JP2006078238A - Powder evaluation device and toner for static charge development - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To manufacture a toner capable of acquiring stably a high image quality having an excellent cleaning property by using an evaluation device having high accuracy of fluidity and generating no individual variation, and to realize stable production. <P>SOLUTION: Concerning a device wherein a long cylindrical member is provided in a compacted powder phase, and the powder phase or the cylindrical member is moved, and a force generated in the cylindrical member at that time is measured, this powder evaluation device is characterized by being equipped with a means for controlling compaction speed at the compaction time. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a powder evaluation apparatus and method, an electrostatic charge developing toner, a one-component developer or two-component developer using the same, and a development method.

  As a conventional technique related to electrophotography, Patent Document 1 discloses that the flowability of the developer in the developing machine is accurately determined by measuring the time required to pass through a narrow portion of a funnel to which a magnetic field is applied. A method of evaluation is described. Japanese Patent Application Laid-Open No. H10-228867 describes that toner is placed on a tiltable plate, the plate is gradually tilted, and an angle is measured when the flow starts and ends. Further, in Patent Document 3, a plurality of sieves are stacked, and toner is put on the sieves, and vibrations in the horizontal direction and the vertical direction are applied to the sieve parts. A method of calculating by multiplying a quantity by a preset coefficient is described. These methods have large data variability, and there are differences depending on the measurer, and it was not possible to evaluate the difference in fluidity between fine toners.

JP-A-1-203941 JP-A-4-116449 JP 2000-292967 A

An object of the present invention is to produce a toner that can stably obtain high image quality with good cleaning properties by using an evaluation apparatus with high fluidity accuracy and no individual difference, and to realize stable production. .
That is, according to the present invention, the fluidity of the toner is quantitatively measured by immersing the cylindrical member in the toner powder phase and measuring the force generated when the cylindrical member moves in the toner powder phase. The purpose is to be able to evaluate accurately and without individual differences, to be able to accurately evaluate the difference in fluidity between fine toners, and to create a consolidated state by controlling the compaction conditions in advance. In order to measure the difference between powders, there is no individual difference and can be evaluated accurately. In addition, the powder phase can be measured as it is in a short time, so it can be introduced into the production line. The purpose is to provide a technology that can stably produce high-quality powder.

  The image quality of copiers and printers has been increasing, and recently it has become important to maintain that image quality. In order to maintain this high image quality, it is important that the developer and the photoconductor do not deteriorate, but the cleaning process on the photoconductor and the transfer belt has become very important. This cleaning process is greatly influenced by the fluidity in addition to the charge amount of the toner, and it is necessary to have a flow characteristic that allows toner particles to be peeled off cleanly by a cleaning member such as a blade. If the fluidity of the toner particles is too good, the toner particles easily pass through the blade, resulting in poor cleaning. On the contrary, when the fluidity of the toner particles is poor, the toner particles are fixed to the photoreceptor or the like, resulting in poor cleaning. Therefore, it is necessary to optimize the fluidity of the toner particles.

Further, as the image quality is improved, the toner used in the toner is becoming smaller in particle size and higher in function. For this reason, the structure of the toner has become complicated, and finer control at the time of production has become necessary. In particular, since the toner fluidity affects various image qualities in addition to the cleaning property and the dot reproducibility, there is a need for a highly accurate evaluation method with no individual differences in evaluation.
In addition, when the toner production method changes from the pulverization method to another method such as a polymerization method, the change in the flow characteristics with respect to the manufacturing conditions is large. Evaluation is required.

The above-mentioned problems are solved by the present invention. However, in order to facilitate understanding, the present invention focuses on the “consolidation speed” when compacting the powder sample for convenience. This can be divided into the first group of inventions and the second group of inventions focusing on “consolidation load”.
Thus, according to the first group of the present invention, (1) “a long columnar member is provided in the compacted powder phase, and the powder phase or the columnar member is moved. In the apparatus for measuring force, a powder evaluation apparatus comprising means for controlling the compaction speed during compaction ";
(2) “The powder phase or the cylindrical member is moved in a direction perpendicular to the consolidation direction in a state where the powder phase is consolidated by the piston, and the force generated in the cylindrical member is measured. The powder evaluation apparatus according to item (1) above;
(3) In the above item (1), the consolidation is performed by changing the function of the consolidation speed with respect to the height displacement amount in at least two stages until the piston collides with the powder phase surface. Powder evaluation equipment "
(4) The powder evaluation apparatus according to (1), wherein the compaction is performed so that the compaction speed when the piston contacts the powder phase surface is 0.1 to 5 mm / min. Is included. Here, the “consolidation speed” means that the piston moves to the surface of the powder phase after passing through the stage where the piston approaches the surface of the powder phase and is not in contact with the surface of the powder phase (the speed is (V1)). It means the speed (V2) of the stage until it comes into contact and is further pushed into the powder phase and stopped. After passing through the speed (V1), the speed until the piston comes into contact with the powder phase surface and the speed at which the piston is pushed into the powder phase after the contact are typically almost the same, both of which are the speed (V2). Be controlled. It is preferable that V2 <V1.

The second group of the present invention is: (5) “A long cylindrical member is provided in the powder phase, the powder phase or the cylindrical member is moved, and the force generated in the cylindrical member at that time is measured. A powder evaluation apparatus characterized by comprising means for measuring the compaction load of the powder phase in the apparatus ";
(6) “While measuring the compaction load of the powder phase while the powder phase is kept in a compacted state by the compaction means, the powder phase or the cylindrical member is moved in a direction perpendicular to the compaction direction to form a cylindrical shape. The powder evaluation apparatus according to (5), wherein the force generated on the member is measured;
(7) “Powder evaluation apparatus according to (5) above, wherein a load cell is used as a means for measuring the consolidation load, and the load cell is provided under the sample container”;
(8) The powder evaluation apparatus according to (5) above, wherein a piston on which a weight is placed is used as the means for compaction, and the value of the compaction load is 0.5 to 50 N. Is included.

The present invention is further characterized in that, as a more preferable aspect, (9) “the porosity of the powder phase compacted by the piston is such that the powder density is 0.4 to 0.7. The powder evaluation apparatus according to (1) or (5) above;
(10) "The powder evaluation apparatus according to (1) or (5), wherein the surface of the cylindrical member has a regular uneven shape";
(11) "The powder evaluation apparatus according to (1) or (5) above, wherein the cylindrical member is made of a rod having a groove or a line having an uneven shape";
(12) “The powder evaluation apparatus according to (1) or (5) above, wherein the cylindrical member has a diameter of 0.1 to 10 mmφ”;
(13) "The powder evaluation apparatus according to (1) or (5) above, wherein the relative movement speed of the cylindrical member is 0.1 to 10 mm / sec";
(14) "Powder evaluation apparatus according to (1) or (5) above, wherein the relative movement of the cylindrical member is 5 to 50 mm";
(15) “The powder evaluation apparatus according to (1) or (5) above, wherein the cylindrical member is reciprocated 1 to 10 times relative to the toner powder phase”. ;
(16) "The powder evaluation apparatus according to (1) or (5) above, wherein the cylindrical member has a relative acceleration of 0.001 to 1 mm / sec ² ";
(17) “Toner cylindrical member (diameter: 0.16 mmφ, nylon fiber) after the mixing step in which the additive is mixed using the evaluation apparatus according to the item (1) or (5). A toner for developing an electrostatic charge characterized in that the value of the force generated when moving relatively in the powder phase is 0.03 to 0.5 N ”;
(18) "The electrostatic charge developing toner according to item (17) above, wherein the toner comprising at least a resin or a pigment contains a charge control agent and / or a release agent";
(19) The electrostatic charge developing toner according to (17) or (18) above, wherein the additive is adhered or fixed to the surface of the toner powder;
(20) "The electrostatic charge developing toner according to any one of (17) to (19) above, wherein an average particle diameter of the toner is 4 to 8 µm";
(21) "The electrostatic charge developing toner according to any of items (17) to (20), wherein the toner is produced by a polymerization method";
(22) "The electrostatic charge developing toner according to any one of (17) to (21) above, wherein the toner has an average circularity of 0.9 to 0.99";
(23) “One-component development method characterized by performing contact or non-contact development using the electrostatic charge developing toner according to any one of (17) to (22)”;
(24) “One-component development method according to item (23), wherein a doctor roller and / or a supply roller is used”;
(25) “A two-component developing method, wherein the developing is performed using the electrostatic charge developing toner according to any one of claims 17 to 22 and a carrier having a particle diameter of 20 to 70 μm”;
(26) "Development method characterized in that in the one-component development method or the two-component development method according to any of claims 23 to 25, development is performed by applying an AC bias voltage component";
(27) "Toner cartridge or process cartridge characterized in that the toner according to any one of claims 17 to 22 is accommodated";
(28) "Toner evaluation method for electrostatic charge development, wherein the fluidity of toner is evaluated using the evaluation apparatus according to any one of claims 1 to 16";
(29) “Evaluation is performed during the toner manufacturing process using the powder fluidity evaluation apparatus according to any one of (1) to (16), and toner is manufactured based on the evaluation. A method for producing a toner for developing electrostatic charge ”.

  According to the present invention, in a powder evaluation apparatus for measuring a force generated when a long cylindrical member is provided in a powder phase and the cylindrical member relatively moves in the powder phase, After controlling and compacting, the cylindrical member is moved relatively in the compacted powder phase and the force is measured, so that the fluidity of the powder is accurate and the difference between the powders is accurate. In addition, measurement without individual differences can be performed, and the conditions of powder such as toner that can obtain high image quality can be accurately defined, and powder such as toner that can obtain high image quality can be stably produced. The extremely excellent effect of becoming like this is exhibited.

Hereinafter, the present invention will be described in detail and specifically.
The first and second groups of the present invention both provide a long cylindrical member in the powder phase, and measure the force generated when the cylindrical member relatively moves in the powder phase. The present invention relates to an evaluation apparatus to be evaluated and a toner for developing electrostatic charge that can be obtained with good cleaning and high image quality, and is provided with a long cylindrical member in the powder phase. The force applied to the cylindrical member at that time is measured in the longitudinal direction, and the fluidity is evaluated by the value of the force.

