Toner processing device and toner manufacturing method

Abstract

To provide a processing apparatus for toner that achieves both economical efficiency and durability of the apparatus and stabilizes the quality of toner.SOLUTION: A processing apparatus for toner processes an object to be processed including toner particles and an external additive, and the processing apparatus for toner comprises: a processing chamber in which the object to be processed is accommodated; a drive shaft that is rotatably provided on the bottom of the processing chamber; and a rotating body that is pivotally supported on the drive shaft. The rotating body has a rotating body main body, and a projecting portion that projects outward in a radial direction from an outer peripheral part of the rotating body main body. The rotating body has a processing member that collides with the object to be processed at the projection portion to process the object to be processed. The processing member forms all or part of the projection portion. The rotating body main body and the processing member are separable from each other. The rotating body main body has a convex part that is convex in a direction in which the rotating body rotates. The processing member is fitted to the convex part.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to a processing apparatus for toner for developing electrostatic images used in electrophotographic image formation, and a method for producing the toner. [Background technology]

[0002] With the development of electrophotographic systems, toners that can handle higher image quality and higher speeds are required. Usually, toners are used in a state where fine particles, particularly inorganic fine particles, are fixed to the surface of toner particles as external additives for the purpose of controlling chargeability, imparting fluidity, etc. As a method for attaching the external additives to the surface of toner particles, there is a method in which a processing object containing toner particles and the external additives is mixed and collided with a high-speed stirring blade in a processing chamber, thereby fixing the external additives to the surface of the toner particles.

[0003] If such external addition treatment is repeated for a long period of time, the collision portion of the blade that collides with the treated object may wear and deteriorate. As the wear progresses, not only the strength of the stirring blade itself is impaired, but it becomes difficult to fix the external additive to the toner particle surface with the desired strength. If the external addition treatment cannot be performed with the required strength, image defects may occur due to lumps of external additive that have not been disintegrated. In addition, free external additive that has not been fixed to the toner particles may contaminate the charging member, etc., and image defects may occur due to member contamination.

[0004] For this reason, it is necessary to suppress deterioration due to wear of the external additive treatment device. In order to increase the mechanical strength of the toner production device, a pulverizer has been proposed in which the components of the production device are subjected to surface treatment, for example, plating treatment, to increase the wear resistance (Patent Document 1).

[0005] In a mixing device having a rotor for external additive treatment, it is described that the treatment section, which has a collision part where the rotor collides with the material to be treated and treats the material, and the rotor body can be separated vertically on a plane perpendicular to the drive shaft (Patent Document 2). This allows for improved maintainability by replacing only the treatment section. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2008-100188 A [Patent Document 2] JP 2017-026915 A Summary of the Invention [Problem to be solved by the invention]

[0007] Patent Document 1 reveals that in external additive processing using toners with added abrasive particles to address image defects such as image deletion, or toners containing magnetic material for one-component development with a high specific gravity, the mechanical load on the pulverizer increases, accelerating wear and tear on the stirring blades, etc. Not only does the toner not grind properly due to wear and tear, but the stirring blades themselves must be replaced, creating problems in terms of maintainability, economy, and productivity due to device shutdowns.

[0008] Furthermore, in Patent Document 2, when the rotating body is used at a high rotation speed or when a large amount of additive is added during external addition treatment, there are problems with maintainability and economy over long-term use, and productivity due to equipment stoppage.

[0009] The present disclosure provides a toner processing apparatus that is economical and has good durability while also providing stable toner quality, and a method for producing toner using the apparatus. [Means for solving the problem]

[0010] One aspect of the present disclosure is a toner processing device for processing a processing target including toner particles and an external additive, The toner processing device comprises: a processing chamber in which the object to be processed is accommodated; a drive shaft rotatably provided at the bottom of the processing chamber; A rotor supported by the drive shaft; Equipped with The rotating body is A rotating body, a protruding portion protruding radially outward from an outer periphery of the rotor main body, the rotor has a processing member at the protruding portion for colliding with the object to be processed to process the object, The treatment member constitutes all or part of the protruding portion, The rotor body and the processing member are separable, The rotor main body has a protruding portion that is protruding in a direction in which the rotor rotates, The processing member is fitted into the protrusion. The present invention relates to a processing device for toner.

[0011] Another aspect of the present disclosure is a toner processing device for processing a processing target including toner particles and an external additive, comprising: The toner processing device comprises: a processing chamber in which the object to be processed is accommodated; a drive shaft rotatably provided at the bottom of the processing chamber; A rotor supported by the drive shaft; Equipped with The rotating body is A rotating body, a protruding portion protruding radially outward from an outer periphery of the rotor main body, the rotor has a processing member at the protruding portion for colliding with the object to be processed to process the object, The treatment member constitutes all or part of the protruding portion, The rotor body and the processing member are separable, The rotor main body has a protruding portion that is protruding in at least one direction in a circumferential direction of the rotor, The treating member relates to a toner treating device which is fitted with the protrusion. Effect of the Invention

[0012] According to the present disclosure, it is possible to provide a toner processing device that achieves both cost-effectiveness and durability of the device and also provides stable toner quality. [Brief description of the drawings]

[0013] [Figure 1] Schematic diagram of a toner processing device [Diagram 2] Schematic diagram of the processing chamber [Diagram 3] FIG. 1 is a schematic diagram showing an example of an agitating blade as a stirring means. [Figure 4] FIG. 4 is a schematic diagram showing an example of a rotating body. [Diagram 5] A drawing (Type 2) showing the dimensions of the rotating body (Example 87) [Figure 6] A diagram showing the dimensions of the treatment component and its surroundings [Figure 7] A diagram showing the dimensions of the rotating body (Example 1) [Figure 8] An explanatory diagram of each part of the rotating body and the processing member. [Figure 9] Schematic diagram for explaining the mechanism by which the effects of the present disclosure are expressed. [Figure 10] Schematic diagram of positioning and fixing of the processing member to the rotating body. [Figure 11] An explanatory diagram of the contact points between the rotating body and each part of the processing member. [Figure 12] An explanatory diagram of the contact points, starting points, and end points of each part of the rotating body and the processing member. [Figure 13] An explanatory diagram of the contact points and penetration angles of each part of the rotating body and the processing member. [Figure 14] An explanatory diagram of the penetration angle of the processing member into the rotor body. [Figure 15] An explanatory diagram of the contact points between the rotating body and each part of the processing member. [Figure 16-1] Outline diagram of the rotor body and processing member used in the embodiment [Figure 16-2] Outline diagram of the rotor body and processing member used in the embodiment [Figure 16-3] Outline diagram of the rotor body and processing member used in the embodiment [Figure 17] Outline drawing of the rotor used in the embodiment [Figure 18] FIG. 1 is a diagram showing the shape of the processing surface of the protruding portion of a rotating body. [Figure 19]FIG. 1 is a diagram showing the shape of the processing surface of the protruding portion of a rotating body. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] In the present disclosure, the description of a numerical range such as "XX or more and YY or less" or "XX to YY" means a numerical range including the lower and upper limits, which are the endpoints, unless otherwise specified. When a numerical range is described in stages, the upper and lower limits of each numerical range can be arbitrarily combined.

[0015] Hereinafter, with reference to the drawings, specific examples of the embodiments for carrying out this disclosure will be described. However, the dimensions, materials, shapes, and relative positions of the components described in these embodiments should be appropriately changed depending on the configuration of the member to which the disclosure is applied and various conditions. In other words, it is not intended to limit the scope of this disclosure to the following embodiments.

[0016] One aspect of the present disclosure is a toner processing device for processing a processing target including toner particles and an external additive, The toner processing device comprises: a processing chamber in which the object to be processed is accommodated; a drive shaft rotatably provided at the bottom of the processing chamber; A rotor supported by the drive shaft; Equipped with The rotating body is A rotating body, a protruding portion protruding radially outward from an outer periphery of the rotor main body, the rotor has a processing member at the protruding portion for colliding with the object to be processed to process the object, The treatment member constitutes all or part of the protruding portion, The rotor body and the processing member are separable, The rotor main body has a protruding portion that is protruding in a direction in which the rotor rotates, The processing member is fitted into the protrusion. The present invention relates to a processing device for toner.

[0017] Another aspect of the present disclosure is a toner processing device for processing a processing target including toner particles and an external additive, comprising: The toner processing device comprises: a processing chamber in which the object to be processed is accommodated; a drive shaft rotatably provided at the bottom of the processing chamber; A rotor supported by the drive shaft; Equipped with The rotating body is A rotating body, a protruding portion protruding radially outward from an outer periphery of the rotor main body, the rotor has a processing member at the protruding portion for colliding with the object to be processed to process the object, The treatment member constitutes all or part of the protruding portion, The rotor body and the processing member are separable, The rotor main body has a protruding portion that is protruding in at least one direction in a circumferential direction of the rotor, The treating member relates to a toner treating device which is fitted with the protrusion.

[0018] With the above-mentioned configuration, in a method of separating and replacing only the part of the rotor that collides with the workpiece and its surrounding parts, which protrudes radially outward from the outer circumferential surface of the rotor, detachment and deformation of parts are suppressed even when replacing only the collision part and its surrounding parts. Therefore, it is possible to provide a toner processing device that is both economical and durable and has stable toner quality. The present inventors consider the reason why the above effect is exhibited as follows: In a conventional mixer having a rotor for performing external additive treatment, when the part of the rotor that processes the toner wears out, the state of the external additives in the toner changes, and the quality of the toner becomes unstable.

[0019] There is a method for replacing a part including a processing part of a rotating body, but the replacement part is usually fixed by a screw. This method has a problem that the replacement part is easily detached or deformed due to the load applied to the screw part.

[0020] Therefore, in a method of separating and replacing only the part of the rotor that collides with the workpiece and that protrudes radially outward from the outer circumferential surface of the rotor, and the surrounding area, the part to be replaced is designed to fit into the rotor body with a specific concave-convex structure. This prevents parts from coming off or deforming due to the action of the moment of inertia, even when replacing only the part that collides and the surrounding area, achieving both cost-effectiveness and durability of the device, and stabilizing the quality of the toner (Figure 9).

[0021] The impact 107 from the workpiece, the action of the resulting moment of inertia 106, and centrifugal force 108 will be described with reference to Fig. 9. When the rotor is rotated, the moment of inertia 106 is applied to the processing member due to the impact 107 received from the collision with the workpiece. Then, a force is applied radially inward to the rotor body from the part that collides with the workpiece, which protrudes radially outward from the outer circumferential surface of the rotor. At this time, the rotor body side to which the force is applied has a convex portion that is convex in the direction in which the rotor rotates, so that a radially inward force is applied to the convex portion with respect to the rotor body due to the moment of inertia 106. The processing member is further fitted into the convex portion, so a force acts on the convex portion so as to pinch it in the radial direction of the rotor.

[0022] As a result, not only is an opposite force resulting from the moment of inertia 106 applied to the centrifugal force 108, but also a force acting to pinch the protrusions of the fitting structure in the radial direction of the rotor is applied. These forces firmly fix the processing member to the rotor body in the radial direction of the rotor, thereby preventing the processing member from coming off the rotor body or shifting in position. At this time, since the convex portion faces the direction of rotation of the rotor, the force that the part of the fitting processing member that is located at the innermost radial direction of the rotor receives from the moment of inertia 106 is directed inward in the radial direction of the rotor. Therefore, it is considered that it is possible to further prevent the processing member from coming off the rotor body and the processing member from being displaced.

[0023] Specifically, the present invention relates to a toner processing device that processes a processing target material including toner particles and an external additive, The toner processing device comprises: a processing chamber in which the object to be processed is accommodated; a drive shaft rotatably provided at the bottom of the processing chamber; A rotor supported by the drive shaft; Equipped with The rotating body is A rotor body and a protruding portion protruding radially outward from an outer periphery of the rotor body, the rotor has a processing member at the protruding portion for colliding with the object to be processed to process the object, The treatment member constitutes all or part of the protruding portion, The rotor body and the processing member are separable, The rotor main body has a protruding portion that is protruding in a direction in which the rotor rotates, The processing member is fitted into the protrusion. The above effects can be obtained by the toner processing device (FIGS. 1, 2, 4, and 8).

[0024] [Toner processing equipment] As the toner processing device, for example, the above configuration can be applied to a known mixer such as an FM mixer (manufactured by Nippon Coke & Engineering Co., Ltd.) or a Super Mixer (manufactured by Kawata Corporation). 1 shows a schematic diagram of a toner processing device 1. The toner processing device 1 has a processing chamber (processing tank) 10 having a bottom and a cylindrical inner peripheral surface 10a, a drive shaft 11 rotatably provided at the bottom of the processing chamber, and a rotor 30 supported by the drive shaft 11 and rotatably provided around the drive shaft 11. The device also includes, as a lifting means, an agitator blade 20 supported by the drive shaft 11 and disposed below the rotor 30 for moving the material to flow upward from the bottom of the processing chamber, a drive motor 50, and a control unit 60.

[0025] The processing chamber 10 has a bottom and a cylindrical inner peripheral surface 10a. The processing chamber 10 is for accommodating objects to be processed, including toner particles and external additives. The drive shaft 11 is disposed approximately at the center of the bottom of the processing chamber 10, and is equipped with an agitating blade 20 and a rotor 30. The agitating blade 20 is supported by the drive shaft 11, and is rotatably provided at the bottom of the processing chamber 10 below the rotor 30 inside the processing chamber.

[0026] The rotor 30 is supported by a drive shaft 11 and is rotatably disposed above the agitator blade 20. The driving force of a drive motor 50 is transmitted to the drive shaft 11 via a drive belt 51. A control unit 60 includes a power switch, a drive ON switch, a drive stop switch, a rotation speed adjustment volume, a rotation speed display unit, a product temperature display unit, etc., and controls the operation of the toner processing device 1.

[0027] [Processing room] Fig. 2 shows a schematic diagram of the processing chamber 10. For convenience of explanation, Fig. 2 shows a state in which the inner peripheral surface (inner wall) 10a of the processing chamber 10 is partially cut away. The treatment chamber 10 is a cylindrical container with a substantially flat bottom, and is provided with a rotatable drive shaft 11 at approximately the center of the bottom for mounting the stirring blade 20 and the rotor 30. From the viewpoint of strength, the treatment chamber 10 is preferably made of a metal such as iron or SUS, and the inner surface is preferably made of a conductive material or is preferably treated to be conductive.

[0028] [Method of raising the ball] FIG. 3 shows a means for lifting up the workpiece, which is supported by a drive shaft and disposed below the rotor. 3A and 3B are schematic diagrams showing an example of an agitating blade 20 as a processing device. Fig. 3(a) shows a top view from above, and Fig. 3(b) shows a front view from the front. The agitating blade 20 is configured to rotate so that the material to be processed, including toner particles and external additives, can flow from the bottom of the processing chamber 10 upward and be thrown up.

[0029] The agitating blade 20 has a blade portion 21 that extends from the center of rotation toward the outside (diametrically outward (outer diameter direction), outer diameter side), and the tip of the blade portion 21 has a kick-up shape so as to lift up the material to be treated. The shape of the blade portion 21 can be appropriately designed depending on the size and operating conditions of the toner processing device 1, the loading amount of the material to be treated, and the specific gravity.

[0030] From the viewpoint of strength, the agitator blade 20 is preferably made of a metal such as iron or SUS, and may be plated or coated for wear resistance as necessary. The agitator blade 20 is fixed to a drive shaft 11 at the bottom of the processing chamber 10, and rotates clockwise when viewed from above (as shown in FIG. 3(a)). In the figure, the rotation direction of the drive shaft 11 is indicated by an arrow R. Due to the rotation of the agitator blade 20, the material to be processed rises in the processing chamber 10 while rotating in the same direction as the agitator blade 20, and then descends due to gravity. In this way, the material to be processed is mixed uniformly.

[0031] [Lathe] Fig. 4 is a schematic diagram showing an example of the rotor 30. Fig. 4(a) shows a top view of the rotor 30 installed in the processing chamber 10, and Fig. 4(b) shows a front view of the rotor 30. The rotor 30 has a rotor main body 31 and a protruding portion 104 protruding radially outward from an outer periphery 31a of the rotor main body 31. The rotor 30 has a processing member 32 at the protruding portion 104 that collides with the workpiece to process the workpiece.

[0032] The outer periphery 31a and the protruding portion 104 are defined as follows. When the rotor 30 is viewed from above in the axial direction of the drive shaft 11 (for example, as shown in FIG. 4(a)), concentric circles are assumed with the axial center of the drive shaft 11 as the center. The maximum concentric circle is drawn, the entire circumference of which fits within the rotor 30. At this time, the circumference of the maximum concentric circle is the outer periphery 31a of the rotor main body. Moreover, the portion protruding radially outward from this maximum concentric circle is the protruding portion 104.

[0033] The processing member 32 constitutes all or part of the protruding portion, and the rotor body 31 and the processing member 32 are configured to be separable. The rotor body 31 has a convex portion that is convex in the direction of rotation of the rotor 30, and the processing member 32 is fitted into the convex portion. The rotor 30 rotates in the direction of arrow R, and the protruding portion collides with the object to be processed to process the object. The number of protruding portions on the rotor 30 is not particularly limited, and is preferably 2 to 8, more preferably 2 to 4, and even more preferably 2. The protruding portions are preferably provided at equal intervals on the outer circumferential portion 31a of the rotor body 31.

