Toner container and toner

Abstract

To provide a technique for reducing degradation of toner even when the toner is stored in a flexible bag.SOLUTION: A toner storage container includes a bag-like storage part which has the flexibility and toner which is stored in the storage part and contains silica particles. In a powder fluidity measurement device, in measurement of Total Energy when making a propeller type blade intrude into a surface of a powder layer of the toner manufactured by applying a vertical load of 88 kPa in a measurement container while rotating at a peripheral velocity of 100 mm / sec of the outermost edge of the propeller type blade, a value of the Total Energy is equal to or less than 300 mJ.SELECTED DRAWING: Figure 4

Description

[Technical Field]

[0001] The present invention relates to a toner storage container and a toner. [Background technology]

[0002] Electrophotographic image forming apparatuses form images by transferring a toner image formed on the surface of a photosensitive drum using toner as a developer onto a transfer material (recording material) as a recording medium. Among such image forming apparatuses, those employing a toner supply system are known (see Patent Document 1). In a toner supply system image forming apparatus, when the toner in the toner storage unit runs low, toner can be replenished to the toner storage unit of the image forming apparatus using a container containing toner, without replacing process components such as the photosensitive drum or developing roller. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2020-086450 Summary of the Invention [Problem to be solved by the invention]

[0004] Toner supply-type image forming devices use containers that can store toner in a toner storage unit. Therefore, it is necessary to minimize deterioration of the toner stored in the toner storage unit even when the toner storage container is stored or transported. In particular, when the toner storage unit of a toner storage container is a flexible bag, the toner tends to become compressed during storage due to the toner's own weight, external forces applied by the bag, and external forces when the container is stored in a stack, which can easily cause the toner to deteriorate.

[0005] The present invention has been made in view of the above-mentioned problems, and has an object to provide a technique for reducing deterioration of toner even when the toner is contained in a flexible container. [Means for solving the problem]

[0006] The present invention employs the following configuration: a flexible bag-shaped storage section; a toner that is contained in the container and contains silica particles; A toner storage container having: In a powder fluidity measuring device, a propeller blade is rotated at a peripheral speed of the outermost edge of the propeller blade of 100 mm / sec and penetrated into the surface of a powder layer of the toner, which is prepared by applying a vertical load of 88 kPa in a measuring container, and the total energy of the toner is measured, and the total energy value is 300 mJ or less. the law of nature, The toner contains hydrotalcite particles containing fluorine. The toner storage container is characterized by the above.

[0007] The present invention also employs the following configuration: a flexible bag-shaped storage section; a toner that is contained in the container and contains silica particles; A toner storage container having: the toner has a total energy value of 300 mJ or less when a propeller blade is rotated at a peripheral speed of 100 mm / sec at the outermost edge of the propeller blade while being intruded into the surface of a powder layer of the toner, the powder layer being prepared in a measurement container by applying a vertical load of 88 kPa in a powder fluidity measuring device, a toner storage container characterized in that the toner contains a surfactant, and a P / N ratio, which is a ratio of a positive component to a negative component of the surfactant, is 0.1 or more and 0.8 or less; is. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a technique for reducing deterioration of toner even when the toner is contained in a flexible container. [Brief explanation of the drawings]

[0009] [Figure 1] Schematic cross-sectional view of an image forming system [Figure 2] Perspective view of an image forming system [Figure 3] Perspective view of an image forming apparatus [Figure 4] Toner pack schematic [Figure 5]An exploded perspective view showing the configuration of a toner pack [Figure 6] Illustration of line analysis in STEM-EDS mapping analysis DETAILED DESCRIPTION OF THE INVENTION

[0010] Preferred embodiments of the present invention will now be described in detail with reference to the drawings. However, the dimensions, materials, shapes, and relative positions of the components described in the following embodiments may be changed as appropriate depending on the configuration of the device to which the present invention is applied and various conditions. Therefore, unless otherwise specified, they are not intended to limit the scope of the present invention.

[0011] [Image forming device] An overview of the image forming apparatus 1 in which the toner pack of the present invention is used will be described. Fig. 1 is a schematic cross-sectional view of an image forming system 1S including the image forming apparatus 1. Fig. 2 is a perspective view showing the configuration of the image forming system 1S including the image forming apparatus 1. Fig. 3 is a perspective view from a different direction from Fig. 2, showing the configuration of the image forming apparatus 1 in a state in which the toner pack 100 is not attached.

[0012] Here, an image forming apparatus using a process cartridge, electrophotography, and toner supply system will be described as an example, but the toner and toner pack according to the present invention can be applied to various image forming apparatuses, not limited to such an image forming apparatus. The toner and toner pack described in the following examples can be applied as long as the toner is stored in a flexible bag. For example, the present invention also covers toner packs used in image forming apparatuses that require the cartridge to be removed for supply, toner packs for storage or transportation, and the toner used therein.

[0013] The present invention can be understood as a toner pack (toner storage container) having a storage portion that is a flexible bag-like portion for storing toner (developer). The present invention can also be understood as toner that is less likely to deteriorate when stored in a flexible bag.

[0014] The image forming system 1S includes an image forming apparatus 1 and a toner pack 100 attached to the image forming apparatus 1. The image forming apparatus 1 includes an apparatus main body 2 and a process cartridge 20 detachably attachable to the apparatus main body 2. The apparatus main body 2 has an image forming unit 10 that forms a toner image on a recording material P, a pickup roller 65 that feeds the recording material P from a tray 64 to the image forming unit 10, a fixing unit 70 that fixes the toner image formed by the image forming unit 10 onto the recording material P, and a pair of discharge rollers 80.

[0015] The image forming section 10 has a scanner unit 11, an electrophotographic process cartridge 20, and a transfer roller 12 that transfers a toner image as a developer image formed on a photosensitive drum 21 of the process cartridge 20 onto a recording material P. The process cartridge 20 has the photosensitive drum 21, a charging roller 22 arranged around the photosensitive drum 21, a cleaning blade 24, and a developing device 30.

[0016] The developing device 30 includes a developing roller 31 as a developer carrier that carries developer, a developing container 32 that forms the frame of the developing device 30, and a supply roller 33 that can supply developer to the developing roller 31. The developing container 32 includes a toner storage chamber 36 that stores toner, and a toner storage chamber 37 that stores toner. The chamber 36 is provided with an agitating member 34 as an agitating means and a developing blade 35. The developing device 30 is provided with a cartridge opening 117a for receiving the nozzle 102 of the toner pack 100. It is preferable that the cartridge opening 117a be closed with a cap or the like except when toner is being replenished.

[0017] A top cover 82 serving as a loading tray is provided on the top of the device main body 2, and a discharge tray 81 serving as a loading surface is formed on the upper surface of the top cover 82. An opening / closing member 83 is supported on the top cover 82 so as to be rotatable about a rotation shaft 83a. The opening / closing member 83 can be moved by rotation between an open state in which the opening 82a is exposed and a closed state in which the opening 82a is closed. Figures 2 and 3 show the open state. The discharge tray 81 of the top cover 82 has an opening 82a that opens upward.

[0018] When replenishing toner, the user inserts the toner pack 100 in the mounting direction M (indicated by the arrow in FIG. 3) so that the nozzle 102 of the toner pack 100 overlaps the mounting portion 106. Then, the nozzle 102 is inserted into the toner storage chamber 36 through the opening 82a of the apparatus main body 2 and the cartridge opening 117a of the developing device 30. As a result, as shown in FIG. 1, the toner T inside the toner pack 100 moves into the toner storage chamber 36 by gravity.

[0019] A reading device 90 that reads documents is provided above the top cover 82. The reading device 90 is provided so as to be rotatable between a state in which it covers the top cover and a state in which it does not cover the top cover as shown in FIG.

[0020] The control unit C is a control device that controls each component of the image forming apparatus 1 to perform various controls. For example, a computer or control circuit having computational resources such as a processor and memory can be used as the control unit C. The control unit C operates the drive unit and image forming unit, and performs a series of controls when forming an image on the recording material P and discharging it based on image data read by the reading device 90 or image data received from an external device (not shown). The control unit C may also detect when toner is low and notify the user to urge them to replenish toner. Any method can be used to detect the amount of toner, such as optical detection or detection by weight measurement. Any method can be used to notify the user, such as audio or on-screen notification.

