain works more effectively to improve lubricity. High lubricity is exhibited when m is 1 or more, and particularly high lubricity is exhibited when m is 10 or more. m is better, but if it is 500 or less, the reactivity of the monofunctional phenyl compound having an unsaturated group is practical without inferior, and if it is 100 or less, the reactivity of the phenyl compound is very high. Highly suitable for use.

In formula (5), R ₃₁ and R ₃₂ are the same or different and are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkoxy group, a nitro group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl. Indicates a group. R ₃₃ and R ₃₄ are the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R _{35 to} R ₃₉ are the same or different and each represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. b represents an integer of 1 to 30, and n represents an integer of 1 to 500. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and an astatine atom. The alkoxy group preferably has 1 to 16 carbon atoms. The alkyl group preferably has 1 to 16 carbon atoms. The aryl group preferably has 6 to 20 carbon atoms.

b is preferably an integer of 1 or more and 30 or less, and more preferably an integer of 1 or more and 3 or less. If b is 1 or more, it is possible to have a material that tends to be concentrated near the surface, such as a methyl group. If b is 30 or less, the lubricity effect of the siloxane part in the compound can be extracted, and if b is 3 or less, the lubricity effect of the siloxane part in the compound can be sufficiently extracted. It is. R _{33 to} R ₃₉ are preferably methyl groups.

  n is an integer of 1 or more and 500 or less, and preferably an integer of 10 or more and 100 or less. In order to obtain sufficient siloxane lubricity, a longer siloxane chain works more effectively to improve lubricity. When n is 1 or more, high lubricity is exhibited, and when n is 10 or more, particularly high lubricity is exhibited. n is preferably large, but if it is 500 or less, the monofunctional phenyl compound having an unsaturated group is practically inferior in reactivity, and if it is 100 or less, the reactivity of the phenyl compound is very high. Highly suitable for use.

  In particular, when m and n are 10 or more, particularly high lubricity is exhibited, and the contact angle of pure resin with pure water is as high as 100 ° or more. This effectively works to avoid troubles such as blade turning and blade scratches that are most likely to occur in the initial stage of use, and in particular, it is effective and effective even in the most severe high humidity environments.

  Below, bisphenol for forming the structural unit represented by the formula (3), a bifunctional siloxane compound for forming the structural unit represented by the formula (4), and the terminal structure represented by the formula (5) The preferable specific example of the monofunctional siloxane compound for forming is shown. However, it is not restricted to these.

  First, the specific example of the bisphenol for forming the structural unit shown by Formula (3) is shown.

  Next, specific examples of the bifunctional siloxane compound for forming the structural unit represented by the formula (4) are shown.

Illustrative compounds (4-1), (4-2), (4-5), (4) wherein the average repeating unit number a in formula (4) is 3 or less, and R _{23 to} R ₂₆ are all methyl groups. -6) and (4-8) are preferable, and exemplary compound (4-1) is particularly preferable.

  Next, specific examples of the monofunctional siloxane compound for forming the terminal structure represented by the formula (5) are shown.

Illustrative compounds (5-1), (5-2), and (5-3) in which the average number of repeating units b of formula (5) is 3 or less and all of R _{33 to} R ₃₉ are methyl groups are preferred, Illustrative compound (5-1) is particularly preferable.

  The mass of the polysiloxane group in the siloxane-modified polycarbonate polymer is preferably 25% by mass or more and 75% by mass or less. When the content of the polysiloxane group is 25% by mass or more, the molecular weight of the siloxane-modified polycarbonate polymer becomes low, and the polymer tends to be concentrated near the surface of the resin coating layer. When the content of the polysiloxane group is 75% by mass or less, the production is easy and the electrophotographic characteristics are hardly hindered. The content of the polysiloxane group is such that the total mass of the part composed of the siloxane structural units in the formulas (4) and (5) accounts for the proportion of the total mass of the siloxane-modified polycarbonate polymer. This is indicated by mass%. The polysiloxane group is derived from polyalkylsiloxane, polyarylsiloxane, polyalkylarylsiloxane or the like. Specific examples include polydimethylsiloxane, polydiethylsiloxane, polydiphenylsiloxane, and polymethylphenylsiloxane. Two or more of these may be used in combination.

  The silicon-modified polycarbonate polymer can be synthesized by condensing bisphenol, a bifunctional siloxane compound, and a monofunctional siloxane compound using phosgene.

  In synthesizing the silicon-modified polycarbonate, in addition to the monofunctional siloxane compound, another monofunctional compound may be used in combination as a terminal terminator in order to adjust the molecular weight. Examples of such a terminator include compounds usually used in producing polycarbonate such as phenol, p-cumylphenol, pt-butylphenol, benzoic acid and benzyl chloride.

  When synthesized using only a monofunctional siloxane compound without adding a bifunctional siloxane compound, a polycarbonate polymer having no siloxane structure in the main chain and having a siloxane structure at one or both ends of the polycarbonate repeating unit. Is synthesized. This polycarbonate polymer may be used in combination with a silicon-modified polycarbonate polymer having a siloxane structure at both the main chain and the terminal according to the present invention.

  The viscosity average molecular weight (Mv) of the silicone-modified polycarbonate polymer is preferably 1,000 or more and 100,000 or less, and particularly preferably 3,000 or more and 20,000 or less. If the viscosity average molecular weight is 1,000 or more, the silicon-modified polycarbonate polymer tends to exhibit characteristics. Further, when the viscosity average molecular weight is 10,000 or less, the viscosity does not become too high, and it is easy to apply uniformly to the developer carrying member.

  Further, when a siloxane-modified polycarbonate polymer and a polydimethylsiloxane represented by the following formula (6) are used in combination as the binder resin, it is preferable that a higher initial slip property is exhibited and the characteristics are not deteriorated.

  In said formula (6), l shows the average value of an average repeating unit.

  The content of polydimethylsiloxane is 5% by mass or more and 20% by mass or less with respect to the siloxane-modified polycarbonate polymer, and the total content of these two types is based on the total solid content contained in the resin coating layer. 0.1 mass% or more and 5.0 mass% or less are preferable. When the content of polydimethylsiloxane is 5% by mass or more, extremely high slipperiness is likely to be manifested particularly in the initial stage when the developer carrying member is used. Moreover, if content of polydimethylsiloxane is 20 mass% or less, a mixing ratio will not be polydimethylsiloxane excess, and a density | concentration fall will not generate | occur | produce easily. Furthermore, if the total content of the two types is 0.1% by mass or more, high slipperiness is exhibited. When the total content of the two types is 5.0% by mass or less, it is possible to suppress a decrease in body wear of the resin coating layer.

  The average value l of the average repeating unit represented by the formula (6) is preferably 10 or more and 100 or less. If l is 10 or more, lubricity can be imparted to the surface of the resin coating layer even if added in a small amount. Further, if l is 100 or less, it tends to be concentrated near the surface of the resin coating layer, and it is possible to easily expose the pigment to the surface of the coating layer instantly at the initial use of the developer carrier. Become.

  In addition, when polydimethylsiloxane is added alone, high slipperiness is hardly exhibited.

  The repeating units m and n of the siloxane structure in the siloxane-modified polycarbonate polymer and the average repeating unit 1 of the siloxane structure in the polydimethylsiloxane preferably satisfy m = n = 1. By producing a developer carrying member using a paint having a uniform number of repeating units, an effect of imparting quick and uniform charging to the developer can be seen. Moreover, the numerical value of an average repeating unit can be measured by MALDI-TOF-MS (made by BRUKER). The value of the average repeating unit is considered to be the same if it is within a range of about ± 3 in consideration of measurement error.

<< Si atom-free polymer >>
Examples of the Si atom-free polymer according to the present invention are given below. Acrylic polymer, acrylonitrile polymer, allyl polymer, alkyd polymer, epoxy polymer, silicone polymer, styrene polymer, cellulose polymer, urea polymer, vinyl polymer, phenoxy polymer , Phenolic polymer, butyral polymer, fluorine polymer, polyacrylamide polymer, polyacetal polymer, polyamide polymer, polyallyl ether polymer, polyarylate polymer, polyimide polymer, polyurethane polymer, polyester Polymer, polyethylene polymer, polyolefin polymer, polycarbonate polymer, polystyrene polymer, polystyrene polymer, polysulfone polymer, polyvinyl butyral polymer, polyphenylene oxide polymer, polybutadiene polymer, polypropylene polymer, methacrylate Le polymers, melamine-based polymers and the like.

  Among these, polyarylate, polycarbonate, and phenol resin are more preferable in terms of compatibility with Si atom-containing polymers, particularly silicon-modified polycarbonate polymers, and improvement in electrophotographic characteristics and durability. These may be used alone or in combination of two or more as a copolymer or a copolymer. These polymers have relatively high solubility in organic solvents, are excellent in dispersibility of carbon black, graphite particles, and other additives, and can be easily thinned. is there. In addition, these polymers are not only excellent in adhesion to the substrate and wear resistance, but also when the developer (toner) is negatively charged, the developer (toner) is appropriately charged. Can be granted. And by making it crosslink-react with other polymers, a prepolymer, resin, etc., it can aim at the further improvement of abrasion resistance, and can improve solvent resistance and a softness | flexibility. Furthermore, any thermoplastic resin or thermosetting resin can be used as long as it has sufficient mechanical strength.

  The Si atom-containing polymer is preferably used by being mixed with a polymer having higher strength and having a relatively large surface free energy. The mixing ratio of the other polymer is preferably 1 part by mass or more and 99 parts by mass or less with respect to 0.5 part by mass of the Si atom-containing polymer according to the present invention. Since the Si atom-containing polymer according to the present invention tends to be concentrated near the surface of the developer carrying member, it exhibits high lubricity even with a small blend ratio.

<< Low molecular weight compound >>
A low molecular compound may be further added to the resin coating layer. The low molecular compound may be a compound that can be dissolved in the solvent of the coating material. By further adding a low molecular compound, it is possible to reduce the hardness near the surface of the resin coating layer. As a result, the pigment is exposed on the surface of the developer carrying member early during the initial use of the developer carrying member, and the developer can be charged quickly and uniformly from the beginning. Next, specific examples of low molecular weight compounds that may be contained in the resin coating layer will be given.

  Two or more kinds of low molecular compounds may be added to the resin coating layer. The addition amount of the low molecular compound is preferably smaller than the number of resin addition parts. By making the addition amount of the low molecular compound not more than the number of added parts of the resin, the problem that the resin coating layer becomes brittle does not occur.

<< Spherical particles >>
In the resin coating layer of the present invention, it is also possible to use spherical particles for forming irregularities on the surface. Examples of such spherical particles include the following. Vinyl polymers and copolymers such as polymethyl methacrylate (PMMA), polyethyl acrylate, polybutadiene, polyethylene, polypropylene, polystyrene, benzoguanamine resin, phenol resin, polyamide resin, fluorine resin, silicone resin, epoxy resin, polyester resin Resin particles such as alumina; oxide particles such as alumina, zinc oxide, silicone, titanium oxide, and tin oxide. In addition, for example, an organic compound such as an imidazole compound can be used in the form of particles. In this case, the imidazole compound also serves to impart a triboelectric charge to the toner.

  The volume average particle size of the spherical particles is preferably 0.3 μm or more and 30 μm or less, and more preferably 0.5 μm or more and 13.0 μm or less. That is, when the spherical particles have a particle size of 0.3 μm or more, it is easy to form uniform irregularities on the resin coating layer, and it is not necessary to excessively add the compounding amount when trying to form the required surface roughness. The coating layer does not become brittle, and it is possible to maintain high wear resistance. On the other hand, when the spherical particles have a particle size of 30 μm or less, the particles do not protrude excessively from the surface of the resin coating layer, and the amount of developer carried (developer layer thickness) is maintained moderately. Apply appropriate charge. Furthermore, there is no fear that it becomes a leak point to the photosensitive drum when a bias voltage is applied.

  The roughness of the surface of the developer carrying member, that is, the surface of the resin coating layer varies depending on the developing method, but in general, the arithmetic average roughness (Ra) defined in JIS B0601-2001 is 0.15 μm or more 3 It is preferably in the range of 0.000 μm or less. Similarly, the film thickness of the resin coating layer is preferably in the range of 5.0 μm or more and 50.0 μm or less, although a suitable film thickness varies depending on the development method.

  For example, as shown in FIG. 3, in a developing device using magnetic toner and having a magnetic blade disposed with a gap between the developer carrier and the developer layer as a developer layer thickness regulating member, Ra is 0.15 μm or more. It is desirable that it is about 50 μm or less. When Ra is 0.15 μm or more, the developer is easily transported, and there is no occurrence of image density thin due to lack of developer or image defect due to uneven developer coating. Further, when Ra is 2.50 μm or less, the frictional charging of the toner is likely to be uniform, and the occurrence of streak unevenness, reversal fogging, and image density thin due to insufficient charging is suppressed.

  For example, as shown in FIGS. 4 and 5, in the case of a developing device in which an elastic member is used in pressure contact with a developer carrier, the surface roughness Ra of the resin coating layer is 0.30 μm or more and 3.50 μm. It is desirable to be in the following order. When Ra is 0.30 μm or more, the developer is easily transported sufficiently, and it is difficult for image density thinning due to lack of developer and image defects due to uneven developer coating to occur, and to the developer carrier. The toner fusing is less likely to occur. Further, when Ra is 3.50 μm or less, it is easy to maintain the toner triboelectrically charged, and streak unevenness, reversal fogging, and low image density due to insufficient charging are less likely to occur.

