JP4934415B2 - toner - Google Patents

Description

  The present invention relates to a toner used in electrophotography, electrostatic recording, electrostatic printing, and toner jet recording.

In recent years, electrophotographic apparatuses such as printer apparatuses have been strongly desired to develop machines that can achieve high-speed printing and low running costs while achieving higher definition, higher image quality, and higher stability than ever. Along with this, the properties required for toners are becoming increasingly high and diverse, and developments are being made from various viewpoints.
From the viewpoint of high definition and high image quality, the direction of finer particles is desired as the toner as the resolution of machines such as 1200 and 2400 dpi increases. There are various types of toner manufacturing methods to achieve micronization, such as pulverization method and polymerization method. Depending on the manufacturing method, the flow characteristics of the toner may change greatly. (For example, Patent Document 1 and Patent Document 2). According to this method, the fluidity between toners can be measured.
However, since only such a method cannot know the fluidity between the toners in a situation where the toner is actually replenished and used, for example, know the relationship between the charge rising characteristics at the time of toner replenishment and the actual image. I couldn't.
When toner is actually replenished and used, the required toner physical properties are considered to play a major role in the charging characteristics, especially the rise of the charge amount, and are the main factors that continuously achieve high definition and high image quality over a long period of time. is there.
At present, the relationship between the rise in toner charge amount at the time of developer replenishment and the fluidity of the developer is not clear.

In addition, in order to stably output a high-definition and high-quality image, it is required to stabilize the flowability of the developer, and thus various proposals have been made so far. For example, there is a proposal that regulates toner fluidity using a powder tester manufactured by Hosokawa Micron that shows toner fluidity (for example, Patent Document 3).
In this proposal, since the metal mesh is used when measuring the fluidity of the toner, in addition to measuring the fluidity between the toners, the adhesion force and the frictional force between the toner and the metal mesh are reflected. Therefore, it has been difficult to effectively measure the fluidity of the toner alone.

As described above, it has been proposed so far to satisfy the requirement for long-term durability stability of high-speed development while achieving high-resolution and high-definition images with toner, particularly as the characteristics required for toner. Technology is not enough and there is still room for improvement.
JP 01-203941 A JP 2004-037651 A JP 2003-43795 A

The present invention is to solve the above-mentioned problems of the prior art.
(1) An object of the present invention is to provide a fine particle toner capable of obtaining a high resolution and high definition image.
(2) Further, an object of the present invention is a toner that can obtain a continuous and stable image (appropriate image density) necessary for achieving the image quality of photographs and printing while achieving the object of (1). Is to provide.
(3) Furthermore, an object of the present invention is to provide a toner having a uniform charge amount and charge amount distribution that rises quickly.

As a result of intensive studies, the present inventors have found that the following problems can be solved by the following configuration, and have completed the present invention. That is, the present invention is as follows.
[1] at least a binder resin, engineering to obtain a release agent及 beauty colorant melt kneaded to colored resin composition
Extent, and the toner particles obtained through the step of pulverizing the colored resin composition, a toner for organic and inorganic fine powder,
The number average particle diameter (D1) of the inorganic fine powder is 80 nm or more and 200 nm or less,
Obtained by analyzing the circularity of toner particles measured by a flow type particle image measuring apparatus with an equivalent circle diameter of 2.00 μm or more and 200.00 μm or less divided into 800 in a circularity range of 0.2 to 1.0. The toner particles have an average circularity of 0.950 or more and 0.987 or less,
The toner has a weight average particle diameter of 4.0 μm or more and 6.5 μm or less,
The toner satisfying the following relational expressions (1) and (2):
100 ≦ Et100 (mJ) ≦ 350 (1)
0.10 ≦ Etd / Et100 ≦ 0.50 (2)
(Et100 in the formula (1) and (2) (mJ) is powder flowability analyzing outermost edge of the propeller blade peripheral speed 1 while rotating at 300 mm / sec toner powder layer in the container in the device The measurement is started from a position 100 mm from the bottom surface of the powder layer, and the sum of the rotational torque and the vertical load obtained when the measurement is entered to a position 10 mm from the bottom surface, Etd in 2) is placed a porous plate in the container bottom, after the measurement of the Et100 while venting the dry air from which the flow rate 0.48 (m m / sec), to stop the aeration, the The measurement is repeated four times in the manner of measuring Et100, and represents the sum of the rotational torque and the vertical load obtained by the fourth measurement.)

