Process cartridge

Abstract

To provide a process cartridge which suppresses an in-plane density difference by stabilizing the amount of supply of toner to a developing roller and which can maintain excellent image quality without generating deterioration in the image quality such as image density reduction and fogging by stabilizing toner coating on the developing roller.SOLUTION: A process cartridge includes a developing roller 25, a toner supply roller 34, a toner regulation member 35, and toner. The developing roller has a surface moving in a direction opposite to a movement direction of a surface of the toner supply roller at a position of contact with the toner supply roller. The developing roller and the toner supply roller are formed in a manner to have a peripheral speed ratio R of 1.1 or more and 2.5 or less, and the toner to be used satisfies a predetermined regulation.SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present invention relates to a process cartridge for use in copying machines and printers using an electrophotographic system or an electrostatic recording system. [Background technology]

[0002] In an image forming apparatus such as a printer using an electrophotographic image forming method (electrophotographic process), an electrophotographic photoconductor (hereinafter referred to as "photoconductor") serving as an image carrier is uniformly charged, and the charged photoconductor is selectively exposed to light to form an electrostatic image on the photoconductor. The electrostatic image formed on the photoconductor is visualized as a toner image using toner as a developer. The toner image formed on the photoconductor is then transferred to a recording material such as recording paper or a plastic sheet, and the toner image transferred to the recording material is fixed to the recording material by applying heat or pressure, thereby recording an image. Such an image forming apparatus generally requires the supply of developer and the maintenance of various process means. In order to facilitate the supply of developer and the maintenance of various process means, a process cartridge has been put into practical use, in which a photoconductor, a charging means, a developing means, a cleaning means, etc. are integrated into a frame to form a cartridge that is detachably mountable to the main body of the image forming apparatus. The process cartridge system makes it possible to provide an image forming apparatus with excellent usability. In recent years, color image forming apparatuses that form color images using multiple color developers have become widespread. As color image forming apparatuses, so-called in-line type image forming apparatuses are known in which photoconductors corresponding to the respective image forming operations using multiple color developers are arranged in a line along the surface movement direction of a transfer target body to which a toner image is transferred. In-line type color image forming apparatuses include those in which multiple photoconductors are arranged in a line in a direction (for example, horizontal direction) that intersects with the vertical direction (gravity direction). The in-line type is a preferred image forming method in that it is easy to meet the demands for high-speed image formation and deployment to multifunction printers. There is an image forming apparatus in which a photoconductor is disposed below an intermediate transfer body as a transferee, or a recording medium carrier that conveys a recording medium as a transferee (Patent Document 1). When the photoconductor is disposed below the intermediate transfer body or recording medium carrier, for example, the fixing device and the developing device (or the exposure device) can be disposed at positions separated from each other in a manner in which the intermediate transfer body or the recording medium carrier is sandwiched between them within the image forming apparatus main body. Therefore, the developing device (or the exposure device) can be disposed at a position separated from the developing device, which has the advantage that the developing device (or the exposure device) is less susceptible to the heat of the fixing device. In recent years, there has been an increasing demand for improved productivity, and printers capable of high-speed printing are in demand. As a cartridge configuration that enables high-speed printing, a cartridge configuration has been proposed in which a developing roller is disposed as a recording material carrier, and a toner supply roller is disposed to supply developer to the developing roller, and the developing roller and the toner supply roller are brought into contact with each other with a difference in peripheral speed, thereby improving toner supply (Patent Documents 2 and 3). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2011-253203 A [Patent Document 2] JP 2015-41047 A [Patent Document 3] JP 2020-79902 A Summary of the Invention [Problem to be solved by the invention]

[0004] In order to enable even faster printing speeds with these proposed configurations, there were issues with the stability of toner supply and charging stability in high temperature and high humidity environments, and there were issues with in-plane density differences and density reductions, which are the difference in density between the top and bottom of the transfer material when developing a high-print image, and fog when printing in white (solid white image). The object of the present invention is to provide a process cartridge that can maintain good image quality without causing degradation of image quality such as a decrease in image density or fogging by stabilizing the amount of toner supplied to the developing roller, thereby suppressing in-plane density differences and stabilizing the toner coat on the developing roller. [Means for solving the problem]

[0005] The process cartridge of the present invention is a process cartridge that can be mounted in an image forming apparatus, The process cartridge has a developing chamber, The developing chamber comprises: a developing roller that develops the electrostatic latent image formed on the surface of the photosensitive drum with toner to form a toner image; a toner supply roller for supplying toner to the developing roller; a toner regulating member for regulating a thickness of a toner layer on the developing roller; Toner; having the surface of the developing roller is in contact with the surface of the toner supply roller, and the direction of movement of the surface of the developing roller is opposite to the direction of movement of the surface of the toner supply roller at a contact position between the surface of the developing roller and the surface of the toner supply roller; a toner supply roller having a surface that is in contact with a developing roller, the toner supply roller having a surface that is in contact with the developing roller, the toner supply roller having a surface that is in contact with the developing roller, the toner supply roller having a surface that is in contact with the developing roller, and the toner supply roller having a surface that is in contact with the developing roller. The developing roller and the toner supply roller have a peripheral speed ratio R represented by the following formula (E1): 1.1≦R≦2.5 It is configured to satisfy R=V RS / V D (E1) (In formula (E1), V RS represents the absolute value of the peripheral speed of the surface of the toner supply roller [m / sec], and V D represents the absolute value of the peripheral speed of the surface of the developing roller [m / sec].) The toner has toner particles and silica fine particles, The toner particles have a crystalline resin component, the content of the silica fine particles is 1.5 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the toner particles, The toner has a degree of cohesion of 70.0% or more and 99.0% or less, When a cross-section of the toner particle is observed using a transmission electron microscope, As is 1.0 area % or less when the average area ratio of the domains of the crystalline resin component in a surface region from the surface of the toner particle to a depth of 200 nm is defined as As. The present invention relates to a process cartridge. Effect of the Invention

[0006] According to the present invention, a process cartridge can be provided which provides stable image density and excellently suppresses in-plane density differences and suppresses fogged images even when printing at high speed in a high-temperature and high-humidity environment. [Brief description of the drawings]

[0007] [Figure 1] 1 is a schematic cross-sectional view of an image forming apparatus to which the present invention can be applied. [Diagram 2] 1 is a schematic cross-sectional view of a process cartridge according to an embodiment to which the present invention can be applied; [Diagram 3] 1 is a schematic cross-sectional view of a developing chamber according to an embodiment to which the present invention can be applied; [Figure 4] 1 is a conceptual cross-sectional view in a lateral direction of a developing blade according to an embodiment to which the present invention can be applied; [Diagram 5] 1A to 1C are diagrams illustrating a method of inputting driving force to a toner supply roller according to an embodiment to which the present invention can be applied. [Figure 6] 1 is a diagram showing the movement of toner in a developing device according to an embodiment to which the present invention can be applied; [Figure 7] 1 is a diagram illustrating the positional relationship between the inner wall of a developing chamber and a supporting end of a developing blade according to an embodiment to which the present invention can be applied. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The process cartridge according to the present invention will be described in more detail below with reference to the drawings. However, unless otherwise specified, the dimensions, materials, shapes, relative positions, etc. of the components described in this embodiment are not intended to limit the scope of the present invention to those alone. Furthermore, the materials, shapes, etc. of the members once described in the following description are the same as those described initially unless otherwise specified. Well-known or publicly known technologies in the relevant technical field can be applied to configurations and processes not particularly shown or described. Furthermore, duplicated descriptions may be omitted.

[0009] The expressions "XX or more and YY or less" or "XX to YY" representing a numerical range mean a numerical range including the endpoints, that is, the lower limit and the upper limit, unless otherwise specified.

[0010] When numerical ranges are stated in stages, the upper and lower limits of each numerical range can be combined in any way.

[0011] [Features of the present invention] In response to the above-mentioned problems, the present inventors have investigated a method for improving the stability of toner supply and charging stability in a cartridge configuration in which the moving direction of the surface of the developing roller is opposite to the moving direction of the surface of the toner supply roller.

[0012] As a result, it was found that the above problem can be solved by appropriately controlling the degree of aggregation of the toner, the state of the crystalline resin component, and the amount of silica microparticles as an external additive, when R represented by formula (E1) is within a certain range.

[0013] That is, the process cartridge of the present invention is a process cartridge that can be mounted in an image forming apparatus, The process cartridge has a developing chamber, The developing chamber comprises: a developing roller that develops the electrostatic latent image formed on the surface of the photosensitive drum with toner to form a toner image; a toner supply roller for supplying toner to the developing roller; a toner regulating member for regulating a thickness of a toner layer on the developing roller; Toner; having the surface of the developing roller is in contact with the surface of the toner supply roller, and the direction of movement of the surface of the developing roller is opposite to the direction of movement of the surface of the toner supply roller at a contact position between the surface of the developing roller and the surface of the toner supply roller; a toner supply roller having a surface that is in contact with a developing roller, the toner supply roller having a surface that is in contact with the developing roller, the toner supply roller having a surface that is in contact with the developing roller, the toner supply roller having a surface that is in contact with the developing roller, and the toner supply roller having a surface that is in contact with the developing roller. The developing roller and the toner supply roller have a peripheral speed ratio R represented by the following formula (E1): 1.1≦R≦2.5 It is configured to satisfy R=V RS / V D (E1) (In formula (E1), V RS represents the absolute value of the peripheral speed of the surface of the toner supply roller [m / sec], and V D represents the absolute value of the peripheral speed of the surface of the developing roller [m / sec].) The toner has toner particles and silica fine particles, The toner particles have a crystalline resin component, the content of the silica fine particles is 1.5 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the toner particles, The toner has a degree of cohesion of 70.0% or more and 99.0% or less, When a cross-section of the toner particle is observed using a transmission electron microscope, As is 1.0 area % or less when the average area ratio of the domains of the crystalline resin component in a surface region from the surface of the toner particle to a depth of 200 nm is defined as As. The process cartridge is characterized in that

[0014] The process cartridge of the present disclosure will be described in detail below.

[0015] [Image forming apparatus] Fig. 1 is a diagram showing a schematic configuration of an image forming apparatus 100 equipped with a process cartridge of the present invention, placed on a horizontal surface in the same position as when actually used. The image forming apparatus 100 is an in-line full-color laser printer that employs an intermediate transfer method. As shown in Fig. 1, four detachable process cartridges 70 (70Y, 70M, 70C, 70K) are mounted by mounting members (not shown). The upstream side of the process cartridges 70 in the mounting direction of the image forming apparatus 100 is defined as the front side, and the downstream side of the mounting direction is defined as the rear side.

[0016] Each process cartridge 70 includes an electrophotographic photosensitive drum (hereinafter referred to as photosensitive drum) 1 (1a, 1b, 1c, 1d). In each process cartridge 70, a charging roller 2 (2a, 2b, 2c, 2d), a developing roller 25 (25a, 25b, 25c, 25d), a cleaning member 6 (6a, 6b, 6c, 6d), and other process means are integrally arranged around the photosensitive drum 1. The charging roller 2 uniformly charges the surface of the photosensitive drum 1. The developing roller 25 develops the latent image formed on the photosensitive drum 1 with a developer (hereinafter referred to as toner) to make it visible. The cleaning member 6 removes the toner remaining on the photosensitive drum 1 after the toner image formed on the photosensitive drum 1 is transferred to a recording medium. The detailed configurations and positional relationships of the photosensitive drum 1, the charging roller 2, the developing roller 25, and the cleaning member 6 will be described later with reference to FIGS. 2 and 3.

[0017] Further, below the process cartridge 70 in the direction of gravity, a scanner unit 3 is provided for selectively exposing the photosensitive drum 1 based on image information and forming a latent image on the photosensitive drum 1.

[0018] A cassette 17 containing a recording medium S is attached to the lower part of the apparatus main body 100a. A recording medium conveying means is provided so that the recording medium S passes through a secondary transfer roller 69 and a fixing section 74 and is conveyed to the upper part of the apparatus main body 100a. An intermediate transfer unit 5 is provided above the process cartridges 70 (70Y, 70M, 70C, 70K) as an intermediate transfer means for transferring the toner images formed on the photosensitive drums 1 (1a, 1b, 1c, 1d). The intermediate transfer unit 5 has a drive roller 56, a driven roller 57, primary transfer rollers 58 (58a, 58b, 58c, 58d) at positions facing the photosensitive drums 1 of the respective colors, and an opposing roller 59 at a position facing the secondary transfer roller 69, and a transfer belt 50 is stretched over the intermediate transfer unit 5. The transfer belt 50 circulates so as to face and be in contact with all the photosensitive drums 1, and primary transfer is performed from the photosensitive drums 1 onto the transfer belt 50 by applying a voltage to primary transfer rollers 58 (58a, 58b, 58c, 58d). Then, the toner on the transfer belt 50 is transferred to the recording medium S by applying a voltage to an opposing roller 59 and a secondary transfer roller 69 arranged inside the transfer belt 50.

[0019] In forming an image, each photosensitive drum 1 is rotated, and the photosensitive drum 1, which is uniformly charged by the charging roller 2, is selectively exposed to light from the scanner unit 3. As a result, an electrostatic latent image is formed on the photosensitive drum 1. The latent image is developed by the developing roller 25. As a result, a toner image of each color is formed on each photosensitive drum 1. In synchronization with this image formation, the pair of registration rollers 55 conveys the recording medium S to a secondary transfer position where the opposing roller 59 and the secondary transfer roller 69 are in contact with each other with the transfer belt 50 interposed therebetween. Then, a transfer bias voltage is applied to the secondary transfer roller 69, so that the toner image of each color on the transfer belt 50 is secondarily transferred to the recording medium S. As a result, a color image is formed on the recording medium S. The recording medium S on which the color image has been formed is heated and pressed by the fixing unit 74, so that the toner image is fixed. Thereafter, the recording medium S is discharged to the discharge unit 75 by the discharge roller 72. The fixing unit 74 is disposed in the upper part of the device main body 100a.

[0020] [Process Cartridge] Next, a process cartridge 70 embodying the present invention will be described with reference to Fig. 2. Fig. 2 is a main cross section of the process cartridge 70 containing toner, in the orientation in which it is mounted in the image forming apparatus 100 in Fig. 1. Note that cartridge 70Y containing yellow toner, cartridge 70M containing magenta toner, cartridge 70C containing cyan toner, and cartridge 70K containing black toner all have the same configuration.

[0021] The process cartridge 70 includes a cleaning unit 26 and a developing unit 4. The cleaning unit 26 includes a photosensitive drum 1, a charging roller 2, and a cleaning member 6. The developing unit 4 includes a developing roller 25.

[0022] As described above, the charging roller 2 and the cleaning member 6 are disposed on the periphery of the photosensitive drum 1. The cleaning member 6 is composed of an elastic member 7 made of a rubber blade and a cleaning support member 8. The tip of the elastic member 7 made of a rubber blade is disposed in contact with the photosensitive drum 1 in the counter direction to the rotation direction of the photosensitive drum 1. Residual toner removed from the surface of the photosensitive drum 1 by the cleaning member 6 falls into a removed toner chamber 27.