  The developer carrier of the present invention can be produced, for example, by a method having a step of forming a resin coating layer by applying a coating film of a coating on the surface of a substrate and then drying and curing the coating film. it can. The paint can be obtained by dispersing and mixing the binder resin raw material, graphite particles, and other components in a solvent. As a raw material of the binder resin, the above-described Si atom-containing polymer precursor (prepolymer, monomer, etc.) containing a siloxane bond and the above-mentioned Si atom-free polymer precursor (prepolymer, monomer, etc.) A composition containing is used. Thereby, the resin coating layer containing much Si atom containing polymer which can be easily shaved near the surface of the resin coating layer can be produced.

  Since the precursor of the Si atom-containing polymer is a siloxane-modified polycarbonate prepolymer and the precursor of the Si atom-free polymer is a polyarylate prepolymer, the siloxane-modified polycarbonate is more closely adjacent to the surface of the resin coating layer. A lot is contained. As a solvent used for the coating material, an organic solvent such as methanol, ethanol, isopropyl alcohol, methyl ethyl ketone, toluene, and monochlorobenzene can be used. For dispersing and mixing each component, a known dispersing device using beads such as a sand mill, paint shaker, dyno mill, pearl mill, or a known medialess dispersing device using a collision type atomization method or a thin film swirling method is preferably used. Is possible. As a coating method, a known method such as a dipping method, a spray method, or a roll coating method can be applied.

  Next, the developing device of the present invention will be described. The developing device of the present invention has the developer carrying member of the present invention.

  FIG. 3 is a schematic diagram illustrating a configuration of an example of an embodiment of a developing device that uses a magnetic one-component developer. The developing device of the embodiment shown in FIG. 3 includes a container (developing container 503) for storing the developer and a developer carrier 510 for carrying and transporting the developer (not shown) stored in the container. have. In this developing apparatus, the developer on the developer carrier 510 is opposed to the electrostatic latent image carrier 501 while a developer layer is formed on the developer carrier 510 by the developer layer thickness regulating member (magnetic blade) 502. To the developing area D to be carried out. The electrostatic latent image on the electrostatic latent image carrier 501 can be developed with a developer to form a toner image. This developer carrier 510 is the developer carrier of the present invention.

  The electrostatic latent image carrier 501 can be formed by a known process. An electrostatic latent image carrier that carries an electrostatic latent image, for example, a photosensitive drum 501 rotates in the direction of arrow B. The developer carrier 510 carries a magnetic one-component developer having magnetic toner particles housed in the developer container 503 and rotates in the direction of arrow A so that the developer carrier 510 and the photosensitive drum 501 face each other. The developer is conveyed to the developing area D. In the developer carrying member 510, a magnet (magnet roller) 509 is disposed in the developing sleeve 508 in order to magnetically attract and hold the magnetic one-component developer on the developer carrying member 510. The developing sleeve 508 is formed by coating a conductive resin coating layer 507 on a metal cylindrical tube as the base 506.

  A magnetic one-component developer is fed into the developer container 503 from a developer supply container (not shown) via a developer supply member (such as a screw) 512. The developing container 503 is divided into a first chamber 514 and a second chamber 515, and the magnetic one-component developer fed into the first chamber 514 is formed by the developing container 503 and the partition member 504 by the stirring and conveying member 505. It passes through the gap and is sent to the second chamber 515. The magnetic one-component developer is carried on the developer carrying member 510 by the action of magnetic force by the magnet roller 509. In the second chamber 515, a stirring member 511 for preventing the developer from staying is provided.

  The magnetic one-component developer generates a triboelectric charge that can develop the electrostatic latent image on the photosensitive drum 501 by friction between the magnetic toner particles and the conductive resin coating layer 507 on the developer carrier. obtain. In order to regulate the layer thickness of the developer conveyed to the development region D, a ferromagnetic metal magnetic blade (doctor blade) 502 is mounted as a developer layer thickness regulating member. The magnetic blade 502 is usually attached to the developer container 503 so as to face the developer carrier 510 with a gap of about 50 μm or more and 500 μm or less from the surface of the developer carrier 510. The magnetic lines of force from the magnetic pole N 1 of the magnet roller 509 are concentrated on the magnetic blade 502, whereby a thin layer of magnetic one-component developer is formed on the developer carrier 510. In the present invention, a nonmagnetic developer layer thickness regulating member can be used instead of the magnetic blade 502.

  The thickness of the thin layer of the magnetic one-component developer formed on the developer carrier 510 may be thinner than the minimum gap between the developer carrier 510 and the photosensitive drum 501 in the development region D. preferable.

  It is effective to incorporate the developer carrying member of the present invention into a developing device that develops an electrostatic latent image with a thin layer of magnetic one-component developer as described above, that is, a non-contact developing device. However, the developer carrier of the present invention can also be used for a non-contact type developing device, a non-magnetic one-component contact type developing device, and a two-component developing device using a non-magnetic one-component developer.

  In addition, a developing bias voltage is applied to the developer carrying member 510 by a developing bias power source 513 as a biasing unit in order to cause the magnetic one-component developer having magnetic toner carried on the developer carrying member 510 to fly. When a DC voltage is used as the developing bias voltage, a voltage having a value between the potential of the image portion of the electrostatic latent image (the region visualized as the developer adheres) and the potential of the background portion is carried by the developer. Application to the body 510 is preferred.

  In order to increase the density of the developed image and improve the gradation, an alternating bias voltage is applied to the developer carrier 510 to form an oscillating electric field whose direction is alternately reversed in the development region D. Also good. In this case, it is preferable to apply to the developer carrier 510 an alternating bias voltage in which a DC voltage component having an intermediate value between the potential of the developed image portion and the potential of the background portion is superimposed.

  At this time, in the case of so-called regular development, in which toner is attached to the high potential portion of the electrostatic latent image having a high potential portion and a low potential portion and visualized, magnetism charged to a polarity opposite to the polarity of the electrostatic latent image. A one-component developer is used. In the case of so-called reversal development, a toner is attached to the low potential portion of an electrostatic latent image having a high potential portion and a low potential portion, and in the case of so-called reversal development, magnetic one-component development that is charged to the same polarity as the electrostatic latent image. Use the agent. In this case, the high potential and the low potential are expressed by absolute values. In any of these cases, the magnetic one-component developer (magnetic toner particles) is charged by at least friction with the conductive resin coating layer 507 of the developer carrier 510.

  FIG. 3 shows an example in which a magnetic blade 502 disposed apart from the developer carrier 510 is used as a developer layer thickness regulating member that regulates the layer thickness of the magnetic one-component developer on the developer carrier 510. showed that. FIG. 4 is a schematic diagram showing another example configuration of the embodiment of the developing device of the present invention using a magnetic one-component developer. As shown in FIG. 4, the developing device of the present invention is an elastic blade made of an elastic plate made of a material having rubber elasticity such as urethane rubber or silicone rubber, or a material having metal elasticity such as phosphor bronze or stainless steel. An embodiment using 516 may be used. The elastic blade 516 may be brought into contact or pressure contact with the developer carrier 510 via a magnetic one-component developer.

  In the present invention, particularly in a system having this form, it is possible to obtain a remarkable effect in terms of wear resistance and charge imparting ability. In such a developing device in which the developer layer thickness regulating member is brought into contact with or in contact with the developer layer, the developer layer is formed on the developer carrying member 510 while being further regulated. For this reason, since the developer layer becomes thinner on the developer carrier 510 than in the embodiment shown in FIG. 3 using the magnetic blade 502, the conductive resin coating layer 507 of the developer carrier 510 is moved to. And the conductive resin coating layer 507 is easily worn. In the present invention, even in such a system, wear of the conductive resin coating layer 507 can be reduced, and high durability can be achieved.

  The contact pressure of the elastic blade 516 with respect to the developer carrying member 510 is a linear pressure of 0.049 N / cm or more and 0.49 N / cm or less, which stabilizes the regulation of the magnetic one-component developer and allows magnetic development. It is preferable at the point which can control the thickness of an agent layer suitably. When the linear pressure of the contact pressure of the elastic blade 516 is 0.049 N / cm or more, the regulation of the magnetic one-component developer becomes uniform, and fogging and leakage of the magnetic one-component developer can be suppressed. Further, when the linear pressure is 0.49 N / cm or less, the rubbing force of the magnetic one-component developer is not excessively large, the deterioration of the magnetic one-component developer, the developer carrier, and the developer layer thickness regulating member. It becomes possible to suppress the fusion of the developer to the surface.

  FIG. 5 is a schematic diagram showing a configuration of an example of an embodiment of the developing device of the present invention using a nonmagnetic one-component developer. In the embodiment shown in FIG. 5, an electrostatic latent image carrier, such as a photosensitive drum 801, carrying an electrostatic latent image formed by a known process is rotated in the direction of arrow B. A developing sleeve 808 as a developer carrying member is composed of a base (metal cylindrical tube) 806 and a conductive resin coating layer 807 formed on the surface thereof. Since a nonmagnetic one-component developer is used, no magnet is provided inside the substrate 806. It is also possible to use a columnar member as the base 806 instead of the metal cylindrical tube.

  In the developing container 803, a stirring / conveying member 810 for stirring and transporting the non-magnetic one-component developer 804 is provided. A developer supply / peeling member 813 for supplying the developer 804 to the developing sleeve 808 and stripping off the developer 804 remaining on the surface of the developed sleeve 808 after development is in contact with the developing sleeve 808. When the developer supply / peeling member (developer supply / peeling roller) 813 rotates in the same direction as the developing sleeve 808, the surface of the supply / peeling roller 813 moves in the counter direction with the surface of the developing sleeve 808. To do. As a result, the nonmagnetic one-component developer 804 is supplied to the developer sleeve 808 in the developing container 803. The developing sleeve 808 carries the supplied non-magnetic one-component developer and rotates in the direction of arrow A, so that the non-magnetic one-component developer is applied to the developing portion D where the developing sleeve 808 and the photosensitive drum 801 face each other. Transport.

  The thickness of the nonmagnetic one-component developer 804 carried on the developing sleeve 808 is regulated by a developer layer thickness regulating member 811 that is in pressure contact with the surface of the developing sleeve 808 via the developer layer. The nonmagnetic one-component developer 804 is sufficiently charged to develop the electrostatic latent image on the photosensitive drum 801 by friction with the developing sleeve 808. In order to avoid complications, a non-contact type developing device will be described below as an example.

  A developing bias voltage is applied to the developing sleeve 808 from a power source 809 in order to cause the non-magnetic one-component developer carried on the developing sleeve 808 to fly. When a DC voltage is used as the development bias voltage, a voltage having a value between the potential of the image portion of the electrostatic latent image (the region visualized with the nonmagnetic developer 804 attached) and the potential of the background portion is obtained. It is preferably applied to the developing sleeve 808. In order to increase the density of the developed image or improve the gradation, an alternating bias voltage may be applied to the developing sleeve 808 to form an oscillating electric field whose direction is alternately reversed in the developing portion. In this case, it is preferable that an alternating bias voltage on which a DC voltage component having a value between the potential of the image portion and the background portion is superimposed is applied to the developing sleeve 808.

  In so-called regular development, where toner is attached to the high potential part of an electrostatic latent image having a high potential part and a low potential part for visualization, a non-magnetic one-component developer that is charged with a polarity opposite to that of the electrostatic latent image is used. To do. In so-called reversal development in which toner is attached to a low potential portion of an electrostatic latent image for visualization, a nonmagnetic one-component developer that is charged with the same polarity as the polarity of the electrostatic latent image is used. High potential and low potential are expressed by absolute values. In any case, the nonmagnetic one-component developer 804 is charged with a polarity for developing the electrostatic latent image by friction with the developing sleeve 808.

  The developer supply / peeling member 813 is preferably an elastic roller member such as resin, rubber, or sponge. As the developer supply / peeling member 813, a belt member or a brush member may be used instead of the elastic roller. When the developer supply / peeling roller 813 made of an elastic roller is used as the developer supply / peeling member, the rotation direction of the developer supply / peeling roller 813 is appropriately the same direction or counter direction with respect to the developing sleeve. It is also possible to select. Usually, it is more preferable to rotate in the counter direction from the viewpoint of stripping and supplying properties.

  The penetration amount of the developer supply / peeling member 813 with respect to the developing sleeve 808 is preferably 0.5 mm or more and 2.5 mm or less from the viewpoint of developer supply and peelability. When the amount of penetration of the developer supply / peeling member 813 is 0.5 mm or more, the stripping property is improved, and the occurrence of ghost can be suppressed. When the intrusion amount is 2.5 mm or less, there is no toner damage, and it is possible to suppress toner deterioration, fusing and fogging.

  In the developing device shown in FIG. 5, an elastic blade 811 made of a material having rubber elasticity such as urethane rubber or silicone rubber, or a material having metal elasticity such as phosphor bronze or stainless copper is used. The elastic blade 811 is pressed against the developing sleeve 808 in a posture opposite to the rotation direction of the developing sleeve 808. As this elastic blade 811, polyamide elastomer (PAE) is attached to the surface of a phosphor bronze plate that can obtain a stable pressurizing force particularly for a stable regulation force and a stable (negative) chargeability to the toner. It is preferable to use a structure. Examples of the polyamide elastomer (PAE) include a copolymer of polyamide and polyether.