  According to the present invention, a toner capable of obtaining a high resolution and high definition image can be provided. Further, it is possible to provide a toner that has a continuously stable image and a rapid rise and uniform charge amount and charge distribution.

Hereinafter, the present invention will be described in detail with reference to embodiments of the present invention.
The toner of the present invention is a toner containing toner particles containing at least a binder resin, a release agent, and a colorant and an inorganic fine powder. The toner satisfies the following relational expressions (1) and (2): The toner is characterized by satisfying.
100 ≦ Et100 (mJ) ≦ 350 (1)
0.10 ≦ Etd / Et100 ≦ 0.50 (2)
Et100 (mJ) in the above formulas (1) and (2) is calculated in the toner powder layer in the container while rotating the peripheral speed of the outermost edge of the propeller blade at 100 mm / sec in the powder flowability analyzer. It represents the sum of the rotational torque and the vertical load obtained when the measurement is started from a position 100 mm from the bottom surface of the powder layer and the position is 10 mm from the bottom surface. Etd in) is placed a porous plate in the container bottom, after the measurement of the Et100 while venting the dry air from which the flow rate 0.48 (m m / sec), to stop the venting, above, The measurement is repeated four times in the manner of measuring Et100, and the total of the rotational torque and the vertical load obtained by the fourth measurement is shown. Details of the Et100 measurement and Etd measurement will be described later.

In the present invention, Et100 (mJ) is controlled to 100 or more and 350 or less to reduce the stress applied to the toner in the replenishing toner bottle and in the developing unit with any method of soft toner with improved low-temperature fixability. I found out that In addition, even during high-speed long-term image rendering, toner contamination such as wax contamination and external additive embedding and toner particle crushing is suppressed, and component contamination due to liberation of external additives is suppressed. And found that a stable image can be obtained.
Et100 is measured in an environment where there is little air between the toners and the toners are in close contact. This is very similar to the toner environment in the actual refill toner bottle and in the developing machine. When the toner in the container is in close contact with the toner in the container with the blade (pressure), the toners with poor fluidity between the toners adhere to each other and aggregate, so that a lot of energy is consumed when the blade rotates. I need. On the other hand, even in the case where the toner is in close contact, even if the toner has good fluidity, even if the toner in the container is sheared by the blade, aggregation between the toners hardly occurs, and energy applied when the blade rotates is reduced. From this, Et100 (mJ)
It was found that an effect can be obtained by controlling the value within the above range.

  In particular, magnetic two-component developers are often used in high-speed copying machines, so a lot of stress is generated on the toner in the developing device, and deteriorated toner accumulates in the developing device in the second half of the long-term durability. It was easy to cause problems such as fogging and poor density. Therefore, it is very important to control Et100 (mJ) to 100 or more and 350 or less. From the same viewpoint, it is preferable to control Et100 (mJ) to 100 or more and 300 or less.

  Further, by controlling Etd / Et100 to be 0.10 or more and 0.50 or less, when toner is continuously supplied in the high speed copying machine, the supplied toner is composed of toner and carrier in the developing device. Mix quickly with two-component developers. As a result, toner can be charged quickly, uniformly and sharply, and there is an effect of preventing fogging and scattering due to poor charging.

The etd, placed a porous plate to the measuring container bottom, after the measurement of the Et100 while venting the drying air flow 0.48 (m m / sec) therefrom, to stop the venting, above, The measurement is repeated four times in the manner of measuring Et100, and the total of the rotational torque and the vertical load obtained by the fourth measurement is shown.

