Cartridge and image forming apparatus

Abstract

To provide a cartridge that, even if it uses toner with a low electrification amount, can prevent fogging regardless of variations in voltage output from a power supply of the cartridge, and has high development efficiency to reduce a likelihood of occurrence of development ghost.SOLUTION: A cartridge comprises: toner; a developing roller; a supply member that supplies the toner to a surface of the developing roller; and a regulation member that regulates the toner carried on the surface of the developing roller. The cartridge includes a first supply electrode to which a voltage is supplied from an outside of the cartridge. The supply member and the regulation member are electrically connected with the same first supply electrode. The toner includes a compound A having a structure represented by a following formula (1). (1) -(CH2CH2O)-. The compound A is eluted in methanol. When supernatant liquid including the component A is analyzed by liquid chromatograph ESI / MS, a specific peak with an average m / z of 300-1000 is present.SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present disclosure relates to a cartridge used in a recording method utilizing an electrophotographic method, an electrostatic recording method, and a toner jet recording method, and to an image forming apparatus equipped with the cartridge. [Background technology]

[0002] Methods for visualizing image information via electrostatic latent images, such as electrophotography, are applied to copiers, multifunction machines, and printers. In recent years, with the diversification of uses, there is a demand for longer life, smaller size, and higher image quality for electrophotographic devices and toner cartridges.

[0003] Moreover, in order to further improve image quality, it is effective to control the chargeability of the toner to a higher degree. In general, in the case of one-component non-magnetic toner, the toner is supplied to the developer carrier using a developer supply member capable of containing the toner in a foam layer. The supplied toner is regulated to an appropriate toner amount by a regulating blade abutting on the developer carrier, and an electric charge is imparted. At this time, in order to increase the toner supply force, a potential difference may be provided between the developer supply member and the developer carrier. In addition, in order to impart an appropriate electric charge to the toner, a potential difference may be provided between the regulating member and the developer carrier.

[0004] In typical electrophotographic processes, the amount of toner supplied and the amount of charge applied can be appropriately controlled by utilizing the characteristics of the toner and the potential difference between the components used in these cartridges, thereby improving the amount of charge and charge stability of the toner.

[0005] One of the purposes of increasing the charge amount of a toner is to prevent the generation of reversely charged toner. Normally, when a toner is charged by friction, the toner has a certain charge amount distribution according to the characteristics of the toner, so that in the case of a toner with a low charge amount, some of the toner may become reversely charged. In the electrophotographic process, the toner carried on the developing roller is developed onto the photosensitive drum by the potential difference between the developing roller, which is a toner carrier, and the photosensitive drum, which is an electrostatic latent image carrier. At this time, the toner with the opposite charge, which is likely to occur with toner with a low charge amount, is developed onto the non-image area on the photosensitive drum, causing a phenomenon called fogging on the photosensitive drum. When toner that causes this fogging is printed on paper, it not only causes image problems in which toner is printed on areas that should be blank, but also consumes more toner than necessary, which is an issue in terms of miniaturizing the cartridge and extending its lifespan.

[0006] Patent Document 1 discloses a toner that can maintain a high charge amount and has improved charge uniformity and charge stability throughout its life by combining a polyester resin containing titanium element with a nonionic surfactant. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2012-098503 A Summary of the Invention [Problem to be solved by the invention]

[0008] As mentioned above, in order to achieve a long life and high image quality, toners having a high charge amount and cartridges using the same have been proposed. On the other hand, a drawback of increasing the charge amount is a decrease in development efficiency. As described in the Background Art section, since the toner has a certain charge amount distribution, some areas have a high charge amount. A toner having a high charge amount is generated. Since a toner having a high charge amount has a high electrostatic adhesion, it is not developed on a photosensitive drum and remains on the developing roller. This remaining toner causes a regulation failure, which may cause an image failure called a development ghost. Therefore, from the viewpoint of development efficiency, it is preferable that the charge amount of the toner is low.

[0009] On the other hand, one issue that can easily become a problem when using toner with a low charge amount is the variation in voltage output from the power supply of the main unit. Since the electronic components used in the power supply of the main unit always have variations, the power supply voltage always has variations in output. This variation can disrupt the balance between the amount of toner supplied and the charge imparted, resulting in variations in the amount of charge on the toner. In particular, with toner with a low charge amount, this variation can easily result in toner with an opposite charge. As a result, fogging is likely to occur on the photosensitive drum, making it difficult to handle.

[0010] From this perspective, the toner described in Patent Document 1 is designed to be used when the toner has a high charge level, and there is room for further improvement in order to use the toner at a low charge level when there is variation in output due to the power supply of the main body. In view of these problems, the present disclosure provides a cartridge that can suppress the generation of reversely charged toner even when a toner having a low charge amount is used, regardless of variations in the voltage output of a power supply of the main body, and an image forming apparatus equipped with the cartridge. [Means for solving the problem]

[0011] The present disclosure relates to a toner and a developing roller carrying the toner on its surface; a developing container that rotatably supports the developing roller; a toner storage section for storing the toner; a supply member that contacts the surface of the developing roller to supply the toner from the toner storage portion to the surface of the developing roller; a regulating member that contacts the surface of the developing roller to regulate the toner carried on the surface of the developing roller, the cartridge includes a first supply electrode to which a voltage is supplied from outside the cartridge; the supply member and the regulating member are electrically connected to the same first supply electrode; The toner contains a compound A having a structure represented by the following formula (1): -(CH2CH2O)- (1) When the toner is subjected to an elution treatment under the following elution condition A, the compound A is eluted in methanol, When the supernatant obtained by centrifuging the eluate in which the compound A was eluted in methanol under the following centrifugation condition A was analyzed by liquid chromatography ESI / MS in the range of m / z = 50 to 1500, There is a base peak defined as follows: The average m / z defined as follows is 300 to 1000, Regarding cartridges. Dissolution condition A: At 25° C., 10 times the mass of the toner is used in methanol (JIS K8891 equivalent), and the toner is stirred for 10 hours at a rotor speed of 200 rpm using a stirring device. Centrifugation condition A: Rotation is performed for 30 minutes at 25° C., a rotation radius of 10.1 cm, and a rotation speed of 3,500 rpm. Reference peak: In the mass spectrum obtained by liquid chromatography ESI / MS of the supernatant, the peak with the highest intensity is taken as 100% abundance to obtain the relative abundance. Peaks are selected in descending order of relative abundance, and the m / z value of the peak top of the selected peak is taken as P. A peak with a relative abundance of 10% or more and a peak top m / z value of P+44 or P-44 is taken as P. Among the selected peaks among which there are peaks having the same relative abundance, the selected peak having the highest relative abundance is determined as the reference peak. Average m / z: The m / z value of the peak top of the reference peak is defined as Ps, and the average m / z value of the peak top of peaks having a relative abundance of 30% or more, where the peak top m / z value = Ps + 44n (n is an integer), is defined as the average m / z value. Effect of the Invention

[0012] According to the present disclosure, it is possible to provide a cartridge that can suppress the generation of reversely charged toner, even when toner having a low charge amount is used, regardless of variations in the voltage output of the power supply of the cartridge. [Brief description of the drawings]

[0013] [Figure 1] Example of a spectrum from liquid chromatography ESI / MS [Diagram 2] Schematic cross-sectional view of the configuration during image formation [Diagram 3] Conceptual diagram of the image forming device drive system [Figure 4-1] Examples of voltage supply components [Figure 4-2] Examples of voltage supply components [Diagram 5] Example Schematic [Figure 6] Example Schematic [Figure 7] Example Schematic [Figure 8] Example Schematic [Figure 9-1] Examples of voltage supply components [Figure 9-2] Examples of voltage supply components [Figure 10] Example Schematic [Figure 11] Schematic cross-sectional view of an image forming apparatus [Figure 12] Conceptual diagram of the image forming device drive system [Figure 13] Detailed cross-sectional view of the process cartridge DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

[0015] As mentioned above, in a toner having a low charge amount, it is required that the charge amount is low and uniform. One of the reasons why the charge amount distribution of the toner becomes broad is that the charge distribution near the toner surface is biased, and there are parts with a high charge amount (hereinafter referred to as a strong charge part) and parts with a low charge amount (hereinafter referred to as a weak charge part). Even in the case of a toner having a low charge amount, even if the charge amount of the toner as a whole is low, the toner having a high charge amount cannot be reduced because a strongly charged portion exists, and the strongly charged toner remains. Therefore, it is difficult to sufficiently improve the development efficiency. Therefore, in order to sufficiently improve the development efficiency with a toner having a low charge amount, a toner that can release the charge from the strongly charged portion and has a sharp charge distribution is required.

[0016] Furthermore, as described above, in the case of toner with a low charge amount, the amount of toner with an opposite charge easily increases due to variations in the voltage output from the cartridge power supply, which is likely to cause fogging and contamination of components. The cartridge has a developing roller that carries the toner, a supplying member that supplies the toner to the surface of the developing roller, and a regulating member that applies an electric charge to the toner on the developing roller and regulates the toner to an appropriate amount. The voltages of the various power sources of the image forming device are generated by combining electronic components. And since electronic components necessarily have variations, the power source voltages necessarily have variations in output. Since power supplies always have this kind of variation in voltage output, even if you set a desired voltage, there may be a deviation of a few percent.

[0017] If the voltage applied to the supply member increases due to this variation in the output of the power supply voltage, the amount of toner supplied increases. At this time, the total charge Q of the toner on the regulating member does not change. However, because the amount of toner supplied has increased, the charge per unit mass, Q / M, which takes into account the mass M of the toner, decreases. That is, the charge amount of each toner particle is reduced, and when the charge distribution of the toner is examined, some toner particles are shifted to the opposite charge side. As mentioned above, even if the charge distribution is sharpened, the amount of opposite charge toner particles increases easily due to the variation in the voltage output from the main body power supply, which can easily cause fogging and contamination of components.

[0018] In order to overcome this phenomenon, the inventors conducted extensive research to suppress the generation of reversely charged toner even when a toner having a low charge amount is used and there is variation in the output voltage supplied to the cartridge, and arrived at the following cartridge.

[0019] That is, the present disclosure relates to a toner and a developing roller carrying the toner on its surface; a developing container that rotatably supports the developing roller; a toner storage section for storing the toner; a supply member that contacts the surface of the developing roller to supply the toner from the toner storage portion to the surface of the developing roller; a regulating member that contacts the surface of the developing roller to regulate the toner carried on the surface of the developing roller, the cartridge includes a first supply electrode to which a voltage is supplied from outside the cartridge; the supply member and the regulating member are electrically connected to the same first supply electrode; The toner contains a compound A having a structure represented by the following formula (1): -(CH2CH2O)- (1) When the toner is subjected to an elution treatment under the following elution condition A, the compound A is eluted in methanol, When the supernatant obtained by centrifuging the eluate in which the compound A was eluted in methanol under the following centrifugation condition A was analyzed by liquid chromatography ESI / MS in the range of m / z = 50 to 1500, There is a base peak defined as follows: The average m / z defined as follows is 300 to 1000, Regarding cartridges. Dissolution condition A: At 25° C., 10 times the mass of the toner is used in methanol (JIS K8891 equivalent), and the toner is stirred for 10 hours at a rotor speed of 200 rpm using a stirring device. Centrifugation condition A: Rotation is performed for 30 minutes at 25° C., a rotation radius of 10.1 cm, and a rotation speed of 3,500 rpm. Reference peak: In the mass spectrum obtained by liquid chromatography ESI / MS of the supernatant, the peak with the highest intensity is taken as an abundance of 100% to obtain a relative abundance. Peaks are selected in descending order of relative abundance, and the m / z value of the peak top of the selected peaks is designated as P. Among the selected peaks having a relative abundance of 10% or more and a peak top m / z value of P+44 or P-44, the peak with the highest relative abundance is designated as the reference peak. Average m / z: The m / z value of the peak top of the reference peak is defined as Ps, and the average m / z value of the peak top of peaks having a relative abundance of 30% or more, where the peak top m / z value = Ps + 44n (n is an integer), is defined as the average m / z value.

[0020] Hereinafter, an embodiment will be described with reference to the drawings. Furthermore, the following embodiments do not limit the invention according to the claims, and not all of the combinations of features described in the embodiments are necessarily essential to the solution of the invention.

[0021] (First embodiment) Fig. 2 is a diagram showing a schematic configuration of an image forming apparatus 100 according to a first embodiment. Fig. 2 shows a schematic configuration diagram during image formation. However, the components, dimensions, arrangement, etc. in the embodiment may be changed as appropriate, and do not limit the scope of the present invention.

[0022] (Overall configuration and operation of the image forming apparatus) The overall configuration of the image forming apparatus will be described with reference to Fig. 2. Fig. 2 shows a cross-sectional view of the schematic configuration of the image forming apparatus. The image forming apparatus 100 is a laser printer capable of forming monochrome (black single-color images) using an electrophotographic method. The image forming apparatus is not limited to a monochrome machine, and may be a device capable of forming color images.

[0023] The image forming apparatus 100 has a rotatable drum-type (cylindrical) photoconductor (photoconductor drum) 11 as an image carrier. When an image forming operation is started, the photoconductor 11 is rotated in the direction of the arrow A1 in the figure (clockwise direction) by a driving force transmitted from a driving motor 161 (FIG. 3) as a driving source constituting a driving means. For example, the photoreceptor 11 is an organic photoreceptor having a conductive core made of a conductive material such as aluminum, a charge generating layer formed on the conductive core, and a charge transport layer formed on the charge generating layer.

[0024] The surface of the rotating photoreceptor 11 is uniformly charged to a predetermined potential of a predetermined polarity (negative polarity in this embodiment) that is the normal polarity of the toner by a charging roller 21, which is a roller-type charging member serving as a charging means. The surface (outer circumferential surface) of the charging roller 21 is in contact with the surface (outer circumferential surface) of the photoreceptor 11. For example, the charging roller 21 is an elastic roller configured by covering the surface of a cylindrical conductive support with an elastic layer having a predetermined electrical resistance characteristic.

[0025] Both ends of the conductive support in the direction of the rotation axis of the charging roller 21 are pressed by springs, so that the charging roller 21 is brought into contact with the surface of the photoreceptor 11 with a predetermined pressure. The charging roller 21 is rotated in accordance with the rotation of the photoreceptor 11. During charging, a predetermined charging voltage (charging bias) is applied to the charging roller 21 at a predetermined timing from a charging power source 171 (FIG. 3) serving as a charging voltage application means (charging voltage application section). For example, a negative DC voltage is applied as a charging voltage to the charging roller 21. The uniformly charged surface (non-image area) of the photoconductor 11 becomes a dark potential of negative polarity.

[0026] The charged surface of the photoreceptor 11 is scanned and exposed by an exposure device (laser exposure unit) 131 serving as an exposure means (electrostatic image forming means), and an electrostatic latent image (electrostatic image) is formed on the photoreceptor 11. The exposure device 131 performs exposure by scanning a laser beam on the surface of the photoreceptor 11 along the main scanning direction of the photoreceptor 11 (substantially parallel to the direction of the rotation axis of the photoreceptor 11) in accordance with image information (image data). Furthermore, the exposure device 131 repeats exposure along the main scanning direction in a timed manner along the sub-scanning direction (substantially parallel to the moving direction of the surface of the photoconductor 11) in accordance with image information. As a result, an electrostatic latent image is formed on the photoconductor 11. The exposed portion (image portion), which is the exposed surface of the photoconductor 11, becomes a bright potential.