[First Group of the Invention]
Although the first group of the present invention will be described in detail, parts common to the second group of the present invention will be described together with avoiding duplication.
The apparatus of the first group of the present invention is provided with a means for controlling the compaction speed, and after compacting by controlling the compaction conditions, the cylindrical member is moved relatively in the compacted powder phase, It measures force. The surface shape of the columnar members in the first and second groups of the present invention may be anything, and the surface shape may be uneven or the surface may not be uneven. However, in the case of a cylindrical member having an uneven surface, it is necessary to have a regular uneven shape so as not to depend on the moving direction of the cylindrical member.
The material of the columnar member may be hard or soft. For example, a rod with a groove, a wire made of Cu, Fe, SUS, etc., a material in which these Cu wires are covered with a resin, etc., or a metal string densely around a metal wire like a guitar metal string Some of them are wound with wires, and all are made of resin like nylon, like Tegs and guitar strings.
A cylindrical member having a diameter of 0.1 to 10 mm is suitable. If the diameter of the columnar member is smaller than 0.1 mm, the contact area with the powder phase is small, so that the force applied to the columnar member is small and a fine difference in fluidity cannot be evaluated. On the contrary, when the diameter of the cylindrical member is larger than 10 mm, the distribution of the force acting between the powder particles and the cylindrical member depending on the location becomes large, and it is difficult to accurately measure the force acting on the cylindrical member. Therefore, it is not suitable for evaluation of fluidity of powder.
The length of the cylindrical member must be long enough so that the cylindrical member continuously exists in the powder phase even if the powdery phase such as toner or the cylindrical member moves. is there.
In addition, when a groove is cut on the surface of the cylindrical member, the friction component between the powder particle and the powder particle is measured instead of the friction component between the material surface of the cylindrical member and the powder particle. It becomes possible to do. For this purpose, when the cylindrical member moves relatively in the powder phase, the powder particles enter the groove cut on the surface of the cylindrical member, and the powder particles and the surrounding It is necessary to measure the friction state with the powder particles. The shape of the groove is not limited, but it is necessary to devise so that the contact between the material surface of the cylindrical member and the powder particles becomes small.

An example of the surface shape of the cylindrical member is shown in FIG. This is obtained by cutting a groove on the circumferential surface of a cylindrical member, and the cross section of the groove has a sawtooth shape having triangular irregularities. In this case, the contact between the cylindrical member material surface and the powder particles is only at the tip of the crest of the triangular groove. Most of the contact is between the powder particles that have entered the groove and the surrounding powder particles.
Any material may be used for the cylindrical member, but a material that is easy to process, has a hard surface, and does not deteriorate is preferable. A material that is not charged is suitable. Examples of this are SUS, Al, Cu, Au, Ag, brass, and the like.

The force characteristics of the powder vary depending on the relative movement speed of the columnar member and the relative movement acceleration of the columnar member. In this measurement, in order to increase the accuracy of the measurement, the measurement was performed by lowering the moving speed and moving acceleration of the cylindrical member so that the delicate contact state between the powder particles can be measured. Therefore, the measurement conditions were as follows.
-Relative moving speed of cylindrical member: 0.1 to 10 mm / sec
-Relative movement acceleration of cylindrical member: 0.001 to 1 mm / sec ²
When the relative movement speed of the cylindrical member is slower than 0.1 mm / sec, it is easily affected by the delicate state of the powder phase, which causes a problem of force measurement variation and is not suitable for measurement. If it is faster than 10 mm / sec, powder scattering, jetting, etc. occur, and it is not suitable because it cannot be measured stably. When the relative movement acceleration of the cylindrical member is smaller than 0.001 mm / sec ^2, it is easily affected by the subtle state of the powder phase, and a measurement variation problem occurs, which is not suitable for measurement. When it is greater than 1 mm / sec ^2, powder scattering, jetting, and the like occur, and the contact state between the powder particles and the cylindrical member changes, which is not suitable for fluidity evaluation.

  The apparatus configuration of the first group of the present invention comprises a consolidation unit and a measurement unit, as shown in the example of FIG. The compaction unit includes a piston that compacts powder in the container, a weight that applies a load to the piston, and an elevating stage that moves the piston and the weight up and down. In addition, this structure is an example and does not limit this invention. Of course, the piston or weight may be fixed and the sample container containing the powder may be moved up and down.

  In the configuration of FIG. 1, the sample container containing the powder is fixed, the piston and the weight are lowered, the compacting piston is brought into contact with the powder, and further lowered so that all the weight load is applied to the piston. Is left floating for a certain period of time. Thereafter, the cylindrical member or the powder phase in the powder phase is moved in a state where the powder phase is consolidated, and the force generated in the cylindrical member (reaction force corresponding to the stress) is measured. In order to prevent the flow of powder on the surface of the powder phase when the piston approaches and contacts the surface of the powder phase, the compaction speed (the stage where the piston approaches and contacts the surface of the powder phase and the powder phase) Both speeds (V2) during the step of being pushed in are controlled together, and the piston slowly contacts the powder phase surface and is pushed in (reducing the collision speed of the piston to the powder phase surface) ).

Specifically, the lowering speed of the piston is controlled in at least two steps. For example, at least two speed change points are set at a height position before the piston contacts the powder phase surface (including the last speed). The change point is the height position immediately before contact), and the consolidation speed (function) with respect to the subsequent height displacement is changed at this speed change point. The height immediately before contact is preferably as small as possible within a range that can cover variations in the amount of powder collected. Thus, for example, as shown in FIG. 4, in the range from the uppermost position of the piston before descent to the speed change point, the moving speed is set by the function of V1 = a1 · h + b1, and the speed is rapidly reduced at the speed change point. In the range from the speed change point through the contact position to the surface to the end of consolidation, control is performed so that the compaction is performed slowly by a function of V2 = a2 · h + b2 (| a1 |> | a2 |, b1> b2).
As another example, a function of V3 = a3 · h + b3 is obtained in the range from the speed change point to the end of consolidation through the contact point through the contact point at a constant high moving speed until the speed change point. It is also possible to slowly reduce the consolidation speed. Further, two speed change points may be provided, and the function of the consolidation speed with respect to the height displacement amount may be changed in three stages. Of course, there is no problem even if a function other than the linear function is used. And it is necessary to control so that the compaction speed may be 0.1-5 mm / min when the piston finally contacts the powder phase surface and compacts the powder phase.
When the compaction speed of the piston with respect to the powder phase is smaller than 0.1 mm / min, the compaction stage itself takes excessive time more than necessary, causing a problem in measurement time. When the compaction speed of the piston with respect to the powder phase is larger than 5 mm / min, powder leakage from the surface of the powder phase occurs, and the variation in the compaction state becomes large, and stable measurement with high accuracy cannot be performed. This consolidation condition was controlled using a PC as shown in FIGS. 1 and 5 so that the consolidation speed varied with the amount of displacement in the height direction.

That is, in the example of the evaluation apparatus shown in FIG. 1, the distance (D1) between the uppermost position (h1) and the speed change point position (h2) before the start of the movement (descent) of the piston is coded in advance. The piston current position (Dn) signal monitored by the position detector (in this example, the linear scale) is encoded via the displacement meter and transmitted to the personal computer. The computing unit of the personal computer computes (D1) and the called distance (D1) (D1-Dn), and stores the computation result (Dx) (Dx = D1-Dn) in the memory. The calculation result (Dx) and the next monitored current position (Dn) signal are calculated in the same manner, and the previous calculation result (Dx) (Dx = D1-Dn) in the memory is updated with the calculation result. And the calculation result (Dx) is zero. This is repeated until the calculation result (Dx) becomes zero, and a command signal is issued to the controller. The controller drives the drive motor (in this example, a synchronous machine but an induction machine or a direct current). The speed (V1) is controlled to a smaller speed (V2) by controlling to reduce the number of pulses per time to a power supply circuit (not shown) for the servo motor (which may be a servo motor). Of course, the distance (D1), the speed (V1), and the speed (V2) can be changed by touching a required part of the NC program.
Similarly, the distance (D2) between the position of the speed change point (h2) and the lowest piston position (h3) after the compaction is similarly encoded and stored in the memory of the PC so that it can be recalled. The piston current position (Dn) signal monitored every moment by the position detector is encoded via the displacement meter and then sent to the personal computer, and the computation unit of the personal computer calls this (Dn). The distance (D2) is calculated (D2-Dn), and the calculation result (Dy = D2-Dn) is newly stored in the memory. The calculation result (Dy) and the next monitored current position (Dn) The signal is calculated in the same manner, and the calculation result (Dy = D2-Dn) in the memory is updated according to the calculation result. This is repeated until the calculation result (Dy) becomes zero, and the calculation result (Dy) is zero. At that point, the controller By ceasing the energization to the power supply circuit (not shown) for moving the motor, speed (V2), it stops the driving motor as zero. In this case, since the weight is used, it is not indispensable, but when no weight is used, the power (current) supply to the drive motor is programmed to increase contrary to the pulse voltage as desired. Of course you can also do.
After the predetermined measurement is completed, the input means (in this example, the keyboard is the keyboard as the input means of the personal computer, but other input means such as button switches are of course used. Instead, it is particularly preferable when using a microcomputer chip that includes a ROM that stores various programs so that they can be called and a RAM that stores distance data and position data as data to be processed. The piston can be raised to the uppermost position (h1) before the start of movement by inputting a signal for, and in this case, the piston ascent speed is initially a low speed similar to the moving speed (V2). After the piston exits the sample container, the speed can be increased and the piston is raised to the uppermost position (h1) before starting the movement. Door can be. As can be understood from the linear scale and the encoder, in the apparatus of this example, the piston speed and position are always monitored for unexpected deviations, and the obtained deviation information is used for the negative feedback control. Although it is also a closed control configuration for returning to the central part of the means, in the present invention, another method using a sequencer or the like may be used.

In the measurement unit, a cylindrical detection member is provided in the powder phase, and the tip thereof is connected to a load cell that is a force detector. Specifically, it differs depending on whether the cylindrical detection member is linear or bar-shaped. When the cylindrical detection member is a linear member, a weight (such as a weight) is attached to the end using a guide pulley as shown in FIG. 1, and the cylindrical detection member is stretched between the load cell. Put it in a state. At that time, the cylindrical detection member is set so as to pass through the center of the powder phase.
On the other hand, when the cylindrical detection member is a rod-shaped member, a guide pulley is provided on both sides of the sample container, and a detection rod is placed thereon. Also at this time, the cylindrical detection member (detection rod) is set so as to pass through the center of the powder phase. Naturally, the cylindrical detection member optimizes the position through holes formed at appropriate positions on both sides of the side surface of the sample container. The hole on the side surface of the sample container needs to be a hole that matches the size of the cylindrical detection member so as not to cause powder leakage. However, when the tolerance of the size of the hole is small, a contact state is likely to occur between the cylindrical detection member and the hole, which is not good because it is reflected in the force characteristics as a friction component. Therefore, an appropriate gap is required between the columnar detection member and the hole. The sample container is placed on the sample stage, and the sample stage is driven by the drive unit in parallel with the arrangement direction of the cylindrical detection member. The force acting on the cylindrical detection member at that time is detected by the load cell. The amount of movement of the sample stage is measured with a sample container position detector, and the relationship between the amount of movement and force is obtained as measurement data on a PC or the like.