The state where Etd / Et100 becomes 1.00 is a state in which dry air is once ventilated to completely return to the state before air is ventilated (A in FIG. 3). B) in 3 is shown.

By aeration at a flow rate of 0.48 ( mm / sec), there is sufficient dry air around the toner, and as a result, Et100 becomes a low value of 50 or less. Thereafter, by stopping the ventilation, the dry air around the toner rises and the fluidity between the toners decreases. Furthermore, dry air around the toner is removed by continuously measuring Et100 immediately after aeration is stopped.
In the present invention, the Et100 measurement is repeated four times, and it is very significant to define the sum of the rotational torque and the vertical load at that time. This is because the present inventors have found that there is a large common point between the Etd / Et100 value when Et100 measurement is repeated four times, the replenishment toner in the two-component developer, and its mixing property. .

As described above, when the number of Et100 measurements is repeated, the toner returns to a state not containing air (aggregated state) (graph in FIG. 3). Therefore, even if the number of continuous Et100 measurements is increased, it is preferable that the Etd / Et100 value be low because air is included and the replenishment toner can be easily adapted to the existing developer. .
On the other hand, since the replenishment toner comes into contact with the air before reaching (replenishing) the inside of the developing device, the dry air of the present invention is vented by 0.48 ( m m / sec). The fluidity is very high. Then, various stirring operations are performed before mixing with the existing developer. By this stirring operation, air around the toner is removed, and the fluidity of the toner is lowered. Therefore, the replenishing toner is a continuous toner if the toner fluidity is maintained at a state where the toner fluidity is not lowered even if the stirring operation is performed in the developing device (if the Etd / Et100 value can be kept low). Even if the replenishment is performed, it is preferable because it quickly becomes compatible with the existing developer.
In the present invention, the situation in which Et100 is measured four times and the state in which the developing device is stirred are very similar to the replenishing toner. As a result, Etd / Et100 is 0.10 or more and 0.50 or less. As a result, it was found that a stable image can be obtained even during continuous toner replenishment. Etd / Et100 is more preferably 0.10 or more and 0.40 or less.

Examples of methods for controlling these Et100 and Etd / Et100 values include the following methods. These methods may be performed independently or may be achieved by combining a plurality of methods.

  For example, there is a method of increasing the average circularity of the toner and reducing the contact area between the toner particles. The average circularity of the toner is preferably 0.950 to 0.987, more preferably 0.958 to 0.987.

  Another example is a method in which an appropriate amount of an inorganic fine particle layer treated with a treatment agent having a low volume resistance and a high hydrophobic property is adhered to the toner surface. That is, a method of performing an external addition process in two or more stages as in Examples described later. The inorganic fine particles are preferably titanium oxide.

<Et100 (mJ) and Etd / Et100 measurement method>
In the present invention, Et100 (mJ) and Etd / Et100 are measured by a fluidity measurement method using a rotary blade. As the measuring device, for example, a powder fluidity analyzer, powder rheometer FT-4 (manufactured by Freeman Technology) (hereinafter may be abbreviated as “FT-4”) can be used.

  The device moves the blades through the powder sample, causing a constant flow measurement and pattern flow. The particles in the sample flow when the blade is in close proximity, and after passing, the blade falls and then rests again. The energy required for the blade to move through the powder is calculated, and from this value the various fluidity indices are calculated. The blade is a propeller type, and at the same time it rotates, it moves in the planting or downward direction, so that the tip draws a helix. The angle and speed of the spiral path of the blade can be adjusted by changing the rotational speed and the vertical movement. When the blade moves along the clockwise spiral path, it acts to mix the powder uniformly. Conversely, when moving along a counterclockwise spiral path, the blade will receive resistance from the powder.