[0021] 1 to 3 show a system (direct replenishment system) in which the user replenishes toner from a toner pack 100 filled with replenishment toner to the developing device 30 while the developing device 30 remains attached to the image forming apparatus 1. This eliminates the need to remove the process cartridge 20 from the apparatus main body 2 and replace it with a new process cartridge when the amount of toner remaining in the process cartridge 20 becomes low, thereby improving usability. Furthermore, toner can be replenished to the developing container 32 more inexpensively than by replacing the entire process cartridge 20. The direct replenishment system also reduces costs compared to replacing only the developing device 30 of the process cartridge 20 because it does not require replacing various rollers, gears, etc. However, the present invention is not limited to the direct replenishment system.

[0022] [Toner contained in the toner pack] The toner used in the present invention, that is, the toner contained in the toner pack 100, will now be described. In the present invention, a toner powder flowability measuring device is used to measure the total energy when a propeller blade is rotated at a peripheral speed of 100 mm / sec at the outermost edge of the propeller blade and penetrated into the surface of a powder layer of the toner, which is prepared by applying a vertical load of 88 kPa in a measuring container, and the total energy value is 300 mJ or less. The smaller the total energy, the easier it is for the toner to break apart from its compacted state; in other words, this value represents the degree of compaction of the toner. The more compacted the toner is, the more susceptible it is to toner deterioration when stored in a pack. For example, If the unevenness of the toner surface formed by additives makes it easier for toner particles to mesh together, the Total Energy value will increase. In this case, it is thought that the load applied accelerates toner degradation, starting from the meshed points. Total Energy can be controlled by the shape of the toner and the type, amount, and coverage of the external additives added.

[0023] The content of silica particles (external additive) is preferably 1.4% by mass or more, and more preferably 2.0% by mass or more. The higher the content of silica particles, the easier it is to reduce total energy. If the amount of external additive is too high, fixing will deteriorate and printer components will become more contaminated, so it needs to be adjusted appropriately.

[0024] The coverage of the toner particle surface with silica particles is preferably 34% to 80%. It is more preferably 39% to 75%. The higher the coverage, the less compaction the toner has, making it easier to reduce total energy and more resistant to toner degradation when subjected to external forces. The coverage can be controlled by the type and amount of silica particles and external addition conditions.

[0025] The toner preferably contains fluorine-containing hydrotalcite particles. More preferably, fluorine is contained inside the hydrotalcite particles. By adding negative fluorine to positive hydrotalcite particles, local overcharging of the toner is easily suppressed. One cause of compaction is electrostatic cohesion within the pack. However, by suppressing local overcharging of the toner as described above, electrostatic cohesion of the toner within the pack is suppressed, improving compaction and, as a result, suppressing toner degradation.

[0026] The toner contains a surfactant, and the P / N ratio, which is the ratio of positive to negative components of the surfactant, is preferably 0.1 to 0.8, more preferably 0.2 to 0.6. This helps to prevent local overcharging of the toner, which in turn prevents compaction due to electrostatic aggregation of the toner in the pack (described later), and thus prevents toner degradation. The P / N ratio can be controlled by the type and amount of surfactant used during toner production.

[0027] [Toner pack composition] Next, the configuration of the toner pack 100 will be described with reference to Figures 4 and 5. Figure 4 is a front view and a schematic cross-sectional view of a toner storage container. Figure 5 is an exploded perspective view showing the internal configuration of the toner pack 100.

[0028] 4 and 5, the toner pack 100 has a storage section 101 for storing toner therein at one end (first end) in the direction of the axis A. In the present invention, the storage section 101 is a flexible bag, and the storage section 101 is formed by pouch processing using a resin sheet as an example in FIGS.

[0029] On the other hand, a nozzle (nozzle portion) 102 is provided on the other end side (second end side) of the toner pack 100. The nozzle 102 and the storage portion 101 are connected by a connecting portion 107. A discharge port (opening, first opening) 102a that communicates with the interior of the storage portion 101 and can discharge the toner stored inside the storage portion 101 to the outside is provided on a side surface (first outer surface, wall surface) 102b of the nozzle 102 that extends in the direction of the axis A. A pack-side shutter 103 (rotating member) is attached to the side of the nozzle 102 opposite to the side where the storage portion 101 is provided (second end side) so as to be rotatable about the axis A.

[0030] A substantially rectangular pack-side seal 105 is attached to the pack-side shutter 103, and the pack-side shutter 103 takes a first position where the pack-side seal 105 covers the discharge port 102a, and a second position where the pack-side seal 105 opens the discharge port 102a without covering it. FIG. 4(a) shows the state in which the pack-side shutter 103 is in position 1, and FIG. 4(b) shows the state in which the pack-side shutter 103 is in position 2. As shown in FIG. 4(a), when the pack-side shutter 103 is in the first position, it is rotated in the direction of arrow K about axis A to reach the second position shown in FIG. 4(b). Conversely, when the pack-side shutter 103 is rotated from the second position in the direction of arrow L, it reaches the first position. During these operations, the pack-side shutter 103 rubs against the side surface 102b of the nozzle 102 via the pack-side seal 105.

[0031] Considering the efficiency of transportation and the space required for product display, the toner pack 100 is required to be small. Furthermore, considering the efficiency of supply, it is preferable that a large amount of toner is filled inside the small toner pack 100. However, it has been found that if the filling amount is increased, the toner is more likely to be compacted during storage and deteriorate. Based on this, a toner pack that is even more optimal for suppressing toner deterioration in a toner containing the above-mentioned fluorine-containing hydrotalcite particles will be described.

[0032] The storage section 101 is made of a flexible material that can be easily deformed by the user's hand (fingers). It is preferable that the toner pack has a cohesion level of 40% or less after the toner storage container is shaken for 5 minutes at an amplitude of 80 mm and 150 times / min. By keeping the cohesion level at 40% or less, electrostatic cohesion of the toner inside the pack caused by shaking during manufacturing and transportation can be suppressed, and toner degradation can be prevented.

[0033] The container is preferably made of a resin sheet. Furthermore, the resin sheet constituting the container is preferably at least one of a polypropylene sheet, a polyethylene sheet, and a PET sheet. These materials have a similar triboelectric series to the toner containing the above-mentioned fluorine-containing hydrotalcite particles, and therefore, it is easy to obtain a pack having the above-mentioned cohesion degree of 40% or less.

[0034] The thickness of the resin sheet is preferably 25 μm or more and 300 μm or less. A thickness of 25 μm or more reduces the effect of temperature and humidity, while a thickness of 300 μm or less makes the sheet flexible and prevents external forces from being applied locally to the toner.

[0035] [Example] [Method for measuring toner physical properties] Hereinafter, methods for measuring various physical properties of the toner will be described.

[0036] <Method for measuring the total energy (TE) of toner> In the present invention, TE is measured using a powder flowability measuring device equipped with a rotary propeller-type blade (Powder Rheometer FT-4, manufactured by Freeman Technology; hereinafter abbreviated as FT-4).

[0037] Specifically, measurements are performed using the following procedure. In all operations, a 23.5 mm diameter propeller blade designed specifically for FT-4 measurements is used, with the rotation axis normal to the center of the 23.5 mm x 6.5 mm blade plate. The blade plate is smoothly twisted counterclockwise, with both outermost edges (12 mm from the rotation axis) twisted at 70° and the part 6 mm from the rotation axis twisted at 35°, and is made of stainless steel.

[0038] The container used is a dedicated container for FT-4 measurement [a split container (model number: C4031) with a diameter of 25 mm and a volume of 25 ml, with a height of approximately 51 mm from the bottom of the container to the split part. Hereinafter, this will be referred to simply as the container.]

[0039] For compressing the toner, a compression test piston (diameter 24 mm, height 20 mm, mesh-covered bottom) is used instead of the propeller blade.

[0040] The measurement procedure is as follows. (1) Sample consolidation Add 17.5g of toner to the dedicated FT-4 measurement container mentioned above (this is the mass when the specific gravity is 1.1; for example, if the specific gravity is 1.5, add 23.9g of toner; adjust the volume so that it is approximately the same depending on the specific gravity). Attach a compression piston dedicated to FT-4 measurement and compress at 88kPa for 30 seconds.

