JP7210236B2 - Developing device, image forming device, and process cartridge - Google Patents

Description

The present invention relates to an image forming apparatus, a developing device, and a process cartridge for forming an image on a recording material (sheet) using an electrophotographic method, and more particularly to a developer (toner) for supplying developer (toner) to developing means. The present invention relates to a developing device having a toner conveying path. Here, an electrophotographic image forming apparatus (hereinafter also simply referred to as an "image forming apparatus") forms an image on a recording material (recording medium) using an electrophotographic image forming method. Examples of image forming apparatuses include copiers, printers (laser beam printers, LED printers, etc.), facsimile machines, word processors, and multifunction machines (multifunction printers).

In recent years, image forming apparatus main bodies (hereinafter referred to as "main bodies") have become smaller in size. However, as each unit inside the main body has become smaller in size, the amount of space that can be arranged within the main body is limited. be. As a result, there are restrictions on the placement of the toner cartridge, and the toner transport path may connect the toner cartridge and the developing means. As a toner conveying device for such a toner conveying path, there is a case where a toner conveying member composed of a screw made of plastic, a coil spring made of metal, or the like is provided. For example, Patent Document 1 discloses a screw-type toner conveying member. When the toner conveying member rotates, the tooth surface of a blade spirally provided on the toner conveying member moves in a path to convey toner. By pushing out, the toner is conveyed to the developing means.

In the configuration in which the toner is supplied using the toner conveying member, a certain amount of space is required for arranging the toner conveying path including the toner conveying member. Therefore, for example, when the toner transport path is to be extended linearly in the direction in which the toner cartridge and the developing means are aligned (opposing direction), the toner transport path including the toner transport member is placed between the toner cartridge and the developing means. It becomes necessary to leave a predetermined interval for providing the That is, in the case of adopting such a configuration, for example, the size of the toner cartridge must be reduced to sacrifice the amount of stored toner in order to secure the space for the toner conveying path.

Japanese Unexamined Patent Application Publication No. 2010-20227

SUMMARY OF THE INVENTION It is an object of the present invention to provide a developing device, an image forming apparatus, and a process cartridge that can reduce the size of the apparatus.

In order to achieve the above object, the developing device in the present invention comprises:
A developing device used in an image forming apparatus,
a developer carrier that carries a developer for developing the latent image formed on the image carrier;
a regulating member for regulating the developer carried on the developer carrier;
a frame that supports the developer carrying member and the regulating member and has a container for storing the developer;
a developer container containing the developer;
a transport path for transporting the developer from the developer container to the storage portion of the frame;
A first conveying member that conveys the developer by rotating and a second conveying member that conveys the developer by rotating downstream of the first conveying member are arranged in the conveying path. ,
The second conveying member has a drive receiving portion that receives a rotational force from the first conveying member,
the developer comprises a toner having toner particles ;
The toner has a Martens hardness of 200 MPa or more and 1100 MPa or less when measured under conditions of a maximum load of 2.0×10 ⁻⁴ N ,
The toner particles have a surface layer containing an organosilicon polymer,
The number of carbon atoms directly bonded to silicon atoms in the organosilicon polymer is 1 or more and 3 or less on average per silicon atom .
In order to achieve the above object, the image forming apparatus of the present invention includes:
an image carrier on which a latent image is formed;
a developer carrier that carries a developer for developing the latent image formed on the image carrier;
a regulating member for regulating the developer carried on the developer carrier;
a frame that supports at least the developer carrying member and the regulating member and has a container for storing the developer;
a developer container containing the developer;
a transport path for transporting the developer from the developer container to the storage portion of the frame;
A first conveying member that conveys the developer by rotating and a second conveying member that conveys the developer by rotating downstream of the first conveying member are arranged in the conveying path. ,
The second conveying member has a drive receiving portion that receives a rotational force from the first conveying member,
the developer comprises a toner having toner particles ;
The toner has a Martens hardness of 200 MPa or more and 1100 MPa or less when measured under conditions of a maximum load of 2.0×10 ⁻⁴ N ,
The toner particles have a surface layer containing an organosilicon polymer,
The number of carbon atoms directly bonded to silicon atoms in the organosilicon polymer is 1 or more and 3 or less on average per silicon atom .
In order to achieve the above object, the process cartridge of the present invention comprises:
A process cartridge used in an image forming apparatus,
a developer carrier that carries a developer for developing the latent image formed on the image carrier;
a regulating member for regulating the developer carried on the developer carrier;
a frame that supports the developer carrying member and the regulating member and has a container for storing the developer;
a developer container containing the developer;
a transport path for transporting the developer from the developer container to the storage portion of the frame;
has
the conveying path includes a first conveying member that conveys the developer by rotating and a second conveying member that conveys the developer by rotating downstream of the first conveying member;
The second conveying member has a drive receiving portion that receives a rotational force from the first conveying member,
the developer comprises a toner having toner particles ;
The toner has a Martens hardness of 200 MPa or more and 1100 MPa or less when measured under conditions of a maximum load of 2.0×10 ⁻⁴ N ,
The toner particles have a surface layer containing an organosilicon polymer,
The number of carbon atoms directly bonded to silicon atoms in the organosilicon polymer is 1 or more and 3 or less on average per silicon atom .

According to the present invention, the occurrence of image defects in image formation can be suppressed while miniaturizing the apparatus.

Schematic cross-sectional view of an image forming apparatus according to Embodiment 1 of the present invention FIG. 1 is an explanatory diagram of a toner cartridge according to Embodiment 1 of the present invention; Explanatory drawing of the toner cartridge and main body conveyance path in Embodiment 1 of the present invention FIG. 1 is an explanatory diagram of a toner cartridge, a main conveyance path, and a process cartridge according to Embodiment 1 of the present invention; Schematic diagram of a connecting portion of a conveying member according to Embodiment 1 of the present invention. Schematic diagram of toner in an embodiment of the present invention Schematic cross-sectional view of an image forming apparatus according to Embodiment 2 of the present invention Explanatory drawing of a toner cartridge according to Embodiment 2 of the present invention An explanatory diagram of a toner cartridge and a main body conveyance path in Embodiment 2 of the present invention. Explanatory drawing of a toner cartridge and a process cartridge according to Embodiment 3 of the present invention Explanatory drawing of a toner cartridge and a process cartridge according to Embodiment 4 of the present invention.

In the present invention, unless otherwise specified, the descriptions of "○○ or more and XX or less" and "○○ to XX", which represent numerical ranges, mean numerical ranges including the lower and upper limits that are endpoints.
Embodiments or examples of the present invention will be exemplarily described in detail below with reference to the drawings. However, the dimensions, materials, shapes, relative positions, and the like of the components described in the embodiment or example may be changed as appropriate depending on the configuration of the device to which the invention is applied and various conditions, and therefore may not be particularly specific. Unless otherwise stated, they are not intended to limit the scope of the invention only to them.

<<Embodiment 1>>
<Image forming apparatus>
An overall configuration of an electrophotographic image forming apparatus according to Embodiment 1 of the present invention will be described with reference to FIG. FIG. 1 is a schematic cross-sectional view of an image forming apparatus 1 according to Embodiment 1 of the present invention. Examples of image forming apparatuses to which the present invention can be applied include copiers and printers using electrophotographic methods. A case where the present invention is applied to a laser beam printer will be described.

As shown in FIG. 1, the image forming apparatus 1 includes an image forming unit that transfers a toner image (developer image) onto a sheet that is a recording material, a sheet feeding unit that feeds the sheet to the image forming unit, and a sheet feeding unit. a fixing unit for fixing the toner image.

The image forming unit includes a process cartridge 4 detachable from the main body of the image forming apparatus 1, a toner cartridge 20 as a developer container storing toner for sending toner (developer) to the process cartridge 4, an intermediate transfer A unit 17 and a laser scanner unit 90 are provided. Four process cartridges 4 are provided inside the apparatus main body of the image forming apparatus 1 corresponding to the respective colors of yellow, magenta, cyan, and black, and are arranged in a line. That is, the process cartridges 4 y , 4 m, 4 c, and 4 k are arranged in a row inside the main body of the image forming apparatus 1 . Each process cartridge 4 includes a photosensitive drum 5 (5y, 5m, 5c, 5k) as an image carrier, a charging roller 6 (6y, 6m, 6c, 6k), a developing roller 7 (7y, 7m, 7c, 7k), regulating blades 9 (9y, 9m, 9c, 9k), and drum cleaning members 8 (8y, 8m, 8c, 8k).
The posture of the image forming apparatus 1 in FIG. 1 shows a state in which the image forming apparatus is installed on a horizontal plane as a normal installation state (installation state during operation), and the vertical direction of the paper surface in each figure is It substantially corresponds to the direction of gravity (vertical direction), and the horizontal direction substantially corresponds to the horizontal direction.

The toner cartridges 20 are detachable from the main body of the image forming apparatus 1, and four toner cartridges 20 are provided corresponding to the yellow, magenta, cyan, and black process cartridges. That is, toner cartridges 20y, 20m, 20c and 20k are arranged to supply toner to process cartridges 4y, 4m, 4c and 4k, respectively. Toner storage portions 44y, 44m, 44c and 44k are provided in the process cartridges 4y, 4m, 4c and 4k, respectively, and toner supplied from the toner cartridges 20y, 20m, 20c and 20k are stored therein.
More specifically, the process cartridge 4 is divided into a drum unit 46 and a developing unit (developing device) 45, which can be attached to and detached from the main body of the image forming apparatus 1 either integrally or individually. ing. The drum unit 46 includes the photosensitive drum 5 , the charging roller 6 , the drum cleaning member 8 , and a waste toner unit that integrally supports them and stores residual toner scraped from the photosensitive drum 5 by the drum cleaning member 8 . The cartridge is integrated with a frame body having a housing portion. The developing unit 45 includes a developing roller 7 as a developer carrying member, a toner supply roller, a regulating blade 9 as a regulating member, and a frame (developing container) that integrally supports them and has a toner container 44 . and are integrated into a cartridge.
In this embodiment, the toner cartridge 20 is arranged substantially horizontally with the developing unit 45 and vertically below the drum unit 46 .
Details of the toner transport path for the process cartridge 4 will be described later.