  The contact pressure of the developer layer thickness regulating member 811 with respect to the developing sleeve 808 is equal to or greater than the linear pressure of 0.049 N / cm or more and 0.49 N in this example, as shown in FIG. 4 using the magnetic one-component developer. / Cm or less is preferable. Such contact pressure is preferable in that the regulation of the developer can be stabilized and the developer layer thickness can be made suitable. When the contact pressure of the developer layer thickness regulating member 811 is set to a linear pressure of 0.049 N / cm or more, the regulation of the developer becomes appropriate, and the fog and the leakage of the non-magnetic one-component developer can be suppressed. It is. If the linear pressure is 0.49 N / cm or less, damage to the nonmagnetic one-component developer can be reduced, and deterioration of the nonmagnetic one-component developer and fusion to the sleeve and blade can be suppressed. .

  FIG. 6 is a schematic diagram showing a configuration of an example of an embodiment using a developing device according to the present invention that uses a two-component developer. Reference numeral 1 denotes a photosensitive drum as an image carrier. The photosensitive drum 1 includes three layers: an undercoat layer that suppresses light interference and improves the adhesion of the upper layer, a photocharge generation layer, and a charge transport layer on the surface of an aluminum cylinder (conductive drum base). It is configured.

  A charging device 2 uniformly charges the peripheral surface of the photosensitive drum 1, which is a magnetic brush type charging device in this example. A magnetic brush made of magnetic particles 2b is formed on the surface of the conveying sleeve 2 as a charging device by the magnetic force of the magnet roller 2a, and the magnetic brush is brought into contact with the surface of the photosensitive drum 1 to charge the photosensitive drum 1. Note that a charging bias is applied to the conveying sleeve 2 by the bias applying means S1. Reference numeral 3 denotes an exposure apparatus as information writing means for forming an electrostatic latent image on the surface of the charged photosensitive drum 1, and this example is a laser beam scanner. A laser beam L modulated in response to an image signal sent from a host device such as an image reading device (not shown) to the printer side is output, and the uniformly charged surface of the photosensitive drum 1 is subjected to laser scanning exposure at an exposure position. do. By this laser scanning exposure, the potential of the surface of the photosensitive drum 1 irradiated with the laser light L is lowered, and electrostatic latent images corresponding to the scanned and exposed image information are sequentially formed on the surface of the photosensitive drum 1. To go.

  Next, the two-component developing device used in the present invention will be described.

  The developing device (developing device) 4 is a developing device (developing device) as developing means for supplying a developer (toner) to the electrostatic latent image on the photosensitive drum 1 to visualize the electrostatic latent image. This is a reversal developing device of a component magnetic brush developing system.

  4a is a developing container. Reference numeral 4b denotes a developing sleeve as a developer carrying member. The developing sleeve 4b has a base, a conductive resin coating layer on the base, and a surface layer on the conductive resin coating layer. The substrate is usually made of a cylindrical body made of metal such as aluminum and its alloys, and stainless steel, but the metal is not particularly limited as long as it can be easily molded into the cylindrical body. The developing sleeve 4b is rotatably disposed in the developing container 4a with a part of its outer peripheral surface exposed to the outside. Reference numeral 4c denotes a magnet roller that is fixed in a non-rotating state and is inserted into the developing sleeve 4b. 4d is a developer coating blade, 4e is a two-component developer housed in the developer container 4a, 4f is a developer stirring member disposed on the bottom side of the developer container 4a, 4g is a toner hopper, and a replenishing toner Is housed.

  The two-component developer 4e in the developing container 4a is a mixture of toner and magnetic carrier and is stirred by the developer stirring material 4f. Basically, the toner is triboelectrically charged to the negative polarity by rubbing against the magnetic carrier by stirring the developer stirring material 4f. Further, the toner present in the vicinity of the developing sleeve 4b is triboelectrically charged by sliding with the developing sleeve 4b. The surface of the developing sleeve 4b is formed with the conductive resin coating layer and the surface layer as described above. In this embodiment, the toner is triboelectrically charged to the negative polarity.

  The developing sleeve 4b is disposed opposite to the photosensitive drum 1 so that the closest distance (referred to as SD gap) to the photosensitive drum 1 is maintained at 350 μm. The SD gap is preferably 100 μm or more and 1000 μm or less. When the SD gap is within the above range, carrier adhesion can be prevented and dot reproducibility can be improved. Further, when the SD gap is 100 μm or more, the supply of the developer is sufficiently ensured and the image density can be kept high. If the SD gap is 1000 μm or less, the magnetic lines of force from the magnetic pole do not spread too much, and the density of the magnetic lines of magnetic brush can be kept high. Thereby, it is possible to prevent deterioration of dot reproducibility and keep the carrier restraining force high and suppress carrier adhesion.

  A facing portion between the photosensitive drum 1 and the developing sleeve 4b is a developing portion. The developing sleeve 4b is rotationally driven in the direction opposite to the traveling direction of the photosensitive drum 1 in the developing unit. A part of the two-component developer 4e in the developing container 4a is adsorbed and held as a magnetic brush layer on the outer peripheral surface of the developing sleeve 4b by the magnetic force of the magnet roller 4c in the sleeve, and is rotated and conveyed as the sleeve rotates. . Then, a predetermined thin layer is formed by the developer coating blade 4d, and in contact with the surface of the photosensitive drum 1 at the developing portion, the surface of the photosensitive drum is rubbed appropriately.

  A predetermined developing bias is applied to the developing sleeve 4b from the power source S2. In this example, the developing bias voltage for the developing sleeve 4b is an oscillating voltage obtained by superimposing a DC voltage (Vdc) and an AC voltage (Vac). The voltage between the peaks of the oscillating voltage is preferably 300 V or more and 3000 V or less, and the frequency is 500 Hz or more and 10,000 Hz or less, preferably 1000 Hz or more and 7000 Hz or less. In this case, a triangular wave, a rectangular wave, a sine wave, a waveform with a changed duty ratio, an intermittent alternating superimposed electric field, or the like can be selected and used as the waveform. The toner in the developer conveyed to the developing unit by the rotating developing sleeve 4b is selectively attached to the surface of the photosensitive drum 1 corresponding to the electrostatic latent image by the electric field due to the developing bias, so that the electrostatic latent image becomes the toner. Developed as an image. In the case of this example, the toner adheres to the exposed bright portion of the surface of the photosensitive drum 1 and the electrostatic latent image is reversely developed.

  The developer thin layer on the developing sleeve 4b that has passed through the developing portion is returned to the developer reservoir in the developing container 4a as the developing sleeve 4b continues to rotate. In order to maintain the toner concentration of the two-component developer 4e in the developing container 4a within a predetermined substantially constant range, the toner concentration is detected by a toner concentration detecting sensor, and the toner is stored in the developing container 4a according to the detection information. The two-component developer 4e is replenished. Specifically, for example, the toner concentration of the two-component developer 4e in the developing container 4a is detected by a toner concentration detection sensor that measures a change in the magnetic permeability of the developer by using, for example, an inductance of a coil (not shown). . The toner hopper 4g is driven and controlled in accordance with the detected information, and the toner in the toner hopper 4g is supplied to the two-component developer 4e in the developing container 4a. The toner supplied to the two-component developer 4e is stirred by the stirring member 4f.

  The toner image formed on the photosensitive drum 1 is transferred to the transfer material P sent between the photosensitive drum 1 and the transfer roller 5, and the toner image on the transfer material P is fixed by the fixing device 6.

  3 to 6 schematically illustrate examples of embodiments in a developing device using the developer carrying member of the present invention. In addition to the developer layer thickness regulating member described above, various embodiments such as the shape of the developer container 503, the presence / absence of the agitating / conveying members 505 and 511, the arrangement of magnetic poles, the shape of the developer supply member 512, and the presence / absence of a replenishment container are available. Needless to say.

  Next, the developer (toner) used in the developing device of the present invention will be described.

  The developer (toner) used in the present invention is obtained by blending a binder resin for developer with a colorant, a charge control agent, a release agent, inorganic fine particles, and the like. There are one-component developers and non-magnetic one-component developers that do not contain magnetic materials. The format is appropriately selected according to the developing device.

  Further, the developer (toner) used in the present invention is preferably in a range of a weight average particle diameter of 4 μm or more and 11 μm or less regardless of the type. If such a toner is used, the toner charge amount or image quality and image density are balanced.

  As the binder resin for the developer (toner), generally known resins can be used, and examples thereof include vinyl resins, polyester resins, polyurethane resins, epoxy resins, phenol resins, etc. Among them, vinyl resins, Polyester resins are preferred.

  In the developer (toner), a charge control agent can be included in the toner particles (internal addition) or mixed with the toner particles (external addition) for the purpose of improving charging characteristics. This is because the charge control agent enables optimal charge amount control according to the development system.

  Examples of the positive charge control agent include the following. Modified products with nigrosine, triaminotriphenylmethane dyes and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate; dibutyltin oxide, dioctyl Diorganotin oxides such as tin oxide and dicyclohexyltin oxide; diorganotin borates such as dibutyltin borate, dioctyltin borate and dicyclohexyltin borate. The positive charge control agent can be used alone or in combination of two or more.

  As the negative charge control agent, for example, organometallic compounds and chelate compounds are effective. Examples thereof include aluminum acetylacetonate, iron (II) acetylacetonate, 3,5-ditertiary butyl salicylate, etc., particularly acetylacetone metal complexes, monoazo metal complexes, naphthoic acid or salicylic acid metal complexes or salts. Is preferred.

  When the developer (toner) is a magnetic developer (toner), for example, the following is blended as a magnetic material. Iron oxide-based metal oxides such as magnetite, maghemite, and ferrite; magnetic metals such as Fe, Co, and Ni; these metals and Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, Sb, Be, and Bi Alloys with metals such as Cd, Ca, Mn, Se, Ti, W, V; and mixtures thereof. In this case, these magnetic materials may also serve as a colorant.

  As the colorant blended in the developer (toner), pigments and dyes conventionally used in this field can be used, and they may be appropriately selected and used.

  A developer (toner) is preferably blended with a release agent. For example, the following are suitable. Low molecular weight polyethylene, low molecular weight polypropylene, aliphatic hydrocarbon waxes such as microcrystalline wax and paraffin wax, waxes mainly composed of fatty acid esters such as carnauba wax, Fischer-Tropsch wax, sazol wax and montan wax.

  Furthermore, inorganic fine powders such as silica, titanium oxide and alumina are externally added to the developer (toner) in order to improve environmental stability, charging stability, developability, fluidity, storage stability and cleaning properties. That is, it is preferably present in the vicinity of the surface of the developer. Among these, silica fine powder is preferable. An external additive other than the inorganic fine powder may be further added. For example, there are lubricants such as tetrafluoroethylene, zinc stearate, polyvinylidene fluoride (in particular, polyvinylidene fluoride), cerium oxide, strontium titanate, strontium silicate and the like.

  In order to prepare a developer (toner), first, a binder resin, a pigment or dye as a colorant, a release agent, a magnetic material, a charge control agent, and other additives as necessary are added to a Henschel mixer, a ball mixer. Thoroughly mix with a mixer. Next, this is melted using a heat kneader such as a heating roll, a kneader, or an extruder, and the release agent, pigment, dye, and magnetic substance are dispersed or dissolved while the resins are mutually compatible. The melt is cooled and solidified, and then pulverized and classified to obtain toner particles. Furthermore, it is possible to add a desired additive as required, and mix well with a mixer such as a Henschel mixer to obtain a developer (toner).

  When such a developer is used after being subjected to a spheroidizing treatment or a surface smoothing treatment by various methods, it is preferable because transferability is good. As such a method, an apparatus having a stirring blade or a blade, and a liner or a casing, for example, smoothes the surface by a mechanical force when the developer passes through a minute gap between the blade and the liner. There is a method of making the developer or spheroidizing the developer. In addition, there are a method of suspending toner in warm water and making it spherical, a method of exposing the toner to hot air and making it spherical.

  Further, as a method for directly producing a spherical developer, there is a method in which a mixture containing a monomer as a developer binder resin as a main component is suspended in water and polymerized to obtain a toner. In general, a monomer by uniformly dissolving or dispersing a polymerizable monomer, a colorant, a polymerization initiator, and, if necessary, a crosslinking agent, a magnetic material, a charge control agent, a release agent, and other additives. It is set as a composition. Thereafter, this monomer composition is dispersed in appropriate layers in a continuous layer containing a dispersion stabilizer, such as an aqueous phase, using an appropriate stirrer, and further subjected to a polymerization reaction to develop a developer having a desired particle size. It is a method of obtaining an agent.

  A known external additive can be used as an external additive externally added to the surface of the toner particles. One of them is inorganic fine particles, and it is preferable to use at least one of titanium oxide, alumina oxide and silica. The particle diameter of the inorganic fine particles is preferably 80 nm or more and 200 nm or less as a peak value based on the number distribution, from the viewpoint of functioning as spacer particles for improving toner separation from the carrier. The external additive is preferably used in combination with fine particles having an average particle diameter of 50 nm or less as a peak value based on the number distribution, in order to improve the chargeability and fluidity of the toner. Further, it is preferable to subject the inorganic fine particles to a hydrophobic treatment. When performing the hydrophobization treatment, it is preferable to use so-called coupling agents such as various titanium coupling agents and silane coupling agents, silicone oils, and the like.