Specifically, the measurement is performed by the following operation. In all operations, the propeller type blade is a 48 mm diameter blade dedicated to FT-4 measurement (Figs. 1 and 2. There is a rotation axis in the normal direction at the center of the 48 mm x 10 mm blade plate. The outermost edge (24mm from the rotating shaft) is 70 ° and the portion 12mm from the rotating shaft is 35 °, and is smoothly twisted counterclockwise, and the material is SUS.Model number: C210. (May be abbreviated as “blade”)
Is used.

  First, a FT-4 measurement dedicated 50mm x 160ml split container (model number: C203, 82mm height from the bottom of the container to the split part. The material is glass, hereinafter may be abbreviated as container) at 23 ° C, 60% environment. The toner powder layer is formed by adding 100 g of toner left for 3 days or more.

(1) Conditioning operation (a) The rotation speed of the blade (peripheral speed of the outermost edge of the blade) is 60 (mm / sec), the vertical approach speed to the powder layer is the outermost edge of the moving blade The angle formed between the locus drawn by the powder layer and the surface of the powder layer (hereinafter sometimes referred to as “the angle formed”) is clockwise with respect to the surface of the powder layer at a speed of 5 (deg) (powdered by rotation of the blade). The blade is advanced from the surface of the powder layer to the position 10 mm from the bottom surface of the toner powder layer in the rotation direction (the direction in which the body layer is loosened).
After that, the rotation speed of the blade is 60 (mm / sec), the vertical approach speed to the powder layer is 2 (deg), and the rotation angle is clockwise with respect to the powder layer surface. Then, the blade is advanced from the bottom surface of the toner powder layer to a position of 1 mm.
After that, the toner powder is rotated clockwise with respect to the surface of the powder layer at a blade rotation speed of 60 (mm / sec) and an angle forming the extraction speed from the powder layer of 5 (deg). The blade is moved to a position of 100 mm from the bottom of the layer and extracted.
When the extraction is completed, the toner attached to the blade is wiped off by rotating the blade alternately in small clockwise and counterclockwise directions.
(B) By performing the series of operations (1) to (a) five times, the air entrained in the toner powder layer is removed, and a stable toner powder layer is formed.

(2) Split operation A toner powder layer having the same volume is formed by grinding the toner powder layer at the split portion of the above-described cell dedicated for FT-4 measurement and removing the toner on the upper part of the powder layer.

(3) Measurement operation (i) Measurement of Et100 (a) The same operation as (1)-(a) above is performed once.
(B) Next, the rotation speed of the blade is 100 (mm / sec), the vertical approach speed to the powder layer is an angle of 5 (deg), and it is counterclockwise with respect to the powder layer surface. In the rotational direction (the direction in which the powder layer is pushed in by the rotation of the blade), the blade is advanced to a position 10 mm from the bottom surface of the toner powder layer.
After that, the rotation speed of the blade is 60 (mm / sec), the vertical approach speed to the powder layer is 2 (deg), and the rotation angle is clockwise with respect to the powder layer surface. Then, the blade is advanced from the bottom of the powder layer to a position of 1 mm.
Then, the rotation speed of the blade is 60 (mm / sec), the angle forming the vertical extraction speed from the powder layer is 5 (deg), and the rotation direction is clockwise with respect to the powder layer surface. The blade is extracted from the bottom surface of the powder layer to a position of 100 mm.
When the extraction is completed, the toner attached to the blade is wiped off by rotating the blade alternately in small clockwise and counterclockwise directions.
(C) The above series of operations (b) is repeated seven times.
In the above operation (c), it is obtained when the blade enters the position from 100 mm to 10 mm from the bottom surface of the toner powder layer when the rotation speed of the blade at the seventh time is 100 (mm / sec). The total Et of rotational torque and vertical load is Et100.