[0034] Fig. 8 is a view focusing on the protruding portion 104 and the vicinity of the outer periphery of the rotor body 31 in the rotor 30. The processing member 32 may constitute a part of the protruding portion 104 as shown in Fig. 8(A), or may constitute the entire protruding portion 104 as shown in Fig. 8(B). The processing member 32 is fitted into the rotor body to form the protruding portion 104. The rotor body 31 has a protruding portion 103 that is protruding in the direction of rotation of the rotor. For example, in FIG. 8A, the rotor body 31 has the protruding portion 103 at a position (protruding portion 104) protruding radially from the outer circumferential portion 31a. Also, as shown in FIG. 8B, the rotor 30 may have the protruding portion 103 on the inside (rotating body 31 side) of the protruding portion 104. The processing member 32 has a shape that fits with the protruding portion 103.

[0035] In another embodiment of the present disclosure, the rotor main body 31 may have a convex portion that is convex in at least one direction in the circumferential direction of the rotor 30. The circumferential surface may have a protruding portion that is protruding in one direction and a protruding portion that is protruding in the other direction in the circumferential direction.

[0036] 1, the rotor 30 is located above the agitator blade 20 in the processing chamber 10, is supported by the same drive shaft 11 as the agitator blade 20, and rotates in the same direction (the direction of arrow R) as the agitator blade 20. The rotation of the agitator blade 20 and the rotor 30 causes the treated material, which is lifted up by the rotation of the agitator blade 20 and the rotor 30, to collide with the processing member 32 at the protruding portion 104, thereby adhering the external additive to the toner particles. The rotor body 31 and the processing member 32 are characterized by being separate and separable, and are used in an assembled and fixed state by fitting the convex portion of the rotor body 31 and the processing member 32 together. In this case, a fixing means such as a screw, a protrusion 109, or a bolt, a pin 110 may be further used (FIGS. 5, 6, 10).

[0037] If the rotor body 31 does not have a protrusion or has a protrusion in the opposite direction to the rotation direction of the rotor 30, the processing member 32 is likely to come off due to the impact it receives when colliding with the workpiece. Also, if the processing member 32 does not have a shape that fits with the protrusion, the effect of the moment of inertia cannot be obtained in the joining of the rotor body 31 and the processing member 32, so the processing member 32 is likely to come off.

[0038] Preferably, the convex portion is a protruding portion, and for example, the cross section of the convex portion has a top and bottom portions on both sides thereof. Examples of the convex portion include a portion having a mountain shape, a U shape, a right-angled U shape, a C shape, a W shape, or a V shape.

[0039] (Mating position) It is preferable that the processing member 32 is fitted into the rotor main body 31 in such a way that the protrusion is sandwiched in the radial direction (FIGS. 8 and 9). This is because when a moment of inertia 106 is applied to the processing member 32 due to the impact 107 received from a collision with the workpiece, a force is applied in the direction in which the processing member 32 sandwiches the protrusion 103, and the more impact is applied, the more the processing member 32 is fixed and the more difficult it becomes to detach. It is also preferable because it functions as a stopper to prevent the processing member 32 from detaching against the centrifugal force 108 applied radially outward from the rotor.

[0040] (Presence of support) It is preferable that the rotor body 31 has a support 105 that protrudes from the rotor body 31 side toward the protruding portion 104 side and supports the processing member 32 from the upstream side in the direction in which the rotor 30 rotates (FIG. 8(A)). That is, it is preferable that the rotor body 31 has a support 105 that protrudes from the rotor body 31 side toward the protruding portion 104 side and supports the processing member 32 from the starting point side of the convexity of the convexity 103. As a result, since the support 105 protrudes toward the protruding portion, it supports the processing member 32 against the force of the impact 107 applied to the processing member 32 in the normal direction to the impact surface of the processing member 32. Therefore, the load due to the impact 107 is also borne by the rotor main body 31 side, and the load on the processing member 32 is dispersed, so that detachment and deformation of the processing member 32 can be further suppressed.

[0041] (Contribution of the support to the fitting structure) It is more preferable that the support 105 has a protrusion 103 (FIG. 8(A)). The support 105 distributes the load by bearing the impact applied to the processing member 32 on the rotating body main body 31 side, and this configuration allows the support 105 and the processing member 32 to fit together. Therefore, misalignment is less likely to occur at the joint surface of the support 105 with the processing member 32, and a more sufficient contact area is obtained, so that the effect of the support 105 in distributing the load can be maximized.

[0042] (Inclination of the support and protruding parts) It is preferable that the surface of the support 105 facing the direction of rotation of the rotor 30 has a surface parallel to the surface of the processing member 32 facing the direction of rotation of the rotor 30. In other words, it is preferable that the surface of the support 105 facing the convex direction of the convex portion 103 has a surface parallel to the surface of the processing member 32 facing the convex direction of the convex portion 103 (FIG. 6). In other words, at least a part of the surface of the protruding portion 104 where the processing member 32 and the rotor main body 31 fit together is parallel to the surface of the processing member 32 that collides with the workpiece. In particular, it is more preferable that the support 105 has the above-mentioned parallel surface in a region of the support 105 farther away from the outer periphery 31a of the rotor main body 31 (a region of the support 105 including the radial tip of the rotor 30).

[0043] With the above-mentioned configuration, the support 105 receives the impact caused by the collision of the object to be treated with the treating member 32 in the normal direction, so that the effect of the support 105 is enhanced. In particular, it is preferable that such a surface exists in an area farther away from the outer periphery 31a of the rotor main body 31. When the peripheral speed of the protruding portion 104 increases, the impact caused by the collision with the workpiece increases. Therefore, when the inclination of the surface of the support 105 in the area farther away from the outer periphery 31a of the rotor main body 31 is parallel to the surface of the processing member 32 facing the direction in which the rotor 30 rotates, the effect of the support 105 increases.

[0044] (High hardness and surface coating) The processing member 32 preferably has a substrate and a coating layer on the surface of the substrate. The HRC hardness of the substrate of the processing member 32 is preferably higher than that of the rotor body 31. Furthermore, the HRC hardness of the coating layer is preferably higher than that of the substrate. This is because the presence of the high-hardness material on the outermost surface of the processing portion improves the wear resistance of the processing portion.

[0045] Specifically, it is preferable to carry out surface treatments such as depolishing, coating or plating with hard metals or ceramics, sintering of ceramics or cemented carbide such as cermet, thermal spraying or deposition, build-up welding, carburizing or nitriding, ion plating, blasting, etc.

[0046] The HRC hardness (Rockwell hardness: depth of permanent indentation from a reference surface) of the rotor body 31 is preferably 20 or more, and more preferably 25 or more. There is no particular upper limit to the HRC hardness of the rotor body 31, but it is preferably 40 or less, and more preferably 35 or less. The HRC hardness (Rockwell hardness) of the processing member 32 is preferably 40 or more, more preferably 50 or more, and even more preferably 55 or more. There is no particular upper limit to the HRC hardness of the processing member 32, but it is preferably 70 or less, and more preferably 65 or less.

[0047] The difference in HRC hardness (Rockwell hardness) between the rotor body 31 and the treatment member 32 is preferably 40 or less, and more preferably 35 or less. There is no particular lower limit to the hardness difference, but it is preferably 0 or more, more preferably 10 or more, even more preferably 20 or more, and even more preferably 25 or more.

[0048] Within the above range, the rotor body 31 and the processing member 32 have sufficient hardness and therefore excellent wear resistance, and the occurrence of gaps and deformation due to wear of the lower HRC hardness caused by stress due to friction at the mating portion between the rotor body and the processing member is suppressed. The HRC hardness is measured in accordance with JIS Z 2245 Rockwell hardness test.

[0049] The processing member 32 preferably has a portion that fits with the rotor body 31 at a position not included in the protruding portion 104 (that is, toward the center of the rotor body 31 from the outer periphery 31a of the rotor). In addition, at a position not included in the protruding portion 104, the rotating body main body 31 and the processing member 32 are fitted together, and the processing member 32 enters from the outer circumferential portion 31a of the rotating body toward the center of the rotating body main body 31. The contact point between the outer circumferential portion 31a of the rotating body at the end of the rotating direction side (the convex direction side of the convex portion) of the rotating body and the processing member 32 is defined as contact point A (116). In this case, it is preferable that contact point A (116) is the same as contact point 124 with the outer circumferential portion 31a of the rotating body at the end of the protruding portion 104 on the rotating direction side of the rotating body, or is located on the rotating direction side of the rotating body (FIG. 15).

[0050] This makes it difficult for a gap to occur at the boundary between the side of the protruding portion 104 in the direction in which the rotor rotates and the outer circumferential portion 31a of the rotor, so that the object to be treated is difficult to enter the gap. Therefore, it is easier to prevent the processing member 32 from shifting position or coming off during use (FIG. 15).

[0051] The angle of penetration of the processing member 32 from the contact point A into the outer circumferential portion 31a of the rotor is defined as a penetration angle α. On the other hand, in the portion where the rotor main body 31 and the processing member 32 are engaged at a position not included in the protruding portion 104 and the processing member 32 enters from the outer periphery 31a of the rotor toward the center of the rotor main body 31, the contact point between the outer periphery 31a of the rotor and the processing member 32 at the end opposite to the direction of rotation of the rotor (the convex direction of the convex portion) is called contact point B (117). The penetration angle of the processing member 32 from contact point B (117) into the outer periphery 31a of the rotor is called penetration angle β (Figure 13).

[0052] Specifically, the penetration angle α is as follows. The tangent line of the contact point A to the outer circumferential portion 31a of the rotor is called tangent line X (119). A normal line Y (122) to the tangent line X (119) is drawn from the contact point A. The angle between the normal line Y and the line segment Z (corresponding to 121 in FIG. 13(A)) formed by the processing member 32 penetrating into the outer circumferential portion 31a at the contact point A (116). The penetration angle α is defined as the angle between the normal line Y and the line segment Z, which is 0° with respect to the normal line Y, a positive value when the line segment Z is located closer to the starting point of the convex portion 103 than the normal line Y, and a negative value when the line segment Z is located closer to the convex direction of the convex portion 103 than the normal line Y. (FIGS. 13(A), (C), and 14)

[0053] Specifically, the penetration angle β is as follows. A line segment (line segment P) is drawn connecting the tangent points between the circumferential end of the protruding portion 104 of the rotor and the outer circumferential portion 31a of the rotor. At the tangent point B, a straight line Q is drawn perpendicular to the line segment P (in FIG. 13(D) , the line C (120) described later and the line Q are the same). The angle between the line segment R formed by the processing member 32 penetrating the outer circumferential portion 31a at the tangent point B (117) and the line Q is defined as the penetration angle β. Note that the penetration angle β is defined as 0° when the line Q and the line segment R coincide with each other, as a positive value when the line segment R is closer to the starting point of the convex portion 103 than the line Q, and as a negative value when the line segment R is closer to the convex direction of the convex portion 103 than the line Q.

[0054] Moreover, angle γ is defined as follows (FIG. 13(B)). If the line connecting the center of drive shaft 11 of the rotor and center of gravity 118 of the protruding part is defined as line C (120), then a line (line 121) parallel to line C is drawn radially inward from tangent point A. In this case, the angle between line 121 and normal line Y (122) is defined as angle γ.

[0055] In this case, the processing member preferably has a configuration that satisfies any one of the following three conditions. (1) 0≦α<β (2) α<0<β (3)0≧α≧γ, β=-60°~+60° When (1) or (2) is satisfied, the centrifugal force acting on the processing member 32 acts in a direction that eliminates the gap at the joint surface of the fitting part with the rotor body, so that the object to be processed does not enter the gap. In addition, since a force is applied in the direction in which the processing member 32 is fixed by the rotating body 31, it is easier to prevent the processing member 32 from shifting or coming off during use.

[0056] When (3) is satisfied, it is assumed that the processing member 32 is fitted into the rotor body 31 in a manner that the protrusion 103 is sandwiched in the radial direction. In this case, even if α≧β, if 0≧α≧γ is satisfied, even if the workpiece enters the gap of the fitting portion between the processing member 32 and the rotor body 31 from the contact point A, the entered workpiece applies a force to the rotor body 31 and the processing member 32 in the circumferential direction of the rotor. Therefore, it is desirable because it increases the force fixing the processing member 32 and the rotor body. It is more desirable if the workpiece contains toner particles or resin particles such as toner, because it acts like an adhesive on the gap of the fitting portion between the processing member 32 and the rotor body 31.

[0057] The angle α is preferably within a range from −18° to +10°, and more preferably within a range from −16° to +5°. β is preferably from −35° to +35°, and more preferably from −20° to +20°. γ is preferably from −20° to −10°, and more preferably from −17° to −13°.

[0058] (The positional relationship between the start point and end point of the convex part in the circumferential direction) It is preferable that the starting point 113 of the convex portion 103 in the circumferential direction of the rotor 30 (preferably the starting point of the convex portion toward the center of the rotor) satisfies the following relationship: Two contact points are provided between the protruding portion 104 and the outer circumferential portion 31a of the rotor. Of the two contact points, the contact point on the side in the direction of rotation (i.e. the side in the convex direction of the convex portion 103) is referred to as contact point 111 in FIG. 11. Moreover, of the two contact points, the contact point on the opposite side in the direction of rotation (i.e. the side on the convex starting point side of the convex portion 103) is referred to as contact point 112 in FIG. 11. Furthermore, a straight line F is drawn connecting the midpoints of the two contact points toward the center of drive shaft 11 of the rotating body. A straight line E is drawn parallel to line F through contact point 112. It is preferable that starting point 113 of the convex portion be on line E or on the line F side of line E. Also, a straight line G is drawn through the center of gravity 115 of the processing member 32 and parallel to the straight line F. At this time, it is more preferable that the starting point 113 of the convex portion is located between the straight lines E and G. By satisfying the above, the protrusion 103 is less likely to be deformed by the impact received when the processing member 32 collides with the workpiece, and the life of the part is extended (FIG. 11).

[0059] It is preferable that the end point 114 of the convex portion 103 in the circumferential direction of the rotor 30 (preferably the end point of the convex portion toward the center of the rotor) satisfies the following relationship: Draw a straight line H that passes through the tangent point 111 and is parallel to the straight line F. It is preferable that the end point 114 is on the straight line G side as viewed from the straight line H. This is because the moment of inertia caused by the impact received when the processing member 32 collides with the workpiece is more likely to act there. (FIG. 11)

[0060] The length from a starting point 113 of the convex portion 103 in the circumferential direction of the rotor 30 (preferably the starting point of the convex portion toward the center of the rotor) to an end point 114 of the convex portion 103 in the circumferential direction of the rotor 30 (preferably the end point of the convex portion toward the center of the rotor) is defined as X. The length between two contact points of the protruding portion 104 with the outer circumferential portion 31a of the rotor is defined as Y. When Y is taken as 100, the length X (that is, the convex length of the convex portion) is preferably about 5 to 90, more preferably about 8 to 75, and even more preferably about 10 to 60.

[0061] (Definition of the starting point) The starting point 113 of the protrusion in the circumferential direction of the rotor 30 is the end opposite the direction of rotation of the rotor (the starting point side of the protrusion). If there are multiple starting points of the protrusion, it is the end closest to the direction of rotation of the rotor. If there are multiple protrusions, it is the end closest to the direction of rotation of the rotor (Fig. 11, Fig. 12).

[0062] (Define the end point) The end point 114 of the protrusion in the circumferential direction of the rotor 30 is the end on the side in the direction of rotation of the rotor (the side in the protruding direction of the protrusion). If there are multiple protrusions, the end point 114 is the end closest to the direction of rotation of the rotor (FIGS. 11 and 12).

[0063] The surface of the protruding portion 104 that collides with the workpiece on the side in the direction of rotation of the rotor 30 (the side in the convex direction of the convex portion) may be located downstream in the direction of rotation of the rotor 30 in an area away from the rotor body than in an area closer to the rotor body than the area, or vice versa.

[0064] The shape of the surface of the protruding portion 104 that collides with the workpiece on the side in the direction of rotation of the rotor 30 (the side in the convex direction of the convex portion) is not particularly limited. For example, it may be rectangular or paddle-shaped. It is preferable that it has a U-shape, a right-angled U-shape, a C-shape, or a V-shape. For example, as shown in FIG. 18, a shape in which the ends of two parallel sides of a rectangle are tapered and the tip of the tapered shape is provided with a radius is preferable. Also, it is preferable that it is rectangular as shown in FIG. 19. The collision surface may be provided with a radius, but is preferably flat.

[0065] It is preferable that the center of gravity of the processing member 32 is located in the direction of rotation of the rotor (on the convex side of the convex portion) from the center of gravity of the protruding portion 104. With the above-mentioned configuration, the moment of inertia due to the impact that the processing member 32 receives when colliding with the workpiece is more likely to act.