  Examples of the surface treatment agent for performing the hydrophobization treatment include the following as a titanium coupling agent. Tetrabutyl titanate, tetraoctyl titanate, isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, bis (dioctyl pyrophosphate) oxyacetate titanate. Furthermore, the following are mentioned as a silane coupling agent. γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) γ -Aminopropyltrimethoxysilane hydrochloride, hexamethyldisilazane, methyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, phenyl Trimethoxysilane, o-methylphenyltrimethoxysilane, p-methylphenyltrimethoxysilane. Moreover, the following are mentioned as a fatty acid and its metal salt. Long chain fatty acids such as undecylic acid, lauric acid, tridecylic acid, dodecylic acid, myristic acid, palmitic acid, pentadecylic acid, stearic acid, heptadecylic acid, arachidic acid, montanic acid, oleic acid, linoleic acid, arachidonic acid. In addition, examples of the metal salt include salts with metals such as zinc, iron, magnesium, aluminum, calcium, sodium, and lithium. Further, examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, and amino-modified silicone oil.

  These surface treatment agents may be coated by adding 1% by mass or more and 10% by mass or less with respect to the inorganic fine particles, and preferably 3% by mass or more and 7% by mass or less. Moreover, it is also possible to use these materials in combination. The content of the inorganic fine particles is preferably 0.1% by mass or more and 5.0% by mass or less in the toner, and more preferably 0.5% by mass or more and 4.0% by mass or less. In addition, various external additives may be used in combination.

  In the case of a two-component developer, the carrier preferably has a number average particle diameter (Dv) of 15.0 μm or more and 70.0 μm or less. By controlling within the above range, the shape of the magnetic carrier can be controlled to be substantially spherical and uniform, so that good charging performance can be maintained. More preferably, the number average particle diameter (Dv) is 20.0 μm or more and 50.0 μm or less, which is excellent in terms of high image quality and durability stability.

The carrier in the present invention preferably has a true specific gravity of 3.0 g / cm ³ or more and 5.0 g / cm ³ or less, more preferably 3.2 g / cm ³ or more and 4.0 g / cm ³ or less. When the true specific gravity is within this range, the load on the toner is small in the stirring and mixing of the carrier and the toner, the toner spent on the carrier is suppressed, and the toner separation can be maintained well for a long period of time. This is preferable because adhesion of the carrier is suppressed.

  In the present invention, a magnetic carrier having a resin component on at least its surface is used. For example, magnetic metal dispersion such as magnetic metal such as iron, copper, nickel, cobalt, etc., having a resin coating layer on the core material of magnetic oxide such as magnetite, ferrite, etc. A mold carrier can be used.

  In particular, in the present invention, in order to obtain a desired circularity, it is preferable to use a magnetic fine particle dispersed resin carrier using a carrier core in which magnetic fine particles are dispersed in a binder resin. Among them, it is preferable to use a magnetic fine particle dispersed resin carrier using a carrier core directly produced through a polymerization step in order to increase the average circularity and narrow the circularity distribution. The particle size of the magnetic fine particles to be used has a peak value of about 80 nm or more and 800 nm or less on the basis of the number distribution, in order to prevent the magnetic fine particles from detaching, to increase the carrier strength, and to make the carrier shape into a substantially spherical shape. It is preferable to suppress.

  The amount of magnetic fine particles used in the magnetic fine particle dispersed resin carrier is 70% by mass to 95% by mass with respect to the carrier in order to reduce the true specific gravity of the carrier and sufficiently secure the mechanical strength. Is preferable. More preferably, it is 80 mass% or more and 92 mass% or less. Moreover, it is also preferable for suppressing the abundance of amorphous carriers with low circularity. Further, in order to change the magnetic properties of the carrier, the magnetic fine particle dispersed core particles may contain a nonmagnetic inorganic compound in addition to the magnetic fine particles. The particle diameter of the nonmagnetic inorganic compound is preferably such that the peak value is about 100 nm to 1000 nm on the basis of the number distribution because the specific resistance of the carrier can be easily controlled.

  When a nonmagnetic inorganic compound is used in combination with a magnetic substance, the magnetic fine particles are contained in an amount of 50% by mass or more based on the total amount of the magnetic fine particles and the nonmagnetic inorganic compound. This is preferable for preventing carrier adhesion.

In the magnetic fine particle dispersed resin carrier, the magnetic fine particles are preferably magnetite fine particles or magnetic ferrite fine particles containing at least an iron element and a magnesium element. The nonmagnetic inorganic compound is more preferably hematite (α-Fe ₂ O ₃ ) fine particles in order to adjust the magnetic properties and true specific gravity of the carrier.

  Examples of the binder resin that forms the carrier core include vinyl resins having a methylene unit in the polymer chain, polyester resins, epoxy resins, phenol resins, urea resins, polyurethane resins, polyimide resins, cellulose resins, and polyether resins. These resins may be used as a mixture.

  The following are mentioned as a vinyl-type monomer for forming the said vinyl resin. Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- n-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene Styrene derivatives such as ethylene, propylene, butylene and isobutylene; unsaturated diolefins such as butadiene and isoprene; vinyl chloride, chloride Halogens such as vinylidene, vinyl bromide, vinyl fluoride Vinyl; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methacrylic acid; methyl methacrylate, ethyl methacrylate, propyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, Α-methylene aliphatic monocarboxylic acid ester such as dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate; acrylic acid; methyl acrylate, ethyl acrylate, acrylic acid-n-butyl, acrylic acid Acrylate esters such as isobutyl, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate Maleic acid, maleic acid half esters; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N-vinyl compounds such as N-vinylindole and N-vinylpyrrolidone; vinylnaphthalene; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide; acrolein and the like. A polymer obtained by polymerizing one or more of these is used as the vinyl resin.

  A preferred method for producing a magnetic fine particle-dispersed resin carrier core is a method of mixing a binder resin monomer and magnetic fine particles and polymerizing the monomer to obtain magnetic fine particle-dispersed carrier core particles. At this time, as the monomer used for the polymerization, the following are used in addition to the above-described vinyl monomers. Bisphenols and epichlorohydrin for forming epoxy resins; Phenols and aldehydes for forming phenolic resins; Urea and aldehydes, melamine and aldehydes for forming urea resins. For example, as a method of producing magnetic fine particle dispersed core particles using a curable phenol resin, magnetic fine particles are placed in an aqueous medium, and phenols and aldehydes are polymerized in the aqueous medium in the presence of a basic catalyst. There are methods for obtaining magnetic fine particle dispersed carrier core particles.

  Examples of phenols for producing a phenol resin include the following compounds in addition to phenol itself. Alkylphenols such as m-cresol, p-tert-butylphenol, o-propylphenol, resorcinol, bisphenol A, and halogenated phenols in which part or all of the benzene nucleus or alkyl group is substituted with chlorine or bromine atoms. A compound having a phenolic hydroxyl group. Of these, phenol (hydroxybenzene) is more preferable.

  Examples of aldehydes include formaldehyde and furfural in the form of either formalin or paraaldehyde. Of these, formaldehyde is particularly preferable. The molar ratio of aldehydes to phenols is preferably 1.0 or more and 4.0 or less, and particularly preferably 1.2 or more and 3.0 or less from the viewpoint of reactivity optimization.

  Examples of the basic catalyst used in the condensation polymerization of phenols and aldehydes include those used in the production of ordinary resol type resins. Examples of such a basic catalyst include aqueous ammonia, hexamethylenetetramine and alkylamines such as dimethylamine, diethyltriamine, and polyethyleneimine. The molar ratio of these basic catalysts to phenols is preferably 0.02 or more and 0.30 or less.

In the present invention, in order to obtain a substantially spherical carrier having an average circularity of 0.935 or more, more preferably 0.950 or more, and as one method for reducing variation in circularity, dissolution at the start of polymerization is performed. It is important to control the amount of oxygen. The amount of dissolved oxygen in the reaction medium at the start of the polymerization reaction is preferably 5.0 g / m ³ or less. From an industrial viewpoint, the inert gas introduced into the reaction medium for the purpose of degassing dissolved oxygen during the polymerization reaction is preferably at least one selected from nitrogen gas, argon gas, and helium gas. The amount of the inert gas introduced is preferably 5% by volume / min to 100% by volume / min of the reaction vessel volume before the polymerization reaction. The amount of gas introduced into the reaction medium during the polymerization reaction is preferably 1% by volume / min or more and 20% by volume / min or less, and the amount introduced during the polymerization reaction is preferably smaller than before the polymerization reaction. By doing so, it is possible to increase the substitution efficiency of dissolved oxygen to prevent the formation of fine particles, and to suppress the incorporation of the fine particles into normal particles and deforming them.

  Furthermore, in order to polymerize the monomer and obtain magnetic fine particle dispersed carrier core particles, it is important to control the stirring blade peripheral speed to 1.0 mm / sec or more and 3.5 mm / sec or less. By controlling within the above range, it is possible to keep the crushing force of the particles during polymerization constant and suppress the generation of amorphous particles.

  As the resin for coating the surface of the carrier, an insulating resin is preferably used. The insulating resin that can be used in this case may be a thermoplastic resin or a thermosetting resin.

  Specific examples of the thermoplastic resin include the following. Acrylic resins such as polystyrene, polymethyl methacrylate and styrene-acrylic acid copolymer, styrene-butadiene copolymer, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinyl acetate, polyvinylidene fluoride resin, fluorocarbon resin, Fluorocarbon resin, solvent-soluble perfluorocarbon resin, polyvinyl alcohol, polyvinyl acetal, polyvinylpyrrolidone, petroleum resin, cellulose, cellulose acetate, cellulose nitrate, methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and other cellulose derivatives, novolak resin, low molecular weight Polyethylene, saturated alkyl polyester resin, polyethylene terephthalate, polybutylene terephthalate, polyarylate Said aromatic polyester resins, polyamide resins, polyacetal resins, polycarbonate resins, polyethersulfone resins, polysulfone resins, polyphenylene sulfide resins, polyether ketone resins.

  Specific examples of the thermosetting resin include the following. Phenol resin, modified phenol resin, maleic resin, alkyd resin, epoxy resin, acrylic resin, or unsaturated polyester obtained by polycondensation of maleic anhydride, terephthalic acid and polyhydric alcohol, urea resin, melamine resin, urea- Melamine resin, xylene resin, toluene resin, guanamine resin, melamine-guanamine resin, acetoguanamine resin, gliptal resin, furan resin, silicone resin, polyimide resin, polyamideimide resin, polyetherimide resin, polyurethane resin and the like.

  The above-mentioned resins can be used alone or in combination. It is also possible to mix a curing agent or the like with a thermoplastic resin and cure it. In a particularly preferred form, it is preferable to use a resin coating material that has a high charge imparting ability with respect to the toner and that has a higher releasability.

  In the present invention, a silicone resin is preferably used from the viewpoint of adhesion to the carrier core, prevention of spent, and strength of the coating layer. The silicone resin can be used alone, but is preferably used in combination with a coupling agent in order to increase the strength of the coating layer and to preferably control the charged state of the toner. Furthermore, it is preferable that the above-mentioned coupling agent is used as a so-called primer agent in which a part thereof is treated on the surface of the carrier core before being coated with the coating material. By treating the surface of the carrier core with a coupling agent, a coating layer formed thereafter with a coating material can be formed in a more adhesive state with a covalent bond.

  Aminosilane is preferably used as the coupling agent. As a result, an amino group having positive chargeability can be introduced on the surface of the carrier, and it is possible to satisfactorily impart high negative charge characteristics to the toner.

Further, when coating the surface of the carrier with the coating resin, it is preferable to coat in a reduced pressure state at a temperature of 30 ° C. or higher and 80 ° C. or lower. The reason is not clear, but is expected to be described below.
(1) A moderate reaction proceeds at the coating stage, and the surface of the carrier core is coated uniformly and smoothly on the surface of the carrier core.
(2) In the baking step, a low temperature treatment at at least 160 ° C. is possible, and excessive crosslinking of the resin can be prevented, and the durability of the coating layer can be enhanced.

  Furthermore, the coating resin contains fine particles at a ratio of 1 part by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the coating resin, thereby controlling minute irregularities on the surface of the carrier and improving toner separation. This is preferable. As the fine particles, either organic or inorganic fine particles can be used, but it is necessary to maintain the shape of the particles when coating the carrier, and it is possible to preferably use crosslinked resin particles or inorganic fine particles. is there. Specifically, as the organic fine particles, a crosslinked polymethyl methacrylate resin, a crosslinked polystyrene resin, a melamine resin, a phenol resin, or a nylon resin can be used. Further, silica, titanium oxide, and alumina can be used as the inorganic fine particles. These organic or inorganic fine particles can be used alone or in admixture of two or more. In particular, it is preferable to use a crosslinked polymethyl methacrylate resin or a melamine resin alone or in combination in order to achieve both a high negative charge amount imparted to the toner and releasability with the toner.

  The particle diameter of the organic or inorganic fine particles has a peak value of 100 nm or more and 500 nm or less on the basis of the number distribution. Depending on the coating amount, fine irregularities on the surface of the carrier are formed, and the toner separation is improved. preferable. More preferably, it is 150 nm or more and 400 nm or less.

  Moreover, it is preferable to add 1 to 40 parts by mass of organic or inorganic fine particles with respect to 100 parts by mass of the coating resin, and further contain 1 to 15 parts by mass of conductive particles. By doing this, the specific resistance of the carrier is not lowered too much, the residual charge on the surface of the carrier is removed, and the toner separation can be improved.