[0023] The photosensitive drum 1 is rotated in response to an image forming operation by transmitting the driving force of a main body drive motor (not shown) serving as a drive source to the cleaning unit 26. At this time, a drum coupling fixed to the longitudinal end of the photosensitive drum 1 engages with a main body side coupling present on the longitudinal axis of the photosensitive drum 1, so that the driving force is input to the photosensitive drum 1. The charging roller 2 is rotatably attached to the cleaning unit 26 via a charging roller bearing, and is pressed toward the photosensitive drum 1 by a charging roller pressure member, and rotates following the photosensitive drum 1.

[0024] The developing unit 4 is composed of a developing roller 25 that rotates in contact with the photosensitive drum 1, and a developing frame 31 that supports the developing roller 25. The developing frame 31 is composed of a developing chamber 31b and a toner storage chamber 31a (toner storage section), and the toner storage section is disposed vertically below the developing chamber.

[0025] On the circumference of the developing roller 25, there are disposed a toner supply roller 34 which rotates in the direction of the arrow C in contact with the developing roller 25, and a regulating member (developing blade 35) for regulating the toner layer on the developing roller 25. In the embodiment described later, the outer diameter of the developing roller 25 is 12 mm, and the outer diameter of the toner supply roller 34 is 13.2 mm. In a cross section of the process cartridge in a plane perpendicular to the rotation axis of the toner supply roller in a state in which the process cartridge 70 is mounted in the image forming apparatus 100, an angle α between a straight line A connecting the rotation center 25e of the developing roller 25 and the rotation center 34e of the toner supply roller 34 and a horizontal line H is 9.85 degrees. However, the angle α is not limited to this, and is preferably 9.5 degrees or more and 10.3 degrees or less.

[0026] The developing unit 4 also receives the driving force of a main body drive motor (not shown) separate from the driving source of the cleaning unit, thereby rotating and driving the developing roller 25 and the toner supply roller 34 in response to the image forming operation. The driving force is input via a coupling, as with the cleaning unit 26, and will be described in detail later. The driving force input method using a coupling is preferable from the standpoint of rotational stability compared to driving force input via gears.

[0027] The developing roller 25 is an elastic roller in which a conductive elastic rubber layer having a predetermined volume resistance is provided as an elastic layer around a metal core. The developing roller 25 is composed of a base layer and a surface layer. Silicone rubber is used for the base layer, and urethane rubber is used for the surface layer, with urethane bead particles dispersed in the urethane rubber of the surface layer to set a desired roughness. The developing roller 25 and the photosensitive drum 1 rotate so that their surfaces move in the same direction (from bottom to top in this embodiment) at the opposing portion (contact portion). In the embodiment described later, toner negatively charged by frictional charging with respect to a predetermined DC bias applied to the developing roller 25 transfers only to the light potential portion due to the potential difference in the developing portion contacting the photosensitive drum 1, thereby visualizing the electrostatic latent image.

[0028] The developing blade 35 (regulating member) is disposed below the developing roller 25 and abuts against the developing roller 25 at a counter position, and regulates the coating amount of the toner supplied by the toner supply roller 34 and imparts an electric charge. In this embodiment, the developing blade 35 is composed of a flexible plate-like member and a developing blade support that fixes the plate-like member. The plate-like member is made of SUS (stainless steel) processed into a leaf spring shape with a thickness of 80 μm, and the abutment portion located at the free end of the plate-like member abuts against the developing roller 25 with a required abutment pressure.

[0029] The toner supplied onto the developing roller 25 is charged by friction between the developing blade 35 and the developing roller 25, and the toner layer thickness is regulated at the same time. In this embodiment, a predetermined voltage is applied to the developing blade 35 from a blade bias power source (not shown) to stabilize the toner coat.

[0030] The charged toner adheres to the surface of the developing roller 25 due to the image force with the developing roller 25. If the adhesion force of this toner to the surface of the developing roller 25 exceeds the regulating force of the developing blade 35, the toner coat on the developing roller 25 becomes disturbed (so-called "regulation failure"). When regulation failure occurs, image defects such as toner adhering to the white background of the image or abnormal density occur.

[0031] Here, the developing blade 35 will be described in detail. As shown in Fig. 7, the developing blade 35 is composed of a supporting metal plate 35a (blade supporting portion) made of stainless steel and a flexible plate-like member 35b (blade portion). The plate-like member is integrated with the supporting metal plate by YAG laser welding. Fig. 4 is a conceptual diagram of a cross section in the short side direction at the tip of the free end of the developing blade 35 according to the present invention. Surface 811 in Fig. 4 is the surface that mainly comes into contact with the developing roller 25.

[0032] 3 is an enlarged schematic cross-sectional view of the inside of the developing chamber 31b, showing the posture in which the problem of the present invention occurs. Although details will be described later, the toner supply roller 34 rotates in the C direction to supply toner to the developing roller 25, but since the contact portion between the developing roller 25 and the toner supply roller 34 contains an upward component, the supplied toner is affected by gravity, which is an unfavorable configuration for supplying toner to the developing roller.

[0033] 4, in this embodiment, a part of the "tip edge portion 818" on the tip (free end) side of the plate-shaped member 35b that is to come into contact with the developing roller 25 is scraped off by polishing. The scraped-off portion is formed over the entire longitudinal area of ​​the plate-shaped member.

[0034] The developing blade 35 is provided at a free end of the plate-shaped member 35b in the short side direction, and has a contact portion for contacting the surface of the developing roller 25.

[0035] More specifically, before the end of the developing blade 35 is ground, a first surface 811 (first portion) which is a surface that contacts the developing roller 25 in a cross section perpendicular to the longitudinal direction intersects with a third surface 813 (third portion) perpendicular to the first surface 811, forming the above-mentioned "end edge portion 818". Then, by performing the grounding process, the end edge portion 818 is scraped off, and a second surface 812 (second portion) which connects the first surface 811 and the third surface 813 is formed. In the state after the grounding process, the point at the end of the first surface 811 on the free end side is designated as point A, and the point at the end of the second surface 812 on the free end side is designated as point B. Also, a virtual line extending the first surface 811 in the free end direction is designated as L1. Also, a point at which a virtual line L2 which is perpendicular to the virtual line L1 and passes through point B intersects with the virtual line L1 is designated as point C. In this case, the distance between point B and point C is defined as h1, and the distance between point A and point C is defined as d1. In the embodiment described later, h1=15 μm, and d1=40 μm.

[0036] Here, the method of polishing the developing blade 35 used in the present invention will be described. The plate-like member before being joined to the support member is fixed to the base by being sandwiched between the base and the pressing member. The tip of the plate-like member is in contact with the polishing film wrapped around a rubber roller under a load. In the examples described later, a lapping film sheet with a grain size of #800 is used as the polishing film, and a load of 500 g is applied to the rubber roller.

[0037] The polishing film on the rubber roller is arranged in a fixed state, and as the base moves left and right in the longitudinal direction, the tip of the plate-like member is rubbed against the polishing film and finely scraped off.

[0038] The amount of scraping of the plate-like member is proportional to the distance of rubbing with the polishing film, and the longer the rubbing distance, the greater the amount of scraping, and the shorter the distance, the less the amount of scraping. In other words, by controlling the amount of movement of the base, the amount of scraping of the tip edge of the plate-like member can be changed. The above polishing method is one example, and is not limited to this as long as the tip shape of the developing blade can be processed into a desired shape.

[0039] The toner supply roller 34 is in contact with the developing roller 25 at a nip portion N2 (FIG. 6 described later), and is rotated in response to the image forming operation by receiving the driving force of a driving motor (not shown). This will be described in detail with reference to FIG.

[0040] The driving force from the main body drive motor is transmitted to a coupling 201 (driving force receiving portion) provided at the shaft end of the toner supply roller 34, and the driving force is transmitted to the toner supply roller 34 via an intermediate body 202 and a driving force transmission member 203 (the intermediate body 202 and the driving force transmission member 203 are a first driving force transmission portion). The driving force of the toner supply roller 34 is transmitted to the developing roller 25 by gears (204a to 204c) provided between the toner supply roller 34 and the developing roller 25, and the developing roller 25 rotates (the gear 204c is a second driving force transmission portion, and the gear 204a is a third driving force transmission portion). In detail, the driving force is transmitted to the idler gear 204b by the rotation of the gear 204c fixed to the toner supply roller 34, and the idler gear 204b rotates. The driving force is transmitted to the gear 204a fixed to the developing roller 25 by the rotation of the idler gear 204b, and the developing roller 25 rotates together with the gear 204a.

[0041] 1 and 2, the driving force from the apparatus main body 100a to the developing unit 4 is input from the longitudinal axis of the toner supply roller 34, but if the driving force from the apparatus main body 100a to the developing unit 4 were input from the longitudinal axis of the developing roller 25, the driving input positions to the cleaning unit 26 and the developing unit 4 would be close to each other due to the relationship of developing by contacting the photosensitive drum 1 and the developing roller 25. With such an input portion arrangement, it is difficult to simply configure the driving input portion of the apparatus main body 100a, and is not preferable when configuring a more stable driving input portion at low cost.

[0042] In contrast, in this embodiment, the driving force to the developing unit 4 is input from the longitudinal axis of the toner supply roller 34, so that the distance between the driving force input position to the cleaning unit 26 and the driving force input position to the developing unit 4 can be increased, which is more preferable when configuring the driving force input portion of the device main body 100a.

[0043] On the other hand, the configuration in which the driving force from the apparatus main body 100a is transmitted to the developing roller 25 via the toner supply roller 34 requires the passage of multiple gears to drive the developing roller 25, and therefore the rotation stability of the developing roller 25 is inferior to the configuration in which the driving force is transmitted to the developing roller 25. As a result, the regulating force of the developing blade 35 may become unstable, and this configuration is disadvantageous in terms of regulating failure.

[0044] In addition, the toner supply roller 34 and the developing roller 25 rotate in opposite directions with a peripheral speed difference at the nip portion N2. This operation recovers the remaining toner on the developing roller 25 while supplying toner to the developing roller 25.

[0045] In the present invention, the peripheral speed of the toner supply roller 34 in the nip portion N2 is V RS , the peripheral speed of the developing roller 25 is V D When this is set, the rotor rotates so that the peripheral speed ratio R shown in the following formula (E1) satisfies 1.1≦R≦2.5. R=V RS / V D (E1) (In formula (E1), V RS represents the absolute value of the peripheral speed of the surface of the toner supply roller [m / s], and V D represents the absolute value of the peripheral speed of the surface of the developing roller [m / s].

[0046] In other words, if the radius of the toner supply roller 34 is rRS, the rotational angular velocity is ωRS, the radius of the development roller 25 is rD, and the rotational angular velocity is ωD, then the relationship between the toner supply roller 34 and the development roller 25 is expressed by the following formula (E2): λ=ωRS / ωD) (E2) (In formula (E2), ωRS represents the rotational angular velocity [rad / sec] of the toner supply roller, and ωD represents the rotational angular velocity [rad / sec] of the developing roller.) This means that the rotational angular velocity ratio λ expressed by is 1.1≦λ×rRS / rD≦2.5, and in the embodiment described later, the radius of the toner supply roller is 3.3 mm and the radius of the developing roller is 3.0 mm, so that λ≈1.14.

[0047] By setting the peripheral speed ratio R to 1.1≦R≦2.5, when performing high-speed development, the rotation speed of the toner supply roller is fast relative to the development roller, so the toner supply speed to the development roller is sufficiently fast and the opposing speed between the development roller and the toner supply roller is large, so that the toner supplied in an aggregated state on the development roller can be disintegrated by the toner supply roller. A more preferable range for R is 1.2≦R≦1.5.

[0048] If the peripheral speed ratio R is less than 1.1, when the toner is supplied to the developing roller in an aggregated state, the opposing speed of the developing roller and the toner supply roller is insufficient to break down the toner. This causes the coating state on the developing roller to become disturbed, resulting in a loss of charge uniformity and the occurrence of fogging. On the other hand, if the peripheral speed ratio R is greater than 2.5, the toner on the developing roller is sufficiently broken down, but the toner supply speed exceeds the supply speed of the toner to the developing chamber, causing the toner supply on the developing roller to be insufficient. This makes it easy for the image density to decrease, and furthermore, the in-plane density difference is likely to occur due to the lack of stability in the toner supply.

[0049] Furthermore, by adjusting the potential difference between the toner supply roller 34 and the developing roller 25, the amount of remaining toner collected on the developing roller 25 and the amount of toner supplied to the developing roller 25 can be adjusted.

[0050] Further, the toner supply roller 34 and the developing roller 25 are in contact with each other with a predetermined intrusion amount, that is, the indentation amount ΔE by which the toner supply roller 34 is made in a concave shape by the developing roller 25 .

[0051] The toner supply roller 34 comprises a conductive support and a foam layer supported by the conductive support. Specifically, the conductive support is a core metal electrode having an outer diameter of φ5 (mm), and a foamed urethane layer is provided around the core metal electrode as a foamed layer made of open cells (open cells) in which air bubbles are connected to each other, and the roller rotates in the direction of C in the figure. By making the urethane surface layer open cells in this way, a large amount of toner can enter the inside of the toner supply roller 34. The resistance of the toner supply roller 34 in the embodiment described later is 1×10 9 (Ω).

[0052] In the embodiment described later, the amount of penetration of the toner supply roller 34 into the developing roller 25, that is, the amount of depression ΔE by which the toner supply roller 34 is made concave by the developing roller 25, is set to 1.0 mm.

[0053] Here, a method for measuring the resistance of the toner supply roller 34 will be described. The toner supply roller 34 is brought into contact with an aluminum sleeve having a diameter of 30 mm so that the intrusion amount, which will be described later, is 1.5 mm. By rotating this aluminum sleeve, the toner supply roller 34 is rotated at 30 rpm relative to the aluminum sleeve.

[0054] Next, a DC voltage of -50V is applied to the developing roller 25. At this time, a resistor of 10 kΩ is provided on the earth side, and the current is calculated by measuring the voltage across the resistor, and the resistance of the toner supply roller 34 is calculated. In this embodiment, the surface cell diameter of the toner supply roller 34 is set to 50 μm to 1000 μm.

[0055] Here, the cell diameter refers to the average diameter of foam cells in an arbitrary cross section, and the area of ​​the largest foam cell is measured from an enlarged image of the arbitrary cross section, and the maximum cell diameter is obtained by converting this area into a diameter equivalent to a perfect circle. After removing foam cells that are 1 / 2 or less of this maximum cell diameter as noise, the remaining individual cell areas are similarly converted to obtain the average cell diameter.