[0066] (Configuration of the rotating body) As shown in FIG. 7, the rotating body 31 may be separable into two parts. For example, one part may be a part A having a convex part 103 and forming a protruding part 104, and the other part may be a part B not having a convex part 103. In this case, it is preferable that the part A having the convex part is based on a shape obtained by cutting the rotating body 31 along a plane perpendicular to the drive shaft 11. For example, as shown in FIG. 7, the rotating body 31 may be separable into a supporting part B of the rotating body supported by the drive shaft 11 and a part A forming a protruding part 104 of the rotating body that can be fixed to the supporting part B (FIG. 7). The numbers between the arrows in FIG. 5 to FIG. 7 indicate the relative dimensions of each part.

[0067] From the viewpoint of wear resistance, if the HRC hardness of the processing part that receives strong impact from collision with the workpiece is set to be high, the HRC hardness of the rotor body must also be high enough, otherwise deformation and detachment will occur due to wear between metals. On the other hand, if the rotor body can be separated into two parts as shown in Figure 7, it can be designed to have the following hardness relationship, for example. HRC hardness of treated material > HRC hardness of part A > HRC hardness of supporting part B By achieving the above relationship, the cost of the support part B, which does not have the largest volume of protrusions, can be reduced. Furthermore, fewer parts need to be replaced when the protrusions wear or deform, reducing the cost and the burden of replacement work. In addition, it is preferable that the rotating body main bodies that can be separated have projections and recesses so that they can be fitted together. This is because it is possible to prevent the rotating body main bodies from detaching from each other or deforming.

[0068] (Material and HRC hardness) The steel material used for the rotor body 31 and the processing member 32 is not particularly limited, and known materials can be used. For example, stainless steel, chromium molybdenum steel, carbon tool steel, alloy tool steel, steel for plastic molds, high-speed tool steel, etc. may be used. From the viewpoint of wear resistance, the base material used for the processing member 32 is preferably a steel material with an HRC hardness of 40 or more, and more preferably carbon tool steel, alloy tool steel, steel for plastic molds, and high-speed tool steel with an HRC hardness of 40 or more. Plastic mold steel and high-speed tool steel are even more preferable. This is desirable because the base material is not only less likely to be dented by the impact of collision with the workpiece due to its hardness, but is also tough and less likely to chip. It is.

[0069] (coating) It is preferable to use a material having a higher hardness than the substrate for the coating layer on the surface of the substrate of the processing member 32. Examples include ceramic coating, ceramic chip lining, ceramic spraying, dichroic plating, diamond-like carbon coating, fluorine composite electroless nickel plating, PEEK coating, cemented carbide build-up, cemented carbide spraying, and the like.

[0070] In addition to coating, the coating surface can be subjected to a shot peening process as a mechanical surface treatment after coating to eliminate microcracks on the coating surface and further improve the wear resistance.

[0071] Shot peening is a process in which particles of steel or the like are blasted onto the surface to be treated, for example by compressed air or centrifugal force, and can eliminate microcracks in the surface treatment. In the present invention, shot peening is preferably performed by blasting ceramic particles.

[0072] It is known that the microcracks generated on the surface tend to decrease due to plastic deformation when the injection pressure is high and the injection time is long. To further improve the surface hardness and wear resistance, it is preferable to perform quenching before shot peening to harden the plating layer and improve adhesion.

[0073] [Fixing the processing member and the rotating body] After fitting the rotor main body 31 and the processing member 32, fixing means such as screws, protrusions 109, bolts, pins 110, etc. may be used for further fixing or positioning (FIG. 10). In that case, it is preferable to fix the processing member 32 in a region not included in the protruding portion 104 in a direction parallel to the drive shaft 11 using uneven portions, pins, bolts, screws, etc. This is because the processing member 32 can be prevented from coming off due to collision with the processing member, since the processing object also moves in a direction parallel to the drive shaft 11 in the processing chamber 10.

[0074] Also, the processing member 32 may be fixed by a fixing means from the inside in the radial direction of the rotor 30 to the outside in the radial direction of the rotor in a direction perpendicular to the drive shaft 11. This is because the processing member can be prevented from coming off due to collision with the processing member, since the processing object also moves in a direction parallel to the drive shaft in the processing chamber. Furthermore, by providing a fixing means from the inside in the radial direction of the rotor 30 to the outside in the radial direction of the rotor, it is possible to prevent the fixing means from coming off or being deformed by the centrifugal force acting on the fixing means (FIG. 10).

[0075] [Circumferential speed of rotating body] The peripheral speed of the radially outermost end of the protruding portion 104 of the rotor 30 is preferably 20 m / s or more, more preferably 30 m / s or more. There is no particular upper limit, but it is preferably 60 m / s or less, more preferably 50 m / s or less. When it is in the above range, the moment of inertia acting on the processing member 32 is sufficiently large, so that the processing member 32 is less likely to come off from the rotor main body 31.

[0076] (Toner manufacturing method) It is preferable to carry out the external additive treatment of the toner using the above-mentioned toner treatment device. That is, the method for producing toner particles containing a binder resin and a toner containing an external additive preferably includes the following steps. (i) a step of producing toner particles containing a binder resin; and (ii) using the toner processing device, the toner particles produced in step (i) A process for adding external additives The toner particles have a particle size of approximately 10 μm or less, and are mainly composed of resin particles containing wax, etc. The size of the additives externally added to the toner is smaller than the particle size of the toner, regardless of the hardness. Therefore, the moment of inertia caused by the impact of the processing member 32 colliding with the workpiece is likely to act.

[0077] The time for the external addition treatment is not particularly limited, but is preferably 3 to 30 minutes, and more preferably 5 to 20 minutes. The temperature during the external addition treatment is not particularly limited, but is preferably 20° C. to 35° C., and more preferably 25° C. to 33° C. The rotation speed of the rotor of the toner treatment device during the external addition is not particularly limited and may be appropriately changed depending on the size of the device used, but is preferably about 200 to 3000 rpm, and more preferably about 300 to 2000 rpm.

[0078] A heating step may be performed during or after the external addition treatment to heat the toner. The temperature of the heating step is T R(℃), the glass transition temperature of the toner particles is Tg (℃), and the temperature of the heating process T R Tg-10(℃)≦T R It is preferable that Tg-5(℃)≦T R It is more preferable that the above condition is satisfied. ≦Tg+5(° C.). This makes it easier to control the dispersion state and adhesion state of the external additive to the toner particles.

[0079] The time for the heating step is not particularly limited, but is preferably 2 to 30 minutes, and more preferably 3 to 10 minutes. From the viewpoint of storage stability, the glass transition temperature Tg of the toner particles is preferably 40° C. to 70° C., and more preferably 50° C. to 65° C. The apparatus used in the heating step is not particularly limited, and the above-mentioned toner treatment apparatus can be used. A jacket that can change the temperature of the treatment chamber 10 and allow water to pass through may be used.

[0080] (Additives in the external addition process) When preparing a toner by adding an external additive to toner particles using a toner processing device, various known inorganic and organic additives can be used for the purpose of imparting various properties. From the viewpoint of durability when added to a toner, the particle diameter of the external additive used is preferably 3 / 10 or less of the weight average particle diameter of the toner particles. The particle diameter of this additive means the average particle diameter determined by observing the surface of the toner particles using a scanning electron microscope.

[0081] In particular, the external additive is preferably at least one selected from the group consisting of inorganic fine particles such as silica, titanium oxide, and alumina, inorganic-organic hybrid particles, and organosilicon polymer particles. Since the elasticity of the external additive is small, the external additive is generated when the processing member 32 and the external additive collide, but is not easily lost, and the moment of inertia applied to the processing member is also large.

[0082] The number average particle diameter of the primary particles of the external additive is preferably 6 nm to 500 nm, and more preferably 6 nm to 350 nm. Within the above range, the external additive is unlikely to be liberated from the toner particles, so that the toner can maintain stable quality even when used for a long period of time.

[0083] These additives may be hydrophobized. As a method of hydrophobization, various coupling agents such as silane coupling agents or titanium coupling agents can be used, but it is preferable to increase the hydrophobicity with silicone oil. This is because it can suppress the moisture adsorption of inorganic fine powder under high humidity conditions, and furthermore, it can suppress the contamination of regulating members, charging members, etc., so that high-quality images can be obtained.

[0084] The amount of these external additives added is preferably 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 0.4 parts by mass or more and 8 parts by mass or less, relative to 100 parts by mass of the toner particles. These additives may be used alone or in combination.

[0085] This is desirable because the toner has sufficient fluidity and chargeability, and can maintain stable performance over a long period of use. In the toner external addition process, it is desirable that the adhesion state and coverage rate of additives such as inorganic fine particles on the toner particle surface are stable over a long period of use. It is desirable that the adhesion index of the external additive is 4.5 or less.

[0086] <Method of measuring adhesion index and coverage rate of external additives> The method of indexing the adhesion state of the external additive is to evaluate the amount of migration of the external additive when the toner is brought into contact with the substrate. As the material of the surface layer of the substrate, a substrate using polycarbonate resin as the surface layer material is used as a substrate simulating the surface layer of a photoreceptor. Specifically, first, bisphenol Z type polycarbonate resin (product name: Iupilon Z-400, Mitsubishi Engineering Plastics Corporation, viscosity average molecular weight (Mv): 40000) is dissolved in toluene to a concentration of 10 mass % to prepare a coating liquid. This coating liquid is applied to an aluminum sheet with a thickness of 50 μm using a No. 50 Mayer bar to form a coating film. This coating film is then dried at 100° C. for 10 minutes to produce a sheet having a polycarbonate resin layer (film thickness 10 μm) on the aluminum sheet. This sheet is held by a substrate holder. The substrate is a square with each side measuring 3 mm. The measurement process will be explained below by dividing it into a process of placing the toner on the substrate, a process of removing the toner from the substrate, and a process of quantifying the amount of the external additive applied to the substrate.

[0087] The process of placing toner on the substrate The toner is contained in a porous flexible material (hereinafter referred to as the "toner holder"), and the toner holder is brought into contact with the substrate. The method of impregnating the toner holder with toner involves repeating the process of immersing the toner holder in a container containing sufficient toner and then removing it five times, and visually confirming that the surface of the toner holder is covered with toner and cannot be seen. A sponge (product name: White Wiper) manufactured by Marusan Sangyo Co., Ltd. is used as the toner holder. The toner-impregnated toner holder is fixed to the tip of a load meter fixed to a stage that moves in a direction perpendicular to the contact surface of the substrate, so that the toner-impregnated toner holder and the substrate can come into contact with each other while measuring the load. The toner-impregnated toner holder and the substrate are brought into contact with each other by moving the stage and pressing the toner-impregnated toner holder against the substrate until the load meter indicates 10 N, and then separating the toner holder from the substrate. This process is repeated five times.

[0088] -Removing toner from the substrate After the toner holder impregnated with toner is brought into contact with the substrate, an elastomer suction port with an inner diameter of about 5 mm connected to the tip of a vacuum cleaner nozzle is brought close to the substrate perpendicular to the toner placement surface, and the toner adhering to the substrate is removed. At this time, the amount of toner remaining is visually confirmed while removing the toner. The distance between the end of the suction port and the substrate is 1 mm, the suction time is 3 seconds, and the suction pressure is 6 kPa.

[0089] A process to quantify the amount of external additives applied to the substrate To quantify the amount and shape of the external additives remaining on the substrate after the toner has been removed, observation and image measurement are performed using a scanning electron microscope. First, platinum is sputtered onto the substrate after the toner has been removed at a current of 20 mA for 60 seconds to prepare a sample for observation. In the observation with a scanning electron microscope, the observation magnification at which the external additive can be observed is arbitrarily selected. As the scanning electron microscope, a Hitachi ultra-high resolution field emission scanning electron microscope (product name: S-4800, Hitachi High-Technologies Corporation) is used, and the observation is performed using the backscattered electron image of S-4800 (product name). The observation magnification is 50,000 times, the acceleration voltage is 10 kV, and the working distance is 3 mm.

[0090] In the image obtained by observation, the additives are shown with high brightness and the substrate with low brightness, so the amount of additives in the field of view can be quantified by binarization. The binarization conditions are appropriately selected depending on the observation device and sputtering conditions. The image analysis software Image J (available from https: / / imagej.nih.gov / ij / ) is used for binarization. The area ratio of the external additive in the observation field is calculated by integrating only the area of ​​the external additive using Image J and dividing by the area of ​​the entire observation field. The above measurement is carried out for 100 binarized images, and the average value is the area ratio [A] (unit: area%) of the external additive on the substrate.

[0091] Next, the coverage [B] (unit: area %) of the external additive on the toner particles is calculated. The coverage of the external additive is measured by observation with a scanning electron microscope and image measurement. In the observation with a scanning electron microscope, the observation magnification for observing the external additive is the same as the magnification for observing the external additive on the substrate. As the scanning electron microscope, the above-mentioned Hitachi ultra-high resolution field emission scanning electron microscope S-4800 (product name) is used. In addition, in the measurement of the area ratio A and the coverage ratio B, when the toner contains fine particles other than the external additive, EDS analysis is performed on each particle of the external additive in the toner observation, and it is judged whether or not the analyzed particle is an external additive based on the presence or absence of an element peak. Specifically, the same operation as for the number average particle size of the primary particles of the external additive is performed. The image capturing conditions are as follows.

[0092] (1) Sample preparation Apply a thin layer of conductive paste to a sample stage (aluminum sample stage 15 mm x 6 mm) and spray toner onto it. Then use air to remove excess toner from the sample stage and dry thoroughly. Set the sample stage in the sample holder and adjust the sample stage height to 36 mm using the sample height gauge.

[0093] (2) S-4800 observation condition setting The coverage rate [B] of the external additive is calculated using the image obtained by backscattered electron image observation with the S-4800. Backscattered electron images have less charge-up compared to secondary electron images, so the coverage rate [B] of the external additive can be measured with high accuracy. Pour liquid nitrogen into the anti-contamination trap attached to the S-4800 housing until it overflows, and leave it for 30 minutes. Start the S-4800's "PC-SEM" and perform flushing (cleaning the FE chip, which is the electron source). Click the accelerating voltage display area on the control panel on the screen, and press the [Flushing] button to open the flushing execution dialog. Check that the flushing intensity is 2, and then execute. Check that the emission current due to flushing is 20 μA to 40 μA. Insert the sample holder into the sample chamber of the S-4800 housing. Press [Origin] on the control panel to move the sample holder to the observation position. Click the accelerating voltage display to open the HV setting dialog, and set the accelerating voltage to [0.8kV] and the emission current to [20μA]. In the [Basic] tab of the operation panel, set the signal selection to [SE], select [Upper (U)] and [+BSE] for the SE detector, and select [LA100] in the selection box to the right of [+BSE] to set the mode to observation using backscattered electron images. Similarly, in the [Basic] tab of the operation panel, set the probe current in the electron optical system condition block to [Normal], the focus mode to [UHR], and the WD to [3.0 mm]. Press the [ON] button in the acceleration voltage display section of the control panel to apply the acceleration voltage.

[0094] (3) Focus adjustment Drag within the magnification display area of ​​the control panel to set the magnification to 5000 (5k). Rotate the focus knob [COARSE] on the operation panel until the entire field of view is in focus to some extent, then adjust the aperture alignment. Click [Align] on the control panel to display the alignment dialog and select [Beam]. Rotate the STIGMA / ALIGNMENT knobs (X, Y) on the operation panel to move the displayed beam to the center of the concentric circles. Next, select [Aperture] and rotate the STIGMA / ALIGNMENT knobs (X, Y) one by one to stop the image movement or adjust it so that it moves as little as possible. Close the aperture dialog and use autofocus to adjust the focus. Repeat this operation two more times to adjust the focus. Next, for the target toner, align the midpoint of the maximum diameter with the center of the measurement screen, and drag within the magnification display area of ​​the control panel to set the magnification to 10,000 (10k). Rotate the focus knob [COARSE] on the operation panel, and once the image is in focus to a certain extent, adjust the aperture alignment. Click [Align] on the control panel to display the alignment dialog, and select [Beam]. Rotate the STIGMA / ALIGNMENT knobs (X,Y) on the operation panel to move the displayed beam to the center of the concentric circle. Next, select [Aperture] and turn the STIGMA / ALIGNMENT knobs (X,Y) one by one to stop the image movement or adjust it so that it moves as little as possible. Close the Aperture dialog and use autofocus to adjust the focus. After that, set the magnification to 50,000 (50k)x and adjust the focus using the focus knob and STIGMA / ALIGNMENT knob as above, then use autofocus to adjust the focus again. Repeat this operation to adjust the focus again. Here, if the inclination angle of the observation surface is large, the measurement accuracy of the coverage rate is likely to be low, so when adjusting the focus, select one that brings the entire observation surface into focus at the same time, and select one with as little surface inclination as possible for analysis.

[0095] (4) Image storage Adjust the brightness in ABC mode, take a photo with a size of 640 x 480 pixels, and save it. Use this image file to perform the following analysis. Take one photo for each toner, and obtain images of at least 100 toner particles.