As the conductive particles, the specific resistance of preferably the following 1 × 10 ⁸ Ω · cm, further, the specific resistance is more preferably the following 1 × 10 ⁸ Ω · cm. Specifically, the conductive particles are preferably particles selected from carbon black, magnetite, graphite, zinc oxide, tin oxide particles, and the like. Among these, carbon black can be preferably used since it has a small particle size and does not obstruct irregularities caused by fine particles on the surface of the carrier. The conductive particles have a peak value of 10 nm or more and 500 nm or less (more preferably 20 nm or more and 200 nm or less) on the basis of the number distribution. It is preferable for preventing desorption well. Furthermore, it is possible to suppress the leakage to the developer carrying member and to form a stable magnetic brush over a long period of time.

  The coating amount of the carrier coat resin is 0.3 parts by mass or more and 4.0 parts by mass or less with respect to 100 parts by mass of the carrier core particles. This is preferable. More preferably, it is 0.8 parts by mass or more and 3.5 parts by mass or less from the viewpoint of uniform spike formation on the developer carrier and prevention of fusion.

  It is preferable that the carrier and the toner used in the present invention are mixed and used so as to have a specific surface area. The toner concentration in the two-component developer is preferably 5% by mass or more and 20% by mass or less from the viewpoint of charge amount provision, fogging, image density, and the like.

  The physical property measurement method according to the present invention will be described below.

(1) Measuring method of ESCA The silicon atom content on the surface of the resin coating layer was measured under the following conditions using X-ray photoelectron spectroscopy on the surface of the resin coating layer. For X-ray photoelectron spectroscopy, Quantum 2000 (trade name) manufactured by ULVAC-PHI Co., Ltd. was used.
X-ray source: Monochrome Al Kα
Xray Setting: 100 μmφ (100 W (20 KV))
Photoelectron extraction angle: 45 degrees Neutralization condition: Combined use of neutralization gun and ion gun Analysis area: 300 × 1500 μm
Pass Energy: 11.75 eV
Step size: 0.05eV
Here, in the quantitative analysis of each atom, each atom concentration (atomic%) was obtained using the following peaks.
C 1s (Bonding Energy: 280 eV to 295 eV)
N 1s (Bonding Energy: 395 eV to 410 eV)
O 1s (Bonding Energy: 525 eV to 540 eV)
S 2p (Bonding Energy: 160 eV to 175 eV)
Fe 2p3 (Bonding Energy: 706 eV to 730 eV)
Three similar developer carriers were prepared for the measurement of one formulation. A developer carrier not printed at all is used for initial ESCA measurement, and an initial image evaluation is performed until the 100th image is printed. The developer carrier is used for 100th ESCA measurement. The developer carrying member that had been evaluated up to the image evaluation was used for ESCA measurement after endurance. As a preparation method of the measurement sample, the developer carrier is cut into 5 mm × 5 mm square, and for measurements other than the initial developer carrier, the toner is immersed in MEK to remove toner adhesion by ultrasonic cleaning, and then dried. And evaluated.

(2) Work function For measurement of the work function, an optoelectronic measuring device AC-1 (trade name) manufactured by Riken Keiki Co., Ltd. was used. This measuring instrument is characterized in that the work function of the surface of the developing sleeve 2 can be easily measured in the atmosphere. Then, it is confirmed that the measured work function shows almost the same value as compared with the literature value of the Kelvin method (contact potential method) (IBM, J. RES. DEVELOP 22, 1978).

  In the measurement, a sodium lamp is used as a measurement light source, and the emission intensity is 500 nW.

(3) Interplanar spacing of the graphite particles and the graphite (002) plane of the resin coating layer (graphite d (002))
For the resin coating layer, a powdered material scraped from the developing sleeve was used as a measurement sample, and the graphite particles were used as they were as a measurement sample. And what was filled in the non-reflective sample board obtained the X-ray-diffraction chart which used CuK (alpha) ray as a radiation source with the sample horizontal type | mold strong X-ray-diffraction apparatus RINT / TTR-II (brand name) made from Rigaku. In the present specification, CuKα rays that are monochromatized with a monochromator are used.

  From this X-ray diffraction chart, the peak position of the diffraction line from the graphite (002) plane was determined from the X-ray diffraction spectrum, and the graphite d (002) was calculated from the Bragg formula (the following formula (2)). Here, the wavelength λ of the CuKα ray is 0.15418 nm.

Graphite d (002) = λ / 2sin θ Formula (2)
Main measurement conditions Optical system: Parallel beam optical system goniometer: Rotor horizontal goniometer (TTR-2)
Tube voltage / current: 50 kV / 300 mA
Measurement method: Continuous scan axis: 2θ / θ
Measurement angle: 10 ° to 50 °
Sampling interval: 0.02 °
Scanning speed: 4 ° / min
Divergent slit: Open divergence longitudinal slit: 10 mm
Scattering slit: Open light receiving slit: 1.00 mm
(4) Volume resistance of resin coating layer A resin coating layer having a thickness of 7 μm to 20 μm was formed on a PET sheet having a thickness of 100 μm, and measurement was performed at 20 ° C. to 25 ° C. and 50% RH to 60% RH. . A voltage drop type digital ohm meter (Kawaguchi Electric Co., Ltd.) provided with a 4-terminal structure electrode for volume resistance measurement of conductive rubber and plastic in accordance with ASTM standard D-991-89 (1994) and Japan Rubber Association standard SRIS 2301-1969. Seisakusho Co., Ltd.) was used.

(5) ¹ H-NMR spectrum measurement and measurement apparatus for polymer: FT NMR apparatus JNM-EX400 (trade name, manufactured by JEOL Ltd.)
Measurement frequency: 400 MHz
Pulse condition: 5.0 μs
Data points: 32768
Frequency range: 10500Hz
Integration count: 10000 times Measurement temperature: 60 ° C
50 mg of a sample to be measured was put in a sample tube having a diameter of 5 mm, CDCl ₃ was added as a solvent, and this was prepared by dissolving in a constant temperature bath at 60 ° C. and measured.

(6) Viscosity average molecular weight of polymer 0.5 g of a sample was dissolved in 100 ml of dichloromethane, and the specific viscosity at 25 ° C. was measured using an Ubelode type viscometer. The intrinsic viscosity was determined from this specific viscosity, and the viscosity average molecular weight (Mv) was calculated by setting K and a in the Mark-Houwink viscosity formula to 1.23 × 10 −4 and 0.83, respectively.

(7) Particle size of conductive particles and spherical particles of 1 μm or more The particle size of conductive particles such as graphite and graphite particles is measured by a laser diffraction particle size distribution meter Coulter LS-230 particle size distribution meter (Beckman Coulter, (Trade name). As a measuring method, a small amount module was used, and isopropyl alcohol (IPA) was used as a measuring solvent. The measurement system of the particle size distribution analyzer was washed with IPA for about 5 minutes, and the background function was executed after washing. Next, 1 mg to 25 mg of a measurement sample was added to 50 ml of IPA. The solution in which the sample was suspended was subjected to a dispersion treatment with an ultrasonic disperser for about 1 minute to 3 minutes to obtain a test sample solution. The test sample solution is gradually added into the measurement system of the measurement device, and the measurement is performed by adjusting the sample concentration in the measurement system so that the PIDS on the screen of the device is 45% to 55%. The volume average particle size calculated from the distribution was determined.

(8) Toner Particle Size Measurement A Coulter Counter TA-II type, Coulter Multisizer II or Coulter Multisizer III (both manufactured by Beckman Coulter, Inc., trade name) was used as a measuring device. As an electrolytic solution, an about 1 mass% NaCl aqueous solution prepared by dissolving sodium chloride (reagent grade 1) or ISOTON-II (trade name, manufactured by Beckman Coulter, Inc.) was used. Surfactant (alkylbenzene sulfonate solution) 0.1 ml or more and 5 ml or less were added as a dispersant in the electrolyte solution 100 ml or more and 150 ml or less. Next, 2 mg or more and 20 mg or less of the sample was added, and a dispersion treatment was performed for about 1 minute or more and 3 minutes or less with an ultrasonic disperser to prepare a test sample. The volume and number of spherical particles or toner particles in the test sample were measured using a 100 μm aperture or a 30 μm aperture of the measuring device.

  The volume distribution and the number distribution are calculated from the measurement results, and the weight-based weight average particle diameter (D4) obtained from the volume distribution and the number-based length average particle diameter (D1) obtained from the number distribution (both for each channel). The median value of each channel is a representative value for each channel).

(9) Surface roughness of the surface of the developer carrying member (Ra: arithmetic average roughness)
With a surface roughness measuring instrument “Surfcoder SE-3500” (trade name) manufactured by Kosaka Laboratory Co., Ltd., which conforms to the surface roughness (JIS B0601-2001), a total of 9 in the axial direction and 3 in the circumferential direction It measured about the location and made the average value surface roughness Ra. The cut-off was 0.8 mm, the measurement distance was 8.0 mm, and the feed rate was 0.5 mm / sec.

  In the measurement during the endurance (100th sheet) or after the endurance, the developer carrying member was once separated from the developing device, and the surface of the developer carrying member was washed with isopropanol.

(10) Layer thickness and scraping amount of the resin coating layer Using a dimension measuring device “LS5000 series” (trade name) manufactured by Keyence Corporation that measures the outer diameter of the cylinder with laser light, the sleeve before the resin coating layer is formed. The outer diameter (S ₀ ), the outer diameter after forming the resin coating layer (S ₁ ), and the outer diameter after durable use (S ₂ ) were measured. Then, from these values, the thickness (S ₁ -S ₀ ) of the resin coating layer and the scraping amount (film scraping) (S ₁ -S ₂ ) of the resin coating layer were calculated.

  For the measurement, a controller LS-5500 and a sensor head LS-5040T of the apparatus were used. The sensor unit is separately fixed to a device equipped with a sleeve fixing jig and a sleeve feeding mechanism, divided into 30 parts in the longitudinal direction of the sleeve, 30 places, and further 30 places after rotating the sleeve 90 ° circumferentially, a total of 60 places The outer diameter of the sleeve was measured for each location. The outer diameter dimension was the average value.

  The outer diameter of the sleeve after endurance use was measured after removing the toner fused material fused on the surface by ultrasonic cleaning in methyl ethyl ketone.

(11) Average circularity of toner particles Measurement was performed under an environment of 23 ° C./60% RH using a flow type particle image analyzer FPIA-2100 (trade name) manufactured by Sysmex Corporation. For toner particles having a circle equivalent diameter in the range of 0.60 μm or more and 400 μm or less, the area of the projected image and the perimeter were measured, and the circle equivalent diameter was determined from the area of the projected image of the toner particles measured there. Further, the circularity of toner particles having an equivalent circle diameter in the range of 0.60 μm or more and 400 μm or less was determined by the following equation. Further, for toner particles having an equivalent circle diameter of 3 μm or more and 400 μm or less, the total circularity and the total number of particles were determined. The value obtained by dividing the total sum of the obtained circularity by the total number of particles was defined as the average circularity.

Circularity a = L ₀ / L
(In the formula, L ₀ indicates the circumference of a circle having the same area as the area of the projected image of the toner particles, and L is image processed at an image processing resolution of 512 × 512 (pixels of 0.3 μm × 0.3 μm). (Indicates the perimeter of the projected image of the toner particles.)
The circularity is an index of the degree of unevenness of the toner particles, and indicates 1.00 when the toner particles are perfectly spherical, and the circularity becomes smaller as the surface shape becomes more complicated. As a specific measurement method, a surfactant, preferably an alkylbenzene sulfonate, is added in an amount of 0.1 ml to 0.5 ml as a dispersant in 200 ml to 300 ml of water from which impurities have been previously removed. Add about 1g to 0.5g. The suspension in which the sample is dispersed is dispersed with an ultrasonic transmitter for 2 minutes to prepare a test sample solution having a toner particle concentration of 20,000 / μl or more and 10,000,000 / μl or less. The circularity distribution of the toner particles is measured. As the ultrasonic transmitter, for example, the following apparatus is used, and the following dispersion conditions are used.
UH-150 (trade name, manufactured by SMT Co., Ltd.)
OUTPUT level: 5
The outline of constant mode measurement is as follows.

  The test sample solution is passed through a flow path (expanded along the flow direction) of a flat and flat flow cell (thickness: about 200 μm). A strobe and a CCD camera are mounted on opposite sides of the flow cell so as to form an optical path that passes across the thickness of the flow cell. While the sample liquid is flowing, stroboscopic light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, and each particle is a two-dimensional projection having a certain range parallel to the flow cell. Taken as an image. From the projected image area of each particle, the diameter of a circle having the same area is calculated as the equivalent circle diameter. Further, the equivalent circle diameter of each particle is obtained from the area of the projected image of each particle having a circle equivalent diameter of 0.60 μm or more and 400 μm or less and the perimeter of the projection image using the above-described circularity calculation formula. Further, based on the obtained result, an average circularity (sometimes referred to as an average circularity) of toner particles having an equivalent circle diameter of 3 μm or more and 400 μm or less is calculated.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. Note that “parts” and “%” in the following formulations represent “parts by mass” and “% by mass”, respectively, unless otherwise specified.