[0056] The toner supplied from the toner supply roller 34 to the surface of the developing roller 25 is frictionally charged by the rubbing between the developing blade 35 and the developing roller 25, and the layer thickness is regulated while the toner is given an electric charge. The toner is then transported to the contact portion (developing portion) between the photosensitive drum 1 and the developing roller 25, and transferred to the light potential portion. Residual toner remaining on the surface of the developing roller 25 returns to the developer container, is collected from the surface of the developing roller 25 by the toner supply roller 34, and is stored inside the toner supply roller 34.

[0057] Here, the flow of toner inside the developing chamber 31b will be described with reference to Fig. 6. Fig. 6 is an enlarged schematic cross-sectional view of the inside of the developing chamber 31b, and shows the movement of toner transported to the toner supply roller 34 by the toner transport member 36 shown in Fig. 2.

[0058] A portion of the toner G transported to the upper portion of the toner supply roller 34 by the toner transport member 36 is sucked into the inside of the toner supply roller 34 due to the restoration of the toner supply roller 34 on the downstream side of the rotation of the nip portion N2 (F1), and is stored inside the toner supply roller 34 together with the remaining toner collected from the surface of the developing roller 25 and stored inside the toner supply roller 34. Then, due to the rotation of the toner supply roller 34 in the C direction, the toner G is transported to the downstream side of the rotation of the toner supply roller 34 at the nip portion N2. On the downstream side of the rotation of the toner supply roller 34, the toner supply roller 34 comes into contact with the developing roller 25, causing the toner supply roller 34 to deform, causing the toner stored inside to be expelled (F2).

[0059] The toner discharged from the toner supply roller 34 that does not reach the surface of the developing roller 25 is gradually transported by the propulsion force toward the developing opening (opening) due to the ejection force from the toner supply roller 34, and passes through the developing opening and is returned to the toner storage chamber 31a (F3).

[0060] In this way, the toner circulates smoothly between the developing chamber 31b and the toner storage chamber 31a, thereby suppressing toner deterioration, and even when images with low print coverage are output continuously, the occurrence of toner aggregation is suppressed, making it possible to stably output high-quality images.

[0061] Here, if the flow (F3) of toner returning to the toner storage chamber 31a becomes insufficient, the toner is pressed down and aggregates in the area below the toner supply roller 34 and the developing roller 25. Then, the toner enters the nip portion N2 between the toner supply roller 34 and the developing roller 25, and the contact of the toner supply roller 34 with the developing roller 25 becomes insufficient. An area occurs where the remaining toner on the developing roller 25 cannot be sufficiently collected by the toner supply roller 34, and a specific toner is carried around by the developing roller 25 and passes through the contact portion between the developing blade 35 and the developing roller 25 more than necessary, resulting in the generation of toner that is excessively charged. As a result, the adhesion force of the toner exceeds the regulating force of the developing blade 35, and a regulating failure may occur.

[0062] This phenomenon is likely to occur, for example, when images with a low printing rate are continuously output in a low-temperature, low-humidity environment. This is because the residual toner collected from the developing roller 25 by the toner supply roller 34 accumulates in the developing chamber 31b. The residual toner collected from the developing roller 25 is charged, so the toner particles tend to electrostatically clump together. This reduces the fluidity of the toner in the developing chamber 31b, making the flow of toner (F3) returning to the toner storage chamber 31a insufficient, and creating a state in which toner clumping is likely to occur in the areas below the toner supply roller 34 and the developing roller 25.

[0063] In response to this, there is a method of arranging a toner transport member below the toner supply roller 34 in the developing chamber 31b, thereby creating a toner flow (F3) that returns to the toner storage chamber 31a. However, when a toner transport member is provided in the developing chamber 31b, the toner deteriorates due to friction between the toner and the toner transport member in the developing chamber 31b, and toner fusion to the developing roller 25 was observed when images with a low printing ratio were continuously output. In addition, since it is necessary to provide a toner transport member as an additional member in addition to the toner supply roller 34 in the developing chamber 31b, the device configuration becomes complicated. Therefore, in the embodiment described below, no members that are driven by motor drive are provided in the developing chamber 31b other than the developing roller 25 and the toner supply roller 34.

[0064] In addition, in a configuration in which only the developing roller 25 and the toner supply roller 34 are arranged in the developing chamber 31b, in order to efficiently use the toner in the developing chamber 31b, the inner wall of the developing chamber 31b is set as follows relative to the toner supply roller 34. This will be specifically explained with reference to FIG.

[0065] 7, R1 and R2 indicate tangents (vertical lines) to the outer peripheral surface of the toner supply roller 34 that extends in the vertical direction. Furthermore, horizontal line H2 indicates a horizontal line that passes through the support end of the developing blade 35. In the region between R1 and R2 of the inner wall of the developing chamber 31b, at least a portion is arranged to be vertically above the horizontal line H2 (region 138 in the figure). This makes it possible to further reduce the amount of toner remaining in the developing chamber 31b that is not used for printing, and toner in the developing chamber 31b can be used efficiently.

[0066] As shown in FIG. 2, a blowout prevention sheet 20 is disposed as a developer contact sheet for preventing toner from leaking from the developing frame 31 in contact with the developing roller 25.

[0067] Further, the toner storage chamber 31a of the developing frame 31 is provided with a toner transport member 36 for stirring the stored toner and transporting the toner to the toner supply roller 34. As shown in Fig. 2, the toner transport member 36 is composed of a stirring shaft 36a that can be rotated by a driving force from the apparatus main body 100a, and a sheet member 36b that is attached to the stirring shaft 36a and rotates together with the stirring shaft 36a, and the sheet member 36b has elasticity.

[0068] Next, the toner transport of the developing unit will be described. In the toner storage chamber 31a, the sheet member 36b of the toner transport member is provided so that the free end of the toner transport member contacts the wall surface of the toner storage section in an area A upstream of the opening 31c (communication port) in the rotation direction of the toner transport member. In addition, the sheet member 36b deforms against elasticity as the toner transport member rotates so that the free end side is located upstream of the rotation direction of the toner transport member rather than the rotation shaft side.

[0069] That is, as the sheet member 36b rotates, it comes into contact with the deformed portion 31a1 on the inner surface of the toner storage chamber. This causes the sheet member 36b to receive force from the deformed portion 31a1. As a result, the sheet member 36b deforms against the elastic force of the sheet member 36b. Furthermore, as the sheet member 36b rotates in contact with the deformed portion 31a1, the toner is carried on the surface downstream in the rotation direction and conveyed. In this embodiment, the deformed portion 31a1 refers to the portion of the inner wall of the toner storage chamber up to the point where the sheet member 36b leaves the wall, as shown in FIG. 2 (also referred to as region A).

[0070] Furthermore, at a predetermined position (also referred to as position B) in the restoring portion 31a2 downstream of the region A in the rotation direction of the toner transport member and upstream of the opening in the rotation direction of the toner transport member, the free end of the toner transport member is released from contact with the wall surface of the toner storage portion. At that time, the deformed toner transport member is restored by elasticity, and the transported toner flies toward the communication opening. In this embodiment, the restoring portion 31a2 is disposed above a horizontal plane including the rotation axis of the agitator.

[0071] Therefore, after the tip of the free end side of the sheet member 36b passes through the deformation portion 31a1 as the sheet member 36b rotates, the contact with the inner wall of the sheet member 36b is released at the restoration portion 31a2. Then, the sheet member 36b is released from the state in which it was deformed by the deformation portion 31a1 and is restored to its natural state (original shape) by its own elastic restoring force. Due to the shape change of the sheet member 36b in the restoration direction, the toner carried and transported on the sheet member 36b flies against gravity toward the opening 31c. This opening 31c is located downstream of the restoration portion 31a2 in the rotation direction of the sheet member 36b. A part of the toner that flies toward the opening 31c is transported into the developing chamber 31b. On the other hand, the toner that does not reach the developing chamber 31b falls into the toner storage chamber 31a and remains at the bottom of the toner storage chamber 31a, and returns to its original state. By repeating this cycle, the toner is stirred and transported.

[0072] In addition, the boundary between the deformation portion 31a1 and the restoration portion 31a2 is located below the lower end of the opening 31c (communication port), and when viewed from the axial direction of the developing roller 25, the center of rotation of the toner transport member 36 and the center of rotation of the developing roller 25 are on the same side of a vertical line passing through the boundary, and the maximum value of the radius of rotation of the toner transport member 36 is greater than the distance between the center of rotation of the transport member and the lower end of the communication port.

[0073] The configuration having the deformation portion 31a1 and the restoration portion 31a2 as described above is advantageous for increasing the efficiency of transporting toner to the developing chamber 31b, but is prone to obstructing the flow of toner (F3) returning to the toner storage chamber, making it prone to regulation failure.

[0074] In the embodiment described later, the length of the sheet member 36b in the direction of the rotation radius of the rotation axis in the natural state is set to be longer than the distance from the rotation axis to the lower end of the developing opening in the same direction. This configuration is advantageous for increasing the efficiency of transporting toner to the developing chamber 31b, but it is likely to obstruct the flow (F3) of toner returning to the toner storage chamber 31a, and is therefore likely to cause regulation failure.

[0075] In the embodiment described later, two sets of sheet members 36b are attached at different positions on the agitator shaft 36a so that a sufficient amount of toner can be transported from the toner storage chamber 31a to the developing chamber 31b. This configuration is advantageous for increasing the efficiency of transporting toner to the developing chamber 31b, but it is likely to obstruct the flow (F3) of toner returning to the toner storage chamber 31a, and is therefore likely to cause regulation problems.

[0076] 〔toner〕 Next, the toner of the present disclosure will be described in detail.

[0077] In the above-mentioned cartridge configuration, the above problems can be solved by using a toner that exhibits the following characteristics.

[0078] That is, the toner is composed of toner particles and silica fine particles. The toner particles have a crystalline resin component, the content of the silica fine particles in the toner is 1.5 parts by mass or more and 5.0 parts by mass or less per 100 parts by mass of the toner particles; The toner has a cohesion of 70.0% or more and 99.0% or less, The toner particle is characterized in that, when a cross-section of the toner particle is observed using a transmission electron microscope, As is 1.0 area % or less, where As is the average area ratio of the domains of the crystalline resin component in a surface region from the surface of the toner particle to a depth of 200 nm.

[0079] Here, the toner in the cartridge of the present invention is characterized by having a high degree of cohesion of 70.0% or more and 99.0% or less. It is believed that if the degree of cohesion is within the above range, the toner is supported on the surface of the toner supply roller in a state of forming an aggregate in the cartridge configuration of the present invention, and the amount of toner supplied to the developing roller increases, resulting in high concentration stability. If the degree of cohesion is less than 70.0%, the aggregates of toner supported on the toner supply roller will collapse when the speed is increased, resulting in insufficient toner transport force and poor concentration stability. On the other hand, if the degree of cohesion is greater than 99.0%, the cohesion force of the toner will be too high, making it difficult for the toner supply roller to break down the toner on the developing roller. As a result, the coating property on the developing roller will be disturbed, the charge of the toner will become unstable, and fogging will easily occur. The degree of cohesion of the toner is preferably 75.0% or more and 97.5% or less, more preferably 80.0% or more and 95.0% or less.

[0080] It has also been suggested that the high cohesion of the toner is due to the contact between the surfaces of the toner particles when they come into contact with each other, and is therefore largely dependent on the amount of silica fine particles that impart fluidity to the toner.

[0081] Furthermore, when a cross-section of the toner particle is observed using a transmission electron microscope, and As is the average ratio of the area occupied by the domains of the crystalline resin component in the surface region from the surface of the toner particle to a depth of 200 nm, by having As be 1.0 area % or less, the toner aggregates in the nip portion between the developing roller and the toner supply roller can be easily disintegrated, the toner supplied to the developing roller can be uniformly coated, and fogging is less likely to occur.

[0082] The domain of the crystalline resin component is a portion where the crystalline resin component is in a crystallized state. On the other hand, a non-crystallized crystalline resin component may be present around the domain of the crystalline resin component. Therefore, the resin around the domain of the crystalline resin component has poor mechanical strength and heat resistance compared to the resin in the portion where no domain exists. In the present invention, it is presumed that the absence of a domain of the crystalline resin component around the toner surface improves the disintegration property of the aggregated toner particles.

[0083] Therefore, by controlling the toner particles so that the domains of the crystalline resin component present near the surface of the toner particles are not present near the surface layer, excellent crushability is achieved under pressure while maintaining high cohesiveness. On the other hand, if As is greater than 1.0 area %, the crystals of the crystalline resin component are present in large amounts on the surface layer, which leads to a decrease in cohesive force and poor crushability. In addition, this crushability is further assisted by the amount of silica fine particles. A more preferable range of As is 0.5 area % or less.

[0084] In addition, the toner used in the cartridge of the present invention preferably has an exposure rate Bs of 55.0 area % or more and 80.0 area % or less, when the average area ratio of the toner particle surface portion not covered with silica microparticles when observed with a scanning electron microscope (SEM) is defined as the exposure rate Bs.

[0085] If the exposure rate Bs is in the above range, the toner shows better disintegration properties while controlling the degree of aggregation in a suitable range, and more preferably, it is 60.0 area % or more and 75.0 area % or less.

[0086] In order to achieve the above-mentioned amount of external additive and exposure rate Bs, the number average major axis of the silica fine particles is preferably 30 nm or more and 150 nm or less, and more preferably 50 nm or more and 120 nm or less.

[0087] Next, the crystalline resin component will be described.

[0088] The crystalline resin component refers to a material that has an endothermic peak when measured in accordance with ASTM D3418-82 using a differential scanning calorimeter (e.g., "Q1000" (manufactured by TA Instruments)). The crystalline resin component refers to an additive that has a component that crystallizes in the resin contained in the toner particles.

[0089] The domain of the crystalline resin component can be controlled by the compatibility between the resin contained in the toner and the crystalline resin component, the cooling conditions in the toner production process, and the annealing process that promotes crystallization of the crystalline resin component.

[0090] Specifically, it refers to known waxes and crystalline resins. In particular, crystalline resin components such as ester wax and crystalline polyester are preferred. These materials are compatible with resins used in toner particles, such as styrene acrylic resins and polyester resins, and also undergo phase separation in the toner to form a crystalline state. By eliminating the exposure of these crystalline components, both high coagulation properties and excellent disintegration properties are achieved.

[0091] The toner particles preferably contain an amorphous polyester, and the weight average molecular weight of the amorphous polyester is preferably 25,000 or more and 75,000 or less.

[0092] Since the amorphous polyester forms a resin structure by ester groups, it can exert cohesive force by the interaction due to the polarity caused by the ester groups. If the weight average molecular weight is 25,000 or more, it is excellent in disintegration property, and if it is 75,000 or less, it is excellent in increasing cohesive force.

[0093] Furthermore, the acid value of the amorphous polyester is preferably 10.0 mgKOH / g or more and 30.0 mgKOH / g or less.

[0094] When the acid value of the amorphous polyester is 10.0 mgKOH / g or more, the charge stability is excellent, while when it is 30.0 mgKOH / g or less, electrostatic aggregation is suppressed, the aggregates are disintegrated, and the charge uniformity is excellent. Therefore, when the acid value of the amorphous polyester is 10.0 mgKOH / g or more and 30.0 mgKOH / g or less, better fogging suppression performance can be obtained.

