JP6566742B2 - Developing apparatus and image forming method - Google Patents

Description

  The present invention relates to a developing device and an image forming method used in a recording method using an electrophotographic method, an electrostatic recording method, and an electrostatic printing method.

  In an image forming apparatus using an electrophotographic image forming process, a process cartridge system is adopted in which a photosensitive member and process means acting on the photosensitive member are integrally formed into a cartridge and the cartridge can be attached to and detached from the image forming apparatus main body. ing.

  According to this process cartridge system, the maintenance of the apparatus can be performed by the user himself / herself without depending on the service person, so that the operability can be remarkably improved. For this reason, this process cartridge system is widely used in image forming apparatuses.

  Further, in the process cartridge type image forming apparatus, since the user himself replaces the process cartridge as described above, a toner remaining amount detecting means for notifying the user when the toner is consumed is provided. Many. As one method of this toner remaining amount detecting means, there is a method of detecting a toner amount by detecting a change in electrostatic capacitance between a plurality of electrodes arranged in a process cartridge.

  As a configuration of these electrodes, an electrode plate detection type in which an electrode plate is arranged at a predetermined interval from the toner carrier and the electrostatic capacitance between the toner carrier and the toner carrier is detected (for example, patent document). 1). In general, SUS304 or SUS316 is used for the electrode plates used in these inventions.

  However, when these SUS electrodes are used, the magnetic toner adheres to the electrodes when the magnetic toner is used. This is because SUS304 or SUS316 austenitic steel is magnetized by being subjected to stress or heat such as cutting or cutting, thereby causing martensitic transformation and precipitation of a ferrite layer.

  As a result, the magnetic toner adheres to the magnetized electrode, and the accuracy of detecting the remaining amount of toner decreases. In particular, since the toner tends to be in a packing state due to its own weight or pressure by the stirring / conveying member in the vicinity of the toner carrier, the toner is more likely to adhere to the SUS electrode, and the accuracy of detecting the remaining amount of toner in the cartridge is further reduced. It will be.

  In order to detect the remaining amount of toner with high accuracy, improvements from toner have also been made. For example, Patent Document 2 proposes that toner with improved toner fluidity is used to improve the accuracy of detecting the remaining amount of toner.

  It is described that this system can accurately determine the remaining amount of toner even in a situation where the remaining amount of toner is low. However, the above proposal is an evaluation based on continuous output, and is not an evaluation that takes into account the situation in which the fluidity of the toner is more likely to change, such as intermittent evaluation and use in a high temperature and high humidity environment.

  In this way, there is still room for studying the remaining amount detection with high accuracy.

JP 2007-264612 A JP 2007-286202 A

  It is an object of the present invention to accurately detect the amount of toner remaining in the developing device regardless of the environment and printing state in a configuration in which toner is supplied to the toner carrier by a specific method, and sequentially determine the remaining amount of toner. It is possible to provide a developing device and an image forming method having a toner remaining amount detecting means that can be notified to the user and extremely useful for the user.

The present invention provides a toner,
A toner carrier;
Accommodates the toner, and a toner container having a toner stirring member for supplying the toner to the toner carrying member therein,
A developing device that can be installed in the main body of the printer ,
There is a region formed of a nonmagnetic conductive resin member on the bottom surface of the toner container,
Said toner carrying member and the first electrode, the region as a second electrode, the amount of the toner in the toner storing portion based on the capacitance between the first electrode and the second electrode the detection is performed are configured so that,
The toner stirring member is a member that is rotatable about a direction parallel to the longitudinal direction of the toner carrier, and the rotation center of the toner stirring member when the developing device is installed in the main body of the printer. installation surface parallel to said line of printers through the shaft, wherein a member which is arranged so as to pass below the lower end of the toner carrying member, and, the toner from the lower side of the toner carrying member to the toner carrying member A member for supplying,
The toner is
Toner particles containing a binder resin and a magnetic material,
An external additive ,
Toner der with is,
Of the toner was measured using a powder flowability analyzer, fifth total energy at the time of measurement after compression, not less than 70 mJ 105MJ less,
The developing apparatus according to claim 1 , wherein the toner has a uniaxial collapse stress at a maximum consolidation stress of 10.0 kPa of 2.5 kPa to 4.5 kPa .

Further, the present invention is that the electrostatic latent image formed on the latent electrostatic image bearing member is developed with toner carried on the toner carrying member in the developing device, and said in the toner accommodating portion in the developing device An image forming method for detecting the amount of toner,
The developing device is
The toner;
The toner carrier;
Accommodates the toner, and, with the toner storage portion that having a toner stirring member for supplying the toner to the toner carrying member therein,
A developing device having,
There is a region formed of a nonmagnetic conductive resin member on the bottom surface of the toner container,
Development by the toner, the toner stirring member, wherein a direction parallel to the longitudinal direction of the toner carrying member is rotated as a rotation axis, said supplying toner from the lower side of the toner carrying member to the toner carrying member, wherein performed by the toner carried on the toner carrying member,
Detection of the amount of the toner in the toner accommodating portion, said toner carrying member and the first electrode, the region as a second electrode, the electrostatic between the first electrode and the second electrode Based on capacity,
The toner is
Toner particles containing a binder resin and a magnetic material,
An external additive ,
Toner der with is,
Of the toner was measured using a powder flowability analyzer, fifth total energy at the time of measurement after compression, not less than 70 mJ 105MJ less,
The present invention relates to an image forming method, wherein the toner has a uniaxial collapse stress at a maximum consolidation stress of 10.0 kPa of 2.5 kPa to 4.5 kPa .

  As described above, according to the present invention, it is possible to accurately detect the amount of toner remaining in the developing device regardless of the environment and the printing state.

1 is a schematic configuration diagram of an image forming apparatus having a developing device according to an embodiment of the present invention. 1 is a schematic cross-sectional view of a developing device according to an embodiment of the present invention. FIG. 3 is a schematic cross-sectional view of a toner remaining amount detecting unit according to an embodiment of the present invention. It is a field diagram in which a conductive resin member is formed. It is explanatory drawing explaining an example of the conductive resin sheet which concerns on this invention. FIG. 6 is a relationship diagram between a remaining toner amount and electrostatic capacity according to an embodiment of the present invention. FIG. 6 is an example of a relationship diagram between a remaining toner amount and electrostatic capacity in an example according to the present invention and a comparative example. FIG. 6 is a diagram illustrating a state of toner in a toner container. It is explanatory drawing of the propeller-type blade used for the measurement of total energy. It is explanatory drawing of the measuring method of resistance.

  As a result of intensive studies on the toner remaining amount detecting means and the toner used therein, the present inventors have used a specific configuration and member as an electrode in a configuration in which toner is supplied to the toner carrier by a specific method. The inventors have found that by controlling the fluidity of toner, the remaining amount of toner can be accurately detected regardless of the environment and the printing state.

  A developing device and an image forming apparatus according to the present invention will be described below with reference to the drawings. However, the dimensions, materials, shapes, and relative arrangements of the components described are to be changed as appropriate according to the configuration of the apparatus to which the invention is applied and various conditions, and the scope of the invention is limited to the following. Not intended to do.

<Description of Image Forming Apparatus and Image Forming Process>
FIG. 1 shows a schematic configuration of an electrophotographic laser beam printer as an example of the image forming apparatus of the present invention.

  An image forming apparatus 12 using the electrophotographic technology of the present case includes a photoreceptor 1 that is an electrostatic latent image carrier. Around the photoconductor 1, in order along the rotation direction of the photoconductor 1, a charging roller 2 as a charging unit, an exposure device 6 as an exposure unit, a developing device 3 as a developing unit, a transfer roller 4 as a transfer unit, A cleaning device 5 having a cleaning blade 5a as a cleaning means is disposed. A fixing device 7 is disposed downstream of the transfer nip N formed between the photosensitive member 1 and the transfer roller 4 in the transfer material conveyance direction.

<Detailed Description of Image Forming Apparatus>
In this embodiment, the photosensitive member 1 has an OPC photosensitive layer on an aluminum drum base, and is driven in a direction indicated by an arrow at a predetermined peripheral speed by a driving unit (not shown) provided on the image forming apparatus main body side. It is rotationally driven (clockwise).

  A charging roller 2 as a charging unit uniformly charges the photosensitive member 1 to a predetermined polarity and potential by a charging bias applied from a charging bias power source (not shown). As the charging bias, an AC voltage Vpp at which the charging roller 2 is sufficiently discharged and a DC voltage Vdc corresponding to the photosensitive member dark portion potential Vd are superimposed and applied. For the AC AC component of the charging bias, constant current control is performed such that a constant current always flows between the photoconductor 1 and the charging roller 2.

  The exposure apparatus 6 uses a laser output unit to output laser light (exposure beam L) obtained by modulating image information input from a personal computer (not shown) or the like according to a time-series electrical digital image signal by a video controller (not shown). (Not shown). The exposure beam L scans and exposes the surface of the charged photoreceptor 1 to form an electrostatic latent image corresponding to image information.

  The developing device 3, the voltage applying unit 15, and the toner remaining amount detecting unit 17 (not shown) will be described in detail later.

  A transfer roller 4 serving as a transfer unit contacts the surface of the photoreceptor 1 with a predetermined pressing force to form a transfer nip portion N, and a transfer bias is applied from a transfer bias power source (not shown). With this transfer bias, the toner image on the surface of the photoconductor 1 is transferred to a transfer material P such as paper at the transfer nip N between the photoconductor 1 and the transfer roller 4.

  The fixing device 7 includes a heating roller and a pressure roller provided with a halogen heater (not shown) inside. While the transfer material P is nipped and conveyed at the fixing nip between the fixing roller and the pressure roller, the toner image transferred onto the surface of the transfer material P is heated, melted and pressed to be thermally fixed to obtain a permanent image. The permanent image on the transfer material P that has been fixed is discharged out of the image forming apparatus 12.

  A cleaning blade 5a as a cleaning unit cleans toner remaining without being transferred onto the photoreceptor 1, and the photosensitive drum 1 is again used for image formation.

  The photosensitive member 1, the charging roller 2, the developing device 3, and the cleaning blade 5a are integrated as a unit, and form a detachable process cartridge in the image forming apparatus main body.