[0041] (2) Split operation The toner layer is leveled off using the split portion of the FT-4 measurement container described above, and the toner at the top of the toner layer is removed to form a toner layer of the same volume (25 ml).

[0042] (3) Measurement operation The blade rotates counterclockwise relative to the surface of the toner powder layer (the direction in which the blade rotates to push into the toner powder layer), with the peripheral speed of the blade (the peripheral speed of the outermost edge of the blade) set to 100 mm / sec, and the vertical penetration speed into the toner powder layer is set to the speed at which the angle between the path drawn by the outermost edge of the moving blade and the surface of the powder layer (hereinafter referred to as the "blade path angle") is 5 degrees. TE is the sum of the rotational torque and vertical load obtained when the propeller-shaped blade penetrates to a position 10 mm from the bottom of the toner powder layer.

[0043] <Method for measuring silica particle content> A wavelength-dispersive X-ray fluorescence analyzer "Axios" (PANalytical) and the accompanying dedicated software "SuperQ ver.4.0F" (PANalytical) for setting measurement conditions and analyzing measurement data were used. Rh was used as the anode of the X-ray tube, the measurement atmosphere was vacuum, the measurement diameter (collimator mask diameter) was 27 mm, and the measurement time was 10 seconds. Light elements were detected using a proportional counter (PC), and heavy elements were detected using a scintillation counter (SC).

[0044] The measurement sample was prepared by placing 4 g of toner in a special aluminum ring for pressing, flattening it, and then pressing it at 20 MPa for 60 seconds using a tablet molding compressor "BRE-32" (manufactured by Maekawa Testing Machinery Manufacturing Co., Ltd.) to form a pellet with a thickness of 2 mm and a diameter of 39 mm.

[0045] To 100 parts of silicon-free resin particles, add 0.5 parts of silica (SiO2) fine powder and mix thoroughly using a coffee mill. Similarly, mix 5.0 and 10.0 parts of silica fine powder with the resin particles, respectively, to use as samples for the calibration curve.

[0046] For each sample, pellets for the calibration curve sample were prepared as described above using a tablet press, and the count rate (unit: cps) of the Si-Kα ray observed at a diffraction angle (2θ) of 109.08° when PET was used as the analyzing crystal was measured. The acceleration voltage and current of the X-ray generator were set to 24 kV and 100 mA, respectively. A linear calibration curve was obtained with the obtained X-ray count rate on the vertical axis and the amount of SiO2 added in each calibration curve sample on the horizontal axis. Next, the toner to be analyzed was pelletized as described above using a tablet press, and the count rate of the Si-Kα ray was measured. The value on the horizontal axis was then read from the calibration curve, and this value was taken as the silica particle content.

[0047] <Method for measuring coverage by silica particles> The backscattered electron images of the toner particle surfaces were obtained using a scanning electron microscope (SEM). The equipment and observation conditions are as follows:

[0048] Equipment used: ULTRA PLUS manufactured by Carl Zeiss Microscopy Co., Ltd. Accelerating voltage: 1.0 kV WD: 2.0 mm Aperture Size: 30.0 μm Detection signal: EsB (energy selective backscattered electrons) EsB Grid:800V Magnification: 50,000x Contrast: 63.0±5.0% (reference value) Brightness: 38.0±5.0% (reference value) Resolution: 1024 x 768 Pretreatment: Toner particles are scattered on carbon tape (no deposition is performed)

[0049] The accelerating voltage and EsB grid of the present invention are set to achieve the following: obtaining structural information on the outermost surface of the toner particles, preventing charging up of undeposited samples, and selectively detecting high-energy reflected electrons. The observation field is selected to be near the vertex where the curvature of the toner particles is smallest.

[0050] The coverage rate is obtained by analyzing the backscattered electron image of the toner particle surface obtained by the above method using image processing software ImageJ (developed by Wayne Rashand). The procedure is as follows:

[0051] First, convert the backscattered electron image to be analyzed to 8-bit using Type in the Image menu. Next, set the Median diameter to 2.0 pixels using Filters in the Process menu to reduce image noise. After excluding the observation conditions display area at the bottom of the backscattered electron image, estimate the center of the image and use the Rectangle Tool on the toolbar to select a 1.5 μm square area from the center of the backscattered electron image.

[0052] Next, select Threshold from Adjust in the Image menu and click Apply to obtain a binarized image of the areas covered with the outer shell and the uncovered missing areas.

[0053] Next, use the straight line tool (Straight Line) on the toolbar to select the scale bar in the observation condition display area displayed below the backscattered electron image. In this state, select Set Scale from the Analyze menu. A new window will open and the pixel distance of the selected line will be entered in the Distance in Pixels field. Enter the value of the scale bar (e.g., 100) in the Known Distance field of the window, enter the unit of the scale bar (e.g., nm) in the Unit of Measurement field, and click OK to complete the scale setting. Next, select Histogram from the Analyze menu, read the Count and Mode values ​​in the window that opens, and perform the following calculations. Coverage = Mode / Count x 100

[0054] The above procedure is carried out for 20 fields of view for the toner particles to be evaluated, and the arithmetic mean value thereof is adopted as the final coverage ratio.

[0055] <Method for measuring and identifying the ratio of elements in hydrotalcite particles> The element ratio of the hydrotalcite particles is measured by EDS mapping measurement of the toner using a scanning transmission electron microscope (STEM). The EDS mapping can be measured with high sensitivity by using a silicon drift detector with a large detection element area.

[0056] By performing statistical analysis on the spectral data for each pixel obtained by EDS mapping measurement, it is possible to obtain a principal component mapping that extracts pixels with similar spectra, making it possible to map specific components.

[0057] The sample for observation is prepared according to the following procedure. 0.5 g of toner is weighed out and placed in a cylindrical mold with a diameter of 8 mm using a Newton press, which is left to stand for 2 minutes under a load of 40 kN to produce a cylindrical toner pellet with a diameter of 8 mm and a thickness of approximately 1 mm, 0.8 mmφ. A 200 nm thick slice is prepared from the toner pellet using an ultramicrotome (Leica, FC7).

[0058] The STEM-EDS mapping analysis is carried out using the following equipment and conditions. [Device] Scanning transmission electron microscope: JEOL JEM-2800 EDS detector: JEOL JED-2300T dry SD100GV detector (detector area: 100 mm 2 ) EDS analyzer: Thermo Fisher Scientific NORAN System 7

[0059] [Conditions for STEM-EDS] STEM accelerating voltage: 200kV ·Magnification: 20,000x Probe size 1nm STEM image size: 1024 x 1024 pixels (EDS elemental mapping images are acquired at the same position.) EDS mapping size: 256 x 256 pixels, Dwell time: 30 μs, Integration count: 100 frames

[0060] The ratio of each element in the hydrotalcite particles is calculated based on multivariate analysis as follows.

[0061] The EDS mapping was obtained using the STEM-EDS analyzer. The collected spectral mapping data was then subjected to multivariate analysis using the COMPASS (PCA) mode in the measurement command of the NORAN System 7, and principal component map images were extracted.

[0062] In this case, the setting values ​​are as follows: Kernel size: 3×3 Quantitative map setting: High (slow) Filter Fit Type: High Precision (Slow)

[0063] At the same time, this operation calculates the area ratio of each extracted principal component to the EDS measurement field of view.Quantitative analysis is then performed on the EDS spectrum of each principal component mapping obtained using the Cliff-Lorimer method.

[0064] The toner particle portion and the hydrotalcite particle are distinguished based on the above quantitative analysis results of the obtained STEM-EDS main component mapping. The particles can be identified as hydrotalcite particles based on the content and ratio of polyvalent metals such as magnesium.

[0065] Furthermore, the presence of fluorine inside the hydrotalcite particles is confirmed by the following method.

[0066] Based on the mapping data obtained by the STEM-EDS mapping analysis using the method described above, the fluorine and aluminum in the hydrotalcite particles are analyzed. Specifically, EDS line analysis is performed in the normal direction to the outer periphery of the hydrotalcite particle, and the fluorine and aluminum present inside the particle are analyzed.

[0067] A schematic diagram of the line analysis is shown in Figure 6(a). For a toner particle 201 and a hydrotalcite particle 203 adjacent to a toner particle 202, line analysis is performed in the normal direction to the outer periphery of the hydrotalcite particle 203, i.e., in the direction of the dotted arrow 205. Note that 204 indicates the boundary of the toner particle.