[0095] The toner particles preferably contain boron, and if the amount of boron present is from 0.1 ppm by mass to 100.0 ppm by mass, it is preferable to obtain toner particles having high cohesive force and excellent crushability.

[0096] This is thought to be because boron atoms have a large ionization potential and are easy to form covalent bonds, which interact with the many ester groups in polyester resins. As a result, it is speculated that polyester resins containing boron atoms form a pseudo-crosslinked state, which gives the resin elasticity while maintaining its viscosity. In particular, when boron forms an oxide, it becomes amphoteric, which makes it easy to form strong interactions with the carboxylic acid in polyester, which makes the toner cohesive force due to the adhesiveness of the polyester resin and the crushability due to its elasticity better.

[0097] The amount of boron atoms present in the toner particles is more preferably 1.0 ppm by mass or more and 30.0 ppm by mass or less.

[0098] [Toner components] Each component constituting the toner and the method for producing the toner will be described in more detail.

[0099] <Resin> The toner particles contain a resin, and the content of the resin is preferably 50% by mass or more based on the total amount of the resin components in the toner particles.

[0100] The resin is not particularly limited, and examples thereof include styrene acrylic resin, epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, mixed resins and composite resins thereof, etc. Styrene acrylic resin and polyester resin are preferred because they are inexpensive, easily available, and have excellent low-temperature fixing properties.

[0101] (polyester resin) The polyester resin can be obtained by combining suitable compounds selected from polyvalent carboxylic acids, polyols, hydroxycarboxylic acids, etc., and synthesizing them using a conventionally known method such as an ester exchange method or a polycondensation method.

[0102] Polycarboxylic acids are compounds containing two or more carboxy groups in one molecule. Among them, dicarboxylic acids are compounds containing two carboxy groups in one molecule and are preferably used.

[0103] Examples of dicarboxylic acids include oxalic acid, succinic acid, glutaric acid, maleic acid, adipic acid, β-methyladipic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-carboxylic acid, hexahydroterephthalic acid, malonic acid, pimelic acid, suberic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediacetic acid, o-phenylenediacetic acid, diphenylacetic acid, diphenyl-p,p'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracenedicarboxylic acid, and cyclohexanedicarboxylic acid.

[0104] Examples of polyvalent carboxylic acids other than dicarboxylic acids include trimellitic acid, trimesic acid, pyromellitic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, pyrene tricarboxylic acid, pyrene tetracarboxylic acid, itaconic acid, glutaconic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid, n-octyl succinic acid, n-octenyl succinic acid, etc. These may be used alone or in combination of two or more.

[0105] A polyol is a compound containing two or more hydroxyl groups in one molecule. Among them, a diol is a compound containing two hydroxyl groups in one molecule, and is preferably used.

[0106] Specifically, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosandecanediol, diethylene glycol, Examples of the bisphenols include triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-butenediol, neopentyl glycol, 1,4-cyclohexanediol, polytetramethylene glycol, hydrogenated bisphenol A, bisphenol A, bisphenol F, bisphenol S, and alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above bisphenols.

[0107] Among these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and their combined use with alkylene glycols having 2 to 12 carbon atoms.

[0108] Examples of trivalent or higher polyols include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, hexamethylolmelamine, hexaethylolmelamine, tetramethylolbenzoguanamine, tetraethylolbenzoguanamine, sorbitol, trisphenol PA, phenol novolac, cresol novolac, alkylene oxide adducts of the above trivalent or higher polyphenols, etc. These may be used alone or in combination of two or more.

[0109] (styrene acrylic resin) Examples of the styrene-acrylic resin include homopolymers made of the following polymerizable monomers, copolymers obtained by combining two or more of these, and mixtures thereof.

[0110] Styrenic monomers such as styrene, α-methylstyrene, β-methylstyrene, o-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; (Meth)acrylic monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, dimethyl phosphate ethyl (meth)acrylate, diethyl phosphate ethyl (meth)acrylate, dibutyl phosphate ethyl (meth)acrylate and 2-benzoyloxyethyl (meth)acrylate, (meth)acrylonitrile, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid, maleic acid; Vinyl ether monomers such as vinyl methyl ether and vinyl isobutyl ether; Vinyl ketone monomers such as vinyl methyl ketone, vinyl ethyl ketone, and vinyl isopropenyl ketone; Polyolefins such as ethylene, propylene, and butadiene.

[0111] The styrene acrylic resin may use a polyfunctional polymerizable monomer as required. Examples of the polyfunctional polymerizable monomer include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 2,2'-bis(4-((meth)acryloxydiethoxy)phenyl)propane, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, divinylbenzene, divinylnaphthalene, and divinyl ether.

[0112] In order to control the degree of polymerization, it is also possible to further add a known chain transfer agent and polymerization inhibitor.

[0113] Examples of the polymerization initiator for obtaining the styrene-acrylic resin include organic peroxide-based initiators and azo-based polymerization initiators.

[0114] Examples of the organic peroxide initiator include benzoyl peroxide, lauroyl peroxide, di-α-cumyl peroxide, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, bis(4-t-butylcyclohexyl)peroxydicarbonate, 1,1-bis(t-butylperoxy)cyclododecane, t-butylperoxymaleic acid, bis(t-butylperoxy)isophthalate, methyl ethyl ketone peroxide, tert-butylperoxy-2-ethylhexanoate, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, and tert-butylperoxypivalate.

[0115] Examples of the azo polymerization initiator include 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobismethylbutyronitrile, and 2,2'-azobis-(methyl isobutyrate).

[0116] Furthermore, a redox initiator, which is a combination of an oxidizing substance and a reducing substance, can also be used as the polymerization initiator.

[0117] Oxidizing substances include inorganic peroxides such as hydrogen peroxide, persulfates (sodium, potassium and ammonium salts) and oxidizing metal salts such as tetravalent cerium salts.

[0118] Examples of reducing substances include reducing metal salts (divalent iron salts, monovalent copper salts, and trivalent chromium salts), ammonia, lower amines (amines having from 1 to 6 carbon atoms, such as methylamine and ethylamine), amino compounds such as hydroxylamine, reducing sulfur compounds such as sodium thiosulfate, sodium hydrosulfite, sodium hydrogensulfite, sodium sulfite, and sodium formaldehyde sulfoxylate, lower alcohols (having from 1 to 6 carbon atoms), ascorbic acid or a salt thereof, and lower aldehydes (having from 1 to 6 carbon atoms).

[0119] The polymerization initiator is selected with reference to its 10-hour half-life temperature and is used alone or in combination. The amount of polymerization initiator added varies depending on the desired degree of polymerization, but is generally 0.5 to 20.0 parts by mass per 100.0 parts by mass of polymerizable monomer.

[0120] <Release agent> The toner may contain a known wax as a releasing agent.

[0121] Specific examples include petroleum waxes and derivatives thereof, such as paraffin wax, microcrystalline wax, and petroleum-based waxes represented by petrolatum, montan wax and derivatives thereof, hydrocarbon waxes produced by the Fischer-Tropsch process and derivatives thereof, polyolefin waxes and derivatives thereof, such as polyethylene, and natural waxes and derivatives thereof, such as carnauba wax and candelilla wax. The derivatives also include oxides, block copolymers with vinyl monomers, and graft modified products.

[0122] Other examples include alcohols such as higher aliphatic alcohols, fatty acids such as stearic acid and palmitic acid or their acid amides, esters and ketones, hydrogenated castor oil and its derivatives, vegetable waxes and animal waxes. These can be used alone or in combination.

[0123] Among these, polyolefin, Fischer-Tropsch hydrocarbon wax, or petroleum wax is preferably used since it tends to improve the developing property and transfer property. Note that these waxes may contain an antioxidant within a range that does not affect the properties of the toner.

[0124] From the viewpoint of phase separation property with respect to the resin or crystallization temperature, preferred examples include higher fatty acid esters such as behenyl behenate and dibehenyl sebacate.

[0125] The content of the release agent is preferably 1.0 part by mass or more and 30.0 parts by mass or less with respect to 100.0 parts by mass of the resin.

[0126] The melting point of the release agent is preferably from 30° C. to 120° C., more preferably from 60° C. to 100° C. By using a release agent having a melting point of from 30° C. to 120° C., the release effect is efficiently exerted and a wider fixing area is secured.

[0127] <Plasticizer> In the toner of the present invention, it is preferable to use a crystalline plasticizer in order to improve the sharp melting property. The plasticizer is not particularly limited, and any of the known plasticizers used in toners such as those described below can be used.

[0128] Esters of monohydric alcohols and fatty carboxylic acids, such as behenyl behenate, stearyl stearate, and palmityl palmitate, or esters of monohydric carboxylic acids and fatty alcohols; esters of dihydric alcohols and fatty carboxylic acids, such as ethylene glycol distearate, dibehenyl sebacate, and hexanediol dibehenate, or esters of dihydric carboxylic acids and fatty alcohols; esters of trihydric alcohols and fatty carboxylic acids, such as glycerol tribehenate, or esters of trihydric carboxylic acids and fatty alcohols; pentaerythritol tetrastearate esters of tetrahydric alcohols and aliphatic carboxylic acids, such as pentaerythritol tetrapalmitate, or esters of tetrahydric carboxylic acids and aliphatic alcohols; esters of hexahydric alcohols and aliphatic carboxylic acids, such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate, or esters of hexahydric carboxylic acids and aliphatic alcohols; esters of polyhydric alcohols and aliphatic carboxylic acids, such as polyglycerin behenate, or esters of polyhydric carboxylic acids and aliphatic alcohols; and natural ester waxes, such as carnauba wax and rice wax. These may be used alone or in combination.

[0129] <Coloring agent> The toner particles may contain a colorant. Known pigments and dyes can be used as the colorant. Pigments are preferred as the colorant because they have excellent weather resistance.

[0130] Cyan colorants include copper phthalocyanine compounds and their derivatives, anthraquinone compounds, and basic dye lake compounds. Specific examples include the following: CI Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and 66.

[0131] 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 Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, and 254, and CI Pigment Violet 19.

[0132] Yellow colorants include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specific examples include the following: CI Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185, 191, and 194.

[0133] Examples of black colorants include those toned to black using the above yellow, magenta and cyan colorants, as well as carbon black.

[0134] These colorants can be used alone or in mixtures, or further in the form of a solid solution.

[0135] The colorant is preferably used in an amount of 1.0 part by mass or more and 20.0 parts by mass or less per 100.0 parts by mass of the resin.

[0136] <Charge control agents and charge control resins> The toner particles may contain a charge control agent or resin.

[0137] As the charge control agent, a known one can be used, and a charge control agent that has a high triboelectric charging speed and can stably maintain a constant triboelectric charge amount is particularly preferred. Furthermore, when the toner particles are produced by a suspension polymerization method, a charge control agent that has low polymerization inhibition properties and is substantially free of solubilized matter in an aqueous medium is particularly preferred.

[0138] Examples of toners that control the toner to be negatively charged include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic and dicarboxylic acid-based metal compounds, aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, phenol derivatives such as bisphenol, urea derivatives, metal-containing salicylic acid-based compounds, metal-containing naphthoic acid-based compounds, boron compounds, quaternary ammonium salts, calixarenes, and charge control resins.

[0139] The charge control resin may be a polymer or copolymer having a sulfonic acid group, a sulfonate group, or a sulfonate ester group. As the polymer having a sulfonic acid group, a sulfonate group, or a sulfonate ester group, a polymer containing a sulfonic acid group-containing acrylamide monomer or a sulfonate group-containing methacrylamide monomer in a copolymerization ratio of 2% by mass or more is preferable, and a polymer containing a sulfonic acid group-containing methacrylamide monomer in a copolymerization ratio of 5% by mass or more is more preferable.

[0140] The charge control resin preferably has a glass transition temperature (Tg) of 35° C. or more and 90° C. or less, a peak molecular weight (Mp) of 10,000 or more and 30,000 or less, and a weight average molecular weight (Mw) of 25,000 or more and 50,000 or less. When used, it is possible to impart preferable triboelectric charging characteristics without affecting the thermal characteristics required for the toner particles. Furthermore, when the charge control resin contains a sulfonic acid group, for example, the dispersibility of the charge control resin itself in the polymerizable monomer composition and the dispersibility of the colorant are improved, and the coloring power, transparency, and triboelectric charging characteristics can be further improved.

[0141] These charge control agents or charge control resins may be added alone or in combination of two or more kinds.

[0142] The amount of the charge control agent or charge control resin added is preferably 0.01 parts by mass or more and 20.0 parts by mass or less, and more preferably 0.5 parts by mass or more and 10.0 parts by mass or less, relative to 100.0 parts by mass of the resin.

[0143] <Silica fine particles> The silica fine particles used as an external additive in the toner of the present invention are preferably dry silica because of the ease of shape control with many recesses. Dry silica uses silicon halide compounds as raw materials. Silicon tetrachloride is used as the silicon halide compound, but silanes such as methyltrichlorosilane and trichlorosilane alone or a mixture of silicon tetrachloride and silanes can also be used as raw materials. After the raw material is vaporized, it reacts with water generated as an intermediate in an oxyhydrogen flame, so-called flame hydrolysis reaction, to obtain the desired silica. For example, the thermal decomposition oxidation reaction of silicon tetrachloride gas in oxygen and hydrogen is utilized, and the reaction formula is as follows: SiCl4+2H2+O2→SiO2+4HCl

[0144] The method for producing silica will be described below.

[0145] Oxygen gas is supplied to the burner, the ignition burner is ignited, hydrogen gas is supplied to the burner to form a flame, the raw material silicon tetrachloride is added to this and gasified, a flame hydrolysis reaction is carried out, and the resulting silica powder is collected.

[0146] The average particle size and shape can be adjusted arbitrarily to produce a shape of silica particles with many recesses by appropriately changing the flow rate of silicon tetrachloride, the flow rate of oxygen gas supply, the flow rate of hydrogen gas supply, and the residence time of silica in the flame. As a means for controlling a shape with many recesses, the obtained silica powder may be transferred to an electric furnace, spread in a thin layer, and then sintered by heat treatment. Sintering increases the coalescence strength of the silica particles.

[0147] Furthermore, the silica particles used in the present invention may be subjected to a surface treatment such as a hydrophobic treatment or a silicone oil treatment.

[0148] Hydrophobization can be achieved by chemically treating the silica with an organosilicon compound that reacts with or physically adsorbs to the silica. A preferred method is to treat silica produced by vapor phase oxidation of a silicon halide with the organosilicon compound.

[0149] Such organosilicon compounds include the following:

[0150] Hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane.

[0151] Further examples include bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilyl mercaptan, trimethylsilyl mercaptan, and triorganosilyl acrylate.

[0152] Further examples include vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, and 1-hexamethyldisiloxane.

[0153] Further examples include 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and dimethylpolysiloxane.

[0154] These may be used alone or in combination of two or more.