[0096] The observed image is binarized using the image analysis software Image J (available from https: / / imagej.nih.gov / ij / ). After binarization, the external additives alone are extracted based on the particle size, circularity, and EDS analysis using [Analyze] - [Analyze Particles], and the coverage rate (unit: area %) of the external additives on the toner particles is calculated. The above measurement is performed on 100 binarized images, and the average value of the coverage rate of the external additive (unit: area %) is taken as the coverage rate of the additive [B]. The adhesion index of the external additive is calculated from the area rate of the external additive on the substrate [A] and the coverage rate of the external additive [B] using the following formula (I). Adhesion index = area ratio of external additive transferred to polycarbonate film [A] / coverage ratio of external additive on toner particle surface [B] × 100 (I)

[0097] <Method for measuring the coverage rate of external additives> The coverage rate of the external additive on the surface of the toner particles is determined by the value of the coverage rate [B] of the external additive on the toner particles in the above-mentioned method for measuring the adhesion index of the external additive (unit: area %).

[0098] [Binding resin] The binder resin is not particularly limited, and for example, the following polymers or resins can be used. Homopolymers of styrene and its substituted derivatives, such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, and styrene-acrylic acid ester copolymers. Styrene-based copolymers such as copolymers, styrene-methacrylate ester copolymers, styrene-α-methyl chloromethacrylate copolymers, styrene-acrylonitrile copolymers, styrene-vinyl methyl ether copolymers, styrene-vinyl ethyl ether copolymers, styrene-vinyl methyl ketone copolymers, and styrene-acrylonitrile-indene copolymers; polyvinyl chloride, phenolic resins, natural resin-modified phenolic resins, natural resin-modified maleic acid resins, acrylic resins, methacrylic resins, polyvinyl acetate, silicone resins, polyester resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumarone-indene resins, and petroleum-based resins can be used. In particular, styrene-based copolymers such as styrene-acrylic acid ester copolymers and styrene-methacrylic acid ester copolymers, and polyester resins are preferred.

[0099] [Polymerizable monomer] As the polymerizable monomer used in the styrene copolymer, a vinyl polymerizable monomer capable of radical polymerization can be used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.

[0100] Examples of monofunctional polymerizable monomers include styrene; styrene derivatives such as α-methylstyrene, β-methylstyrene, ο-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, and p-phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, and dibutyl phosphate. Examples of the polymerizable monomer include acrylic polymerizable monomers such as ethyl acrylate and 2-benzoyloxyethyl acrylate; methacrylic polymerizable monomers such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, and dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, and vinyl formate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether; and vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and vinyl isopropyl ketone.

[0101] Examples of polyfunctional polymerizable monomers include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis(4-(acryloxy-diethoxy)phenyl)propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, Examples of suitable vinyl acrylates include acrylate, polypropylene glycol dimethacrylate, 2,2'-bis(4-(methacryloxy-diethoxy)phenyl)propane, 2,2'-bis(4-(methacryloxy-polyethoxy)phenyl)propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, and divinyl ether.

[0102] The above-mentioned monofunctional polymerizable monomers may be used alone or in combination of two or more kinds, or the above-mentioned monofunctional polymerizable monomers may be used in combination with polyfunctional polymerizable monomers. As the polymerizable monomer other than styrene, styrene derivatives, acrylic polymerizable monomers such as n-butyl acrylate and 2-ethylhexyl acrylate, or methacrylic polymerizable monomers such as n-butyl methacrylate and 2-ethylhexyl methacrylate are preferred, because the binder resin obtained by polymerizing the polymerizable monomers has excellent strength and flexibility.

[0103] The polyester resin is preferably an amorphous polyester resin. The weight average molecular weight (Mw) of the polyester resin is preferably 6,000 to 100,000, more preferably 6,500 to 85,000, and further preferably 6,500 to 45,000. When the weight average molecular weight is 6,000 or more, the external additives on the toner surface are less likely to be embedded in the toner during continuous image output due to long-term use, and the deterioration of transferability is suppressed.When the weight average molecular weight is 100,000 or less, it is easier to obtain a toner with a small particle size and a uniform particle size distribution.

[0104] The amorphous polyester resin can be produced, for example, by a method utilizing a dehydration condensation reaction from a carboxylic acid component and an alcohol component, or by an ester exchange reaction. The catalyst may be a general acidic or alkaline catalyst used in an esterification reaction, such as zinc acetate or a titanium compound. The product may then be highly purified by a recrystallization method, a distillation method, or the like. A preferred production method is a dehydration condensation reaction from a carboxylic acid component and an alcohol component, because of the variety of raw materials and the ease of reaction.

[0105] The polyester resin preferably contains 43 mol % to 57 mol % of alcohol components and 43 mol % to 57 mol % of acid components out of all components. In producing the polyester resin, known alcohol components can be used, such as ethylene glycol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, a bisphenol derivative represented by the following formula (A), or a diol such as a diol represented by the following formula (B). [ka]

[0106] (In the formula, R represents an ethylene or propylene group, x and y each represent an integer of 1 or more, and the average value of x+y is 0 or more and 10 or less.) [ka]

[0107] Examples of divalent carboxylic acids include benzenedicarboxylic acids or their anhydrides, such as phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, diphenyl-P·P'-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, diphenylmethane-P·P'-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, and 1,2-diphenoxyethane-P·P'-dicarboxylic acid; alkyldicarboxylic acids or their anhydrides, such as succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, cyclohexanedicarboxylic acid, triethylenedicarboxylic acid, and malonic acid, and further, succinic acid or its anhydride substituted with an alkyl or alkenyl group having 6 to 18 carbon atoms; and unsaturated dicarboxylic acids or their anhydrides, such as fumaric acid, maleic acid, citraconic acid, and itaconic acid.

[0108] Particularly preferred alcohol components are the bisphenol derivatives represented by the formula (A) and ethylene glycol. Preferred acid components include dicarboxylic acids such as terephthalic acid or its anhydride, succinic acid, n-dodecenylsuccinic acid or its anhydride, fumaric acid, maleic acid, and maleic anhydride. Terephthalic acid and fumaric acid are particularly preferred.

[0109] The polyester resin may use a trivalent or higher polycarboxylic acid or polyol. Examples of trivalent or higher polycarboxylic acids include trimellitic acid, pyromellitic acid, cyclohexanetricarboxylic acids, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxylpropane, 1,3-dicarboxyl-2-methyl-methylenecarboxylpropane, tetra(methylenecarboxyl)methane, 1,2,7,8-octanetetracarboxylic acid, and anhydrides thereof.

[0110] Examples of trihydric or higher polyols include sorbitol, 1,2,3,6-hexanetetol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4-methanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene.

[0111] The trivalent or higher polycarboxylic acid is preferably 10.00 mol% or less based on the total acid monomer units. Similarly, the trivalent or higher polyol is preferably 10.00 mol% or less based on the total alcohol monomer units. This range is preferable in terms of pigment dispersibility because the insoluble matter due to crosslinking is small. In addition, the proportion of branched polyester resin is small, and the strength is excellent, so it is preferable in terms of durability.

[0112] The polyester resin is preferably an aromatic saturated polyester, because the toner has excellent electrostatic chargeability, durability, and fixability, and the physical properties of the toner and polyester are easily controlled. The aromatic π electrons have excellent chargeability due to their interaction. In addition, the toner is less likely to crosslink, which improves fixability.

[0113] The crystalline polyester resin can be obtained by reacting a polyvalent carboxylic acid having a valence of 2 or more with an alcohol having a valence of 2 or more. Among them, a polyester mainly composed of an aliphatic diol and an aliphatic dicarboxylic acid is preferable because it has a high degree of crystallinity. The crystalline polyester resin may be used alone or in combination with a plurality of types. A crystalline polyester resin and an amorphous polyester resin may be used in combination.

[0114] Crystalline polyester resin refers to a polyester resin that has an endothermic peak when heating and an exothermic peak when cooling in differential scanning calorimetry (DSC). D 3417-99.

[0115] Examples of alcohol monomers for obtaining such crystalline polyester resins include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, neopentyl glycol, 1,4-butadiene glycol, and the like.

[0116] In addition to the above components, dihydric alcohols such as polyoxyethylenated bisphenol A, polyoxypropylenated bisphenol A, 1,4-cyclohexanedimethanol, aromatic alcohols such as 1,3,5-trihydroxymethylbenzene, trihydric alcohols such as pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and the like may also be used.

[0117] Examples of carboxylic acid monomers for obtaining crystalline polyesters include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, isophthalic acid, terephthalic acid, n-dodecylsuccinic acid, n-dedecenylsuccinic acid, cyclohexanedicarboxylic acid, anhydrides or lower alkyl esters of these acids, and the like.

[0118] In addition to the above components, a polyvalent carboxylic acid having three or more valences may be used. Examples of trivalent or higher polyvalent carboxylic acid components include trimellitic acid, 2,5,7-naphthalene tricarboxylic acid, 1,2,4-naphthalene tricarboxylic acid, pyromellitic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, and derivatives such as their acid anhydrides or lower alkyl esters. These may be used alone or in combination of two or more.

[0119] Particularly preferred crystalline polyester resins include polyesters obtained by reacting 1,4-cyclohexanedimethanol with adipic acid, polyesters obtained by reacting tetramethylene glycol and ethylene glycol with adipic acid, polyesters obtained by reacting hexamethylene glycol with sebacic acid, polyesters obtained by reacting ethylene glycol with succinic acid, polyesters obtained by reacting ethylene glycol with sebacic acid, and polyesters obtained by reacting tetramethylene glycol with succinic acid. Examples of the crystalline polyester resin include polyesters obtained by reacting diethylene glycol with decanedicarboxylic acid, diethylene glycol, and decanedicarboxylic acid. It is more preferable that the crystalline polyester resin is a saturated polyester resin. This is because, compared to the case where the crystalline polyester resin has an unsaturated portion, a crosslinking reaction does not occur in the reaction with the peroxide-based polymerization initiator, and therefore, the crystalline polyester resin has an advantage in terms of solubility.

[0120] The crystalline polyester resin can be produced by a conventional polyester synthesis method, for example, by subjecting a dicarboxylic acid component and a dialcohol component to an esterification reaction or an ester exchange reaction, followed by a conventional polycondensation reaction under reduced pressure or by introducing nitrogen gas.

[0121] The melting point (DSC endothermic peak) of the crystalline polyester resin is preferably 50.0° C. or more and 90.0° C. or less. When it is in this range, the toner particles are less likely to aggregate, the storage stability and fixability of the toner particles can be maintained, and the solubility in the polymerizable monomer is increased when the toner particles are produced by a polymerization method. The melting point (DSC endothermic peak) of the crystalline polyester resin can be measured by differential scanning calorimetry (DSC). The melting point of the crystalline polyester resin can be adjusted by the type of alcohol monomer or carboxylic acid monomer used, the degree of polymerization, etc.

[0122] The weight average molecular weight (Mw) of the crystalline polyester resin is preferably from 5,000 to 35,000, and more preferably from 10,000 to 35,000. The crystalline polyester having the above weight average molecular weight (Mw) improves the dispersibility of the crystalline polyester resin in the obtained toner particles, and improves the durability stability.

[0123] When the weight average molecular weight (Mw) of the crystalline polyester resin is 5,000 or more, the density of the crystalline polyester is high and durability stability is improved, whereas when the weight average molecular weight (Mw) of the crystalline polyester resin is 35,000 or less, the crystalline polyester resin is melted quickly and the dispersion state becomes uniform, improving development stability. The weight average molecular weight (Mw) of the crystalline polyester can be adjusted by the types of alcohol monomers and carboxylic acid monomers used, the polymerization time, the polymerization temperature, and the like.

[0124] The acid value (AV) of the crystalline polyester resin is preferably 0.0 mgKOH / g or more and 20.0 mgKOH / g or less, more preferably 0.0 mgKOH / g or more and 10.0 mgKOH / g or less, and even more preferably 0.0 mgKOH / g or more and 5.0 mgKOH / g or less. By lowering the acid value, the adhesion between the toner and paper during image formation is improved. When toner particles are produced by polymerization, if the acid value (AV) of the crystalline polyester resin is 20.0 mgKOH / g or less, the toner particles tend not to aggregate with each other. In addition, the distribution state of the crystalline polyester resin in the toner is less likely to be uneven, improving the charging stability and durability stability.

[0125] <Molecular weight and molecular weight distribution of crystalline polyester resin, amorphous polyester resin, and styrene-acrylic resin> The molecular weight and molecular weight distribution of the sample are calculated in terms of polystyrene by gel permeation chromatography (GPC). When measuring the molecular weight of a resin having an acid group, the column elution rate also depends on the amount of acid group, so a sample is prepared in which the acid group has been capped in advance. Methyl esterification is preferable for capping, and a commercially available methyl esterification agent can be used. Specifically, a method of treatment with trimethylsilyldiazomethane can be mentioned.

[0126] The molecular weight is measured by GPC as follows. First, the measurement sample is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. The obtained solution is then filtered through a solvent-resistant membrane filter "Myshoridisc" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of components soluble in THF is 0.8 mass%. This sample solution is used to perform measurements under the following conditions. Equipment: HLC8120 GPC (detector: RI) (Tosoh Corporation) Column: Shodex KF-801, 802, 803, 804, 805, 806, 807 (Showa Denko) Eluent: tetrahydrofuran (THF) Flow rate: 1.0mL / min Oven temperature: 40.0℃ Sample injection volume: 0.10 mL In calculating the molecular weight of the measurement sample, a molecular weight calibration curve prepared using standard polystyrene resins (for example, trade names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500" manufactured by Tosoh Corporation) is used.

[0127] <Glass transition temperature of resin, toner particles, etc.> The glass transition temperature of a sample such as a resin is measured using a differential scanning calorimeter (DSC measuring device). The differential scanning calorimeter uses a differential scanning calorimeter analyzer "Q1000" (manufactured by TA Instruments) and performs measurements in accordance with ASTM D3418-82 as follows. Accurately weigh out 3 mg of the measurement sample. Place it in an aluminum pan, and use an empty aluminum pan as a control. After maintaining equilibrium at 20°C for 5 minutes, perform measurements at a heating rate of 10°C / min in the measurement range of 20 to 180°C. The glass transition temperature can be determined by the midpoint method.

[0128] <Structural analysis of resins such as binder resins> The structure of resins such as binder resins is determined using a nuclear magnetic resonance spectrometer ( 1 H-NMR, 13 This can be done using C-NMR and FT-IR spectroscopy. The instruments used are described below. Each resin sample may be collected by separating it from the toner and analyzed. (i) 1 H-NMR, 13 C-NMR JEOL FT-NMR JNM-EX400 (solvent used: deuterated chloroform) (ii) FT-IR spectrum Thermo Fisher Scientific Inc. AVATAR360FT-IR

[0129] <Measurement of the acid value of resins such as polyester resin and styrene-acrylic resin> The acid value is the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1 g of a sample. The acid value is measured in accordance with JIS K 0070-1992, and specifically, is measured according to the following procedure. Titration is performed using a 0.1 mol / L potassium hydroxide ethyl alcohol solution (Kishida Chemical Co., Ltd.). The factor of the potassium hydroxide ethyl alcohol solution can be determined using a potentiometric titrator (potentiometric titration measuring device AT-510, Kyoto Electronics Manufacturing Co., Ltd.). 100 mL of 0.100 mol / L hydrochloric acid is placed in a 250 mL tall beaker and titrated with the potassium hydroxide ethyl alcohol solution, and the factor is determined from the amount of the potassium hydroxide ethyl alcohol solution required for neutralization. The 0.100 mol / L hydrochloric acid used is prepared in accordance with JIS K 8001-1998.

[0130] The conditions for measuring the acid value are shown below. Titrator: Potentiometric titrator AT-510 (Kyoto Electronics Manufacturing Co., Ltd.) Electrode: Composite glass electrode double junction type (Kyoto Electronics Manufacturing Co., Ltd.) Control software for titrator: AT-WIN Titration analysis software: Tview

[0131] The titration parameters and control parameters during the titration are as follows: (Titration parameters) Titration mode: Blank titration Titration method: Total volume titration Maximum titer: 20mL Waiting time before titration: 30 seconds Titration direction: automatic (Control parameters) End point potential: 30dE End point potential: 50 dE / dmL End point detection judgment: Not set Control speed mode: Standard Gain: 1 Data collection potential: 4mV Data collection titration volume: 0.1mL

[0132] This test; Weigh out 0.100 g of the measurement sample into a 250 mL tall beaker, add 150 mL of a mixed solution of toluene / ethanol (3:1), and dissolve for 1 hour. Using the potentiometric titration apparatus, titrate with the potassium hydroxide ethyl alcohol solution. Blank test; The titration is carried out in the same manner as above, except that no sample is used (i.e., only the toluene / ethanol (3:1) mixed solution is used). The obtained result is substituted into the following formula to calculate the acid value. A = [(CB) × f × 5.61] / S (In the formula, A is the acid value (mgKOH / g), B is the amount of potassium hydroxide solution added for the blank test (mL), C is the amount of potassium hydroxide solution added for the main test (mL), f is the factor of the potassium hydroxide solution, and S is the mass of the sample (g).)