[0027] The electrostatic latent image formed on the photoconductor 11 is transferred to a developing device (developing cartridge) Toner as a developer is supplied by developing device 2, and developed (visualized) to form a toner image (toner image, developer image) on photoconductor 11. For example, one-component non-magnetic toner is used as the developer contained in developing device 2. The toner will be described in detail later.

[0028] The developing device 2 has a developing roller 31 as a developer carrier (developing member). During development, the surface (outer circumferential surface) of the developing roller 31 is brought into contact with the surface (outer circumferential surface) of the photoconductor 11. During development, a predetermined developing voltage (developing bias) is applied to the developing roller 31 at a predetermined timing from a developing power source 172 (FIG. 3) as a developing voltage application means (developing voltage application section). For example, a negative DC voltage is applied as a developing voltage to the developing roller 31. Then, toner charged with the same polarity (e.g., negative polarity) as the charging polarity of the photoconductor 11 adheres to the exposed portion (image portion) on the photoconductor 11, which has been uniformly charged and then exposed to light, thereby decreasing the absolute value of the potential (reverse development method).

[0029] That is, for example, the normal charging polarity of the toner, which is the main charging polarity of the toner during development, is negative. Since development is performed by a potential difference (development contrast) formed between the development voltage applied to the development roller 31 and the light potential on the photoconductor 11, a predetermined development voltage is applied to the development roller 31. It is assumed that the magnitude of the surface potential formed on the surface of the development roller 31 and the development voltage applied to the development roller 31 are approximately the same. The development roller 31 rotates in the direction of the arrow A2 in the figure (counterclockwise direction) opposite to the photoconductor 11 (the movement direction at the contact portion is forward). Also, for example, there is a speed difference (the moving speed of the surface of the developing roller 31 is faster) between the moving speed of the surface of the photoconductor 11. The developing device 2 will also be described later in more detail. Here, the moving speed of the surface of each member may be rephrased as the rotation speed of each member.

[0030] A transfer roller 111, which is a roller-type transfer member serving as a transfer means, is disposed facing the photoreceptor 11. The transfer roller 111 is pressed toward the photoreceptor 11 to form a transfer portion (transfer nip) N3, which is a contact portion between the photoreceptor 11 and the transfer roller 111. The toner image formed on the photoreceptor 11 is transferred by the action of the transfer roller 111 at the transfer portion N3 onto the recording material R that is sandwiched between the photoreceptor 11 and the transfer roller 111 and transported.

[0031] During transfer, a predetermined transfer voltage (transfer bias) is applied at a predetermined timing from a transfer power source 174 (FIG. 3) serving as a transfer voltage application means (transfer voltage application unit) to the transfer roller 111. For example, a positive DC voltage, which is the opposite polarity to the normal charging polarity of the toner, is applied to the transfer roller 111 as the transfer voltage. A sheet-like recording material (transfer material, recording medium, sheet) R such as paper is supplied from a paper feed section (feed section) to the transfer section N3. The paper feed section has, for example, a cassette as a recording material storage section, a transport roller as a transport member, etc. The recording material R is stored in the cassette, and is transported to the transfer section N3 by the transport roller etc. in synchronization with the toner image on the photoconductor 11.

[0032] Since the present disclosure has a cleanerless configuration as described later, after the toner developed on the surface of the photosensitive drum 11 is transferred to the outside, the toner remaining on the surface of the photosensitive drum 11 is collected by the developing roller 31. Furthermore, when the photosensitive drum 11 is rotated outside the image forming apparatus, the area of ​​the photosensitive drum 11 that forms the developing unit N1 does not come into contact with a contact member while the area moves to the charging unit N2. The contact member is a cleaning member that cleans the surface of the photosensitive drum 11.

[0033] The recording material R onto which the toner image has been transferred is conveyed to a fixing device 121 serving as a fixing means. The fixing device 121 applies heat and pressure to the recording material R carrying the unfixed toner image, thereby fixing (melting and bonding) the toner image to the recording material R. The recording material R with the fixed toner image is discharged (output) from a paper discharge section (discharge section) 191, and is stacked on a tray 192 provided on the upper part of the device body (herein also simply referred to as the "device body") 110 of the image forming apparatus 100.

[0034] The configuration of this embodiment is a so-called cleanerless configuration. Because it is a cleanerless configuration, there is no cleaning member in contact with the photoconductor 11. Toner (transfer residual toner) that remains on the photoconductor 11 without being transferred to the recording material R at the transfer portion N3 is not accommodated in a toner accommodation portion (waste toner accommodation portion) separate from the developing unit 2, but is accommodated in the developing device 2 by the developing roller 31 attached to the developing unit 2.

[0035] As shown in Fig. 2, which is a cross-sectional view of an image forming apparatus 100 including the process cartridge 1, Fig. 11, which will be described later, and Fig. 13, which shows the details of the process cartridge, in the process cartridge 1, the only members arranged so as to be able to come into contact with the image forming area of ​​the photoconductor 11 are the charging roller 21 and the developing roller 31. In other words, the surface of the photoconductor 11 that has passed through the charging portion N2, which is the contact portion between the photoconductor 11 and the charging roller 21, passes through the developing portion N1, which is the contact portion between the photoconductor 11 and the developing roller 31, without coming into contact with anything. In other words, when the photoconductor 11 is rotated in the process cartridge 1 outside the image forming apparatus 100, the surface of the photoconductor 11 that has passed the developing section N1 passes through the charging section N2 without coming into contact with anything in particular.

[0036] Next, a process will be described in which the transfer residual toner is collected by the developing roller 31. Of the toner that forms the toner image, toner that is charged with the opposite polarity (positive charge) or has a low absolute value (amount of charge close to 0) mainly becomes the transfer residual toner. Here, most of the toner in the toner image is charged to the normal negative polarity. The absolute value of the surface potential formed on the photoconductor 11 is reduced by irradiating the photoconductor 11, on which the transfer residual toner exists, with light by the pre-exposure means 6. The photoconductor 11 is charged to a dark potential by discharge caused by the potential difference between the potential formed on the surface of the photoconductor 11 and the charging voltage applied to the charging roller 21. At this time, the photoconductor 11 is charged and the transfer residual toner is simultaneously charged to the negative polarity.

[0037] When the transfer residual toner is negatively charged, due to the potential relationship at the contact portion N2 between the photoconductor 11 and the charging roller 21, it passes through the contact portion N2 while remaining on the photoconductor 11. Thereafter, at the contact portion N1 between the photoconductor 11 and the developing roller 31, due to the potential relationship (back contrast) between the developing roller 31 and the dark area potential, the transfer residual toner charged to the normal polarity adheres to the developing roller 31 and is collected in the developing unit 2. In a cleanerless configuration such as this embodiment, it is essential to minimize the amount of transfer residual toner at the transfer section N3. To achieve this, it is important that the charge of the developed toner is within an appropriate range, that is, it is required that the toner forming the toner image on the photoconductor 11 has few toners with reverse polarity (positive charge) or charges close to zero.

[0038] In a cleanerless configuration such as this embodiment, it is essential to minimize the amount of transfer residual toner at the transfer section N3. To achieve this, it is important that the charge of the developed toner is within an appropriate range, that is, it is required that the toner forming the toner image on the photoconductor 11 has few toners with reverse polarity (positive charge) or charges close to zero.

[0039] In this embodiment, the photoconductor 11, the charging roller 21 as a process means acting on the photoconductor 11, and the developing device 2 constitute a process cartridge 1 that is detachably attached to the main body 110 of the apparatus. The transfer roller 111, the exposure device 131, the fixing device 121, the pre-exposure means 6, the control unit 141, various power sources, etc. are attached to the main body 110 of the apparatus. .

[0040] (Process cartridge) Next, the process cartridge 1 will be further described. The process cartridge 1 is configured to include a developing device (developing cartridge which is a developing unit) 2 and a photosensitive unit 3. As will be described in detail later, the developing device 2 includes a developing roller 31, a supply roller 32, a developing blade 33, and a developing container 36. The developing container 36 also serves as a developing frame which supports the developing roller 31, the supply roller 32, and the developing blade 33. The photosensitive unit 3 includes and supports a photosensitive member (photosensitive drum) 11 which is an image carrier, and a charging roller 21 which is a charging member which charges the surface of the photosensitive drum. The developing device 2 and the photosensitive unit 3 are connected so that the developing device 2 can swing relative to the photosensitive unit 3 about a rotation axis that is substantially parallel to the rotation axis direction of the photosensitive member 11. More specifically, the developing container (developing frame) 36 of the developing device 2 and the photosensitive member support container (photosensitive member unit frame) 61 of the photosensitive member unit 3 are swingably connected to each other, thereby forming an integrated process cartridge 1.

[0041] This allows the developing device 2 to move between a contact position where the developing roller 31 contacts the photoconductor 11 and a separation position where the developing roller 31 is separated from the photoconductor 11. By moving between the contact position and the separation position, unnecessary wear of the developing device 2 and the photoconductor 11 is suppressed. In other words, at the separation position, the driving of the developing device is stopped, which stops the rotation of the developing roller 31 and the supply roller 32 and suppresses the wear of the toner, and the photoconductor 11 is no longer in contact with the developing roller 31, thereby suppressing wear of the charge transport layer. The surface movement speed of the developing roller rotates at 1.4 times the speed of the photoconductor surface movement speed. By rotating the developing roller faster than the photoconductor (creating a difference in peripheral speed), toner development (fog) on ​​the non-developed areas (white areas) is suppressed.

[0042] The process cartridge 1 is also equipped with a non-volatile memory 34 as a storage means. The non-volatile memory 34 stores information such as life information that is information about the life of the process cartridge 1 and toner amount information that is information about the amount of toner in the developing device 2. Examples of life information include the rotation distance of the photoconductor 1, the rotation distance of the developing roller 31, and the number of prints of the recording material R. The non-volatile memory 34 is connected to a control unit 141 provided in the device main body 110 when the process cartridge 1 is attached to the device main body 110. The control unit 141 reads information stored in the nonvolatile memory 34 and writes information to the nonvolatile memory 34. This makes it possible to provide the control unit 141 with appropriate information even when the power to the image forming apparatus 100 is turned off or when one process cartridge 1 is used in two or more image forming apparatuses 100.

[0043] (Developing device (developing cartridge)) Next, a further description will be given of the developing device (developing cartridge) 2. The developing device 2 may be a developing cartridge. The developing device 2 has a developing roller 31 as a developer carrier (developing member) that carries and transports toner as a developer and develops the electrostatic latent image formed on the surface of the photoconductor 11 by supplying the toner to the electrostatic latent image. The developing device 2 also has a supply roller (supply stripping roller) 32 as a developer supply member (developer supply stripping member) that comes into contact with the surface of the developing roller to supply toner to the developing roller 31 and strips the toner from the developing roller 31. The developing device 2 also has a developing blade 33 as a regulating member (regulating blade) that contacts the surface of the developing roller 31 to regulate the toner carried on the surface of the developing roller 31 to a predetermined toner amount. The developing device 2 also has a developing container 36 that forms a toner storage section 37 therein. The toner container 37 contains, for example, one-component non-magnetic toner as a developer.

[0044] The developing roller 31 and the supply roller 32 are each rotatably supported in a developing container 36. The supply roller 32 is disposed so that its surface (outer peripheral surface) is in contact with the surface (outer peripheral surface) of the developing roller 31. Toner is supplied from a toner storage section 37 by the supply roller 32 to the developing roller 31, and the developing roller 31 carries the toner on its surface. The toner carried on the surface of the developing roller 31 is regulated in amount by the developing blade 33 and is triboelectrically charged, and is transported to the contact portion N1 (developing portion) between the photoconductor 11 and the developing roller 31. The toner remaining on the surface of the developing roller 31 after passing through the contact portion N1 (developing portion) between the photoconductor 11 and the developing roller 31 is peeled off from the surface of the developing roller 31 by the supply roller 32 and returned into the toner storage portion 37.

[0045] The developing roller 31 and the supply roller 32 are each driven to rotate by a driving force transmitted from a drive motor 161 (FIG. 3) that drives the photoconductor 11. The developing roller 31 is driven to rotate in the direction of the arrow A2 in the figure (counterclockwise direction). The rotation direction of the photoconductor 11 and the rotation direction of the developing roller 31 are opposite directions. In other words, the developing roller 31 is driven to rotate in a direction in which the movement direction of the surface of the photoconductor 11 and the movement direction of the surface of the developing roller 31 are forward directions at the opposing portion (contact portion) of the photoconductor 11 and the developing roller 31. Further, a drive motor 162 (FIG. 3) is attached to the apparatus main body 110, and transmits drive to the developing device 2 through gears and couplings serving as drive transmission means, thereby driving the developing roller 31 and the supply roller 32.

[0046] Furthermore, supply roller 32 is driven to rotate in the direction of arrow A3 in the figure (counterclockwise direction). The rotation direction of developing roller 31 and the rotation direction of supply roller 32 are the same. That is, supply roller 32 is driven to rotate in a direction opposite to the movement direction of the surface of developing roller 31 and the movement direction of the surface of supply roller 32 at the opposing portion (contact portion) of developing roller 31 and supply roller 32. The surface movement speed of the supply roller is 0.83 times the surface movement speed of the developing roller.

[0047] For example, the developing roller 31 is an elastic roller configured by providing a conductive elastic rubber layer having a predetermined volume resistance as an elastic layer around a metal core. The developing roller 31 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 the desired roughness. Also, for example, the supply roller 32 is a foamed elastic roller configured by providing a foamed urethane layer adjusted to a predetermined volume resistance as an elastic layer around a metal core. The surface layer of this foamed urethane layer has open foam cells, making it easy to hold and transport toner.

[0048] Moreover, for example, the developing blade 33 is made of a flexible plate-like member. For example, the developing blade 33 is made of an elastic plate formed using SUS (stainless steel) or the like. The developing blade 33 is disposed such that its longitudinal direction is substantially parallel to the direction of the rotation axis of the developing roller 31. Moreover, one end (fixed end) of the developing blade 33 in the lateral direction is fixed to the developing container 36.

[0049] The toner supplied to the developing roller 31 from the supply roller 32 is regulated by the developing blade 33 to form a uniform toner coat on the developing roller 31. The developing blade 33 is disposed so that a plate surface (a side surface extending along the longitudinal direction of the developing blade 33) close to the tip on the other end (free end) side in the lateral direction of the developing roller 31 rubs against the surface of the conductive elastic rubber layer of the developing roller 31. Therefore, the toner on the developing roller 31 is regulated by the developing blade 33. At the same time as the coat is formed, the toner on the developing roller 31 is triboelectrically charged and given an electric charge.

[0050] Furthermore, the image forming apparatus 100 is configured to be able to appropriately set the potentials (applied voltages) of the developing roller 31, the supply roller 32, and the developing blade 33. The voltage applied to the developing roller 31 is set to a voltage that provides an appropriate contrast (development contrast, back contrast) for the above-mentioned light potential and dark potential. The voltage applied to the supply roller 32 is set to a voltage that allows the toner to be appropriately supplied to the development roller 31. The voltage applied to the development blade 33 is set to a voltage that allows the toner to be appropriately charged.