<Details of developing device>
Details of the developing device 3 will be described with reference to FIG. The developing device 3 includes a developing container 3a as a toner storage unit, toner T, a toner agitating member 10 for agitating the toner T, a toner carrier 8 and a magnet roller 8a as a developer carrier, and a toner T on the toner carrier 8. The developing blade 11 that regulates the layer thickness and frictionally charges, the seal member 3 b that seals the toner T, and the antenna member 14 that detects the remaining amount of toner.

  The toner carrier 8 is a non-magnetic aluminum sleeve surface coated with a medium resistance resin layer. The arrangement is opposite the surface of the photoreceptor 1, and both ends of the sleeve are rotatably supported by the opening of the developing device 3. The sleeve is connected to voltage application means 15 disposed in the image forming apparatus main body, and applies a bias at a predetermined timing during printing.

  The stirring member 10 includes a support rod and a stirring sheet. Both ends of the support bar are supported by the developing container 3a, rotate about a direction parallel to the longitudinal direction as a rotation axis, and rotate clockwise in the figure. The agitating member 10 is disposed such that a line parallel to the printer installation surface passing through the rotation center axis of the agitating member 10 passes below the lower end of the toner carrier when the developing device 3 is installed in the printer body. . Thereby, the stirring member 10 supplies the toner to the toner carrier from below the toner carrier. As the stirring sheet, a PPS sheet having a thickness of 100 μm was used, and one end in the short direction was pressure-bonded to the support rod.

  A magnet roller 8a, which is a magnetic field generating means, is in the toner carrier 8, and a plurality of magnetic poles N and S are alternately formed. In addition, the magnetic poles are always kept in the same direction because they are always held at a fixed position without rotating.

  The developing blade 11 has a urethane rubber blade bonded and fixed to a support sheet metal. The support sheet metal is fixed to the developing container 3a so as to come into contact with the toner carrier 8 with an appropriate contact pressure in order to appropriately regulate the layer thickness of the toner T and to perform frictional charging.

  The seal member 3b is adhered in the developing container 3a so that the toner T does not leak from the region in the drawing in order to prevent toner leakage during transportation. The antenna member 14 will be described in detail later.

  With the above configuration, after the seal member 3 b is removed, the toner T is sent to the vicinity of the toner carrier 8 by the stirring member 10. The toner T in the vicinity of the toner carrier 8 is supplied to the surface of the toner carrier 8 by the magnetic field of the magnet roller 8a. Thereafter, the toner T on the surface of the toner carrier 8 is optimized by the developing blade 11 and is charged by friction charging. The charged toner T visualizes the electrostatic latent image on the photosensitive member as a toner image in the development region.

<Detailed Explanation of Toner Remaining Detection Unit>
Next, with reference to FIG. 3, the toner remaining amount detecting means, which is a feature of the present invention, will be described.

  In the present invention, the toner remaining amount detecting means 17 includes a voltage applying means 15 for applying a bias to the electrodes, a toner carrier 8 as an electrode, an antenna member 14 as an opposite electrode, and a toner remaining amount detecting device 18. Become. The toner carrier 8 is as described above.

  The antenna member 14 is a nonmagnetic conductive resin member in which conductivity is ensured by dispersing carbon in polystyrene resin (hereinafter referred to as PS resin). Thus, by using the non-magnetic conductive resin member as the antenna member, the remaining amount detection accuracy of the toner can be improved without magnetizing the electrode.

  Further, the conductive resin member is preferably a flexible conductive resin sheet. The conductive resin sheet having flexibility is installed along the lower surface of the toner container. As a result, the conductive resin sheet can contact toner more densely with the toner accumulated by gravity as a surface instead of a point, and the remaining amount of toner can be measured more accurately.

  It is not necessary to use PS resin or carbon as long as it is non-magnetic and conductive.

  The conductive resin member was bonded and fixed with a double-sided tape near the toner carrier 8 on the bottom surface of the inner wall of the developing container 3a. The fixing method may be any method that can be fixed to the frame as an electrode, such as insert molding, coating, and two-color molding. The conductive resin member is disposed so as to be in contact with a contact (not shown) disposed in front of the bottom surface of the conductor developing container 3a, and is grounded via a toner remaining amount detecting device 18 disposed in the image forming apparatus. It is connected to the.

  In the above configuration, by applying a bias to the toner carrier 8 by the voltage application means 15, the electrostatic capacity between the toner carrier 8 and the antenna member 14 can be detected by the toner remaining amount detection device 18. At this time, since the dielectric constant of the toner is larger than the dielectric constant of air, the detected capacitance increases as the amount of toner existing between the electrodes increases. In the configuration of the present embodiment, sequential remaining amount detection for sequentially detecting capacitance during printing is performed.

<About antenna members>
The antenna member 14 is arranged so that a nonmagnetic or diamagnetic conductive resin member is opposed to the vertically lower side of the toner carrier so that the toner, which is a magnetic material, does not adhere. Specifically, the bottom surface of the inner wall of the developer container 3a was adhered and fixed to the vicinity of the toner carrier 8 with a double-sided tape.

  The antenna member 14 is preferably arranged in the vicinity of the toner carrier 8 in the short direction. This is because the toner that is regulated and dropped by the developing blade 11 is accurately detected as the remaining toner.

  In this embodiment, the conductive resin sheet is provided so that a part of the conductive resin sheet overlaps with a part of the toner carrier in the direction of gravity so that the electrostatic capacity can be detected more appropriately (see FIG. 3). Region A).

  When the antenna member 14 is in the vicinity of the lower portion of the toner carrier 8 and the toner is likely to be deposited on the electrode surface by gravity, the conductive resin sheet containing resin adheres to the magnetic toner with magnetic force. Therefore, the remaining amount of toner can be measured accurately.

  Also in this embodiment, a conductive resin sheet is provided below the toner carrier in the direction of gravity.

  Further, as shown in FIG. 4, an area formed of the nonmagnetic conductive resin member on the bottom surface of the toner storage portion is 50% or more with respect to the longitudinal direction of the toner carrier when the developing device is viewed from above. It is preferable for the presence of 40% or more in the direction orthogonal to the longitudinal direction of the toner carrier to improve the accuracy of remaining toner detection. In particular, it is effective in an environment where the toner is loosened as in continuous use and has good fluidity.

Further, the resistance of the conductive resin member measured by the method described later is 1.0 × 10 ³ Ω or more and 1.0 × 10 ⁵ Ω or less, so that the adhesion of the magnetic toner to the antenna member is controlled. It is preferable when doing.

  FIG. 5 shows a cross-sectional view of the conductive resin member. Here, a configuration in which a carbon material is dispersed in a resin, a configuration in which another resin layer is sandwiched between resin layers in which the carbon material is dispersed, and a configuration in which a carbon material is applied to the surface of the resin layer on the toner carrier side will be described.

  FIG. 5A shows a conductive resin sheet having a three-layer structure in which a resin layer of PS resin 14d is sandwiched between conductive layers 14c (20 μm to 40 μm) in which carbon black is mixed with PS resin and dispersed.

  In this case, the conductive layer becomes the electrode portion, and the entire conductive resin sheet becomes the electrode. In the electrical connection with the outside, when the conductive resin sheet is cut, the conductive layers on both sides are deformed and connected. It is conceivable to connect an external electrical contact to that part.

  Further, it is also possible to use a conductive resin sheet having a single layer structure (single layer structure) in which carbon black 14e is mixed with EVA resin 14d as shown in FIG. 5B. In this case, the whole becomes an electrode part.

  Furthermore, a conductive resin sheet having a two-layer structure in which carbon black 14e is printed on PS resin 14d as shown in FIG. 5C can also be used.

  In this embodiment, a flexible single-layer conductive resin sheet in which carbon black is dispersed in the EVA substrate shown in FIG. 5B is used.

<Toner remaining amount calculation method>
Next, a method for calculating the remaining amount of toner will be described with reference to FIG.

  FIG. 6 is a relationship diagram between the remaining amount of toner and the capacitance according to the present invention. The vertical axis represents the electrostatic capacity detected by the toner remaining amount detecting means 17, and the horizontal axis represents the toner remaining amount. In the configuration of this embodiment, the capacitance does not change from the initial time (when the toner is fully loaded) to 20% (dotted line A). This is because a sufficient amount of toner remains, and the amount of toner between the toner carrier 8 and the antenna member 14 does not change. When the remaining amount of toner is 20% or later, the electrostatic capacity decreases linearly as the remaining amount of toner decreases. This indicates that the amount of toner between the toner carrier 8 and the antenna member 14 changes according to the remaining amount of toner.

Here, when new, the difference between the electrostatic capacity C _{0 when} no toner is present between the toner carrier 8 and the antenna member 14 and the electrostatic capacity when the toner remaining amount is in the range of Full to 20% is ΔE ₀ . did. Further, when the average value of the electrostatic capacity during printing of one image is output as the electrostatic capacity C, the toner is placed between the electrostatic capacity during image printing and the toner carrier 8 and the antenna member 14. The difference from the electrostatic capacity C ₀ in the absence of this was taken as ΔE. Therefore, the current remaining toner amount is calculated by the following equation (1).
Current remaining toner amount = 20% × ΔE / ΔE ₀ Formula (1)

  The detection result is transmitted to the user by being displayed on a display unit (not shown) in the image forming apparatus or a monitor (not shown) of a personal computer.

  FIG. 7A shows the relationship between the remaining amount of toner actually measured after endurance and the output electrostatic capacity in the configuration of this embodiment. FIG. 7B shows the relationship between the remaining amount of toner actually measured and measured in Comparative Example 1 and the output capacitance. The horizontal axis is the remaining amount of toner actually remaining in the developer container 3a, and the vertical axis is the capacitance.

  In FIG. 7A, which is the configuration of the present embodiment, there is no change in capacitance when the remaining amount of toner is between 100% and 20%. In the area where the remaining amount of toner is 20% or less, the electrostatic capacity decreases linearly as the remaining amount of toner decreases. Here, white spots occurred on the image at the timing of (1) in FIG. At this time, no toner adhered to the antenna member 14. Therefore, even if the developing device is shaken at the timing (1), the white spots were not recovered.