(Ii) Measurement of Etd 23 mm in a 50 mm × 200 ml container (model number: C200 and C620 (bottom plate for aeration). Height: 100 mm. Material is glass, hereinafter may be abbreviated as aeration container). A toner powder layer is obtained by adding 80 g of toner left in a 60% environment for 3 days or more.
(A) The toner powder for which the measurement of Et100 has been completed is put into an aeration container, and the above operations (1) to (a) are performed once.
(B) Next, a porous plate of the container bottom, a flow rate such that 0.48 (m m / sec), is vented gradually dry air. At this time, a dedicated ventilation unit for FT-4 measurement is used.
(C) The above operations (i) and (b) are performed once in a state where dry air has become familiar to the toner.
(D) Here, the supply of dry air is stopped, and then Et100 is measured four times. From the surface of the toner powder layer when the rotation speed of the fourth blade is 100 (mm / sec). Let Etd be the total Et of rotational torque and vertical load obtained when the blade enters the position 10 mm from the bottom.

Until now, there are many known examples that discuss the fluidity of the toner using a powder tester manufactured by Hosokawa Micron. However, since these use a metal mesh, in addition to measuring the fluidity between the toners, the adhesion force and friction force between the toner and the metal mesh are reflected. For this reason, it has been difficult to effectively measure the fluidity of the toner alone.
Further, the evaluation is not sufficient when the evaluation is performed in consideration of the influence of air when the toner is replenished.

The inventors of the present invention have compared the toner measured for Et100 with the general measurement using the above apparatus. As a result, in the Et100 measurement in this application, the toner showing a low value (good fluidity) Measurement using a tester showed a high degree of aggregation (poor fluidity). This is because, when evaluating the fluidity of the toner, about 5 g of toner is placed on the metal mesh, and the phenomenon between the toner that occurs when the toner is sieved off by vibration, and the toner is fixed as in the FT-4 of the present invention. It can be said that this phenomenon is very different from the phenomenon between toners that occurs when a blade is used for sharing in a state of being held in space. The environment of the replenishment toner and the toner of the one-component developer is placed in an environment close to the latter, and the toner replenished with the two-component developer contains a lot of air on the toner surface. The measurement method in the present application is considered to be very similar to the actual toner behavior.

The toner of the present invention has a circle equivalent diameter of 2.00 μm or more and 20 measured by a flow type particle image measuring apparatus having an image processing resolution of 512 × 512 pixels (0.37 μm × 0.37 μm per pixel).
The average circularity of the toner particles obtained by dividing the circularity of the toner particles of 0.00 μm or less into 800 in the circularity range of 0.2 to 1.0 and being analyzed is 0.950 or more and 0.987 or less. Is preferred. This is because, in recent printers and copiers where the resolution of latent images is increased to 1200 and 2400 dpi, finer latent image dots are faithfully developed to achieve further higher image quality. In addition, the improvement in the hiding power enables the toner consumption to be reduced, leading to a reduction in running cost. From the same viewpoint, the average circularity is more preferably 0.955 or more and 0.987 or less. Examples of the flow type particle image measuring device include “FPIA-3000 type” (manufactured by Sysmex Corporation).

If the average circularity of the toner particles is less than 0.950, the toner transferability is poor. This is considered to be because the contact area between the toner particles and the photosensitive member is large, and the adhesion force of the toner particles to the photosensitive member due to mirror image force, van der Waals force, or the like increases. As a result, the transfer efficiency is lowered, and as a result, the toner consumption is increased.
Furthermore, toner particles having an average circularity of less than 0.950 have a lot of edge portions on the surface, so that charge localization tends to occur within one particle, and the charge amount distribution tends to be wide. , It will be easy to cause fogging.
Further, the reason is not clear or Et100, which is an essential requirement of the present invention, tends to increase.

  On the other hand, when the average circularity of the toner particles exceeds 0.987, the average circularity of the toner particles is increased, so that the fluidity of the toner is improved and the toner charge amount distribution is widened. This is presumably because the frictional force with the magnetic carrier carrying the toner decreases and becomes non-uniform. On the other hand, if the average circularity of the toner particles exceeds 0.987, it is difficult to obtain the effect of suppressing the photoconductor cleaning failure.