  When measuring powder, a certain amount of powder is put in a sample container and set in this apparatus. Thereafter, the elevating stage is lowered at a speed controlled by the compaction unit, the piston is brought into contact with the powder phase, the powder phase is compacted, and the powder phase is initialized to a certain compaction state. By this compaction operation, the compacted state of the powder phase is kept from individual difference, and highly accurate measurement can be realized. The porosity of the powder phase after compacting the powder phase is such that the powder density is 0.4 to 0.7, and the gap between the particles of the powder is as large as possible. . Thereafter, the sample stage is driven to perform measurement. At that time, the sample stage is moved in the vertical direction with respect to the compaction direction of the powder phase. This configuration is merely an example, and other configurations such as fixing a sample container containing powder and moving the cylindrical detection member itself to measure the force applied to the cylindrical detection member may be used. In other words, since the friction component generated between the powder phase and the cylindrical member is measured, the powder phase may be moved while fixing the cylindrical member, or conversely, the powder phase is fixed. Then, the cylindrical member may be moved.

As described above, the cylindrical member may have a surface with unevenness or a surface with no unevenness, and a diameter of 0.1 to 10 mmφ is suitable. The length of the columnar member needs to be long enough so that the columnar member continuously exists in the powder phase even when the columnar member moves.
The shape of the groove may be any shape, but it is necessary to have a regular uneven shape so as not to depend on the moving direction of the cylindrical member. Further, the groove shape of the columnar member should have a simple uneven shape so that the same columnar member can be formed any number of times.
An example of this is shown in FIG. 3, which includes a sawtooth shape having triangular irregularities, an irregular shape in which a coil is wound around a core wire, and a surface having no irregularities. The material of the container is not limited, but a conductive material is suitable so as not to be affected by charging with the powder. In addition, since the measurement is performed while changing the powder, it is preferable that the surface is close to a mirror surface in order to reduce contamination. The size of the container is important. In order to increase the uniformity of compaction when the powder phase is compacted, it is necessary to select a size that increases the diameter of the powder container relative to the thickness of the powder phase.

  A load cell with a wide load range and high resolution is suitable. The position detector includes a linear scale, a displacement sensor using light, etc., but a specification of 0.01 mm or less is suitable for accuracy. The drive unit is preferably one that can be driven with high accuracy using a servo motor or a stepping motor. Further, in order to move the sample stage in parallel with the columnar member, a guide rail is provided, and the sample stage is moved along the guide rail. Since the sample stage not only moves in a certain direction but also reciprocates back and forth, the level of the sample stage must be adjusted accurately using a level or the like. .

  The piston for compacting the powder phase is made of Cu, Al, SUS, brass, or the like, and the surface and side surfaces need to have a smooth surface close to a mirror surface with no irregularities on the surface. Since the powder is compacted many times, a hard material that does not easily scratch is suitable.

  The sample container is also preferably made of a hard material that is not easily deformed, but Cu, Al, SUS, brass or the like is used from the viewpoint of workability. Since the sample is changed and used many times, the inner surface of the container may be surface-treated so as to be hard so as not to be damaged.

  In the measurement, the cylindrical detection member is placed on the sample stage through the hole on the side surface of the sample container, and powder is put into the container. The powder phase is consolidated by a piston. Thereafter, the piston is mounted, and the sample stage is moved under a predetermined driving condition in a state where the piston is kept compact, so that the cylindrical member is relatively moved in the powder phase. At that time, the force acting on the cylindrical member is measured by the load cell. Force measurement is performed under the specified speed and acceleration conditions. It is also necessary to determine the driving direction of the sample stage and the number of reciprocations. Of course, it is possible to measure only in a certain direction, but it is better to perform reciprocal measurement when looking at the dependency of the moving direction. In that case, the number of reciprocations is preferably 1 to 10 times. Even if the reciprocating measurement is performed more than 10 times, there is almost no change and the measurement is meaningless. The moving distance is basically arbitrary, and it is preferable to move to a position where data is stable. However, a moving amount of 5 to 50 mm is suitable from the relationship of measurement time and the like. If it is smaller than 5 mm, there arises a problem that the data is not stable in a region where the force characteristic is greatly changed. If it is larger than 50 mm, the force characteristic is stabilized, but there is a problem that the measurement time becomes long. The measurement mode can be performed under any conditions, but examples include the following measurement modes.

(1) A cylindrical member is set through the hole on the side surface of the sample container.
(2) Fill the container with powder.
(3) Pressurize the powder phase with a piston to create a compacted state.
(4) The sample stage is driven in a compacted state, and the force at that time is measured.
(5) When moving to a preset distance, the moving operation is stopped.
(6) The sample stage is returned to the start position (first home position).
Measurement is performed by repeating the operations (1) to (6). The change in force may be measured by reciprocating a certain distance without stopping the movement of the sample stage.

  As another measurement method, after compacting the powder phase with a piston, the sample stage is moved and stopped for a fixed distance, and then the fixed phase is moved and stopped repeatedly (a single operation may be used). Measure the force change at that time.

In this measurement method, the porosity of the powder phase becomes important, but in our experimental results, stable measurement was possible when the porosity was 0.40 or more. If it is less than 0.40, the subtle difference in the compacted state has an effect on the force characteristics, and stable measurement is difficult. The range of the porosity of the powder phase was 0.40 to 0.70 including the cases of various measurement methods. When it is larger than 0.70, the contact state between the toner powder phase and the cylindrical member is not fixed, and is not suitable for stable measurement.
However, the measurement system and measurement conditions are not limited to this.

[Second Group of the Invention]
Next, the second group of the present invention will be described in detail, but the description of the parts common to the first group of the present invention is omitted to avoid duplication.
The apparatus configuration of the second group of the present invention is as shown in FIG. 2 and comprises a consolidation zone and a measurement zone. The compaction zone is a container that contains powder such as toner, a load cell that measures the compaction load, a piston that compacts the powder in the container, a weight that applies a load to the piston, and the piston and weight are moved up and down. It is composed of an elevating stage etc. The load cell for measuring the consolidation load is provided as close to the sample container as possible under the sample container in order to measure the consolidation load applied to the powder phase. This configuration is an example of the second group of the present invention, and does not limit the present invention. The sample container containing the powder may be moved up and down by fixing the piston and the weight.

In the configuration of FIG. 2, the sample container containing the powder is fixed, the piston and the weight are lowered, the compacting piston is brought into contact with the powder, and further lowered so that all the weight load is applied to the piston. Is left floating for a certain period of time. The consolidation load at that time is accurately measured with a load cell. The mode and degree of consolidation are such that excess gas slowly escapes from the powder. The gas adsorbed or sorbed on the surface of the powder particles or the gas existing in the gap formed between the overlapping particles does not escape due to the compaction and therefore does not correspond to the excess gas. Excess gas in the powder may escape from between the inner wall of the sample container and the outer periphery of the compacted portion of the piston, but in the present invention, the gap between the sample container opening diameter and the outer diameter of the compacted portion of the piston is significantly increased. It is not necessary to make the difference in size between the two very large. When it is slowly consolidated as in the present invention, even if it is a powder having excellent fluidity, it is substantially discharged from the hole provided in the sample container so as to penetrate the cylindrical detection member and make it slide smoothly. Without this, the gas in the powder can escape.
Thereafter, the cylindrical member or the powder phase in the powder phase is moved in a compacted state, and the force generated in the cylindrical member is measured. A load cell that measures the consolidation load has a wide load range and a high resolution. The piston approaches and contacts the surface of the toner phase while maintaining a minute gap with the side surface of the container, and applies a load to the surface of the powder phase. Therefore, the material of the piston is preferably a material that is easy to process, has a hard surface, and does not deteriorate. Further, it is necessary to prevent the powder from adhering due to charging, and a conductive material is suitable. Examples of this material include SUS, Al, Cu, Au, Ag, brass and the like.

In the measurement zone, a cylindrical detection member is provided in the powder phase, and its tip is connected to a load cell that is a force detector. Specifically, it differs depending on whether the cylindrical detection member is linear or bar-shaped. When the cylindrical detection member is a linear member, a weight (such as a weight) is attached to the end of the guide pulley using a guide pulley as shown in FIG. 2, and the cylindrical detection member is stretched between the load cell. Put it in a state. At that time, the columnar detection member is set so as to pass through the central portion of the toner phase.
On the other hand, when the cylindrical detection member is a rod-like member, it is the same as the apparatus shown in FIG. 5 as an example of the apparatus of the first group of the present invention, and guide pulleys are provided on both sides of the sample container. Put a detection rod on it. Also at this time, the cylindrical detection member (detection rod) is set so as to pass through the center of the powder phase. Naturally, the cylindrical detection member optimizes the position through holes formed at appropriate positions on both sides of the side surface of the sample container. The hole on the side surface of the sample container needs to be a hole that matches the size of the cylindrical detection member so as not to cause powder leakage. However, when the tolerance of the size of the hole is small, a contact state is likely to occur between the cylindrical detection member and the hole, which is not good because it is reflected in the force characteristics as a friction component. Therefore, an appropriate gap is required between the columnar detection member and the hole. The sample container is placed on the sample stage, and the sample stage is driven by the drive unit in parallel with the arrangement direction of the cylindrical detection member. The force acting on the cylindrical detection member at that time is detected by the load cell. The amount of movement of the sample stage is measured with a position detector, and the relationship between the amount of movement and the force is obtained as measurement data on a PC or the like. In other words, it may have a control means for controlling the pressure contact state in the same way as the apparatus example shown in FIG. 1, and a cylindrical detection using a monitor or storage means attached to the personal computer of the control means. The consolidation load of the member can be displayed and recorded, and is actually preferred.