  On the other hand, as shown in FIG. 7B, in Comparative Example 1, as in the configuration of the present embodiment, there is no change in the electrostatic capacity when the remaining amount of toner is between 100% and 20%. In the area where the remaining amount of toner is 20% or less, the electrostatic capacity decreases linearly as the remaining amount of toner decreases. However, a blank image occurred at a timing when the remaining amount of toner is larger than that in the configuration of the present embodiment ((2) in FIG. 7B). When the antenna member 14 was confirmed at this time, the toner adhered to the antenna member 14. Even if the same amount of toner remains between the electrodes, the toner adhering to the antenna member 14 cannot be developed. Therefore, white spots have occurred at timing (2) when the detected toner amount is large.

  The toner is attached to the antenna member 14 because the antenna member 14 is magnetized. Further, when the toner adhering to the antenna member 14 was sucked and the remaining amount of toner was measured again, the detected remaining amount of toner (3) was obtained as in Example 1. The image at that time was a blank image as in the timing (2). As described above, in the first comparative example, the generation timing of the whiteout image differs depending on the amount of toner attached to the antenna member 14. Further, the amount of toner attached to the antenna member 14 varies from one developing device to another. Therefore, the remaining toner detection accuracy is lowered.

  As described above, in the configuration of this example, since the toner does not adhere to the antenna member 14 at the timing (1), it is shown that the toner between the electrodes can be used with good reproduction. That is, a decrease in the remaining toner detection accuracy due to the toner adhering to the antenna member 14 can be suppressed, and the remaining toner detection accuracy is improved.

  To improve the accuracy of toner remaining amount detection, toner design is also important.

  In the toner remaining amount detecting means of the present invention, a conductive resin member is present as a part of the bottom surface of the toner containing portion as an electrode. Then, the AC voltage component of the developing bias is applied to the toner carrier 8 by the voltage application means 15, and the electrostatic capacitance between the toner carrier 8 and the antenna member 14 is observed for detection. Therefore, the presence of the toner layer in a uniform state with no voids on this surface is important in improving the accuracy of toner remaining amount detection.

  In the toner storage unit, the toner is agitated by the agitating member 10 and the toner rises in the toner storage unit, so that the toner cannot be sufficiently supplied to the toner carrier 8 and the accuracy of the remaining toner detection may deteriorate. is there. In addition, when white spots occur from the analysis when white spots occur, white spots occur due to toner adhering to the antenna member 14 and the toner carrier 8, and the remaining toner amount. In some cases, the accuracy of detection deteriorates. In addition, when the toner supplied to the toner carrier 8 by the stirring member forms the toner layer, the toner forms the toner layer with a gap and is unevenly placed on the toner remaining amount detecting means. There is also. Further, when the toner supplied to the toner carrier 8 forms a toner layer, the toner is concentrated on the toner remaining amount detecting means due to toner aggregation and the toner is loaded, so that the accuracy of the toner remaining amount detection is deteriorated. The above four phenomena are conspicuous when the remaining amount of toner is low, and cause the accuracy of detecting the remaining amount of toner to deteriorate.

  As a result of intensive studies, the present inventors need to control the fluidity of the toner, in particular, the fluidity of the toner when the toner is loosened and the ease of aggregation of the toner after the toner is loosened, as in the present invention. Found that there is. That is, the total energy of the toner at the fifth measurement after compression, measured using a powder flowability analyzer, is 70 mJ or more and 105 mJ or less, and the uniaxial collapse stress of the toner at the maximum consolidation stress of 10.0 kPa is 2. It is the present inventor that the pressure of 5 kPa or more and 4.5 kPa or less is important in controlling the fluidity of the toner when the toner is stirred by the stirring member and the ease of aggregation of the toner after being loosened. Found.

  More preferably, the total energy of the toner at the fifth measurement after compression is 75 mJ or more and 90 mJ or less, and the uniaxial collapse stress of the toner at the maximum consolidation stress of 10.0 kPa is 2.7 kPa or more and 4.0 kPa or less. It is preferable.

  The total energy of the toner at the fifth measurement after compression, measured using a powder fluidity analyzer, is considered to be an index of the toner indicating whether the toner is likely to fly by the stirring member. The smaller this value, the easier it is to dance. By controlling the total energy at the fifth measurement after compression to 70 mJ or more and 105 mJ or less, even when the toner is sufficiently loosened by the stirring member 10 in a state where the printer is continuously used in a high temperature and high humidity environment, stirring is performed. The present inventors have found that toner rising by the member 10 is suppressed, toner is uniformly supplied to the toner carrier, and toner adhesion to the stirring member 10 is also suppressed.

  When the total energy at the fifth measurement after the compression of the toner, measured using a powder fluidity analyzer, is less than 70 mJ, the toner is likely to rise when the toner is stirred by the stirring member. In particular, since the toner layer is in a packed state in the initial printing after leaving the printer, the force of the agitating member 10 is transmitted to the entire toner layer and the toner is likely to rise, so there is a remaining amount of toner. Regardless, the antenna member 14 recognizes that the remaining amount of toner is low (the state as shown in FIG. 8A). On the other hand, when the toner is larger than 105 mJ, even when the toner is agitated by the agitating member, the adhesion force between the toners is high, so that the raised toner is likely to adhere to the toner carrier 8 and the agitating member 10. Despite the amount, toner aggregates in the vicinity of the antenna member 14 and the toner carrier 8, and white spots occur (state as shown in FIG. 8B). In particular, in a high temperature and high humidity environment, an external additive that imparts fluidity to the toner is embedded in the toner surface due to the influence of temperature and humidity, and the fluidity of the toner tends to deteriorate. As a result, in a high-temperature and high-humidity environment, toner packing is likely to occur near the antenna member 14 and the toner carrier 8, and white spots occur despite the remaining amount of toner.

  On the other hand, the uniaxial collapse stress of the toner at the maximum consolidation stress of 10.0 kPa is considered as an index indicating whether the toner layer is easily formed after the toner is stirred by the stirring member 10 and then loosened. The smaller this value, the easier it is to have voids in the toner layer. In order to improve the residual toner detection accuracy, in order to form a uniform toner layer without voids, the uniaxial collapse stress at the maximum compaction stress of 10.0 kPa can be controlled to 2.5 kPa to 4.5 kPa. The inventors have found that this is necessary. As a result, even if the toner is supplied to the toner layer near the toner carrier by the stirring member 10, a toner layer with few voids can be formed, so that the toner layer can be prevented from collapsing due to the toner supply. That is, it is possible to balance the supply of the toner to the toner carrier 8 by the stirring member 10 and the formation of a uniform toner layer without a gap on the antenna member 14.

  When the uniaxial collapse stress when the maximum compaction stress of the toner is 10.0 kPa is smaller than 2.5 kPa, the toner supplied to the toner carrier 8 by the stirring member can easily form a toner layer with many voids on the antenna member 14. Become. As a result, the toner supplied to the vicinity of the toner carrier 8 by the stirring member 10 collapses the toner layer on the antenna member 14, so that the antenna member 14 has a small amount of toner despite the remaining amount of toner. (Figure as shown in FIG. 8- (c)). In particular, in the initial printing after the printer is left stationary, the entire toner layer is supplied to the vicinity of the toner carrier by the stirring member 10, so that the toner layer on the antenna member 14 is collapsed, and the antenna member 14 is It is recognized that the remaining amount is low. On the other hand, when the pressure is higher than 4.5 kPa, the toner supplied to the toner carrier 8 by the stirring member forms a strong toner layer having no voids on the bottom surface of the antenna member 14 and the toner containing portion. As a result, even if the toner is supplied to the toner carrier 8 by the stirring member, the toner layer on the antenna member 14 does not circulate in the toner accommodating portion, and the antenna member 14 remains in the toner remaining state although there is no remaining toner. We recognize that there is much quantity. In particular, in a high-temperature and high-humidity environment, the adhesion force between the toners increases, so that the toner adheres to the antenna member 14 and the bottom surface in the toner container, and the residual toner detection accuracy deteriorates (FIG. 8- ( d)).

  Further, in the developing device used in the present invention, when the developing device 3 is installed in the printer body, a line parallel to the printer installation surface passing through the rotation center axis of the stirring member 10 passes below the lower end of the toner carrier. It is preferable to use a developing device (hereinafter referred to as a developing device having a pumping configuration). The developing device having the above-described pumping configuration is preferable because the toner can be prevented from being rubbed in the state where the toner is pressurized by its own weight in the vicinity of the developing sleeve 8 even when the toner filling amount in the toner storage portion is increased. Thereby, the change in toner fluidity can be suppressed even in a state where the toner is used in a high-temperature and high-humidity environment until the remaining amount of toner decreases.

  As described above, in the pumping-up development device, a specific configuration and members are used as electrodes, and toner fluidity is controlled to accurately detect the remaining amount of toner regardless of the environment or printing state. I can do it.

  The binder resin used for the toner base particles of the present invention will be described below.

  Examples of the binder resin include polyester resins, vinyl resins, epoxy resins, and polyurethane resins. In particular, from the viewpoint of uniformly dispersing a charge control agent having a polarity, it is generally preferable in terms of developability to contain a polyester resin having a high polarity.

  The binder resin preferably has a glass transition point (Tg) of 30 ° C. or higher and 70 ° C. or lower from the viewpoint of storage stability.

  The toner of the present invention preferably contains a release agent. The release agent is not limited as long as it can improve the releasability at the time of fixing, but a preferable release agent will be described below.

  Examples thereof include aliphatic hydrocarbon waxes such as polyolefin copolymer, polyolefin wax, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax.

  Further, these mold release agents include those obtained by sharpening the molecular weight distribution using a press perspiration method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method or a melt liquid crystal deposition method.

  Specific examples of the release agent include the following.

  Biscol (registered trademark) 330-P, 550-P, 660-P, TS-200 (Sanyo Chemical Industries), High Wax 400P, 200P, 100P, 410P, 420P, 320P, 220P, 210P, 110P (Mitsui Chemicals) ), Sazole H1, H2, C80, C105, C77 (Schumann Sazol), HNP-1, HNP-3, HNP-9, HNP-10, HNP-11, HNP-12 (Nippon Seiki Co., Ltd.), Unilin (registered trademark) 350, 425, 550, 700, Unicid (registered trademark), Unicid (registered trademark) 350, 425, 550, 700 (Toyo Adre Co., Ltd.), wood wax, beeswax, rice wax, candelilla wax Carnauba wax (available from Celerica NODA).

  The timing of adding the release agent may be added at the time of melt-kneading during toner production or may be at the time of production of the binder resin, and is appropriately selected from existing methods. These release agents may be used alone or in combination.