[0133] <Measurement of hydroxyl value of resins such as polyester resin and styrene-acrylic resin> The hydroxyl value is the number of milligrams of potassium hydroxide required to neutralize the acetic acid bonded to the hydroxyl group when 1 g of a sample is acetylated. The hydroxyl value is measured according to JIS K 0070-1992, and specifically, it is measured according to the following procedure. Put 25.0 g of special grade acetic anhydride into a 100 mL measuring flask, add pyridine to make the total volume 100 mL, and shake thoroughly to obtain the acetylation reagent. Store the obtained acetylation reagent in a brown bottle to avoid contact with moisture, carbon dioxide, etc. Titration is performed using 1.0 mol / L potassium hydroxide ethyl alcohol solution (Kishida Chemical Co., Ltd.). The factor of the potassium hydroxide ethyl alcohol solution is determined using a potentiometric titrator (Kyoto Electronics Co., Ltd. Potentiometric titration measuring device AT-510). Specifically, 100 mL of 1.00 mol / L hydrochloric acid is placed in a 250 mL tall beaker and titrated with potassium hydroxide ethyl alcohol solution, and the factor is determined from the amount of potassium hydroxide ethyl alcohol solution required for neutralization. 1.00 mol / L hydrochloric acid prepared in accordance with JIS K 8001-1998 is used.

[0134] The measurement conditions for measuring the hydroxyl value are shown below. Titrator: Potentiometric titrator AT-510 (Kyoto Electronics Manufacturing Co., Ltd.) Electrode: Composite glass electrode double junction type (Kyoto Electronics Manufacturing Co., Ltd.) Control software for titrator: AT-WIN Titration analysis software: Tview

[0135] The titration parameters and control parameters during the titration are as follows: (Titration parameters) Titration mode: Blank titration Titration method: Total volume titration Maximum titer: 80mL Waiting time before titration: 30 seconds Titration direction: automatic (Control parameters) End point potential: 30dE End point potential: 50 dE / dmL End point detection judgment: Not set Control speed mode: Standard Gain: 1 Data collection potential: 4mV Data collection titration volume: 0.5mL

[0136] <Actual exam> Weigh out 2.00 g of the sample to be measured into a 200 mL round-bottom flask, and add 5.00 mL of the acetylation reagent described above accurately using a volumetric pipette. If the sample is difficult to dissolve in the acetylation reagent, add a small amount of special grade toluene to dissolve it. Place a small funnel on the mouth of the flask and immerse the bottom 1 cm of the flask in a glycerin bath at 97°C. To prevent the temperature of the neck of the flask from rising due to the heat of the bath, it is preferable to cover the base of the neck of the flask with a piece of cardboard with a round hole. After 1 hour, remove the flask from the glycerin bath and allow it to cool. After allowing it to cool, add 1.00 mL of water through the funnel and shake to hydrolyze the acetic anhydride. To further complete the hydrolysis, heat the flask again in the glycerin bath for 10 minutes. After allowing it to cool, wash the funnel and the walls of the flask with 5.00 mL of ethyl alcohol. The obtained sample was transferred to a 250 mL tall beaker, and 100 mL of a mixture of toluene and ethanol (3:1) was added and dissolved for 1 hour. Using a potentiometric titrator, the sample was titrated with potassium hydroxide ethyl alcohol solution.

[0137] <Blank Test> The titration is carried out in the same manner as above, except that no sample is used (i.e., only a mixed solution of toluene and ethanol (3:1) is used). The obtained result is substituted into the following formula to calculate the hydroxyl value. A = [{(BC) × 28.05 × f} / S] + D where A is the hydroxyl value (mgKOH / g), B is the amount of potassium hydroxide ethyl alcohol solution added for the blank test (mL), C is the amount of potassium hydroxide ethyl alcohol solution added for the main test (mL), f is the factor of the potassium hydroxide ethyl alcohol solution, S is the mass of the sample (g), and D is the acid value of the sample (mgKOH / g).

[0138] [wax] The toner may contain a wax. The wax is not particularly limited, and any known wax may be used. For example, paraffin wax, polyolefin wax, microcrystalline wax It is possible to use known waxes, such as hydrocarbon waxes such as Fischer-Tropsch wax, petroleum waxes such as polymethylene wax, amide wax, petrolatum, and derivatives thereof, montan wax and derivatives thereof, natural waxes such as carnauba wax and candelilla wax, and derivatives thereof, hydrogenated castor oil and derivatives thereof, vegetable waxes, animal waxes, higher fatty acids, long-chain alcohols, ester waxes, ketone waxes, and derivatives thereof such as graft compounds and block compounds thereof. These may be used alone or in combination. Preferred is a hydrocarbon wax, from the viewpoints of blocking resistance, durability for multiple sheets, low-temperature fixability and offset resistance of the toner.

[0139] At least one of the waxes preferably has a melting point of 65° C. or more and 120° C. or less, more preferably 65° C. or more and 90° C. or less. Also, it is preferable that the wax is solid at room temperature, and in particular, a solid wax having a melting point of 65° C. or more and 90° C. or less is preferable from the viewpoints of blocking resistance, durability for multiple sheets, low-temperature fixing property, and offset resistance of the toner.

[0140] The wax content in the toner is preferably 3 parts by mass or more and 30 parts by mass or less per 100 parts by mass of the binder resin. If the wax content is more than the lower limit, the offset prevention effect is not reduced. If the wax content is less than the upper limit, the blocking prevention effect is not reduced, the offset prevention effect is easily obtained, and the toner can be prevented from fusing to the drum or the developing sleeve.

[0141] In addition, when it is necessary to extract the wax from the toner in order to obtain the above physical properties, the extraction method is not particularly limited, and any method can be used. For example, a predetermined amount of toner is subjected to Soxhlet extraction with toluene, and the solvent is removed from the obtained toluene-soluble matter, and then a chloroform-insoluble matter is obtained. Then, identification analysis is performed by an IR method or the like. Quantitative analysis is performed using a differential scanning calorimeter (DSC) or the like. Specifically, measurements are performed using a DSC-2920 manufactured by TA Instruments Japan. The glass transition point is the intersection of the line at the midpoint between the baseline before and after the specific heat change during measurement and the differential heat curve. The maximum endothermic peak temperature of the wax component is obtained from the obtained DSC curve during heating.

[0142] (Charge control agent) A known charge control agent can be used in the toner. The content of the charge control agent is preferably 0.01 parts by mass or more and 20 parts by mass or less, and more preferably 0.5 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the binder resin.

[0143] (Pigments) The toner may contain a colorant, such as a pigment or a dye. Pigments that can be used as cyan colorants include copper phthalocyanine compounds and their derivatives, anthraquinone compounds, and basic dye lake compounds. Specific examples include CI Pigment Blue 15, 15:1, 15:2, 15:3, and 15:4. Pigments for magenta colorants include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specific examples include CI Pigment Violet 19, CI Pigment Red 31, 32, 122, 150, 254, 264, and 269.

[0144] Pigments used for yellow colorants include condensed azo compounds and isoindolinone compounds. Compounds, anthraquinone compounds, azo metal complexes, methine compounds and allylamide compounds can be used. Specific examples include the following: CI Pigment Yellow 74, 93, 120, 139, 151, 155, 180 and 185. As the black colorant, carbon black, magnetic materials, and those toned to black using the above-mentioned yellow, magenta, and cyan colorants can be used.

[0145] The pigment is preferably carbon black, CI Pigment Blue 15:3, CI Pigment Red 122, 150, 32, 269, CI Pigment Yellow 155, 93, 74, 180, or 185. Particularly desirable pigments are carbon black, CI Pigment Blue 15:3, or CI Pigment Red 122. In the case of carbon black, it is preferable that the pH is 6 or more and the oil absorption (DBP) is 30 (ml / 100g) or more and 120 (ml / 100g) or less. The content of these colorants is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin.

[0146] (Other additives) Various known inorganic and organic additives can be used in the toner to impart various properties to the extent that the above effects are not impaired. From the viewpoint of durability when added to the toner, the additives used preferably have a particle size of 3 / 10 or less of the weight average diameter of the toner particles. The particle size of the additive means the average particle size determined by observing the surface of the toner particles using a scanning electron microscope. The content of these additives is preferably 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 0.02 parts by mass or more and 3 parts by mass or less, relative to 100 parts by mass of the toner particles. These additives may be used alone or in combination. These additives may be hydrophobized. As a method of hydrophobization, various coupling agents such as silane coupling agents or titanium coupling agents can be used, but it is preferable to increase the hydrophobicity with silicone oil. This is because it can suppress the moisture adsorption of inorganic fine powder under high humidity conditions, and furthermore, it can suppress the contamination of regulating members, charging members, etc., so that high-quality images can be obtained.

[0147] A method for producing the toner particles will now be described. The method for producing the toner particles is not particularly limited. For example, methods for producing toner particles directly in a hydrophilic medium, such as suspension polymerization, interfacial polymerization, dispersion polymerization, emulsion aggregation, and dissolution suspension methods (hereinafter also referred to as polymerization methods), may be used. A pulverization method may also be used, and the toner particles obtained by the pulverization method may be thermally spherical. Among these, toner particles produced by the suspension polymerization method, emulsion aggregation method, and solution suspension method are preferred, since the individual particles are substantially spherical and the distribution of charge amount is relatively uniform, resulting in high transferability.

[0148] As a method for producing toner particles by the pulverization method, the following example can be given. In the raw material mixing step, predetermined amounts of materials constituting the toner particles, such as a binder resin, a colorant if necessary, and other additives, can be weighed, blended, and mixed. Examples of the mixing device include a double cone mixer, a V-type mixer, a drum type mixer, a super mixer, an FM mixer, a Nauta mixer, and a Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.).

[0149] Next, the mixed materials are melt-kneaded to disperse the colorant and the like in the binder resin. In the melt-kneading step, a batch-type kneader such as a pressure kneader or a Banbury mixer, or a continuous-type kneader can be used. A single-screw or twin-screw extruder is preferred because it allows for continuous production. Examples of such extruders include a KTK type twin screw extruder (manufactured by Kobe Steel, Ltd.), a TEM type twin screw extruder (manufactured by Toshiba Machine Co., Ltd.), a PCM kneader (manufactured by Ikegai), a twin screw extruder (manufactured by KCK Corporation), a Co-Kneader (manufactured by Buss Co., Ltd.), and a Kneadex (manufactured by Nippon Coke and Engineering Co., Ltd.). Furthermore, the resin composition obtained by melt kneading may be rolled with a two-roll mill or the like, and cooled with water or the like in a cooling step.

[0150] The cooled resin composition may then be pulverized to a desired particle size in a pulverization step. In the pulverization step, the resin composition may be coarsely pulverized in a pulverizer and then finely pulverized in a fine pulverizer. Examples of the pulverizer include a crusher, a hammer mill, and a feather mill. Examples of the fine pulverizer include a Cryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), a Super Rotor (manufactured by Nisshin Engineering, Inc.), a Turbo Mill (manufactured by Freund Turbo Corp.), and a fine pulverizer using an air jet system.

[0151] Thereafter, the toner particles can be obtained by classifying the toner particles using a classifier or sieve as required. For classification, an inertial classification type such as Elbow Jet (manufactured by Nittetsu Mining Co., Ltd.), a centrifugal classification type such as Turboplex (manufactured by Hosokawa Micron Corporation), TSP Separator (manufactured by Hosokawa Micron Corporation), or Faculty (manufactured by Hosokawa Micron Corporation) can be used.

[0152] The toner particles may be spheroidized. Examples of systems that can be used to spheroidize the toner particles after pulverization include the following: Hybridization System (manufactured by Nara Machinery Works, Ltd.), Mechanofusion System (manufactured by Hosokawa Micron Corporation), Faculty (manufactured by Hosokawa Micron Corporation), and Meteor Rainbow MR Type (manufactured by Nippon Pneumatic Mfg. Co., Ltd.).

[0153] As a production method, the emulsion aggregation method will be described. The emulsion aggregation method is a manufacturing method in which resin fine particles that are sufficiently small for the target particle diameter are prepared in advance, and the resin fine particles are aggregated in an aqueous medium to manufacture core particles. In the emulsion aggregation method, toner particles are manufactured through a resin fine particle emulsification process, an aggregation process, a fusion process, a cooling process, and a washing process. If necessary, a shell formation process can be added after the cooling process to produce a core-shell toner.

[0154] Resin microparticle emulsification process Resin particles mainly composed of a resin such as a polyester resin can be prepared by a known method. For example, the resin is dissolved in an organic solvent and added to an aqueous medium, and dispersed in the aqueous medium together with a surfactant or a polymer electrolyte using a dispersing machine such as a homogenizer, and then the solvent is removed by heating or reducing pressure to prepare a resin particle dispersion. Any organic solvent that dissolves the resin can be used, but tetrahydrofuran, ethyl acetate, chloroform, etc. are preferred from the viewpoint of high solubility.

[0155] From the viewpoint of environmental load, it is preferable to add the resin, a surfactant, a base, etc. to an aqueous medium, and emulsify and disperse the resin in an aqueous medium that is substantially free of organic solvents using a dispersing machine that applies high-speed shear force, such as a Clearmix, a Homomixer, or a Homogenizer. In particular, the content of organic solvents having a boiling point of 100°C or less is preferably 100μg / g or less. Within the above range, no additional process of removing and recovering the organic solvent is required during toner production, and no burden is placed on wastewater treatment measures. The organic solvent content in the aqueous medium can be measured using gas chromatography (GC).

[0156] The surfactant used for emulsification is not particularly limited, but examples thereof include the following: Examples of such surfactants include anionic surfactants such as sulfate salts, sulfonates, carboxylates, phosphates, and soaps; cationic surfactants such as amine salts and quaternary ammonium salts; and nonionic surfactants such as polyethylene glycols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. These surfactants may be used alone or in combination of two or more. The volume distribution-based median diameter of the resin fine particles is preferably 0.05 to 1.0 μm, more preferably 0.05 to 0.4 μm. If it is 1.0 μm or less, it is easy to obtain toner particles with a volume distribution-based median diameter of 4.0 to 7.0 μm, which is appropriate for toner particles. The volume distribution-based median diameter can be measured using a dynamic light scattering particle size distribution meter (Nanotrac UPA-EX150: manufactured by Nikkiso Co., Ltd.).

[0157] ·Agglomeration process The aggregation step is a step of preparing a mixed liquid by mixing the above-mentioned resin fine particles and, if necessary, colorant fine particles, wax fine particles, etc., and then aggregating the particles contained in the prepared mixed liquid to form aggregates. A suitable example of a method for forming the aggregates is a method in which an aggregating agent is added and mixed into the above-mentioned mixed liquid, and temperature, mechanical power, etc. are appropriately applied. Examples of the flocculant include metal salts of monovalent metals such as sodium and potassium; metal salts of divalent metals such as calcium and magnesium; and metal salts of trivalent metals such as iron and aluminum.

[0158] The addition and mixing of the flocculant is preferably carried out at a temperature equal to or lower than the glass transition temperature (Tg) of the resin particles contained in the mixed liquid. When the mixing is carried out under this temperature condition, the flocculation proceeds in a stable state. The mixing can be carried out using a known mixing device, homogenizer, mixer, etc. The weight average particle size of the aggregates formed here is not particularly limited, but it is usually controlled to 4.0 μm to 7.0 μm so that it is approximately the same as the weight average particle size of the toner particles to be obtained. The control can be easily performed, for example, by appropriately setting and changing the temperature during addition and mixing of the aggregating agent and the conditions of the stirring and mixing. The particle size distribution of the toner particles can be measured using a particle size distribution analyzer (Coulter Multisizer III: manufactured by Beckman Coulter, Inc.) using the Coulter method.

[0159] ·Fusion process The fusion process is a process in which the aggregates are heated to a temperature equal to or higher than the glass transition temperature (Tg) of the resin to fuse them, thereby producing particles with smooth aggregate surfaces. Prior to the primary fusion process, a chelating agent, a pH adjuster, a surfactant, etc. may be appropriately added to prevent fusion between toner particles. Examples of chelating agents include: ethylenediaminetetraacetic acid (EDTA) and its alkali metal salts such as the Na salt, sodium gluconate, sodium tartrate, potassium and sodium citrate, nitrotriacetate (NTA) salts, many water-soluble polymers containing both COOH and OH functionality (polyelectrolytes). The heating temperature may be between the glass transition temperature (Tg) of the resin contained in the aggregate and the temperature at which the resin thermally decomposes. The heating / fusion time is short if the heating temperature is high, and long if the heating temperature is low. That is, the heating / fusion time depends on the heating temperature and cannot be generally specified, but is generally 10 minutes to 10 hours.

[0160] ·Cooling process The cooling step is a step of cooling the temperature of the aqueous medium containing the particles to a temperature lower than the glass transition temperature (Tg) of the resin used. If the cooling is not performed to a temperature lower than Tg, coarse particles may be generated. The specific cooling rate is 0.1 to 50°C / min.

[0161] Shelling process If necessary, a shelling step can be inserted before the washing and drying step described below. The shelling step is a step in which fine resin particles are newly added to and attached to the particles produced in the previous steps to form a shell. The resin particles added here may have the same structure as the resin particles used in the core, or may have a different structure.