<Measurement of average circularity of toner particles>
The average circularity of the toner particles is measured by a flow type particle image analyzer “FPIA-3000 type” (manufactured by Sysmex Corporation) under measurement / analysis conditions during calibration.
The measurement principle of the flow-type particle image analyzer “FPIA-3000 type” (manufactured by Sysmex Corporation) is to take a flowing particle as a still image and perform image analysis. The sample added to the sample chamber is fed into the flat sheath flow cell by a sample suction syringe. The sample fed into the flat sheath flow is sandwiched between sheath liquids to form a flat flow. The sample passing through the flat sheath flow cell is irradiated with strobe light at 1/60 second intervals, and the flowing particles can be photographed as a still image. Further, since the flow is flat, the image is taken in a focused state. The particle image is captured by a CCD camera, and the captured image is processed with an image processing resolution of 512 x 512 pixels (0.37 x 0.37 µm per pixel), the contour of each particle image is extracted, and the projected area of the particle image And the perimeter are measured.
Next, the projected area S and the perimeter L of each particle image are obtained. Using the area S and the perimeter L, the equivalent circle diameter and the circularity are obtained. The circular equivalent diameter is the diameter of a circle having the same area as the projected area of the particle image, and the circularity is a value obtained by dividing the circumference of the circle obtained from the circular diameter by the circumference of the projected particle image. Defined and calculated by the following formula.

When the particle image is circular, the degree of circularity is 1, and the degree of unevenness on the outer periphery of the particle image increases, and the degree of circularity decreases.
After calculating the circularity of each particle, the range of the circularity of 0.2 to 1.0 of toner particles having an equivalent circle diameter of 2.00 μm to 200.00 μm is divided into 800, and the average circularity is calculated using the number of measured particles. Is calculated.

More specifically, measurement of the average circularity of toner particles will be described. This specific measuring method is described in the FPIA-3000 type operation manual issued by Sysmex Corporation, and is as follows.
As a specific measurement method, for example, an appropriate amount of a surfactant, preferably an alkylbenzene sulfonate, is added to 20 ml of ion-exchanged water, and then 0.06 g of a measurement sample is added, an oscillation frequency of 50 kHz, and electrical output. Dispersion treatment is performed for 2 minutes using a 150 W tabletop type ultrasonic cleaner / disperser (for example, “VS-150” (manufactured by VervoCrea)) to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC.
For the measurement, the flow type particle image analyzer equipped with a high-magnification imaging unit (objective lens (20 times)) is used, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) is used as the sheath liquid. The dispersion liquid prepared according to the above procedure is introduced into the flow type particle image analyzer, and 2000 toner particles are measured in the total count mode in the HPF measurement mode, and the binarization threshold at the time of particle analysis is 85%. And the analysis particle diameter is 2.00 μm or more equivalent circle diameter,
The average circularity of the toner particles is obtained by limiting to 200.00 μm or less.
In measurement, automatic focus adjustment is performed using standard latex particles (for example, Duke Scientific 5100A diluted with ion-exchanged water) before the start of measurement. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.
In the examples described later in this application, a flow type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, is used. Except for limiting to 0.000 μm or more and 200.00 μm or less, the measurement was performed under the measurement and analysis conditions when the calibration certificate was received.

The toner of the present invention preferably further contains fine powder having a number average particle diameter (D1) of 80 nm or more and 200 nm or less. This greatly contributes to keeping Et100 of the present invention low and Etd / Et100 low. This can be expected to be related to the circularity of the toner. In the case of a toner with a low degree of circularity, since there are many irregularities on the toner surface, the contact area between the toners inevitably increases. Therefore, the above-described relatively large particles adhere to and adhere to the toner surface, so that fine irregularities on the toner surface can be filled. Thereby, it is expected that the contact area between the toners can be reduced, and Et100 and Etd / Et100, which are essential requirements of the present invention, can be controlled within a preferable range. In addition, since these fine powders are present in the toner, it is possible to obtain a toner having excellent charge rise and contribute to the releasability with respect to the transfer member, and as a result, the transfer efficiency is increased. From the same viewpoint, the number average particle diameter (D1) of the fine powder is more preferably 80 nm or more and 160 nm or less.