When measuring powder, a certain amount of powder is put into a sample container and set in the apparatus (a certain amount of powder, for example, toner may be put into the sample container set in the main body). Thereafter, the piston is lowered in the compaction zone, the piston is brought into contact with the powder phase, the powder phase is compacted, the compaction load at that time is measured, and the powder phase is initialized to a certain compaction state. By this compaction operation, it is possible to realize highly accurate measurement by making the compacted state of the powder phase without individual differences and evaluating the compacting load with high accuracy. For the measurement of powder, it is better to select a weight so that the consolidation load is 0.5 to 50N. When the consolidation load is smaller than 0.5N, the contact state between the cylindrical detection member and the powder particles varies depending on the location, and the force acting on the cylindrical detection member also varies widely and is not suitable for measurement. When the consolidation load is larger than 50 N, the powder particles are likely to be deformed, and the characteristics cannot be evaluated as normal powder particles, which is not suitable for measurement.
As in the case of the first group of the present invention, the porosity of the powder phase after compacting the powder phase is set so that the powder density is 0.4 to 0.7, and between the particles of the powder as much as possible. Make the gap change large. Thereafter, the sample stage is driven to perform measurement. At that time, the sample stage is moved in the vertical direction with respect to the compaction direction of the powder phase. This configuration is merely an example, and other configurations such as fixing a sample container containing powder and moving the cylindrical detection member itself to measure the force applied to the cylindrical detection member may be used. In other words, since the friction component generated between the powder phase and the columnar member is measured, the powder phase may be moved while the columnar member is fixed, or conversely the powder phase is fixed. Then, the cylindrical member may be moved.

As described above, the cylindrical member may have a surface with unevenness or a surface with no unevenness, and a diameter of 0.1 to 10 mmφ is suitable. The length of the columnar member needs to be long enough so that the columnar member continuously exists in the powder phase even when the columnar member moves.
The shape of the groove may be any shape as in the case of the first group of the present invention, but it is necessary to have a regular uneven shape so as not to depend on the moving direction of the columnar member. is there. Also, the groove shape of the cylindrical member is better to have a simple concavo-convex shape so that the same cylindrical member can be made any number of times, an example of which is also shown in FIG. There are sawtooth-shaped ones, uneven ones in which a coil is wound around a core wire, and ones having a surface without unevenness. The material of the container is not limited, but a conductive material is suitable so as not to be affected by charging with the powder. In addition, since the measurement is performed while changing the powder, it is preferable that the surface is close to a mirror surface in order to reduce contamination. The size of the container is important, and in order to increase the uniformity of compaction when the powder phase is compacted, it is necessary to select a size that increases the diameter of the powder sample container with respect to the thickness of the powder phase.

  In the second group of the present invention, a load cell for measuring force is suitable to have a wide load range and high resolution. The position detector includes a linear scale, a displacement sensor using light, etc., but a specification of 0.01 mm or less is suitable for accuracy. The drive unit is preferably one that can be driven with high accuracy using a servo motor or a stepping motor. Further, in order to move the sample stage in parallel with the columnar member, a guide rail is provided, and the sample stage is moved along the guide rail. Since the sample stage not only moves in a certain direction but also reciprocates back and forth, the level of the sample stage must be adjusted accurately using a level or the like. .

  As in the case of the first group of the present invention, also in the second group of the present invention, the piston for compacting the powder phase is made of Cu, Al, SUS, brass, etc., and the surface and side surfaces have no irregularities on the surface. It must have a smooth surface close to the mirror surface. Since the powder is compacted many times, a hard material that does not easily scratch is suitable.

  The sample container is also preferably made of a hard material that is not easily deformed, but Cu, Al, SUS, brass or the like is used from the viewpoint of workability. Since the sample is changed and used many times, the inner surface of the container may be surface-treated so as to be hard so as not to be damaged.

  In the measurement of the second group of the present invention, the sample container containing the powder is placed on the sample stage, and the cylindrical detection member is set through the hole on the side surface of the sample container. Powder may be charged into the container). The powder phase is consolidated by a piston, and the consolidation load is measured. Thereafter, the piston is mounted (while being consolidated), the sample stage is moved under a predetermined driving condition while measuring the consolidation load, and the columnar member is relatively moved in the powder phase. At that time, the force acting on the cylindrical member is measured by the load cell. Force measurement is performed under the specified speed and acceleration conditions. It is also necessary to determine the driving direction of the sample stage and the number of reciprocations. Of course, it is possible to measure only in a certain direction, but it is better to perform reciprocal measurement when looking at the dependency of the moving direction. In that case, the number of reciprocations is preferably 1 to 10 times. Even if the reciprocating measurement is performed more than 10 times, there is almost no change and the measurement is meaningless. The moving distance is basically arbitrary, and it is preferable to move to a position where data is stable. However, a moving amount of 5 to 50 mm is suitable from the relationship of measurement time and the like. If it is smaller than 5 mm, there arises a problem that the data is not stable in a region where the force characteristic is greatly changed. If it is larger than 50 mm, the force characteristic is stabilized, but there is a problem that the measurement time becomes long. The measurement mode in the second group of the present invention is also possible under any conditions, but examples include the following measurement modes.

The measurement mode in the second group of the present invention is also possible under any conditions, but examples include the following measurement modes.
(1) A cylindrical member is set through the hole on the side surface of the sample container.
(2) Fill the container with powder.
(3) Pressurize the powder phase with a piston to create a compacted state.
(4) Measure the consolidation load.
(5) The sample stage is driven while measuring the consolidation load in the consolidated state, and the force at that time is measured.
(6) When moving to a preset distance, the moving operation is stopped.
(7) The sample stage is returned to the start position (first home position).
Measurement is performed by repeating the operations (1) to (7). The change in force may be measured by reciprocating a certain distance without stopping the movement of the sample stage.

  As another measurement method, after compacting the powder phase with a piston, the sample stage is moved and stopped for a fixed distance, and then the fixed phase is moved and stopped repeatedly (a single operation may be used). Measure the force change at that time.

Even in the measurement method of the second group of the present invention, the porosity of the powder phase is important, but in our experimental results, stable measurement was possible when the porosity was 0.40 or more. If it is less than 0.40, the subtle difference in the compacted state has an effect on the force characteristics, and stable measurement is difficult. The range of the porosity of the powder phase was 0.40 to 0.70 including the cases of various measurement methods. When it is larger than 0.70, the contact state between the powder phase and the cylindrical member is not constant, and is not suitable for stable measurement.
However, the measurement system, measurement conditions, etc. are not limited to this, as in the case of the first group of the present invention.

[Toner, Developer]
The toner used in the evaluation methods of the first and second groups of the present invention needs to have an average particle diameter of 4 to 8 μm in order to realize a high quality image. The weight average particle size of the toner is 4 to 8 μm, more preferably 5 to 7 μm. If the weight average particle size is less than 4 μm, problems such as contamination inside the machine due to toner scattering during long-term use, image density reduction in a low-humidity environment, poor photoconductor cleaning, and the like are likely to occur, and there are concerns about the effects on the human body. When the weight average particle diameter exceeds 8 μm, the resolution of fine spots of 100 μm or less is not sufficient, and the image quality tends to be inferior due to many scattering to non-image areas.

  The developer using this toner needs to have an average particle diameter of the carrier of 20 to 70 μm in order to realize a high quality image. When the average particle diameter of the carrier is in the range of 20 to 70 μm, the charge amount of the toner can be made more uniform when the toner concentration in the developing machine is in the range of 2 to 10% by weight. When it is smaller than 20 μm, carrier particles are likely to adhere to the photoreceptor, and the stirring efficiency with the toner is deteriorated, so that it is difficult to obtain a uniform charge amount of the toner. On the other hand, when the average particle diameter of the carrier exceeds 70 μm, fine image reproducibility deteriorates and high image quality cannot be obtained.

Details of the toner and developer are shown below.
As resins, polystyrene resin, epoxy resin, polyester resin, polyamide resin, styrene acrylic resin, styrene methacrylate resin, polyurethane resin, vinyl resin, polyolefin resin, styrene butadiene resin, phenol resin, polyethylene resin, silicon resin, butyral resin, terpene There are resins, polyol resins and the like.

  Examples of vinyl resins include styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, and homopolymers thereof: styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer. Polymer, styrene-vinyl naphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methacrylic copolymer Acid methyl copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer Coalescence, styrene-vinyl ethyl acetate Copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester Styrene copolymers such as copolymers: polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate and the like.

The polyester resin is composed of a dihydric alcohol as shown in the following group A and a dibasic acid salt as shown in the group B, and further a trivalent or higher alcohol as shown in the group C or Carboxylic acid may be added as a third component.
Group A: ethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4 butanediol, neopentyl glycol, 1,4 butenediol, 1,4-bis (hydroxymethyl) cyclohexane Bisphenol A, hydrogenated bisphenol A, polyoxyethylenated bisphenol A, polyoxypropylene (2,2) -2,2′-bis (4-hydroxyphenyl) propane, polyoxypropylene (3,3) -2, 2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2,0) -2,2′-bis (4 -Hydroxyphenyl) propane and the like.
Group B: maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, malonic acid, linolenic acid, or These acid anhydrides or esters of lower alcohols.
Group C: Trivalent or higher alcohols such as glycerin, trimethylolpropane and pentaerythritol, and trivalent or higher carboxylic acids such as trimellitic acid and pyromellitic acid.

  As the polyol resin, an alkylene oxide adduct of an epoxy resin and a dihydric phenol, or a compound having one active hydrogen in the molecule that reacts with the glycidyl ether and the epoxy group, and an active hydrogen that reacts with the epoxy resin in the molecule. There are those obtained by reacting two or more compounds.

The following are used as the pigment used in the present invention.
Examples of black pigments include azine dyes such as carbon black, oil furnace black, channel black, lamp black, acetylene black, and aniline black, metal salt azo dyes, metal oxides, and composite metal oxides.
Examples of yellow pigments include cadmium yellow, mineral fast yellow, nickel titanium yellow, navel yellow, naphthol yellow S, Hansa yellow G, Hansa yellow 10G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, and tartrazine lake. .
Examples of the orange pigment include molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, indanthrene brilliant orange RK, benzidine orange G, and indanthrene brilliant orange GK.
Examples of red pigments include Bengala, Cadmium Red, Permanent Red 4R, Resol Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red D, Brilliant Carmine 6B, Eosin Lake, Rhodamine Lake B, Alizarin Lake, Brilliant Carmine 3B.
Examples of purple pigments include fast violet B and methyl violet lake.
Examples of blue pigments include cobalt blue, alkali blue, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partially chlorinated, first sky blue, and indanthrene blue BC.
Examples of green pigments include chrome green, chromium oxide, pigment green B, and malachite green lake.
These can use 1 type (s) or 2 or more types.
Especially for color toners, uniform dispersion of good pigments is essential. Instead of putting pigments directly into a large amount of resin, a master batch in which pigments are once dispersed at a high concentration is prepared and diluted. The method of throwing in is used. In this case, a solvent is generally used to assist dispersibility. However, there is a problem of environment and the like, and in the present invention, water is used for dispersion. When water is used, temperature control is important so that residual moisture in the masterbatch does not become a problem.