[0162] The resin constituting such a shell layer is not particularly limited, and may be any known resin used in toner. For example, polyester resins, vinyl polymers such as styrene-acrylic copolymers, epoxy resins, polycarbonate resins, polyurethane resins, etc. Among these, polyester resins or styrene-acrylic copolymers are preferred, and polyester resins are more preferred from the viewpoint of high fixability and durability. When a polyester resin has a rigid aromatic ring in the main chain, it has more flexibility than a vinyl polymer such as a styrene-acrylic copolymer, and therefore even if it has a lower molecular weight than a vinyl polymer, it can provide the same mechanical strength. Therefore, polyester resins are also preferred as resins suitable for low-temperature fixability. The resins constituting the shell layer may be used alone or in combination of two or more kinds.

[0163] · Washing and drying process The particles produced through the above steps are washed and filtered with ion-exchanged water whose pH has been adjusted with sodium hydroxide or potassium hydroxide, and then washed and filtered with ion-exchanged water several times. Thereafter, the particles are dried to obtain emulsion aggregate toner particles.

[0164] In the case of suspension polymerization, it is possible to directly produce a toner by the following production method. The suspension polymerization method is a method for producing toner particles through a granulation process and a polymerization process. In the granulation process, a polymerizable monomer composition containing a polymerizable monomer for forming a binder resin and, if necessary, additives such as a colorant and wax, is dispersed in an aqueous medium to produce droplets of the polymerizable monomer composition. In the polymerization process, the polymerizable monomer in the droplets can be polymerized. Suitable examples of the polymerizable monomer that can be used to produce the binder resin include the vinyl polymerizable monomers described above.

[0165] A polar resin such as a polyester resin, a wax, a colorant, a crosslinking agent, and other additives are added to the polymerizable monomer as necessary, and the mixture is dissolved or dispersed uniformly using a homogenizer, an ultrasonic disperser, or the like to obtain a polymerizable monomer composition. The obtained polymerizable monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer by a normal stirrer, homomixer, homogenizer, etc. At that time, the stirring speed and time are adjusted so that droplets of the polymerizable monomer composition have a desired toner size, and the polymerizable monomer composition is granulated to form particles. Thereafter, stirring may be performed to such an extent that the particle state is maintained and the settling of the particles is prevented by the action of the dispersion stabilizer. If necessary, a polymerization initiator is added to carry out the polymerization reaction. The polymerization temperature is usually set to a temperature of 40°C or higher, preferably 50 to 120°C. When the polymerization temperature is 95°C or higher, the container in which the polymerization reaction is carried out may be pressurized to suppress evaporation of the aqueous medium.

[0166] The temperature may be raised in the latter half of the polymerization reaction, and the pH may be changed as necessary. Furthermore, in order to remove unreacted polymerizable monomers, by-products, etc. that cause odor during fixing, the reaction temperature may be increased in the latter half of the reaction. Alternatively, the concentration may be increased, or a portion of the aqueous medium may be distilled off during the latter half of the reaction or after completion of the reaction. After completion of the reaction, a toner particle precursor dispersion is obtained. The toner particle precursor dispersion is then concentrated, cooled, washed, filtered, and collected, and dried. The pH of the aqueous medium during granulation is not particularly limited, but is preferably 3.0 to 13.0, more preferably 3.0 to 7.0, and even more preferably 3.0 to 6.0. When granulation is performed in an acidic range, it is possible to prevent the content of metals derived from the dispersion stabilizer in the toner from becoming excessive.

[0167] It is also preferable to wash the toner particles with an acid having a pH of 2.5 or less, more preferably 1.5 or less. By washing the toner particles with an acid, the amount of dispersion stabilizer present on the surface of the toner particles can be reduced. The acid used for washing is not particularly limited, and inorganic acids such as hydrochloric acid and sulfuric acid can be used. This makes it possible to adjust the chargeability of the toner particles to a desired range.

[0168] In addition to the poorly water-soluble inorganic fine particles as a dispersion stabilizer, an organic compound such as polyvinyl alcohol, gelatin, methcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, and starch may be used in combination. These dispersion stabilizers are preferably used in an amount of 0.01 to 2.0 parts by mass per 100 parts by mass of the polymerizable monomer.

[0169] Furthermore, in order to make these dispersion stabilizers finer, a surfactant may be used in an amount of 0.001% by mass to 0.1% by mass. Specifically, commercially available nonionic, anionic, or cationic surfactants can be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, and calcium oleate are preferably used.

[0170] Other manufacturing equipment will be described below. Known equipment can be used, but examples of the stirring means in the granulation step include those having stirring blades such as paddle blades, inclined paddle blades, triple swept blades, anchor blades, full zone blades (manufactured by Kobe Steel Pantech Co., Ltd.), Max Blend (manufactured by Sumitomo Heavy Industries Co., Ltd.), Super Mix (manufactured by Satake Chemical Machinery Co., Ltd.), and Hi-F Mixer (manufactured by Soken Chemical Industries Co., Ltd.). In addition, a mixer capable of applying high shear force is more preferable. As the high shear mixer, one having a mixing chamber formed by a mixing rotor rotating at high speed and a screen provided so as to surround the mixing rotor is preferably used. Specifically, Ultra Turrax (manufactured by IKA), Polytron (manufactured by Kinematica), TK Homo Mixer (manufactured by Primix), Clearmix (manufactured by M Technique), W Motion (manufactured by M Technique), Cavitron (manufactured by Cavitron), Sharp Flow Mill (manufactured by Pacific Machinery Co., Ltd.), etc. can be used.

[0171] The weight average particle diameter (D4) of the toner is preferably 4.0 μm to 12.0 μm, more preferably 4.0 μm to 9.0 μm. If the weight average particle diameter is 4.0 μm or more, durability and heat resistance during long-term use are good, and if the weight average particle diameter is 12.0 μm or less, the toner coloring power and image resolution are good.

[0172] <Weight average particle size (D4) and number average particle size (D1) of toner particles> The weight average particle diameter (D4) and number average particle diameter (D1) of the toner particles are calculated as follows. The measurement device used is a precision particle size distribution measurement device using the narrow hole electrical resistance method, equipped with a 100 μm aperture tube, "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.). Setting of measurement conditions and analysis of measurement data The analysis is performed using the accompanying dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.). The measurement is performed with an effective measurement channel count of 25,000 channels. The aqueous electrolyte solution used for the measurement is prepared by dissolving special grade sodium chloride in ion-exchanged water to a concentration of 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter). Before performing measurements and analysis, the dedicated software is set as follows. In the "Change Standard Measurement Method (SOM)" screen of the dedicated software, the total count number in the control mode is set to 50,000 particles, the number of measurements is set to 1, and the Kd value is set to the value obtained using "Standard particle 10.0 μm" (manufactured by Beckman Coulter). The threshold and noise level are automatically set by pressing the "Threshold / Noise Level Measurement Button." In addition, the current is set to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and "Flush aperture tube after measurement" is checked. In the "Pulse to particle size conversion setting" screen of the dedicated software, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm to 60 μm.

[0173] The specific measurement method is as follows. (1) Pour 200 mL of the electrolyte solution into a 250 mL round-bottom glass beaker made exclusively for the Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 revolutions per second. Then, remove dirt and air bubbles from inside the aperture tube using the "Aperture Tube Flush" function of the dedicated software. (2) 30 mL of the electrolyte solution is placed in a 100 mL flat-bottom glass beaker, and 0.3 mL of a dilution of "Contaminon N" (a 10% aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments made of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) diluted 3 times by mass with ion-exchanged water is added as a dispersant. (3) Prepare an ultrasonic disperser "Ultrasonic Dispersion System Tetora150" (manufactured by Nikkaki Bios Co., Ltd.) with two built-in oscillators with an oscillation frequency of 50 kHz and a phase shift of 180 degrees, and an electrical output of 120 W. Pour 3.3 L of ion-exchanged water into the water tank of the ultrasonic disperser, and add 2 mL of Contaminon N to this water tank. (4) Set the beaker from (2) in the beaker fixing hole of the ultrasonic disperser, and operate the ultrasonic disperser. Then, adjust the height position of the beaker so that the resonance state of the liquid surface of the electrolyte solution in the beaker is maximized. (5) While the electrolyte solution in the beaker in (4) is irradiated with ultrasonic waves, 10 mg of toner is added little by little to the electrolyte solution and dispersed. Then, ultrasonic dispersion treatment is continued for another 60 seconds. During ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10°C or higher and 40°C or lower. (6) Using a pipette, the electrolytic solution (5) in which the toner is dispersed is dropped into the round-bottom beaker (1) placed in the sample stand, and the measurement concentration is adjusted to 5%. Then, measurements are continued until the number of particles measured reaches 50,000. (7) The measurement data is analyzed using the dedicated software that comes with the device, and the weight average particle size (D4) and number average particle size (D1) are calculated. Note that when the dedicated software is set to Graph / Volume %, the "Average diameter" on the "Analysis / Volume Statistics (Arithmetic Mean)" screen is the weight average particle size (D4). When the dedicated software is set to Graph / Number %, the "Average diameter" on the "Analysis / Number Statistics (Arithmetic Mean)" screen is the number average particle size (D1).

[0174] The glass transition temperature of the toner particles is preferably 52° C. or more and 75° C. or less from the viewpoints of storage stability and fixability. The average circularity of the toner particles is preferably 0.950 or more, and more preferably 0.960 or more. This is because the probability that the toner particles are uniformly triboelectrically charged between the toner particles, the toner carrier, and the toner layer regulating member is high, and the stress that the toner particles receive is also uniform. This is preferable from the viewpoint of fusion to the toner layer regulating member.

[0175] <Method for measuring the average circularity of toner particles> The average circularity of the toner particles is measured using a flow type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration process. The specific measurement method is as follows. First, about 20 ml of ion-exchanged water from which impurities such as solids have been removed is placed in a glass container. About 0.2 ml of a dilution of "Contaminon N" (a 10% aqueous solution of a neutral detergent for cleaning precision measuring instruments with a pH of 7, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) diluted about three times by mass with ion-exchanged water is added to the container. About 0.02 g of the measurement sample is further added, and the dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion liquid for measurement. At that time, the dispersion liquid is appropriately cooled so that the temperature is 10°C or higher and 40°C or lower. As the ultrasonic disperser, a tabletop ultrasonic cleaner disperser (e.g., "VS-150" (manufactured by Vervoclear Co., Ltd.) with an oscillation frequency of 50 kHz and an electrical output of 150 W is used, a predetermined amount of ion-exchanged water is placed in the water tank, and about 2 ml of the Contaminon N is added to the water tank. For the measurement, the flow type particle image analyzer equipped with "LUCPLFLN" (magnification 20x, numerical aperture 0.40) is used as the objective lens, and particle sheath "PSE-900A" (manufactured by Sysmex Corporation) is used as the sheath liquid. The dispersion liquid prepared according to the above procedure is introduced into the flow type particle image analyzer, and 2000 toner particles are measured in HPF measurement mode and total count mode. Then, the binarization threshold for particle analysis is set to 85%, and the analyzed particle diameter is limited to a circle equivalent diameter of 1.977 μm or more and less than 39.54 μm, and the average circularity of the toner particles is obtained. Before starting the measurement, automatic focus adjustment is performed using standard latex particles (e.g., Duke Scientific's "RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5100A" diluted with ion-exchanged water). After that, it is preferable to perform focus adjustment every 2 hours from the start of the measurement. In the examples of the present application, a flow-type particle image analyzer was used that had been calibrated by Sysmex Corp. and had a calibration certificate issued by Sysmex Corp. Measurements were performed under the same measurement and analysis conditions as when the calibration certificate was received, except that the particle diameters analyzed were limited to a circle-equivalent diameter of 1.977 μm or more and less than 39.54 μm. EXAMPLES

[0176] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited thereto. Note that the number of parts in the following formulations is based on mass unless otherwise specified.

[0177] [Production of amorphous polyester resin 1] Terephthalic acid: 75 parts Bisphenol A-propylene oxide 2 mole adduct: 100 parts Tetrabutoxytitanate: 0.125 parts The polyester monomer was charged into an autoclave equipped with a pressure reducing device, a water separator, a nitrogen gas introducing device, a temperature measuring device, and a stirrer, and reacted for 5 hours at 200°C under a nitrogen atmosphere and normal pressure. Then, 2.1 parts of trimellitic acid and 0.120 parts of tetrabutoxy titanate were added, and reacted for 3 hours at 220°C, and further reacted for 2 hours under a reduced pressure of 10 to 20 mmHg to obtain amorphous polyester resin 1. The physical properties of the obtained amorphous polyester resin 1 were acid value=8.3 mgKOH / g, hydroxyl value=33.3 mgKOH / g, weight average molecular weight (Mw)=10000, and DSC endothermic peak=72.5°C.

[0178] [Production of amorphous polyester resin 2] Terephthalic acid: 60 parts Fumaric acid: 15 parts Bisphenol A-propylene oxide 2 mole adduct: 100 parts Tetrabutoxytitanate: 0.125 parts The polyester monomer was charged into an autoclave equipped with a pressure reducing device, a water separator, a nitrogen gas introducing device, a temperature measuring device, and a stirrer, and reacted for 5 hours at 200°C under a nitrogen atmosphere and normal pressure. Then, 2.1 parts of trimellitic acid and 0.120 parts of tetrabutoxy titanate were added, and reacted for 3 hours at 220°C, and further reacted for 2 hours under a reduced pressure of 10 to 20 mmHg to obtain amorphous polyester resin 2. The physical properties of the obtained amorphous polyester resin 2 were acid value=12.3mgKOH / g, hydroxyl value=27.6mgKOH / g, weight average molecular weight (Mw)=12600, and DSC endothermic peak=72.1°C.

[0179] [Crystalline polyester resin production example 1] In an autoclave equipped with a pressure reducing device, a water separator, a nitrogen gas inlet device, a temperature measuring device, and a stirrer, Sebacic acid: 175 parts 1,6-Hexanediol: 170 parts Ethylene glycol: 50 parts Potassium oxalate titanate: 0.40 parts The above polyester monomer was charged and reacted in a nitrogen atmosphere under normal pressure at 200° C. for 6 hours, and then further reacted at 220° C. for 1.5 hours under reduced pressure of 10 to 20 mmHg to obtain crystalline polyester resin 1. The physical properties of the obtained crystalline polyester resin 1 were as follows: acid value=1.3 mgKOH / g, weight average molecular weight (Mw)=21000, and DSC endothermic peak=79.8°C.

[0180] [Production example of hydrophobic silica 1] 100 parts of silica (AEROSIL 200CF, manufactured by Nippon Aerosil) was treated with 10 parts of hexamethyldisilazane, and further treated with 20 parts of dimethylsilicone oil to obtain hydrophobic silica 1. The number average diameter of the primary particles of hydrophobic silica 1 was 12 nm, and the degree of hydrophobicity was 97% by volume.

[0181] [Production example of hydrophobic silica 2] 100 parts of silica (AEROSIL OX50, manufactured by Nippon Aerosil) was treated with 10 parts of hexamethyldisilazane, and further treated with 10 parts of dimethylsilicone oil to obtain hydrophobic silica 2. The number average diameter of the primary particles of hydrophobic silica 2 was 40 nm, and the degree of hydrophobicity was 97% by volume.

[0182] [Production example of hydrophobic silica 3] 100 parts of silica (AEROSIL 300CF, manufactured by Nippon Aerosil) was treated with 15 parts of hexamethyldisilazane, and further treated with 20 parts of dimethylsilicone oil to obtain hydrophobic silica 3. The number average diameter of the primary particles of hydrophobic silica 3 was 7 nm, and the degree of hydrophobicity was 97% by volume.

[0183] [Production example of hydrophobic silica 4] 100 parts of silica (AEROSIL 130, manufactured by Nippon Aerosil) was treated with 10 parts of hexamethyldisilazane, and further treated with 20 parts of dimethylsilicone oil to obtain hydrophobic silica 4. The number average diameter of the primary particles of hydrophobic silica 4 was 16 nm, and the degree of hydrophobicity was 97% by volume.

[0184] [Titania 1] Rutile-type titanium oxide (manufactured by Teika Corporation, product name: JR-301, primary particle size: 0.30 μm, Al-treated) was designated as titania 1.

[0185] [Titania 2] Anatase type titanium oxide (manufactured by Teika Corporation, product name: JA-1, primary particle size: 0.18 μm) was used as titania 2.

[0186] <How to calculate hydrophobicity> It is determined from the methanol drop transmittance curve obtained as follows. First, 70 ml of water is placed in a cylindrical glass container having a diameter of 5 cm and a thickness of 1.75 mm, and the water is dispersed for 5 minutes using an ultrasonic disperser to remove air bubbles and the like. Next, 0.1 g of inorganic fine particles is precisely weighed and added to the container containing the water to prepare a sample liquid for measurement. The sample liquid for measurement is then set in a powder wettability tester "WET-101P" (manufactured by Rhesca Corporation). The sample liquid for measurement is stirred for 6.7 s using a magnetic stirrer. -1 The mixture is stirred at a speed of 400 rpm. The rotor of the magnetic stirrer is a fluororesin-coated spindle-shaped rotor having a length of 25 mm and a maximum body diameter of 8 mm. Next, methanol is continuously added to this measurement sample liquid through the above-mentioned device at a dropping rate of 1.3 ml / min while measuring the transmittance with light of a wavelength of 780 nm, and a methanol dropping transmittance curve as shown in Figure 3 is created. The methanol concentration (volume %) when the transmittance becomes 50% of that at the start of dropping is defined as the degree of hydrophobicity.