[0068] The area in the acquired STEM image where the relevant hydrotalcite particles are present is selected using the rectangular selection tool, and line analysis is performed under the following conditions.

[0069] [Line analysis conditions] STEM magnification: 800,000x Line length: 200nm Line width: 30nm Number of line divisions: 100 points (measure intensity every 2 nm) or 50 points (every 4 nm)

[0070] When the peak intensity of the relevant fluorine or aluminum element in the EDS spectrum of the hydrotalcite particle is 1.5 times or more the background intensity, and when the peak intensity of the fluorine or aluminum element at both ends of the hydrotalcite particle in line analysis (points a and b in Figure 6(a)) does not exceed 3.0 times the peak intensity at point c, the element is determined to be contained inside the hydrotalcite particle. Point c is the midpoint of line segment ab (i.e., the midpoint of the above-mentioned both ends).

[0071] Examples of X-ray intensities of fluorine and aluminum obtained by line analysis are shown in Figures 6(b) and 6(c). When hydrotalcite particles contain fluorine and aluminum inside, the graph of X-ray intensity normalized by peak intensity will have a shape like that shown in Figure 6(b). When hydrotalcite particles contain fluorine derived from a surface treatment agent, the graph of X-ray intensity normalized by peak intensity will have peaks near points a and b at both ends of the fluorine graph, as shown in Figure 6(c). By checking the X-ray intensities derived from fluorine and aluminum in line analysis, it can be confirmed that the hydrotalcite particles contain fluorine inside. It is determined that these elements are contained inside the particles in question.

[0072] <Method for measuring shaking coagulation> The degree of toner cohesion after shaking the toner pack is measured as follows.

[0073] The toner pack is used after being left in an environment of 23°C and 60% RH for 24 hours and then shaken for 5 minutes at an amplitude of 80 mm and 150 times / min. The following measurements are started within 10 minutes after shaking.

[0074] The measuring device used was a "Powder Tester PTX Type" (manufactured by Hosokawa Micron Corporation) with a digital display vibrometer "DigiVibro MODEL 1332A" (manufactured by Showa Sokki Co., Ltd.) attached to the side of the vibration table. A sieve with a 20 μm (635 mesh) opening, a 38 μm (390 mesh) opening, and a 75 μm (200 mesh) opening are placed on top of each other on the vibration table of the powder tester. Measurements are carried out in an environment of 23°C and 60% RH as follows:

[0075] (1) Adjust the vibration amplitude of the vibration table in advance so that the displacement value on the digital display vibrometer is 0.60 mm (peak-to-peak). (2) After the shaking, 5.0 g of the toner is weighed out and gently placed on the top sieve with 75 μm openings. (3) After vibrating the sieves for 30 seconds, the mass of the toner remaining on each sieve is measured and the degree of cohesion is calculated according to the following formula. Coagulation degree (%) = {(mass of sample on sieve with 75 μm opening (g)) / 5 (g)} × 100 + {(Sample mass (g) on ​​38 μm mesh sieve) / 5 (g)} x 100 x 0.6 + {(Sample mass (g) on ​​20 μm mesh sieve) / 5 (g)} x 100 x 0.2

[0076] (Method for measuring P / N ratio) The measurement is carried out as follows. Dissolve 1 mg of toner in 10 mL of methanol and leave to stand for 24 hours. After that, collect the supernatant and measure it. If there are any unwanted substances floating in the supernatant, filter it using the filter recommended for the equipment as necessary.

[0077] Equipment: Mass spectrometer LCQ-Fleet (ThermoFisher Scientific Co., Ltd.) HPLC equipment Ultimate 3000 series (ThermoFisher Scientific Co., Ltd.) Measurement method: Flow injection method (direct introduction without a column) Eluent: methanol Flow rate: 0.5ml / min Ionization method: ESI Measurement range: 100-1500 m / z

[0078] In the obtained total ion chromatograms of ESI+ and ESI-, the peak areas calculated by selecting the retention time from 0 minutes to 5 minutes are designated as P and N, respectively, and the ratio P / N is calculated.

[0079] <Measurement of toner particle size> The particle size of the toner is measured as follows: Using a precision particle size distribution measuring device equipped with a 100 μm aperture tube and using the narrow-pore electrical resistance method, the Coulter Counter Multisizer 3 (registered trademark, manufactured by Beckman Coulter), and the accompanying dedicated software for setting measurement conditions and analyzing measurement data, the particle size is measured with an effective number of 25,000 measurement channels, and the measurement data is analyzed and calculated.

[0080] The aqueous electrolyte solution used for the measurement is prepared by dissolving special grade sodium chloride in ion-exchanged water to a concentration of approximately 1% by mass, such as "ISOTON II" (manufactured by Beckman Coulter).

[0081] Before carrying out the measurements and analysis, the dedicated software is set up as follows. In the "Change Standard Measurement Method (SOM) screen" of the dedicated software, the total count number in the control mode was set to 50,000 particles, the number of measurements was set to 1, and the Kd value was set to "Standard particle 10 Set the value obtained using a 1.0 μm (Beckman Coulter) filter. Press the threshold / noise level measurement button to automatically set the threshold and noise level. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check the option to flush the aperture tube after measurement.

[0082] In the dedicated software's "Pulse to particle size conversion setting screen," set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm or more and 60 μm or less.

[0083] The specific measurement method is as follows. (1) Pour approximately 200 ml of the electrolyte solution into a 250 ml round-bottom glass beaker made specifically for the Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 revolutions per second. Then, use the "aperture tube flush" function of the dedicated software to remove any dirt and air bubbles from inside the aperture tube.

[0084] (2) Approximately 30 ml of the above-mentioned aqueous electrolyte solution is placed in a 100 ml flat-bottom glass beaker, and approximately 0.3 ml of a dilution obtained by diluting "Contaminon N" (a 10% by weight aqueous solution of a neutral detergent for cleaning precision measuring instruments, pH 7, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) three times by weight with ion-exchanged water is added as a dispersant.

[0085] (3) A predetermined amount of ion-exchanged water is placed in the water tank of an ultrasonic disperser, "Ultrasonic Dispersion System Tetora150" (manufactured by Nikkaki Bios Co., Ltd.), which has two built-in oscillators with an oscillation frequency of 50 kHz and a phase difference of 180 degrees and an electrical output of 120 W, and approximately 2 ml of the Contaminon N is added to this water tank.

[0086] (4) Set the beaker (2) in the beaker fixing hole of the ultrasonic disperser, operate the ultrasonic disperser, and adjust the height of the beaker so that the resonance state of the liquid surface of the electrolytic solution in the beaker is maximized.

[0087] (5) While the electrolyte solution in the beaker in (4) is being irradiated with ultrasonic waves, approximately 10 mg of toner or toner particles is added little by little to the electrolyte solution and dispersed. The ultrasonic dispersion process is then continued for another 60 seconds. During the ultrasonic dispersion process, the water temperature in the water tank is appropriately adjusted to be between 10°C and 40°C.

[0088] (6) Using a pipette, add dropwise the electrolytic solution (5) containing the toner or toner particles dispersed therein to the round-bottom beaker (1) placed in the sample stand, and adjust the measurement concentration to approximately 5%. Then, measurements are continued until the number of particles measured reaches 50,000.

[0089] (7) The measurement data is analyzed using the dedicated software provided with the device to calculate the weight average particle diameter, which is the toner particle diameter. Note that when the dedicated software is set to Graph / Volume %, the "Average diameter" on the Analysis / Volume Statistics (Arithmetic Mean) screen is the weight average particle diameter.

[0090] <Method for measuring the BET specific surface area of ​​toner> The BET specific surface area (BETA) of the toner was measured in accordance with JIS Z8830 (2001). The specific measurement method is as follows.

[0091] The measurement device used was the "Automatic Specific Surface Area and Pore Distribution Measurement Device TriStar3000 (Shimadzu Corporation)," which employs the gas adsorption method based on the constant volume method.

[0092] The measurement conditions and the analysis of the measurement data were set using the dedicated software "TriStar3000 Version 4.00" that came with the device. Nitrogen gas was used as the adsorption gas, and the value calculated by the BET multipoint method was taken as the BET specific surface area in the present invention.