  The average particle size of the toner is preferably 4.0 μm or more and 6.5 μm or less. By controlling the toner particle diameter within this range, the running cost can be reduced while realizing high definition, high image quality, and high stability. Also, within this range, the value of Etd / Et100, which is an essential requirement of the present invention, can be kept low, and stable image output is possible even with continuous toner replenishment.

  The toner of the present invention preferably contains a polyester unit as a main component of the binder resin. This is effective in order to obtain a toner having low temperature fixability and charge rise corresponding to ecology. In order to impart uniform chargeability, it is also effective to use a resin containing a vinyl polymer unit that improves the dispersibility of the release agent. Therefore, the binder resin used in the toner of the present invention includes (a) a polyester resin, (b) a hybrid resin having a polyester unit and a vinyl polymer unit, or (c) a hybrid resin and a vinyl polymer. Or (d) a mixture of a polyester resin and a vinyl copolymer, or (e) a mixture of a hybrid resin and a polyester resin, or (f) a polyester resin and a hybrid resin, and a vinyl polymer. Resins selected from any of the mixtures are preferred. Among these, it is particularly preferable to use one containing a hybrid resin.

  In the present specification, “polyester unit” refers to a portion derived from polyester, and “vinyl polymer unit” refers to a portion derived from vinyl polymer. The polyester monomer constituting the polyester unit is a polyvalent carboxylic acid component and a polyhydric alcohol component, and the vinyl polymer unit is a monomer component having a vinyl group.

When a polyester resin is used as the binder resin, alcohol and carboxylic acid, carboxylic acid anhydride, carboxylic acid ester, or the like can be used as a raw material monomer. Specifically, for example, as the dihydric alcohol component, 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) -polyoxyethylene (2.0) -2,2 -Alkylene oxide adducts of bisphenol A such as bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, Opentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A And hydrogenated bisphenol A.

  Examples of the trivalent or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. Can be mentioned.

  Examples of the carboxylic acid component include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; Succinic acid substituted with 12 alkyl groups or anhydrides thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof.

  Among these, in particular, a bisphenol derivative represented by the following general formula (1) is used as a diol component, and a carboxylic acid component (for example, fumaric acid) composed of a divalent or higher carboxylic acid or an acid anhydride thereof or a lower alkyl ester thereof. A polyester resin obtained by polycondensation using acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) as an acid component is preferable because it imparts good charging characteristics to the toner.

  Examples of the trivalent or higher polyvalent carboxylic acid component for forming a polyester resin having a crosslinking site include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2 , 4-naphthalenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and anhydrides and ester compounds thereof. The amount of the trivalent or higher polyvalent carboxylic acid component is preferably 0.1 to 1.9 mol% based on the total monomer.

  Further, when a hybrid resin having a polyester unit and a vinyl polymer unit is used as the binder resin, further improved release agent dispersibility, low-temperature fixability, and offset resistance can be expected. The “hybrid resin component” used in the present invention means a resin in which a vinyl polymer unit and a polyester unit are chemically bonded. Specifically, a polyester unit and a vinyl polymer unit obtained by polymerizing a monomer having a carboxylic acid ester group such as (meth) acrylic acid ester are formed by a transesterification reaction, preferably a vinyl polymer. Is used to form a graft copolymer (or block copolymer) having a backbone polymer and a polyester unit as a branch polymer.