[0155] In addition, in the silicone oil-treated silica, the preferred silicone oil is one having a viscosity of 30 mm at 25° C. 2 / s or more 1000mm 2 / s or less are used. Examples include dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, and fluorine modified silicone oil.

[0156] The silicone oil treatment method includes the following methods. A method in which silica treated with a silane coupling agent and silicone oil are directly mixed using a mixer such as a Henschel mixer. A method of spraying silicone oil onto the silica base, or a method of dissolving or dispersing silicone oil in a suitable solvent, adding silica, mixing, and then removing the solvent.

[0157] It is more preferable that the silicone oil-treated silica is heated to a temperature of 200° C. or higher (more preferably 250° C. or higher) in an inert gas after the silicone oil treatment to stabilize the surface coating. A preferred silane coupling agent is hexamethyldisilazane (HMDS).

[0158] The amount of these silica fine particles added is 1.5 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the toner particles.

[0159] As the external addition conditions, the adhesion state of the external additive and the coating state of the toner particles with the external additive can be controlled arbitrarily by changing the rotation speed (rpm) of the stirring spring provided in the external adder and the external addition time.

[0160] In order to make the particles stick more firmly, it is effective to increase the rotation speed and extend the external addition time, and in particular, it is possible to increase the adhesion strength by increasing the rotation speed. Since the external additive particles having a small particle size form aggregates, the external additive is coated on the toner particles while performing a disintegration process by controlling the external addition conditions. Disintegration can be achieved by increasing the rotation speed and extending the external addition time, but in order to further disintegrate the particles while suppressing the adhesion strength, it is effective to reduce the rotation speed and extend the external addition time.

[0161] [Toner manufacturing method] The method for producing the toner is not particularly limited, and any known method can be used, such as a pulverization method, a suspension polymerization method, a solution suspension method, an emulsion aggregation method, a dispersion polymerization method, etc. Here, the toner is preferably produced by the emulsion aggregation method.

[0162] The toner manufacturing method includes the following steps (1) to (3): (1) a dispersing step of preparing a resin fine particle dispersion liquid containing the resin; (2) an aggregation step of aggregating the resin fine particles contained in the resin fine particle dispersion to form aggregates; and (3) a fusion step of heating the aggregates to fuse them together in that order, In the method for producing a toner, a boric acid source is added in at least one of the aggregation step and the coalescence step.

[0163] In addition, during or after the fusion step, the following steps (4) to (6) are carried out: (4) a spheronization step of further heating the agglomerates at an elevated temperature; (5) a cooling step of cooling the aggregate at a cooling rate of 0.1° C. / sec or more; and (6) an annealing step of heating and holding the aggregate at a temperature equal to or higher than the crystallization temperature or glass transition temperature of the resin; It is preferable to have them in this order.

[0164] When the toner is produced by the emulsion aggregation method, it is preferable because the toner shape can be controlled and boric acid can be easily dispersed uniformly in the vicinity of the surface of the toner. Details of the emulsion aggregation method will be described below.

[0165] <Emulsification aggregation method> The emulsion aggregation method is a method in which an aqueous dispersion of fine particles made of the constituent materials of toner particles, which are sufficiently small relative to the target particle size, is prepared in advance, and the fine particles are aggregated in an aqueous medium until they reach the particle size of the toner particles, and the resin is fused by heating or the like to produce toner particles.

[0166] That is, in the emulsion aggregation method, toner particles are manufactured through a dispersion process in which a fine particle dispersion liquid made of the constituent materials of the toner particles is prepared, an aggregation process in which fine particles made of the constituent materials of the toner particles are aggregated and the particle size is controlled until it reaches the particle size of the toner particles, a fusion process in which the resin contained in the obtained aggregated particles is fused, a further melting process by heating or the like to control the surface shape of the toner, a subsequent cooling process, a metal removal process in which the obtained toner is filtered and excess polyvalent metal ions are removed, a filtration / washing process in which the toner particles are washed with ion-exchanged water or the like, and a process in which moisture is removed from the washed toner particles and they are dried.

[0167] "Process for preparing a resin fine particle dispersion (dispersion process)" The resin microparticle dispersion liquid can be prepared by a known method, but is not limited to these methods.The known methods include, for example, emulsion polymerization method, self-emulsification method, phase inversion emulsification method in which resin is emulsified by adding aqueous medium to the resin solution dissolved in organic solvent, and forced emulsification method in which resin is forcedly emulsified by high temperature treatment in aqueous medium without using organic solvent.

[0168] Specifically, the resin is dissolved in an organic solvent capable of dissolving the resin, and a surfactant or a basic compound is added. In this case, if the resin is a crystalline resin having a melting point, it may be dissolved by heating to above the melting point. Then, while stirring with a homogenizer or the like, an aqueous medium is slowly added to precipitate the resin fine particles. Then, the solvent is removed by heating or decompression to prepare an aqueous dispersion of the resin fine particles. Any organic solvent can be used to dissolve the resin as long as it can dissolve the resin, but it is preferable to use an organic solvent that forms a homogeneous phase with water, such as toluene, from the viewpoint of suppressing the generation of coarse powder.

[0169] The surfactant used in the emulsification is not particularly limited, but examples thereof include anionic surfactants such as sulfate salts, sulfonate salts, carboxylate salts, phosphate esters, and soap salts; cationic surfactants such as amine salts and quaternary ammonium salts; and nonionic surfactants such as polyethylene glycols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. The surfactants may be used alone or in combination of two or more.

[0170] Examples of the basic compound used in the dispersion step include inorganic bases such as sodium hydroxide and potassium hydroxide, and organic bases such as ammonia, triethylamine, trimethylamine, dimethylaminoethanol, and diethylaminoethanol. The basic compound may be used alone or in combination of two or more.

[0171] The 50% particle size (D50) based on volume distribution of the resin microparticles in the aqueous dispersion of the resin microparticles is preferably 0.05 μm to 1.0 μm, and more preferably 0.05 μm to 0.4 μm. By adjusting the 50% particle size (D50) based on volume distribution to the above range, it becomes easy to obtain toner particles with a volume average particle size of 3 μm to 10 μm, which is appropriate for toner particles.

[0172] The 50% particle size (D50) based on volume distribution is measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso).

[0173] (Colorant particle dispersion) A colorant particle dispersion may be used as necessary. The colorant particle dispersion may be prepared by the following known methods, but is not limited to these methods. The colorant, the aqueous medium, and the dispersant may be mixed by a known mixer such as a stirrer, an emulsifier, or a disperser. The dispersant used here may be a known one such as a surfactant or a polymer dispersant. Both the surfactant and the polymer dispersant can be removed in the washing step described below, but the surfactant is preferred from the viewpoint of washing efficiency.

[0174] Examples of the surfactant include anionic surfactants such as sulfate ester salts, sulfonate salts, phosphate esters, 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. Among these, nonionic surfactants or anionic surfactants are preferred. In addition, nonionic surfactants and anionic surfactants may be used in combination. The surfactants may be used alone or in combination of two or more. The concentration of the surfactant in the aqueous medium is preferably 0.5% by mass to 5% by mass.

[0175] The content of the colorant particles in the colorant particle dispersion is not particularly limited, but is preferably 1% by mass to 30% by mass with respect to the total mass of the colorant particle dispersion.

[0176] From the viewpoint of dispersibility of the colorant in the toner finally obtained, the dispersed particle size of the colorant particles in the aqueous dispersion of the colorant is preferably 0.5 μm or less in terms of the 50% particle size (D50) based on volume distribution. For the same reason, it is preferable that the 90% particle size (D90) based on volume distribution is 2 μm or less. The dispersed particle size of the colorant particles dispersed in the aqueous medium is measured using a dynamic light scattering particle size distribution meter (Nanotrac UPA-EX150: manufactured by Nikkiso).

[0177] Known mixers such as stirrers, emulsifiers, and dispersers used when dispersing a colorant in an aqueous medium include ultrasonic homogenizers, jet mills, pressure homogenizers, colloid mills, ball mills, sand mills, and paint shakers. These may be used alone or in combination.

[0178] (Release agent (aliphatic hydrocarbon compound) fine particle dispersion) If necessary, a dispersion of releasing agent particles may be used. The dispersion of releasing agent particles can be prepared by the following known methods, but is not limited to these methods.

[0179] A release agent microparticle dispersion can be produced by adding the release agent to an aqueous medium containing a surfactant, heating the mixture to above the melting point of the release agent, dispersing the mixture into particles using a homogenizer with strong shearing capabilities (e.g., M Technique's "Clearmix W Motion") or a pressure discharge type disperser (e.g., Golin Homogenizer) and then cooling the mixture below the melting point of the release agent.

[0180] The particle size of the dispersion of the release agent particles in the aqueous dispersion of the release agent is preferably 50% particle size (D50) based on volume distribution of 0.03 μm to 1.0 μm, more preferably 0.1 μm to 0.5 μm. It is also preferable that no coarse particles of 1 μm or more exist.

[0181] By setting the particle size of the release agent fine particle dispersion within the above range, the release agent can be finely dispersed in the toner, the exudation effect during fixing can be maximized, and good separation properties can be obtained. The particle size of the release agent fine particle dispersion dispersed in the aqueous medium can be measured using a dynamic light scattering particle size distribution analyzer (Nanotrac UPA-EX150: manufactured by Nikkiso).

[0182] "Mixing process" In the mixing step, a mixture is prepared by mixing the resin fine particle dispersion and, if necessary, at least one of the release agent fine particle dispersion and the colorant fine particle dispersion, using a known mixing device such as a homogenizer or a mixer.

[0183] "Step of forming aggregate particles (aggregation step)" In the aggregating step, the fine particles contained in the mixed liquid prepared in the mixing step are aggregated to form aggregates having a desired particle size. At this time, an aggregating agent is added and mixed, and at least one of heating and mechanical power is appropriately applied as necessary to form aggregates in which the resin fine particles and at least one of the release agent fine particles and the colorant fine particles are aggregated as necessary.

[0184] Examples of the flocculant include organic flocculants such as cationic surfactants of quaternary salts and polyethyleneimine; inorganic metal salts such as sodium sulfate, sodium nitrate, sodium chloride, calcium chloride, calcium nitrate; inorganic ammonium salts such as ammonium sulfate, ammonium chloride, ammonium nitrate; and inorganic flocculants such as divalent or higher metal complexes. It is also possible to add an acid to lower the pH and cause soft flocculation, and for example, sulfuric acid, nitric acid, etc. can be used.

[0185] The aggregating agent may be added in the form of either a dry powder or an aqueous solution dissolved in an aqueous medium, but in order to cause uniform aggregation, it is preferable to add it in the form of an aqueous solution. The addition and mixing of the aggregating agent is preferably performed at a temperature equal to or lower than the glass transition temperature or melting point of the resin contained in the mixed liquid. By performing mixing under this temperature condition, the aggregation proceeds relatively uniformly. The mixing of the aggregating agent into the mixed liquid can be performed using a known mixing device such as a homogenizer or a mixer. The aggregation process is a process of forming aggregates of the toner particle size in an aqueous medium. The volume average particle size of the aggregates produced in the aggregation process is preferably 3 μm to 10 μm. The volume average particle size can be measured using a particle size distribution analyzer (Coulter Multisizer III: manufactured by Coulter) using the Coulter method.

[0186] "A shell formation step of further adding resin fine particles containing a resin for a shell to the dispersion liquid containing the aggregates and aggregating them to form aggregates having a shell" It is preferable to have a shell forming step in which, after forming aggregated particles (core particles) in the aggregation step, resin fine particles containing a shell resin are further added and aggregated to form a shell. That is, it is preferable that the toner particles have core particles containing a binder resin and a shell on the surface of the core particles. The resin for the shell may be the same as the binder resin, or a different resin may be used. The amount of the resin for the shell added is preferably 5 parts by mass or more and 40 parts by mass or less, more preferably 10 parts by mass or more and 30 parts by mass or less, based on 100 parts by mass of the binder resin contained in the core particles.

[0187] At this time, in order to facilitate the incorporation of boron into the toner particles, it is preferred that in the shell formation step, a boron compound is added to the dispersion liquid containing the aggregates together with the resin particles containing the shell resin.

[0188] The boron compound may be boric acid or a compound that can be converted to boric acid by pH control during toner production. For example, at least one selected from the group consisting of boric acid, borax, organic boric acid, borate salts, borate esters, etc. may be used. For example, a boric acid source may be added and controlled so that boric acid is contained in the aggregate. Preferably, the pH is controlled to an acidic condition in the aggregation step, and the shell formation step is performed.

[0189] The boric acid may be present in the aggregate in an unsubstituted state. The boric acid source is preferably at least one selected from the group consisting of boric acid and borax. When the toner is produced in an aqueous medium, it is preferable to add a borate salt as the boric acid source from the viewpoint of reactivity and production stability. Specifically, the boric acid source more preferably includes at least one selected from the group consisting of sodium tetraborate, borax, ammonium borate, etc., and further preferably is borax.

[0190] Borax is represented by the decahydrate of sodium tetraborate Na2B4O7, and is converted to boric acid in an acidic aqueous solution, so borax is preferably used when used in an aqueous medium under an acidic environment. The borax may be added in the form of either a dry powder or an aqueous solution dissolved in an aqueous medium, but in order to cause uniform aggregation, it is preferable to add it in the form of an aqueous solution. The concentration of the aqueous solution may be appropriately changed depending on the concentration to be contained in the toner, and is, for example, 1 to 20% by mass. In order to convert it to boric acid, it is preferable to make the pH an acidic condition before, during, or after the addition. For example, it may be controlled to 1.5 to 5.0, preferably 2.0 to 4.0.

[0191] "Process for obtaining a dispersion liquid containing toner particles (fusion process)" In the fusion step, the dispersion containing the aggregates obtained in the aggregation step is first subjected to termination of aggregation under stirring in the same manner as in the aggregation step by adding an aggregation terminator such as a base capable of adjusting the pH, a chelating compound, or an inorganic salt compound such as sodium chloride.

[0192] After the dispersion state of the aggregated particles in the dispersion liquid becomes stable due to the action of the aggregation terminator, the dispersion liquid is heated to a temperature equal to or higher than the glass transition temperature or melting point of the resin to fuse the aggregated particles and adjust the particle size to a desired size. The 50% particle size (D50) based on volume of the toner particles is preferably 3 μm to 10 μm.

[0193] "Process for obtaining the desired toner surface shape (spheronization process)" During or after the fusion step, it is preferable to carry out a spheronization step in which the temperature is further increased and maintained until the toner particles reach a desired circularity or surface shape.Specific temperatures in the spheronization step are, for example, preferably 90° C. or higher, more preferably 92° C. or higher, and preferably 95° C. or lower.The heating time in the spheronization step can be, for example, 3 hours or more, 5 hours or more, or 8 hours or more.This step makes it easier for hydrogen bonds derived from boric acid to form in the toner particles.