[0093] Specifically, the BET specific surface area is calculated as follows. First, nitrogen gas is adsorbed onto the toner, and the equilibrium pressure P (Pa) in the sample cell and the amount of nitrogen adsorbed onto the toner Va (mol g -1 ) is measured. The equilibrium pressure P (Pa) in the sample cell is divided by the saturated vapor pressure Po (Pa) of nitrogen, and the relative pressure Pr is plotted on the horizontal axis. The amount of nitrogen adsorption Va (mol g -1 ) on the vertical axis, an adsorption isotherm is obtained. Next, the monolayer adsorption amount Vm (mol g -1 ) is calculated by applying the BET formula below. Pr / Va(1-Pr)=1 / (Vm×C)+(C-1)×Pr / (Vm×C) (Here, C is a BET parameter, which varies depending on the type of sample being measured, the type of adsorbed gas, and the adsorption temperature.)

[0094] The BET equation can be interpreted as a straight line with a slope of (C-1) / (Vm×C) and an intercept of 1 / (Vm×C), where Pr is the X-axis and Pr / Va(1-Pr) is the Y-axis (this straight line is called a BET plot). Slope of the line = (C-1) / (Vm×C) Line intercept = 1 / (Vm × C)

[0095] By plotting the measured values ​​of Pr and Pr / Va(1-Pr) on a graph and drawing a line using the least squares method, the slope and intercept of the line can be calculated. By using these values ​​to solve the simultaneous equations for the slope and intercept above, Vm and C can be calculated.

[0096] Furthermore, the calculated Vm and the molecular occupancy cross section of the nitrogen molecule (0.162 nm 2 ) and calculate the BET specific surface area S (m 2 ·g -1 ) is calculated. S=Vm×N×0.162×10 -18 (where N is Avogadro's number (mol -1 )

[0097] Measurements using this device should be performed in accordance with the "TriStar3000 Instruction Manual V4.0" that comes with the device, specifically by following the steps below.

[0098] The taring of a thoroughly washed and dried dedicated glass sample cell (stem diameter 3 / 8 inch, volume approximately 5 ml) is precisely weighed. Then, 1.0 g of toner is placed into this sample cell using a funnel.

[0099] The sample cell containing the toner was placed in a pretreatment device, VacuPrep 061 (Shimadzu Corporation), connected to a vacuum pump and nitrogen gas pipe, and vacuum degassing was performed for approximately 10 hours at 23°C. During vacuum degassing, the valve was adjusted to gradually degas the toner so that it would not be sucked into the vacuum pump. The pressure inside the cell gradually decreased with degassing, eventually reaching approximately 0.4 Pa (approximately 3 mTorr). After vacuum degassing was complete, nitrogen gas was gradually injected to return the sample cell to atmospheric pressure, and the sample cell was removed from the pretreatment device. The mass of the sample cell was then accurately weighed, and the exact mass of the toner was calculated from the difference with the tare weight. During this process, the sample cell was covered with a rubber stopper to prevent contamination of the toner in the sample cell with moisture from the atmosphere.

[0100] Next, a special "isothermal jacket" is attached to the stem of the sample cell containing the toner. Then, a special filler rod is inserted into the sample cell, and the sample cell is set in the analysis port of the device. The isothermal jacket is a tube with a porous inner surface and an impermeable outer surface that can suck up liquid nitrogen to a certain level by capillary action. It is a component shaped like a rod.

[0101] Next, the free space of the sample cell, including the connecting equipment, is measured. The free space is calculated by measuring the volume of the sample cell at 23°C using helium gas, then measuring the volume of the sample cell after cooling it with liquid nitrogen, again using helium gas, and converting it from the difference between these volumes. The saturated vapor pressure Po (Pa) of nitrogen is also measured automatically using a Po tube built into the instrument.

[0102] Next, the sample cell was vacuum-evacuated, and then cooled with liquid nitrogen while continuing the vacuum evacuation. Nitrogen gas was then gradually introduced into the sample cell to adsorb nitrogen molecules onto the toner. The adsorption isotherm was obtained by constantly measuring the equilibrium pressure P (Pa) during this process. This adsorption isotherm was then converted into a BET plot. Data was collected at six relative pressure Pr points: 0.05, 0.10, 0.15, 0.20, 0.25, and 0.30. A line was drawn through the obtained measurement data using the least-squares method, and Vm was calculated from the slope and intercept of the line. Furthermore, this Vm value was used to calculate the BET specific surface area of ​​the toner as described above.

[0103] [Evaluation of toner deterioration during storage] The degree of toner deterioration during storage with and without load is measured and the toner storage container is evaluated as follows.

[0104] The toner pack was left standing for 5 days in an environment at 45°C and 90% RH. It was then left standing for 24 hours in an environment at 23°C and 60% RH. The toner was removed from the pack and checked for blocking. For toners that showed no blocking, the BET specific surface area of ​​the toner was measured before and after exposure to the above environment. The BET maintenance rate was calculated using the following formula to evaluate the degree of toner degradation without load. The change in the BET specific surface area is primarily an indicator of the embedding of silica particles into the toner particle surface. Embedding of silica particles into the toner particle surface can change the toner's fluidity and chargeability, potentially preventing the desired values ​​from being obtained during image formation. Here, blocking was determined to have occurred if clumped toner was present in at least a portion of the toner pack. The presence or absence of blocking can be inspected visually or manually using fingers, for example. BET maintenance rate (%) = BET specific surface area before storage / BET specific surface area after storage × 100

[0105] Toner: 18g / cm 2The degree of toner deterioration under load is evaluated under the same conditions as above, except that a load of 18g / cm is applied. The method of applying the load is adjusted appropriately depending on the size of the pack so that the load is applied evenly to the entire toner storage section. Specifically, a plate slightly larger than the toner storage section is prepared, placed on the toner storage section, and a weight is placed on the plate. At this time, the load applied to the toner is calculated using the following formula, and the value is 18g / cm 2 Adjust the weight so that Load on toner = total weight of weight and plate / contact area

[0106] Example 1 (Toner 1 production) <Preparation of Toner Particles 1> Relative to 100 parts by mass of styrene monomer, 16.5 parts by mass of carbon black (Nipex 35) and 3.0 parts by mass of an aluminum compound of di-tertiary butyl salicylic acid [Bontron E88 (manufactured by Orient Chemical Industry Co., Ltd.)] were prepared. These were introduced into an attritor (manufactured by Mitsui Mining Co., Ltd.) and stirred at 200 rpm at 25°C for 180 minutes using zirconia beads (140 parts by mass) with a radius of 1.25 mm to prepare a masterbatch dispersion.

[0107] On the other hand, 450 parts by mass of 0.1M Na3PO4 aqueous solution was added to 710 parts by mass of ion-exchanged water. After heating to 60°C, 67.7 parts by mass of a 1.0M aqueous CaCl2 solution was gradually added to obtain an aqueous medium containing a calcium phosphate compound. Masterbatch dispersion: 40 parts by mass Styrene: 49.5 parts by weight n-Butyl acrylate: 16.5 parts by mass Hydrocarbon wax: 9 parts by weight (Fischer-Tropsch wax, maximum endothermic peak temperature = 78°C, Mw = 750) Saturated polyester resin: 5.0 parts by weight

[0108] The above materials were heated to 65°C and uniformly dissolved and dispersed at 5,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) To this, 7.1 parts by mass of a 70% toluene solution of the polymerization initiator 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate was dissolved to prepare a polymerizable monomer composition.

[0109] The polymerizable monomer composition was added to the aqueous medium and stirred at 65°C under a N2 atmosphere at 12,000 rpm in a TK homomixer for 10 minutes to granulate the polymerizable monomer composition. The mixture was then heated to 67°C while stirring with a paddle impeller. When the polymerization conversion rate of the polymerizable vinyl monomer reached 90%, 0.1 mol / L of aqueous sodium hydroxide was added to adjust the pH of the aqueous dispersion medium to 9. The temperature was then raised to 80°C at a rate of 40°C / h and the mixture was allowed to react for 4 hours. After the polymerization reaction was completed, the remaining monomer in the toner particles was distilled off under reduced pressure. After cooling the aqueous medium, hydrochloric acid was added to adjust the pH to 1.4, and the mixture was stirred for 6 hours to dissolve the calcium phosphate salt. The toner particles were filtered, washed with water, and then dried at 40°C for 48 hours. The obtained dried product was subjected to strict classification and removal of ultrafine powder and coarse powder at the same time using a multi-division classifier (Nitetsu Mining Co., Ltd. Elbow Jet Classifier) ​​to obtain toner particles 1 having a particle size of 6.0 μm.