The intermediate transfer unit 17 includes primary transfer rollers 10 (10y, 10m, 10c, 10k), an intermediate transfer belt 11, a driving roller 12, a tension roller 13, a secondary transfer opposing roller 14a, and a cleaning device 30. The intermediate transfer belt 11 is an endless cylindrical belt, and is stretched by a drive roller 12, a tension roller 13, and a secondary transfer counter roller 14a.

At the time of image formation, when a control section (not shown) issues a print signal, the sheets stacked and housed in the sheet stacking section 2 are sent out by the feeding roller 3 .

On the other hand, the surface of the photosensitive drum 5 is charged by the charging roller 6 . Then, the laser scanner unit 90 emits a laser beam from an internal light source (not shown) to irradiate the photosensitive drum 5 with the laser beam. An electrostatic latent image is thereby formed on the surface of the photosensitive drum 5 . A toner image (developer image) is formed on the photosensitive drum 5 by developing the electrostatic latent image with toner (developer) carried by a developing roller 7 as a developer carrier. A toner image formed on the photosensitive drum 5 of each process cartridge 4 is primarily transferred onto the intermediate transfer belt 11 . The intermediate transfer belt 11 rotates in the direction of arrow A when the driving roller 12 receives a rotational force from a driving source such as a motor (not shown). The primarily transferred toner image reaches the secondary transfer portion formed by the secondary transfer opposing roller 14a and the secondary transfer roller 14b located downstream in the rotation direction due to the rotation of the intermediate transfer belt 11, where the toner image is transferred. transferred to the sheet.
The sheet on which the toner image has been transferred is sent to a fixing device 15, where the toner image is fixed on the sheet by heating and pressure, and then conveyed by a discharge roller 16 and discharged to a discharge section (discharge tray). .

<development blade>
The developing blade 9 is arranged so as to face in the counter direction with respect to the rotation of the developing roller 7 , and is a member that regulates the amount of toner carried on the developing roller 7 . Further, the toner is triboelectrically charged by rubbing between the developing blade 9 and the developing roller 7, and is given an electric charge, and at the same time, the layer thickness is regulated. One end of the developing blade 9 in the short direction is fixed to the developing container by a fastener such as a screw, and the other end is a free end.

In this embodiment, as the developing blade 9, a thin plate of SUS304-1/2H having leaf spring-like elasticity with a free length in the lateral direction of 8 mm and a thickness of 0.07 mm or more and 0.10 mm or less is used. The blade can be used with a linear pressure of 20 N/m to 40 N/m on the surface of the developing roller 7 on the free end side. A linear pressure of 30 N/m was used in this embodiment.

<Development roller>
As the developing roller 7, a roller coated with an elastic rubber layer was used. In order to maintain a uniform contact state with the photosensitive drum 5, the elastic rubber layer preferably has a MD1 hardness of 20° to 50°. In the embodiment, one having a rubber hardness of 38° was used. The rubber hardness was measured with an MD-1 hardness tester (indenter shape: type A) manufactured by Kobunshi Keiki Co., Ltd. The surface roughness is set to 0.2 μm to 2 μm in terms of center line average roughness Ra, and the necessary amount of toner is retained on the surface. When Ra is less than 0.2 μm, it is difficult to obtain a desired amount of toner, and the density tends to be low. On the other hand, when Ra is larger than 2 μm, it is difficult to sufficiently charge the toner individually, and the toner easily adheres to the non-image portion, so that so-called "fogging" tends to occur. In the examples, one with Ra=1.0 μm was used. The center line average roughness Ra was measured by "Surfcoder SE3500" manufactured by Kosaka Laboratory.

<Toner Conveyance>
Since the description from here on is the same for each of the yellow, magenta, cyan, and black process cartridges, the notations of y, m, c, and k are omitted. As shown in FIGS. 2A, 2B, and 2C, the toner cartridge 20 as a toner container (developer replenishing device) for supplying toner to the process cartridge 4 includes a toner outlet 24 and a toner conveying device. A screw 23 is arranged. 2A is a schematic perspective view of the toner cartridge 20, FIG. 2B is a schematic cross-sectional view of the toner cartridge 20 taken along the dotted line A in FIG. 2A, and FIG. 2A is a schematic cross-sectional view of the toner cartridge 20 along the dotted line B in FIG.

The internal space of the toner cartridge 20 is composed of a toner storage chamber 201 in which toner 40 is stored and a toner transport chamber 202 in which a toner transport screw 23 as a developer transport member is arranged. The toner cartridge 20 has a connecting portion 203 that is connected to a conveying path forming member 70 that forms a toner conveying path on the main body side, which will be described later. communicates with the outside of the toner cartridge 20 through the .

The connecting portion 203 protrudes further downstream in the mounting direction from the side surface facing the downstream side in the mounting direction of the toner cartridge 20 to the main body of the image forming apparatus (the inner side of the accommodating portion of the toner cartridge 20 in the main body of the apparatus). is provided. When the toner cartridge 20 is attached to the main body of the image forming apparatus, the toner discharge port 24 of the connecting portion 203 is moved to a position where toner can be transferred to the transport path forming member 70 (a toner receiving port 71 of the transport path forming member 70 to be described later). communicatively overlapped).

In the toner storage chamber 201 , a stirring blade 22 as a stirring and conveying member for stirring the contained toner 40 and conveying it to the toner conveying chamber 202 is provided rotatably about the stirring shaft 21 . The toner 40 thrown up by the stirring blade 22 as the stirring shaft 21 rotates is transferred to the toner conveying chamber 202 in which the toner conveying screw 23 is arranged. As the toner conveying screw 23 rotates, the toner is conveyed in the toner conveying chamber 202 toward the toner discharge port 24 and discharged from the toner discharge port 24 .

3(a) is a schematic perspective view of the toner cartridge 20 attached to the main body 1, and FIG. 3(b) is the toner cartridge 20 and the main body transport path forming member at the dotted line C in FIG. 3(a). 70 shows a schematic cross-sectional view of 70. FIG.
FIG. 4(a) is a schematic perspective view of the configuration around the main body conveyance path forming member 70 in a state in which the toner cartridge 20 and the process cartridge 4 are attached to the main body 1; ) shows a schematic cross-sectional view along the dotted line H in FIG.
The toner discharged from the toner cartridge 20 is transferred to the toner receiving port 71 of the main conveyance path forming member 70 by its own weight. Then, it is conveyed in the direction of the arrow D by the rotation of the conveying screw 36 .

The conveying path forming member 70 is a duct-shaped hollow member, and the hollow inner space constitutes a toner conveying path. The conveying path forming member 70 has a first conveying portion 701 and a second conveying portion 702 which convey toner in different directions. A connecting portion 703 is provided to connect the toner conveying path between them. A toner receiving port 71 is provided on the upper surface of the connecting portion 703 to receive toner falling from the toner discharge port 24 of the toner cartridge 20 . The first conveying portion 701 forms a conveying path extending in the mounting direction of the toner cartridge 20 to the apparatus main body 1, and the second conveying portion 702 continues downstream thereof. The second conveying portion 702 makes the conveying path extending in the mounting direction of the toner cartridge 20 to the apparatus main body 1 by the first conveying portion 701 parallel to the direction in which the toner cartridge 20 and the process cartridge 4 (developing unit 45) are arranged. turn to direction. A toner discharge port 72 that opens below the conveying path is provided on the downstream side of the conveying path of the second conveying section 702 . The toner conveying path extending from the toner cartridge 20 through the first conveying portion 701 and the second conveying portion 702 extends from the toner discharge port 72 to the toner receiving port 41 provided in the connecting portion 43 of the process cartridge 4 (developing unit 45). It is connected to the toner containing portion 44 via. The connection portion 43 of the process cartridge 4 further protrudes downstream in the mounting direction from the side surface facing the downstream side (the inner side of the accommodating portion of the process cartridge 4 in the apparatus main body) in the mounting direction of the process cartridge 4 to the apparatus main body 1 . It is designed to When the process cartridge 4 is attached to the main body of the image forming apparatus, the toner receiving port 41 opened on the upper surface of the connecting portion 43 on the downstream side in the attachment direction is positioned so as to receive the toner discharged from the conveying path forming member 70 (toner receiving port 41). (position overlapping the discharge port 72 so as to be communicable).

In this embodiment, the toner transport path is configured to extend in a detour in a direction different from the alignment direction of the process cartridge 4 and the toner cartridge 20, so that the direction of the transport path changes in a substantially U-shape. . With this configuration, the process cartridge 4 and the toner cartridge 20 can be arranged as close as possible, and the size of the apparatus can be reduced. Any length can be secured. It should be noted that the configuration of the toner transport path is not limited to that shown here.

FIG. 5 is a schematic perspective view showing a joint portion (driving force transmission portion) between the toner conveying screw 36 as the first conveying member and the toner discharge screw 37 as the second conveying member provided in the conveying path forming member 70. It is a diagram.

The toner conveying screw 36 is arranged in the first conveying portion 701 and conveys the toner fed into the first conveying portion 701 from the toner cartridge 20 through the connecting portion 703 toward the second conveying portion 702 . The toner conveying screw 36 has a rotating shaft 36k at its center, and a screw portion (spiral blade) having a first blade tooth surface 36g spirally provided on its outer peripheral surface so as to convey toner in the direction of the rotating shaft 36k. ). Then, a drive gear (drive receiving means) (not shown) provided at the end of the rotating shaft 36k of the toner conveying screw 36 receives a rotational force from a drive source (not shown) such as a motor, and the toner conveying screw 36 rotates in the direction of arrow E in FIG. Rotate.
Alternatively, the toner discharge screw 37 may receive a rotational force directly from a driving source such as a motor (not shown), and the toner conveying screw 36 may be rotated by receiving the rotational force from the toner discharge screw 37 .