[0194] "Cooling process" After the spheronization step, it is preferable to carry out a cooling step in which the temperature of the dispersion liquid containing the obtained toner particles is lowered to a temperature lower than the crystallization temperature or glass transition temperature of the resin and the crystalline resin component by controlling the cooling rate. By carrying out the cooling step, it is possible to suppress the change in domain shape caused by the crystallization of the crystalline resin component. As a result, it is easy to control the proportion of the domain area of ​​the crystalline resin component near the surface of the toner particles.

[0195] A specific cooling rate is 0.1° C. / sec or more, preferably 0.5° C. / sec or more, more preferably 2° C. / sec or more, and further preferably 4° C. / sec or more.

[0196] "Annealing process" After the cooling step, it is preferable to carry out an annealing step in which the toner particles are heated and held at a temperature equal to or higher than the crystallization temperature of the resin or the glass transition temperature, and, in the case of a release agent, equal to or lower than the crystallization temperature of the release agent. By carrying out the annealing step, the crystalline resin component that was dissolved in the resin of the toner particles is crystallized, and the change in the domain shape can be further suppressed.

[0197] "Post-processing process" In the toner production method, post-treatment steps such as a washing step, a solid-liquid separation step, and a drying step may be further carried out, and by carrying out the post-treatment steps, toner particles in a dry state are obtained.

[0198] "External addition process" In the external addition step, silica fine particles are externally added to the toner particles obtained in the drying step.

[0199] As the external addition conditions, the adhesion state of the external additive and the coating state of the toner particles with the external additive can be controlled arbitrarily by changing the rotation speed (rpm) of the stirring spring provided in the external adder and the external addition time.

[0200] In order to make the particles stick more firmly, it is effective to increase the rotation speed and extend the external addition time, and in particular, the adhesion strength can be increased by increasing the rotation speed. Since the external additive particles having a small particle size form aggregates, the external addition conditions are controlled to perform a disintegration process while coating the toner particles with the external additive. Disintegration can be achieved by increasing the rotation speed and extending the external addition time, but in order to further disintegrate the particles while suppressing the adhesion strength, it is effective to reduce the rotation speed and extend the external addition time.

[0201] [Methods for measuring each physical property] Next, the measurement methods for each physical property according to the present disclosure will be described.

[0202] <Measurement of weight average particle size (D4) and number average particle size (D1) of toner or toner particles> The weight-average particle size (D4) and number-average particle size (D1) of the toner or toner particles are measured with a precision particle size distribution measuring device using a 100 μm aperture tube equipped with an electrical resistance method for a narrow hole, "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.), and the accompanying dedicated software for setting measurement conditions and analyzing measurement data, "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.), with an effective measurement channel count of 25,000, and the measurement data is analyzed and calculated.

[0203] The electrolyte solution used for the measurement is prepared by dissolving special grade sodium chloride in ion-exchanged water to a concentration of approximately 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter).

[0204] Before carrying out the measurements and analyses, the dedicated software is set up as follows.

[0205] In the "Change Standard Measurement Method (SOM) screen" of the dedicated software, set the total count number in the control mode to 50,000 particles, the number of measurements to 1, and the Kd value to the value obtained using "Standard Particle 10.0 μm" (Beckman Coulter). Press the threshold / noise level measurement button to automatically set the threshold and noise level. In addition, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check the aperture tube flush after measurement.

[0206] 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.

[0207] The specific measurement method is as follows. (1) Pour about 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) Approximately 30 ml of the above-mentioned aqueous electrolyte solution is placed in a 100 ml flat-bottom glass beaker, and approximately 0.3 ml of a solution prepared by diluting "Contaminon N" (a 10% by weight aqueous solution of a neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, with a pH of 7, manufactured by Wako Pure Chemical Industries, Ltd.) three times by weight with ion-exchanged water is added as a dispersant. (3) A predetermined amount of ion-exchanged water is placed in the water tank of an ultrasonic disperser "Ultrasonic Dispersion System Tetora150" (manufactured by Nikkaki Bios Co., Ltd.) that has two oscillators with an oscillation frequency of 50 kHz built in with a phase shift of 180 degrees and an electrical output of 120 W, and approximately 2 ml of the Conaminon N is added to this water tank. (4) The beaker (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid 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, about 10 mg of toner or toner particles is added little by little to the electrolyte solution and dispersed. Then, ultrasonic dispersion treatment is continued for another 60 seconds. During the ultrasonic dispersion treatment, the water temperature in the water tank is appropriately adjusted so that it is 10°C or higher and 40°C or lower. (6) Using a pipette, add the electrolytic solution (5) in which the toner or toner particles are dispersed to the round-bottom beaker (1) placed in the sample stand, and adjust the measurement concentration to about 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) is 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), and 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).

[0208] <Method for measuring the amount of elements in toner> The measurement of fluorescent X-rays for each element conforms to JIS K 0119-1969, and specifically, is as follows.

[0209] The measurement equipment used is a wavelength dispersive X-ray fluorescence analyzer "Axios" (PANalytical) and the accompanying dedicated software "SuperQ ver.4.0F" (PANalytical) for setting measurement conditions and analyzing measurement data. Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 27 mm, and the measurement time is 10 seconds. In addition, a proportional counter (PC) is used to measure light elements, and a scintillation counter (SC) is used to measure heavy elements.

[0210] The measurement sample was prepared by placing approximately 4 g of toner in a special aluminum ring for pressing, flattening it, and then pressing it at 20 MPa for 60 seconds using a tablet molding compression machine "BRE-32" (manufactured by Maekawa Test Machinery Manufacturing Co., Ltd.) to form a pellet with a thickness of approximately 2 mm and a diameter of approximately 39 mm.

[0211] Measurements are performed under the above conditions, and elements are identified based on the peak positions of the obtained X-rays, and their concentrations are calculated from the counting rate (unit: cps), which is the number of X-ray photons per unit time.

[0212] <Quantitative Analysis of SiO2 in Toner> Add 0.10 parts by weight of silica (SiO2) fine powder to 100 parts by weight of toner particles and mix thoroughly using a coffee mill. Similarly, mix 0.20 parts by weight and 0.50 parts by weight of silica fine powder with the toner particles, respectively, to prepare samples for the calibration curve.

[0213] For each sample, a pellet of the calibration curve sample is prepared as described above using a tablet press, and the count rate (unit: cps) of the Si-Kα ray observed at a diffraction angle (2θ) = 109.08° when PET is used as the analyzing crystal is measured. In this case, the acceleration voltage and current value of the X-ray generator are 24 kV and 100 mA, respectively. A linear function calibration curve is obtained by plotting the obtained X-ray count rate on the vertical axis and the amount of SiO2 added in each calibration curve sample on the horizontal axis.

[0214] Next, the toner to be analyzed is pelletized as described above using a tablet molding press, and the count rate of the Si-Kα radiation is measured. The SiO2 content in the toner is then calculated from the calibration curve.

[0215] <Method for measuring toner cohesion> The degree of cohesion of the toner was measured as follows.

[0216] The measuring device used was a "Powder Tester" (manufactured by Hosokawa Micron Corporation) with a digital display vibration meter "DigiVibro MODEL 1332A" (manufactured by Showa Sokki Co., Ltd.) connected to the side of the vibration table. A sieve with a mesh size of 25 μm (635 mesh), a sieve with a mesh size of 38 μm (390 mesh), and a sieve with a mesh size of 75 μm (200 mesh) were placed on top of each other on the vibration table of the powder tester from the bottom up. The measurements were carried out in an environment of 23°C and 60% RH as follows. (1) The vibration amplitude of the vibration table was adjusted in advance so that the displacement value on the digital display vibrometer was 0.60 mm (peak-to-peak). (2) 5 g of the toner that had been left to stand for 24 hours in an environment of 23° C. and 60% RH was precisely weighed and gently placed on the top sieve with 150 μm openings. (3) After the sieves were vibrated for 15 seconds, the mass of the toner remaining on each sieve was measured and the degree of cohesion was calculated according to the following formula. Coagulation degree (%) = {(mass of sample on 75 μm sieve (g)) / 5 (g)} × 100 + {(Sample mass (g) on ​​38 μm mesh sieve) / 5(g)} x 100 x 0.6 + {(Sample mass (g) on ​​25 μm mesh sieve) / 5(g)} x 100 x 0.2

[0217] <Calculation of the average ratio As of the area occupied by the domains of the crystalline resin component in the surface layer region up to a depth of 200 nm from the surface of the toner particle> The distribution state of the crystalline resin component in the toner is evaluated by observing the cross-section of a toner particle with a transmission electron microscope, calculating As from the cross-sectional area of ​​the domain formed by the crystalline resin component, and taking the average value of 100 arbitrarily selected toner particles.

[0218] In detail, the toner is embedded in a visible light curable embedding resin (D-800, manufactured by Nissin EM Co., Ltd.), cut to a thickness of 60 nm using an ultrasonic ultramicrotome (EM5, manufactured by Leica), and Ru stained using a vacuum staining device (manufactured by Filgen Co., Ltd.). Then, the toner is observed using a transmission electron microscope (H7500, manufactured by Hitachi Co., Ltd.) at an acceleration voltage of 120 kV. For the toner cross section to be observed, 100 pieces within ±2.0 μm of the weight average particle diameter are selected and photographed. The obtained image is processed using image processing software (Photoshop (registered trademark) 5.0, manufactured by Adobe) to clearly distinguish the domain of the crystalline resin component from the region of the resin. In detail, the domain of the crystalline resin component can be distinguished as follows. The captured TEM image is binarized by setting the threshold value of brightness (gradation 255) to 160 using image processing software. At this time, the crystalline resin component of the toner and the photocurable resin D800 become the bright areas, and the areas other than the crystalline resin component of the toner become the dark areas. The contours of the toner can be distinguished by the brightness of the toner and the photocurable resin.

[0219] A surface region of the cross section of the toner particle is masked to a depth of 200 nm from the toner particle surface (contour of the cross section). Specifically, a line is drawn from the center of gravity of the toner particle cross section to a point on the contour of the toner particle cross section. On the line, a position 200 nm from the contour in the direction of the center of gravity is identified. This operation is then performed for one circumference of the contour of the toner particle cross section, and the surface region from the contour of the toner particle cross section to 200 nm is clearly indicated. The area percentage occupied by the domain of the crystalline resin component in the area of ​​the obtained surface region is calculated, and this is designated as As.

[0220] <Method for measuring the exposure rate Bs of toner particles> The exposure rate Bs of the toner particles was measured according to the following procedure.

[0221] (Measurement of the major axis of external additives) Using a scanning electron microscope Gemini560 (product name, manufactured by Carl Zeiss), a backscattered electron image and a secondary electron image are taken of the external additive on the surface of the toner particles at an accelerating voltage of 0.7 kV and an observation magnification of 50,000 times. At that time, a field of view that does not include the outline of the toner is selected and taken using the secondary electron image.

[0222] The toner is fixed to the sample stage with carbon tape or the like and then observed as it is.

[0223] The major axis of the external additive was measured using the obtained backscattered electron image, and those having a major axis of 5 nm or more were defined as external additives.

[0224] The same procedure can also be used for toner particles that contain multiple types of external additives on their surface. When observing backscattered electron images with the Gemini560, an energy dispersive X-ray spectrometer is used to perform elemental analysis at an accelerating voltage of 10 kV, making it possible to identify the elements of each particle. If the toner particles charge up when the accelerating voltage is high, the elements of each particle can be identified by first evaporating platinum onto the toner surface and then performing elemental analysis.

[0225] It is also possible to select particles of the same kind from their shape characteristics, etc. By carrying out the above-mentioned measurements on particles of the same kind, it is possible to calculate the major axis of each type of particle.

[0226] (Method of measuring the coverage rate of external additives and the exposure rate of toner particles) The coverage rate of the external additive in the present invention is measured from an observed image in which the major axis of the external additive is determined. From the observed image, the coverage rate is calculated as follows using the image processing software "ImageJ".

[0227] By particle analysis, only particles derived from external additives are selected on the software. Next, the area of ​​the selection screen is displayed by setting the measurement. This value is divided by the area of ​​the entire field of view to obtain the coverage rate (area %) of the external additives in that field of view. This measurement is performed for 100 fields of view, and the average value is used as the coverage rate of the external additives. Furthermore, "100 - (coverage rate of the external additives)" is used as the exposure rate (area %) of the toner particles.

[0228] <Method of measuring molecular weight> The molecular weight distribution of the THF soluble matter of the toner is measured by gel permeation chromatography (GPC) as follows.

[0229] First, the toner is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. The resulting 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 approximately 0.8% by mass. This sample solution is used to perform measurements under the following conditions. Equipment: HLC8320 GPC (detector: RI) (Tosoh Corporation) Column: Shodex LF-404, 2 columns of LF-404 (Showa Denko) Eluent: tetrahydrofuran (THF) Flow rate: 1.0ml / min Oven temperature: 40.0℃ Sample injection volume: 0.10 ml

[0230] In calculating the molecular weight of a sample, a molecular weight calibration curve prepared using a standard polystyrene resin (for example, trade name "EasiVial PS-H Polystyrene", manufactured by Agilent) is used.

[0231] <Acid value measurement> 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 of a resin is measured in accordance with JIS K 0070-1992, and specifically, it is measured according to the following procedure.

[0232] (1) Preparation of reagents Dissolve 1.0 g of phenolphthalein in 90 ml of ethyl alcohol (95 vol%) and add ion-exchanged water to make 100 ml to obtain a phenolphthalein solution.

[0233] Dissolve 7 g of special grade potassium hydroxide in 5 ml of water and add ethyl alcohol (95 vol%) to make 1 liter. Place in an alkali-resistant container to avoid contact with carbon dioxide, etc., leave for 3 days, then filter to obtain potassium hydroxide solution. Store the obtained potassium hydroxide solution in an alkali-resistant container. The factor of the potassium hydroxide solution is obtained by placing 25 ml of 0.1 mol / l hydrochloric acid in an Erlenmeyer flask, adding several drops of the phenolphthalein solution, and titrating with the potassium hydroxide solution, from the amount of the potassium hydroxide solution required for neutralization. The 0.1 mol / l hydrochloric acid used is prepared in accordance with JIS K 8001-1998.

[0234] (2) Operation (A) Main Test 2.0 g of the crushed resin sample is weighed out accurately in a 200 ml Erlenmeyer flask, and 100 ml of a toluene / ethanol (2:1) mixed solution is added and dissolved over 5 hours. Next, several drops of the phenolphthalein solution are added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of the titration is when the light red color of the indicator continues for about 30 seconds. (B) 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 (2:1) mixed solution is used).

[0235] (3) The obtained result is substituted into the following formula to calculate the acid value. A = [(CB) × f × 5.61] / S Here, 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 sample (g).

[0236] <Method for quantifying boron atoms contained in toner particles> The content of boron (B) atoms contained in the toner particles is quantified using an inductively coupled plasma atomic emission spectrometer (ICP-AES, manufactured by Seiko Instruments Inc.). As a pretreatment, 100.0 mg of the toner particles are subjected to acid decomposition using 8.00 ml of 60% nitric acid (manufactured by Kanto Chemical, for atomic absorption spectrometry).