[Conductive agent G-1]
Mesocarbon microbeads obtained by heat treatment of heavy coal oil were washed and dried, then mechanically dispersed with an atomizer mill, and carbonized by primary heat treatment at 800 ° C. in a nitrogen atmosphere. . Next, secondary dispersion was performed with an atomizer mill, followed by heat treatment at 2900 ° C. in a nitrogen atmosphere, and further classified to collect graphitized particles having a volume average particle size of 4.7 μm to obtain a conductive agent G-1.

[Conductive agent G-2]
Carbon black # 5500 (manufactured by Tokai Carbon Co., Ltd. (trade name), primary particle diameter 25 nm, DBP oil absorption 155 ml / 100 g) was used as the conductive agent G-2.

[Unevenness imparting particles P-1]
As the irregularity imparting particles P-1, Nika beads ICB-0520 (Nippon Carbon Co., Ltd. (trade name), average particle size 6.1 μm) made of glassy carbon, which is spherical particles, were used.

[Unevenness imparting particles P-2]
As the irregularity imparting particles P-2, Nika beads ICB-1020 (Nippon Carbon Co., Ltd. (trade name), average particle diameter of 11.7 μm) made of glassy carbon, which is spherical particles, were used.

[Toner Production Example Z-1]
Polyester resin 100 parts (Glass transition temperature (Tg): 58.3 ° C., weight average molecular weight: 7500)
Magnetic material (average particle size: 0.24 μm) 96 parts Monoazo iron complex 2 parts Polypropylene (melting point: 145 ° C) 3.4 parts The mixture was premixed with a Henschel mixer and then heated to 110 ° C 2 The kneaded material was melt-kneaded with a shaft extruder and the cooled kneaded material was coarsely pulverized with a hammer mill to obtain a coarsely pulverized toner product. The obtained coarsely pulverized toner was coated with a mechanical pulverizer turbo mill (trade name, manufactured by Turbo Kogyo Co., Ltd .; chromium alloy plating containing chromium carbide on the surfaces of the rotor and stator (plating thickness 150 μm, surface hardness HV1050). )) Was mechanically pulverized. The finely pulverized product obtained was classified and removed at the same time with a multi-division classifier (manufactured by Nippon Steel Mining Co., Ltd., trade name: Elbow Jet Classifier) using the Coanda effect. Through the above steps, negatively chargeable toner particles having a weight average particle diameter (D ₄ ) of 6.3 μm and an average circularity of 0.962 measured by a Coulter counter method were obtained.

  100 parts of the toner particles and 1.2 parts of hydrophobic silica fine powder treated with hexamethyldisilazane and then treated with dimethylsilicone oil were mixed with a Henschel mixer to prepare negatively charged toner Z-1. .

[Toner Production Example Z-2]
Styrene-butyl acrylate-acrylic acid copolymer (Tg: 62.1 ° C., weight average molecular weight: 13000) 100 parts Magnetic substance (average particle size: 0.21 μm) 96 parts Monoazo iron complex 1.5 parts Paraffin (melting point: 76 ° C.) 4.2 parts The weight average particle diameter (D ₄ ) measured by the Coulter counter method through the same steps as in toner production example Z-1 except that the above mixture was used. Negatively charged toner particles having a thickness of 6.5 μm and an average circularity of 0.949 were obtained.

  100 parts of the toner particles and 1.2 parts of hydrophobic silica fine powder treated with hexamethyldisilazane and then treated with dimethylsilicone oil were mixed with a Henschel mixer to prepare negatively charged toner Z-2. .

[Toner Production Example Z-3]
A polymerization toner was prepared according to the following procedure.

  To 900 parts of ion-exchanged water heated to 60 ° C., 3 parts of tricalcium phosphate is added and stirred at 10,000 rpm using a TK homomixer (trade name, manufactured by Tokushu Kika Kogyo Co., Ltd.). A medium was made.

In addition, the following formulation was put into a homogenizer (manufactured by Nippon Seiki Co., Ltd.), heated to 60 ° C., and then stirred at 8,000 rpm using a TK homomixer (trade name, manufactured by Tokushu Kika Kogyo Co., Ltd.) Distributed. Further, 5 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.
-Styrene 130 parts-n-butyl acrylate 60 parts-C.I. I. Pigment Blue 15: 3 18 parts, aluminum salicylate compound 3 parts (Bontron E-88 (trade name): manufactured by Orient Chemical Co., Ltd.)
Polyester resin 14 parts (polycondensation product of propylene oxide modified bisphenol A and isophthalic acid, Tg = 65 ° C., Mw = 10000, Mn = 6000)
・ 40 parts of stearyl stearate wax (DSC main peak 60 ° C.)
・ Divinylbenzene 0.5 part The above polymerizable monomer composition was put into the aqueous medium, and the mixture was used at 60 ° C. under a nitrogen atmosphere using a TK homomixer (trade name, manufactured by Tokushu Kika Kogyo Co., Ltd.). The mixture was stirred and granulated at 1,000 rpm.

  Thereafter, the mixture was transferred to a reaction vessel equipped with a propeller type stirring device and stirred, and the temperature was raised to 70 ° C. over 2 hours. After another 4 hours, the temperature was raised to 80 ° C. at a heating rate of 40 ° C./Hr. Reaction was carried out at 5 ° C. for 5 hours to produce polymer particles. After completion of the polymerization reaction, the slurry containing the polymer particles is cooled, washed with 10 times the amount of water as the slurry, filtered and dried, and then the particle size is adjusted by classification to obtain cyan toner base particles (weight average particle size). 6.4 μm, average circularity 0.972).

To 100 parts of the toner base particles, the following were dry-mixed with a Henschel mixer (Mitsui Mining Co., Ltd.) for 5 minutes to obtain toner Z-3 as a non-magnetic one-component developer having an average circularity of 0.972. .
-Toner base particle 100 parts-Hydrophobic silica fine powder surface-treated with hexamethylene disilazane 1.0 part (average primary particle size 7 nm)
-0.18 part of rutile titanium oxide fine powder (average primary particle size 45 nm)
・ 0.5 parts of rutile titanium oxide fine powder (average primary particle size 200 nm)
[Toner Production Example Z-4]
As a vinyl copolymer material, 10 parts of styrene, 5 parts of 2-ethylhexyl acrylate, 2 parts of fumaric acid, 5 parts of dimer of α-methylstyrene, and 5 parts of dicumyl peroxide were placed in a dropping funnel. Further, the following materials were charged into a glass 4-liter four-necked flask as a material for the polyester unit.
・ Polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane
25 parts polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane
15 parts ・ 9 parts of terephthalic acid ・ 4 parts of trimellitic anhydride ・ 25 parts of fumaric acid ・ 0.3 part of tin 2-ethylhexanoate 0.3 parts A thermometer, a stirring bar, a condenser and a nitrogen inlet tube are attached to this four-necked flask. This four-necked flask was placed in a mantle heater. Next, after the inside of the four-necked flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and while stirring at a temperature of 130 ° C., the monomer of the vinyl copolymer and The polymerization initiator was added dropwise over about 5 hours. Next, the temperature was raised to 200 ° C. and the reaction was carried out for about 5 hours to obtain a resin having a weight average molecular weight of 80500 and a number average molecular weight of 4100.
-100 parts of the above resin-5 parts of purified normal paraffin (maximum endothermic peak temperature 80 ° C, weight average molecular weight 800)
・ Aluminium 3,5-di-t-butylsalicylate compound 0.6 parts I. Pigment Blue 15: 3 5 parts A biaxial kneader (commercial product: FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.) after mixing the ingredients of the above formulation with a Henschel mixer (commercial name: FM-75) Name: Kneaded with PCM-30 type, manufactured by Ikekai Tekko Co., Ltd. The obtained kneaded product was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized toner. The obtained coarsely pulverized toner was finely pulverized using a collision-type airflow pulverizer using high-pressure gas to obtain a finely pulverized product. The obtained toner fine powder was classified by a multi-division classifier using the Coanda effect to obtain cyan particles having a weight average particle size of 6.0 μm and an average circularity of 0.935. This is designated as toner intermediate 1. Further, the toner intermediate 1 was subjected to surface modification with a hybridizer (manufactured by Nara Machinery Co., Ltd.) at a rotational speed of 6600 rpm, a processing time of 4 minutes, and a processing frequency of 2 times, and a weight average particle diameter of 6.1 μm and an average circularity of 0. 952 of cyan toner Z-4 was obtained.

(Synthesis of polymer 1)
To 500 ml of 10% aqueous sodium hydroxide solution, 120 g of bisphenol represented by the exemplary compound (3-13) was added and dissolved. To this solution, 300 ml of dichloromethane was added and stirred, and 100 g of phosgene was blown in over 1 hour while maintaining the solution temperature at 10 to 15 ° C. When about 70% of phosgene was blown, 140 g of a siloxane compound having an average repeating unit m = 90 represented by Example Compound (4-1) and a siloxane compound having an average repeating unit n = 90 represented by Example Compound (5-1) 140 g was added to the solution. After the introduction of phosgene was completed, the mixture was vigorously stirred to emulsify the reaction solution, 0.2 ml of triethylamine was added, and the mixture was stirred for 1 hour. Thereafter, the dichloromethane phase was neutralized with phosphoric acid and further washed with water until the pH reached about 7. Subsequently, this liquid phase was dropped into isopropanol, and the precipitate was filtered and dried to obtain a white powdery polymer 1 (siloxane-modified polycarbonate polymer).

When the infrared absorption spectrum of the obtained polymer 1 was measured, absorption due to a carbonyl group, absorption due to an ether bond at 1240 cm ⁻¹ , and absorption due to a carbonate bond were confirmed. Furthermore, although a peak attributable to siloxane at 1100 to 1000 cm ⁻¹ was also observed, there was almost no absorption at 3650 to 3200 cm ⁻¹ and no hydroxyl group was observed. ^{Also in 1} H-NMR, it was confirmed that siloxane sites and polycarbonate sites were present. Moreover, when the obtained polymer 1 was measured by MALDI-TOF-MS (made by BRUKER), the siloxane part formed from the exemplary compound (4-1) and the siloxane formed from the exemplary compound (5-1) The site was confirmed to be about 1: 1. It was also confirmed that the average of the average repeating units in the polymer 1 was approximately m: n = 90: 90. Moreover, the viscosity average molecular weight (Mv) of the polymer 1 was 6900, and the mass structure ratio of the siloxane part was about 70.0%. The viscosity average molecular weight was calculated as follows. 0.5 g of a sample was dissolved in 100 ml of dichloromethane, and the specific viscosity at 25 ° C. was measured using an Ubelode type viscometer. The intrinsic viscosity was determined from this specific viscosity, and the viscosity average molecular weight (Mv) was calculated by setting K and a in the Mark-Houwink viscosity formula to 1.23 × 10 ⁻⁴ and 0.83, respectively.

  Therefore, this polycarbonate polymer 1 had a structure having polysiloxane sites at both ends of the polycarbonate resin and polymerizing the siloxane sites in the main chain of the polycarbonate resin.

(Synthesis of polymer 2)
A polycarbonate polymer 2 was obtained in the same manner as the synthesis of the polymer 1 except that the compounds shown in Table 1 were used. The obtained polymer 2 has a structure having a polysiloxane moiety at both ends of the polycarbonate resin and a structure in which the siloxane moiety is polymerized in the main chain of the polycarbonate resin. MALDI-TOF-MS, infrared absorption It was confirmed by spectrum and ¹ H-NMR. In addition, the average of the average repeating unit in the obtained polymer 2 is about m: n = 30: 30, the viscosity average molecular weight (Mv) is 22000, and the mass composition ratio of the siloxane moiety is about 22.2%. there were.

(Synthesis of Polymer 3)
A polycarbonate polymer 3 was obtained in the same manner as the synthesis of the polymer 1 except that the compounds shown in Table 1 were used. MALDI-TOF-MS, infrared absorption indicates that the obtained polymer 3 has a structure having a polysiloxane moiety at both ends of the polycarbonate resin and a siloxane moiety also polymerized in the main chain of the polycarbonate resin. It was confirmed by spectrum and ¹ H-NMR. In addition, the viscosity average molecular weight (Mv) of the obtained polymer 3 was 16400, and the mass composition ratio of the siloxane part was about 26.0%.

(Synthesis of polymer 4)
・ Glycidoxypropyltriethoxysilane 29.51 g (0.106 mol)
Tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane (FTS, carbon number of perfluoroalkyl group 6) 11.20 g (0.022 mol)
・ Phenyltriethoxysilane (PhTES) 30.77 g (0.128 mol)
-Hexyltrimethoxysilane (HeTMS) 13.19 g (0.064 mol)
After mixing these hydrolyzable silane compounds with 25.93 g of water and 66.75 g of ethanol, the mixture was stirred at room temperature, then heated for 24 hours and refluxed (110 ° C.) to cause reaction and hydrolyzable condensation. A product (polymer 4) was obtained.

(Synthesis of polymers 5 and 6)
Polycarbonate polymers 5 and 6 were obtained in the same manner as in the synthesis of polymer 1 except that the compounds shown in Table 1 were used. The obtained polymers 5 and 6 have a structure having polysiloxane moieties at both ends of the polycarbonate resin, and having a structure in which the siloxane moiety is polymerized in the main chain of the polycarbonate resin, MALDI-TOF-MS, This was confirmed by infrared absorption spectrum and ¹ H-NMR. In addition, the viscosity average molecular weight (Mv) of the obtained polymer 5 is 7200, the mass composition ratio of the siloxane moiety is about 70.0%, and the viscosity average molecular weight (Mv) of the obtained polymer 6 is 18000, siloxane The mass composition ratio of the part was about 30.0%.