  The release agent is preferably added in an amount of 0.5 to 20.0 parts by mass with respect to 100.0 parts by mass of the total amount of the binder resin.

  The melting point peak temperature of the release agent is preferably 60 ° C. or higher and 180 ° C. or lower, and more preferably 70 ° C. or higher and 110 ° C. or lower, from the viewpoint of toner durability and low-temperature fixability.

  The toner of the present invention may contain a crystalline polyester resin as a binder resin.

  Examples of the crystalline polyester resin include aliphatic polyester resins obtained by polycondensation of aliphatic diols having 4 to 18 carbon atoms and aliphatic dicarboxylic acid compounds having 4 to 18 carbon atoms.

  Examples of the aliphatic diol include 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1, Examples include 12-dodecanediol.

  Examples of the aliphatic dicarboxylic acid compound include fumaric acid, 1,8-octanedioic acid, 1,9-nonanedioic acid, 1,10-decanedioic acid, 1,11-undecanedioic acid, and 1,12-dodecanedioic acid. Etc.

  The toner of the present invention is a magnetic toner, and the magnetic material includes iron oxides such as magnetite, hematite, and ferrite, metals such as iron, cobalt, and nickel or these metals and aluminum, cobalt, copper, lead, magnesium, Examples include alloys of metals such as tin, zinc, antimony, bismuth, calcium, manganese, titanium, tungsten, vanadium, and mixtures thereof.

  For the purpose of improving the fine dispersibility in the toner particles, the magnetic material is preferably subjected to a treatment for shearing the slurry at the time of production and temporarily loosening the magnetic material.

  These magnetic materials have a number average particle diameter of 0.01 μm or more and 2.0 μm or less, preferably 0.05 μm or more and 0.50 μm or less.

  In order to control the saturation magnetization of the toner at a magnetic field of 796 kA / m, a desired shape such as octahedron, hexahedron, or sphere can be selected as the shape of the magnetic material.

The true density of the toner of the present invention is 1.35 g / cm ³ or more and 1.75 g / cm ³ or less, preferably 1.40 g / cm ³ or more and 1.70 g / cm ³ or less.

  In the toner remaining amount detecting means of the present invention, a conductive resin member is present as a part of the bottom surface of the toner containing portion as an electrode. Therefore, the toner needs to be uniformly present on the surface. Therefore, by controlling the specific gravity of the toner, it is preferable because the conductive resin member can be uniformly contacted, and the accuracy of the remaining amount is improved particularly in a high temperature and high humidity environment where the fluidity is deteriorated.

  The amount of the magnetic substance contained in the toner of the present invention is preferably 30 parts by mass or more and 80 parts by mass or less, and 40 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the binder resin in controlling the specific gravity of the toner. Is more preferable.

  If necessary, conventionally known pigments and dyes may be used in combination for adjusting the color of the toner.

  The toner of the present invention preferably contains a charge control agent from the viewpoint of further improving the charging stability.

  As the charge control agent, an organometallic complex or a chelate compound in which the acid group or hydroxyl group present at the terminal of the binder resin used in the present invention and the central metal are likely to interact is preferable.

  For example, monoazo metal complexes; acetylacetone metal complexes; aromatic hydroxycarboxylic acid or aromatic dicarboxylic acid metal complexes or metal salts are preferably used. As specific examples, Spiro Black TRH, T-77, T-95 (Hodogaya Chemical Co., Ltd.), BONTRON (registered trademark) S-34, S-44, S-54, E-84, E -88, E-89 (Orient Chemical Co., Ltd.).

  One kind of charge control agent may be used, or two or more kinds may be used in combination.

  The toner of the present invention is a toner measured by a flow-type particle image measuring device from the viewpoint of suppressing adhesion between toners and controlling the ease of loosening when the toner in the developing container is stirred by a stirring member. The average circularity is preferably 0.940 or more and 0.960 or less.

  Further, the toner of the present invention preferably has toner particles containing a binder resin and a magnetic substance and at least organic-inorganic composite fine particles and strontium titanate fine particles as external additives. Among the organic-inorganic composite fine particles, a structure in which a plurality of convex portions derived from inorganic fine particles are present on the surface of the organic-inorganic composite fine particles is preferable. Examples of such organic-inorganic composite fine particles include those having a structure in which inorganic fine particles are embedded in resin particles so that there are a plurality of convex portions derived from the inorganic fine particles.

  By having such a structure, when the toner is agitated by the agitating member, the organic / inorganic fine particles as spacer particles improve the ease of loosening of the toner. In addition, after the toner is agitated by the agitating member, when the toner settles from the loosened state, organic inorganic fine particles present on the surface of the toner particles are meshed as a gear between the toner particles to promote toner aggregation. This makes it easier to form a uniform toner layer without voids.

  The number average particle diameter (D1) of the primary particles of the organic / inorganic composite fine particles is preferably 60 nm or more and 300 nm or less, more preferably 80 nm or more and 200 nm or less. The addition amount of the organic / inorganic composite fine particles is preferably 0.3 parts by mass or more and 3.1 parts by mass or less, and more preferably 0.7 parts by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the toner particles.

  It is known that the toner causes so-called toner deterioration in which the external additive is embedded in the toner particles by rubbing at the nip portion between the toner carrier 8 and the developing blade 11 in the developing device. This situation is likely to occur in the second half of the endurance when the toner amount is low. When toner deterioration occurs, the adhesion between the toner particles increases, and the toners tend to aggregate and become aggregated particle lumps. As a result, since toner adheres to the antenna member 14, the accuracy of detecting the remaining amount of toner tends to be lowered. However, the inclusion of organic-inorganic composite fine particles having such a specific particle size suppresses the occurrence of toner deterioration and improves the remaining toner detection accuracy. In particular, when used in a high-temperature and high-humidity environment where toner deterioration is likely to occur, the effect is likely to appear significantly.

  The organic / inorganic composite fine particles can be produced, for example, according to the description in the examples of WO 2013/066291, but the present invention is not limited thereto.

  In addition, in the present invention, it is preferable to use strontium titanate fine particles in combination with organic / inorganic composite fine particles. This is because in the state where the toner remaining in the toner container is low and the toner is loosened by stirring, particles having a large specific gravity such as strontium titanate fine particles are present on the surface of the toner, thereby promoting the sedimentation of the toner. This is preferable in that the gear effect of the inorganic fine particles is further promoted.

  Although there is no restriction | limiting in particular as a manufacturing method of strontium titanate microparticles, For example, it manufactures with the following method.

As a general method for producing strontium titanate fine particles, there is a method of sintering after solid-phase reaction between titanium oxide and strontium carbonate. The well-known reaction employ | adopted in this manufacturing method can be represented by a following formula.
TiO ₂ + SrCO ₃ → SrTiO ₃ + CO ₂

That is, a mixture containing titanium oxide and strontium carbonate is prepared by washing, drying, sintering, mechanical pulverization and classification. At this time, a composite inorganic fine powder containing strontium titanate, strontium carbonate, and titanium oxide can be obtained by adjusting raw materials and firing conditions. The raw material strontium carbonate is not particularly limited as long as it has a SrCO ₃ composition, and any commercially available one can be used. The titanium oxide as the raw material is not particularly limited as long as it is a substance having a TiO ₂ composition. Examples of the titanium oxide include metatitanic acid slurry (undried hydrous titanium oxide) obtained by a sulfuric acid method, titanium oxide powder, and the like. The sintering is preferably performed at a temperature of 500 to 1300 ° C, more preferably 650 to 1100 ° C. When the firing temperature is higher than 1300 ° C., secondary agglomeration due to sintering between particles is likely to occur, and the load in the pulverization process increases. On the other hand, when the firing temperature is lower than 600 ° C., many unreacted components remain, and it is difficult to produce stable strontium titanate fine particles. Moreover, preferable baking time is 0.5 to 16 hours, More preferably, it is 1 to 5 hours. Similarly, when calcination time is longer than 16 hours, strontium carbonate and titanium oxide may all react and the resulting strontium titanate fine particles may be secondary agglomerated. When the calcination time is shorter than 0.5 hour, unreacted components Therefore, it is difficult to produce stable strontium titanate fine particles.

  On the other hand, as a method for producing strontium titanate fine particles without undergoing a sintering step, strontium hydroxide was added to a dispersion of titania sol obtained by adjusting the pH of a hydrous titanium oxide slurry obtained by hydrolyzing a titanyl sulfate aqueous solution. There is a method of synthesizing by adding to the reaction temperature. By setting the pH of the hydrous titanium oxide slurry to 0.5 to 1.0, a titania sol having good crystallinity and particle size can be obtained. For the purpose of removing ions adsorbed on the titania sol particles, an alkaline substance such as sodium hydroxide is preferably added to the dispersion of the titania sol. At this time, it is preferable that the pH of the slurry is not 7 or higher so that sodium ions and the like are not adsorbed on the surface of the hydrous titanium oxide. The reaction temperature is preferably 60 ° C. to 100 ° C., and in order to obtain a desired particle size distribution, the temperature rising rate is preferably 30 ° C./hour or less, and the reaction time is preferably 3 to 7 hours.

As a method for subjecting the strontium titanate fine particles produced by the above method to a surface treatment with a fatty acid or a metal salt thereof, there are the following methods. For example, a strontium titanate fine particle slurry can be placed in an aqueous solution of sodium fatty acid in an Ar gas or N ₂ gas atmosphere to deposit a fatty acid on the perovskite crystal surface. In addition, for example, in a Ar gas or N ₂ gas atmosphere, a strontium titanate fine particle slurry is placed in a fatty acid sodium aqueous solution, and the desired metal salt aqueous solution is dropped while stirring to precipitate the fatty acid metal salt on the perovskite crystal surface. Can be adsorbed. For example, if a sodium stearate aqueous solution and aluminum sulfate are used, aluminum stearate can be adsorbed.

  It is possible to use a positively charged external additive such as titanium oxide or melamine resin in place of strontium titanate, but strontium titanate is more effective in terms of filling properties that promote aggregation in the toner. The number average particle diameter (D1) of the strontium titanate primary particles is preferably 500 nm or more and 2 μm or less. The addition amount is preferably 0.4 parts by mass or more and 0.8 parts by mass or less with respect to 100 parts by mass of the toner particles.