[0051] Therefore, the voltage applied to the supply roller 32 and the voltage applied to the development blade 33 are set to be appropriate for the voltage applied to the development roller 31. For example, the voltage applied to the supply roller 32, which is a supply member, and the voltage applied to the development blade 33, which is a regulating member, are the same, and are set so that the potential difference with respect to the voltage applied to the development roller 31 is -100V. Specifically, the voltage applied to the development roller 31 is -325V, and the voltage applied to the supply roller 32 and the voltage applied to the development blade 33 are -425V. With such a configuration, for example, a negatively charged toner can be applied. For example, the same voltage can be applied to the supply member and the regulating member from the image forming apparatus via a first supply electrode electrically connected to the supply member and the regulating member. For example, the same voltage can be applied from the same power source.

[0052] That is, the potential of the supply roller 32 and the potential of the developing blade 33 are set so that the potential difference with respect to the potential of the developing roller 31 is a negative potential difference. That is, the potential of the supply roller 32 and the potential of the developing blade 33 are set so that the potential is higher toward the normal charging polarity of the toner (negative polarity in this embodiment) than the potential of the developing roller 31. This allows the toner to be urged from the supply roller 32 toward the developing roller 31, so that the toner can be appropriately supplied to the developing roller 31. Also, the developing blade 33 can appropriately impart a charge of the normal charging polarity to the toner. In addition, the light area potential is set to -70 V, and the dark area potential is set to -525 V. In other words, the development potential difference for development (development contrast) is 255 V, and the potential difference for non-image formation (back contrast) is 200 V.

[0053] The voltages supplied to the developing blade 33 and the supply roller 32 will be described in more detail with reference to Figs. 4-1, 4-2, and 5. Figs. 4-1 and 4-2 are a perspective view (Fig. 4-1(a)), a front view (Fig. 4-2(b)), and a rear view (Fig. 4-2(c)) of a voltage supply part 300 for supplying voltages from the developing voltage main body contact 182 and the supply / regulation main body contact 183 to the developing roller 31, the developing blade 33, and the supply roller 32.

[0054] The front view is a view seen from the side where it is installed in the image forming apparatus, and the rear view is a view seen from the side where the developing roller 31, supply roller 32, etc. of the voltage supply component 300 are installed. In other words, the front view is a view seen from the side where the developing roller 31, etc. are arranged, and the rear view is a view seen from the side that can be seen when the process cartridge 1 is viewed from the outside. FIG. 5 is a circuit diagram showing the circuitry for applying voltages from the developing voltage main body contact 182 and the supply / regulation voltage main body contact 183 of the image forming apparatus 100 to the developing roller 31, the supply roller 32 and the regulation blade 33 of the process cartridge 1.

[0055] The voltage supply component 300 has a development voltage contact 301 that contacts the development power supply main body contact 182 provided in the image forming apparatus 100, and a supply / regulation voltage contact 302 that contacts the supply / regulation voltage main body contact 183. The conductive path 311 is formed of a conductive resin so as to provide electrical continuity to the roller holding portion 310 (the black portions in FIG. 4-1, FIG. 4-2(a), (b) and (c)).

[0056] Similarly, a conductive path 321 that connects the supply / regulation voltage contact 302 to the supply roller holding part 320 that holds the shaft 32a of the supply roller 32 and the regulation blade contact 330 that contacts the regulation blade 33 is formed of a conductive resin (shaded areas in Figs. 4-1, 4-2(a), (b), and (c)). The conductive resin 311 that connects the development voltage contact 301 to the development roller holding part 310 and the conductive resin 321 that connects the supply / regulation voltage contact 302 to the supply roller holding part 320 and the regulation blade contact 330 are formed independently. Therefore, it is possible to apply independent voltages to each of them (see the circuit diagram in Fig. 5).

[0057] As described above, the image forming apparatus 100 supplies one power source to the supply roller 32 and the developing blade 33, which is the supply / regulation power source 173 (FIG. 3). When the supply / regulation voltage main body contact 183 of the supply / regulation power source 173 provided in the image forming apparatus 100 comes into contact with the supply / regulation voltage contact 302 of the voltage supply component 300 attached to the developing unit 2, the output voltage of the image forming apparatus 100 main body can be supplied to the developing unit 2.

[0058] When the process cartridge 1 is mounted in the image forming apparatus 100, the supply / regulation voltage contact 302 is connected to the supply / regulation voltage main body contact 183, and a voltage is supplied from the supply / regulation power source 173. As described above, by branching the voltage from the same power source within the cartridge, the same voltage can be applied to the developing blade 33 and the supply roller 32.

[0059] When the power source supplying voltage to the supply roller 32 and the power source supplying voltage to the developing blade 33 are separate, the supply voltages differ strictly due to individual differences in the power sources, making it difficult to make the supply roller 32 and the developing blade 33 have the same potential. In general, when an inexpensive power source is used, the voltage variation due to the individual differences in the power source becomes large. By configuring the developing unit 2 to apply the voltage as described above, it is possible to supply a voltage with no potential difference to the developing blade 33 and the supply roller 32 with an inexpensive configuration, even with individual differences in the power source of the image forming apparatus 100. In this embodiment, the voltage supply from the image forming apparatus to the process cartridge is performed by conductive resin in the voltage supply component 300. The voltage supply does not necessarily have to be performed by conductive resin, and the conductive resin may be replaced with metal, or a part of the conductive resin may be replaced with metal.

[0060] In this way, during development, a predetermined development voltage (development bias) is applied to the development roller 31 at a predetermined timing from a development power source 172 (FIG. 3) serving as a development voltage application means (development voltage application section). A negative DC voltage is applied to the development roller 31 as the development voltage. Also, during development, a predetermined voltage (supply / regulation bias) is applied to the development blade 33 and the supply roller 32 at a predetermined timing from a supply / regulation power source 173 (FIG. 3) serving as a supply / regulation voltage application means (supply / regulation voltage application section). It is also possible to configure the development roller 31 to receive a voltage from the supply / regulation power source 173 in the same manner as the development blade 33 and the supply roller 32. A DC voltage that is higher than the development voltage and is closer to the normal charging polarity (negative polarity in this embodiment) of the toner is applied to the developing blade 33 and the supply roller 32 as a supply / regulation voltage.

[0061] The control unit 141 includes a CPU 142, a ROM 143, and a RAM 144. The CPU 142 instructs image display operations such as voltage application timing, voltage value, drive timing, etc. The ROM 143 stores information for determining operations instructed by the CPU. The RAM 144 stores information instructed by the CPU, similar to the ROM 143, and the information can be updated. The controller also transmits image information to be printed to the control unit 141.

[0062] The developing cartridge may also include an electric element between the first supply electrode (e.g., supply / regulating voltage contact 302) and the supply member 32. The developing cartridge may also include an electric element between the first supply electrode and the regulating member 33. The developing cartridge may also include an electric element between the second supply electrode (e.g., development voltage contact 301) and the developing roller 31. The electric element here refers to an electric element that changes the applied voltage, such as a resistor or a diode.

[0063] By providing an electric element between the first supply electrode and the supply member 32, the applied voltage can be controlled to a desired value different from that of the regulating member 33. By providing an electric element between the first supply electrode and the regulating member 33, the applied voltage can be controlled to a desired value different from that of the supply member 32. Furthermore, by providing an electric element between the second supply electrode and the developing roller 31, it is possible to control the applied voltage to a desired value different from that of the regulating member 33 and the supply member 32. Even if a resistor or the like is inserted in the voltage supply path as described above, if the supply power source is the same, it is possible to suppress the effect of power source variations, which will be described later, on the charge of the toner.

[0064] (toner) Next, the toner will be further described in light of the estimated mechanism by which fogging and development ghosts can be suppressed regardless of variations in the voltage output of the power supply of the main body.

[0065] As described above, the cartridge is provided with a first supply electrode to which a voltage is supplied from outside the cartridge, and the supply member and the regulating member are electrically connected to the same first supply electrode, supply / regulating power source 173 (FIG. 3). This makes it possible for the supply member and the regulating member to experience the same fluctuation in applied voltage due to variations in the voltage output of the supply electrode. Here, an example will be described in which the voltage applied to the supply member and the regulating member increases due to variations in the voltage output of the power source. The present disclosure is a cleaner-less configuration, and as described above, it is required that the toner forming the toner image on the photoconductor 11 has few toners with reverse polarity (positive charge) or charges close to zero. However, as described above, when the voltage applied to the supply member increases, the amount of toner supplied increases, which reduces the charge per unit mass Q / M, which takes into account the mass M of the toner. From this perspective, it is not easy to use toners with low charge amounts, especially in consideration of variations in the supply bias and regulating bias, in a cleaner-less configuration.

[0066] However, in the cartridge of the present disclosure, since the supply member and the regulating member are electrically connected to the same first supply electrode, the voltage applied to the regulating member rises to the same extent as the voltage applied to the supply member. When the voltage applied to the regulating member rises, the charge amount of the toner increases when passing through the regulating member, so that the decrease in Q / M can be compensated for. Therefore, even for toner having a low charge amount, reverse charging of the toner can be appropriately suppressed. By applying a specific toner to such a configuration, it is possible to obtain the effect of suppressing fog and development ghost. The configuration of the present disclosure is also desirable in view of the fact that it is a cleaner-less configuration.

[0067] If the voltage supply contact between the image forming device and the developing unit is the same, the voltages supplied to the supply roller and the developing blade do not need to be the same. For example, the contact between the image forming device and the developing unit is the same, but the potential difference between the supply roller or the developing blade with respect to the developing roller can be changed by inserting an electric element such as a resistor into the voltage supply path that supplies voltage from the contact to the supply roller or the developing blade. Preferably, the developing roller is not electrically connected to the supply member and the regulating member. Preferably, the developing cartridge includes a second supply electrode that is different from the first supply electrode and receives a voltage from outside the cartridge. And, preferably, the developing roller is electrically connected to the second supply electrode.

[0068] If the voltage supply contact between the image forming device and the developing unit is the same, the voltages supplied to the supply roller and the regulating blade do not need to be the same. For example, the contact between the image forming device and the developing unit is the same, but a resistor or the like is inserted in the voltage supply path that supplies voltage from the contact to the supply roller or the regulating blade, so that the potential difference between the supply roller or the regulating blade and the developing roller can be changed. A circuit diagram with a resistor inserted on the way to the supply roller is shown in Fig. 6, and a circuit diagram with a resistor inserted on the way to the developing blade is shown in Fig. 7. Even if a resistor is inserted in the voltage supply path, the effect of power supply variations on the charge of the toner can be suppressed by the effect of applying charge to the supply roller, developing blade, and toner.

[0069] Also, a circuit diagram when the image forming apparatus has one voltage output contact is shown in Figure 8. Even if there is one voltage output from the image forming apparatus, the absolute value of the voltage applied to the developing roller in the process cartridge can be made smaller than the voltage applied to the supply roller and developing blade by inserting a resistor or the like. In this way, while making the absolute value of the voltage applied to the supply roller and developing blade larger than the voltage applied to the developing roller, the voltage applied to the supply roller and developing blade can be changed in the same way even when there is variation in the voltage output.

[0070] The toner contains a compound A having a partial structure represented by the following formula (1). -(CH2CH2O)- (1) When the toner is subjected to an elution treatment under elution condition A, compound A is eluted into methanol. Furthermore, the eluate in which compound A is eluted into methanol is centrifuged under centrifugation condition A to obtain a supernatant, which is then analyzed by liquid chromatography ESI / MS in the range of m / z=50 to 1500. At this time, it is necessary that a reference peak defined as below is present. Also, it is necessary that the average m / z defined as below is 300 to 1000.

[0071] Reference peak: In the mass spectrum obtained by liquid chromatography ESI / MS of the above supernatant, the peak with the highest intensity is taken as an abundance of 100% to obtain a relative abundance. Peaks are selected in descending order of relative abundance, and the m / z value of the peak top of the selected peaks is designated as P. Among the selected peaks having a relative abundance of 10% or more and a peak top m / z value of P+44 or P-44, the selected peak with the highest relative abundance is designated as the reference peak. Average m / z: The m / z value of the peak top of the reference peak defined above is defined as Ps, and the average m / z value of the peak top of peaks whose relative abundance is 30% or more and whose m / z value = Ps + 44n (n is an integer) is defined as the average m / z value.

[0072] With such characteristics, the charge is appropriately leaked from the strongly charged area on the toner surface caused by the uneven distribution of the external additives described above to the weakly charged area or to the outside via the structure represented by formula (1) of compound A. This is believed to provide a toner having an appropriately low charge amount and a sharp charge distribution.

[0073] The inventors consider the reason for this as follows. The structure represented by formula (1) is composed of alternating alkyl groups having electron-donating properties and oxygen atoms having electron-withdrawing properties, and it is believed that charge can be easily transferred via this structure. In addition, the fact that the substance is eluted into methanol, which is a highly polar solvent, when elution is performed under elution condition A means that the substance is highly polar and easily electrically charged. Since this component is dissolved into the methanol side when the toner is immersed in methanol, it is considered that this indicates that it is unstable in the toner, regardless of whether it is on the surface or inside the toner, and is in a state that is likely to have polarity. Therefore, the structure represented by formula (1) has a strong binding property. It is presumed that this is a state in which the charge can be easily removed from the conductive part.

[0074] In addition, having an appropriate average m / z in liquid chromatography ESI / MS means that it is easy to ionize and has an appropriate molecular weight for the number of charges. Because of its characteristic of being easy to ionize, it is thought that the structure represented by formula (1) has the property of easily removing charge from strongly charged parts. In addition, since compound A has an appropriate molecular weight relative to the number of charges, charge transfer is likely to occur via molecular chains, and it is believed that compound A has loose, continuous connections within the toner, which facilitate the transfer of charge from strongly charged areas to weakly charged areas of the toner via these connections.

[0075] The presence of the structure represented by formula (1) is confirmed by confirming the presence of a peak with an m / z value of P+44 or P-44 relative to the selected peak P. The presence of at least two or more peaks observed at equal intervals with a period of m / z=44 means that multiple compound A's, which differ only in the number of repetitions of the structure represented by formula (1), are included. An example of a mass spectrometry spectrum by liquid chromatography ESI / MS is shown in Figure 1. It is believed that compounds with a small number of repeats of the structure represented by formula (1) are more likely to interact with each other and therefore more likely to take charge from strongly charged parts, while compounds with a large number of repeats are more likely to promote charge transfer. Therefore, it is speculated that the effect is achieved by including multiple compounds A with different numbers of repeats of the structure represented by formula (1) so as to satisfy the average m / z.

[0076] In order to have this characteristic, the average m / z must be 300 to 1000. The average m / z is preferably 400 to 900, more preferably 450 to 800, and further preferably 500 to 720.

[0077] When the average m / z is smaller than 300, the continuous bond of compound A in the toner is weak, and charge transfer is not promoted, so that the development ghost is not improved. Also, when the average m / z is larger than 1000, charge transfer is excessive, and it is considered that reversely charged toner is likely to occur when a toner with a low charge amount is used, and fog occurs. The average m / z can be appropriately adjusted by changing the synthesis time, the type of aliphatic alcohol used in the synthesis, the number of parts of the aliphatic alcohol, the number of parts of ethylene oxide, and the like.