The toner contacting the toner conveying screw 36 is conveyed in the rotation axis direction (arrow D direction) by the first blade tooth surface 36g that moves as the toner conveying screw 36 rotates. Then, it is pushed out in the direction (arrow D direction) toward the upstream end of the toner discharging screw 37 provided downstream of the toner conveying screw 36 in the toner conveying direction, and begins to come into contact with the toner discharging screw 37 .

The toner discharge screw 37 is arranged in the second conveying portion 702 and directs the toner fed from the first conveying portion 701 into the second conveying portion 702 by the toner conveying screw 36 toward the connecting portion 43 of the process cartridge 4 . transport. The toner discharge screw 37 has a rotating shaft 37k, and a screw portion ( spiral blade). In addition, it is provided in a direction substantially perpendicular to the toner conveying screw 36 in order to reduce the size of the apparatus. Further, the toner discharge screw 37 has a drive receiving portion 50 for receiving a rotational force from the toner conveying screw 36, and rotates in the arrow F direction following the rotation of the toner conveying screw 36. As shown in FIG. The drive receiving portion 50 is configured in such a shape that a force for rotating the toner discharging screw 37 is applied from the rotating toner conveying screw 36 by contact with the first blade tooth surface 36 g of the toner conveying screw 36 . When the drive receiving portion 50 receives a rotational force from the toner conveying screw 36 , the toner is held and rubbed between the toner conveying screw 36 and the drive receiving portion 50 .

The toner in contact with the toner discharge screw 37 is directed (arrow G direction) is conveyed in the form of being pushed out. After that, the toner is discharged from the toner discharge port 72 by its own weight and transferred to the receiving port 41 of the process cartridge 4 . The toner is supplied to the process cartridge 4 by being transported into the process cartridge 4 by the transport screw 42 .
Note that the rotating shaft 36k of the toner conveying screw 36 and the rotating shaft 37k of the toner discharge screw 37 are in a positional relationship that is displaced from each other in a direction orthogonal to both (vertical direction in FIG. 5). Therefore, the movement area of the first blade tooth surface 36g of the toner conveying screw 36 (the space area where the blade tooth surface directly exerts a conveying action on (contacts) the toner) and the second blade tooth of the toner discharge screw 37 The movement regions of the surface 37g also have a positional relationship that is shifted from each other. Therefore, corresponding to the displacement of the movement area of the tooth surface of each blade of each screw, the hollow space of the conveying path forming member 70, the hollow space of the first conveying section 701 and the hollow space of the second conveying section 702 are arranged respectively. It is preferable to have a configuration that is shifted in a direction perpendicular to the axis of rotation of the screw. That is, the heights of the bottom surface and the ceiling of the toner conveying path are vertically shifted between the first conveying section 701 and the second conveying section 702 . In this manner, it is preferable to set the gap between each screw and the hollow inner wall surface of the conveying path forming member 70 so as to be suitable for toner conveying, thereby enhancing the toner conveying efficiency.
In FIG. 4, the first conveying section 701 and the second conveying section 702 are configured to have the same height. , so as to be shifted from each other in accordance with the displacement of the movement area of the tooth surface of the blade. Alternatively, if the thickness of the wall is made uniform throughout the transport path forming member 70, the heights of the upper and lower surfaces of the first transport section 701 and the second transport section 702 are vertically displaced as an external configuration in FIG. It is good also as a structure.
Changing the configuration of the conveying path forming member according to the shift in the height of the moving region of the tooth surface of the blade in this manner may also be applied to configurations of other embodiments.

<Toner>
FIG. 6 shows a schematic diagram of the toner 40 used in the embodiment of the invention.
The developer contains toner having toner particles, the toner particles having a surface layer containing an organosilicon polymer.
As described above, conventionally used toner may be deformed while being conveyed in the drive receiving portion. A study of the Martens hardness of the toner required to suppress deformation of the toner revealed that the Martens hardness measured under the condition of a maximum toner load of 2.0×10 ⁻⁴ N was 200 MPa or more. Also, the Martens hardness is preferably 400 MPa or more.
On the other hand, the Martens hardness is 1100 MPa or less. If the Martens hardness is higher than 1100 MPa, the regulating blade and the developing roller may be damaged, resulting in image defects (vertical streak image) such as vertical streak-like density unevenness in a solid black image or halftone image.

Toner particles having a surface layer containing an organosilicon polymer were used as a means of controlling Martens hardness. The toner used in this embodiment is a non-magnetic one-component polymerized toner having a negatively charged polarity, and has a particle size of 7 μm.

<Method for producing toner particles>
A known means can be used as a method for producing toner particles, and a kneading pulverization method or a wet production method can be used. A wet production method can be preferably used from the viewpoint of uniformity of particle size and shape controllability. Furthermore, the wet production method includes a suspension polymerization method, a dissolution suspension method, an emulsion polymerization aggregation method, an emulsion aggregation method, and the like.

Here, the suspension polymerization method will be explained. In the suspension polymerization method, first, a polymerizable monomer for producing a binder resin and, if necessary, a colorant and other additives are dispersed using a dispersing machine such as a ball mill or an ultrasonic dispersing machine. A polymerizable monomer composition is prepared by uniformly dissolving or dispersing these components by means of a method (step of preparing a polymerizable monomer composition). At this time, if necessary, a polyfunctional monomer, a chain transfer agent, a wax as a release agent, a charge control agent, a plasticizer, and the like can be appropriately added.

Next, the polymerizable monomer composition is put into an aqueous medium prepared in advance, and droplets of the polymerizable monomer composition are formed by a stirrer or a disperser having a high shear force. (granulation step).

It is preferable that the aqueous medium in the granulation step contain a dispersion stabilizer in order to control the particle size of the toner particles, sharpen the particle size distribution, and suppress coalescence of the toner particles in the production process. Dispersion stabilizers are generally classified broadly into macromolecules that generate a repulsive force due to steric hindrance and poorly water-soluble inorganic compounds that stabilize dispersion by electrostatic repulsive force. Fine particles of poorly water-soluble inorganic compounds are preferably used because they are dissolved by acid or alkali and can be dissolved and easily removed by washing with acid or alkali after polymerization.

After the granulation step or while performing the granulation step, the temperature is preferably set to 50° C. or higher and 90° C. or lower to polymerize the polymerizable monomer contained in the polymerizable monomer composition to obtain a toner. A particle dispersion is obtained (polymerization step).

In the polymerization step, it is preferable to perform a stirring operation so that the temperature distribution in the container becomes uniform. When the polymerization initiator is added, it can be added at any timing and required time. Further, in order to obtain a desired molecular weight distribution, the temperature may be raised in the second half of the polymerization reaction, and further, in order to remove unreacted polymerizable monomers, by-products, etc. from the system, the second half of the reaction or the end of the reaction may be heated. Afterwards, a portion of the aqueous medium may be distilled off by a distillation operation. The distillation operation can be performed under normal pressure or reduced pressure.

From the viewpoint of obtaining high-definition and high-resolution images, the weight-average particle size of the toner is preferably 3.0 μm or more and 10.0 μm or less. The weight average particle size of the toner can be measured by a pore electric resistance method. For example, "Coulter Counter Multisizer
3” (manufactured by Beckman Coulter, Inc.). The toner particle dispersion thus obtained is sent to a filtration step for solid-liquid separation of the toner particles and the aqueous medium.

Solid-liquid separation for obtaining toner particles from the obtained toner particle dispersion can be carried out by a general filtration method. It is preferable to carry out further washing, such as by spraying. After sufficient washing is performed, solid-liquid separation is performed again to obtain a toner cake. Thereafter, it is dried by a known drying means, and if necessary, is classified to separate a particle group having a particle size other than the predetermined one to obtain toner particles. The separated particle groups having non-predetermined particle sizes may be reused to improve the final yield.

<Method for Measuring Martens Hardness of Toner>
Hardness is one of the mechanical properties of the surface or the vicinity of the surface of an object. There are various measurement methods and definitions. For example, different measurement methods are used depending on the size of the measurement area. Vickers method is often used when the measurement area is 10 μm or more, nanoindentation method when the measurement area is 10 μm or less, and AFM when the measurement area is 1 μm or less. . As definitions, for example, Brinell hardness and Vickers hardness are used as indentation hardness, Martens hardness as scratch hardness, and Shore hardness as rebound hardness.

In the measurement of toner, since the particle size is generally 3 μm or more and 10 μm or less, the nanoindentation method is a preferred measurement method. According to the studies of the inventors, Martens hardness, which represents scratch hardness, is suitable as a definition of hardness.

The method for measuring the Martens hardness of the toner by the nanoindentation method is calculated from the load-displacement curve obtained according to the procedure of the indentation test specified in ISO14577-1 using a commercially available device conforming to ISO14577-1. be able to. In the present invention, an ultra-micro indentation hardness tester "ENT-1100b" (manufactured by Elionix Co., Ltd.) was used as a device conforming to the ISO standard. The measuring method is described in the "ENT1100 Operation Manual" attached to the apparatus, and the specific measuring method is as follows.

As for the measurement environment, the inside of the shield case was kept at 30.0° C. by an attached temperature control device. Keeping the ambient temperature constant is effective in reducing variations in measurement data due to thermal expansion, drift, and the like. The set temperature was set to 30.0° C. assuming the temperature around the developing device where the toner is rubbed. A standard sample stage attached to the device was used as the sample stage, and after the toner was applied, a weak air was blown to disperse the toner. .