[0110] <Preparation of Toner 1> Toner particles 1 (100 parts by mass) and silica particles RX300 (manufactured by Nippon Aerosil Co., Ltd.) (1.4 parts by mass) were dry mixed in a Henschel mixer FM10C (manufactured by Mitsui Mining Co., Ltd.) at 3600 rpm for 12 minutes to obtain toner 1. The physical properties are shown in Table 1.

[0111] [Table 1]

[0112] (Manufacturing example of toner storage container 1) The toner storage containers shown in Figures 4 and 5 were prepared using the toner storage section 1 described in Table 2, and toner 1 was filled so that the filling rate (the ratio of the volume of filled toner to the maximum space volume of the toner storage section) was 0.7. The discharge port was then closed, and toner storage container 1 was obtained.

[0113] [Table 2]

[0114] (Evaluation of Toner Storage Container 1) The obtained toner storage container 1 was evaluated for the degree of toner deterioration.

[0115] Evaluation Criteria A: No blocking and BET maintenance rate of 90% or more B: No blocking and BET maintenance rate of 80% or more C: No blocking and BET maintenance rate of 70% or more D: Blocking or BET maintenance rate less than 70%

[0116] In this evaluation, a rating of C or higher was deemed to be at a practical level. The evaluation results are shown in Table 3. [Table 3]

[0117] <Example 2> (Toner 2 production) <Preparation of binder resin particle dispersion> 89.5 parts of styrene, 9.2 parts of butyl acrylate, 1.3 parts of acrylic acid, and 3.2 parts of n-lauryl mercaptan were mixed and dissolved, and an aqueous solution prepared by mixing 1.5 parts of Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) in 150 parts of ion-exchanged water was added to this solution and dispersed.

[0118] An aqueous solution of 0.3 parts of potassium persulfate mixed with 10 parts of ion-exchanged water was added thereto while stirring slowly for another 10 minutes.

[0119] After nitrogen substitution, emulsion polymerization was carried out for 6 hours at 70° C. After completion of polymerization, the reaction solution was cooled to room temperature, and ion-exchanged water was added to obtain a binder resin particle dispersion liquid having a solid content concentration of 12.5 mass % and a volume-based median diameter of 0.2 μm.

[0120] <Preparation of Release Agent Dispersion> 100 parts of a release agent (behenyl behenate, melting point: 72.1°C) and 15 parts of Neogen RK were mixed with 385 parts of ion-exchanged water, and the mixture was dispersed for about 1 hour using a wet jet mill JN100 (manufactured by Joko Co., Ltd.) to obtain a release agent dispersion. The solid content of the release agent dispersion was 20% by mass.

[0121] <Preparation of Colorant Dispersion> 100 parts of carbon black (Nipex 35) and 15 parts of Neogen RK were mixed with 885 parts of ion-exchanged water, and the mixture was dispersed for about 1 hour using a wet jet mill JN100 to obtain a colorant dispersion.

[0122] <Preparation of Toner Particles 2> 265 parts of binder resin particle dispersion, 10 parts of release agent dispersion, and 10 parts of colorant dispersion were placed in a container and dispersed using a homogenizer (Ultra Turrax T50, manufactured by IKA).

[0123] The temperature inside the vessel was adjusted to 30°C while stirring, and a 1 mol / L aqueous solution of sodium hydroxide was added to adjust the pH to 8.0.

[0124] As a flocculant, an aqueous solution of 0.25 parts aluminum chloride dissolved in 10.0 parts ion-exchanged water was added over 10 minutes with stirring at 30°C. After leaving it for 3 minutes, the temperature was raised to 50°C to generate flocculated particles. When the weight average particle size (D4) reached 6.0 μm, 0.90 parts sodium chloride and 5.0 parts NEOGEN RK were added to stop particle growth.

[0125] After adjusting the pH to 9.0 by adding 1 mol / L aqueous sodium hydroxide solution, the temperature was raised to 95°C to spheroidize the aggregated particles. When the average circularity reached 0.960, the temperature was lowered to 30°C, and a toner particle dispersion was obtained.

[0126] Hydrochloric acid was added to the resulting toner particle dispersion to adjust the pH to 1.5 or less, and the mixture was left to stand with stirring for 1 hour, after which the mixture was subjected to solid-liquid separation using a pressure filter to obtain a toner cake. This was reslurried with ion-exchanged water to form a dispersion again, and then subjected to solid-liquid separation using the aforementioned filter. The reslurrying and solid-liquid separation were repeated until the electrical conductivity of the filtrate became 5.0 μS / cm or less, and then final solid-liquid separation was performed to obtain a toner cake.

[0127] The obtained toner cake was dried using a flash jet dryer (manufactured by Seishin Enterprises). The drying conditions were an inlet temperature of 90°C, a dryer outlet temperature of 40°C, and the toner cake supply speed was adjusted according to the moisture content of the toner cake so that the outlet temperature did not deviate from 40°C. Furthermore, a multi-division classifier utilizing the Coanda effect was used to remove fine and coarse particles, yielding toner particles 2. The particle size of toner particles 2 was 7.5 μm.

[0128] <Preparation of fluorine-containing hydrotalcite particles> A mixed solution of 1.03 mol / L magnesium chloride and 0.239 mol / L aluminum sulfate (liquid A), a 0.753 mol / L sodium carbonate solution (liquid B) and 3 A 0.39 mol / L aqueous solution of sodium hydroxide (liquid C) was prepared.

[0129] Next, solutions A, B, and C were pumped into a reaction vessel at a flow rate of 4.5:1 by volume. The pH of the reaction solution was maintained at 9.3–9.6 with solution C, and the reaction temperature was 40°C to form a precipitate. After filtration and washing, the mixture was re-emulsified in ion-exchanged water to obtain the starting hydrotalcite slurry. The resulting hydrotalcite slurry had a concentration of 5.6% by mass. The resulting hydrotalcite slurry was vacuum-dried overnight at 40°C. NaF was dissolved in ion-exchanged water to a concentration of 100 mg / L, and the pH was adjusted to 7.0 with 1 mol / L HCl or 1 mol / L NaOH. The dried hydrotalcite was added to the slurry to a concentration of 0.1% (w / v%). The mixture was stirred at a constant speed using a magnetic stirrer for 48 hours to prevent settling. The mixture was then filtered through a 0.5 μm pore membrane filter and washed with ion-exchanged water. The obtained hydrotalcite was vacuum dried overnight at 40°C and then crushed. Line analysis of the obtained fluorine-containing hydrotalcite particles in STEM-EDS mapping analysis revealed that fluorine was present inside.

[0130] <Preparation of Toner 2> The obtained toner particles 2 (100 parts) were dry-mixed with fluorine-containing hydrotalcite particles (0.3 parts) and silica particles RX300 (2.2 parts by mass) in a Henschel mixer FM10C (manufactured by Mitsui Mining Co., Ltd.) at 3600 rpm for 12 minutes to obtain toner 2. The physical properties are shown in Table 1.

[0131] (Manufacturing of toner storage container 2) Using the toner and toner storage unit shown in Tables 2 and 3, a toner storage container 2 was obtained in the same manner as the toner storage container 1.

[0132] (Evaluation of Toner Storage Container 2) The toner deterioration degree of the obtained toner storage container 2 was evaluated. The results are shown in Table 3.

[0133] Example 3 (Toner 3 production) Toner 3 was obtained in the same manner as in the above <Preparation of Toner 1> (Production of Toner 1), except that RX300 (1.4 parts by mass) was changed to RX300 (2.0 parts by mass). The physical properties are shown in Table 1.

[0134] (Manufacturing of toner storage container 3) Using the toner and toner storage unit shown in Tables 2 and 3, a toner storage container 3 was obtained in the same manner as the toner storage container 1.