  If necessary, other external additives may be added to the toner. For example, charging aids, conductivity imparting agents, anti-caking agents, release agents at the time of heat roller fixing, lubricants, resin fine particles and inorganic fine powders that function as abrasives.

  Examples of the lubricant include polyfluoroethylene fine particles, zinc stearate fine particles, and polyvinylidene fluoride fine particles. Of these, polyvinylidene fluoride fine particles are preferred. Examples of the abrasive include cerium oxide fine particles and silicon carbide fine particles.

  The method for producing the toner particles of the present invention is not particularly limited, and the kneaded product obtained by melt-kneading the resin component and, if necessary, toner constituent materials such as a colorant, a release agent, and a charge control agent after uniform mixing. After cooling, pulverization and classification, and a so-called pulverization method can be used in which the fluidity modifier and the like are sufficiently mixed using a mixer such as a Henschel mixer to obtain the toner of the present invention.

  As another method, toner particles can be produced by a so-called polymerization method such as an emulsion polymerization method or a suspension polymerization method.

  The following method can be used as a method for producing toner particles obtained through at least the melt-kneading step and the pulverizing step. The resin component and, if necessary, the wax, colorant, charge control agent, and other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill. The mixture is melt kneaded using a thermal kneader such as a twin-screw kneading extruder, a heating roll, a kneader, or an extruder. At that time, wax, magnetic iron oxide particles, and a metal-containing compound may be added. The melt-kneaded product is cooled and solidified, and then pulverized and classified to obtain toner particles. Further, if necessary, the toner particles and the external additive can be mixed with a mixer such as a Henschel mixer to obtain a toner. In the present invention, the external addition step may be multistage external addition.

  The following are mentioned as a mixer. Mitsui Henschel Mixer (Mitsui Miike Chemical Co., Ltd.); Super Mixer (Kawata); Ribocorn (Okawara Seisakusho); Nauta Mixer, Turbulizer, Cyclomix (Hosokawa Micron); Spiral Pin Mixer (Pacific Ocean) Kiko Co., Ltd.); Redige mixer (manufactured by Matsubo). Examples of the kneader include the following. KRC Kneader (manufactured by Kurimoto Iron Works); Bus Co Kneader (manufactured by Buss); TEM type extruder (manufactured by Toshiba Machine); TEX twin-screw kneader (manufactured by Nippon Steel Works); Steel mill); three roll mill, mixing roll mill, kneader (Inoue Seisakusho); kneedex (Mitsui Mining Co.); MS pressure kneader, Nider Ruder (Moriyama Seisakusho); Banbury mixer (Kobe Steel) (Made by the company). Examples of the pulverizer include the following. Counter jet mill, micron jet, inomizer (manufactured by Hosokawa Micron); IDS type mill, PJM jet crusher (manufactured by Nippon Pneumatic Industrial Co., Ltd.); cross jet mill (manufactured by Kurimoto Iron Works); Urmax (manufactured by Nisso Engineering Co., Ltd.) SK; jet mill (manufactured by Seishin Enterprise Co., Ltd.); kryptron (manufactured by Kawasaki Heavy Industries, Ltd.); turbo mill (manufactured by Turbo Industry Co., Ltd.); super rotor (manufactured by Nisshin Engineering Co., Ltd.).

  Examples of the classifier include the following. Classifier, Micron Classifier, Spedic Classifier (manufactured by Seishin Enterprise); Turbo Classifier (manufactured by Nissin Engineering); Micron Separator, Turboplex (ATP), TSP Separator (manufactured by Hosokawa Micron); Elbow Jet (Japan) Iron Mining Co., Ltd.), Dispersion Separator (Nihon Pneumatic Kogyo Co., Ltd.);

  Examples of the sieving apparatus used for sieving coarse particles include the following. Ultrasonic (manufactured by Sakae Sangyo Co., Ltd.); Resonator Sheave, Gyroshifter (Tokuju Kosakusha Co., Ltd.); Vibrasonic System (manufactured by Dalton Co.); Soniclean (manufactured by Shinto Kogyo Co., Ltd.); Micro shifter (manufactured by Hadano Sangyo Co., Ltd.); circular vibrating sieve.

  Next, it describes regarding the measuring method of each physical property which concerns on this invention.

<Uniaxial collapse stress measurement method>
The uniaxial collapse stress was measured by shear scan TS-12 (manufactured by Sci-Tec). Virendra M.M. The measurement is performed according to the principle of the Morcoulomb model described in 'CHARACTERIZING POWDER FLOWABILITY' (published 2002.1.24) written by Puri.

Specifically, the measurement was performed in a room temperature environment (23 ° C., 60% RH) using a linear shear cell (columnar shape, diameter 80 mm, capacity 140 cm ³ ) capable of linearly applying a shearing force in the cross-sectional direction. A developer is put in this cell, a vertical load is applied so as to be 2.5 kPa, and a compacted powder layer is produced so as to be in a close packed state under this vertical load. Similarly, a compacted powder layer with a vertical load of 5.0 kPa and 10.0 kPa is formed. A test was conducted to apply shear force gradually while continuously applying the vertical load applied when forming the compacted powder layer to the sample formed at each vertical load, and to measure the fluctuation of the shear stress at that time. Determine the point. Judgment that the steady point has been reached is determined when, in the above test, the displacement of the shearing stress and the vertical displacement of the load applying means for applying the vertical load become small and both take stable values. Assume that a point has been reached. Next, the vertical load is gradually unloaded from the compacted powder layer that has reached the steady point, a fracture envelope (vertical load stress vs. shear stress plot) at each load is created, and the Y intercept and inclination are obtained. In the analysis by the Moul-Coulomb model, the uniaxial collapse stress and the maximum consolidation stress are expressed by the following equations, and the Y intercept becomes “cohesive force” and the inclination becomes “internal friction angle”.
Uniaxial collapse stress = 2c (1 + sinφ) / cosφ
Maximum consolidation stress = ((A− (A2sin2φ−τssp2cos2φ) 0.5) / cos2φ) × (1 + sinφ) − (c / tanφ)
(A = σssp + (c / tanφ), c = cohesive force, φ = internal friction angle, τssp = c + σssp × tanφ, σssp = normal load at a steady point)

  The uniaxial collapse stress and the maximum consolidation stress calculated at each load are plotted (Flow Function Plot), and a straight line is drawn based on the plot. From this straight line, the uniaxial collapse stress at the maximum consolidation stress of 10.0 kPa is obtained.

<Total energy measurement method>
Measurement is performed using a powder fluidity analyzer (powder rheometer FT-4, manufactured by Freeman Technology) (hereinafter abbreviated as FT-4) equipped with a rotary propeller blade.

  Specifically, the measurement is performed by the following operation. In all operations, the propeller-type blade is a 23.5 mm diameter blade dedicated to FT-4 measurement (see FIG. 9A). The rotation axis in the normal direction is the center of the 23.5 mm × 6.5 mm blade plate. The blade plate is smoothly twisted counterclockwise such that both outermost edge portions (12 mm from the rotating shaft) are 70 °, and 6 mm from the rotating shaft is 35 ° (FIG. 9). (See (b)), and the material is SUS.

  First, a FT-4 measurement container (a split container (model number: C4031) having a diameter of 25 mm and a volume of 25 mL, a height of about 51 mm from the bottom of the container to the split part, hereinafter also simply referred to as a container) at 23 ° C. and 60% environment. The toner powder layer is formed by compressing 24 g of the toner left for 3 days.

  For compression of the toner, a compression test piston (diameter 24 mm, height 20 mm, lower mesh tension) is used instead of the propeller blade.

(1) Consolidation operation of toner 8 g of toner is added to the above-mentioned container exclusively for FT-4 measurement. A compression piston dedicated to FT-4 measurement is attached and consolidation is performed at 88 kPa for 60 seconds. Further, 8 g of toner is added, and the compression operation is performed three times in a similar manner so that a total of 24 g of the compacted toner is in a dedicated container.

(2) Split operation The toner powder layer is ground at the split portion of the above-mentioned container dedicated to FT-4 measurement, and the toner powder layer having the same volume (25 mL) is always formed by removing the toner above the toner powder layer. .

(3) Measurement operation (a) A circumferential speed (peripheral speed of the outermost edge of the blade) of 10 mm in a counterclockwise direction (direction in which the powder layer is pushed in by rotation of the blade) with respect to the toner powder layer surface. Rotate the blade at / sec. The angle between the trajectory drawn by the outermost edge portion of the moving blade and the powder layer surface (hereinafter referred to as “blade trajectory angle”) indicating the vertical approach speed to the toner powder layer is 5 (deg). The speed is set, and the propeller blade is advanced to a position 10 mm from the bottom of the toner powder layer.

  In the above measurement operation, the total energy of the rotational torque and the vertical load obtained when the blade is moved from the uppermost surface of the toner powder layer to the position 10 mm from the bottom surface is defined as the total energy. Thereafter, the blade is rotated clockwise with respect to the powder layer surface so that the peripheral speed of the blade is 60 mm / sec (the direction in which the powder layer is loosened by the rotation of the blade), and the blade locus angle is 2 (deg). The blade is advanced to a position 1 mm from the bottom of the toner powder layer. Further, the blade is moved to a position of 80 mm from the bottom surface of the powder layer at a speed at which the blade locus angle becomes 5 (deg), and is extracted. When the extraction is completed, the toner attached to the blade is wiped off by rotating the blade alternately clockwise and counterclockwise.

  (B) Repeat the same operation as in (a).

  (C) The same operation as in (a) is repeated except that the blade is rotated at a peripheral speed of 20 mm / sec in a counterclockwise rotation direction with respect to the toner powder layer surface.

  (D) The same operation as in (a) is repeated except that the blade is rotated at a peripheral speed of 30 mm / sec in the counterclockwise rotation direction with respect to the toner powder layer surface.

  (E) The same operation as (a) is repeated except that the blade is rotated at a peripheral speed of 50 mm / sec in the counterclockwise rotation direction with respect to the surface of the toner powder layer.

  The value measured in (e) was defined as the total energy of the toner.

<Measurement method of number average particle diameter of organic / inorganic composite fine particles and strontium titanate fine particles>
The number average particle diameter of the organic / inorganic composite fine particles and the strontium titanate fine particles is measured using a scanning electron microscope “S-4800” (trade name; manufactured by Hitachi, Ltd.). The toner with the external additive added is observed, and the major axis of the primary particles of 100 external additives is randomly measured in the field of view enlarged up to 200,000 times to obtain the number average particle diameter (D1). . The observation magnification is appropriately adjusted according to the size of the external additive.