[0078] In order to incorporate Compound A having such characteristics into the toner, it is preferable to use a material that does not bond with the binder resin of the toner and exists independently. For example, a surfactant having the structure of the following formula (1) can be used. Preferably, compound A includes at least one compound selected from the group consisting of polyoxyethylene lauryl ether, polyoxyethylene hexadecyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene dodecyl ether, polyoxyethylene sorbitan monooleate ether, polyoxyethylene styryl phenyl ether, polyoxyethylene (2) lauryl ether sodium sulfate, polyoxyethylene lauryl ether sodium acetate, and the like.

[0079] Preferably, it is at least one compound selected from the group consisting of an ethylene oxide adduct of a linear aliphatic alcohol having 8 to 16 carbon atoms (more preferably 10 to 14 carbon atoms) and sodium polyoxyethylene lauryl ether acetate, and more preferably, it is an ethylene oxide adduct of lauryl alcohol. In order to obtain a peak having an m / z value of P+44 or P-44 relative to the selected peak P, for example, a method of obtaining an ethylene oxide adduct by condensation polymerization of an aliphatic alcohol and ethylene oxide can be used. This allows the degree of polymerization to have a distribution, resulting in the presence of a desired peak.

[0080] There is no particular limitation on the method of addition, but for example, when a toner is produced by an emulsion aggregation method, a method of adding compound A having a structure of formula (1) in any step of preparing a colorant dispersion, a release agent dispersion, a resin particle dispersion, or the like, or in a step of washing the toner, can be mentioned. It is preferable to add compound A when preparing each dispersion such as a colorant dispersion, a release agent dispersion, or a resin particle dispersion. It is also preferable to add compound A to a mixture when preparing these aggregated particles (i.e., in a dispersion step). The method for producing the toner is not particularly limited, and any method may be used, such as a suspension polymerization method, a dissolution suspension method, an emulsion aggregation method, a pulverization method, etc. From the viewpoint of ease of production, the emulsion aggregation method, in which a surfactant is generally used in the toner formation process, can be preferably used.

[0081] The toner is preferably a negatively charged toner. The supernatant obtained through the treatment under the elution condition A and the centrifugation condition A is supplied to a liquid chromatograph ESI / MS analyzer and analyzed under the analysis condition A. At this time, it is preferable that the compound A contained in the supernatant is ionized as a cation and detected.

[0082] Analysis condition A: Sheath Gas: 10 (arb. unit.), Aux Gas: 5 (arb. unit.), spray voltage: 5 kV, capillary temperature: 275°C. Ionized substances are detected as cations under the conditions of capillary voltage: 35 V, tube lens voltage: 110 V, and ionized substances are detected as anions under the conditions of capillary voltage: -35 V, tube lens voltage: -110 V.

[0083] This property means that the compound A is likely to have positive charging properties, and therefore, it is more likely to take charge from the negatively charged strongly charged portion generated in the negatively charged toner, and therefore the effect is more pronounced. As the compound A having such characteristics, a cationic surfactant having the structure of formula (1), a nonionic surfactant having the structure of formula (1), etc. can be used. As specific examples, the compounds exemplified in the surfactant having the structure of formula (1) described above can be preferably used.

[0084] The toner preferably contains compound B that dissolves in methanol when the toner is subjected to an elution treatment under elution condition A. The supernatant obtained through the treatment of the toner under elution condition A and centrifugal separation condition A is supplied to a liquid chromatograph ESI / MS analyzer and analyzed under analysis condition A. At this time, compound B contained in the supernatant is preferably ionized as an anion and detected. By using compound B, which tends to be negatively charged, in combination with compound A, which tends to be positively charged, it becomes easier to suppress development ghosts and fogging. This is presumably because compound A is more evenly distributed in the toner due to electrical repulsion, resulting in more even charging, and therefore less likely to cause reversely charged toner due to variations in the power supply voltage output of the main unit.

[0085] Furthermore, when the supernatant obtained through the treatment under the toner elution condition A and the centrifugation condition A is analyzed by a liquid chromatograph ESI / MS analyzer, it is preferable that a peak is detected at m / z=325. When the peak detected at m / z=325 is analyzed by a tandem mass spectrometer directly connected to the liquid chromatograph ESI / MS analyzer under analysis condition B, it is preferable that a peak is detected at m / z=183 or m / z=197.

[0086] Analysis condition B: Sheath Gas: 10 (arb. unit.), Aux Gas: 5 (arb. unit.), spray voltage: 5 kV, capillary temperature: 275 °C, capillary voltage: -35 V, tube lens voltage: -110 V, ionized substances were detected as anions, and the ion detected at m / z = 325 was used as the anion. Ions selected as motive ions are detected by collision-induced dissociation in an inert gas (He) at a collision energy of 35 eV.

[0087] The detection of these anions and the detection of a specific peak by tandem mass spectrometry means that a compound having a dodecylbenzenesulfonic acid structure is contained as compound B in the toner. As a result, reverse charging is suppressed, and fogging can be suppressed even when there is variation in the output of the power supply voltage. This is presumably because compound B, which tends to have a negative charge, is also easily ionized and has an appropriate molecular weight for the number of charges, so that charge transfer between compounds A and B is appropriately carried out, making it easy to maintain the desired low charge amount.

[0088] In order to incorporate compound B into the toner, it is preferable to use a material that does not bind to the binder resin of the toner and exists independently. For example, an anionic surfactant can be preferably used. Compound B is preferably at least one compound selected from the group consisting of aliphatic soaps such as sodium stearate and sodium laurate, sodium lauryl sulfate, (linear or branched) sodium dodecylbenzenesulfonate, and sodium polyoxyethylene (2) lauryl ether sulfate. Compound B is preferably linear or branched sodium dodecylbenzenesulfonate.

[0089] In particular, in order to control the detection of a peak at m / z=325 and, when analyzed under analytical condition B, a peak at m / z=183 or 197, a material having a dodecylbenzenesulfonic acid structure can be more preferably used.

[0090] There is no particular limitation on the method of addition, but for example, when a toner is manufactured by an emulsion aggregation method, the above-mentioned compound may be added in any step of preparing a colorant dispersion, a release agent dispersion, a resin particle dispersion, or the like, or in a step of washing the toner. It is preferable to add compound B when preparing each dispersion, such as a colorant dispersion, a release agent dispersion, or a resin particle dispersion. It is also preferable to add compound B to the mixture when preparing these aggregated particles (i.e., in the dispersion step). The method for producing the toner is not particularly limited, and any method may be used, such as a suspension polymerization method, a dissolution suspension method, an emulsion aggregation method, a pulverization method, etc. From the viewpoint of ease of production, the emulsion aggregation method, in which a surfactant is generally used in the process of forming the toner, can be preferably used.

[0091] The content of the structure represented by formula (1) in compound A based on the mass of the toner is preferably 50 to 1500 mass ppm, more preferably 70 to 1200 mass ppm, and further preferably 250 to 1060 mass ppm. When the content of the structure of formula (1) is 1500 ppm by mass or less, in a toner with a low charge amount, the charge leakage due to compound A becomes more moderate, the charge amount is easily maintained, and fogging can be more effectively suppressed. On the other hand, when the content is 50 ppm by mass or more, the development efficiency is improved and development ghosts can be more easily suppressed.

[0092] The content of the structure represented by formula (1) can be controlled by changing the amount of compound A added, the cleaning strength of the toner, or the number of structures represented by formula (1) contained in the molecule of compound A. Examples of a method for changing the number of structures represented by formula (1) in the molecule of compound A include a method of changing the amount of a precursor having a structure represented by formula (1) or polymerization conditions when producing compound A.

[0093] The method used to quantify the structure represented by formula (1) is as follows: 1 The peaks derived from the structure of formula (1) were identified by H nuclear magnetic resonance spectroscopy, and the peaks were analyzed using the internal standard method. 1 A method for quantification by H nuclear magnetic resonance spectroscopy can be used.

[0094] In addition, in the analysis under the analysis conditions A of the supernatant obtained through the treatment under the toner elution conditions A and the centrifugation conditions A, a chromatogram is obtained under the analysis conditions C below. Analysis condition C: In an apparatus configuration using methanol as the mobile phase and no stationary phase, 10 μL of solution was injected at a flow rate of 1 ml / min, the acquisition time was 5 min, and the detector was a UV detector, and the range of m / z = 50 to 1500 was analyzed to obtain a chromatogram. In the obtained chromatogram, the ratio P / N of the peak area P of the cation including compound A to the peak area N of the anion including compound B is preferably 0.20 to 2.00, more preferably 0.25 to 1.20, and further preferably 0.30 to 1.00.

[0095] This characteristic indicates that a material that is easily positively charged, such as compound A, and a material that is easily negatively charged, such as compound B, are contained in the toner in an appropriate balance. When the P / N ratio is 0.20 or more, development ghosts are more easily suppressed. This is presumably because the positively charged component is appropriately large or the negatively charged component is appropriately small, thereby suppressing excessive negative charging. On the other hand, when the P / N ratio is 2.00 or less, fogging is more easily suppressed, and this is presumably because the amount of negatively charged components is appropriately large or the amount of positively charged components is appropriately small, which makes it easier to suppress the generation of oppositely charged toner. The P / N ratio can be controlled by the amount of compound A and compound B added. P is, for example, preferably 300,000 to 1,500,000, and more preferably 500,000 to 1,100,000. N is, for example, preferably 400,000 to 4,000,000, and more preferably 800,000 to 2,000,000.

[0096] The components constituting the toner and the method for producing the toner will be described below. The toner particles contain a binder resin, and the content of the binder resin is preferably 50% by mass or more based on the total amount of the resin components in the toner particles. The binder 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 or composite resins thereof, etc. The binder resin is preferably at least one selected from the group consisting of styrene-acrylic resin and polyester resin.

[0097] Examples of the styrene-acrylic resin include a polymer made of the following monofunctional or polyfunctional polymerizable monomers, a copolymer obtained by combining two or more of these, and a mixture thereof. Preferably, it is a polymer of a monomer mixture containing styrene and at least one selected from the group consisting of an acrylic polymerizable monomer and a methacrylic polymerizable monomer. The monomer mixture may contain (meth)acrylic acid.

[0098] Examples of the monofunctional polymerizable monomer include the following. 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, p-phenylstyrene, and other styrene derivatives; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate, ethyl acrylate, diethyl phosphate, methacrylic polymerizable monomers such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl ketone acrylic acid, methacrylic acid, such as vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropyl ketone.

[0099] Examples of the polyfunctional polymerizable monomer include the following. Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis(4-(acryloxy-diethoxy)phenyl)propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol divinyl dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis(4-(methacryloxy-diethoxy)phenyl)propane, 2,2'-bis(4-(methacryloxy-polyethoxy)phenyl)propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether, etc.

[0100] The polyester resin may be a condensation polymer of a carboxylic acid component and an alcohol component as listed below. Examples of the carboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, cyclohexanedicarboxylic acid, and trimellitic acid. Examples of the alcohol component include bisphenol A, hydrogenated bisphenol, an ethylene oxide adduct of bisphenol A, a propylene oxide adduct of bisphenol A, glycerin, trimethylolpropane, and pentaerythritol. The polyester resin may be a polyester resin containing a urea group. It is preferable that the carboxyl groups at the terminals of the polyester resin are not capped.

[0101] 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. Examples of cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specific examples include: CI Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62 and 66.

[0102] Examples of 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. Specifically, the following can be mentioned: 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.

[0103] Examples of yellow colorants include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specific examples include: 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.

[0104] Examples of black colorants include carbon black and those toned to black using the above-mentioned yellow, magenta and cyan colorants. These colorants can be used alone or in mixture, or in the form of a solid solution. The colorant is preferably used in an amount of 1.0 to 20.0 parts by mass per 100.0 parts by mass of the binder resin. The toner is preferably a non-magnetic toner that does not contain a magnetic material.

[0105] The toner can also be made magnetic by incorporating a magnetic material. In this case, the magnetic material can also serve as a colorant. Examples of magnetic materials include iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel; and alloys of these metals with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof.

[0106] The toner particles may contain a release agent. As the release agent, any known wax may be used without any particular limitation. Specific examples of the release agent include the following. Paraffin wax, microcrystalline wax, petroleum waxes and their derivatives, such as petroleum waxes and their derivatives, montan wax and its derivatives, hydrocarbon waxes and their derivatives produced by the Fischer-Tropsch process, polyolefin waxes and their derivatives, such as polyethylene, natural waxes and their derivatives, such as carnauba wax and candelilla wax. The derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. Further, 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.

[0107] Among these, polyolefins, hydrocarbon waxes produced by the Fischer-Tropsch process, and petroleum-based waxes are preferred because they tend to improve developability and transferability. Incidentally, an antioxidant may be added to these waxes as long as it does not affect the above-mentioned effects.

[0108] 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 binder resin or the polymerizable monomer that forms the binder resin. 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 the above-mentioned thermal characteristics, the release effect is efficiently exerted and a wider fixing area is secured.

[0109] If necessary, external additives such as various organic or inorganic fine particles can be added to the toner particles. That is, the toner may contain toner particles and external additives on the surface of the toner particles. The surface exposure rate of the toner particles is preferably 50% by area or more. By sufficiently exposing the surface of the toner particles, charge transfer by the toner particles becomes easy, and the effect of suppressing development ghosts and fogging can be more easily obtained regardless of variations in the output of the power supply voltage. The surface exposure rate is more preferably 50 to 95 area %, and further preferably 55 to 70 area %. The surface exposure rate can be controlled by the amount of external additive added, etc. From the viewpoint of durability when added to toner particles, the external additive such as organic or inorganic fine particles preferably has a particle size of 1 / 10 or less of the weight average particle size of the toner particles. The content of the external additive is preferably 0.1 to 2.0 parts by mass, more preferably 0.3 to 0.9 parts by mass, relative to 100 parts by mass of the toner particles.

[0110] As the organic or inorganic fine particles, for example, the following can be used: Inorganic fine particles such as silica are preferred. (1) Fluidity imparting agents: silica, alumina, titanium oxide, carbon black and carbon fluoride. (2) Abrasives: metal oxides (e.g., strontium titanate, cerium oxide, alumina, magnesium oxide, chromium oxide), nitrides (e.g., silicon nitride), carbides (e.g., silicon carbide), metal salts (e.g., calcium sulfate, barium sulfate, calcium carbonate). (3) Lubricants: Fluorine-based resin powder (e.g., vinylidene fluoride, polytetrafluoroethylene), fatty acid metal salts (e.g., zinc stearate, calcium stearate). (4) Charge control particles: metal oxides (e.g., tin oxide, titanium oxide, zinc oxide, silica, alumina), carbon black.

[0111] The organic or inorganic fine particles may be subjected to a hydrophobic treatment on the surface in order to improve the fluidity of the toner and to make the toner particles uniformly charged. Examples of the treatment agent for the hydrophobic treatment of the organic or inorganic fine particles include unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organic silicon compounds, and organic titanium compounds. These treatment agents may be used alone or in combination.

[0112] An example of a method for obtaining toner particles will be described below, but the method is not limited to the following. The method for producing the toner particles is not particularly limited, and may be a suspension polymerization method, a dissolution suspension method, an emulsion aggregation method, a pulverization method, etc. As an example, a method for obtaining toner particles by an emulsion aggregation method will be described below.

[0113] <Toner manufacturing method using emulsion aggregation method> (Preparation process of resin particle dispersion) The resin particle dispersion liquid containing the binder resin can be prepared by a known method, but is not limited to these methods. For example, there are an emulsion polymerization method, a self-emulsification method, a phase inversion emulsification method in which an aqueous medium is added to a resin solution dissolved in an organic solvent to emulsify the resin, and a forced emulsification method in which a resin is forcedly emulsified by high-temperature treatment in an aqueous medium without using an organic solvent.