[0187] [Manufacturing example of magnetic material 1] An aqueous solution containing ferrous hydroxide was prepared by mixing 1.0 equivalent of caustic soda solution (containing 1% by mass of sodium hexametaphosphate calculated as P relative to Fe) with an aqueous solution of ferrous sulfate. While maintaining the pH of the aqueous solution at 9, air was blown in and an oxidation reaction was carried out at 80°C to prepare a slurry liquid for generating seed crystals. Next, an aqueous solution of ferrous sulfate was added to the slurry in an amount equivalent to 1.0 relative to the initial alkali amount (sodium component of caustic soda). The pH of the slurry was maintained at 8, and the oxidation reaction was allowed to proceed while blowing in air. At the end of the oxidation reaction, the pH was adjusted to 6, and the slurry was washed with water and dried to obtain magnetic iron oxide 1, which was spherical magnetite particles with a number-average particle size of the primary particles of 200 nm. The magnetic acid was added to Simpson Mixed Mara (manufactured by Shin-Nitto Kogyo Co., Ltd., model MSG-0L). 10.0 kg of magnetic iron oxide 1 was added and crushed for 30 minutes. Then, 95 g of n-decyltrimethoxysilane was added as a silane coupling agent to the device and the device was operated for 1 hour to hydrophobize the particle surfaces of the magnetic iron oxide 1 with the silane coupling agent, thereby obtaining magnetic material 1. The obtained magnetic material 1 had a spherical particle shape and the number average particle size of the primary particles was 200 nm.

[0188] (Production Example of Toner Particle 1) Dispersion medium (aqueous medium 1) 19.2 parts of sodium phosphate and 6.2 parts of 10% hydrochloric acid were added to 1000 parts of ion-exchanged water in a reaction vessel, and the mixture was kept at 65°C for 60 minutes while purging with N2. An aqueous calcium chloride solution in which 10.7 parts of calcium chloride were dissolved in 13.8 parts of ion-exchanged water was added all at once while stirring at 12000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to prepare an aqueous medium 1 containing a dispersion stabilizer.

[0189] Polymerizable monomer composition 60 parts styrene Carbon black (Orion Engineered Carbons, product name "Printex35") 7 parts Charge control agent (Orient Co., Ltd.: Bontron E-89) 0.25 parts The above materials were put into an attritor disperser (Mitsui Miike Chemical Engineering Co., Ltd.), and further dispersed using zirconia particles having a diameter of 1.7 mm at 220 rpm for 5 hours to obtain a polymerizable monomer composition.

[0190] The polymerizable monomer composition Styrene 20 parts · n-Butyl acrylate 20 parts Amorphous polyester resin 1 / 4 Fischer-Tropsch wax (manufactured by Schumann Sasol, product name "C80": DSC endothermic peak 83.0°C) 9.00 parts Added.

[0191] The above materials were kept at 65°C in a separate container, and were uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Into this, 10.0 parts of a polymerization initiator t-hexyl peroxypivalate (manufactured by NOF Corporation, trade name "Perhexyl PV", molecular weight: 202, 10-hour half-life temperature: 53.2°C) was dissolved to prepare a polymerizable monomer composition. The polymerizable monomer composition was added to the aqueous medium 1 in the granulation tank, and stirred at 10,000 rpm for 5 minutes with a TK homomixer under N2 purging at 65°C, and granulated at pH 5.2. The mixture was then transferred to a polymerization tank, and stirred with a paddle impeller at 30 revolutions / min at 70°C for 6 hours (the conversion rate was 90%), and then heated to 95°C for 2 hours to react. After the polymerization reaction was completed, a cooling step was carried out by mixing water at 5° C. with the toner particle precursor dispersion at 95° C. and cooling to 30° C. at a cooling rate of 4,000° C. / sec. Thereafter, the temperature was increased to 55°C at a rate of 1.00°C / min, and the temperature was maintained at 55°C for 180 minutes, after which 5°C water was mixed and the mixture was cooled to 30°C at a rate of 5°C / sec. Hydrochloric acid was added to the obtained toner particle dispersion 1 to adjust the pH to 1.5 or less, and the mixture was left to stand with stirring for 1 hour, after which solid-liquid separation was performed using a pressure filter to obtain a toner cake. This was reslurried with ion-exchanged water to make a dispersion again, and then solid-liquid separation was performed using the aforementioned filter. The reslurry and solid-liquid separation were repeated until the electrical conductivity of the filtrate became 5.0 μS / cm or less, and finally solid-liquid separation was performed to obtain a toner cake. The obtained toner cake was dried using a flash jet dryer (manufactured by Seishin Enterprises). The drying conditions were an inlet temperature of 90°C, a dryer outlet temperature of 40°C, and the toner cake supply speed was adjusted according to the moisture content of the toner cake so that the outlet temperature did not deviate from 40°C. Furthermore, fine and coarse powders were removed using a multi-division classifier utilizing the Coanda effect, and toner particles 1 were obtained. The weight average particle size (D4) of toner particles 1 was 6.5 μm.

[0192] (Production Example of Toner Particle 2) Dispersion medium (aqueous medium 2) 23.2 parts of sodium phosphate and 7.2 parts of 10% hydrochloric acid were added to 1000 parts of ion-exchanged water in a reaction vessel, and the mixture was kept at 65°C for 60 minutes while purging with N2. Using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), an aqueous calcium chloride solution in which 12.7 parts of calcium chloride was dissolved in 16.8 parts of ion-exchanged water was added all at once while stirring at 12000 rpm to prepare an aqueous medium 2 containing a dispersion stabilizer. Toner particles 2 were obtained in the same manner as in toner particle production example 1, except that this aqueous medium 2 was used. The weight average particle size (D4) of toner particles 2 was 5.0 μm.

[0193] (Production Example of Toner Particle 3) Dispersion medium (aqueous medium 3) 15.2 parts of sodium phosphate and 5.2 parts of 10% hydrochloric acid were added to 1000 parts of ion-exchanged water in a reaction vessel, and the mixture was kept at 65°C for 60 minutes while purging with N2. A calcium chloride aqueous solution in which 8.7 parts of calcium chloride were dissolved in 11.8 parts of ion-exchanged water was added all at once while stirring at 12000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to prepare an aqueous medium 3 containing a dispersion stabilizer. Toner particles 3 were obtained in the same manner as in Toner Particle Production Example 1, except that this aqueous medium 3 was used. The weight average particle size (D4) of toner particles 3 was 7.5 μm.

[0194] (Production Example of Toner Particle 4) Dispersion medium (aqueous medium 4) 11.2 parts of sodium phosphate and 4.2 parts of 10% hydrochloric acid were added to 1000 parts of ion-exchanged water in a reaction vessel, and the mixture was kept at 65°C for 60 minutes while purging with N2. A calcium chloride aqueous solution in which 6.7 parts of calcium chloride were dissolved in 9.8 parts of ion-exchanged water was added all at once while stirring at 12000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), to prepare aqueous medium 4 containing a dispersion stabilizer. Toner particles 4 were obtained in the same manner as in toner particle production example 1, except that this aqueous medium 4 was used. The weight average particle size (D4) of toner particles 4 was 10.0 μm.

[0195] (Production Example of Toner Particle 5) Toner particles 5 were obtained in the same manner as in Toner Particle Production Example 1, except that the amount of carbon black was changed from 7 parts to 65 parts of magnetic material 1. The weight average particle size (D4) of toner particles 5 was 6.5 μm.

[0196] (Production Example of Toner Particle 6) Except for changing the carbon black: 7 parts to PY155: 7 parts, the same procedure as in Toner Particle Production Example 1 was carried out to obtain toner particles 6. The weight average particle size (D4) of toner particles 6 was 6.5 μm.

[0197] (Production Example of Toner Particle 7) Except for changing the carbon black: 7 parts to PR122: 7 parts, the same procedure as in Toner Particle Production Example 1 was carried out to obtain toner particles 7. The weight average particle size (D4) of toner particles 7 was 6.5 μm.

[0198] (Production Example of Toner Particle 8) Except for changing the carbon black: 7 parts to PB15:3 (7 parts), the same procedure as in Toner Particle Production Example 1 was carried out to obtain toner particles 8. The weight average particle size (D4) of toner particles 8 was 6.5 μm.

[0199] <Preparation of Resin Particle Dispersion 1> 3,000 parts of amorphous polyester resin 1, 10,000 parts of ion-exchanged water, and 150 parts of surfactant sodium dodecylbenzenesulfonate were added to the emulsification tank of a high-temperature, high-pressure emulsification device (Cavitron CD1010, slit: 0.4 mm). The mixture was then heated to 130°C to melt, dispersed at 110°C and a flow rate of 3 L / m at 10,000 rpm for 30 minutes, and passed through a cooling tank to recover the amorphous polyester resin dispersion (High-temperature, high-pressure emulsification device (Cavitron CD1010, slit 0.4 mm, Cavitron Co., Ltd.). The obtained dispersion was cooled to room temperature, and ion-exchanged water was added to obtain resin particle dispersion 1, which was a dispersion of amorphous polyester resin 1 having a solid content of 12.5% ​​by mass and a volume-based median diameter of 0.15 μm.

[0200] <Preparation of Resin Particle Dispersion 2> 3,000 parts of crystalline polyester resin 1, 10,000 parts of ion-exchanged water, and 150 parts of surfactant sodium dodecylbenzenesulfonate were added to the emulsification tank of a high-temperature, high-pressure emulsification device (Cavitron CD1010, slit: 0.4 mm). The mixture was then heated to 130°C to melt, dispersed at 110°C and 10,000 rpm for 30 minutes at a flow rate of 3 L / m, and passed through a cooling tank to recover the crystalline polyester resin dispersion (High-temperature, high-pressure emulsification device (Cavitron CD1010, slit 0.4 mm, Cavitron Co., Ltd.). The obtained dispersion was cooled to room temperature, and ion-exchanged water was added to obtain a resin particle dispersion 2, which was a dispersion of crystalline polyester resin 1 having a solid content of 12.5% ​​by mass and a volume-based median diameter of 0.15 μm.

[0201] (Volume-based median diameter of resin particles (D50)) The volume-based median diameter (D50) of resin particles such as resin particle dispersions is measured using a laser diffraction / scattering type particle size distribution measuring device. The measurement is performed according to the standard (1 year). The measurement device used is the laser diffraction / scattering particle size distribution analyzer "LA-920" (manufactured by HORIBA, Ltd.). The measurement conditions are set and the measurement data is analyzed using the dedicated software "HORIBA LA-920 for Windows" that comes with the LA-920. The measurement solvent used was ion-exchanged water from which solid impurities had been removed in advance. The measurement procedure was as follows. (1) Attach the batch type cell holder to the LA-920. (2) A specified amount of ion-exchanged water is placed in a batch cell, and the batch cell is set in the batch cell holder. (3) Stir inside the batch cell using a dedicated stirrer tip. (4) Press the "Refractive Index" button on the "Display Condition Setting" screen and set the relative refractive index to a value corresponding to the resin particles. (5) On the "Display Condition Setting" screen, set the particle size standard to the volume standard. (6) After warming up for at least one hour, adjust the optical axis, fine-tune the optical axis, and perform a blank measurement. (7) Put 3 ml of the resin particle dispersion into a 100.0 ml flat-bottom glass beaker. Add 57 ml of ion-exchanged water to dilute the resin particle dispersion. Add 0.3 ml of a solution of "Contaminon N" (a 10% aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments made from a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) diluted 3 times by mass with ion-exchanged water as a dispersant. (8) Prepare an ultrasonic disperser "Ultrasonic Dispension System Tetora150" (manufactured by Nikkaki Bios Co., Ltd.) with an electrical output of 120 W and two built-in oscillators with an oscillation frequency of 50 kHz and a phase shift of 180 degrees. Pour 3.3 liters of ion-exchanged water into the tank and add 2.0 ml of Contaminon N to the tank. (9) The beaker of (7) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid surface of the aqueous solution in the beaker is maximized. (10) Continue ultrasonic dispersion for 60 seconds. During ultrasonic dispersion, adjust the water temperature in the water tank appropriately so that it is between 10°C and 40°C. (11) The dispersion liquid of the resin particles prepared in (10) is immediately added to the batch cell in small amounts while being careful not to introduce air bubbles, and the transmittance of the tungsten lamp is adjusted to 90% to 95%. Then, the particle size distribution of the resin particles is measured. D50 is calculated based on the obtained volume-based particle size distribution data.

[0202] <Preparation of Colorant Dispersion 1> As a colorant, 100 parts of carbon black "Nipex35 (manufactured by Orion Engineered Carbons)" and 15 parts of Neogen RK were mixed with 885 parts of ion-exchanged water, and dispersed for about 1 hour using a wet jet mill JN100 to obtain colorant dispersion 1.

[0203] <Preparation of Wax Dispersion 1> 100 parts of Fischer-Tropsch wax (manufactured by Schumann Sasol, product name "C80": DSC endothermic peak 83.0°C) and 15 parts of NEOGEN RK were mixed with 385 parts of ion-exchanged water, and dispersed for about 1 hour using a wet jet mill JN100 (manufactured by Jokou Co., Ltd.) to obtain wax dispersion 1. The concentration of the wax dispersion was 20 mass%. The volume-based median diameter of the wax particles was measured using a dynamic light scattering particle size distribution diameter (Nanotrac, manufactured by Nikkiso Co., Ltd.) and was found to be 0.20 μm.

[0204] <Production Example of Toner Particle 9> Resin particle dispersion 1:195 parts, resin particle dispersion 2:265 parts, wax dispersion 1:20 parts, and colorant dispersion 1:20 parts were dispersed using a homogenizer (IKA: Ultra Turrax T50). The temperature in the container was adjusted to 30°C while stirring, and a 1 mol / L aqueous sodium hydroxide solution was added to adjust the pH to 8.0. As a flocculant, an aqueous solution in which 0.250 parts of magnesium sulfate was dissolved in 10 parts of ion-exchanged water was added over 10 minutes at 30°C while stirring. After leaving it for 3 minutes, the temperature was raised to 50°C to generate associated particles. After keeping the mixture at 50°C for 30 minutes, 70.0 parts of resin particle dispersion 1 were added. In this state, the particle size of the associated particles was measured using a Coulter Counter Multisizer 3 (registered trademark, manufactured by Beckman Coulter, Inc.). When the weight average particle size reached 4.5 μm, 3.0 parts of sodium chloride and 8.0 parts of NEOGEN RK were added to stop particle growth. The temperature was then raised to 95°C to fuse the associated particles and make them spherical. When the average circularity reached 0.980, a cooling step was carried out. The 95°C toner particle precursor dispersion was mixed with 5°C water and cooled to 30°C at a cooling rate of 4,000°C / sec. Thereafter, the temperature was increased to 55°C at a rate of 1.00°C / min, and the temperature was maintained at 55°C for 180 minutes, after which 5°C water was mixed and the mixture was cooled to 30°C at a rate of 5°C / sec. Hydrochloric acid was added to the obtained toner particle dispersion 1 to adjust the pH to 1.5 or less, and the mixture was left to stand with stirring for 1 hour, after which solid-liquid separation was performed using a pressure filter to obtain a toner cake. This was reslurried with ion-exchanged water to make a dispersion again, and then solid-liquid separation was performed using the aforementioned filter. The reslurry and solid-liquid separation were repeated until the electrical conductivity of the filtrate became 5.0 μS / cm or less, and finally solid-liquid separation was performed to obtain a toner cake. The obtained toner cake was dried using a flash jet dryer (manufactured by Seishin Enterprises). The drying conditions were an inlet temperature of 90°C, a dryer outlet temperature of 40°C, and the toner cake supply speed was adjusted according to the moisture content of the toner cake so that the outlet temperature did not deviate from 40°C. Furthermore, fine and coarse powders were removed using a multi-division classifier utilizing the Coanda effect, and toner particles 9 were obtained. The weight average particle size (D4) of toner particles 9 was 6.5 μm.

[0205] (Production Example of Toner Particle 10) (Synthesis of toner binder solution) Amorphous polyester resin 1: 1000 parts was dissolved in 2000 parts of ethyl acetate solvent and mixed to obtain an ethyl acetate solution of toner binder (1).