  In the toner of the present invention, a charge control agent is blended (internally added) inside the toner particles. However, it may be used by mixing (external addition) with toner particles. The charge control agent makes it possible to control the optimum charge amount according to the development system. In particular, in the present invention, the balance between the particle size distribution and the charge amount can be further stabilized.

  For controlling the toner to be positively charged, nigrosine and quaternary ammonium salts, triphenylmethane dyes, imidazole metal complexes and salts can be used alone or in combination of two or more. Further, salicylic acid metal complexes, salts, organic boron salts, calixarene compounds, and the like are used for controlling the toner to be negatively charged.

  Further, a release agent can be internally added to the toner in the present invention to prevent offset at the time of fixing. Release agents include natural waxes such as candelilla wax, carnauba wax, rice wax, montan wax and derivatives thereof, paraffin wax and derivatives thereof, polyolefin wax and derivatives thereof, sazol wax, low molecular weight polyethylene, and low molecular weight polypropylene. And alkyl phosphate esters. The melting point of these release agents is preferably 65 to 90 ° C. When the temperature is lower than this range, blocking during storage of the toner tends to occur, and when the temperature is higher than this range, an offset is likely to occur in a region where the fixing roller temperature is low.

  Additives may be added for the purpose of improving the dispersibility of a release agent or the like. Additives include styrene acrylic resin, polyethylene resin, polystyrene resin, epoxy resin, polyester resin, polyamide resin, styrene methacrylate resin, polyurethane resin, vinyl resin, polyolefin resin, styrene butadiene resin, phenol resin, butyral resin, terpene resin, There are polyol resins and the like, and two or more of these resins may be mixed.

  Examples of the method for producing the toner according to the present invention include a pulverization method and a polymerization method (suspension polymerization, emulsion polymerization dispersion polymerization, emulsion aggregation, emulsion association, etc.), but are not limited to these production methods.

As an example of the pulverization method, first, the above-described resin, a pigment or dye as a colorant, a charge control agent, a release agent, other additives, etc. are sufficiently mixed by a mixer such as a Henschel mixer, and then batch type. The constituent materials are well kneaded using a two-roll, Banbury mixer, continuous twin-screw extruder, continuous single-screw kneader or the like, and cut after rolling and cooling. The toner kneaded product after cutting is crushed, coarsely pulverized using a hammer mill, etc., and further pulverized by a fine pulverizer or mechanical pulverizer using a jet stream, and a classifier or Coanda effect using a swirling airflow Is classified to a predetermined particle size by a classifier using Thereafter, an additive composed of inorganic particles or the like is adhered or fixed to the particle surface by a mixer. The fluidity of the toner particles after this mixing step is evaluated using this evaluation apparatus. In this case, in the sampling inspection, a sample is put in a sample container, and the sample container is directly placed on the sample stage of the evaluation apparatus shown in FIG. The relative movement speed of the cylindrical member is set to 0.1 to 10 mm / sec, and the relative movement acceleration of the cylindrical member and 0.001~1mm / sec ^2. In the measurement, the cylindrical member is fixed, the sample stage is driven by a preset moving distance of 5 mm or more, and then returned to the original initial position. The force applied to the cylindrical member at this time is measured, and the fluidity of the toner is evaluated.

When the toner fluidity is evaluated by the evaluation apparatus of the present invention, the measured value (force) and the toner fluidity have the following relationship.
If the force is small, the fluidity is good.
If the force is large, the fluidity is bad.

The characteristics of the evaluation apparatus of the present invention of the first and second groups using the cylindrical member are as follows, and the extracted sample can be measured quickly and simply as it is, so there is no individual difference and high accuracy measurement. There is in being able to.
(1) Non-destructive inspection.
(2) The sample can be measured as it is.
(3) It can be measured in a short time.
(4) Anyone can easily measure.

Therefore, measurement on the production line is also possible, and it can be installed between each process in the production process to evaluate the quality during the process. For example, after passing through the mixing process, a sample extraction / measurement zone is provided in the middle of transporting the powder sample to the next process, and a valve is opened and closed at a certain timing to transport a certain amount of sample to the measurement unit. The tip of the measurement part is a container made of SUS or the like, and is directly measured by the evaluation apparatus of the first and second groups of the present invention. Alternatively, the container is taken to the evaluation apparatus of the present invention in another nearby place, placed on a sample stage, and measured by the evaluation apparatus of the present invention. After the measurement, the toner is returned to the original sample. As a result of the evaluation, if the numerical value is out of the predetermined setting range, the sample is not sent to the filling process but is sent to the toner reprocessing process. These mechanisms can be applied to the inspection after the pulverization / classification process, which is the process before the mixing process, the inspection after the air sieving process after the mixing process, and the inspection before filling (see FIG. 7).
Further, the toner evaluation apparatus of the present invention having these functions can be used alone as an evaluation apparatus in the development stage.

  In the case of toner, as described above, measured values of torque and load in this evaluation method indicate fluidity, and quantitative evaluation is possible. Conventional conventional evaluation devices can evaluate differences between toners, but there is a problem that evaluation cannot be performed on the same soil if the types of toner are different. However, the value measured by the evaluation apparatus of the present invention is a value of force as a powder characteristic, and is a value that can be evaluated on the same earth regardless of the type of toner or the particle size. Evaluation value.

The force characteristics at the time of movement of the columnar member in the toner powder phase are closely related to the fluidity of the powder. When the fluidity of the powder is good, it is between the individual powder particles. Since the adhesion is small, it is easy to move, and even if the cylindrical member is moved within the powder phase, the force is small. However, on the contrary, when the fluidity of the powder is poor, the adhesive force between the individual powder particles is large, so that it is difficult to move, and when the columnar member is moved within the powder phase, The force applied to the columnar member is increased.
Therefore, in the evaluation method using the evaluation apparatus of the present invention, the fluidity can be evaluated in the following relationship.
When fluidity is good → The force when moving in the powder phase is small.
When the fluidity is poor → The force when moving in the powder phase is large.

  The fluidity of the toner is almost determined by the mixing process in the toner preparation process. That is, the fluidity of the toner particles varies greatly depending on the state in which the additive composed of inorganic particles adheres to or adheres to the surface of the toner particles. The mixing state of the toner varies depending on the mixing conditions (amount charged, the number of rotations, a mixing time, etc.) in the mixing step. Therefore, the mixing conditions play an important role in the fluidity, and the evaluation of the fluidity after the mixing process is important.

  In order to achieve high image quality in printers and copiers, it is necessary to improve the reproducibility of extremely minute dots. In order to realize this, toner development that is faithful to a very small latent image is required. In order to enable this faithful development, it is necessary to supply a uniform toner brush to the development area. For this purpose, it is necessary that the toner charge amount is in an appropriate condition. However, the toner is easy to move and transport so that a uniform toner brush can be constantly supplied to the development area. It becomes important. That is, in order to improve the fine dot reproducibility, it is necessary to increase the fluidity of the toner.

  In order to realize high image quality, it is necessary to improve the cleaning property so that past images are not affected even if different images are created many times. For this purpose, it is necessary to have fluidity so that the toner particles can be neatly removed by a cleaning member such as a blade. If the fluidity of the toner particles is too good, the toner particles easily pass through the blade, resulting in poor cleaning. On the contrary, when the fluidity of the toner particles is poor, the toner particles are fixed to the photoreceptor or the like, resulting in poor cleaning. Therefore, it is necessary to optimize the fluidity of the toner particles.

Therefore, as a result of evaluating the fluidity of the toner by the evaluation apparatus of the present invention using a cylindrical member and examining the relationship between the dot reproducibility and the cleaning property, a very strong correlation exists, and the following force It was found that dot reproducibility and cleanability improved when showing the characteristics. In order to produce these toners, production conditions (particularly mixing conditions) different from conventional ones were required.
When the cylindrical member (diameter: 0.16 mmφ, nylon fiber) moves relatively in the toner powder phase, the maximum value of the force generated in the cylindrical member is 0.03 to 0.5N.
After the mixing step, the toner of the present invention is obtained by passing through a sieve of 250 mesh or more to remove coarse particles and aggregated particles.

  As a method for producing the toner according to the present invention, methods other than the pulverization method are conceivable. As an example of the polymerization method, a monomer composition in which a colorant, a charge control agent and the like are added to a monomer is suspended in an aqueous medium. Toner particles are obtained by turbidity and polymerization. The granulation method is not particularly limited.

  For example, in the toner of the present invention, an oily dispersion in which at least a polyester-based prepolymer containing an isocyanate group is dissolved in an organic solvent, a pigment-based colorant is dispersed, and a release agent is dissolved or dispersed in an aqueous medium. A urea-modified polyester resin having a urea group by dispersing in the presence of inorganic fine particles and / or polymer fine particles and reacting the prepolymer with a polyamine and / or a monoamine having an active hydrogen-containing group in the dispersion. And a liquid medium contained in the dispersion containing the urea-modified polyester resin is removed.

  In the urea-modified polyester resin, the Tg is 40 to 65 ° C, preferably 45 to 60 ° C. The number average molecular weight Mn is 2500 to 50000, preferably 2500 to 30000. The weight average molecular weight Mw is 10,000 to 500,000, preferably 30,000 to 100,000.

The toner contains a urea-modified polyester-based resin having a high molecular weight by a reaction between the prepolymer and the amine and having a urea bond as a binder resin. The colorant is highly dispersed in the binder resin.
Also in the case of these methods, for inspection after granulation, inspection after treatment with charge control agent, inspection after mixing process of additive, inspection after air sieving process after mixing process, inspection before filling, etc. Applicable.

  The fluidity is influenced by the toner particle size and greatly influenced by the toner shape. However, in the case of a very nearly spherical toner having an average circularity of 0.9 to 0.99, the fluidity And high image quality with excellent dot reproducibility and cleanability. Even if it is a pulverized toner, if it satisfies the average particle diameter and the average circularity of the toner of 0.9 to 0.99, and an external additive for ensuring fluidization is added, The fluidity in the present invention can be satisfied.

  Further, when used as a two-component developer, a two-component developer is obtained by mixing with a magnetic carrier described later at a predetermined mixing ratio.

  This toner is used as a one-component developer used in a contact or non-contact development system. As the contact or non-contact development method, various known methods are used. For example, a contact development method using an aluminum sleeve, a contact development method using a conductive rubber belt, and a non-contact development method using a development sleeve in which a conductive resin layer containing carbon black or the like is formed on the surface of an aluminum base tube. .