(Synthesis of polymer 7)
A polycarbonate polymer 7 was obtained in the same manner as the synthesis of the polymer 1 except that only 140 g of bisphenol represented by the exemplary compound (3-13) was used.

(Resin liquid 1)
40 parts of a compound represented by the structural formula (7-1) 6 parts of a compound represented by the structural formula (7-2) 50 parts of a polyarylate resin having a structural unit represented by the following structural formula (8) (weight average) (Molecular weight: 65000, molar ratio of terephthalic acid skeleton to isophthalic acid skeleton: terephthalic acid skeleton / isophthalic acid skeleton = 50/50)

-Polydimethylsiloxane represented by formula (6) (l = 90) 0.2 part-Polymer 1 Resin liquid 1 in which 2 parts or more of components were dissolved in 400 parts of monochlorobenzene was prepared.

(Resin liquid 2-4, 6-19, 23)
Resin liquids 2 to 4, 6 to 18, and 23 were prepared in the same manner as the resin liquid 1 except that the components shown in Table 2 were used. In the production of the resin liquid 2, the weight average molecular weight of the polyarylate resin having the structural unit represented by the structural formula (8) was set to 20000 (described as “formula (8) modification” in Table 2). In the resin liquids 4 and 19, the polymer (A) was not added.

(Resin liquid 5)
-Polymer 4 20 parts-Polyarylate resin having a structural unit represented by structural formula (8) Resin liquid 5 was prepared by dissolving 80 parts or more of components in 400 parts of monochlorobenzene.

(Resin liquid 20)
Acrylic silicon resin Zemlac YC3623 (manufactured by Kaneka Corporation, trade name) was used as the resin liquid 20.

(Resin liquid 21)
A reaction solution was prepared by dissolving the following components in 10 parts of toluene in a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel, a nitrogen gas inlet / outlet and a thermometer.
(Monomer component)
N-butyl methacrylate 3.20 parts (22.5 mmol)
(BMA)
Trimethoxysilylpropyl methacrylate 1.24 parts (5 mmol)
(SMA)
-Glycidyl methacrylate 3.20 parts (22.5 mmol)
(GMA)
[Chain transfer agent]
・ 0.98 parts (5 mmol) of γ-mercaptopropyltrimethoxysilane
A solution prepared by dissolving 0.025 part (0.15 mmol) of azobisisobutyronitrile in 3 parts of toluene was dropped into this reaction solution under a nitrogen stream and reacted at 68 ° C. for 4 hours. As a result, an acrylic resin solution containing a polymer (acrylic resin) having a weight average molecular weight of 3000 is obtained, and the solid content is adjusted to 40%.

(Resin liquid 22)
A solution obtained by dissolving the polymer 1 in 400 parts of monochlorobenzene was used as a resin liquid 22.

(Resin liquid 24)
A silicone resin SH804 (trade name, manufactured by Toshiba Silicone Co., Ltd.) was used as the resin liquid 24.

Example 1
-Resin liquid 1 (solid content 20%) 100 parts-Conductive agent G-1 25 parts-Conductive agent G-2 25 parts-Chlorobenzene 150 parts The above is a sand mill (using glass beads with a diameter of 1 mm as media particles) The paint R-1 was obtained by dispersing for 2 hours and separating the glass beads using a sieve.

  As a base, a cylindrical aluminum tube having an outer diameter of 24.5 mmφ and an arithmetic average roughness Ra of 0.2 μm with masking on the upper and lower ends was prepared. The substrate was erected vertically, rotated at a constant speed, and the paint R-1 was applied while lowering the spray gun at a constant speed. Subsequently, the coating layer was dried and cured by heating at 150 ° C. for 30 minutes in a hot air drying oven to form a conductive resin coating layer on the substrate, and developer carrier A-1 was produced. The layer thickness of the conductive resin coating layer of developer carrier A-1 was 13 μm. Table 3 shows the composition of the paint, and Table 4 shows the physical properties of the conductive resin coating layer of developer carrier A-1.

  A magnet roller is inserted into the obtained developer carrying member A-1, and flanges are attached to both ends. The electrostatic latent image carrying member is an amorphous silicon drum photosensitive member, and is a digital copying machine IR6570 manufactured by Canon (trade name). ) To develop a developing device. In order to strengthen the regulation force, the magnet roller was an all-pole magnetic up magnet roll in which the magnetic force was all increased by 10% compared to the magnet roller used in the product. Further, the toner coat forming means (magnetic blade) formed of ferromagnetic iron was disposed so that the tip thereof was opposed to the magnetic pole of the magnet. The toner coat forming means is formed with a slope so that the portion supported by the toner container has a thickness of 1.6 mm and the tip of the portion facing the developer carrier has a thickness of 0.6 mm. It is. One million images were printed (durability) in continuous mode. The developing device is roughly as shown in FIG.

  Using toner Z-1, an image for evaluation was output at the initial stage of image output, at the time of 100 sheets, and at the end of 1,000,000 sheets, and image evaluation was performed. The image output and evaluation image output were performed in a normal temperature and normal humidity environment (23 ° C., 60% RH; N / N). The evaluation was performed on the basis of the following evaluation method and evaluation criteria for image density, rise of initial density, fog, sleeve ghost, surface roughness Ra of the resin coating layer, and wear resistance of the resin coating layer. The obtained evaluation results are shown in Table 5.

(1) Image Density Copy image density of φ5 mm solid black circle on the copy obtained by outputting a test chart with an image ratio of 5.5% is reflected by a reflection densitometer RD918 (manufactured by Macbeth, trade name). Measurement was performed, and the average value of the 10 points was defined as the image density.
A: Image density is 1.40 or more.
B: The image density is 1.35 or more and less than 1.40.
C: The image density is 1.30 or more and less than 1.35.
D: The image density is 1.20 or more and less than 1.30.
E: Image density is less than 1.20.

(2) Rise of initial image density Reflection of density difference between initial and 100 sheets, copy image density of φ5mm solid black circle on copy obtained by outputting test chart with image ratio of 5.5% The reflection density was measured with a densitometer RD918 (trade name, manufactured by Macbeth Co., Ltd.), and the average value of 10 points was defined as the image density.
A: Image density difference less than 0.02 B: Image density difference between 0.02 and less than 0.03.
C: Image density difference of 0.03 or more and less than 0.04.
D: Image density difference of 0.04 or more and less than 0.05.
E: Image density difference 0.05 or more.

(3) Fogging Measure the reflectance of solid white areas on the copy obtained in (1) at random at 10 locations and subtract the reflectance of unused transfer paper (average value at 10 locations) from the lowest value. Was the fog density. Based on this value, the following evaluation was performed. The reflectance was measured with a reflectometer TC-6DS (trade name, manufactured by Tokyo Denshoku).
A: Less than 0.5% B: 0.5% or more and less than 1.0%.
C: 1.0% or more and less than 2.0%.
D: 2.0% or more and less than 3.0%.
E: 3.0% or more.

(4) Sleeve ghost After copying 100 sheets and enduring 1 million sheets initially, after copying a solid black belt-like image X having a width a and a length l shown in FIG. A halftone image Y having a width b (> a) shown in FIG. At this time, the difference in density appearing on the halftone image (maximum density-minimum density of portions A, B, and C in FIG. 8C) was evaluated.
A: A density difference is hardly observed (density difference is less than 0.02).
B: A slight density difference is observed (density difference of 0.02 or more and less than 0.04).
C: A slight density difference is observed (density difference of 0.04 or more and less than 0.07).
D: A remarkable density difference is observed (density difference of 0.07 or more and less than 0.10).
E: A very significant density difference is observed (density difference of 0.10 or more).

(5) Abrasion resistance of resin coating layer Measure the outer diameter of the developer carrier and subtract the value after durability from the value before use to obtain the scraping amount of the resin coating layer. The amount. In measurement after endurance, the surface of the developer carrying member was washed with isopropanol. Evaluation was made according to the following criteria.
A: The amount of shaving is less than 2 μm.
B: The amount of scraping is 2 μm or more and less than 3 μm.
C: The amount of scraping is 3 μm or more and less than 4 μm.
D: The amount of scraping is 4 μm or more and less than 5 μm.
E: The amount of shaving is 5 μm or more.

(6) Surface roughness Ra of the resin coating layer
The arithmetic average roughness Ra of the surface of the developer carrying member was measured initially, after 100 sheets and after 1 million sheets of durability.

(Examples 2 to 4)
Developer carriers A-2 to A-4 were prepared in the same manner as in Example 1 except that the coating compositions R-2 to R-4 shown in Table 3 were used. Then, the physical properties were measured and evaluated. When resin solutions having different solid contents were used, the dispersion was carried out by adjusting the amount of a solvent such as monochlorobenzene or ethanol added at the time of dispersion so as to obtain the same solid contents. The obtained results are shown in Tables 4 and 5.

(Example 5)
-Resin liquid 5 (solid content 10%) 100 parts-Conductive agent G-1 25 parts-Conductive agent G-2 25 parts-Chlorobenzene 150 parts The above is a sand mill (using glass beads with a diameter of 1 mm as media particles) A paint R-5 was obtained which was dispersed for 2 hours and separated glass beads using a sieve.

Using this coating material R-5, a conductive resin coating layer was formed in the same manner as in Example 1. However, prior to drying the formed coating layer, the surface of the coating film is cured (curing by a crosslinking reaction) by irradiating the developer carrier with ultraviolet light having a wavelength of 254 nm so that the integrated light amount is 8500 mJ / cm ^2. I let you. Then, the cured product was allowed to stand for several seconds (2 to 3 seconds) and dried to form a surface layer on the conductive resin coating layer. A low-pressure mercury lamp manufactured by Harrison Toshiba Lighting Co., Ltd. was used for ultraviolet irradiation. Thereafter, in the same manner as in Example 1, the resin-carrying layer was dried and cured by heating at 150 ° C. for 30 minutes in a hot-air drying furnace, and a developer carrying member A- having a conductive resin coating layer formed on the substrate. 5 was produced. The physical properties were measured and evaluated in the same manner as in Example 1. The obtained results are shown in Tables 4 and 5.

(Comparative Example 1)
A developer carrying member A-6 was produced in the same manner as in Example 1 except that the coating composition was changed to the coating composition R-6 shown in Table 3 and coating was repeated three times. The layer thickness of the conductive resin coating layer was 8 μm. The physical properties were measured and evaluated in the same manner as in Example 1. The obtained results are shown in Tables 4 and 5.

(Example 6)
-Resin liquid 6 (solid content 20%) 100 parts-Conductive agent G-1 25 parts-Conductive agent G-2 25 parts-Chlorobenzene 150 parts The above is a sand mill (using glass beads with a diameter of 1 mm as media particles) A paint R-7 was obtained which was dispersed for 2 hours and separated glass beads using a sieve.

  As a base, a cylindrical aluminum tube having an outer diameter of 12.0 mmφ and an arithmetic average roughness Ra of 0.2 μm with masking on the upper and lower ends was prepared. The substrate was erected vertically, rotated at a constant speed, and the paint R-7 was applied while lowering the spray gun at a constant speed. Subsequently, the coating layer was dried and cured by heating at 150 ° C. for 30 minutes in a hot air drying oven to form a conductive resin coating layer on the substrate to prepare a developer carrier A-7. The layer thickness of the conductive resin coating layer of Developer Carrier A-7 was 10 μm. Table 3 shows the composition of the paint, and Table 6 shows the physical properties of the conductive resin coating layer of developer carrier A-7.

  The obtained developer carrier A-7 was incorporated into a genuine cyan cartridge of a commercially available laser beam printer (trade name: LBP5000, manufactured by Canon Inc.) to form a developing device. The developing device was mounted on the laser beam printer, and 3000 images were output (durability) in an intermittent mode of 1 sheet / 10 seconds. The developing device is roughly as shown in FIG.

  Using toner Z-3, an image for evaluation was output at the initial stage of image output, at the time of 100 sheets, and at the end of 3000 sheets, and image evaluation was performed. The image output and evaluation image output were performed in a normal temperature and normal humidity environment (23 ° C., 60% RH; N / N). Evaluation was performed about the item (1)-(6) described in Example 1, and following evaluation (7). Table 7 shows the obtained evaluation results.

(7) Blade turning, blade scratches A developer carrier is incorporated into the developing device, and further, before the developer is supplied onto the developer carrier, it is incorporated into the evaluation machine and the evaluation machine is turned on. After the rotation, the developing device was taken out of the evaluation machine, and then the plate turning and blade scratches were evaluated according to the following criteria.
A: No blade turning or blade damage.
B: Small scratches are seen on the blade but not appearing in the image.
C: Several scratches are seen on the blade, but not appearing in the image.
D: Blade scratches appearing in the image.
E: Blade turning occurred.

  When no blade scratches occurred, the evaluation was continued as it was, and when blade turning occurred, the developer carrying member was coated with a developer, replaced with a new blade, and other evaluation items were evaluated.

(Examples 7 to 10, Comparative Example 2)
Developer carriers A-8 to A-12 were produced in the same manner as in Example 6 except that the coating compositions R-8 to R-12 shown in Table 3 were used, respectively. Then, the physical properties were measured and evaluated. When resin solutions having different solid contents were used, the dispersion was performed by adjusting the amount of the solvent added at the time of dispersion so as to obtain the same solid contents. The obtained results are shown in Tables 6 and 7.