<Method for quantifying organic-inorganic composite fine particles and strontium titanate fine particles>
When measuring the content of each external additive in a toner in which a plurality of external additives are externally added to the toner particles, the external additives are removed from the toner particles, and a plurality of types of external additives are isolated. It needs to be recovered.

Specific examples of the method include the following methods.
(1) Put 5 g of toner into a sample bottle and add 200 ml of methanol.
(2) The sample is dispersed for 5 minutes with an ultrasonic cleaner to separate the external additive.
(3) Separating toner particles and external additives by suction filtration (10 μm membrane filter). Alternatively, in the case of magnetic toner, a neodymium magnet may be applied to the bottom of the sample bottle to fix the magnetic toner particles and only the supernatant liquid may be separated.
(4) The above (2) and (3) are performed until a desired sample amount is obtained.

  By the above operation, the externally added external additive is isolated from the toner particles. The recovered aqueous solution is centrifuged to separate and recover each external additive for each specific gravity. Next, the content of each external additive can be obtained by removing the solvent, sufficiently drying with a vacuum dryer, and measuring the mass.

<Measurement method of true density of toner>
The true density of the toner was measured with a dry automatic densimeter autopycnometer (manufactured by Yuasa Ionics). The conditions are as follows.
Cell SM cell (10ml)
Sample amount about 2.0g

  This measurement method measures the true density of a solid / liquid based on a gas phase substitution method. Similar to the liquid phase replacement method, it is based on Archimedes' principle, but gas (argon gas) is used as the replacement medium.

<Method for Measuring Softening Point Tm of Binder Resin and Toner>
The softening point is measured as follows. The softening point is measured by using a constant load extrusion type capillary rheometer “Flow Characteristic Evaluation Device Flow Tester CFT-500D” (manufactured by Shimadzu Corporation) according to the manual attached to the device. In this device, while applying a constant load from the top of the measurement sample with the piston, the measurement sample filled in the cylinder is heated and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder, and the piston drop amount at this time A flow curve showing the relationship between temperature and temperature can be obtained.

  In the present invention, the “melting temperature in the 1/2 method” described in the manual attached to the “flow characteristic evaluation apparatus Flow Tester CFT-500D” is the softening point. The melting temperature in the 1/2 method is calculated as follows. First, ½ of the difference between the piston lowering amount Smax at the time when the outflow ends and the piston lowering amount Smin at the time when the outflow starts is obtained (this is X. X = (Smax−Smin) / 2). And the temperature of the flow curve when the amount of piston descent in the flow curve is the sum of X and Smin is the melting temperature Tm in the 1/2 method.

  As a measurement sample, about 1.0 g of a sample is compression-molded at about 10 MPa using a tablet molding compressor (for example, NT-100H, manufactured by NPA System) in an environment of 25 ° C. for about 60 seconds. A cylindrical shape having a diameter of about 8 mm is used.

The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising start temperature: 50 ° C
Achieving temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature increase rate: 4.0 ° C./min
Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm

<Method for Measuring Glass Transition Temperature (Tg) of Binder Resin and Toner and Melting Point of Release Agent>
The glass transition temperature (Tg) and the melting point of the release agent are measured at room temperature and normal humidity according to ASTM D3418-82 using a differential scanning calorimeter (DSC) and MDSC-2920 (manufactured by TA Instruments). To do.

  As a measurement sample, a binder resin or a product obtained by accurately weighing about 3 mg of toner is used. This is put in an aluminum pan and an empty aluminum pan is used as a reference. The measurement temperature range is 30 ° C. or more and 200 ° C. or less, once the temperature is increased from 30 ° C. to 200 ° C. at a temperature increase rate of 10 ° C./min, the temperature is decreased from 200 ° C. to 30 ° C. at a temperature decrease rate of 10 ° C./min The temperature is raised to 200 ° C. at a temperature rising rate of 10 ° C./min. In the DSC curve obtained in the second temperature raising process, the intersection point between the baseline intermediate line before and after the specific heat change and the differential heat curve is defined as the glass transition temperature Tg of the resin. The maximum endothermic peak temperature of the DSC curve obtained in the second temperature raising process is defined as the melting point.

<Method for Measuring Weight Average Particle Size (D4) of Toner Particles>
The weight average particle diameter (D4) of the toner is calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. Note that the measurement is performed with 25,000 effective measurement channels.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, the dedicated software was set as follows.

  On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.

  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 bin, and the particle size range is set to 2 μm to 60 μm.

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic aqueous solution is put in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rotations / second. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. As a dispersant, “Contaminone N” (trade name; 10% by weight aqueous solution of a neutral detergent for cleaning a precision measuring instrument having a pH of 7 comprising a nonionic surfactant, an anionic surfactant and an organic builder, Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting about 3 times by mass with ion exchange water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora150” (trade name; manufactured by Nikka Ki Bios) with an electrical output of 120 W is prepared. To do. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . The measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the “analysis / volume statistics (arithmetic average)” screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

<Measuring method of average circularity of toner particles>
The average circularity of the toner was measured with a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during calibration.

  A specific measurement method is as follows. First, about 20 ml of ion-exchanged water from which impure solids are removed in advance is put in a glass container. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.2 ml of a diluted solution obtained by diluting the solution with ion exchange water about 3 times by mass. Further, about 0.02 g of a measurement sample is added, and dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. At that time, the dispersion is appropriately cooled so that the temperature of the dispersion becomes 10 ° C. to 40 ° C. As the ultrasonic disperser, a desktop type ultrasonic cleaner disperser (for example, “VS-150” (manufactured by VervoCrea)) having an oscillation frequency of 50 kHz and an electric output of 150 W is used. Ion exchange water is added, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.

  For the measurement, the above-mentioned flow type particle image analyzer equipped with “LUCPLFLN” (magnification 20 ×, numerical aperture 0.40) as an objective lens is used, and particle sheath “PSE-900A” (manufactured by Sysmex Corporation) is used as the sheath liquid. It was used. The dispersion prepared in accordance with the above procedure is introduced into the flow type particle image analyzer, and 2000 toners are measured in the HPF measurement mode and in the total count mode. Then, the binarization threshold at the time of particle analysis was set to 85%, the analysis particle diameter was limited to the equivalent circle diameter of 1.975 μm or more and less than 39.54 μm, and the average circularity of the toner was determined.

  In measurement, automatic focus adjustment is performed using standard latex particles (for example, “RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5100A” manufactured by Duke Scientific) diluted with ion-exchanged water before starting the measurement. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.

  In the examples of the present application, a flow-type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, was used. Measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that the analysis particle diameter was limited to a circle equivalent diameter of 1.975 μm or more and less than 39.54 μm.

<Method for measuring resistance of conductive resin member>
A method for measuring the resistance of the conductive resin member in this embodiment will be described.

  The resistance of the conductive resin member varies depending on the distance from the contact. Therefore, the resistance of the conductive resin member is defined by the following two measurement methods.

  As shown in FIG. 10, the surface of the conductive resin member that is in contact with the toner with the corresponding position in the surface of the conductive resin member on the side in contact with the toner as a contact (point A) as shown in FIG. The point (point B) that is the farthest among the contacts on the toner carrier 8 side is defined as the measurement point (1). Conductive grease is applied to the measurement point (1) in a circle with a diameter of 5 mm, and resistance measurement is performed between the measurement point (1) and the contact point using Fluke 87V manufactured by Fluke.

  Hereinafter, the present invention will be specifically described with reference to examples.

  This embodiment was evaluated according to the above description of the image forming apparatus and image forming process, and the detailed description of the image forming apparatus. As an applied bias, a short waveform having an AC voltage Vpp of 1400 V, a DC voltage of Vdc of −400 V, and a frequency of 2500 Hz was applied.

  Further, in this embodiment, the exposure beam L is adjusted so that the bright portion potential Vl on the photosensitive drum becomes −130V.

<Antenna member 1>
The conductive resin sheet as the antenna member 1 was obtained by dispersing 35% by mass of carbon black in EVA. The resistance measured by the method described above was 1.0 × 10 ⁴ Ω.

  Further, the total thickness t of the conductive resin sheet is 0.1 mm, the long width is 210 mm, and the short width is 35 mm. From the short end far from the toner carrier at the front end in FIG. The conductive resin sheet is extended to the outside of the developer container 3a in order to conduct to the contact point. From there, it is connected to ground via a contact (not shown) of the main body and a toner remaining amount detecting device 18 arranged in the above-mentioned image forming apparatus.

  Here, as a fixing method of the conductive resin sheet 14, any method can be used as long as it can be fixed to the frame body as an electrode such as insert molding, coating, and two-color molding. Here, for example, when insert molding is performed, the position accuracy of the arrangement of the conductive resin sheet 14 is compatible or bonded and fixed to the inner wall of the developing container 3a with higher accuracy than in the case of the fixing method using the double-sided tape described in the present embodiment. can do. As a result, the distance accuracy with the toner carrier, which is an electrode, is improved, leading to improved residual detection accuracy.

<Antenna members 2 to 5>
It was produced in the same manner as the antenna member 1 except that the amount of carbon and dispersion were adjusted so that the resistance of the conductive resin sheet was adjusted as shown in Table 1 below.

<Antenna member 6>
As the antenna member 6, SUS304 which was rolled to a thickness of 500 μm and cut into a strip shape of 216 mm in the longitudinal direction and 15 mm in the lateral direction was used. Although SUS304 is non-magnetic, application of stress causes the austenite layer to undergo martensitic transformation and become magnetized. The antenna member 14 of Comparative Example 1 is also stressed and magnetized by rolling and cutting.

<Example of production of binder resin 1>
-Bisfer A ethylene oxide adduct (2.0 mol addition) 40.0 mol part-Bisfer A propylene oxide adduct (2.3 mol addition) 60.0 mol part-Terephthalic acid 60.0 mol part-Trimellitic anhydride 20. 0 mol part / acrylic acid 10.0 mol part 70 parts by mass of the above polyester monomer mixture was charged into a four-necked flask and equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, under a nitrogen atmosphere. And stir at 160 ° C. A mixture of 30 parts by mass of a vinyl polymerization monomer (styrene: 90.0 mol parts, butyl acrylate: 10.0 mol parts) constituting the vinyl polymer portion and 2.0 mol parts of benzoyl peroxide as a polymerization initiator. It dropped over 4 hours from the dropping funnel. Then, after reacting at 160 ° C. for 5 hours, the temperature was raised to 230 ° C., 0.05% by mass of tetraisobutyl titanate was added, and the reaction time was adjusted so as to obtain a desired viscosity. The obtained resin 1 had a softening point of 110 ° C. and Tg of 58 ° C.