[0237] <Method for Obtaining Toner Particles by Removing External Additives from Toner> Add 160 g of sucrose (Kishida Chemical) to 100 mL of ion-exchanged water and dissolve in a hot water bath to prepare a concentrated sucrose solution. In a centrifuge tube (50 mL capacity), add 31 g of the concentrated sucrose solution and 6 mL of Contaminon N (a 10% aqueous solution of a neutral detergent for cleaning precision measuring instruments with a pH of 7 consisting of nonionic surfactants, anionic surfactants, and organic builders, manufactured by Wako Pure Chemical Industries, Ltd.). Add 1.0 g of toner to this and break up the toner clumps with a spatula or the like. Shake the centrifuge tube at 300 strokes per minute (spm) for 20 minutes in a shaker (AS-1N, sold by AS ONE Corporation). After shaking, transfer the solution to a glass tube for a swing rotor (50 mL) and separate it in a centrifuge (H-9R, manufactured by Kokusan Corporation) at 3,500 rpm for 30 minutes.

[0238] This operation separates the toner particles from the external additives. Visually check that the toner particles and the aqueous solution are sufficiently separated, and collect the toner particles that have separated to the top layer with a spatula or similar. The collected toner particles are filtered through a vacuum filter, and then dried in a dryer for at least one hour to obtain a sample for measurement. This operation is carried out multiple times to ensure the required amount.

[0239] [Configuration included in the embodiment of the present invention] The disclosure of this embodiment includes the following configuration. (Configuration 1) A process cartridge that can be installed in an image forming apparatus, The process cartridge has a developing chamber, The developing chamber comprises: a developing roller that develops the electrostatic latent image formed on the surface of the photosensitive drum with toner to form a toner image; a toner supply roller for supplying toner to the developing roller; a toner regulating member for regulating a thickness of a toner layer on the developing roller; Toner; having the surface of the developing roller is in contact with the surface of the toner supply roller, and the direction of movement of the surface of the developing roller is opposite to the direction of movement of the surface of the toner supply roller at a contact position between the surface of the developing roller and the surface of the toner supply roller; a toner supply roller having a surface that is in contact with a developing roller, the toner supply roller having a surface that is in contact with the developing roller, the toner supply roller having a surface that is in contact with the developing roller, the toner supply roller having a surface that is in contact with the developing roller, and the toner supply roller having a surface that is in contact with the developing roller. The developing roller and the toner supply roller have a peripheral speed ratio R represented by the following formula (E1): 1.1≦R≦2.5 It is configured to satisfy R=V RS / V D (E1) (In formula (E1), V RS represents the absolute value of the peripheral speed of the surface of the toner supply roller [m / sec], and V D represents the absolute value of the peripheral speed of the surface of the developing roller [m / sec].) The toner has toner particles and silica fine particles, The toner particles have a crystalline resin component, the content of the silica fine particles is 1.5 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the toner particles, The toner has a degree of cohesion of 70.0% or more and 99.0% or less, When a cross-section of the toner particle is observed using a transmission electron microscope, As is 1.0 area % or less when the average area ratio of the domains of the crystalline resin component in a surface region from the surface of the toner particle to a depth of 200 nm is defined as As. A process cartridge comprising: (Configuration 2) The process cartridge according to configuration 1, wherein in a cross section of the process cartridge in a plane perpendicular to the rotation axis of the toner supply roller when the process cartridge is attached to the main body of the image forming device, an angle between a horizontal line H and a straight line A connecting the centers of the rotation axes of the toner supply roller and the developing roller is 9.5 degrees or more and 10.3 degrees or less. (Configuration 3) A process cartridge according to configuration 1 or 2, wherein, when the average area ratio of the toner particle surface portion not covered with the silica microparticles is defined as an exposure rate Bs, the exposure rate Bs is 55.0 area % or more and 80.0 area % or less. (Configuration 4) The process cartridge according to any one of Configurations 1 to 3, wherein the toner particles contain an amorphous polyester, and the weight average molecular weight of the amorphous polyester is 25,000 or more and 75,000 or less. (Configuration 5) The process cartridge according to Configuration 4, wherein the acid value of the amorphous polyester is 10.0 mgKOH / g or more and 30.0 mgKOH / g or less. (Configuration 6) The process cartridge according to any one of Configurations 1 to 5, wherein the toner particles contain boron, and the boron content is 0.1 ppm by mass or more and 100.0 ppm by mass or less. (Configuration 7) The process cartridge has a toner storage section for storing the toner, the developing chamber has a communication port communicating with the toner storage portion, the toner storage section is disposed vertically below the developing chamber, The process cartridge according to any one of configurations 1 to 6, further comprising a toner transport member that transports the toner contained in the toner container onto the toner supply roller through the communication port provided in the developing chamber. (Configuration 8) The toner transport member has elasticity and transports the toner by rotating, The toner transport member includes: a free end of the toner transport member contacts a wall surface of the toner accommodating section in an area A upstream of the communication opening in a rotation direction of the toner transport member, and the toner transport member is configured to deform against the elasticity as the toner transport member rotates such that the free end side is located upstream of the rotation axis side of the toner transport member in the rotation direction of the transport member, and at a position B downstream of the region A in the rotation direction of the toner transport member and upstream of the communication opening in the rotation direction of the toner transport member, a free end of the toner transport member is released from contact with a wall surface of the toner accommodating section, and the deformed transport member is restored by the elasticity so that the transported toner is caused to fly toward the communication opening, The position B is provided below a lower end of the communication port, When viewed from the axial direction of the developing roller, the center of rotation of the toner transport member and the center of rotation of the developing roller are on the same side with respect to a vertical line passing through the position B, 8. The process cartridge according to claim 7, wherein a maximum value of a radius of rotation of the toner transport member is greater than a distance between a center of rotation of the transport member and a lower end of the communication port. (Configuration 9) A driving force receiving portion provided on an end portion of the shaft of the toner supply roller; a first driving force transmission portion for transmitting the driving force from the driving force receiving portion to the toner supply roller; The process cartridge according to any one of configurations 1 to 8, further comprising: a second driving force transmission unit provided on the toner supply roller for transmitting the driving force received by the first driving force transmission unit to the developing roller; and a third driving force transmission unit provided on the developing roller for transmitting the driving force from the second driving force transmission unit to the developing roller. (Configuration 10) A process cartridge as described in Configuration 9, wherein, when the radius of the developing roller is rD [mm] and the radius of the toner supply roller is rRS [mm], the second driving force transmission portion and the third driving force transmission portion are drivingly connected so that the rotational angular velocity ratio λ, expressed by the following formula (E2), satisfies 1.1≦λ×rRS / rD≦2.5. λ=ωRS / ωD (E2) (In formula (E2), ωRS represents the rotational angular velocity [rad / sec] of the toner supply roller, and ωD represents the rotational angular velocity [rad / sec] of the developing roller.) (Configuration 11) The process cartridge according to any one of Configurations 1 to 10, wherein the peripheral speed ratio R satisfies 1.2≦R≦1.5. EXAMPLES

[0240] The present invention will be described in more detail below using examples and comparative examples. The present invention is not limited to the following examples without departing from the gist of the present invention. In the following description of the examples, "parts" are by mass unless otherwise specified.

[0241] <Synthesis of polyester resin 1> Bisphenol A-ethylene oxide 2 mole adduct 48 mol parts Bisphenol A-propylene oxide 2 mole adduct 48 mol parts Terephthalic acid 65 mol parts Dodecenylsuccinic acid 30 mol parts The above monomers were added to a flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and distillation column, and the temperature was raised to 195°C in one hour, and it was confirmed that the reaction system was uniformly stirred. 0.7 parts of tin distearate were added to 100 parts of these monomers. The temperature was then raised from 195°C to 240°C over five hours while distilling off the water produced, and a dehydration condensation reaction was carried out at 240°C for another two hours. The temperature was then lowered to 190°C, and 5 mol parts of trimellitic anhydride were gradually added, and the reaction was continued at 190°C for one hour.

[0242] As a result, a soluble polyester resin 1 having a glass transition temperature of 55.2° C., an acid value of 14.3 mgKOH / g, a hydroxyl value of 24.1 mgKOH / g, a weight average molecular weight of 43,600 and a number average molecular weight of 6,200 was obtained.

[0243] <Synthesis of polyester resin 2> Bisphenol A-ethylene oxide 2 mole adduct 48 mol parts Bisphenol A-propylene oxide 2 mole adduct 48 mol parts Terephthalic acid 65 mol parts Dodecenylsuccinic acid 30 mol parts The above monomers were added to a flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and distillation column, and the temperature was raised to 195°C in 1 hour, and it was confirmed that the reaction system was uniformly stirred. 0.7 parts of tin distearate were added to 100 parts of these monomers. The temperature was then raised from 195°C to 240°C over 5 hours while distilling off the water produced, and a dehydration condensation reaction was carried out at 240°C for another 2 hours. The temperature was then lowered to 190°C, and 5 mol parts of trimellitic anhydride were gradually added, and the reaction was continued at 190°C for 4 hours.

[0244] As a result, amorphous polyester resin 2 having a glass transition temperature of 56.2° C., an acid value of 10.0 mgKOH / g, a hydroxyl value of 20.1 mgKOH / g, a weight average molecular weight of 74,800 and a number average molecular weight of 10,200 was obtained.

[0245] <Synthesis of polyester resin 3> Bisphenol A-ethylene oxide 2 mole adduct 48 mol parts Bisphenol A-propylene oxide 2 mole adduct 48 mol parts Terephthalic acid 65 mol parts Dodecenylsuccinic acid 30 mol parts The above monomers were added to a flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and distillation column, and the temperature was raised to 195°C in 1 hour, and it was confirmed that the reaction system was uniformly stirred. 0.7 parts of tin distearate were added to 100 parts of these monomers. The temperature was then raised from 195°C to 240°C over 5 hours while distilling off the water produced, and a dehydration condensation reaction was carried out at 240°C for another 2 hours. The temperature was then lowered to 190°C, and 5 mol parts of trimellitic anhydride were gradually added, and the reaction was continued at 190°C for 6 hours.

[0246] As a result, amorphous polyester resin 3 having a glass transition temperature of 57.2° C., an acid value of 9.0 mgKOH / g, a hydroxyl value of 18.1 mgKOH / g, a weight average molecular weight of 81,000 and a number average molecular weight of 13,200 was obtained.

[0247] <Synthesis of polyester resin 4> Bisphenol A-ethylene oxide 2 mole adduct 48 mol parts Bisphenol A-propylene oxide 2 mole adduct 48 mol parts Terephthalic acid 65 mol parts Dodecenylsuccinic acid 30 mol parts The above monomers were added to a flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and distillation column, and the temperature was raised to 195°C in one hour, and it was confirmed that the reaction system was uniformly stirred. 0.7 parts of tin distearate were added to 100 parts of these monomers. The temperature was then raised from 195°C to 240°C over five hours while distilling off the water produced, and a dehydration condensation reaction was carried out at 240°C for another two hours. The temperature was then lowered to 190°C, and 8 mol parts of trimellitic anhydride were gradually added, and the reaction was continued at 190°C for one hour.

[0248] As a result, amorphous polyester resin 4 having a glass transition temperature of 58.5° C., an acid value of 30.0 mgKOH / g, a hydroxyl value of 18.1 mgKOH / g, a weight average molecular weight of 38,000 and a number average molecular weight of 9,200 was obtained.

[0249] <Synthesis of polyester resin 5> Bisphenol A-ethylene oxide 2 mole adduct 48 mol parts Bisphenol A-propylene oxide 2 mole adduct 48 mol parts Terephthalic acid 65 mol parts Dodecenylsuccinic acid 30 mol parts The above monomers were added to a flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and distillation column, and the temperature was raised to 195°C in one hour, and it was confirmed that the reaction system was uniformly stirred. 0.7 parts of tin distearate were added to 100 parts of these monomers. The temperature was then raised from 195°C to 240°C over five hours while distilling off the water produced, and a dehydration condensation reaction was carried out at 240°C for another two hours. The temperature was then lowered to 190°C, and 10 mol parts of trimellitic anhydride were gradually added, and the reaction was continued at 190°C for one hour.

[0250] As a result, amorphous polyester resin 5 having a glass transition temperature of 58.5° C., an acid value of 34.0 mgKOH / g, a hydroxyl value of 16.1 mgKOH / g, a weight average molecular weight of 36,000 and a number average molecular weight of 8,700 was obtained.

[0251] <Synthesis of polyester resin 6> Bisphenol A ethylene oxide 2 mole adduct 9 mol parts Bisphenol A propylene oxide 2 mole adduct 95 mol parts Terephthalic acid 50 mol parts Fumaric acid 30 mol parts Dodecenylsuccinic acid 25 mol parts The above monomers were charged into a flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and distillation column, and the temperature was raised to 195°C in 1 hour, and it was confirmed that the reaction system was stirred uniformly. 1.0 part of tin distearate was added to 100 parts of these monomers. The temperature was then raised from 195°C to 250°C over 5 hours while distilling off the water produced, and the dehydration condensation reaction was carried out at 250°C for another 4 hours.

[0252] As a result, amorphous polyester resin 6 having a glass transition temperature of 61.5° C., an acid value of 16.0 mgKOH / g, a hydroxyl value of 25.2 mgKOH / g, a weight average molecular weight of 25,200, and a number average molecular weight of 6,100 was obtained.

[0253] <Synthesis of polyester resin 7> Bisphenol A ethylene oxide 2 mole adduct 9 mol parts Bisphenol A propylene oxide 2 mole adduct 95 mol parts Terephthalic acid 50 mol parts Fumaric acid 30 mol parts Dodecenylsuccinic acid 25 mol parts The above monomers were charged into a flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and distillation column, and the temperature was raised to 195°C in 1 hour, and it was confirmed that the reaction system was stirred uniformly. 1.0 part of tin distearate was added to 100 parts of these monomers. The temperature was then raised from 195°C to 250°C over 5 hours while distilling off the water produced, and the dehydration condensation reaction was carried out at 250°C for another 2 hours.

[0254] As a result, amorphous polyester resin 7 having a glass transition temperature of 60.2° C., an acid value of 19.8 mg KOH / g, a hydroxyl value of 28.2 mg KOH / g, a weight average molecular weight of 11,200 and a number average molecular weight of 4,100 was obtained.

[0255] <Preparation of Resin Particle Dispersion 1> 100 parts polyester resin 1 Methyl ethyl ketone 50 parts 20 parts isopropyl alcohol The above methyl ethyl ketone and isopropyl alcohol were put into the container. Then, the above polyester resin 1 was gradually put in, stirred, and completely dissolved to obtain a polyester resin 1 solution. The container containing this polyester resin 1 solution was set to 65°C, and while stirring, 10% aqueous ammonia solution was gradually dropped to a total of 5 parts, and 230 parts of ion-exchanged water was gradually dropped at a rate of 10 ml / min to cause phase inversion emulsification. Furthermore, the pressure was reduced with an evaporator to remove the solvent, and a resin particle dispersion 1 of polyester resin 1 was obtained. The particle size of this resin particle dispersion 1 was measured using a particle size measuring device (LA-950, manufactured by Horiba, Ltd.), and the volume average particle size of the resin particle dispersion 1 was 135 nm. In addition, the resin particle solid content was adjusted to 20% with ion-exchanged water.