[0114] As an example, a method for preparing a resin microparticle dispersion by phase inversion emulsification is described below. Resin components including a binder resin are dissolved in an organic solvent in which they dissolve, and a surfactant and a basic compound are added. In this case, if the resin component is a crystalline resin having a melting point, it can be dissolved by heating it to above its melting point. Next, while stirring with a homogenizer or the like, an aqueous medium is slowly added to precipitate the resin microparticles. Thereafter, the solvent is removed by heating or reducing pressure to prepare an aqueous dispersion of the resin microparticles. The organic solvent used to dissolve the resin components including the binder resin may be any solvent capable of dissolving them, and specific examples include toluene and xylene.

[0115] As the surfactant used in the preparation step, it is preferable to use a surfactant containing at least one compound selected from the group consisting of compound A and compound B. More preferably, a surfactant containing compound A and compound B is used. Other surfactants can be used in combination as long as the above-mentioned effects are not impaired. Examples of such surfactants include anionic surfactants such as sulfate ester salts, sulfonate salts, carboxylate salts, phosphate esters, and soap-based surfactants; cationic surfactants such as amine salts and quaternary ammonium salts; and nonionic surfactants such as polyethylene glycols, alkylphenol ethylene oxide adducts, and polyhydric alcohols.

[0116] Examples of the basic compound used in the adjustment 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.

[0117] (Preparation of Colorant Dispersion) The colorant dispersion liquid can be prepared by a known dispersion method, and is not limited to any particular method, such as a homogenizer, a ball mill, a colloid mill, an ultrasonic disperser, etc. Examples of the surfactant used during dispersion include the surfactants described above, and a surfactant containing at least one compound selected from the group consisting of compound A and compound B can be preferably used.

[0118] (Preparation of release agent dispersion) In preparing the release agent dispersion, the release agent is dispersed in water together with a surfactant, a basic compound, etc., and then heated to a temperature equal to or higher than the melting point of the release agent, and a dispersion treatment is performed using a homogenizer or a dispersing machine that applies a strong shear force. Through such treatment, the release agent dispersion is obtained. Examples of the surfactant used during dispersion include the above-mentioned surfactants, and a surfactant containing at least one compound selected from the group consisting of compound A and compound B can be preferably used. Examples of the basic compound used during dispersion include the above-mentioned basic compounds.

[0119] (Agglomerated particle formation process) In the aggregated particle forming process, first, a resin fine particle dispersion, a colorant dispersion, a release agent dispersion, etc. are mixed to obtain a mixed liquid (dispersion process). Next, the resin fine particles are aggregated by heating at a temperature equal to or lower than the melting point of the resin fine particles and adjusting the pH to acidic to form aggregated particles containing the resin fine particles, colorant particles, and release agent particles, thereby obtaining an aggregated particle dispersion.

[0120] (First fusion process) In the first fusion step, the pH of the aggregated particle dispersion is increased under stirring conditions similar to those in the aggregated particle formation step to stop the progression of aggregation, and the dispersion is heated at a temperature equal to or higher than the melting point of the resin component to obtain a fused particle dispersion.

[0121] (filtration process, washing process, drying process, classification process, external addition process) Thereafter, a filtration process for filtering out the solid content of the toner particles, a washing process, a drying process, and a classification process for particle size adjustment are performed as necessary to obtain toner particles. The toner particles may be used as they are as toner. If necessary, the toner particles and external additives such as inorganic fine particles may be mixed and adhered using a mixer to obtain a toner.

[0122] <Method for confirming that compound A is contained and that compound A is detected as a cation and compound B as an anion> The method of confirming that the compound A having the structure represented by formula (1) is contained may be a method using liquid chromatography ESI / MS (electrospray ionization mass spectrometry), 1 Known analytical methods such as H nuclear magnetic resonance spectroscopy can be used. In the present disclosure, an analytical method using liquid chromatography ESI / MS is used. The analytical method is described below. The sample is prepared by using a toner under the dissolution condition A described below, and then separated into a solid content and a supernatant liquid under the centrifugation condition A. The supernatant obtained by the above adjustment is supplied to the liquid chromatograph ESI / MS analyzer described below, and ESI / MS analysis is carried out under analysis condition A.

[0123] Dissolution condition A: At 25°C, 10 times the mass of methanol (JISK8891 equivalent) is used for 10 g of toner, and a multi-stirrer (KSS-8; AS ONE Corporation) is used as the stirring device, and stirring is performed for 10 hours at 200 rpm. A triangle rotor (001.440; AS ONE Corporation) with total length x side length: 40 x 14 mm is used for stirring.

[0124] Centrifugation condition A: Rotation is performed for 30 minutes at 25° C., a rotation radius of 10.1 cm, and a rotation speed of 3500 rpm. As the centrifugation device, a centrifuge (H-9R; manufactured by Kokusan Co., Ltd.) can be used.

[0125] Measurement device: Ultimate3000 (Thermo Fisher Scientific) Mass spectrometer: LCQ Fleet (manufactured by Thermo Fisher Scientific) Analysis condition A: Under the following conditions, ionized materials are detected as cations under the capillary voltage of 35 V and tube lens voltage of 110 V, and ionized materials are detected as anions under the capillary voltage of -35 V and tube lens voltage of -110 V, and MS spectra of the cations and anions are obtained. Ionization method: Electrospray Ionization (ESI) Sheath Gas: 10 (arb. unit.) Aux Gas: 5 (arb. unit.) Spray voltage: 5kV Capillary temperature: 275℃ Mobile phase: Methanol (JISK8891 standard equivalent) Column: Not used (no stationary phase) Flow rate: 1ml / min Injection volume: 10μl Chromatogram detector: UV detector MS acquisition time: 5min MS measurement range: 50-1500 m / z

[0126] The relative abundance is calculated by taking the most intense peak in the obtained mass spectrum as 100% abundance. First, the peak with the highest relative abundance is selected as the selected peak. When the m / z value of the peak top of the selected peak is taken as P, confirm whether there is a peak having a relative abundance of 10% or more and an m / z value of P+44 or P-44 at the peak top. If such a peak exists, define the selected peak as the reference peak. If such a peak does not exist, define the peak with the next highest relative abundance as the selected peak and the m / z value of its peak top as P, and confirm whether there is a peak having an m / z value of P+44 or P-44 at the peak top. Repeat this procedure until the reference peak is defined. For example, in Figure 1, the peak at m / z = 563 is the reference peak. When the reference peak is defined, it is determined that the compound A having the structure represented by formula (1) is contained.

[0127] <Calculation of the average m / z value of compound A having a structure represented by formula (1)> After the above-mentioned reference peak is specified, the m / z value of the peak top of the reference peak is defined as Ps. Then, the average m / z value of the peak tops of peaks having a relative abundance of 30% or more is calculated as the average m / z, where the m / z value of the peak top=Ps+44n (n is an integer).

[0128] <Calculation method of m / z value of compound B> The m / z value of compound B is calculated by performing analysis by the MS / MS (mass-mass) method using a tandem mass spectrometer directly connected to a liquid chromatograph ESI / MS analyzer. The MS / MS method is a mass spectrometry technique that allows the detection of fragments with smaller molecular weights by measuring fragments extracted in a first analytical system using a second analytical system, making it easy to perform structural analysis of a sample.

[0129] The sample is prepared by using a toner under the above-mentioned elution condition A, and then separated into a solid content and a supernatant liquid under the above-mentioned centrifugation condition A. The supernatant obtained by the above adjustment is supplied to the measuring device described below, and liquid chromatograph ESI / MS analysis is performed under the analytical condition B described below. A mass spectrum of the anions is obtained, and it is confirmed that a peak is detected at m / z=325. In addition, the ion detected as a peak at m / z=325 is supplied as a precursor ion to a tandem mass spectrometer, and an MS / MS spectrum is obtained under the analytical condition B. Measurement device: Ultimate3000 (Thermo Fisher Scientific) Mass spectrometer: LCQ Fleet (manufactured by Thermo Fisher Scientific) Analysis condition B: Under the following conditions, the ionized material is detected as anion under the capillary voltage: -35 V, tube lens voltage: -110 V, and the ion detected at m / z = 325 is selected as a precursor ion, and the ion that is collision-induced dissociated in an inert gas: He with a collision energy of 35 eV is detected. Ionization method: Electrospray Ionization (ESI) Sheath Gas: 10 (arb. unit.) Aux Gas: 5 (arb. unit.) Spray voltage: 5kV Capillary temperature: 275℃ Mobile phase: Methanol (JISK8891 standard equivalent) Column: Not used (no stationary phase) Flow rate: 1ml / min Injection volume: 10μl Chromatogram detector: UV detector MS acquisition time: 5min MS measurement range: 50-1500 m / z Collision inert gas: He (helium) Collision energy: 35 eV It is confirmed that a peak is detected at m / z=183 or m / z=197 in the obtained MS / MS mass spectrum.

[0130] <Method of analyzing chromatographic peak area P of cation and chromatographic peak area N of anion> The chromatographic peak areas P and N are calculated using a chromatogram obtained from a UV detector of a liquid chromatograph during analysis to confirm that compound A is contained and that compound A is detected as a cation and compound B as an anion. Specifically, a chromatogram obtained under analytical condition C is used during analysis under analytical condition A. Analysis condition C: In an apparatus configuration using methanol as the mobile phase and no stationary phase, 10 μL of solution was injected at a flow rate of 1 ml / min, the acquisition time was 5 min, and the detector was a UV detector, and the range of m / z = 50 to 1500 was analyzed to obtain a chromatogram. The chromatograms of the cations and anions obtained are integrated using a line connecting the points from 0.1 min to 1.0 min as the baseline, and the integrated values ​​are calculated as the peak area value P of the cation and the peak area value N of the anion. From the obtained P and N, the ratio P / N of the peak area P of the cations including compound A to the peak area N of the anions including compound B is calculated.

[0131] <Measuring method of weight average particle size (D4) and number average particle size (D1)> The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are calculated as follows. The measurement device used is a precision particle size distribution measurement device using the narrow hole electrical resistance method, "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.), equipped with a 100 μm aperture tube. The measurement conditions are set and the measurement data is analyzed using the accompanying dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.). The measurement is performed with an effective measurement channel count of 25,000 channels. The 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, Inc.). Before carrying out the measurement and analysis, the dedicated software is set up as follows.

[0132] In the "Change standard measurement method (SOMME)" 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 "Flush aperture tube after measurement." In the "Pulse to particle size conversion setting" screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bins, and the particle size range is set to 2 μm to 60 μm. The specific measurement method is as follows.

[0133] (1) Pour 200 ml of the electrolyte solution into a 250 ml round-bottom glass beaker made exclusively for the Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 revolutions per second. Then, use the "Aperture tube flush" function of the dedicated software to remove dirt and air bubbles from inside the aperture tube. (2) 30 ml of the electrolyte solution is placed in a 100 ml flat-bottom glass beaker, and 0.3 ml of a dilution of Contaminon N (a 10% aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments made of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) diluted approximately 3 times by mass with ion-exchanged water is added as a dispersant. (3) Prepare an ultrasonic disperser "Ultrasonic Dispension System Tetra150" (manufactured by Nikkaki Bios Co., Ltd.) that has two built-in oscillators with an oscillation frequency of 50 kHz and a phase shift of 180 degrees, and has an electrical output of 120 W. Place 3.3 L of ion-exchanged water in the ultrasonic disperser's water tank, and add 2 ml of Conaminon N to this water tank. (4) Set the beaker (2) in the beaker fixing hole of the ultrasonic disperser and operate the ultrasonic disperser. Then, adjust the liquid surface of the electrolyte solution in the beaker so that the resonance state becomes maximum. Adjust the height of the beaker accordingly. (5) While the electrolyte solution in the beaker in (4) is irradiated with ultrasonic waves, 10 mg of toner is added little by little to the electrolyte solution and dispersed. Then, ultrasonic dispersion treatment is continued for another 60 seconds. During ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10°C or higher and 40°C or lower. (6) Using a pipette, add the electrolytic solution (5) in which the toner is dispersed to the round-bottom beaker (1) placed in the sample stand, and adjust the measurement concentration to 5%. Then, measurements are continued until the number of particles measured reaches 50,000. (7) The measurement data is analyzed using the dedicated software that comes with the device, and the weight average particle size (D4) and number average particle size (D1) are calculated. Note that when the dedicated software is set to graph / volume %, the "average diameter" on the "analysis / volume statistics (arithmetic mean)" screen is the weight average particle size (D4), 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).

[0134] <Method for measuring the content of the structure represented by formula (1)> To confirm the content of the structure represented by formula (1), 1 H nuclear magnetic resonance spectroscopy ( 1 H-NMR) is used. Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measurement frequency: 400MHz Pulse condition: 5.0μs Frequency range: 10500Hz Number of times of accumulation: 1024 times Measurement temperature: 30℃ Sample: In the method for confirming that the sample contains a compound having a molecular structure represented by formula (1), elution is performed using 10 g of toner under elution condition A, followed by centrifugation under centrifugation condition A to obtain a supernatant. The entire amount of the obtained supernatant is evaporated to dryness under the concentration condition A described below to obtain an eluate. Concentration condition A: The sample flask containing the supernatant is immersed in a thermostatic water bath at 50° C., and concentration is performed for 12 hours at a rotation speed of 50 rol and a vacuum degree of 80 mbar. A rotary evaporator (ARE-V1200 1; AS ONE Corporation) is used as the apparatus. To the eluate obtained, 1 ml of deuterated methanol (CD3OD) is added as a solvent to obtain a deuterated methanol solution. The entire amount of the deuterated methanol solution is transferred to a sample tube, and a reference substance of 100 ppm based on the mass of the deuterated methanol solution is added to obtain a measurement sample. The standard substance used is the deuterated methanol solution. 1 It has a chemical shift with a known number of protons, is different from any signal detected in H-NMR analysis, is soluble in a quantitative amount in a deuterated methanol solution, and has a boiling point of 100° C. or higher. Here, hexamethyldisilazane, which has a boiling point of 127° C. and a signal derived from (SiCH3)6 at a chemical shift of 0 ppm, is used as the reference substance.

[0135] Obtained 1 For the H-NMR spectrum, phase correction is performed so that all detected NMR signals are upward and the slope of both tails is the same for each NMR signal. Next, the line connecting the points at 0 ppm and 8 ppm with a straight line is set as the baseline. After the above correction, the integral value I1 of the reference substance is calculated by setting the start and end points at points ±0.05 ppm from the peak top of the NMR signal of the reference substance, and the integral value of the signal intensity from 3.4 ppm to 3.6 ppm is calculated as the integral value I2 of the structure of formula (1) derived from compound A. The structure of formula (1) is quantified taking into consideration the molecular weight, number of protons, and concentration of the reference substance and the structure of formula (1). Specifically, the content of the structure represented by formula (1) is quantified based on the following calculation formula: Content of the structure represented by formula (1) [mass ppm] ={(M×m) / (T×w2 / w1)}×(n1 / n2)×(I2 / I1)×10 6

[0136] The mass of the toner used for elution is T [g], the mass of the methanol used for elution is w1 [mg], 1 The mass of the supernatant used in H-NMR was w2 [mg], the number of moles of the reference substance used in the analysis was m [mol], the molecular weight of the structure of formula (1) was M [g / mol], the number of hydrogen atoms in the component to which the peak of interest of the reference substance is assigned was n1, and the number of hydrogen atoms in the structure of formula (1) was n2.