<Manufacture of magnetic body 1>
Using ferrous sulfate, 50 liters of an aqueous iron sulfate solution containing 2.0 mol / liter of Fe (2+) was prepared. Moreover, 10 liters of sodium silicate aqueous solution containing 0.23 mol / liter of Si (4+) was prepared using sodium silicate, and this was added to the iron sulfate aqueous solution. Subsequently, 42 liters of 5.0 mol / liter NaOH aqueous solution was stirred and mixed with the mixed aqueous solution to obtain a ferrous hydroxide slurry. This ferrous hydroxide slurry was adjusted to a pH of 12.0 and a temperature of 90 ° C., and 30 liter / min of air was blown in, and an oxidation reaction was performed until 50% of the ferrous hydroxide became magnetic iron oxide particles. Next, 20 l / min of air was blown until 75% of the magnetic iron oxide particles were produced, and then 10 l / min of air was blown until 90% of the magnetic iron oxide particles were produced. Further, when the ratio of the magnetic iron oxide particles exceeded 90%, air was blown in at 5 liters / min to complete the oxidation reaction, thereby obtaining a slurry containing octahedral core particles.

94 ml of an aqueous solution of sodium silicate (containing 13.4% by mass of Si) and 288 ml of an aqueous aluminum sulfate solution (containing 4.2% by mass of Al) were simultaneously added to the slurry containing the core particles. Thereafter, the temperature of the slurry was adjusted to 80 ° C., the pH was adjusted to 5 or more and 9 or less with dilute sulfuric acid, and a coating layer containing silicon and aluminum was formed on the surface of the core particles. The obtained magnetic body was filtered by a conventional method, dried and pulverized to obtain a magnetic body 1. Magnetic substance 1 having a number-average particle size of 0.12nm, Hc = 11.5kA / m, was ^{σs = 85.0Am 2 /kg,σr=14.0Am 2 / kg} .

<Toner particle production example 1>
-Resin 1 100.0 parts by mass-Magnetic substance 1 60.0 parts by mass-Fischer-Tropsch wax (DSC peak temperature: 105 ° C) 2.0 parts by mass-Charge control agent (T-77: manufactured by Hodogaya Chemical Co., Ltd.) 0 parts by mass The above materials were mixed with a Mitsui Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.), and then rotated at a twin-screw kneader (Ikegai Iron Works Co., Ltd. PCM-30 type)). The mixture was kneaded under the conditions of 3.3 s ⁻¹ and a kneading temperature of 130 ° C. The obtained kneaded material was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized material. The resulting coarsely pulverized product was finely pulverized by using a turbo mill T-250 (manufactured by Turbo Kogyo Co., Ltd.) with a feed amount of 25.0 kg / hr and adjusting the air temperature so that the exhaust temperature was 38 ° C. Classification was performed using a multi-division classifier using the Coanda effect. The toner particles obtained after classification are subjected to a surface modification device faculty (manufactured by Hosokawa Micron Co., Ltd.), the input amount of finely pulverized product is 8.0 kg per cycle, and the rotational peripheral speed of the dispersion rotor is 105 m / sec. , Adjusting the cycle time (the time from the end of the raw material supply to the opening of the discharge valve) 82 seconds, adjusting the discharge temperature to 38 ° C., surface modification and fine powder removal, the weight average particle size (D4) is Toner particles 1 having 7.1 μm and an average circularity of 0.948 were obtained. The production conditions of the toner particles 1 are shown in Table 2.

<Toner particle production example 2>
Toner particles 2 having a weight average particle diameter (D4) of 6.9 μm and an average circularity of 0.951 are the same except that the amount of magnetic material 1 is changed from 60 parts by mass to 50 parts by mass in the production of toner particles 1. Got. The production conditions of the toner particles 2 are shown in Table 2.

<Toner particle production example 3>
Toner particles 3 having a weight average particle diameter (D4) of 7.0 μm and an average circularity of 0.954 are the same except that the amount of magnetic material 1 is changed from 60 parts by mass to 70 parts by mass in the production of toner particles 1. Got. The production conditions of the toner particles 3 are shown in Table 2.

<Toner particle production example 4>
In the production of toner particles 1, the amount of magnetic material 1 is changed from 60 parts by mass to 40 parts by mass, the feed rate of Turbo Mill T-250 (manufactured by Turbo Kogyo Co., Ltd.) is 22.0 kg / hr, and the surface modification device Faculty (Hosokawa Micron) The toner particles 4 having a weight average particle diameter (D4) of 7.2 μm and an average circularity of 0.952 were obtained in the same manner except that the input amount per cycle was 7.0 kg. The production conditions of the toner particles 4 are shown in Table 2.

<Toner particle production example 5>
In the production of the toner particles 2, the weight average particle diameter (D4) was similarly used except that the toner particles classified by using a multi-division classifier were used as they were without passing through the surface modification device faculty (manufactured by Hosokawa Micron). ) Was 7.3 μm, and an average circularity of 0.940 was obtained. The production conditions of the toner particles 5 are shown in Table 2.

<Toner particle production example 6>
In the production of the toner particles 2, the weight average particle diameter (D4) is 7.1 μm in the same manner except that the rotational peripheral speed of the dispersion rotor of the surface modification device faculty (manufactured by Hosokawa Micron Corporation) is 115 m / sec. Toner particles 6 having an average circularity of 0.960 were obtained. The production conditions for the toner particles 6 are shown in Table 2.

<Toner particle production example 7>
In the production of toner particles 1, the amount of magnetic material 1 is changed from 60 parts by mass to 30 parts by mass, the feed rate of Turbomill T-250 (manufactured by Turbo Kogyo Co., Ltd.) is 20.0 kg / hr, The weight average particle diameter (D4) is 6.8 μm and the average circularity is the same except that the input amount per cycle of Hosokawa Micron Co., Ltd. is 6.5 kg and the rotational peripheral speed of the dispersion rotor is 125 m / sec. 0.962 toner particles 7 were obtained. The production conditions for the toner particles 7 are shown in Table 2.

<Toner particle production example 8>
In the production of toner particles 1, the amount of magnetic material 1 is changed from 60 parts by weight to 80 parts by weight, the pulverizing apparatus is changed to a jet mill pulverizer, the feed amount is 3.3 kg / hr, and the pulverization pressure is 3.3 kPa. The weight average particle diameter (D4) is 7.2 μm in the same manner except that the toner particles classified using a multi-division classifier are used as they are without passing through the surface modification device Faculty (manufactured by Hosokawa Micron). Toner particles 8 having an average circularity of 0.936 were obtained. The production conditions of the toner particles 8 are shown in Table 2.

<Toner particle production example 9>
In the production of toner particles 7, toner particles having a weight average particle diameter (D4) of 6.9 μm and an average circularity of 0.967 are similarly obtained except that the amount of the magnetic material 1 is changed from 30 parts by mass to 20 parts by mass. 9 was obtained. The production conditions for the toner particles 9 are shown in Table 2.

<Toner particle production example 10>
In the production of the toner particles 8, the amount of the magnetic material 1 was changed from 80 parts by mass to 90 parts by mass, the feed amount of the jet mill pulverizer was set to 3.0 kg / hr, and the pulverization pressure was set to 3.2 kPa. Toner particles 10 having a weight average particle diameter (D4) of 7.4 μm and an average circularity of 0.931 were obtained. The production conditions of the toner particles 10 are shown in Table 2.

<Toner Particle Production Example 11>
In the production of the toner particles 9, the amount of magnetic material 1 is changed from 20 parts by weight to 90 parts by weight, the feed amount of turbo mill T-250 (manufactured by Turbo Kogyo Co., Ltd.) is 26.0 kg / hr, Toner particles 11 having a weight average particle diameter (D4) of 7.0 μm and an average circularity of 0.967 were obtained in the same manner except that the input amount per cycle of Hosokawa Micron Corporation was 8.5 kg. The production conditions of the toner particles 11 are shown in Table 2.

<Toner Particle Production Example 12>
In the production of the toner particles 11, the weight average particle diameter (D4) is 7.2 μm and the average is the same except that the rotational peripheral speed of the dispersion rotor of the surface modification device faculty (manufactured by Hosokawa Micron Corporation) is 105 m / sec. Toner particles 12 having a circularity of 0.951 were obtained. The production conditions of the toner particles 12 are shown in Table 2.

<Toner particle production example 13>
In the production of the toner particles 10, the weight average particle diameter (D4) is 7.3 μm, the average circularity is the same except that the feed amount of the jet mill pulverizer is 2.0 kg / hr and the pulverization pressure is 1.6 kPa. As a result, toner particles 13 having a particle size of 0.921 were obtained. The production conditions for the toner particles 13 are shown in Table 2.

<Toner Particle Production Example 14>
After adding 450 parts by mass of 0.1M Na ₃ PO ₄ aqueous solution to 720 parts by mass of ion-exchanged water and heating to 60 ° C., 67.7 parts by mass of 1.0 M CaCl ₂ aqueous solution was added to stabilize the dispersion. An aqueous medium containing the agent (Ca ₃ (PO ₄ ) ₂ ) is obtained.
-Styrene 74.00 parts by mass-n-butyl acrylate 26.00 parts by mass-Divinylbenzene 0.52 parts by mass-Iron complex of monoazo dye (T-77: manufactured by Hodogaya Chemical Co., Ltd.) 1.00 parts by mass-Hydrophobic treatment 90.00 parts by mass of magnetic substance, 3.00 parts by mass of amorphous polyester (saturated polyester resin obtained by condensation reaction of EO adduct of bisphenol A and terephthalic acid Mn = 5000, acid value = 12 mgKOH / g , Tg = 68 ° C.)
The above components are uniformly dispersed and mixed using an attritor (manufactured by Mitsui Mining Co., Ltd.) to obtain a monomer composition. This monomer composition was heated to 60 ° C., and 15.0 parts by mass of paraffin wax (endothermic peak top temperature: 77.2 ° C.) was mixed and dissolved therein, followed by polymerization initiator 2,2′-azobis ( 2,4-dimethylvaleronitrile) (4.5 parts by mass) is dissolved.