[0135] (Evaluation of Toner Storage Container 3) The toner deterioration degree of the obtained toner storage container 3 was evaluated. The results are shown in Table 3.

[0136] Example 4 (Toner 4 production) Toner 4 was obtained in the same manner as in the above (Production of Toner 2), except that in the above <Preparation of Toner Particles 2>, the spheronization step was carried out until the average circularity reached 0.990, and in the above <Production of Toner 2>, RX300 (2.2 parts by mass) was changed to RX300 (2.0 parts by mass). The physical properties are shown in Table 1.

[0137] (Manufacturing of toner storage container 4) Using the toner and toner storage unit shown in Tables 2 and 3, a toner storage container 4 was obtained in the same manner as the toner storage container 1.

[0138] (Evaluation of Toner Storage Container 4) The toner deterioration degree of the obtained toner storage container 4 was evaluated. The results are shown in Table 3.

[0139] <Example 5> (Toner 5 production) <Preparation of binder resin particle dispersion> 89.5 parts of styrene, 9.2 parts of butyl acrylate, 1.3 parts of acrylic acid, and 3.2 parts of n-lauryl mercaptan were mixed and dissolved, and an aqueous solution prepared by mixing 1.5 parts of Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 3.0 parts of an ethylene glycol surfactant in 150 parts of ion-exchanged water was added to the solution and dispersed.

[0140] An aqueous solution of 0.3 parts of potassium persulfate mixed with 10 parts of ion-exchanged water was added thereto while stirring slowly for another 10 minutes.

[0141] After nitrogen substitution, emulsion polymerization was carried out for 6 hours at 70° C. After completion of polymerization, the reaction solution was cooled to room temperature, and ion-exchanged water was added to obtain a binder resin particle dispersion liquid having a solid content concentration of 12.5 mass % and a volume-based median diameter of 0.2 μm.

[0142] <Preparation of Release Agent Dispersion> 100 parts of a release agent (hydrocarbon wax (Fischer-Tropsch wax, peak temperature of the maximum endothermic peak = 78°C, Mw = 750)) and 15 parts of NEOGEN RK were mixed with 385 parts of ion-exchanged water, and the mixture was dispersed for about 1 hour using a wet jet mill JN100 (manufactured by Joko Corporation) to obtain a release agent dispersion. The solid content concentration of the release agent dispersion was 20 mass%.

[0143] <Preparation of Colorant Dispersion> 100 parts of carbon black (Nipex 35) and 15 parts of Neogen RK were mixed with 885 parts of ion-exchanged water, and the mixture was dispersed for about 1 hour using a wet jet mill JN100 to obtain a colorant dispersion.

[0144] <Preparation of Toner Particles 5> 265 parts of binder resin particle dispersion, 10 parts of release agent dispersion, and 10 parts of colorant dispersion were placed in a container and dispersed using a homogenizer (Ultra Turrax T50, manufactured by IKA).

[0145] The temperature inside the vessel was adjusted to 30°C while stirring, and a 1 mol / L aqueous solution of sodium hydroxide was added to adjust the pH to 8.0.

[0146] As a flocculant, an aqueous solution of 0.25 parts of aluminum chloride dissolved in 10.0 parts of ion-exchanged water was added over 10 minutes with stirring at 30°C. After leaving it for 3 minutes, the temperature was raised to 50°C to generate flocculated particles. When the weight average particle size (D4) reached 7.0 μm, 0.90 parts of sodium chloride and 5.0 parts of NEOGEN RK were added to stop particle growth.

[0147] After adjusting the pH to 9.0 by adding 1 mol / L aqueous sodium hydroxide solution, the temperature was raised to 95°C to spheroidize the aggregated particles. When the average circularity reached 0.960, the temperature was lowered to 30°C, and a toner particle dispersion was obtained.

[0148] Hydrochloric acid was added to the obtained toner particle dispersion to adjust the pH to 1.5 or less, and the mixture was stirred and left for 1 hour. After leaving the mixture, the mixture was subjected to solid-liquid separation using a pressure filter to obtain a toner cake.

[0149] This was reslurried with ion-exchanged water to form a dispersion again, and then subjected to solid-liquid separation using the aforementioned filter. The reslurrying and solid-liquid separation were repeated until the electrical conductivity of the filtrate became 5.0 μS / cm or less, and then final solid-liquid separation was performed to obtain a toner cake.

[0150] The obtained toner cake was dried using a flash jet dryer (manufactured by Seishin Enterprises). The drying conditions were an inlet temperature of 90°C, a dryer outlet temperature of 40°C, and the toner cake supply speed was adjusted according to the moisture content of the toner cake so that the outlet temperature did not deviate from 40°C. Furthermore, a multi-division classifier utilizing the Coanda effect was used to remove fine and coarse particles, yielding toner particles 5. The particle size of toner particles 5 was 7.5 μm.

[0151] <Preparation of Toner 5> Toner particles 5 (100 parts by mass) and silica particles RX300 (manufactured by Nippon Aerosil Co., Ltd.) (1.5 parts by mass) were dry mixed in a Henschel mixer FM10C (manufactured by Mitsui Mining Co., Ltd.) at 3600 rpm for 12 minutes to obtain toner 5. The physical properties are shown in Table 1.

[0152] (Manufacturing of toner storage container 5) Using the toner and toner storage unit shown in Tables 2 and 3, a toner storage container 5 was obtained in the same manner as the toner storage container 1.

[0153] (Evaluation of Toner Storage Container 5) The toner deterioration degree of the obtained toner storage container 5 was evaluated. The results are shown in Table 3.

[0154] Example 6 (Toner 6 production) Toner 6 was obtained in the same manner as in the above (production of toner 5), except that the amount of ethylene glycol surfactant in <preparation of binder resin particle dispersion> was changed from 3.0 parts to 1.5 parts. The physical properties are shown in Table 1.

[0155] (Manufacturing of toner storage container 6) Using the toner and toner storage unit shown in Tables 2 and 3, a toner storage container 6 was obtained in the same manner as the toner storage container 1.

[0156] (Evaluation of Toner Storage Container 6) The toner deterioration degree of the obtained toner storage container 6 was evaluated. The results are shown in Table 3.

[0157] Example 7 (Toner 7 production) Toner 7 was obtained in the same manner as in the above (production of toner 5), except that the amount of ethylene glycol surfactant in <preparation of binder resin particle dispersion> was changed from 3.0 parts to 2.0 parts. The physical properties are shown in Table 1.

[0158] (Manufacturing of toner container 7) Toner storage container 7 was obtained in the same manner as Toner Storage Container 7, using the toner and toner storage unit shown in Tables 2 and 3.

[0159] (Evaluation of Toner Storage Container 7) The toner deterioration degree of the obtained toner storage container 7 was evaluated. The results are shown in Table 3.

[0160] Example 8 (Toner 8 production) Toner 8 was obtained in the same manner as in the above (production of toner 5), except that the amount of ethylene glycol surfactant in <preparation of binder resin particle dispersion> was changed from 3.0 parts to 4.0 parts. The physical properties are shown in Table 1.

[0161] (Manufacturing of toner container 8) Using the toner and toner storage unit shown in Tables 2 and 3, a toner storage container 8 was obtained in the same manner as in the toner storage container 8.

[0162] (Evaluation of Toner Storage Container 8) The toner deterioration degree of the obtained toner storage container 8 was evaluated. The results are shown in Table 3.

[0163] Example 9 (Toner 9 production) Toner 9 was obtained in the same manner as in the above (production of toner 5), except that the amount of ethylene glycol surfactant in <preparation of binder resin particle dispersion> was changed from 3.0 parts to 5.0 parts. The physical properties are shown in Table 1.

[0164] (Manufacturing of toner storage container 9) Using the toner and toner storage unit shown in Tables 2 and 3, a toner storage container 9 was obtained in the same manner as in the toner storage container 9.

[0165] (Evaluation of Toner Storage Container 9) The toner deterioration degree of the obtained toner storage container 9 was evaluated. The results are shown in Table 3.

[0166] Example 10 (Toner 10 production) Toner 10 was obtained in the same manner as in (Production of Toner 1), except that RX300 (1.4 parts by mass) was changed to RX300 (3.2 parts by mass).

[0167] (Manufacturing of toner storage container 10) Using the toner and toner storage unit shown in Tables 2 and 3, a toner storage container 10 was obtained in the same manner as the toner storage container 1.