[0137] <Calculation of surface exposure rate of toner particles> (Method of Obtaining a Reflected Electron Image of a Toner Surface) The surface exposure rate of the toner particles is calculated using a backscattered electron image of the toner surface, which is obtained by a scanning electron microscope (SEM). The backscattered electron images obtained from an SEM are also called "composition images," and elements with smaller atomic numbers are detected as darker, while elements with larger atomic numbers are detected as brighter. Toner particles are generally resin particles that mainly contain a carbon-based composition such as a resin component and a release agent. When silica fine particles or metal oxides are present on the surface of a toner particle, the silica fine particles and metal oxides are observed as bright areas and the toner particle surfaces as dark areas in a backscattered electron image obtained from an SEM.

[0138] The SEM equipment and observation conditions are as follows. Equipment used: Carl Zeiss Microscopy ULTRA PLUS Acceleration voltage: 1.0 kV WD:2.0mm Aperture Size: 30.0μm Detection signal: EsB (energy selective backscattered electrons) ESB Grid: 800V Magnification: 50,000x Contrast: 63.0±5.0% (reference value) Brightness: 38.0±5.0% (reference value) Image size: 1024 x 768 pixels Pretreatment: Toner particles are scattered onto carbon tape (no deposition is performed)

[0139] Contrast and brightness are set appropriately according to the state of the device used. The accelerating voltage and EsB Grid are set to achieve the following: obtaining structural information on the outermost surface of the toner particles, preventing charge-up of undeposited samples, and selective detection of high-energy reflected electrons. The observation field is selected to be near the apex where the curvature of the toner particles is the smallest.

[0140] (Method for confirming that the dark areas in the reflected electron image are derived from the toner particle surface) The fact that the dark areas in the observed reflected electron image originate from the toner particle surface is confirmed by overlaying the above reflected electron image with an element mapping image obtained by energy dispersive X-ray analysis (EDS) that can be obtained with a scanning electron microscope (SEM). The SEM / EDS equipment and observation conditions are as follows. Equipment used (SEM): ULTRA PLUS manufactured by Carl Zeiss Microscopy Co., Ltd. Equipment used (EDS): Thermo Fisher Scientific NORANSystem 7, Ultra Dry EDS Detector Accelerating voltage: 5.0 kV WD:7.0mm Aperture Size: 30.0μm Detection signal: SE2 (secondary electrons) Magnification: 50,000x Mode:Spectral Imaging Pretreatment: Toner particles are scattered on carbon tape and platinum sputtered. The element mapping image obtained by this method is superimposed on the above reflected electron image, and it is confirmed that the carbon atom parts of the mapping image and the dark parts of the reflected electron image match. The part where the carbon atom parts of the mapping image and the dark parts of the reflected electron image match is determined to be the toner particle surface.

[0141] (Calculation method for surface exposure rate) The surface exposure rate of the toner is calculated from the backscattered electron image of the outermost surface of the toner particles obtained by the above-mentioned method using image processing software ImageJ (developed by Wayne Rashand). The procedure is as follows. First, convert the backscattered electron image to be analyzed to 8-bit from Type in the Image menu. Next, set the median diameter to 2.0 pixels from Filters in the Process menu to reduce image noise. After excluding the observation condition display area displayed at the bottom of the backscattered electron image, estimate the center of the image and use the Rectangle tool (Rectangle Using the tool, select a 1.5 μm square area from the center of the backscattered electron image.

[0142] Next, use the Freehand selections function in the Image menu to select only the areas where the carbon atom parts of the mapping image and the dark areas of the reflected electron image match, and paint them all black. Also, paint everything except the areas where the carbon atom parts of the mapping image and the dark areas of the reflected electron image match with white. Next, select Threshold from Adjust. In manual operation, select 128 as the threshold, which is the middle gradation between black and white in an 8-bit image, and click Apply to obtain a binarized image. With this operation, pixels that correspond to toner particles are displayed in black (pixel group A1), and pixels that correspond to external additives that cover the surfaces of the toner particles are displayed in white (pixel group A2). Again, estimate the center of the image after excluding the observation condition display area shown at the bottom of the backscattered electron image, and use the Rectangle Tool on the toolbar to select a 1.5 μm square area from the center of the backscattered electron image.

[0143] Next, use the straight line tool on the toolbar to select the scale bar in the observation condition display area shown below the backscattered electron image. In this state, select Set Scale from the Analyze menu to open a new window and enter the pixel distance of the selected straight line in the Distance in Pixels field. Enter the value of the scale bar (eg, 100) in the Known Distance field of the window, enter the unit of the scale bar (eg, nm) in the Unit of Measurement field, and click OK to complete the scale setting.

[0144] Next, select Set Measurements from the Analyze menu, check Area and Ferret's diameter, select Analyze Particles from the Analyze menu, check Display Result, and click OK to perform domain analysis. From the newly opened Results window, the area (Area) of each domain corresponding to the non-covered domain D1 formed by the pixel group A1 and the covered domain D2 formed by the pixel group A2 is obtained.

[0145] The total area of ​​the uncovered domain D1 obtained is S1 (μm 2 ), and the total area of ​​the coating domain D2 is S2 (μm 2 ) The surface exposure rate S is calculated from the obtained S1 and S2 using the following formula. S(area%)={S1 / (S1+S2)}×100 The above procedure is carried out for 10 visual fields for the toner particles to be evaluated, and the arithmetic mean value is used as the surface exposure ratio. EXAMPLES

[0146] The present invention will be specifically described with reference to the following Production Examples and Examples. However, these do not limit the present invention in any way. In the following formulations, "parts" and "%" are all by mass unless otherwise specified.

[0147] <Method for producing aliphatic alcohol alkylene oxide adduct 1> 190 parts of lauryl alcohol and 0.06 parts of aluminum perchlorate nonahydrate were added to a glass autoclave equipped with stirring and temperature control functions, and the mixture was replaced with nitrogen. The mixture was then dehydrated at 95°C under reduced pressure (approximately 20 mmHg) for 1 hour. Next, 90 parts of ethylene oxide (added in the first stage) was added at 95°C until the gauge pressure reached 1 to 3 kgf / cm. 2 It was introduced so that To this adduct, 0.3 parts of potassium hydroxide was added, and 220 parts (5 moles) of ethylene oxide (added in the second stage) was added at 150°C until the gauge pressure reached 1 to 3 kgf / cm. 2 Three parts of Kyoward 600 (Kyowa Chemical Industry Co., Ltd.) were added to the reaction mixture, and the catalyst was adsorbed at 90° C., after which an aliphatic alcohol alkylene oxide adduct 1 was obtained by filtration.

[0148] <Method for Producing Aliphatic Alcohol Alkylene Oxide Adducts 2 to 7> Aliphatic alcohol alkylene oxide adducts 2 to 7 were obtained in the same manner as in the production of aliphatic alcohol alkylene oxide adduct 1, except that the type of aliphatic alcohol, the number of parts of aliphatic alcohol, and the number of parts of ethylene oxide were changed as shown in Table 1. In each production method, ethylene oxide was added in the first and second stages so that the ratio, on a mass basis, was the same as in the production method for aliphatic alcohol alkylene oxide adduct 1.

[0149] [Table 1]

[0150] <Preparation of Resin Particle Dispersion 1> 78.0 parts of styrene, 20.7 parts of butyl acrylate, 1.3 parts of acrylic acid as a carboxyl group-imparting monomer, and 3.2 parts of n-lauryl mercaptan were mixed and dissolved. To this solution, a solution of 1:1.0 part of an aliphatic alcohol alkylene oxide adduct as compound A and 1.5 parts of linear alkylbenzene sulfonate (linear sodium dodecylbenzene sulfonate) (product name: NEOGEN RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)) as compound B dissolved in 150 parts of ion-exchanged water was added in its entirety and dispersed. An aqueous solution of 0.3 parts of potassium persulfate and 10 parts of ion-exchanged water was added while slowly stirring for another 10 minutes. After nitrogen replacement, emulsion polymerization was carried out at 70°C for 6 hours. After polymerization was completed, the reaction solution was cooled to room temperature, and ion-exchanged water was added to obtain resin particle dispersion 1 with a solid content concentration of 12.5 mass% and a volume-based median diameter of 0.2 μm.

[0151] <Preparation of Resin Particle Dispersions 2 to 13> Resin particle dispersions 2 to 13 were obtained in the same manner as in the preparation of resin particle dispersion 1, except that the types and amounts of compound A and compound B were as shown in Table 2. The compounds used are shown in Table 2. In Table 2, the polyoxyethylene lauryl ether sodium acetate used was RLM-100NV manufactured by Kao Corporation, the branched sodium dodecylbenzenesulfonate (branched sodium alkylbenzenesulfonate) used was product number 37202-11 manufactured by Kanto Chemical Co., Ltd., and the sodium stearate used was product number 37275-01 manufactured by Kanto Chemical Co., Ltd.

[0152] <Preparation of Resin Particle Dispersion 14> Into a reaction vessel equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple, monomers to be an acid component and an alcohol component were introduced so as to have the following molar ratios. Terephthalic acid: 40.0 Isopropyl acrylate: 3.0 Trimellitic anhydride: 6.0 Bisphenol A propylene oxide 2 mole adduct: 30.0 Bisphenol A ethylene oxide 2 mole adduct: 10.0 Ethylene glycol: 6.0 As a catalyst, 1.5 parts of dibutyltin were added per 100 parts of the total amount of monomers. Next, the temperature was quickly raised to 180°C under normal pressure in a nitrogen atmosphere, and then condensation polymerization was carried out by distilling off water while heating from 180°C to 210°C at a rate of 10°C / hour. After reaching 210°C, the pressure inside the reaction vessel was reduced to 5 kPa or less, and condensation polymerization was carried out under conditions of 210°C and 5 kPa or less to obtain polyester resin 1. At that time, the polymerization time was adjusted so that the softening point of the obtained polyester resin 1 was 126°C.

[0153] 100.0 parts of polyester resin 1 and 350 parts of ion-exchanged water were placed in a stainless steel container and melted by heating to 95° C. in a warm bath. Then, while thoroughly stirring at 7800 rpm using a homogenizer (IKA Ultra Turrax T50), 0.1 mol / L sodium bicarbonate was added to adjust the pH to more than 7.0. Thereafter, a mixed solution of 3.0 parts of linear alkylbenzenesulfonate sodium and 300 parts of ion-exchanged water was gradually added dropwise to emulsify and disperse the mixture, thereby obtaining a polyester resin particle dispersion liquid. The dispersion liquid was cooled to room temperature, and ion-exchanged water was added to obtain a resin particle dispersion liquid 14 having a solid content concentration of 12.5 mass% and a volume-based median diameter of 0.2 μm.

[0154] [Table 2]

[0155] <Preparation of release agent dispersion 1> 100 parts of a release agent (behenyl behenate, melting point: 72.1°C), 1:15 parts of an aliphatic alcohol alkylene oxide adduct, and 385 parts of ion-exchanged water were mixed and milled in a wet jet mill. The mixture was dispersed for about 1 hour using JN100 (manufactured by Jokou Co., Ltd.) to obtain a release agent dispersion liquid. The concentration of the release agent dispersion liquid was 20% by mass.

[0156] <Preparation of release agent dispersion 2> A release agent dispersion 2 was obtained in the same manner as in the preparation of the release agent dispersion 1, except that the aliphatic alcohol alkylene oxide adduct 1 in the preparation of the release agent dispersion 1 was changed to linear alkylbenzene sulfonate sodium.

[0157] <Preparation of release agent dispersion 3> A release agent dispersion 3 was obtained in the same manner as in the preparation of the release agent dispersion 2, except that 100 parts of the release agent (behenyl behenate, melting point: 72.1° C.) was changed to 25 parts of a release agent (hydrocarbon wax, melting point: 79° C.) and 70 parts of a plasticizer (ethylene glycol distearate).

[0158] <Preparation of Colorant Dispersion 1> As a colorant, 100 parts of carbon black "Nipex35 (manufactured by Orion Engineered Carbons)" and 1:15 parts of an aliphatic alcohol alkylene oxide adduct were mixed with 885 parts of ion-exchanged water, and dispersed for about 1 hour using a wet jet mill JN100 to obtain a colorant dispersion.

[0159] <Preparation of Colorant Dispersion 2> Colorant dispersion liquid 2 was obtained in the same manner as in preparation of colorant dispersion liquid 1, except that the aliphatic alcohol alkylene oxide adduct 1 in preparation of colorant dispersion liquid 1 was changed to linear sodium alkylbenzene sulfonate.

[0160] <Preparation of magnetic material dispersion 1> Fe 2+ 50 liters of an aqueous solution of ferrous sulfate containing 2.0 mol / L of sodium hydroxide was mixed with 55 liters of an aqueous solution of sodium hydroxide containing 4.0 mol / L, and the aqueous solution was stirred to obtain an aqueous solution of ferrous salt containing ferrous hydroxide colloid. The aqueous solution was kept at 85°C and air was blown in at 20 L / min. The oxidation reaction was carried out for 2 hours to obtain a slurry containing core particles. The obtained slurry was filtered and washed using a filter press, and the core particles were dispersed in water again. Sodium silicate was added to the obtained reslurry in an amount of 0.20 mass% in terms of silicon per 100 parts of core particles, the pH of the slurry was adjusted to 6.0, and the mixture was stirred to obtain magnetic iron oxide particles having a silicon-rich surface. The obtained slurry was filtered and washed with a filter press, and then reslurried with ion-exchanged water. 500 parts (10% by mass relative to the magnetic iron oxide) of ion-exchange resin SK110 (manufactured by Mitsubishi Chemical) was added to this reslurry (solid content 50 parts / L) and stirred for 2 hours to perform ion exchange. The ion-exchange resin was then removed by filtration with a mesh, filtered and washed with a filter press, dried and crushed to obtain magnetic material 1 with a number-average particle size of primary particles of 0.21 μm. Magnetic material dispersion 1 using magnetic material 1 as a colorant was obtained in the same manner as in preparation of colorant dispersion 1, except that the carbon black was changed to magnetic material 1:300 parts.

[0161] <Preparation Example of Toner Particle 1> <Dispersion process> Resin particle dispersion 1:265 parts, release agent dispersion 1:10 parts, colorant dispersion 1:10 parts, aliphatic alcohol alkylene oxide adduct 1:2.9 parts, linear alkylbenzene sulfonate sodium (Neogen RK):0.6 parts were dispersed using a homogenizer (IKA: Ultra Turrax T50). The temperature inside the container was adjusted to 30°C while stirring, and 1 mol / L sodium hydroxide aqueous solution was added to adjust the pH to 8.0.

[0162] <Agglomeration process> As a flocculant, an aqueous solution of 0.08 parts of aluminum chloride dissolved in 10 parts of ion-exchanged water was added over 10 minutes at 30°C while stirring. After leaving it for 3 minutes, the temperature was raised to 50°C to generate associated particles. In this state, the particle size of the associated particles was measured using a Coulter Counter Multisizer 3 (registered trademark, manufactured by Beckman Coulter, Inc.). When the weight average particle size reached 7.0 μm, 0.9 parts of sodium chloride and 5.0 parts of aliphatic alcohol were added to stop particle growth. After adjusting the pH to 9.0 by adding 1 mol / L aqueous sodium hydroxide solution, the temperature was raised to 95° C. to spheroidize the aggregated particles. When the average circularity reached 0.980, the temperature was lowered and the mixture was cooled to room temperature to obtain toner particle dispersion 1.