The monomer composition is put into the aqueous medium, and stirred at 12,000 rpm for 15 minutes with CLEARMIX (manufactured by M Technique Co., Ltd.) in an N ₂ atmosphere at 60 ° C. and granulated. Thereafter, the temperature is raised to 70 ° C. at a rate of 0.5 ° C./min while stirring with a paddle stirring blade, and the reaction is continued for 5 hours while maintaining the temperature at 70 ° C. Thereafter, the temperature is raised to 90 ° C. and held for 2 hours. After completion of the reaction, the suspension was cooled, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ , filtered, washed with water, and dried to have a weight average particle diameter (D4) of 8.0 μm and an average circularity of 0. 981 toner particles 14 were obtained.

<Production Examples 1 to 6 of organic / inorganic composite fine particles>
The organic-inorganic composite fine particles can be produced according to the description in the examples of WO 2013/063291.

  As the organic-inorganic composite fine particles used in Examples described later, those prepared according to Example 1 of WO 2013/066291 using silica shown in Table 3 were prepared. Table 3 shows the physical properties of the organic-inorganic composite fine particles 1 to 6.

<Production example of strontium titanate fine particles 1>
The titanyl sulfate powder was dissolved in distilled water so that the Ti concentration in the solution was 1.5 (mol / l). Subsequently, sulfuric acid and distilled water were added to this solution so that the sulfuric acid concentration at the end of the reaction was 2.8 (mol / l). This solution was heated at 110 ° C. for 36 hours in a sealed container to carry out a hydrolysis reaction. Thereafter, washing with water was performed to sufficiently remove sulfuric acid and impurities to obtain a metatitanic acid slurry. To this slurry, strontium carbonate (number average particle size 490 nm) is added so as to have an equimolar amount with respect to titanium oxide. After thorough mixing in an aqueous medium, washing and drying, followed by sintering at 800 ° C. for 6 hours, pulverization and classification by mechanical impact force, strontium titanate fine particles 1 having a number average particle diameter of 997 nm are obtained. It was.

<Production example of strontium titanate fine particles 2>
Except for changing the particle size of strontium carbonate to be used at 280 nm and firing conditions to 850 ° C. for 7 hours, and adjusting the pulverization and classification conditions as appropriate, Similarly, strontium titanate fine particles 2 having a number average particle diameter of 512 nm were obtained.

<Production Example of Toner 1>
Hydrophobic silica fine powder surface-treated with hexamethyldisilazane, 1.0 part by mass of organic / inorganic composite fine particles 1, 0.6 part by mass of strontium titanate fine particles 1 with respect to 100.0 parts by mass of toner particles 1 0.8 parts by mass (number average particle diameter of primary particles: 10 nm) was added and mixed for 2 minutes at 3200 rpm with a Mitsui Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.) to obtain toner 1. It was. The number average particle diameter of the organic-inorganic composite particles observed on the toner was the same as that measured with the organic-inorganic composite particles alone. Table 5 shows the physical properties of Toner 1.

<Production Examples of Toners 2 to 18>
Toners 2 to 18 were obtained in the same manner as in Toner 1 except that the types and addition amounts of the toner particles and organic-inorganic composite fine particles used and the types and addition amounts of the strontium titanate fine particles were changed as shown in Table 4. Table 5 shows the physical properties of Toner 2 to 18 obtained.

<Production Examples of Comparative Toners 1 to 6>
Comparative toners 1 to 6 were obtained in the same manner as toner 1 except that the types and addition amounts of the toner particles and organic-inorganic composite fine particles used and the types and addition amounts of the strontium titanate fine particles were changed as shown in Table 6. . Table 7 shows the physical properties of the obtained comparative toners 1 to 6.

[Example 1]
A commercially available laser printer (Laser Jet P4515n, manufactured by hp) was used for unfixed image output in the examples.

  The evaluation machine was modified so that each of the developing devices shown in FIGS. 2 (a) and 2 (b) could enter. Further, the evaluation machine was modified and used so that the applied bias and the like were in the above-described conditions. The developing device 1 in the embodiment shows the type of FIG. 2A, and the developing device 2 shows the type of FIG. 2B. The developing device was filled with 1 kg of toner and evaluated as follows.

<Toner level detection accuracy>
Normal paper for copying machines (75 g / m ² ) was used and output in an intermittent mode in which two images with a printing rate of 5% were output in 10 seconds in a high-temperature, high-humidity environment (32.5 ° C., 80% RH). . The image was output for 6 days, and the number of output sheets was adjusted so that the remaining amount of toner at the end of image output on the 5th day was 10% (100 g). At that time, the number of images per day was set to be the same as the number of images output each day. The remaining amount detection error was obtained by comparing the remaining amount of toner at the time of the first sheet immediately after the startup of the printer on the 6th evaluation with the value of the output signal from the remaining amount detection device. Further, the remaining amount detection error was obtained by outputting an image with a printing rate of 5% so that the remaining amount of toner is 5% (50 g), and comparing the remaining amount of toner with the value of the output signal from the remaining amount detection device. . The evaluation results are shown in Table 8.

Further, after the developing device 1 filled with the toner 1 in a harsh environment (40 ° C., 95% RH) was left for 30 days, the same evaluation as the above evaluation was performed. That is, the remaining amount detection error was obtained by comparing the remaining amount of toner at the time of the first sheet immediately after the printer startup on the sixth day of evaluation with the value of the output signal from the remaining amount detection device. Further, the remaining amount detection error was obtained by outputting an image with a printing rate of 5% so that the remaining amount of toner is 5% (50 g), and comparing the remaining amount of toner with the value of the output signal from the remaining amount detection device. . The evaluation results are shown in Table 8.
Remaining amount detection error (%) = {| (actually remaining amount) − (remaining amount detected value) | / (actually remaining amount)} × 100
A: The remaining amount detection error is less than 3% B: The remaining amount detection error is 3% or more and less than 5% C: The remaining amount detection error is 5% or more and less than 8% D: The remaining amount detection error is 8 %that's all

[Examples 2 to 18]
Evaluation was performed in the same manner as in Example 1 except that the toner, the toner filling amount, and the developing device were changed as shown in Table 8. The evaluation results are shown in Table 8.

[Comparative Examples 1 to 6]
Evaluation was performed in the same manner as in Example 1 except that the toner and the developing device were changed as shown in Table 8. The evaluation results are shown in Table 8.

  DESCRIPTION OF SYMBOLS 1 Electrophotographic photosensitive member (image carrier), 2 charging roller (charging means), 3 developing device (developing means), 3a developing container (toner storage part), 4 transfer device (transfer means), 5 cleaning device, 5a cleaning Blade, 6 exposure device, 7 fixing device, 8 developing sleeve (toner carrier), 8a magnet roller, 9 cartridge side memory, 10 toner stirring member, 11 developing blade, 12 image forming device, 14 antenna member (conductive resin sheet) ), 15 voltage applying means, 17 toner remaining amount detecting means, 18 toner remaining amount detecting device, N transfer nip, T toner, P transfer material

Claims (6)

Toner and
A toner carrier;
Accommodates the toner, and a toner container having a toner stirring member for supplying the toner to the toner carrying member therein,
A developing device that can be installed in the main body of the printer ,
There is a region formed of a nonmagnetic conductive resin member on the bottom surface of the toner container,
Said toner carrying member and the first electrode, the region as a second electrode, the amount of the toner in the toner storing portion based on the capacitance between the first electrode and the second electrode the detection is performed are configured in so that,
The toner stirring member is a member that is rotatable about a direction parallel to the longitudinal direction of the toner carrier, and the rotation center of the toner stirring member when the developing device is installed in the main body of the printer. installation surface parallel to said line of printers through the shaft, wherein a member which is arranged so as to pass below the lower end of the toner carrying member, and, the toner from the lower side of the toner carrying member to the toner carrying member A member for supplying,
The toner is
Toner particles containing a binder resin and a magnetic material,
An external additive ,
Toner der with is,
Of the toner was measured using a powder flowability analyzer, fifth total energy at the time of measurement after compression, not less than 70 mJ 105MJ less,
The toner, uniaxial collapse stress at the maximum consolidation stress 10.0kPa is, a developing device, characterized in that at least 2.5 kPa 4.5 kPa or less. The conductive resin member, a developing device according to 請 Motomeko 1 Ru conductive resin sheet der having flexibility. The conductive resin sheet resistance, developing device according to 請 Motomeko 2 Ru der 1.0 × 10 ³ Ω or more 1.0 × 10 ⁵ Ω or less. The true density of the toner, the developing device according to any one of 1.35 g / cm ³ or more 1.75 g / cm ³ or less der Ru請 Motomeko 1-3. The external additive is
Organic-inorganic composite fine particles ;
Strontium titanate ,
An apparatus according to any one of to that請 Motomeko 1-4 contain. An electrostatic latent image formed on the latent electrostatic image bearing member is developed with toner carried on the toner carrying member in the developing device, and the detection of the amount of the toner in the toner accommodating portion in the developing device An image forming method to perform,
The developing device is
The toner;
The toner carrier;
Accommodates the toner, and, with the toner storage portion that having a toner stirring member for supplying the toner to the toner carrying member therein,
A developing device having,
There is a region formed of a nonmagnetic conductive resin member on the bottom surface of the toner container,
Development by the toner, the toner stirring member, wherein a direction parallel to the longitudinal direction of the toner carrying member is rotated as a rotation axis, said supplying toner from the lower side of the toner carrying member to the toner carrying member, wherein performed by the toner carried on the toner carrying member,
Detection of the amount of the toner in the toner accommodating portion, said toner carrying member and the first electrode, the region as a second electrode, the electrostatic between the first electrode and the second electrode Based on capacity,
The toner is
Toner particles containing a binder resin and a magnetic material,
An external additive ,
Toner der with is,
Of the toner was measured using a powder flowability analyzer, fifth total energy at the time of measurement after compression, not less than 70 mJ 105MJ less,
The image forming method, wherein the toner has a uniaxial collapse stress at a maximum compaction stress of 10.0 kPa of 2.5 kPa to 4.5 kPa .

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