(Example 11)
-Resin liquid 11 (solid content 20%) 100 parts-Conductive agent G-1 50 parts-Concavity and convexity imparted particles P-1 50 parts-Chlorobenzene 150 parts The above-mentioned sand mill (using glass beads with a diameter of 1 mm as media particles) The paint R-13 was obtained by dispersing for 2 hours and separating the glass beads using a sieve.

  As a base, a cylindrical aluminum tube having an outer diameter of 20.0 mmφ and an arithmetic average roughness Ra of 0.2 μm with masking on the upper and lower ends was prepared. The substrate was erected vertically, rotated at a constant speed, and the paint R-13 was applied while lowering the spray gun at a constant speed. Subsequently, the coated layer was dried and cured by heating at 130 ° C. for 1 hour in a hot air drying oven to form a conductive resin coating layer on the substrate to prepare a developer carrier A-13. The layer thickness of the conductive resin coating layer of Developer Carrier A-13 was 8 μm. Table 3 shows the composition of the paint, and Table 8 shows the physical properties of the conductive resin coating layer of developer carrier A-13.

  The obtained developer carrier A-13 was assembled with a magnet roller and incorporated in a genuine cartridge for a commercially available laser beam printer (trade name: LASER JET4300, manufactured by Hewlett-Packard Company) to obtain a developing device. This developing device was mounted on the laser beam printer, and 18,000 images were output in a 1/10 sec intermittent mode. The developing device is roughly as shown in FIG.

  Using toner Z-2, an image for evaluation was output at the initial stage of image output, at 100 sheets, and at 18,000 sheets, and image evaluation was performed. The image output and evaluation image output were performed in a normal temperature and normal humidity environment (23 ° C., 60% RH; N / N). Image evaluation was performed in the same manner as in Example 1. Table 9 shows the obtained evaluation results.

(Examples 12 to 16, Comparative Example 3)
Developer carriers A-14 to A-19 were produced in the same manner as in Example 11 except that the coating compositions R-14 to R-19 shown in Table 3 were used, respectively. Then, the physical properties were measured and evaluated. When resin solutions having different solid contents were used, the dispersion was performed by adjusting the amount of the solvent added at the time of dispersion so as to obtain the same solid contents. The obtained results are shown in Table 8 and Table 9.

(Example 17)
-Resin liquid 17 (solid content 20%) 100 parts-Conductive agent G-1 50 parts-Concavity and convexity imparting particles P-2 25 parts-Chlorobenzene 150 parts The above-mentioned sand mill (using glass beads with a diameter of 1 mm as media particles) The paint R-20 was obtained by dispersing for 2 hours and separating the glass beads using a sieve.

An aluminum cylindrical tube having an outer diameter of 16.0 mmφ was attached to a sand blasting apparatus, and blasted using # 100 spherical glass beads as abrasive grains, and this was used as a substrate K-1. The blasting process was performed using a pneumatic blast machine (trade name, manufactured by Fuji Seisakusho), which is a general air type blasting machine, and the air pressure was 4 kg / cm ² as a blasting condition. The processing time at this time was 50 seconds, and the work was rotated at 50 rpm. The arithmetic average roughness (Ra) of the substrate was 1.9 μm.

  The base K-1 with the upper and lower support portions masked was vertically set and rotated at a constant speed, and the coating material R-20 was applied while lowering the spray gun at a constant speed. Subsequently, the coating layer was dried and cured by heating at 150 ° C. for 30 minutes in a hot air drying oven to form a conductive resin coating layer on the substrate to prepare a developer carrier A-20. The layer thickness of the conductive resin coating layer of Developer Carrier A-20 was 14 μm. Table 3 shows the composition of the paint, and Table 10 shows the physical properties of the conductive resin coating layer of developer carrier A-20.

  The obtained developer carrier A-20 was assembled with a magnet roller and incorporated in a developing device of a commercially available copying machine (manufactured by Canon Inc., trade name: IRC3200N) to form a developing device. The developing device was mounted on the copying machine, and 30,000 sheets were output (durability) in an intermittent mode of 1 sheet / 10 seconds. The developing device is roughly as shown in FIG.

  Using toner Z-4, an image for evaluation was output at the initial stage of image output, at the time of 100 sheets, and at the end of 50,000 sheets, and image evaluation was performed. The image output and evaluation image output were performed in a normal temperature and normal humidity environment (23 ° C., 60% RH; N / N). Evaluation was performed about the above-mentioned item (1)-(6). The obtained evaluation results are shown in Table 11.

(Examples 18 and 20)
Developer carriers A-21 and A-23 were prepared in the same manner as in Example 17 except that the coating compositions R-21 and R-23 shown in Table 3 were used, respectively. Then, the physical properties were measured and evaluated. When resin solutions having different solid contents were used, the dispersion was performed by adjusting the amount of the solvent added at the time of dispersion so as to obtain the same solid contents. The obtained results are shown in Table 10 and Table 11.

(Example 19, Example 21, Comparative Example 4)
A developer carrier was produced in the same manner as in Example 17 until drying, except that the coating compositions R-22, R-24, and R-25 shown in Table 3 were used. In Example 19, first, an undried developer carrying member was rotated at a constant speed, and the resin liquid 22 was applied while lowering a spray gun at a constant speed. Subsequently, the coating layer is dried and cured by heating at 150 ° C. for 30 minutes in a hot air drying oven to form a conductive resin coating layer on the substrate, and the developer liquid A-22 having a resin liquid 22 thickness of 1 μm is formed. Was made. In Example 21, a developer carrier A-24 was produced in the same manner as in Example 19, by applying the resin liquid 11 to the developer carrier five times and drying it. In Comparative Example 4, in the same manner as in Example 19, the resin liquid 22 was applied to the developer carrier and dried to obtain a developer carrier A-25 having a thickness of 3 μm. Table 3 shows the composition of the paint, and Table 10 shows the physical properties of the conductive resin coating layer of the developer carrier. Evaluation was performed about the above-mentioned item (1)-(6). The obtained evaluation results are shown in Table 11.

It is a schematic diagram which shows an example of the polishing apparatus which concerns on this invention. FIG. 3 is a schematic partial cross-sectional view of a developer carrier according to the present invention. It is a schematic diagram showing an example of an embodiment of a developing device using a magnetic one-component developer according to the present invention. It is a schematic diagram which shows another example of embodiment of the image development apparatus which uses the magnetic one-component developer concerning this invention. It is a schematic diagram showing an example of an embodiment of a developing device using a non-magnetic one-component developer according to the present invention. It is a schematic diagram showing an example of an embodiment of a developing device using a two-component developer according to the present invention. It is a figure explaining the evaluation method of a sleeve ghost.

Explanation of symbols

1 Electrostatic latent image carrier (photosensitive drum)
2 Charging device 2a Magnet roller 2b Magnetic particle 3 Exposure device 4 Developing device 4a Developing container 4b Developer carrier (developing sleeve)
4c Magnet roller 4d Developer coating blade 4e Two component developer 4f Developer stirring member 4g Toner hopper 5 Transfer roller 6 Fixing device 7 Developer carrier 8 Strip abrasive 9 Feed roller 10 Take-up roller 11 Tape traveling direction 12 Resin coating Layer 13 Substrate 14 Magnet roller 15 Resin coating layer 16 Development sleeve a Binding resin b Graphite particles c Additive (solid particles)
L laser beam P transfer material S1 to S3 bias voltage application power source 501 electrostatic latent image carrier (photosensitive drum)
502 Developer layer thickness regulating member (magnetic blade)
503 Development container 504 Partition member 505 Stirring conveyance member 506 Base 507 Resin coating layer 508 Development sleeve 509 Magnet (magnet roller)
510 developer carrier 511 agitating and conveying member 512 developer supplying member 513 developing bias power source 514 first chamber 515 second chamber 516 developer layer thickness regulating member (elastic blade)
801 Electrostatic latent image carrier (photosensitive drum)
803 Developing container 804 Developer 806 Base 807 Resin coating layer 808 Developer carrier (developing sleeve)
809 Development bias power source 810 Agitating and conveying member 811 Developer layer thickness regulating member (elastic blade)
813 Developer supply / stripping member (Developer supply / stripping roller)
N, S Magnetic pole A Developing sleeve rotation direction B Electrostatic latent image carrier (photosensitive drum) rotation direction D Development area

Claims (12)

A developer carrier having a substrate and a resin coating layer formed on the surface of the substrate;
The resin coating layer contains a binder resin and graphite particles,
The binder resin comprises a Si atom-containing polymer having a siloxane bond and a Si atom-free polymer, and
The resin coating layer is
A (atomic%) is the existing ratio of silicon (Si) element on the surface of the resin coating layer measured by X-ray photoelectron spectroscopy,
The first abrasive tape having a ten-point average roughness Rzjis having a # 3000 alumina abrasive grain on the surface of the polyester film and provided with an abrasive layer of 9 μm or more and 16 μm or less is pressed against the surface of the developer carrier and a load of 0.5 kgf ( 4.9 N), and the developer carrying member is rotated 10 revolutions at 200 rpm while winding the first polishing tape at a speed of 15 mm / sec, and developed by rubbing and polishing with the first polishing tape. The abundance ratio of Si element measured by X-ray photoelectron spectroscopic analysis on the surface of the resin coating layer of the agent carrier is B (atomic%),
Development in which a second polishing tape provided with a polishing layer having a ten-point average roughness Rzjis of 26 μm or more and 34 μm or less having # 500 alumina abrasive grains on the surface of a polyester film is rubbed and polished with the first polishing tape The second abrasive tape is wound up at a speed of 15 mm / sec while being pressed against the surface of the agent carrier with a load of 2 kgf (19.6 N) and rotating the developer carrier 20 at 1000 rpm. When the Si element abundance ratio measured by X-ray photoelectron spectroscopic analysis on the surface of the resin coating layer of the developer carrying member that has been rubbed and polished with the polishing tape is C (atomic%),
A developer carrier, wherein A, B and C satisfy the following formulas (1) and (2).
C <B ≦ 0.70A Formula (1)
0 <BC <AB Formula (2).   The developer carrier according to claim 1, wherein the Si atom-containing polymer contains a siloxane-modified polycarbonate. The siloxane-modified polycarbonate has a repeating structural unit represented by the following formula (3) and a repeating unit represented by the following formula (4), and either one or both of the terminals have the following formula (5). The developer carrying member according to claim 2.
(In formula (3), X represents a single bond, —O—, —S—, or a substituted or unsubstituted alkylidene group. R _{11 to} R ₁₈ are the same or different and each represents a hydrogen atom, a halogen atom, An alkoxy group, a nitro group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group is shown.)
(In Formula (4), R ₂₁ and R ₂₂ are the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R _{23 to} R ₂₆ are the same or Differently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, a is the same or different, an integer of 1 to 30 and m is 1 to 500 Indicates an integer.)
(In the formula (5), R ₃₁ and R ₃₂ are the same or different and each represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkoxy group, a nitro group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted group. R ₃₃ and R ₃₄ are the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and R _{35 to} R ₃₉ are the same or different. And a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, b is an integer of 1 to 30 and n is an integer of 1 to 500.) A in Formula (4) is an integer of 1 or more and 3 or less, R _{23 to} R ₂₆ are all methyl groups, and
The developer carrying member according to claim 3, wherein b in the formula (5) is an integer of 1 to 3, and R _{33 to} R ₃₉ are all methyl groups. The developer carrying member according to any one of claims 2 to 4, wherein the Si atom-containing polymer further contains polydimethylsiloxane represented by the following formula (6).
(In formula (6), l represents the average value of the average repeating units.)   The content of the polydimethylsiloxane is 5% by mass or more and 20% by mass or less with respect to the siloxane-modified polycarbonate, and the total content of the siloxane-modified polycarbonate and the polydimethylsiloxane is included in the resin coating layer. The developer carrier according to claim 5, wherein the content is 0.1% by mass or more and 5.0% by mass or less based on the total solid content. The siloxane-modified polycarbonate has a repeating structural unit represented by the formula (3) and a repeating unit represented by the formula (4), and either one or both of the terminals have the structure represented by the formula (5). And
The developer carrier according to claim 5 or 6, wherein m in the formula (4), n in the formula (5), and l in the formula (6) are equal.   The developer carrying member according to claim 1, wherein the Si atom-free polymer is polyarylate. A developing device having a developer carrying member for carrying a developer carried on the outermost surface and carrying the developer carried on a developing region, which is used when developing and visualizing a latent image formed on the latent image carrying member with a developer. Because
The developing device according to claim 1, wherein the developer carrying member is the developer carrying member according to claim 1. A method for producing a developer carrier according to claim 1,
After forming a coating film of a paint containing a binder resin raw material and graphite particles on the surface of the substrate, the resin coating layer is formed by curing the coating film,
A method for producing a developer carrier, wherein the raw material of the binder resin contains a precursor of a Si atom-containing polymer containing a siloxane bond and a precursor of a Si atom-free polymer.   The method for producing a developer carrier according to claim 10, wherein the precursor of the Si atom-containing polymer is a prepolymer of a siloxane-modified polycarbonate.   The method for producing a developer carrier according to claim 10 or 11, wherein the precursor of the Si atom-free polymer is a prepolymer of polyarylate.