[0163] <Cleaning process> Hydrochloric acid was added to the obtained toner particle dispersion 1 to adjust the pH to 1.5 or less, and the mixture was left to stir for 1 hour, and then the mixture was subjected to solid-liquid separation using a pressure filter to obtain a toner cake. This was reslurried with ion-exchanged water to make a dispersion again, and then the mixture was subjected to solid-liquid separation using the above-mentioned filter. The reslurry and solid-liquid separation were repeated until the electrical conductivity of the filtrate became 5.0 μS / cm or less, and finally the mixture was subjected to solid-liquid separation to obtain a toner cake. The obtained toner cake was dried and further classified using a classifier to obtain toner particles 1. The number average particle size of the primary particles of toner particles 1 was 6.5 μm.

[0164] <Preparation Examples of Toner Particles 2 to 24> Toner particles 2 to 24 were obtained in the same manner as in the preparation example of toner particle 1, except that the resin particle dispersion, release agent dispersion, colorant dispersion, and the types and amounts of compound A and compound B added in the dispersion process were changed as shown in Table 3.

[0165] [Table 3]

[0166] <Toner 1 Manufacturing Example> <External addition process> For the toner particles 1 (100.00 parts) obtained above, 0.5 parts of silica fine particles (RY300: manufactured by Nippon Aerosil Co., Ltd.) were added as an external additive to an FM mixer (FM10C type manufactured by Nippon Coke and Engineering Co., Ltd.) with 7°C water passing through the jacket. was added to an FM mixer (FM10C type manufactured by Nippon Coke and Engineering Co., Ltd.) with 7°C water passing through the jacket. After the water temperature inside the jacket stabilized at 7°C ± 1°C, the mixture was mixed for 5 minutes at a peripheral speed of 38 m / sec to obtain toner mixture 1. At this time, the amount of water passing through the jacket was appropriately adjusted so that the temperature inside the FM mixer tank did not exceed 25°C. The obtained toner mixture 1 was sieved through a mesh having an opening of 75 μm to obtain toner 1. The surface exposure rate of Toner 1 was 64%. Table 4 shows the production conditions and physical properties of Toner 1.

[0167] <Toner 2-26 Preparation Examples> Toners 2 to 26 were obtained in the same manner as in Production Example of Toner 1, except that in Production Example of Toner 1, the type of toner particles and the parts of external additives were changed to the conditions shown in Table 4. The physical properties of the toners are shown in Table 4.

[0168] [Table 4] In the toners 1 to 21, 23 and 24, a base peak was present in the mass spectrum. In addition, in the case of toners 1 to 21, 23, and 24, compound A was ionized and detected as a cation in the analysis under analysis condition A. In the case of toners 1, 2, and 5 to 26, compound B was ionized and detected as an anion in the analysis under analysis condition A. In the table, (1) Content [ppm] is the content ratio (mass ppm) of the structure represented by formula (1) contained in compound A based on the mass of the toner.

[0169] <Production examples of cartridges 1 to 3> Cartridges 1 to 3 were produced by changing the power supply as shown in Table 5 so that the voltages applied to the supply roller, regulating member, and developing roller of the process cartridge could be applied independently. As described in the first embodiment, in the process cartridge 1, the same power supply is applied to the supply roller and the regulating member, and the power supply to the developing roller is different. As described in the first embodiment, in the process cartridge 2, the supplying roller, the regulating member, and the developing roller share the same power supply. The process cartridge 3 differs in the power supply applied to the supply roller, the regulating member, and the developing roller. More specifically, the process cartridge 3 is a comparative example in which voltages are supplied to the supply roller 32 and the regulating blade 33 from separate power sources.

[0170] In the configuration of the process cartridge 3, a case will be described in which a voltage that results in a potential difference of -100V with respect to the voltage applied to the developing roller 31 as a set voltage is applied to the supply roller 32 and the regulating blade 33. Figs. 9-1 and 9-2 are a perspective view (Fig. 9-1(a)), a front view (Fig. 9-2(b)), and a rear view (Fig. 9-2(c)) of a voltage supply part 400 attached to the developing unit 2 in the process cartridge 3. Fig. 10 is a circuit diagram when the process cartridge 3 is installed.

[0171] The process cartridge 3 of the comparative example is mounted on an image forming apparatus 100' having two power sources (173, 174) for supplying voltages to the supply roller 32 and the regulating blade 33, respectively. The developing power source 172 and the developing voltage main body contact 182 have the same configurations as those in FIGS. 4-1 and 4-2. The process cartridge 3 has a supply voltage main body contact 193 and a regulating voltage main body contact 194 to supply voltages individually to the supply roller 32 and the regulating blade 33. When the process cartridge 3 is mounted in the image forming apparatus 100', electrical continuity is established as follows: a supply voltage contact 402 and a regulating blade voltage contact 403, which are contacts arranged on a voltage supply component 400 attached to the process cartridge 3, come into contact with and establish electrical continuity with the supply voltage main body contact 193 and the regulating voltage main body contact 194 arranged in the image forming apparatus 100', respectively. The supply voltage contact 402 is formed of conductive resin within the voltage supply component 400, and is electrically connected to the supply voltage contact 402 and the supply roller holding portion 420 (shaded areas in FIGS. 9-1 and 9-2(a), (b), and (c)), supplying voltage to the supply roller 32.

[0172] Similarly, in the voltage supply component 400, the regulating blade voltage contact 403 is electrically connected to a regulating blade contact 430 that contacts the regulating blade 33 (blackened parts in FIGS. 9-1 and 9-2(a), (b), and (c)), and supplies voltage to the regulating blade 33. The developing voltage contact 401 is electrically connected to the developing roller holding portion 410 as in FIG. 3, and supplies voltage to the developing roller 31. Since the developing voltage contact 401, the supply voltage contact 402, and the developing blade voltage contact 403 are insulated from each other, each power supply output voltage of the image forming apparatus 100' can be applied individually. The other configurations of the image forming apparatus 100' are similar to those of the image forming apparatus 100.

[0173] [Table 5]

[0174] <Examples of manufacturing the image forming apparatuses 100, 100', and 200> As image forming apparatuses used in the examples, image forming apparatuses 100 and 100', which are laser printers capable of forming monochrome images using the electrophotographic method described in the first embodiment, were prepared. In addition, an image forming apparatus 200 was prepared as a tandem type full-color laser printer that employs an intermediate transfer method and is capable of forming a full-color image by using an electrophotographic method. Fig. 11 is a schematic cross-sectional view of the image forming apparatus 200 of this embodiment.

[0175] The image forming apparatus 200 of this embodiment has four image forming units PY, PM, PC, and PK that respectively form images of yellow (Y), magenta (M), cyan (C), and black (K). Elements in the image forming units PY, PM, PC, and PK that have the same or corresponding functions or configurations may be generally described by omitting the Y, M, C, or K at the end of the reference numeral indicating that the element is for one of the colors.

[0176] The image forming unit P has a detachable process cartridge 1. The four process cartridges 1Y, 1M, 1C, and 1K each contain a different color of toner, and there are four of them: the three primary colors of yellow (Y), magenta (M), and cyan (C) plus black (K). The configuration and operation of the process cartridge 1 in this embodiment are the same as those of the process cartridge 1 described in the first embodiment. The process cartridge 1 has a photoconductor 11, a charging roller 21, and a developing device 2. Moreover, the image forming portion P has a primary transfer roller 211 which is a roller-type primary transfer member as a primary transfer means. Moreover, in this embodiment, the image forming apparatus 200 has an exposure device 131 configured as one unit for exposing the photoconductors 11 of the four image forming portions PY, PM, PC, and PK.

[0177] An intermediate transfer belt 213, which is a rotatable endless belt serving as an intermediate transfer body, is disposed so as to face the photoconductor 11 of each image forming portion P. The intermediate transfer belt 213 is stretched around a drive roller 214 and a tension roller 215 serving as a plurality of tension rollers (support rollers) and stretched with a predetermined tension. The intermediate transfer belt 213 rotates (moves in a circular motion) when the drive roller 214 is rotationally driven by a driving force transmitted from a belt drive motor (not shown) serving as a driving source constituting a driving means.

[0178] The above-mentioned primary transfer rollers 211 are disposed on the inner peripheral surface side of the intermediate transfer belt 213 in correspondence with the photoconductors 11 of the image forming stations P. The primary transfer rollers 211 press the intermediate transfer belt 213 against the photoconductors 11 to form a primary transfer portion (primary transfer nip) N3 which is a contact portion between the photoconductors 11 and the intermediate transfer belt 213. Further, a secondary transfer roller 212, which is a roller-type secondary transfer member serving as a secondary transfer means, is disposed at a position facing the driving roller 214, which also serves as a secondary transfer opposing roller, on the outer circumferential surface side of the intermediate transfer belt 213. The secondary transfer roller 212 abuts against the driving roller 214 via the intermediate transfer belt 213, and forms a secondary transfer portion (secondary transfer nip) N4, which is a contact portion between the intermediate transfer belt 213 and the secondary transfer roller 212.

[0179] For example, when a full-color image is formed, the toners of the colors Y, M, C, and K formed on the photoconductors 11 are sequentially transferred (primary transfer) in a superimposed manner onto the rotating intermediate transfer belt 213 by the action of the primary transfer rollers 213 at the primary transfer portion N3. The toner images formed on the intermediate transfer belt 213 are transferred (secondary transfer) onto the recording material R, which is sandwiched and transported between the intermediate transfer belt 213 and the secondary transfer roller 212, at the secondary transfer portion N4 by the action of the secondary transfer roller 212. The recording material R is transported from the paper feed portion 181 to the secondary transfer portion N4 in synchronization with the toner images on the intermediate transfer belt 213.

[0180] In addition, the image forming apparatus 200 of this embodiment is roughly divided into 1Y, 1M, 1C and 1K systems in terms of image forming operations. This is to accommodate monochrome printing, and image forming operations are performed only in PK during monochrome printing. In this example, only the 1K developing unit is in contact with the photosensitive drum, while 1Y, 1M, and 1C are in a separated state. This configuration prevents 1Y, 1M, and 1C, which do not contribute to image formation, from being wasted.

[0181] During full-color printing, image formation is performed on all cartridges at appropriate timing. The image forming device 200 is roughly divided into a voltage supply system for PY, PM, and PC, and a voltage supply system for PK. In other words, the same voltage is supplied to 1Y, 1M, and 1C at the same timing (FIG. 12). In both monochrome and color machines, if the voltages applied to the supply roller, regulating member, and developing roller of the process cartridge can be modified to be the same or independent from the power supply for the process cartridge being used, then a modified version of an existing laser printer can be used.

[0182] <Example 1> First, a monochrome image forming apparatus 100 was prepared as an electrophotographic apparatus. Next, the process cartridge in which the toner 1 was filled in the cartridge for the image forming apparatus 100 and the electrophotographic apparatus were left in a normal temperature and humidity environment (25° C. / 50% RH) for 48 hours in order to acclimate them to the measurement environment. After that, the evaluation described below was carried out.

[0183] <Examples 2 to 23, Comparative Examples 1 to 6> The combination of the toner, cartridge and image forming apparatus shown in Table 6 was evaluated in the same manner as in Example 1. In Example 23, image forming apparatus 200 was used as a color machine, and in Comparative Example 6, image forming apparatus 100' was used in which the voltages applied to the supply roller, regulating member, and developing roller were all independent.

[0184] <Evaluation of development ghost> When the cartridge 1 was used in the image forming apparatus left in the above environment, the configuration was as shown in FIG. 5, and the set voltage of the supply / regulation power source was set to a potential difference of −100 V with respect to the voltage applied to the developing roller. When using Cartridge 2, the voltage setting of the supply / regulation power supply was the same as that used for Cartridge 1, but a resistor was inserted as shown in Figure 8 to set the potential difference to -100 V with respect to the voltage applied to the developing roller. When cartridge 3 is used, the configuration is as shown in Figure 10, the set voltage of the supply power source is set so as to result in a potential difference of -100 V with respect to the voltage applied to the developing roller, and the set voltage of the regulated power source is set so as to result in a potential difference of -80 V with respect to the voltage applied to the developing roller. Using the above settings, multiple 10mm x 10mm solid images were formed on the front half of the transfer paper, and a 2 dot 3 space halftone image was formed on the back half. The extent to which the solid images were left on the halftone images was visually confirmed, and ranks A to C were judged to be good. The evaluation results are shown in Table 6. A: No ghosting occurs B: Very slight development ghosting occurs C: Slight development ghosting occurs D: Development ghosting is evident

[0185] <Evaluation of Fog on Photosensitive Drum> The measurement of fogging on the photosensitive drum was performed using a Tokyo Denshoku REFLECTMETER MODEL. Measure using TC-6DS with a green filter. When the cartridge 1 is used in the image forming apparatus left in the above environment, the cartridge is arranged as shown in FIG. The set voltage of the supply / regulation power source was set to a potential difference of −100 V with respect to the voltage applied to the developing roller. When using Cartridge 2, the voltage setting of the supply / regulation power supply was the same as that used for Cartridge 1, but a resistor was inserted as shown in Figure 8 to set the potential difference to -100 V with respect to the voltage applied to the developing roller. When cartridge 3 is used, the configuration is as shown in Figure 10, the set voltage of the supply power source is set so as to result in a potential difference of -100 V with respect to the voltage applied to the developing roller, and the set voltage of the regulated power source is set so as to result in a potential difference of -80 V with respect to the voltage applied to the developing roller.

[0186] With the above settings, immediately after outputting a solid black image, a white image is taped onto the photosensitive drum with Mylar tape, and the reflectance of the Mylar tape applied to a piece of paper is measured. The reflectance of the Mylar tape applied directly to the paper is subtracted from the measured reflectance to calculate the fogging on the photosensitive drum (%), and the result is evaluated according to the following criteria. Fog on photosensitive drum (reflectance) (%) = reflectance of tape taped on drum (%) - reflectance of tape directly applied to paper (%) Ranks A to C were judged to be good. The evaluation results are shown in Table 6. A: Fog on the photosensitive drum is less than 0.4% B: Fog on the photosensitive drum is 0.4% or more and less than 0.7% C: Fog on the photosensitive drum is 0.7% or more and less than 1.0% D: Fog on the photosensitive drum is 1.0% or more

[0187] <Change in fog on photosensitive drum when power supply voltage output variations are assumed> As mentioned above, when the voltage applied to the supply electrode increases due to output variations in the power supply voltage, fogging becomes more likely to occur on the photosensitive drum. Therefore, we confirmed whether the amount of fogging on the photosensitive drum would change when we assumed that output variations in the power supply voltage occurred. In the image forming apparatus left in the above environment, when cartridge 1 was used, the set voltage of the supply / regulation power supply was set to a potential difference of -120 V with respect to the voltage applied to the developing roller, and to a potential difference of -80 V. The fogging was measured using the same calculation method as for the fogging on the photosensitive drum in each of these settings, and the average value was calculated as the fogging on the photosensitive drum (%) when there is variation in the power supply voltage. When using Cartridge 2, the voltage setting of the supply / regulation power supply was the same as that used for Cartridge 1, but by inserting a resistor as shown in Figure 8, the potential difference was set to -120V or -80V with respect to the voltage applied to the developing roller. When cartridge 3 is used, the configuration shown in Fig. 10 is used, and the set voltage of the power supply is set to a potential difference of -120V with respect to the voltage applied to the developing roller. The set voltage of the regulated power supply is set to a potential difference of -100V with respect to the voltage applied to the developing roller, and the set voltage of the power supply is set to a potential difference of -100V with respect to the voltage applied to the developing roller and the set voltage of the regulated power supply is set to a potential difference of -80V with respect to the voltage applied to the developing roller. The fogging was measured using the same calculation method as for the fogging on the photosensitive drum in each of the following settings, and the average value was calculated as the fogging on the photosensitive drum (%) when there is variation in the power supply voltage. This makes it possible to evaluate the set voltage of the power supply as a setting that is unfavorable to fogging on the photosensitive drum due to output variation in the power supply voltage.