A flat indenter (titanium indenter, tip made of diamond) attached to the device and having a 20 μm square flat tip was used as the indenter. A flat indenter is used for objects with a small diameter and spherical shape such as toner, objects with adhering external additives, and objects with uneven surfaces if a sharp indenter is used, which greatly affects the measurement accuracy. The maximum load for the test is set to 2.0×10 ⁻⁴ N. By setting this test load, it is possible to measure the hardness without destroying the surface layer of the toner under the condition corresponding to the stress that one toner particle receives in the developing section. In the present invention, since abrasion resistance is important, it is important to measure the hardness while maintaining the surface layer without breaking it.

As the particles to be measured, particles that are present alone in the measurement screen (field size: width 160 μm, height 120 μm) of a microscope attached to the apparatus are selected. However, in order to minimize errors in the amount of displacement, the particle diameter (D) should be within the range of ±0.5 μm of the number average particle diameter (D1) (D1−0.5 μm≦D≦D1+0.5 μm). . The particle diameter of the particles to be measured was measured by measuring the long diameter and short diameter of the toner using software attached to the device, and [(long diameter + short diameter)/2] was defined as the particle diameter D (μm). The number average particle diameter is measured by the following method using "Coulter Counter Multisizer 3 (manufactured by Beckman Coulter, Inc.).
<Measurement of particle size of toner (particles)>
A precision particle size distribution measuring device (trade name: Coulter Counter Multisizer 3) using a pore electrical resistance method and dedicated software (trade name: Beckman Coulter Multisizer 3 Version 3.51, manufactured by Beckman Coulter) were used. An aperture diameter of 100 μm was used, measurement was performed with 25,000 effective measurement channels, and the measurement data was analyzed and calculated. As an electrolytic aqueous solution for measurement, ISOTON II (trade name) manufactured by Beckman Coulter Co., Ltd. was used, which was obtained by dissolving special grade sodium chloride in ion-exchanged water so that the concentration was about 1% by mass. Before conducting the measurement and analysis, the dedicated software was set as follows.
In the "change standard measurement method (SOM) screen" of the dedicated software, set the total number of counts in control mode to 50000 particles, set the number of measurements to 1, and set the Kd value to (standard particle 10.0 μm, Beckman Coulter (manufactured) was set. The threshold and noise level were automatically set by pressing the threshold/noise level measurement button. Also, the current was set to 1600 μA, the gain was set to 2, the electrolyte was set to ISOTON II (trade name), and flashing of the aperture tube after measurement was checked.
In the "pulse-to-particle size conversion setting screen" of the dedicated software, the bin interval was set to logarithmic particle size, the particle size bin was set to 256 particle size bins, and the particle size range was set to 2 μm or more and 60 μm or less.
A specific measuring method is as follows.
(1) About 200 mL of the electrolytic aqueous solution was placed in a 250 mL round-bottomed glass beaker exclusively for Multisizer 3, set on a sample stand, and stirred with a stirrer rod counterclockwise at 24 rpm. Then, the dirt and air bubbles inside the aperture tube were removed by the "flush aperture tube" function of the analysis software.
(2) About 30 mL of the electrolytic aqueous solution was placed in a 100 mL flat-bottom glass beaker. Here, about 0.5% of a diluted solution obtained by diluting Contaminon N (trade name) (a 10% by mass aqueous solution of a neutral detergent for cleaning precision measuring instruments, manufactured by Wako Pure Chemical Industries, Ltd.) with ion-exchanged water to 3 times its mass is added. Added 3 mL.
(3) An ultrasonic disperser (trade name: Ultrasonic Dispersion System Tetora 150, manufactured by Nikkaki Bios Co., Ltd.) having an electric output of 120 W and containing two oscillators with an oscillation frequency of 50 kHz with a phase shift of 180 degrees. A predetermined amount of ion-exchanged water and about 2 mL of Contaminon N (trade name) were added to the water tank.
(4) The beaker of (2) was set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser was operated. Then, the height position of the beaker was adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker was maximized.
(5) About 10 mg of toner (particles) was added little by little to the electrolytic aqueous solution in the beaker of (4) while the electrolytic aqueous solution was being irradiated with ultrasonic waves, and dispersed. Then, the ultrasonic dispersion treatment was continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water in the water tank was appropriately adjusted to 10°C or higher and 40°C or lower.
(6) The electrolytic aqueous solution of (5), in which toner (particles) are dispersed, is dripped into the round-bottomed beaker of (1) set in the sample stand using a pipette so that the measured concentration is about 5%. adjusted to The measurement was continued until the number of measured particles reached 50,000.
(7) The measurement data was analyzed with the dedicated software attached to the apparatus, and the weight average particle size (D4) was calculated. The weight average particle diameter (D4) is the "average diameter" on the analysis/volume statistics (arithmetic mean) screen when graph/vol% is set using dedicated software. The number average particle size (D1) is the "average diameter" on the "analysis/number statistical value (arithmetic mean)" screen when graph/number % is set on the dedicated software.

In the measurement, 100 arbitrary toner grains satisfying the above conditions are selected for the particle diameter D (μm). The conditions to be input at the time of measurement are as follows.
Test mode: load-unload test Test load: 2.0×10 ^-4 N
Number of divisions: 1000 steps
Step interval: 10msec

When the analysis menu "data analysis (ISO)" is selected and the measurement is performed, the Martens hardness is analyzed by the software attached to the device after the measurement and is output. The above measurements were performed on 100 toner particles, and the arithmetic average value was taken as the Martens hardness in the present invention.

<Method for Controlling Hardness of Toner>
As one means for adjusting the hardness to the above specific range, for example, the surface layer of the toner is formed with a material such as an inorganic material having an appropriate hardness, and the chemical structure and macrostructure thereof are controlled so as to have an appropriate hardness. method.

As a specific example, an organic silicon polymer can be mentioned as a substance that can have the above-mentioned specific hardness, and selection of materials includes the number of carbon atoms directly bonded to the silicon atoms of the organic silicon polymer, the length of the carbon chain, and the like. It is possible to adjust the hardness by
The toner particles have a surface layer containing an organosilicon polymer, and the number of carbon atoms directly bonded to silicon atoms of the organosilicon polymer is on average 1 to 3 (preferably 1 or more and 2 or less, more preferably 1) is preferable because it is easy to adjust the specific hardness.

As a means for adjusting the Martens hardness by chemical structure, it is possible to adjust the chemical structure such as cross-linking of the surface layer material and the degree of polymerization. Means for adjusting the Martens hardness by the macrostructure can be achieved by adjusting the uneven shape of the surface layer or adjusting the network structure connecting the protrusions. When an organosilicon polymer is used as the surface layer, these adjustments can be made by adjusting the pH, concentration, temperature, time, etc. when pretreating the organosilicon polymer. In addition, it can be adjusted by the timing, form, concentration, reaction temperature, etc. of forming the surface layer of the organosilicon polymer on the core particles of the toner.

The following method is particularly preferred in this embodiment. First, core particles of toner particles are prepared and dispersed in an aqueous medium to obtain a core particle dispersion. The concentration at this time is preferably such that the solid content of the core particles is 10% by mass or more and 40% by mass or less with respect to the total amount of the core particle dispersion liquid. The temperature of the core particle dispersion is preferably adjusted to 35° C. or higher. Further, it is preferable to adjust the pH of the core particle dispersion to a pH at which condensation of the organosilicon compound does not easily proceed. Since the pH at which the condensation of the organosilicon polymer is difficult to proceed differs depending on the substance, it is preferably within ±0.5 around the pH at which the reaction is most difficult to proceed.

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

The obtained hydrolyzate and the core particle dispersion are mixed to adjust the pH to a value suitable for condensation (preferably 6 to 12, or 1 to 3, more preferably 8 to 12) to obtain an organosilicon compound. It can surface the core particle surface of the toner particles while condensing. Condensation and surface layering are preferably carried out at 35° C. or higher for 60 minutes or longer. In addition, it is possible to adjust the macrostructure of the surface by adjusting the time to hold at 35 ° C. or higher before adjusting the pH to a suitable condensation, but in order to easily obtain a specific Martens hardness, 3 minutes to 120 minutes. The following are preferred.

By the means described above, the reaction residues can be reduced, the surface layer can be made uneven, and a network structure can be formed between the convexes. .

<Surface Layer Containing Organosilicon Polymer>
In this embodiment, the toner 40 is used which has toner particles each having a surface layer 40b containing an organosilicon polymer on the toner base particles 40a.
The organosilicon polymer preferably has a structure represented by the following formula (1).
R-SiO _3/2 formula (1)
(The R represents a hydrocarbon group having 1 or more and 6 or less carbon atoms.)

In the organosilicon polymer having the structure of formula (1), one of the four valences of Si atoms is bonded to R and the remaining three are bonded to O atoms. The O atom forms a state in which both of its two valences are bonded to Si, that is, a siloxane bond (Si--O--Si). Considering Si atoms and O atoms as an organosilicon polymer, it is expressed as —SiO _3/2 because it has two Si atoms and three O atoms. The —SiO _3/2 structure of this organosilicon polymer is considered to have properties similar to those of silica (SiO ₂ ) composed of many siloxane bonds. Therefore, it is considered possible to make the Martens hardness higher than that of the organic resin and lower than that of the inorganic silica because of the structure closer to the inorganic substance than the conventional toner having the surface layer formed of the organic resin.
In the structure represented by formula (1), R is preferably a hydrocarbon group having 1 or more and 6 or less carbon atoms. This tends to stabilize the charge amount. An aliphatic hydrocarbon group having 1 or more and 5 or less carbon atoms or a phenyl group, which is particularly excellent in environmental stability, is preferable.
Further, R is more preferably a hydrocarbon group having 1 or more and 3 or less carbon atoms in order to further improve chargeability. If the chargeability is good, the transferability is good and the amount of residual toner after transfer is small, so that the contamination of the drum, the charging member and the transfer member is improved.
Preferred examples of the hydrocarbon group having 1 or more and 3 or less carbon atoms include a methyl group, an ethyl group, a propyl group and a vinyl group. From the viewpoint of environmental stability and storage stability, R is more preferably a methyl group.