Further, in the one-component development method, the present toner is used in a development method in which a roller-shaped blade for uniformizing the toner layer and a supply roller for supplying toner are provided at the outlet of the toner supply unit. To do. In the case of such a system, not only filming on the photoconductor but also filming on the doctor roller and the supply roller occurs. For this reason, the toner layer cannot be formed uniformly, the toner charge becomes non-uniform, and the toner charge amount becomes small. For this reason, poor development occurs.
However, when the toner of the present invention is used, filming on the doctor roller and the supply roller does not occur, stable development is performed, and the system has excellent durability characteristics. (See Figure 8.)

  Since the present toner is excellent in fluidity, it can be stored in a cartridge container and is suitable for an apparatus configured to convey toner from the cartridge container to the developing unit.

  Further, when the magnetic toner is used, magnetic particles may be internally added to the toner particles. Examples of the magnetic material include ferromagnetic materials such as ferrite, magnetite, iron, nickel, cobalt, and alloys thereof. The average particle size of the magnetic material is preferably 0.1 to 1 μm. The content of the magnetic material is preferably 10 to 70 parts by weight with respect to 100 parts by weight of the toner.

  As the carrier used in the two-component developer, known carriers can be used. For example, magnetic particles such as iron powder, ferrite powder, nickel powder, magnetite powder, or the surface of these magnetic particles are made of fluorine resin or vinyl resin. And those treated with a silicone-based resin or the like, or magnetic particle-dispersed resin particles in which magnetic particles are dispersed in the resin. The average particle size of these magnetic carriers is preferably 20 to 70 μm.

As described above, the one-component or two-component developer of the present invention can be used by adding inorganic fine powder to the toner as a fluidity improver.
As the inorganic fine powder of the present invention, Si, Ti, Al, Mg, Ca, Sr, Ba, In, Ga, Ni, Mn, W, Fe, Co, Zn, Cr, Mo, Cu, Ag, V, Zr, etc. And oxides and composite oxides. Of these, fine particles of silicon dioxide (silica), titanium dioxide (titania), and alumina are preferably used. Furthermore, it is effective to perform surface modification treatment with a hydrophobizing agent or the like. Typical examples of the hydrophobizing agent include the following.

Dimethyldichlorosilane, trimethylchlorosilane, methyltrichlorosilane, allyldimethyldichlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, p-chloroethyltrichlorosilane, Chloromethyldimethylchlorosilane, chloromethyltrichlorosilane, hexaphenyldisilazane, hexatolyldisilazane, etc.
The inorganic fine powder is preferably used in an amount of 0.1 to 2% by weight based on the toner. If it is less than 0.1% by weight, the effect of improving toner aggregation is poor, and if it exceeds 2% by weight, problems such as toner scattering between fine wires, contamination in the machine, scratches and abrasion of the photoreceptor tend to occur. is there.

  Further, the developer of the present invention may further contain other additives, for example, a lubricant powder such as Teflon (registered trademark) powder, zinc stearate powder, and polyvinylidene fluoride powder; Abrasives such as cerium powder, silicon carbide powder, and strontium titanate powder; or a conductivity-imparting agent such as carbon black powder, zinc oxide powder, and tin oxide powder can be used in small amounts as a developability improver.

[First Group of the Invention]
Hereinafter, although an Example is described, this does not limit this invention at all. Here, toners with different mixing conditions are prepared, toner fluidity is evaluated using this evaluation apparatus (first group) shown in FIG. 1, and cleaning performance is an image on the photoreceptor after passing through the blade. Evaluation was based on density, and dot reproducibility was evaluated on a five-point scale as the roughness of the image. The fluidity of the toner is preliminarily adjusted under optimum compaction conditions (two-stage function change, compaction speed at the time of contact is 2 mm / min), and after measuring toner leakage and space ratio, it is measured under the following conditions. The force when the columnar member was moved relatively in the toner powder phase was measured. Toner leakage during compaction was evaluated by the presence or absence of toner leakage.

・ Cylindrical member: Nylon fiber (diameter: 0.16 mmφ)
-Relative moving speed of cylindrical member: 0.7 mm / sec
-Relative movement acceleration of cylindrical member: 0.14 mm / sec ²
In addition, all the parts in the following mixing | blending are a weight part.

Example 1
Resin: Polyester resin 100 parts Pigment: Magenta pigment (CI Pigment Red 57) 4 parts Charge control agent: Zinc salicylate 5 parts After thoroughly mixing the above raw materials with a mixer, barrel temperature 100 with a twin screw extruder Melt kneading was performed at a rotation speed of 100 ° C. at 100 ° C. The kneaded product was rolled and cooled, coarsely pulverized with a cutter mill, pulverized with a fine pulverizer using a jet stream, and then classified into a particle size distribution with an average particle size of 6.5 μm using a swirling air classifier. Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.0 part
: Titanium oxide fine powder 0.3 part Mixing rotation speed: 1000 rpm
Mixing time: 120 sec
Mixer: Supermixer After the toner was prepared, it was compacted by the evaluation apparatus shown in FIG. 1, and the compacted state (toner leakage, space ratio) and fluidity were measured.
The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Example 2
Kneading, pulverization, and classification were performed using the same raw materials and production methods as in Example 1, and the particles were classified into a particle size distribution with an average particle size of 6.5 μm.
Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.2 parts
: Titanium oxide fine powder 0.3 part Mixing rotation speed: 1000 rpm
Mixing time: 120 sec
Mixer: Supermixer After the toner was prepared, it was compacted by the evaluation apparatus shown in FIG. 1, and the compacted state (toner leakage, space ratio) and fluidity were measured.
The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Example 3
Kneading, pulverization, and classification were performed using the same raw materials and production methods as in Example 1, and the particles were classified into a particle size distribution with an average particle size of 6.5 μm.
Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.5 parts
: Titanium oxide fine powder 0.3 part Mixing rotation speed: 1100 rpm
Mixing time: 120 sec
Mixer: Supermixer After the toner was prepared, it was compacted by the evaluation apparatus shown in FIG. 1, and the compacted state (toner leakage, space ratio) and fluidity were measured.
The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Example 4
Kneading, pulverization, and classification were performed using the same raw materials and production methods as in Example 1, and the particles were classified into a particle size distribution with an average particle size of 6.5 μm.
Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.8 parts
: Titanium oxide fine powder 0.3 part Mixing rotation speed: 1100 rpm
Mixing time: 120 sec
Mixer: Supermixer After the toner was prepared, it was compacted by the evaluation apparatus shown in FIG. 1, and the compacted state (toner leakage, space ratio) and fluidity were measured.
The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Comparative Example 1
Kneading, pulverization, and classification were performed using the same raw materials and production methods as in Example 1, and the particles were classified into a particle size distribution with an average particle size of 6.5 μm.
Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.0 part Mixing rotation speed: 700 rpm
Mixing time: 120 sec
Mixer: Supermixer After the toner was prepared, it was compacted by the evaluation apparatus shown in FIG. 1, and the compacted state (toner leakage, space ratio) and fluidity were measured.
The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Example 5
(Toner binder synthesis)
724 parts of bisphenol A ethylene oxide 2-mole adduct, 276 parts of isophthalic acid and 2 parts of dibutyltin oxide were placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and reacted at 230 ° C. under normal pressure for 8 hours. The reaction was further carried out at a reduced pressure of 10 to 15 mmHg for 5 hours, followed by cooling to 160 ° C., and 32 parts of phthalic anhydride was added thereto and reacted for 2 hours. Subsequently, it cooled to 80 degreeC and reacted with 188 parts of isophorone diisocyanate in ethyl acetate for 2 hours, and the isocyanate containing prepolymer I was obtained. Next, 267 parts of prepolymer I and 14 parts of isophoronediamine were reacted at 50 ° C. for 2 hours to obtain urea-modified polyester I having a weight average molecular weight of 64,000. In the same manner as above, 724 parts of bisphenol A ethylene oxide 2-mole adduct and 276 parts of terephthalic acid were polycondensed at 230 ° C. for 8 hours under normal pressure, and then reacted for 5 hours at a reduced pressure of 10 to 15 mmHg. Polyester A was obtained. 200 parts of urea-modified polyester I and 800 parts of unmodified polyester A were dissolved and mixed in 2000 parts of an ethyl acetate / MEK (1/1) mixed solvent to obtain an ethyl acetate / MEK solution of toner binder I. Part of the mixture was dried under reduced pressure to isolate toner binder I. As a result of analysis, Tg was 62 ° C.