[0256] <Preparation of Resin Particle Dispersions 2 to 7> Resin particle dispersions 2 to 7 were obtained in the same manner as in preparation of resin particle dispersion 1, except that polyester resin 1 was replaced with polyester resins 2 to 7. The obtained resin particle dispersions are shown in Table 1.

[0257] [Table 1]

[0258] <Preparation of Colorant Particle Dispersion> Copper phthalocyanine (pigment blue 15:3) 45 parts Anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts 190 parts deionized water The above components were mixed and dispersed for approximately 1 hour using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo) to prepare an aqueous dispersion (colorant microparticle dispersion) containing dispersed colorant with a concentration of 20% colorant microparticles.

[0259] <Preparation of release agent particle dispersion 1> Release agent (HNP-51, melting point 78°C, made by Nippon Seiro) 45 parts Anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts 190 parts deionized water The above was placed in a mixing vessel equipped with a stirrer, heated to 90°C, and circulated through a Clearmix W Motion (M Technique) for 60 minutes for dispersion treatment. The conditions for dispersion treatment were as follows: Rotor outer diameter 3cm Clearance 0.3mm Rotor speed: 19000 r / min Screen rotation speed: 19000 r / min

[0260] After the dispersion treatment, the mixture was cooled to 40°C under cooling treatment conditions of a rotor rotation speed of 1000 r / min, a screen rotation speed of 0 r / min, and a cooling rate of 10°C / min, to obtain a release agent particle dispersion liquid with a volume average particle size of 160 nm and a solid content of 20%.

[0261] <Preparation of release agent particle dispersion 2> Release agent (behenyl behenate, melting point 74°C) 45 parts Anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts 190 parts deionized water The above was placed in a mixing vessel equipped with a stirrer, heated to 90°C, and circulated through a Clearmix W Motion (M Technique) for 60 minutes for dispersion treatment. The conditions for dispersion treatment were as follows:

[0262] Rotor outer diameter 3cm Clearance 0.3mm Rotor speed: 19000 r / min Screen rotation speed: 19000 r / min

[0263] After the dispersion treatment, the mixture was cooled to 40°C under cooling treatment conditions of a rotor rotation speed of 1000 r / min, a screen rotation speed of 0 r / min, and a cooling rate of 10°C / min, to obtain a release agent particle dispersion liquid with a volume average particle size of 170 nm and a solid content of 20%.

[0264] <Production of Toner Particle 1> ·Resin particle dispersion 1 700 parts Colorant particle dispersion 80 parts Release agent particle dispersion 1 30 parts Release agent particle dispersion 2 90 parts 1000 parts of ion-exchanged water First, in the core formation process, the above materials were put into a round stainless steel flask and mixed. Then, the materials were dispersed for 10 minutes at 5000 r / min using a homogenizer Ultra Turrax T50 (manufactured by IKA). After adding a 1.0% nitric acid aqueous solution to adjust the pH to 3.0, the mixture was heated to 45°C in a heating water bath using a stirring blade while appropriately adjusting the rotation speed so that the mixture was stirred.

[0265] The volume average particle size of the formed agglomerated particles was appropriately confirmed using a Coulter Multisizer III. When agglomerated particles (cores) having a particle size of 5.0 μm were formed, the following materials were added as the shell formation step and stirred for another hour to form a shell. ·Resin particle dispersion 1 300 parts 300 parts deionized water ·2.0 mass% borax aqueous solution 50 parts (Borax; Sodium tetraborate decahydrate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0266] Thereafter, in the spheronization step, the pH was adjusted to 9.0 using a 5% aqueous sodium hydroxide solution, and the mixture was heated to 90° C. while continuing to stir.

[0267] Thereafter, the average circularity of the formed aggregated particles was appropriately measured using a flow type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation).

[0268] Heating was continued until the average circularity of the aggregated particles reached 0.970 (heating time was 3 hours), and then, as a cooling step, ice was quickly added to cool the mixture to 25°C so that the cooling rate was 10°C / sec or more, thereby obtaining toner particle dispersion 1.

[0269] <Production of toner particles 2 to 14> Toner particles 2 to 14 were obtained in the same manner as toner particle 1, except that the conditions were changed to those shown in Table 2.

[0270] [Table 2]

[0271] <Silica fine particles> As an external additive to be added to the toner particles, the following silica fine particles were prepared. Silica microparticles 1: RX50 (manufactured by Nippon Aerosil Co., Ltd.) Silica microparticles 2: TGC191 (manufactured by Cabot Corporation) Silica microparticles 3: RX200 (manufactured by Nippon Aerosil Co., Ltd.)

[0272] <Toner 1 Manufacturing Example> Toner particles 1 100.0 parts Silica fine particles 1 2.2 parts Silica fine particles 3 1.0 parts The above materials were mixed at 3000 rpm for 7.5 minutes using a Henschel mixer FM10C (manufactured by Nippon Coke Corporation) to obtain Toner 1. The external addition conditions for Toner 1 are shown in Table 3. In addition, the results of the various analyses described above for Toner 1 are shown in Table 4.

[0273] <Production Examples of Toners 2 to 22 and Comparative Toners 1 to 5> Toners 2 to 22 and comparative toners 1 to 5 were obtained in the same manner as in the production example of toner 1, except that the conditions were changed to those shown in Table 3. The above-mentioned various analyses were also carried out on these toners, and the results are shown in Table 4.

[0274] [Table 3]

[0275] [Table 4]

[0276] Example 1 As an evaluation machine, a Color Laser Jet Enterprise 6701dn manufactured by HP was prepared, which was modified so that the printing speed could be changed. Furthermore, a process cartridge (where the moving direction of the surface of the developing roller is opposite to the moving direction of the surface of the toner supply roller) was prepared and set to a peripheral speed ratio R of 1.2 according to the present invention, which can be mounted on the above-mentioned evaluation machine, and filled with 200 g of the above-mentioned toner 1. A durability test was performed by continuously passing (printing) 15,000 sheets of horizontal lines with an image ratio of 1% at a printing speed of 75 sheets / min under conditions of a high temperature and high humidity environment (temperature 30°C, humidity 80% RH), and then evaluating the density, density stability, and fogging. The evaluation results are shown in Table 5.

[0277] [Concentration evaluation and concentration stability evaluation] The density evaluation and density stability evaluation were performed by outputting a solid black image after the durability test. For the solid black image, the average value of the solid black image density was measured at three points, the left, center, and right, in the printed area at the top and bottom of the transfer material. The image density stability was evaluated from the difference in the average image density at the top and bottom. The transfer material was A4 size GF-C081 (Canon, 81.4 g / m 2 ) was used, and concentration measurements were performed using X-rite exact advance (manufactured by X-rite).

[0278] The evaluation criteria are as follows: - Criteria for concentration evaluation In both the upper and lower printed parts of the transfer material, it is considered excellent if the average image density is 1.20 or more. If the average image density of both the upper printed portion and the lower printed portion of the transfer material is less than 1.20, there is a problem. · Criteria for evaluating concentration stability It is excellent if the difference between the average image densities at the top and bottom of the transfer material is less than 0.20. If the difference between the average image densities at the top and bottom of the transfer material is 0.20 or more, there is a problem.

[0279] [Evaluation of fogging] The fogging was measured using a Tokyo Denshoku REFLECTOMETER MODEL TC-6DS. A green filter was used. A solid white image was printed on the drum (electrostatic latent image carrier) and taped with Mylar tape. The reflectance of the Mylar tape on paper was calculated by subtracting it from the Macbeth density of the Mylar tape directly on paper, and the fogging was evaluated according to the following criteria. Fog (%) = Reflectance (%) of tape directly applied to paper - Reflectance (%) of tape taped onto drum ·Fog evaluation criteria If the fog (%) is less than 2.0%, it is excellent. If the fog (%) is 2.0% or more, there is a problem.

[0280] [Examples 2 to 25 and Comparative Examples 1 to 7] Examples 2 to 25 and Comparative Examples 1 to 7 were performed in the same manner as in Example 1, except that the peripheral speed ratio R and the toner were changed as shown in Table 5. The evaluation conditions and results are shown in Table 5.

[0281] [Table 5] [Explanation of symbols]

[0282] 1 photosensitive drum, 2 charging roller, 3 scanner unit, 4 developing unit, 5 intermediate transfer unit, 6 cleaning member, 7 elastic member made of rubber blade, 8 cleaning blade support member, 17 cassette containing recording medium S, 25 developing roller, 25e developing roller rotation center, 26 cleaning unit, 27 removed toner chamber, 31 developing frame, 31a toner storage chamber, 31b developing chamber, 34 toner supply roller, 34e toner supply roller rotation center, 35 developing blade, 35a developing blade support plate, 35b flexible plate-shaped member, 36 toner conveying member, 36a stirring shaft, 36b sheet member, 50 transfer belt, 55 registration roller, 56 driving roller, 57 driven roller, 58 primary transfer roller, 59 opposing roller, 69 secondary transfer roller, 70 process cartridge, 72 discharge roller, 74 fixing unit, 75 Discharge section, 100 image forming apparatus, 201 coupling, 202 intermediate body, 203 drive transmission section, 204 gear, 204a third drive transmission section, 204b idler gear, 204c second drive transmission section, 811 first section, 812 second section, 813 third section, 818 leading edge section

Claims

1. A process cartridge that can be mounted in an image forming apparatus, The process cartridge has a developing chamber, The developing chamber comprises: a developing roller that develops the electrostatic latent image formed on the surface of the photosensitive drum with toner to form a toner image; a toner supply roller for supplying toner to the developing roller; a toner regulating member for regulating a thickness of a toner layer on the developing roller; Toner; having the surface of the developing roller is in contact with the surface of the toner supply roller, and the direction of movement of the surface of the developing roller is opposite to the direction of movement of the surface of the toner supply roller at a contact position between the surface of the developing roller and the surface of the toner supply roller; a toner supply roller having a surface that is in contact with a developing roller, the toner supply roller having a surface that is in contact with the developing roller, the toner supply roller having a surface that is in contact with the developing roller, the toner supply roller having a surface that is in contact with the developing roller, and the toner supply roller having a surface that is in contact with the developing roller. The developing roller and the toner supply roller have a peripheral speed ratio R represented by the following formula (E1): 1.1≦R≦2.5 It is configured to satisfy R=V RS / V D (E1) (In formula (E1), V RS represents the absolute value of the peripheral speed of the surface of the toner supply roller [m / sec], and V D represents the absolute value of the peripheral speed of the surface of the developing roller [m / sec].) The toner has toner particles and silica fine particles, The toner particles have a crystalline resin component, the content of the silica fine particles is 1.5 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the toner particles, The toner has a degree of cohesion of 70.0% or more and 99.0% or less, when a cross-section of the toner particle is observed using a transmission electron microscope, As is an average ratio of an area occupied by domains of the crystalline resin component in a surface region from the surface of the toner particle to a depth of 200 nm, As is 1.0 area % or less; A process cartridge comprising:

2. 2. The process cartridge according to claim 1, wherein in a cross section of the process cartridge in a plane perpendicular to the rotation axis of the toner supply roller when the process cartridge is mounted in the main body of the image forming apparatus, an angle between a straight line A connecting the centers of the rotation axes of the toner supply roller and the developing roller and a horizontal line H is 9.5 degrees or more and 10.3 degrees or less.

3. 3. The process cartridge according to claim 1, wherein the average area ratio of the toner particle surface portions not covered with the silica fine particles is defined as an exposure rate Bs, and the exposure rate Bs is 55.0 area % or more and 80.0 area % or less.

4. 3. The process cartridge according to claim 1, wherein the toner particles contain an amorphous polyester, and the weight average molecular weight of the amorphous polyester is from 25,000 to 75,000.

5. 5. The process cartridge according to claim 4, wherein the acid value of said amorphous polyester is from 10.0 mgKOH / g to 30.0 mgKOH / g.

6. 3. The process cartridge according to claim 1, wherein the toner particles contain boron, and the boron content is from 0.1 ppm by mass to 100.0 ppm by mass.

7. the process cartridge has a toner storage section for storing the toner, the developing chamber has a communication port communicating with the toner storage portion, the toner storage section is disposed vertically below the developing chamber, 3. The process cartridge according to claim 1, further comprising a toner transport member that transports the toner contained in the toner container onto the toner supply roller through the communication port provided in the developing chamber.

8. the toner transport member is a member that has elasticity and transports the toner by rotating, The toner transport member includes: a free end of the toner transport member contacts a wall surface of the toner accommodating section in an area A upstream of the communication opening in a rotation direction of the toner transport member, and the toner transport member is deformed against the elasticity as the toner transport member rotates such that the free end side is located upstream of the rotation axis side of the toner transport member in the rotation direction of the transport member, and at a position B downstream of the region A in the rotation direction of the toner transport member and upstream of the communication opening in the rotation direction of the toner transport member, a free end of the toner transport member is released from contact with a wall surface of the toner accommodating section, and the deformed transport member is restored by the elasticity so that the transported toner is caused to fly toward the communication opening, The position B is provided below a lower end of the communication port, When viewed from the axial direction of the developing roller, the center of rotation of the toner transport member and the center of rotation of the developing roller are on the same side of a vertical line passing through the position B, 8. The process cartridge according to claim 7, wherein a maximum value of a radius of rotation of said toner transport member is greater than a distance between a center of rotation of said transport member and a lower end of said communication port.

9. a driving force receiving portion provided at an end of the shaft of the toner supply roller; a first driving force transmitting portion for transmitting a driving force from the driving force receiving portion to the toner supply roller; 3. The process cartridge according to claim 1, further comprising: a second driving force transmission portion provided on the toner supply roller for transmitting the driving force received by the first driving force transmission portion to the developing roller; and a third driving force transmission portion provided on the developing roller for transmitting the driving force from the second driving force transmission portion to the developing roller.

10. 10. The process cartridge according to claim 9, wherein, when a radius of the developing roller is rD [mm] and a radius of the toner supply roller is rRS [mm], the second driving force transmission portion and the third driving force transmission portion are drivingly connected so that a rotational angular velocity ratio λ expressed by the following formula (E2) satisfies 1.1≦λ×rRS / rD≦2.5: λ=ωRS / ωD (E2) (In formula (E2), ωRS represents the rotational angular velocity [rad / sec] of the toner supply roller, and ωD represents the rotational angular velocity [rad / sec] of the developing roller.)

11. 3. The process cartridge according to claim 1, wherein the peripheral speed ratio R satisfies 1.2≦R≦1.5.

Images