A sol-gel method is preferable as an example of the production of the organosilicon polymer. The sol-gel method is a method of hydrolyzing and condensation-polymerizing a liquid raw material as a starting raw material to form a sol state and then gelling, and is used in a method of synthesizing glasses, ceramics, organic-inorganic hybrids, and nanocomposites. By using this production method, functional materials in various shapes such as surface layers, fibers, bulk bodies, and fine particles can be produced from the liquid phase at low temperatures.

Specifically, the organosilicon polymer present on the surface layer of the toner particles is preferably produced by hydrolysis and polycondensation of a silicon compound represented by alkoxysilane.
By providing the surface layer containing the organosilicon polymer on the toner particles, it is possible to obtain a toner with improved environmental stability, less deterioration in toner performance during long-term use, and excellent storage stability. .

Furthermore, the sol-gel method starts from a liquid and forms a material by gelling the liquid, so various microstructures and shapes can be produced. In particular, when the toner particles are produced in an aqueous medium, the particles are easily precipitated on the surface of the toner particles due to the hydrophilicity of the hydrophilic group such as the silanol group of the organosilicon compound. The fine structure and shape can be adjusted by the reaction temperature, reaction time, reaction solvent, pH, the type and amount of the organometallic compound, and the like.

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

（式（Ｚ）中、Ｒ_１は、炭素数が１以上、６以下の炭化水素基を表し、Ｒ_２、Ｒ_３及びＲ_４は、それぞれ独立して、ハロゲン原子、ヒドロキシ基、アセトキシ基、又は、アルコキシ基を表す。）

(In the formula (Z), R ₁ represents a hydrocarbon group having 1 to 6 carbon atoms; R ₂ , R ₃ and R ₄ each independently represent a halogen atom, a hydroxy group, an acetoxy group, Or represents an alkoxy group.)

Hydrophobicity can be improved by the hydrocarbon group (preferably alkyl group) of R ₁ , and toner particles with excellent environmental stability can be obtained. In addition, an aryl group that is an aromatic hydrocarbon group such as a phenyl group can also be used as the hydrocarbon group. When the hydrophobicity of R ₁ is large, the charge amount tends to increase in various environments. Therefore, in view of environmental stability, R ₁ is preferably a hydrocarbon group having 1 or more and 3 or less carbon atoms. It is preferably a methyl group, more preferably a methyl group.

R ₂ , R ₃ and R ₄ are each independently a halogen atom, a hydroxy group, an acetoxy group, or an alkoxy group (hereinafter also referred to as a reactive group). These reactive groups are hydrolyzed, addition-polymerized and polycondensed to form a cross-linked structure, and a toner excellent in member contamination resistance and development durability can be obtained. It is preferably an alkoxy group having 1 to 3 carbon atoms, and more preferably a methoxy group or an ethoxy group, from the viewpoint of moderate hydrolyzability at room temperature and deposition and coating properties on the surface of toner particles. . Also, the hydrolysis, addition polymerization and condensation polymerization of R ₂ , R ₃ and R ₄ can be controlled by reaction temperature, reaction time, reaction solvent and pH.

To obtain the organosilicon polymer used in this embodiment, an organosilicon polymer having three reactive groups (R ₂ , R ₃ and R ₄ ) in one molecule excluding R ₁ in the formula (Z) shown above Compounds (hereinafter also referred to as trifunctional silanes) may be used singly or in combination.

Furthermore, the content of the organosilicon polymer in the toner particles is preferably 0.5% by mass or more and 10.5% by mass or less.
When the content of the organosilicon polymer is 0.5% by mass or more, the surface free energy of the surface layer can be further reduced, the fluidity can be improved, and the contamination of the member and the occurrence of fogging can be suppressed. . When the content is 10.5% by mass or less, charge-up can be made difficult to occur. The content of the organosilicon polymer is controlled by the type and amount of the organosilicon compound used to form the organosilicon polymer, the method of producing toner particles during the formation of the organosilicon polymer, reaction temperature, reaction time, reaction solvent and pH. can be done.

It is preferable that the surface layer containing the organosilicon polymer and the toner core particles are in contact without any gap. As a result, the occurrence of bleeding due to the resin component, release agent, etc. inside the toner particles is suppressed from the surface layer of the toner particles, and a toner excellent in storage stability, environmental stability and development durability can be obtained. In addition to the organosilicon polymer described above, the surface layer may contain resins such as styrene-acrylic copolymer resins, polyester resins and urethane resins, and various additives.

(Method for preparing THF-insoluble portion of toner particles for NMR measurement)
The tetrahydrofuran (THF)-insoluble portion of the toner particles was prepared as follows.
10.0 g of toner particles are weighed, placed in a thimble (No. 86R manufactured by Toyo Roshi Kaisha Ltd.), and placed in a Soxhlet extractor. Extraction was performed using 200 mL of THF as a solvent for 20 hours, and the filter cake in the thimble was vacuum-dried at 40° C. for several hours.

When the surface of the toner particles is treated with an external additive or the like, the external additive is removed by the following method to obtain toner particles.
160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water and dissolved in a hot water bath to prepare a concentrated sucrose solution. 31 g of the sucrose concentrate and Contaminon N (a pH 7 neutral detergent for cleaning precision measuring instruments consisting of a nonionic surfactant, an anionic surfactant, and an organic builder) were placed in a centrifugation tube (capacity: 50 mL). 6 mL of a mass % aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) is added to prepare a dispersion. 1.0 g of toner is added to this dispersion, and clumps of toner are loosened with a spatula or the like.
The centrifuge tube is shaken on a shaker at 350 spm (strokes per min) for 20 minutes. After shaking, the solution is transferred to a swing rotor glass tube (capacity 50 mL) and separated in a centrifuge (manufactured by H-9R Kokusan Co., Ltd.) at 3500 rpm for 30 minutes. This operation separates the toner particles from the detached external additive. It is visually confirmed that the toner and the aqueous solution are sufficiently separated, and the separated toner on the uppermost layer is collected with a spatula or the like. After filtering the collected toner with a vacuum filter, it is dried with a dryer for 1 hour or more to obtain toner particles. This operation is carried out multiple times to ensure the required amount.

<<Method for Confirming Structure Represented by Formula (1)>>
The following method is used to confirm the structure represented by formula (1) in the organosilicon polymer contained in the toner particles.
The hydrocarbon group represented by R in Formula (1) was confirmed by ¹³ C-NMR.

<< ¹³ C-NMR (solid) measurement conditions >>
Device: JNM-ECX500II manufactured by JEOLRESONANCE
Sample tube: 3.2 mmφ
Sample: 150 mg of tetrahydrofuran-insoluble matter of toner particles for NMR measurement
Measurement temperature: Room temperature Pulse mode: CP/MAS
Measurement nuclear frequency: 123.25 MHz ( ¹³ C)
Reference substance: adamantane (external standard: 29.5 ppm)
Sample rotation speed: 20 kHz
Contact time: 2ms
Delay time: 2s
Accumulated times: 1024 times

In this method, a methyl group (Si—CH ₃ ), an ethyl group (Si—C ₂ H ₅ ), a propyl group (Si—C ₃ H ₇ ), a butyl group (Si—C ₄ H ₉ ), pentyl group (Si—C ₅ H ₁₁ ), hexyl group (Si—C ₆ H ₁₃ ) or phenyl group (Si—C ₆ H ₅ —), etc. The hydrocarbon group represented by R was confirmed.

<<Method for calculating the ratio of the peak area attributed to the structure of formula (1) in the organosilicon polymer contained in the toner particles>>
²⁹ Si-NMR (solid) measurement of the THF-insoluble portion of the toner particles is performed under the following measurement conditions.
<< ²⁹ Si-NMR (solid) measurement conditions >>
Device: JNM-ECX500II manufactured by JEOLRESONANCE
Sample tube: 3.2 mmφ
Sample: 150 mg of tetrahydrofuran-insoluble matter of toner particles for NMR measurement
Measurement temperature: Room temperature Pulse mode: CP/MAS
Measured nuclear frequency: 97.38 MHz ( ²⁹ Si)
Reference substance: DSS (external standard: 1.534 ppm)
Sample rotation speed: 10 kHz
Contact time: 10ms
Delay time: 2s
Accumulated times: 2000 to 8000 times

After the above measurement, a plurality of silane components having different substituents and bonding groups in the tetrahydrofuran-insoluble portion of the toner particles were peak-separated into the following X1 structure, X2 structure, X3 structure, and X4 structure by curve fitting. Calculate area.
X1 structure: (Ri) (Rj) (Rk) SiO _1/2 (2)
X2 structure: (Rg)(Rh)Si(O _1/2 ) ₂ (3)
X3 structure: RmSi(O _1/2 ) ₃ (4)
X4 structure: Si(O _1/2 ) ₄ (5)

(Ri, Rj, Rk, Rg, Rh, and Rm in formulas (2), (3), and (4) are bonded to silicon, organic groups such as hydrocarbon groups having 1 to 6 carbon atoms, halogen atoms , indicates a hydroxy group, an acetoxy group, or an alkoxy group.)
If it is necessary to confirm the structure represented by the above formula (1) in more detail, it may be identified by the measurement results of ¹ H-NMR together with the measurement results of ¹³ C-NMR and ²⁹ Si-NMR.

[External additive]
Toner particles can be made into toner without externally adding external additives. may be added to form a toner.

Examples of external additives include inorganic oxide fine particles such as alumina fine particles and titanium oxide fine particles, inorganic stearic acid compound fine particles such as aluminum stearate fine particles and zinc stearate fine particles, or strontium titanate and zinc titanate. and inorganic titanate compound fine particles. These can be used individually by 1 type or in combination of 2 or more types.

These inorganic fine particles are preferably surface-treated with a silane coupling agent, a titanium coupling agent, a higher fatty acid, a silicone oil, or the like in order to improve heat-resistant storage stability and environmental stability. The BET specific surface area of the external additive is preferably 10 m ² /g or more and 450 m ² /g or less.