Preparation of toner Toner binder I in ethyl acetate / MEK solution 240 parts Pentaerythritol tetrabehenate (melt viscosity 25 cps) 20 parts Copper phthalocyanine blue pigment (CI Pigment Blue 15: 3) 5 parts The above raw materials in a beaker The mixture was stirred at 12000 rpm with a TK homomixer at 60 ° C. and uniformly dissolved and dispersed to prepare a toner material solution.
Ion-exchanged water 706 parts Hydroxyapatite 10% suspension (Superpatite 10 manufactured by Nippon Chemical Industry Co., Ltd.) 294 parts Sodium dodecylbenzenesulfonate 0.2 part The above raw materials were placed in a beaker and dissolved uniformly. Thereafter, the temperature was raised to 60 ° C., and the toner material solution was added and stirred for 10 minutes while stirring at 12000 rpm with a TK homomixer. The mixture was then transferred to a stirring bar and a flask equipped with a thermometer, heated to 30 ° C., the solvent was removed under reduced pressure, filtered, washed, dried, and then classified by air to obtain toner particles. The volume average particle size was 6.5 μm. To 100 parts of the toner particles, an additive was mixed under the following mixing conditions to obtain a toner.
Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.0 part
: Titanium oxide fine powder 0.3 part Mixing rotation speed: 1000 rpm
Mixing time: 120 sec
Mixer: Q mixer After the toner was prepared, it was compacted by the evaluation apparatus shown in FIG. 1, and the compacted state (toner leakage, space ratio) and fluidity were measured.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Example 6
Toner was prepared using the same raw materials and preparation method as in Example 5, and classified into a particle size distribution having an average particle size of 6.5 μm.
Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.2 parts
: Titanium oxide fine powder 0.3 part Mixing rotation speed: 1000 rpm
Mixing time: 120 sec
Mixer: Q mixer After the toner was prepared, it was compacted by the evaluation apparatus shown in FIG. 1, and the compacted state (toner leakage, space ratio) and fluidity were measured.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Example 7
Toner was prepared using the same raw materials and preparation method as in Example 5, and classified into a particle size distribution having an average particle size of 6.5 μm.
Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.5 parts
: Titanium oxide fine powder 0.3 part Mixing rotation speed: 1100 rpm
Mixing time: 120 sec
Mixer: Q mixer After the toner was prepared, it was compacted by the evaluation apparatus shown in FIG. 1, and the compacted state (toner leakage, space ratio) and fluidity were measured.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Example 8
Toner was prepared using the same raw materials and preparation method as in Example 5, and classified into a particle size distribution having an average particle size of 6.5 μm.
Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.8 parts
: Titanium oxide fine powder 0.3 part Mixing rotation speed: 1100 rpm
Mixing time: 120 sec
Mixer: Q mixer After the toner was prepared, it was compacted by the evaluation apparatus shown in FIG. 1, and the compacted state (toner leakage, space ratio) and fluidity were measured.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Comparative Example 2
Toner was prepared using the same raw materials and preparation method as in Example 5, and classified into a particle size distribution having an average particle size of 6.5 μm.
Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.0 part Mixing rotation speed: 700 rpm
Mixing time: 120 sec
Mixer: Q mixer After the toner was prepared, it was compacted by the evaluation apparatus shown in FIG. 1, and the compacted state (toner leakage, space ratio) and fluidity were measured.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Example 9
Resin: Polyester resin 100 parts Colorant: Carbon black 10 parts Charge control agent: Salicylic acid zinc salt 2 parts Release agent: Rice wax 5 parts Additive: Styrene acrylic resin 3 parts After mixing the above raw materials thoroughly with a mixer, The mixture was melt-kneaded with a twin-screw extruder at a barrel temperature of 100 ° C. and a rotation speed of 120 rpm. The kneaded product was rolled and cooled, coarsely pulverized with a cutter mill, pulverized with a fine pulverizer using a jet stream, and then classified into a particle size distribution with an average particle size of 6 μm using a swirling air classifier. Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.2 parts
: Titanium oxide fine powder 0.3 part Mixing rotation speed: 1000 rpm
Mixing time: 120 sec
Mixer: Q mixer After the toner was prepared, it was compacted by the evaluation apparatus shown in FIG. 1, and the compacted state (toner leakage, space ratio) and fluidity were measured.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Example 10
Toners were prepared using the same raw materials and preparation methods as in Example 9, and classified into a particle size distribution with an average particle size of 6 μm.
Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.5 parts
: Titanium oxide fine powder 0.3 part Mixing rotation speed: 1000 rpm
Mixing time: 120 sec
Mixer: Q mixer After the toner was prepared, it was compacted by the evaluation apparatus shown in FIG. 1, and the compacted state (toner leakage, space ratio) and fluidity were measured.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Example 11
Toners were prepared using the same raw materials and preparation methods as in Example 9, and classified into a particle size distribution with an average particle size of 6 μm.
Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.8 parts
: Titanium oxide fine powder 0.3 part Mixing rotation speed: 1100 rpm
Mixing time: 120 sec
Mixer: Q mixer After the toner was prepared, it was compacted by the evaluation apparatus shown in FIG. 1, and the compacted state (toner leakage, space ratio) and fluidity were measured.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Comparative Example 3
Toners were prepared using the same raw materials and preparation methods as in Example 9, and classified into a particle size distribution with an average particle size of 6 μm.
Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.0 part Mixing rotation speed: 700 rpm
Mixing time: 120 sec
Mixer: Q mixer After the toner was prepared, it was compacted by the evaluation apparatus shown in FIG. 1, and the compacted state (toner leakage, space ratio) and fluidity were measured.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.
The measurement results of Examples 1 to 11 and Comparative Examples 1 to 3 are shown in Table 1.
The data of Table 1 is graphed and shown in FIG.

As can be seen from the above results, there is a strong correlation between the fluidity evaluation value of the first group of the toner powder phase by the evaluation device and the cleaning property, and the cleaning property can be evaluated by the evaluation device. I understand. Table 1 also shows that there is a strong correlation between the fluidity evaluation value by the first group of the present evaluation apparatus and the dot reproducibility, and the dot reproducibility can be evaluated by the first group of the present evaluation apparatus. . From the results shown in FIG. 6 and Table 1, it is necessary to satisfy the following conditions in order to obtain a toner with good fluidity necessary for obtaining high image quality with good dot reproducibility and cleanability. .
The value of the force (pulling force) generated when the cylindrical member (diameter: 0.16 mmφ, nylon fiber) moves relatively in the powder phase is 0.03 to 0.5N.
Further, under the above conditions, there were no problems in toner transportability such as blocking in the developing section when running 20,000 sheets. Further, as can be seen from Table 1, this apparatus showed a stable space ratio without toner leakage during compaction.

[Second Group of the Invention]
Example 12
Resin: Polyester resin 100 parts Pigment: Carbon black 10 parts Charge control agent: Salicylic acid zinc salt 5 parts The above raw materials are thoroughly mixed with a mixer, and then melt-kneaded at a barrel temperature of 120 ° C and a kneader rotation speed of 100 rpm by a twin-screw extruder. did. The kneaded product was rolled and cooled, coarsely pulverized with a cutter mill, pulverized with a fine pulverizer using a jet stream, and then classified into a particle size distribution with an average particle size of 6 μm using a swirling air classifier. Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.0 part
: Titanium oxide fine powder 0.3 part Mixing rotation speed: 1000 rpm
Mixing time: 120 sec
Mixer: Supermixer After the toner was prepared, it was compacted by the present evaluation device (second group) shown in FIG. 2 and the compacted state (consolidated load, space ratio) and fluidity were measured. It became so.
The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 2.

Example 13
Kneading, pulverization, and classification were performed using the same raw materials and production methods as in Example 12, and the particles were classified into a particle size distribution with an average particle size of 6 μm.
Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.2 parts
: Titanium oxide fine powder 0.3 part Mixing rotation speed: 1000 rpm
Mixing time: 120 sec
Mixer: Supermixer After the toner was prepared, it was compacted by the evaluation apparatus shown in FIG. 2, and the compacted state (consolidated load, space ratio) and fluidity were measured.
The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 2.

Example 14
Kneading, pulverization, and classification were performed using the same raw materials and production methods as in Example 12, and the particles were classified into a particle size distribution with an average particle size of 6 μm.
Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.5 parts
: Titanium oxide fine powder 0.3 part Mixing rotation speed: 1100 rpm
Mixing time: 120 sec
Mixer: Supermixer After the toner was prepared, it was compacted by the evaluation apparatus shown in FIG. 2, and the compacted state (consolidated load, space ratio) and fluidity were measured.
The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 2.

Example 15
Kneading, pulverization, and classification were performed using the same raw materials and production methods as in Example 12, and the particles were classified into a particle size distribution with an average particle size of 6 μm.
Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.8 parts
: Titanium oxide fine powder 0.3 part Mixing rotation speed: 1100 rpm
Mixing time: 120 sec
Mixer: Supermixer After the toner was prepared, it was compacted by the evaluation apparatus shown in FIG. 2, and the compacted state (consolidated load, space ratio) and fluidity were measured.
The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 2.

Comparative Example 4
Kneading, pulverization, and classification were performed using the same raw materials and production methods as in Example 12, and the particles were classified into a particle size distribution with an average particle size of 6 μm.
Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.0 part Mixing rotation speed: 700 rpm
Mixing time: 120 sec
Mixer: Supermixer After the toner was prepared, it was compacted by the evaluation apparatus shown in FIG. 2, and the compacted state (consolidated load, space ratio) and fluidity were measured.
The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 2.

Example 16
(Toner binder synthesis)
724 parts of bisphenol A ethylene oxide 2-mole adduct, 276 parts of isophthalic acid and 2 parts of dibutyltin oxide were placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and reacted at 230 ° C. under normal pressure for 8 hours. The reaction was further carried out at a reduced pressure of 10 to 15 mmHg for 5 hours, followed by cooling to 160 ° C., and 32 parts of phthalic anhydride was added thereto and reacted for 2 hours. Subsequently, it cooled to 80 degreeC and reacted with 188 parts of isophorone diisocyanate in ethyl acetate for 2 hours, and the isocyanate containing prepolymer I was obtained. Next, 267 parts of prepolymer I and 14 parts of isophoronediamine were reacted at 50 ° C. for 2 hours to obtain urea-modified polyester I having a weight average molecular weight of 64,000. In the same manner as above, 724 parts of bisphenol A ethylene oxide 2-mole adduct and 276 parts of terephthalic acid were polycondensed at 230 ° C. for 8 hours under normal pressure, and then reacted for 5 hours at a reduced pressure of 10 to 15 mmHg. Polyester A was obtained. 200 parts of urea-modified polyester I and 800 parts of unmodified polyester A were dissolved and mixed in 2000 parts of an ethyl acetate / MEK (1/1) mixed solvent to obtain an ethyl acetate / MEK solution of toner binder I. A portion was dried under reduced pressure, and toner binder I was isolated. As a result of analysis, Tg was 62 ° C.

Preparation of toner Toner binder I in ethyl acetate / MEK solution 240 parts Pentaerythritol tetrabehenate (melt viscosity 25 cps) 20 parts Copper phthalocyanine blue pigment (CI Pigment Blue 15: 3) 5 parts The above raw materials in a beaker The mixture was stirred at 12000 rpm with a TK homomixer at 60 ° C. and uniformly dissolved and dispersed to prepare a toner material solution.
706 parts of ion-exchanged water 10% suspension of hydroxyapatite (Superite 10 manufactured by Nippon Kagaku Kogyo Co., Ltd.) 294 parts Sodium dodecylbenzenesulfonate 0.2 part The above raw materials were placed in a beaker and dissolved uniformly. Thereafter, the temperature was raised to 60 ° C., and the toner material solution was added and stirred for 10 minutes while stirring at 12000 rpm with a TK homomixer. The mixture was then transferred to a stirring bar and a flask equipped with a thermometer, heated to 30 ° C., the solvent was removed under reduced pressure, filtered, washed, dried, and then classified by air to obtain toner particles. The volume average particle size was 6.5 μm. To 100 parts of the toner particles, an additive was mixed under the following mixing conditions to obtain a toner.
Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.0 part
: Titanium oxide fine powder 0.3 part Mixing rotation speed: 1100 rpm
Mixing time: 120 sec
Mixer: Q mixer After the toner was prepared, it was compacted by the present evaluation apparatus shown in FIG. 2, and the compacted state (consolidated load, space ratio) and fluidity were measured.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 2.