[0168] (Evaluation of Toner Storage Container 10) The toner deterioration degree of the obtained toner storage container 10 was evaluated. The results are shown in Table 3.

[0169] <Examples 11 to 13> (Manufacturing of toner storage containers 11 to 13) Toner storage containers 11 to 13 were obtained in the same manner as toner storage container 1 using the toners and toner storage parts shown in Tables 2 and 3.

[0170] (Evaluation of Toner Storage Containers 11 to 13) The obtained toner storage containers 11 to 13 were evaluated for the degree of toner deterioration. The results are shown in Table 3.

[0171] Example 14 (Toner 12 production) <Preparation of Toner Particles 12> Binder resin A: 80.0 parts (Styrene acrylic resin with a mass ratio of styrene and n-butyl acrylate of 78:22; Mw = 180,000, Tg = 58°C) Binder resin B: 20.0 parts (Styrene acrylic resin with a mass ratio of styrene and n-butyl acrylate of 90:10; Mw = 5300, Tg = 58°C) Hydrocarbon wax (paraffin wax HNP-9, Nippon Seiro): 5.0 parts 3,5-di-t-butylsalicylic acid aluminum compound: 0.5 parts Carbon black: 5.0 parts

[0172] The above materials were mixed using a Henschel mixer (FM-75, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 20 s for 5 min, and then kneaded in a twin-screw kneader (PCM-30, manufactured by Ikegai Corporation) set at a temperature of 130°C (kneading was performed twice). The resulting kneaded material was cooled to 25°C and coarsely pulverized to 1 mm or less using a hammer mill to obtain a coarsely pulverized material. The resulting coarsely pulverized material was finely pulverized using a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.). The toner particles were classified using a multi-division classifier utilizing the Coanda effect to obtain toner particles 12 with a particle size of 8.9 μm.

[0173] <Preparation of Toner 12> Toner particles 12 (100 parts by mass) and silica particles RX300 (manufactured by Nippon Aerosil Co., Ltd.) (1.1 parts by mass) were dry mixed in a Henschel mixer FM10C (manufactured by Mitsui Mining Co., Ltd.) at 3600 rpm for 12 minutes to obtain toner 12. The physical properties are shown in Table 1.

[0174] (Manufacturing of toner storage container 15) Using the toner and toner storage unit shown in Tables 2 and 3, a toner storage container 15 was obtained in the same manner as the toner storage container 1.

[0175] (Evaluation of Toner Storage Container 15) The toner deterioration degree of the obtained toner storage container 15 was evaluated. The results are shown in Table 3.

[0176] <Comparative Example 1> (Toner 11 production) <Preparation of Toner Particles 11> Binder resin A: 80.0 parts (Styrene acrylic resin with a mass ratio of styrene and n-butyl acrylate of 78:22; Mw = 180,000, Tg = 58°C) Binder resin B: 20.0 parts (Styrene acrylic resin with a mass ratio of styrene and n-butyl acrylate of 90:10; Mw = 5300, Tg = 58°C) Hydrocarbon wax (paraffin wax HNP-9, Nippon Seiro): 5.0 parts 3,5-di-t-butylsalicylic acid aluminum compound: 0.5 parts Carbon black: 5.0 parts

[0177] The above materials were mixed using a Henschel mixer (FM-75, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 20 s for 5 min, and then kneaded in a twin-screw kneader (PCM-30, manufactured by Ikegai Corporation) set at a temperature of 130°C (kneading was performed twice). The resulting kneaded material was cooled to 25°C and coarsely pulverized to 1 mm or less using a hammer mill to obtain a coarsely pulverized material. The coarsely pulverized material was then finely pulverized using a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.). The toner particles were classified using a multi-division classifier utilizing the Coanda effect to obtain toner particles 11 with a particle size of 9.6 μm.

[0178] <Production of Toner 11> Toner particles 11 (100 parts by mass) and silica particles RX300 (manufactured by Nippon Aerosil Co., Ltd.) (1.5 parts by mass) were dry mixed in a Henschel mixer FM10C (manufactured by Mitsui Mining Co., Ltd.) at 3600 rpm for 12 minutes to obtain toner 11. The physical properties are shown in Table 1.

[0179] (Manufacturing of toner storage container 14) Using the toner and toner storage unit shown in Tables 2 and 3, a toner storage container 14 was obtained in the same manner as the toner storage container 1.

[0180] (Evaluation of Toner Storage Container 14) The toner deterioration degree of the obtained toner storage container 14 was evaluated. The results are shown in Table 3.

[0181] Since Example 1 using Toner 1 was evaluated as being practical, the content of silica particles (external additive) is preferably 1.4% by mass or more. Furthermore, since Example 4 using Toner 4 was evaluated as being better, the content of silica particles (external additive) is more preferably 2.0% by mass or more.

[0182] Since Example 1 using Toner 1 was evaluated as being suitable for practical use, it is preferable that the coverage rate of the toner particle surfaces with silica particles is 34% or more. Since Example 10 using Toner 10 was evaluated as being suitable for practical use, it is preferable that the coverage rate of the toner particle surfaces with silica particles is 80% or less. Furthermore, based on the coverage rates of the toners evaluated as being suitable for practical use, it can be said that a coverage rate of the toner particle surfaces with silica particles of 39% or more and 75% or less is more preferable.

[0183] As described above, by using the toner described in each example, it is possible to reduce deterioration of the toner even when the toner is stored in a flexible bag. That is, even if a toner storage container containing the toner is subjected to the toner's own weight, external forces acting on the bag, and external forces when stored in a stack during storage, the toner is less likely to form a compacted state, and toner deterioration is reduced. [Explanation of symbols]

[0184] 100: Toner pack (toner storage container), 101: Storage section, T: Toner (developer)

Claims

1. a flexible bag-shaped storage section; a toner that is contained in the container and contains silica particles; A toner storage container having: the toner has a total energy value of 300 mJ or less when a propeller blade is rotated at a peripheral speed of 100 mm / sec at the outermost edge of the propeller blade while being intruded into the surface of a powder layer of the toner, the powder layer being prepared in a measurement container by applying a vertical load of 88 kPa in a powder fluidity measuring device; The toner contains hydrotalcite particles containing fluorine. A toner storage container characterized by:

2. The content of the silica particles in the toner is 1.4% by mass or more.

2. The toner storage container according to claim 1.

3. The content of the silica particles in the toner is 2.0% by mass or more.

3. The toner storage container according to claim 2.

4. The coverage of the toner particle surfaces with the silica particles is 34% or more and 80% or less.

4. The toner storage container according to claim 2 or 3.

5. The coverage of the toner particle surfaces with the silica particles is 39% or more and 75% or less.

5. The toner storage container according to claim 4.

6. The toner container is shaken at an amplitude of 80 mm and 150 times / min for 5 minutes, and then the cohesion degree of the discharged toner is 40% or less.

6. The toner storage container according to claim 1, wherein the toner storage container is a container for storing toner.

7. In a line analysis in the STEM-EDS mapping analysis, fluorine is present inside the hydrotalcite particles contained in the toner.

2. The toner storage container according to claim 1.

8. The bag-shaped storage section is made of a resin sheet.

8. The toner storage container according to claim 1 or 7.

9. The resin sheet is at least one of a polypropylene sheet, a polyethylene sheet, and a PET sheet.

9. The toner storage container according to claim 8.

10. The thickness of the resin sheet is 25 μm or more and 300 μm or less.

10. The toner storage container according to claim 8 or 9.

11. A flexible bag-shaped storage section, a toner that is contained in the container and contains silica particles; A toner storage container having: the toner has a total energy value of 300 mJ or less when a propeller blade is rotated at a peripheral speed of 100 mm / sec at the outermost edge of the propeller blade while being intruded into the surface of a powder layer of the toner, the powder layer being prepared in a measurement container by applying a vertical load of 88 kPa in a powder fluidity measuring device; The toner contains a surfactant, and the P / N ratio, which is the ratio of the positive component to the negative component of the surfactant, is 0.1 or more and 0.8 or less. A toner storage container characterized by:

12. The P / N ratio of the toner is 0.2 or more and 0.6 or less.

12. The toner storage container according to claim 11.

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