The BET specific surface area can be determined by a low temperature gas adsorption method using a dynamic constant pressure method according to the BET method (preferably the BET multipoint method). For example, using a specific surface area measuring device (trade name: Gemini 2375 Ver.5.0, manufactured by Shimadzu Corporation), nitrogen gas is adsorbed on the surface of the sample, and the BET multipoint method is used for measurement. BET specific surface area (m ² /g) can be calculated.

The total amount of these various external additives added is preferably 0.05 parts by mass or more and 5 parts by mass or less, more preferably 0.1 parts by mass or more and 3 parts by mass, based on 100 parts by mass of the toner particles. Part by mass or less. In addition, various external additives may be used in combination.

(Example)
Methods for producing toners a to e used in the study are described below. In addition, "parts" of each material are all based on mass unless otherwise specified.

(Example 1: Method for producing toner a)
(Preparation step of aqueous medium 1)
To 1000.0 parts of ion-exchanged water in a reaction vessel, 14.0 parts of sodium phosphate (12 hydrate, manufactured by Rasa Kogyo Co., Ltd.) was added, and the mixture was kept at 65° C. for 1.0 hour while purging with nitrogen.
T. K. Using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12000 rpm, a calcium chloride aqueous solution obtained by dissolving 9.2 parts of calcium chloride (dihydrate) in 10.0 parts of ion-exchanged water is mixed together. to prepare an aqueous medium containing a dispersion stabilizer. Furthermore, 10% by mass hydrochloric acid was added to the aqueous medium to adjust the pH to 5.0, and an aqueous medium 1 was obtained.

(Hydrolysis step of organosilicon compound for surface layer)
60.0 parts of ion-exchanged water was weighed into a reactor equipped with a stirrer and a thermometer, and the pH was adjusted to 3.0 using 10% by mass hydrochloric acid. This was heated with stirring to bring the temperature to 70°C. Thereafter, 40.0 parts of methyltriethoxysilane, which is an organosilicon compound for the surface layer, was added and hydrolyzed by stirring for 2 hours or longer. The end point of the hydrolysis was visually confirmed by confirming that the oil and water did not separate and became one layer, and then cooled to obtain a hydrolyzate of the organosilicon compound for the surface layer.

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

(Granulation process)
The temperature of the aqueous medium 1 is set at 70°C, T.E. K. While maintaining the rotation speed of the homomixer at 12000 rpm, the polymerizable monomer composition was charged into the aqueous medium 1, and 9.0 parts of t-butyl peroxypivalate as a polymerization initiator was added. The mixture was granulated for 10 minutes while maintaining 12000 rpm with the stirring device.

(Polymerization process)
After the granulation step, the agitator was changed to a propeller agitating blade, and while stirring at 150 rpm, the mixture was maintained at 70°C and polymerized for 5.0 hours. core particles were obtained. When the temperature of the slurry was cooled to 55° C. and the pH was measured, it was pH=5.0. While stirring was continued at 55° C., 20.0 parts of the hydrolyzate of the organosilicon compound for the surface layer was added to start forming the surface layer of the toner particles. After holding for 30 minutes as it is, the slurry was adjusted to pH=9.0 for completion of condensation using an aqueous sodium hydroxide solution and held for an additional 300 minutes to form a surface layer.

(Washing and drying process)
After completion of the polymerization process, the slurry of toner particles is cooled, and hydrochloric acid is added to the slurry of toner particles to adjust the pH to 1.5 or less, and the mixture is left with stirring for 1 hour, followed by solid-liquid separation with a pressurized filter to form a toner cake. got This was reslurried with ion-exchanged water to form a dispersion again, and then subjected to solid-liquid separation with the aforementioned filter. After reslurry and solid-liquid separation were repeated until the electrical conductivity of the filtrate became 5.0 μS/cm or less, solid-liquid separation was finally performed to obtain a toner cake.

The resulting toner cake was dried with a flash jet dryer (manufactured by Seishin Enterprise Co., Ltd.), and a multi-division classifier utilizing the Coanda effect was used to cut fine and coarse particles to obtain toner particles. The drying conditions were a blowing temperature of 90.degree. C., a dryer outlet temperature of 40.degree.

Silicon mapping was performed in cross-sectional TEM observation of the toner particles, and the presence of silicon atoms in the surface layer was confirmed. In the following toner production examples as well, it was confirmed by similar silicon mapping that silicon atoms were present in the surface layer containing the organosilicon polymer. In this production example, the obtained toner particles were used as the toner a as they were without external addition. Table 1 shows the measurement results of the obtained toner a. Martens hardness was measured by the method described above.

(Example 2: Method for producing toner b)
Toner b was prepared in the same manner as in Example 1, except that the conditions for adding the hydrolyzate in (polymerization step) and the retention time after addition were changed as shown in Table 1. In addition, pH adjustment of the slurry was performed with hydrochloric acid and sodium hydroxide aqueous solution. Table 1 shows the measurement results of the obtained toner b.

(Example 3: Method for producing toner c)
Toner c was prepared in the same manner as in Example 1, except that the conditions for adding the hydrolyzate in (polymerization step) and the retention time after addition were changed as shown in Table 1. In addition, pH adjustment of the slurry was performed with hydrochloric acid and sodium hydroxide aqueous solution. Table 1 shows the measurement results of the obtained toner c.

(Comparative Example 1: Method for producing toner d)
Toner d was prepared in the same manner as in Example 1, except that the conditions for adding the hydrolyzate in (polymerization step) and the holding time after addition were changed as shown in Table 1. In addition, pH adjustment of the slurry was performed with hydrochloric acid and sodium hydroxide aqueous solution. Table 1 shows the measurement results of the obtained toner d.

(Comparative Example 2: Method for producing toner e)
Toner e was prepared in the same manner as in Example 1, except that the conditions for adding the hydrolyzate in (polymerization step) and the retention time after addition were changed as shown in Table 1. In addition, pH adjustment of the slurry was performed with hydrochloric acid and sodium hydroxide aqueous solution. Table 1 shows the measurement results of the obtained toner e.

<Experiment content>
In order to check the deformation of the toner of Examples 1-3 and Comparative Examples 1-2, the occurrence of vertical streak images, and the streak scraping of the developing roller, 600 dpi, 2 dots, 100 space horizontal lines were printed on 5,000 sheets per day while conveying the toner to the process cartridge 4. Image samples were taken after the intermittent feeding, and the following evaluations were carried out. In the intermittent feeding, an intermittent time of 3 seconds was provided for every two images formed.
The amount of toner conveyed (the amount of toner replenished to the process cartridge 4) was about 8 g for 1000 sheets, which is almost the same as the amount of toner printed. The image sample was evaluated by printing one halftone image. Evaluation is as follows.
Paper feeding and image sample formation were performed in an environment of 32° C. and 80% RH. The total number of sheets passed was 50,000 sheets. The following evaluation is the evaluation for 50,000 sheets.

(Vertical streak image)
〇: No occurrence No vertical streak-like density unevenness across the entire image △: Slight occurrence Slight vertical streak-like density unevenness occurred in part of the image, but there is no problem in use ×: Occurs in part or all of the image Occurrence of vertical streak density unevenness

(deformation of toner)
◯: No occurrence 100 toner particles were observed by scanning microscope, and no crushed toner particles were detected. △: Slight occurrence of 100 particles was confirmed by scanning microscope observation. 100 pieces were confirmed by observation with a type microscope, and crushed toner was found. The scanning microscope was SU8020 manufactured by Hitachi High Technology, and observation was performed under the condition of an acceleration voltage of 3 kV (magnification of 5000 times).
Determination regarding deformation is as follows.
Circularity of 100 toner particles was measured before passing through paper, and the circularity of average value - standard deviation 3σ was taken as the standard MIN circularity, and toner with less than the standard MIN circularity x 0.9 was judged to be crushed. . On the other hand, it was determined that the toner particles with the standard MIN circularity or more were not crushed. In addition, the toner having a degree of less than the standard MIN circularity and having a standard MIN circularity of 0.9 or more was judged to be slightly deformed.

(Scraping of streaks on the developing roller)
〇: Not generated Visually observed after cleaning the developing roller, no trace of scraping △: Slightly generated Visually observed after cleaning the developing roller, slight scraping traces can be seen, but there is no problem in use ×: Occurred Cleaning the developing roller After visual observation, there are traces of scraping.

<Confirmation of effect>
Table 2 shows the results.

(Table 2)

As shown in Examples 1 to 3, the toner having a Martens hardness of 200 MPa to 1100 MPa when measured under the condition of a maximum load of 2.0×10 ⁻⁴ N produced vertical streak images and deformed the toner up to 50,000 sheets. , and streaks on the developing roller were not observed.
This indicates that with the hardness of the toner of this embodiment, the deformation of the toner does not occur even in the configuration in which the toner conveying member has the drive receiving portion in the toner conveying path.
In addition, in Comparative Example 1, a vertical streak image and toner deformation occurred. This is probably because the toner deforms at the drive receiving portion of the toner conveying member when the Martens hardness is less than 200 MPa.
In Comparative Example 2, a vertical streak image occurs. This is probably because the developing roller 7 and the developing blade 9 were damaged by the toner when the Martens hardness exceeded 1100 MPa. When the developing roller 7 and the developing blade 9 were actually observed, it was confirmed that scraped grooves were generated at positions corresponding to the vertical streak images.
It should be noted that the setting conditions used in the description of this embodiment are only examples, and the present invention is not limited to these.
As described above, by using a toner having a Martens hardness of 200 MPa or more and 1100 MPa or less when measured under the condition of a maximum toner load of 2.0×10 ⁻⁴ N, it is possible to reduce friction between conveying members in the toner conveying path. Deformation of toner can be suppressed even in a configuration having a drive receiving portion.