[0206] (Preparation of toner particles) In a beaker, 240 parts of the ethyl acetate solution of the toner binder (1), 6.0 parts of carbon black (manufactured by Orion Engineered Carbons, trade name "Printex 35"), and an aluminum compound of 3,5-di-tert-butylsalicylic acid [Bon Toner material solution was obtained by adding 1.0 part of TRON E88 (manufactured by Orient Chemical Industry Co., Ltd.) and 13 parts of Fischer-Tropsch wax (manufactured by Schumann Sasol, product name "C80": DSC endothermic peak 83.0°C) and stirring at 12,000 rpm at 55°C with a TK homomixer to dissolve and disperse uniformly. Aqueous medium 1 (1036.3 parts) and 0.27 parts of sodium dodecylbenzenesulfonate were added to a beaker and dissolved uniformly. The toner material solution was then added and stirred for 3 hours while stirring at 12,000 rpm with a TK homomixer at 60° C. The mixture was then transferred to a flask equipped with a stirrer and a thermometer, and heated to 98° C. to remove the solvent. After the removal of the solvent, a cooling step was carried out by mixing water at 5° C. with the toner particle precursor dispersion at 95° C. and cooling to 30° C. at a cooling rate of 4,000° C. / sec. Thereafter, the temperature was increased to 55°C at a rate of 1.00°C / min, and the temperature was maintained at 55°C for 180 minutes, after which 5°C water was mixed and the mixture was cooled to 30°C at a rate of 5°C / sec. Hydrochloric acid was added to the obtained toner particle dispersion to adjust the pH to 1.5 or less, and the mixture was left to stand with stirring for 1 hour, after which it was subjected to solid-liquid separation using a pressure filter to obtain a toner cake. This was reslurried with ion-exchanged water to make a dispersion again, and then the solid-liquid separation was performed using the aforementioned filter. The reslurry and solid-liquid separation were repeated until the electrical conductivity of the filtrate became 5.0 μS / cm or less, and finally the mixture was subjected to solid-liquid separation to obtain a toner cake. The obtained toner cake was dried in a flash jet dryer (manufactured by Seishin Enterprises). The drying conditions were an inlet temperature of 90°C, a dryer outlet temperature of 40°C, and the toner cake supply speed was adjusted according to the moisture content of the toner cake so that the outlet temperature did not deviate from 40°C. Furthermore, fine and coarse powders were removed using a multi-division classifier utilizing the Coanda effect, and toner particles 10 were obtained. The weight average particle size (D4) of toner particles 10 was 6.5 μm.

[0207] (Toner 11 manufacturing example) Amorphous polyester resin 2: 100.0 parts Carbon black "Nipex35 (Orion Engineered Carbons): 7.00 copies Fischer-Tropsch wax (manufactured by Schumann Sasol, product name "C80": DSC endothermic peak 83.0°C): 5.00 parts The above materials were mixed in a Henschel mixer, and then melt-kneaded at 125°C using a twin-screw kneading extruder. The kneaded product was gradually cooled to room temperature, and then coarsely pulverized using a cutter mill, pulverized using a fine pulverizer using a jet stream, and air-classified to produce toner particles 11. The toner particles 11 had a weight average particle size (D4) of 6.5 μm.

[0208] (Preparation of Rotating Body 7) The protruding portion and its surrounding portion of the Y1 blade for an FM mixer, model FM500L, manufactured by Nippon Coke & Engineering Co., Ltd., were processed as shown in Figures 6 and 7 to obtain a rotor 7 that can be separated into a treatment member and a rotor main body (the numbers between the arrows in Figures 6 and 7 indicate the relative dimensions of each part). The rotor main body was made separable into part A forming the protruding portion and supporting part B. The shape of the treatment member was the shape of rotor 7 shown in Figure 16-1. At that time, the materials of the treatment member and the rotor main body (part A forming the protruding portion and supporting part B) were as shown in Tables 1-1 and 1-2.

[0209] In addition, the protruding portion and its surrounding portion of the Y1 blade for the FM500L FM mixer manufactured by Nippon Coke & Engineering Co., Ltd. were processed as shown in Figs. 5 and 6 to obtain a rotor 7-2 that can be separated into a treatment member 32 and a rotor main body 31 and is used in Example 87. (Blade shape: rotor 7 shown in Fig. 16-1)

[0210] (Production of rotating bodies 1-6, 8-43) Rotating bodies 1 to 6, 8 to 43 were obtained in the same manner as rotating body 7, except that they were processed to have the shapes, angles, and dimensions shown in Figures 6 and 7 and Tables 1-1, 1-2, 1-3, and 1-4. The shapes of the protruding parts including the rotor 7 are shown in Figs. 16-1, 16-2 and 16-3. At that time, the ratio of the inner diameter of the processing chamber to the outermost diameter in the radial direction of the rotor 7 was set to be the same as that of the rotor 7.

[0211] (Making of rotors 44 and 45) Rotating bodies 44 and 45 were obtained in the same manner as rotating body 7, except that they were processed to have the shapes, angles, and dimensions shown in FIG. 15 and Tables 1-3 and 1-4. At that time, the ratio of the inner diameter of the processing chamber to the outermost diameter in the radial direction of the rotating body was set to be the same as that of rotating body 7.

[0212] [Example 1] <Toner processing device 1> An FM mixer (FM500L; manufactured by Nippon Coke and Engineering Co., Ltd.) was used. As the rotor, an S0 blade (manufactured by Nippon Coke and Engineering Co., Ltd.) having the shape shown in Fig. 3 was used as the lower blade, and rotor 7 as shown in Tables 1-1 and 1-2 was used as the upper blade.

[0213] <External addition process> The obtained toner particles (1:100 parts), hydrophobic silica (1:2.50 parts), titania (1:0.30 parts), and titania (2:0.20 parts) were mixed for 15 minutes at a rotation speed of 1450 rpm using a toner processing device 1. Mixing was started after the temperature stabilized at 30°C, and the temperature was adjusted to be maintained at 30°C±1°C during mixing.

[0214] <Heating process> Next, warm water was passed through the jacket so that the temperature of the toner processing device 1 configured as above became 43° C. Mixing was started after the temperature stabilized at 43° C., and the temperature was adjusted to be maintained at 43° C.±1° C. during mixing. The toner that had been subjected to the above-mentioned external addition process was put into toner processing device 1 and then heated at 1450 rpm for 7 minutes. After the heating process was completed, the toner was sieved through a 75 μm mesh to obtain toner 1. The manufacturing conditions for toner 1 are shown in Table 2, and the physical properties of toner 1 are shown in Table 4.

[0215] This operation was counted as one set, and after discharging the toner produced by external addition, the same operation was repeated, and the condition of the rotating body and the toner were evaluated at the 1000th set, 5000th set, and 10000th set. The evaluation method will be described later. The evaluation results are shown in Tables 3-1 and 3-2.

[0216] [Examples 2 to 87] Toners 2 to 87 were obtained in the same manner as in Example 1, except that the toner treatment device, rotor body (shape and material), treatment member (α, β, and γ were appropriately changed to obtain the values ​​in the table), toner particles, type and amount of hydrophobic silica, and external addition conditions were set as shown in Tables 1-1, 1-2, 1-3, 1-4, and Table 2. The state of the obtained rotor and toner was evaluated. The evaluation method will be described later. The evaluation results are shown in Tables 3-1, 3-2, and Table 4. In addition, the "20L spherical" in Example 79 was based on Mechanohybrid (MH20, manufactured by Nippon Coke and Engineering Co., Ltd.). The HRC hardness of the coating layer on the surface of the treated member in Examples 12 to 14 was 68 for Example 12, 80 for Example 13, and 78 for Example 14, respectively.

[0217] [Comparative Examples 1 to 5] Toners 88 to 92 were obtained in the same manner as in Example 1, except that the toner processing device, rotor body (shape and material), processing member, toner particles, and types and amounts of hydrophobic silica were set as shown in Tables 1-3, 1-4, and 2, and the rotor and toner conditions were evaluated. The evaluation method will be described later. The evaluation results are shown in Tables 3-1, 3-2, and 4. For the rotor used in Comparative Example 4, a Y1 blade (integral type) manufactured by Nippon Coke and Engineering Co., Ltd. was used.

[0218] The materials in the table are based on the following standards. SCM440: Chromium molybdenum steel SUS821L1: Lean duplex stainless steel SUS304: Austenitic stainless steel S45C: Carbon steel for machine structures SKT4: Alloy tool steel HPM38: Plastic mould steel HPM31: Plastic mould steel SKH51: Molybdenum-based high-speed tool steel SKH55: Molybdenum-based high-speed tool steel SKH40: Molybdenum-based high-speed tool steel

[0219] <Evaluation of Rotating Body and Toner> As shown in Tables 1-1, 1-2, 1-3, and 1-4, the corresponding rotating body was installed in the corresponding toner processing device, and external addition was repeatedly performed under the conditions shown in Table 2. The physical properties of the rotating body and the produced toner were confirmed after 1,000 sets, 5,000 sets, and 10,000 sets of external addition work were performed, respectively.

[0220] <Removal of processing material> After repeating the external additive treatment process a specified number of times, the state of the treated member was visually confirmed. A: No change from the initial state. No detachment or displacement. B: No detachment, but slight misalignment C: No detachment, but some misalignment has occurred. Misalignment has occurred in the vertical direction. D: Detached.

[0221] <Deformation of the fitting portion between the rotor body and the processing member, including the protruding portion> After repeating the external addition treatment step a predetermined number of times, the state of the protrusions was visually confirmed. A: No change from the original state, no deformation B: Very slight deformation, but no practical problems C: Deformed, but the rotor body and processing member can be fitted and separated. D: The rotor body and the processing member are deformed so much that they cannot be fitted or separated.

[0222] <Deformation and curling of the rotating body> After repeating the external addition treatment step a predetermined number of times, the condition of the rotor body was visually checked, particularly the portion of the rotor body that was to be fitted with the treatment member and the surrounding area. A: No change from the original state, no deformation. B: The rotor body is slightly deformed, but this does not affect its practical use. C: The rotor body is deformed, and the part that fits with the processing member is slightly curled up on the side facing in the direction of rotation of the rotor or the side facing opposite. D: Largely deformed, and the part that fits with the processing member is turned up on the side facing in the direction of rotation of the rotating body or the side facing opposite thereto.

[0223] <Wear of processing components> After repeating the external addition treatment step a predetermined number of times, the change in weight of the treated member was confirmed. A: Weight change is less than 0.10% B: Weight change is 0.10% or more and less than 0.50% C: Weight change is 0.50% or more but less than 1.00% D: Weight change is 1.00% or more

[0224] <Load when replacing processing parts> After repeating the external addition treatment process a predetermined number of times, the ease of replacing the rotor body and treatment members was checked. A: The weight of the replacement part is small, so only a small part is replaced. B: The weight of the replacement parts is small, but multiple parts need to be replaced or the replacement frequency is somewhat high. C: The weight of the replacement parts is small, but there are many replacement parts or the replacement frequency is high D: Replace the entire rotating body

[0225] <Toner clogging in the gap between the rotating body and the processing member> After repeating the external addition treatment step a predetermined number of times, it was visually confirmed whether or not the toner had become clogged in the gap where the rotor body and the treatment member were fitted together. A: There is no toner at all in the gaps or there is only a small amount of toner, but it does not cause any problems in practical use. B: Toner is stuck in the gap, causing deformation or misalignment of processing parts.

[0226] <Changes in adhesion index of additives in toner> After repeating the external additive treatment process a predetermined number of times, the amount of change in the adhesion index of the external additive of the first set of toner (the difference between the adhesion index of the first set and the adhesion index of each set to be evaluated) was evaluated. A: The difference in adhesion index is less than 0.3 B: The difference in adhesion index is 0.3 or more and less than 0.5 C: The difference in adhesion index is 0.5 or more and less than 0.8 D: The difference in adhesion index is 0.8 or more.

[0227] <Changes in the coverage of additives in toner> After repeating the external additive treatment process a predetermined number of times, the rate of change in the coating rate of the additive of the first set of toner was evaluated. A: Change in coverage is less than 1.0% B: Change in coverage is 1.0% or more but less than 2.0% C: Change in coverage is 2.0% or more but less than 3.0% D: Change in coverage is 3.0% or more

[0228] [Table 1-1]

[0229] [Table 1-2]

[0230] [Table 1-3]

[0231] [Table 1-4]

[0232] In the table, each item indicates the following: The numbers of the processing member shapes refer to the numbers of each rotating body in Figures 16-1, 16-2, and 16-3. "Position of starting point A" indicates whether starting point 113 of the convex portion exists between line E and line G (FIG. 11) (◯ if it exists, × if it does not). "Position of B end point" indicates whether end point 114 of the convex portion exists on the side of line G as viewed from line H (FIG. 11) (◯ if it exists, × if it does not). "C clamping shape" indicates whether the processing member is fitted with the rotor body in a manner that clamps the protrusion in the radial direction (◯ if fitted, × if not fitted). "D Support" indicates whether the rotating body has a support (◯ if yes, × if no). "E. Convexity of support" indicates whether or not the support has a convex portion (◯ if yes, × if no). "F Parallel surface" indicates whether the surface on the convex side (downstream side in the direction of rotation) of the convex portion of the support has a surface parallel to the surface on the convex side (downstream side in the direction of rotation) of the convex portion of the processing member (○ if yes, × if not). "G center of gravity" indicates whether the center of gravity of the processing member is located on the convex side of the convex portion (downstream in the direction of rotation) relative to the center of gravity of the protruding portion (◯ if located, × if not located). The number 500L indicates that the base equipment is the FM mixer, model FM500L, manufactured by Nippon Coke and Engineering Co., Ltd. The (1) in the fastener indicates whether it is fixed with a bolt pin or other fixing member in a direction parallel to the drive shaft. (If it is fixed, mark it with a circle.) The (2) of the fastener indicates whether it is fixed by a fixing means such as a screw from the radial inside to the radial outside of the rotating body (if fixed, it is marked with a circle). The hardness difference indicates the value of (hardness of the processing member)-(hardness of portion A).

[0233] [Table 2]

[0234] [Table 3-1]

[0235] [Table 3-2]

[0236] [Table 4] [Explanation of symbols]

[0237] 1: toner processing device, 10: processing chamber, 10a: inner peripheral surface (inner wall) of the processing chamber 10, 11: drive Shaft, 20: stirring blade as a lifting means, 21: blade portion of the stirring blade 20 extending from the center of rotation toward the outside (outward in the radial direction (outer diameter direction), outer diameter side), 30: rotor, 31: rotor main body, 31a: outer periphery of the rotor main body, 32: processing member, 50: drive motor, 51: drive belt, 60: control unit, 103: convex portion, 104: protruding portion, 105: support, 106: moment of inertia, 107: Impact, 108: centrifugal force, 109: screw or protrusion, 110: bolt or pin, 111: contact point between the protruding part and the outer periphery of the rotating body (side in the direction of rotation), 112: contact point between the protruding part and the outer periphery of the rotating body (side opposite to the direction of rotation), 113: convex start point, 114: convex end point, 115: center of gravity of the processing member, 116: contact point A, 117: contact point B, 118: center of gravity of the protruding part, 119: tangent line X of the processing member to the outer periphery of the rotating body at contact point A, 120: straight line C (straight line connecting the center of gravity of the protruding part to the drive shaft direction), 121: straight line parallel to the straight line C drawn from contact point A, 122: normal line Y to the tangent line X drawn from contact point A, 124: contact point between the end of the protruding part on the side in the direction of rotation of the rotating body and the outer periphery of the rotating body

Claims

1. A toner processing device for processing a processing target containing toner particles and an external additive, The toner processing device comprises: a processing chamber in which the object to be processed is accommodated; a drive shaft rotatably provided at the bottom of the processing chamber; A rotor supported by the drive shaft; Equipped with The rotating body is A rotating body, a protruding portion protruding radially outward from an outer periphery of the rotor main body; having the rotor has a processing member at the protruding portion for colliding with the object to be processed to process the object, The treatment member constitutes all or part of the protruding portion, The rotor body and the processing member are separable, The rotor main body has a protruding portion that is protruding in a direction in which the rotor rotates, The processing member is fitted into the protrusion.

23. A toner processing device comprising:

2. A toner processing device for processing a processing target containing toner particles and an external additive, The toner processing device comprises: a processing chamber in which the object to be processed is accommodated; a drive shaft rotatably provided at the bottom of the processing chamber; A rotor supported by the drive shaft; Equipped with The rotating body is A rotating body, a protruding portion protruding radially outward from an outer periphery of the rotor main body; having the rotor has a processing member at the protruding portion for colliding with the object to be processed to process the object, The treatment member constitutes all or part of the protruding portion, The rotor body and the processing member are separable, The rotor main body has a protruding portion that is protruding in at least one direction in a circumferential direction of the rotor, The processing member is fitted into the protrusion.

23. A toner processing device comprising:

3. The toner processing device according to claim 1 , wherein the processing member is fitted into the rotating body so as to sandwich the protrusion in a radial direction.

4. The rotating body has a support that protrudes from the rotating body side to the protruding portion side and supports the processing member from the starting point side of the protrusion of the protrusion portion. The toner processing device according to any one of claims 1 to 3.

5. The toner processing device according to claim 4 , wherein the support has the protrusions.

6. The surface of the support member on the side where the protrusion faces the protrusion has a surface parallel to the surface of the processing member on the side where the protrusion faces the protrusion. The toner processing device according to claim 4 or 5.

7. The processing member has a substrate and a coating layer on a surface of the substrate, the HRC hardness of the substrate is higher than the HRC hardness of the rotor body; The HRC hardness of the coating layer is higher than the HRC hardness of the substrate. The toner processing device according to any one of claims 1 to 6.

8. 8. The toner processing device according to claim 1, wherein the center of gravity of the processing member is located on the protruding direction side of the convex portion with respect to the center of gravity of the protruding portion.

9. A method for producing a toner containing toner particles containing a binder resin and an external additive, comprising the steps of: (i) producing the toner particles containing the binder resin; and (ii) a step of adding the external additive to the toner particles produced in the step (i) by using the toner processing device according to any one of claims 1 to 8. A toner manufacturing method comprising the steps of:

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