Example 17
Toner was prepared using the same raw materials and preparation method as in Example 16, and classified into a particle size distribution with an average particle size of 6.5 μm.
Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.2 parts
: Titanium oxide fine powder 0.3 part Mixing rotation speed: 1100 rpm
Mixing time: 120 sec
Mixer: Q mixer After the toner was prepared, it was compacted by the present evaluation apparatus shown in FIG. 2, and the compacted state (consolidated load, space ratio) and fluidity were measured.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 2.

Example 18
Toner was prepared using the same raw materials and preparation method as in Example 16, and classified into a particle size distribution with an average particle size of 6.5 μm.
Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.5 parts
: Titanium oxide fine powder 0.3 part Mixing rotation speed: 1200 rpm
Mixing time: 120 sec
Mixer: Q mixer After the toner was prepared, it was compacted by the present evaluation apparatus shown in FIG. 2, and the compacted state (consolidated load, space ratio) and fluidity were measured.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 2.

Example 19
Toner was prepared using the same raw materials and preparation method as in Example 16, and classified into a particle size distribution with an average particle size of 6.5 μm.
Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.8 parts
: Titanium oxide fine powder 0.3 part Mixing rotation speed: 1200 rpm
Mixing time: 120 sec
Mixer: Q mixer After the toner was prepared, it was compacted by the present evaluation apparatus shown in FIG. 2, and the compacted state (consolidated load, space ratio) and fluidity were measured.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 2.

Comparative Example 5
Toner was prepared using the same raw materials and preparation method as in Example 16, and classified into a particle size distribution with an average particle size of 6.5 μm.
Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.0 part Mixing rotation speed: 700 rpm
Mixing time: 120 sec
Mixer: Supermixer After the toner was prepared, it was compacted by the evaluation apparatus shown in FIG. 2, and the compacted state (consolidated load, space ratio) and fluidity were measured.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 2.

Example 20
Resin: 100 parts of polyester resin Colorant: 3.5 parts of copper phthalocyanine blue pigment
(C.I. Pigment Blue 15: 3)
Charge control agent: Zinc salicylate 2 parts Mold release agent: Carnauba wax 5 parts Additive: Styrene acrylic resin 3 parts After thoroughly mixing the above raw materials with a mixer, barrel temperature 100 ° C rotation speed 120 rpm with a twin screw extruder Was melt kneaded. The kneaded product was rolled and cooled, coarsely pulverized with a cutter mill, pulverized with a fine pulverizer using a jet stream, and then classified into a particle size distribution with an average particle size of 6 μm using a swirling air classifier. Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.2 parts
: Titanium oxide fine powder 0.3 part Mixing rotation speed: 1100 rpm
Mixing time: 120 sec
Mixer: Q mixer After the toner was prepared, it was compacted by the present evaluation apparatus shown in FIG. 2, and the compacted state (consolidated load, space ratio) and fluidity were measured.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 2.

Example 21
Toners were prepared using the same raw materials and preparation methods as in Example 20, and classified into a particle size distribution with an average particle size of 6 μm.
Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.5 parts
: Titanium oxide fine powder 0.3 part Mixing rotation speed: 1200 rpm
Mixing time: 120 sec
Mixer: Q mixer After the toner was prepared, it was compacted by the present evaluation apparatus shown in FIG. 2, and the compacted state (consolidated load, space ratio) and fluidity were measured.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 2.

Example 22
Toners were prepared using the same raw materials and preparation methods as in Example 20, and classified into a particle size distribution with an average particle size of 6 μm.
Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.8 parts
: Titanium oxide fine powder 0.3 part Mixing rotation speed: 1200 rpm
Mixing time: 120 sec
Mixer: Q mixer After the toner was prepared, it was compacted by the present evaluation apparatus shown in FIG. 2, and the compacted state (consolidated load, space ratio) and fluidity were measured.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 2.

Comparative Example 6
Toners were prepared using the same raw materials and preparation methods as in Example 20, and classified into a particle size distribution with an average particle size of 6 μm.
Further, an additive was mixed with 100 parts of the base coloring particles under the following mixing conditions to prepare a toner.
Additive: Silica fine powder 1.0 part Mixing rotation speed: 700 rpm
Mixing time: 120 sec
Mixer: Supermixer After the toner was prepared, it was compacted by the evaluation apparatus shown in FIG. 2, and the compacted state (consolidated load, space ratio) and fluidity were measured.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 2.
Table 2 shows the measurement results of Examples 12 to 22 and Comparative Examples 4 to 6.
The data of Table 2 is graphed and shown in FIG.

  From the above results, it can be seen that there is a strong correlation between the fluidity evaluation value of the second group of the toner powder phase evaluated by this evaluation device and the cleaning property, and the cleaning property can be evaluated by this evaluation device. Table 2 also shows that there is a strong correlation between the fluidity evaluation value by the second group of the present evaluation apparatus and the dot reproducibility, and the dot reproducibility can be evaluated by the present evaluation apparatus. Moreover, it can be seen from Table 2 that the consolidation load shows a stable value, and the accuracy of the fluidity evaluation value is high.

From the results shown in FIG. 9 and Table 2, it is necessary to satisfy the following conditions in order to obtain a toner with good fluidity necessary for obtaining high image quality with good dot reproducibility and cleaning properties.
The value of the force (pulling force) generated when the cylindrical member (diameter: 0.16 mmφ, nylon fiber) moves relatively in the powder phase is 0.03 to 0.5N.

It is a figure which shows the outline | summary of the powder evaluation apparatus example of this invention. It is a figure which shows the outline | summary of another example of the powder evaluation apparatus of this invention. It is a figure which shows the outline | summary of the surface shape of a cylindrical member. It is a figure which shows the change of the consolidation speed with respect to the amount of height displacement. It is another figure which shows the outline | summary of the example of the powder evaluation apparatus of this invention. It is a figure which shows the relationship between the force at the time of the relative drive of a cylindrical member (drawing force), and cleaning property. It is a figure which shows the example of the toner manufacturing apparatus using the evaluation apparatus of this invention. It is a figure which shows the example of the image development apparatus using the toner produced using the evaluation method of this invention. It is a figure which shows another relationship between the force at the time of the relative drive of a cylindrical member (drawing force), and cleaning property.

Claims (29)

In an apparatus for measuring a force generated in a cylindrical member by moving a powder phase or a cylindrical member in a compacted powder phase and moving the powder phase or the cylindrical member, means for controlling the compaction speed at the time of compaction A powder evaluation apparatus comprising: 2. The force generated in the cylindrical member is measured by moving the powder phase or the columnar member in a direction perpendicular to the consolidation direction while the powder phase is being consolidated by the piston. The powder evaluation apparatus described in 1. 2. The powder evaluation apparatus according to claim 1, wherein the compaction is performed by changing the function of the compaction speed with respect to the height displacement amount in at least two stages until the piston collides with the powder phase surface. The powder evaluation apparatus according to claim 1, wherein the compaction is performed such that the compaction speed when the piston contacts the powder phase surface is 0.1 to 5 mm / min. In an apparatus for measuring a force generated in a cylindrical member at that time by providing a long cylindrical member in the powder phase and moving the powder phase or the cylindrical member, means for measuring the compaction load of the powder phase A powder evaluation apparatus comprising: While the powder phase is kept in the compacted state by the compaction means, the powder phase or the cylindrical member is moved in the direction perpendicular to the compaction direction while measuring the compaction load of the powder phase, and is generated in the cylindrical member. The powder evaluation apparatus according to claim 5, wherein force is measured. 6. The powder evaluation apparatus according to claim 5, wherein a load cell is used as means for measuring the consolidation load, and the load cell is provided under the sample container. 6. The powder evaluation apparatus according to claim 5, wherein a piston carrying a weight is used as a means for compaction, and a value of the compaction load is set to 0.5 to 50N. 6. The powder evaluation apparatus according to claim 1, wherein the powder phase compacted by the piston has a powder density of 0.4 to 0.7. 6. The powder evaluation apparatus according to claim 1, wherein the surface of the cylindrical member has a regular uneven shape. 6. The powder evaluation apparatus according to claim 1, wherein the cylindrical member is formed of a rod having a groove or a line having an uneven shape. The powder evaluation apparatus according to claim 1 or 5, wherein the diameter of the cylindrical member is 0.1 to 10 mmφ. The powder evaluation apparatus according to claim 1 or 5, wherein a relative movement speed of the cylindrical member is 0.1 to 10 mm / sec. The powder evaluation apparatus according to claim 1 or 5, wherein a relative movement amount of the cylindrical member is 5 to 50 mm. 6. The powder evaluation apparatus according to claim 1, wherein the cylindrical member is reciprocated relatively 1 to 10 times relative to the toner powder phase. 6. The powder evaluation apparatus according to claim 1, wherein the cylindrical member has a relative acceleration of 0.001 to 1 mm / sec ² . When the cylindrical member (diameter: 0.16 mmφ, nylon fiber) of the toner after the mixing step of mixing the additive moves relatively in the powder phase using the evaluation apparatus according to claim 1 or 5. The electrostatic charge developing toner is characterized in that the value of the force generated in the toner is 0.03 to 0.5N. 18. The electrostatic charge developing toner according to claim 17, wherein a charge control agent and / or a release agent is contained in the toner composed of at least a resin and a pigment. The toner for electrostatic charge development according to claim 17 or 18, wherein an additive adheres to or adheres to a surface of the toner powder. The electrostatic charge developing toner according to claim 17, wherein the toner has an average particle diameter of 4 to 8 μm. 21. The electrostatic charge developing toner according to claim 17, wherein the toner is produced by a polymerization method. The toner for electrostatic charge development according to any one of claims 17 to 21, wherein the toner has an average circularity of 0.9 to 0.99. 23. A one-component developing method comprising performing contact or non-contact development using the electrostatic charge developing toner according to claim 17. 24. The one-component developing method according to claim 23, wherein a doctor roller and / or a supply roller are used. 23. A two-component developing method comprising developing using the electrostatic charge developing toner according to claim 17 and a carrier having a particle diameter of 20 to 70 [mu] m. 26. The one-component development method or the two-component development method according to claim 23, wherein the development is performed by applying an AC bias voltage component. 23. A toner cartridge or a process cartridge containing the toner according to claim 17. A toner evaluation method for electrostatic charge development, wherein the fluidity of the toner is evaluated using the evaluation apparatus according to claim 1. An electrostatic charge developing toner, wherein the evaluation is performed in a toner manufacturing process using the powder fluidity evaluation apparatus according to any one of claims 1 to 16, and the toner is manufactured based on the evaluation. Production method.

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