<<Embodiment 2>>
A second embodiment of the present invention will be described. In the second embodiment, the parts different from the first embodiment will be explained in detail, and the explanation of the same parts as the first embodiment will be omitted.

<Image forming apparatus>
FIG. 7 is a simplified diagram of the main body 1 in this embodiment. Unlike the first embodiment, the toner cartridge 25 is arranged substantially horizontally with the drum unit 46 under the frame of the developing unit 45, which is the developing container housing the developing roller 7 and the like. there is By arranging the toner cartridge 25 in this manner, there is an advantage that the toner conveying path to the developing frame 45 can be shortened and the structure of the main body can be simplified.

<Toner Conveyance>
FIG. 8 is a schematic perspective view showing the external configuration of the toner cartridge 25. As shown in FIG. The toner cartridge 25 of the present embodiment has a configuration in which the configuration of the toner cartridge 20 of Embodiment 1 is horizontally reversed. Description is omitted.

FIG. 9A shows a schematic perspective view of the configuration around the main body conveying path forming member 80 in a state where the toner cartridge 25 and the process cartridge 4 are attached to the main body 1. FIG. FIG. 9(b) shows a schematic cross-sectional view along the dotted line H in FIG. 9(a).
The toner discharged from the toner discharge port 24 of the connecting portion 253 of the toner cartridge 25 (which has the same configuration as the connecting portion 203 of the toner cartridge 20 of the first embodiment) is brought to the receiving port 81 of the main conveyance path forming member 80 by its own weight. passed by.

The conveying path forming member 80 is a duct-shaped hollow member similar to the conveying path forming member 70, and the hollow inner space constitutes the toner conveying path. The conveying path forming member 80 extends from the connecting portion 253 of the toner cartridge 25 on the upstream side of the toner conveying path to the connecting portion 43 of the process cartridge 4 on the downstream side of the toner conveying path. It has a transport section 802 and a third transport section 803 . A toner conveying screw 86 and a toner discharging screw 87 are arranged in the second conveying portion 802 and the third conveying portion 803, respectively.

The first conveying portion 801 is provided with the receiving port 81 on its upper surface, and an inclined surface 85 for moving the toner, which has entered through the receiving port 81, toward the downstream side of the toner conveying path by its own weight. is formed on the bottom surface of the toner transport path. The inclined surface 85 is provided so that the angle with respect to the horizontal surface is larger than the angle of repose of the toner so as to facilitate the movement of the toner.

The toner moved from the first conveying portion 801 to the lower portion (upstream side) of the second conveying path 802 by the action of the inclined surface 85 contacts the toner conveying screw 86 arranged inside the second conveying portion 802 . The toner contacting the toner conveying screw 86 is conveyed upward in the direction of arrow J from the upstream end of the toner conveying screw 86 toward the downstream end thereof as the toner conveying screw 86 rotates.

The toner conveyed downstream (upper) of the toner conveying path of the second conveying portion 802 by the toner conveying screw 86 contacts the toner discharge screw 87 arranged inside the third conveying portion 803 . The toner contacting the toner discharge screw 87 is conveyed in the direction of arrow K (substantially horizontally) in the toner conveying path of the third conveying portion 803 by the rotation of the toner discharge screw 87 .

Here, the toner conveying screw 86 rotates following the rotation of the toner discharging screw 87 when the drive receiving portion 50 receives a rotational force from the toner discharging screw 87 . The toner discharge screw 87 receives a rotational force from a drive source (not shown) such as a motor by a drive gear (drive receiving means) (not shown) provided at the end of the rotating shaft, and rotates in the direction of the arrow K. Convey the toner. When the drive receiving portion 50 receives the rotational force, the toner is held and rubbed between the toner conveying screw 86 and the drive receiving portion 50 .
Alternatively, the toner conveying screw 86 may receive a rotational force directly from a driving source such as a motor (not shown), and the toner discharge screw 87 may receive the rotational force from the toner conveying screw 86 and be driven to rotate.

The toner conveyed to the downstream of the toner conveying path of the third conveying portion 803 is discharged by its own weight from the toner discharge port 82 provided on the bottom surface of the third conveying portion 803 , and is discharged to the receiving port 41 of the connecting portion 43 of the process cartridge 4 . be handed over. The toner is supplied to the process cartridge 4 (the toner containing portion 44 of the developing unit 45) by being conveyed into the process cartridge 4 by the conveying screw 42 .

The conveying path forming member 70 of the first embodiment has a configuration in which the toner conveying path extends in a substantially U-shape in the mounting direction of the process cartridge 4 and the drum cartridge 20 to the apparatus main body. On the other hand, the conveying path forming member 80 of the second embodiment forms the toner conveying path in a U-shape in a direction substantially parallel to the direction in which the process cartridge 4 and the drum cartridge 25 are arranged (opposing direction) at the inner side of the cartridge. This is a structure that is laid out, and is a structure that is superior in miniaturization of the device.

(Example)
Toners a to f were used for the study. Toners a to e are the same as in the first embodiment. Toner f was prepared in the same manner as toner a, except that the conditions for adding the hydrolyzate in (polymerization step) and the retention time after addition were changed as shown in Table 3. In addition, pH adjustment of the slurry was performed with hydrochloric acid and sodium hydroxide aqueous solution. Table 3 shows the measurement results of the obtained toner f.

<Experiment content>
In order to check the deformation of the toner of Examples 4-7 and Comparative Examples 3-4, the generation of vertical streak images, and the streak scraping of the developing roller, 5,000 sheets per day were printed with a horizontal line of 600 dpi, 2 dots, and 100 spaces while conveying the toner to the process cartridge 4. Image samples were taken after the intermittent feeding, and the following evaluations were carried out. In the intermittent feeding, an intermittent time of 3 seconds was provided for every two images formed.
The amount of toner conveyed (the amount of toner replenished to the process cartridge 4) was about 8 g for 1000 sheets, which is almost the same as the amount of toner printed. The image sample was evaluated by printing one halftone image. Evaluation is as follows.
Paper feeding and samples were performed in an environment of 32° C. and 80% RH. The total number of sheets passed was 50,000 sheets. The following evaluation is the evaluation for 50,000 sheets.

<Confirmation of effect>
The method for confirming the effect was the same as in the first embodiment. Table 4 shows the results.

As shown in Examples 4 to 6, a toner having a Martens hardness of 200 MPa or more and 1100 MPa or less when measured under the condition of a maximum load of 2.0×10 ⁻⁴ N can be used up to 50,000 sheets, which poses a problem in use. There was no occurrence of vertical streak images, toner deformation, or streak scraping of the developing roller.
This indicates that with the hardness of the toner of the present embodiment, deformation of the toner that causes problems in use does not occur even in the configuration in which the toner conveying member has a drive receiving portion in the toner conveying path. there is

Here, while the toner b did not deform in Embodiment 1, some deformation of the toner was observed in Embodiment 2 (however, the effect of the present invention was exhibited). Observing the vicinity of the engaging portion (drive receiving portion 50) between the toner conveying screw 86 and the toner discharging screw 87, it was found that the toner sandwiched by the engaging portion was transferred to the toner discharging screw 87 and immediately spilled from the toner discharging screw 87. It was found that there was something falling between the toner conveying screw 86 and the wall of the conveying path. As a result, the toner is repeatedly sandwiched between the engaging portions.
As a result of investigation, it was found that the condition for the toner to fall from the discharge screw 87 is that the angle of the rotating shaft of the toner discharge screw 87 is equal to or greater than the angle of repose of the toner with respect to the horizontal plane. Even in such a severe environment, if the Martens hardness of the toner satisfies the above numerical range, deformation of the toner can be suppressed, and vertical streak-like density unevenness can be suppressed.

Here, the angle of repose of toner will be described. The angle of repose of the toner is the inclination angle of the ridge line of the toner pile formed on the flat surface when the toner is dropped on the flat surface. In this embodiment, a powder tester PT-S (manufactured by Hosokawa Micron Corporation) was used to measure the angle of repose. 150 g of toner is placed on a mesh with an opening of 250 μm and vibrated to deposit the toner on a circular table with a diameter of 8 cm through a funnel. At this time, the toner is deposited so that it overflows from the end of the table. The angle formed between the ridgeline of the toner deposited on the table at this time and the circular table surface was measured as the angle of repose.

Since Comparative Examples 3 and 4 are the same as Embodiment 1, description thereof is omitted.

As described above, even in the configuration having the drive receiving portion between the conveying members in the toner conveying path and the toner conveying direction being upward, the maximum load of the toner is 2.0×10 ⁻⁴ N. Deformation of the toner can be suppressed by using a toner having a Martens hardness of 200 MPa or more and 1100 MPa or less when measured under the conditions of . If the lower limit of the Martens hardness is 200 MPa or more, a sufficient effect in suppressing toner deformation can be expected. If it can be done, further effects can be expected. That is, a more suitable range of Martens hardness is 400 MPa or more and 1100 MPa or less.
It should be noted that the setting conditions used in the description of this embodiment are only examples, and the present invention is not limited to these.

<<Embodiment 3>>
A third embodiment of the present invention will be described. Embodiment 3 is characterized in that the conveying path forming member 70 provided in the apparatus main body in Embodiment 1 is configured as a part of the toner cartridge 20 . That is, the configuration is such that the conveying path forming member 70 of Embodiment 1 is integrated with the toner cartridge 20 so as to be detachable from the apparatus main body 1 .