[0188] Using these values, the amount of change in fog on the photosensitive drum (%) is calculated and evaluated according to the following criteria. Amount of change in fog on the photosensitive drum (%) = Fog on the photosensitive drum when there is output variation in the power supply voltage (%) - Fog on the photosensitive drum (%) Ranks A and B were judged to be good. The evaluation results are shown in Table 6. A: The change in fog on the photosensitive drum is less than 0.2%. B: The amount of change in fog on the photosensitive drum is 0.2% or more and less than 0.5%. C: The amount of change in fog on the photosensitive drum is 0.5% or more and less than 0.7%. D: The change in fog on the photosensitive drum is 0.7% or more.

[0189] [Table 6]

[0190] The present disclosure relates to the following configurations. (Configuration 1) Toner; a developing roller carrying the toner on its surface; a developing container that rotatably supports the developing roller; a toner storage section for storing the toner; a supply member that contacts the surface of the developing roller to supply the toner from the toner storage portion to the surface of the developing roller; a regulating member that contacts the surface of the developing roller to regulate the toner carried on the surface of the developing roller, the cartridge includes a first supply electrode to which a voltage is supplied from outside the cartridge; the supply member and the regulating member are electrically connected to the same first supply electrode; The toner contains a compound A having a structure represented by the following formula (1): -(CH2CH2O)- (1) When the toner is subjected to an elution treatment under the following elution condition A, the compound A is eluted in methanol, When the supernatant obtained by centrifuging the eluate in which the compound A was eluted in methanol under the following centrifugation condition A was analyzed by liquid chromatography ESI / MS in the range of m / z = 50 to 1500, There is a base peak defined as follows: The average m / z defined as follows is 300 to 1000, A cartridge characterized by: Dissolution condition A: At 25° C., 10 times the mass of the toner is used in methanol (JIS K8891 equivalent), and the toner is stirred for 10 hours at a rotor speed of 200 rpm using a stirring device. Centrifugation condition A: Rotation is performed for 30 minutes at 25° C., a rotation radius of 10.1 cm, and a rotation speed of 3,500 rpm. Reference peak: In the mass spectrum obtained by liquid chromatography ESI / MS of the supernatant, the peak with the highest intensity is taken as an abundance of 100% to obtain a relative abundance. Peaks are selected in descending order of relative abundance, and the m / z value of the peak top of the selected peaks is designated as P. Among the selected peaks having a relative abundance of 10% or more and a peak top m / z value of P+44 or P-44, the peak with the highest relative abundance is designated as the reference peak. Average m / z: The m / z value of the peak top of the reference peak is defined as Ps, and the average m / z value of the peak top of peaks having a relative abundance of 30% or more, where the peak top m / z value = Ps + 44n (n is an integer), is defined as the average m / z value. (Configuration 2) The toner is a negatively charged toner, When the supernatant was supplied to a liquid chromatograph ESI / MS analyzer and analyzed under the following analysis condition A, 2. The cartridge according to configuration 1, wherein the compound A contained in the supernatant is ionized as a cation and detected. Analysis condition A: Sheath Gas: 10 (arb. unit.), Aux Gas: 5 (arb. unit.), spray voltage: 5 kV, capillary temperature: 275°C. Ionized substances are detected as cations under the conditions of capillary voltage: 35 V, tube lens voltage: 110 V, and ionized substances are detected as anions under the conditions of capillary voltage: -35 V, tube lens voltage: -110 V. (Configuration 3) the toner contains a compound B which dissolves in methanol when the toner is subjected to an elution treatment under the elution condition A, When the supernatant was supplied to a liquid chromatograph ESI / MS analyzer and analyzed under the following analysis condition A, 3. The cartridge according to configuration 1 or 2, wherein compound B contained in the supernatant is ionized as an anion and detected. Analysis condition A: Sheath Gas: 10 (arb. unit.), Aux Gas: 5 (arb. unit.), spray voltage: 5 kV, capillary temperature: 275°C. Ionized substances are detected as cations under the conditions of capillary voltage: 35 V, tube lens voltage: 110 V, and ionized substances are detected as anions under the conditions of capillary voltage: -35 V, tube lens voltage: -110 V. (Configuration 4) When the supernatant was analyzed by a liquid chromatograph ESI / MS analyzer, a peak was detected at m / z=325; The peak detected at m / z=325 was analyzed by the liquid chromatograph ESI / MS analyzer. The cartridge according to configuration 3, in which a peak is detected at m / z=183 or m / z=197 when analyzed under analysis condition B using a directly connected tandem mass spectrometer. Analysis condition B: Sheath Gas: 10 (arb. unit.), Aux Gas: 5 (arb. unit.), spray voltage: 5 kV, capillary temperature: 275°C. Ions generated under the conditions of capillary voltage: -35 V, tube lens voltage: -110 V are detected as anions, and the ion detected at m / z = 325 is selected as a precursor ion, and ions that are collision-induced dissociated in inert gas: He with a collision energy of 35 eV are detected. (Configuration 5) 5. The cartridge according to any one of configurations 1 to 4, wherein the content of the structure represented by formula (1) contained in compound A is 50 to 1500 ppm by mass based on the mass of the toner. (Configuration 6) In the analysis of the supernatant under the analysis condition A, The cartridge according to configuration 3 or 4, wherein a ratio P / N of a peak area P of a cation including the compound A to a peak area N of an anion including the compound B, calculated from a chromatogram analyzed under the following analytical condition C, is 0.20 to 2.00. Analysis condition C: In an apparatus configuration using methanol as the mobile phase and no stationary phase, 10 μL of solution was injected at a flow rate of 1 ml / min, the acquisition time was 5 min, and the detector was a UV detector, and the range of m / z = 50 to 1500 was analyzed to obtain a chromatogram. (Configuration 7) The toner includes toner particles and an external additive on the surface of the toner particles, 7. The cartridge according to any one of Configurations 1 to 6, wherein the surface exposure rate of the toner particles is 50 area % or more. (Configuration 8) 8. The cartridge according to any one of configurations 1 to 7, wherein the toner is a non-magnetic toner. (Configuration 9) The cartridge according to any one of configurations 1 to 8, further comprising an electric element between the first supply electrode and the supply member. (Configuration 10) The cartridge according to any one of configurations 1 to 9, further comprising an electric element between the first supply electrode and the regulating member. (Configuration 11) the cartridge includes a second supply electrode different from the first supply electrode and to which a voltage is supplied from outside the cartridge; 11. The cartridge according to any one of configurations 1 to 10, further comprising an electric element between the second supply electrode and the developing roller. (Configuration 12) the developing roller is not electrically connected to the supply member and the regulating member, 12. The cartridge according to configuration 11, wherein the developing roller is electrically connected to the second supply electrode. (Configuration 13) 13. The cartridge according to any one of configurations 1 to 12, comprising a photosensitive drum as an image bearing member, and a charging member for charging the surface of the photosensitive drum. (Configuration 14) An image forming apparatus including the cartridge according to any one of configurations 1 to 13, an image forming apparatus that applies the same voltage to the supply member and the regulating member via the first supply electrode; (Configuration 15) After the toner developed on the surface of the photosensitive drum is transferred to the outside, 14. The cartridge according to claim 13, wherein the toner remaining on the surface is collected by the developing roller. (Configuration 16) A cartridge as described in configuration 13, wherein when the photosensitive drum is rotated, the area of ​​the photosensitive drum that forms a developing section where the photosensitive drum and the developing roller contact each other does not come into contact with a contact member while moving to a charging section where the photosensitive drum and the charging member contact each other. (Configuration 17) 17. The cartridge according to configuration 16, wherein the contact member is a cleaning member that cleans the surface of the photosensitive drum. [Explanation of symbols]

[0191] 1: process cartridge 1, 2: developing device, 3: photosensitive unit 3, 31: developing roller, 32: supply roller, 33: developing blade, 36: developing container, 11: photosensitive member, 21: charging roller 21

Claims

1. A toner, a developing roller for carrying the toner on its surface, a developing container for rotatably supporting the developing roller, a toner storage section for storing the toner, a supply member that abuts on the surface of the developing roller and supplies the toner from the toner storage section to the surface of the developing roller, a regulating member that abuts on the surface of the developing roller and regulates the toner carried on the surface of the developing roller, and a cartridge comprising: the cartridge includes a first supply electrode to which a voltage is supplied from outside the cartridge, the supply member and the regulating member are electrically connected to the same first supply electrode, the toner contains a compound A having a structure represented by the following formula (1), -(CH ２ CH ２ O)-...(1) the content ratio of the structure represented by the formula (1) contained in the compound A based on the mass of the toner is 50 to 1500 ppm by mass, when the toner is subjected to an elution treatment under the following elution condition A, the compound A elutes into methanol, when the supernatant obtained by centrifuging the eluate in which the compound A has eluted into the methanol under the following centrifugation condition A is analyzed by liquid chromatography ESI / MS in the range of m / z = 50 to 1500, there is a reference peak defined as follows, the average m / z defined as follows is 300 to 1000, A cartridge characterized by the above. Elution condition A: At 25°C, use methanol (equivalent to the JIS K8891 standard product) 10 times the mass of the toner, and stir for 10 hours at a rotor rotation speed of 200 rpm using a stirrer. Centrifugation condition A: At 25°C, rotate for 30 minutes at a rotation radius of 10.1 cm and a rotation speed of 3500 rpm. Reference peak: In the mass spectrometry spectrum obtained by liquid chromatography ESI / MS of the supernatant, the relative abundance is obtained with the peak having the highest intensity as 100%. Select peaks in descending order of relative abundance, and let the m / z value of the peak top of the selected peak be P. Among the selected peaks where there is a peak with a relative abundance of 10% or more and the m / z value of the peak top is P + 44 or P - 44 the selected peak with the highest relative abundance among them is defined as the reference peak. Average m / z: Let the m / z value of the peak top of the reference peak be Ps, and the m / z value of the peak top = Ps + 44n (n is an integer), and the average value of the m / z of the peak top of the peak with a relative abundance of 30% or more is defined as the average m / z.

2. The toner is a negatively charged toner, when the supernatant liquid is supplied to a liquid chromatograph ESI / MS analyzer and analyzed under the following analysis condition A, the cartridge according to claim 1, wherein the compound A contained in the supernatant liquid is ionized as a cation and detected. Analysis condition A: Under the conditions of Sheath Gas: 10 (arb. unit), Aux Gas: 5 (arb. unit), spray voltage: 5 kV, capillary temperature: 275°C, those ionized under the conditions of capillary voltage: 35 V and tube lens voltage: 110 V are detected as cations, and those ionized under the conditions of capillary voltage: -35 V and tube lens voltage: -110 V are detected as anions.

3. the toner contains a compound B that elutes in methanol when the toner is eluted under the elution condition A, when the supernatant liquid is supplied to a liquid chromatograph ESI / MS analyzer and analyzed under the following analysis condition A, the cartridge according to claim 1 or 2, wherein the compound B contained in the supernatant liquid is ionized as an anion and detected. Analysis condition A: Under the conditions of Sheath Gas: 10 (arb. unit), Aux Gas: 5 (arb. unit), spray voltage: 5 kV, capillary temperature: 275°C, those ionized under the conditions of capillary voltage: 35 V and tube lens voltage: 110 V are detected as cations, and those ionized under the conditions of capillary voltage: -35 V and tube lens voltage: -110 V are detected as anions.

4. when the supernatant liquid is analyzed with a liquid chromatograph ESI / MS analyzer, a peak is detected at m / z = 325, the cartridge according to claim 3, wherein when the peak detected at m / z = 325 is analyzed with a tandem mass spectrometer directly connected to the liquid chromatograph ESI / MS analyzer under analysis condition B, peaks are detected at m / z = 183 or m / z = 197. Analysis condition B: Under the conditions of Sheath Gas: 10 (arb. unit), Aux Gas: 5 (arb. unit), Spray voltage: 5 kV, and Capillary temperature: 275 °C, those ionized under the conditions of Capillary voltage: -35 V and Tube lens voltage: -110 V are detected as anions, and the ions detected at m / z = 325 are selected as precursor ions, and the ions collision-induced dissociated with Collision energy: 35 eV in Inert gas: He are detected.

5. In the analysis of the supernatant under the analysis condition A, The cartridge according to claim 3, wherein the value P / N of the ratio of the peak area P of the cation containing the compound A to the peak area N of the anion containing the compound B, calculated from the chromatogram analyzed under the following analysis condition C, is 0.20 to 2.

00. Analysis condition C: In a device configuration using methanol as the mobile phase and not using a stationary phase, when injecting a 10 μL solution at a flow rate of 1 ml / min, the acquisition time is 5 min, the detector is a UV detector, and the range of m / z = 50 to 1500 is analyzed to obtain a chromatogram.

6. The toner contains toner particles and an external additive on the surface of the toner particles, The cartridge according to claim 1 or 2, wherein the surface exposure rate of the toner particles is 50 area% or more.

7. The cartridge according to claim 1 or 2, wherein the toner is a non-magnetic toner.

8. The cartridge according to claim 1 or 2, comprising an electrical element between the first supply electrode and the supply member.

9. The cartridge according to claim 1 or 2, comprising an electrical element between the first supply electrode and the restricting member.

10. The cartridge comprises a second supply electrode to which a voltage is supplied from outside the cartridge, different from the first supply electrode, The cartridge according to claim 1 or 2, comprising an electrical element between the second supply electrode and the developing roller.

11. The developing roller is not electrically connected to the supply member and the restricting member, The cartridge according to claim 10, wherein the developing roller is electrically connected to the second supply electrode.

12. The cartridge according to claim 1 or 2, comprising a photosensitive drum as an image carrier and a charging member for charging the surface of the photosensitive drum.

13. An image forming apparatus comprising the cartridge according to claim 1 or 2, An image forming apparatus that applies the same voltage to the supply member and the regulating member via the first supply electrode. **Claim 14** The cartridge according to claim 12, wherein after transferring the toner developed on the surface of the photosensitive drum to the outside, the toner remaining on the surface of the photosensitive drum is collected by the developing roller. **Claim 15** The cartridge according to claim 12, wherein when the photosensitive drum is rotated, a region of the photosensitive drum that forms a developing portion in contact with the developing roller does not contact the contact member while moving to a charging portion where the photosensitive drum contacts the charging member. **Claim 16** The cartridge according to claim 15, wherein the contact member is a cleaning member that cleans the surface of the photosensitive drum.

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