FIG. 10 is a schematic perspective view of the process cartridge 4 and toner cartridge 26 according to the third embodiment.
The toner cartridge 26 of Embodiment 3 is provided with a conveying path forming portion 27 on the side surface on the downstream side in the mounting direction to the apparatus main body.
The conveying path forming portion 27 is composed of a duct-like hollow member similar to the conveying path forming member 70, and the hollow inner space constitutes a toner conveying path. The toner transport path formed by the transport path forming portion 27 communicates between the internal space of the toner cartridge 26 and the internal space of the connecting portion 43 of the process cartridge 4 . The conveying path forming section 27 includes a first conveying section 271, a second conveying section 272, and a third conveying section 273 having different conveying directions from the upstream toner cartridge 26 side to the downstream process cartridge 4 connecting section 43 side. have.
The internal structure of the toner cartridge 26 is the same as that of the toner cartridge 20 of Embodiment 1, and the tip of the toner conveying screw 26 extends to the inside of the first conveying portion 271 of the conveying path forming portion 27 . Therefore, the toner is conveyed to the upper part inside the first conveying portion 271 by the toner conveying screw 26 and falls inside the first conveying portion 271 . Subsequent toner transport is performed by a toner transport screw and a toner discharge screw (not shown) disposed inside the second transport portion 272 and the third transport portion 273, respectively, similarly to the transport path forming member 70 of the first embodiment. .

By providing the toner cartridge 26 with the transport path, the number of toner transfer parts between the transport paths is reduced, so the number of toner leakage prevention members (not shown) in the transfer part can be reduced.
It should be noted that the setting conditions used in the description of this embodiment are only examples, and the present invention is not limited to these.

<<Embodiment 4>>
A fourth embodiment of the present invention will be described. Embodiment 4 is characterized in that the conveying path forming member 70 provided in the apparatus main body in Embodiment 1 becomes a part of the process cartridge 4 . That is, the configuration is such that the transport path forming member 70 of Embodiment 1 is integrated with the process cartridge 4 and can be attached to and detached from the apparatus main body 1 .

FIG. 11 is a schematic perspective view of the process cartridge 4 and toner cartridge 20 according to the fourth embodiment.
The process cartridge 4 of Embodiment 4 is provided with a conveying path forming portion 47 on the side surface on the downstream side in the mounting direction to the apparatus main body.
The toner cartridge 20 has the same configuration as that of the first embodiment.
The conveying path forming portion 47 is composed of a duct-like hollow member similar to the conveying path forming member 70, and the hollow inner space constitutes a toner conveying path. The toner transport path formed by the transport path forming portion 47 communicates between the internal space of the toner cartridge 20 and the internal space of the process cartridge 4 (the toner containing portion 44 of the developing unit 45). The transport path forming portion 47 includes a first transport portion 471, a second transport portion 472, a third transport portion 473, a third 4 transport section 474 is provided.
A toner conveying screw (not shown) is disposed in each of the second conveying portion 472, the third conveying portion 473, and the fourth conveying portion 474, and these screws are sequentially connected so as to transmit the rotational driving force in series.

By providing the transport path to the process cartridge 4, the number of toner transfer parts between the transport paths is reduced, so that the number of toner leakage prevention members (not shown) in the transfer part can be reduced.
It should be noted that the setting conditions used in the description of this embodiment are only examples, and the present invention is not limited to these.

DESCRIPTION OF SYMBOLS 1... Image forming apparatus 4... Process cartridge 20... Toner cartridge 21... Stirring shaft 22... Stirring blade 23... Toner conveying screw 24... Discharge port 36... Toner conveying screw 36g... First blade tooth surface , 36k... rotary shaft 37... toner discharge screw 37g... second blade tooth surface 37k... rotary shaft 40... toner 40a... toner base particles 40b... surface layer containing organosilicon polymer 41... toner receiving Mouth 70 Main Conveying Path Forming Member 71 Toner Receiving Port 72 Toner Discharging Port

Claims (18)

A developing device used in an image forming apparatus,
a developer carrier that carries a developer for developing the latent image formed on the image carrier;
a regulating member for regulating the developer carried on the developer carrier;
a frame that supports the developer carrying member and the regulating member and has a container for storing the developer;
a developer container containing the developer;
a transport path for transporting the developer from the developer container to the storage portion of the frame;
A first conveying member that conveys the developer by rotating and a second conveying member that conveys the developer by rotating downstream of the first conveying member are arranged in the conveying path. ,
The second conveying member has a drive receiving portion that receives a rotational force from the first conveying member,
the developer comprises a toner having toner particles ,
The toner has a Martens hardness of 200 MPa or more and 1100 MPa or less when measured under conditions of a maximum load of 2.0×10 ⁻⁴ N ,
The toner particles have a surface layer containing an organosilicon polymer,
A developing device, wherein the number of carbon atoms directly bonded to the silicon atoms of the organosilicon polymer is 1 or more and 3 or less on average per silicon atom . a rotating shaft of either the first conveying member or the second conveying member is larger than an angle of repose of the developer with respect to a horizontal plane during operation;
2. The developing device according to claim 1, wherein the toner has a Martens hardness of 400 MPa or more and 1100 MPa or less when measured under conditions of a maximum load of 2.0×10 ⁻⁴ N. 3. The developing device according to claim 1, wherein said organosilicon polymer has a structure represented by the following formula (1).
R-SiO _3/2 formula (1)
(The above R represents a hydrocarbon group having 1 or more and 6 or less carbon atoms.) 4. The developing device according to claim 3 , wherein said R is a hydrocarbon group having 1 or more and 3 or less carbon atoms. 5. The transport path according to any one of claims 1 to 4 , wherein the conveying path detours in a direction different from the facing direction of the frame and the developer container and extends from the developer container to the storage portion of the frame. 1. The developing device according to item 1. the developer carrying member, the regulating member, and the frame are detachable from an apparatus main body of an image forming apparatus as a first cartridge;
the developer container is attachable/detachable to/from the main body of the image forming apparatus as a second cartridge separately from the first cartridge;
The transport path is provided in the device main body,
The developing device according to any one of claims 1 to 5 . an image carrier on which a latent image is formed;
a developer carrier that carries a developer for developing the latent image formed on the image carrier;
a regulating member for regulating the developer carried on the developer carrier;
a frame that supports at least the developer carrying member and the regulating member and has a container for storing the developer;
a developer container containing the developer;
a transport path for transporting the developer from the developer container to the storage portion of the frame;
A first conveying member that conveys the developer by rotating and a second conveying member that conveys the developer by rotating downstream of the first conveying member are arranged in the conveying path. ,
The second conveying member has a drive receiving portion that receives a rotational force from the first conveying member,
the developer comprises a toner having toner particles ,
The toner has a Martens hardness of 200 MPa or more and 1100 MPa or less when measured under conditions of a maximum load of 2.0×10 ⁻⁴ N ,
The toner particles have a surface layer containing an organosilicon polymer,
An image forming apparatus, wherein the number of carbon atoms directly bonded to the silicon atoms of the organosilicon polymer is 1 or more and 3 or less on average per silicon atom . a rotating shaft of either the first conveying member or the second conveying member is larger than an angle of repose of the developer with respect to a horizontal plane during operation;
8. The image forming apparatus according to claim 7 , wherein the toner has a Martens hardness of 400 MPa or more and 1100 MPa or less when measured under conditions of a maximum load of 2.0×10 ⁻⁴ N. 9. The image forming apparatus according to claim 7 , wherein the organosilicon polymer has a structure represented by formula (1) below.
R-SiO _3/2 formula (1)
(The above R represents a hydrocarbon group having 1 or more and 6 or less carbon atoms.) 10. The image forming apparatus according to claim 9 , wherein said R is a hydrocarbon group having 1 or more and 3 or less carbon atoms. 11. The conveying path according to any one of claims 7 to 10 , wherein the conveying path extends from the developer container to the accommodating portion of the frame by making a detour in a direction different from the facing direction of the frame and the developer container. 2. The image forming apparatus according to item 1. The developer carrying member, the regulating member, and the frame are detachable as a first cartridge, and the developer container is detachable as a second cartridge, separately from the first cartridge. further comprising a device body,
The transport path is provided in the device main body,
The image forming apparatus according to any one of claims 7 to 11 . A process cartridge used in an image forming apparatus,
a developer carrier that carries a developer for developing the latent image formed on the image carrier;
a regulating member for regulating the developer carried on the developer carrier;
a frame that supports the developer carrying member and the regulating member and has a container for storing the developer;
a developer container containing the developer;
a transport path for transporting the developer from the developer container to the storage portion of the frame;
the conveying path includes a first conveying member that conveys the developer by rotation and a second conveying member that conveys the developer by rotating downstream of the first conveying member;
The second conveying member has a drive receiving portion that receives a rotational force from the first conveying member,
the developer comprises a toner having toner particles ,
The toner has a Martens hardness of 200 MPa or more and 1100 MPa or less when measured under conditions of a maximum load of 2.0×10 ⁻⁴ N ,
The toner particles have a surface layer containing an organosilicon polymer,
A process cartridge, wherein the number of carbon atoms directly bonded to silicon atoms in the organosilicon polymer is 1 or more and 3 or less on average per silicon atom . a rotating shaft of either the first conveying member or the second conveying member is larger than an angle of repose of the developer with respect to a horizontal plane during operation;
14. The process cartridge according to claim 13 , wherein said toner has a Martens hardness of 400 MPa or more and 1100 MPa or less when measured under conditions of a maximum load of 2.0×10 ⁻⁴ N. 15. A process cartridge according to claim 13 , wherein said organosilicon polymer has a structure represented by the following formula (1).
R-SiO _3/2 formula (1)
(The above R represents a hydrocarbon group having 1 or more and 6 or less carbon atoms.) 16. A process cartridge according to claim 15 , wherein said R is a hydrocarbon group having 1 or more and 3 or less carbon atoms. 17. The transport path according to any one of claims 13 to 16 , wherein the transport path detours in a direction different from a direction in which the frame and the developer container face each other, and extends from the developer container to the accommodating portion of the frame. 2. The process cartridge according to item 1. the developer carrying member, the regulating member, and the frame are detachable from an apparatus main body of an image forming apparatus as a first cartridge;
the developer container is attachable/detachable to/from the main body of the image forming apparatus as a second cartridge separately from the first cartridge;
The transport path is provided in the device main body,
The process cartridge according to any one of claims 13-17 .

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