The following are mentioned as a vinyl-type monomer for producing | generating a vinyl-type polymer. Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert- Butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-chloro styrene, 3, Styrene and derivatives thereof such as 4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene; styrene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated such as butadiene and isoprene Polyenes; vinyl chloride, vinyl chloride, vinyl bromide, fluoride Vinyl halides such as vinyl; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-methacrylate Α-methylene aliphatic monocarboxylic acid esters such as octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate Propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-acrylate Acrylic esters such as lorethyl and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole; N-vinyl compounds such as N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

  Further, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride Unsaturated dibasic acid anhydride; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, Alkenyl succinic acid half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester unsaturated dibasic acid half ester; dimethylmaleic acid, dimethyl fumaric acid unsaturated dibasic acid ester; acrylic acid, meta Α, β-unsaturated acids such as rillic acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic acid anhydride, the α, β-unsaturated acid and lower fatty acids And monomers having a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof.

  Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1) -Methylhexyl) Monomers having a hydroxy group such as styrene.

Further, the vinyl polymer unit of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. Examples of the crosslinking agent used in this case include divinylbenzene and divinylnaphthalene as aromatic divinyl compounds; examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate and 1,3-butylene glycol diene. Examples include acrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate and those obtained by replacing acrylate of the above compounds with methacrylate; ether Examples of diacrylate compounds linked by an alkyl chain containing a bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene, and the like. Glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate and the above compounds in which acrylate is replaced by methacrylate; diacrylates linked by chains containing aromatic groups and ether linkages Examples of the compounds include polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate and the like The thing which replaced the acrylate of the compound of this with the methacrylate is mentioned.

  As polyfunctional cross-linking agents, pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and acrylates of the above compounds are replaced by methacrylate; triallylcia Examples include nurate and triallyl trimellitate.

  The binder resin has a main peak in the molecular weight region of 3,500 to 30,000 in the molecular weight distribution measured by gel permeation chromatography (GPC), and preferably has a molecular weight of 5,000 to 20,000. It is preferable that Mw / Mn is 5.0 or more. When the main peak of the binder resin is in a region having a molecular weight of less than 3,500, the hot offset resistance of the toner is insufficient. On the other hand, when the main peak is in the region where the molecular weight exceeds 30,000, sufficient low-temperature fixability of the toner cannot be obtained, and application to high-speed fixing becomes difficult. Moreover, when Mw / Mn is less than 5.0, it becomes difficult to obtain good offset resistance.

  The glass transition temperature (Tg) of the binder resin contained in the toner of the present invention is preferably 40 to 90 ° C, more preferably 45 to 85 ° C. The acid value of the resin is preferably 1 to 40 mgKOH / g.

As a polymerization initiator used when producing a vinyl polymer used for a binder resin, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2, 4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate 1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4 -Dimethyl-4-methoxyvaleronitrile, 2,2'-azobis (2-methyl-propane), methyl ethyl ketone peroxide, acetylacetone peroxide, cyclo Ketone peroxides such as xanone peroxide, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroper Oxide, di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α, α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl Peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, -N-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t -Butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxylaurate, t-butyl peroxy Benzoate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxyisophthalate, t-butyl peroxyallyl carbonate, t-amyl peroxy 2-ethylhexanoate, di-t-butyl peroxyhexa Idro terephthalate, di -t- butyl peroxy azelate and the like.

Examples of the method for synthesizing the hybrid resin used in the toner of the present invention include the following production methods (1) to (5).
(1) A vinyl polymer, a polyester resin, and a hybrid resin component are respectively produced, dissolved and swollen in an organic solvent (for example, xylene), and then the organic solvent is distilled off. Hybrid resin component is synthesized by separately producing vinyl polymer and polyester resin, dissolving and swelling in a small amount of organic solvent, adding esterification catalyst and alcohol, heating and synthesizing. Can do.
(2) After the production of the vinyl polymer unit, the polyester unit and / or the hybrid resin component are reacted in the presence thereof.
(3) After producing the polyester unit, the vinyl polymer unit and / or the hybrid resin component are reacted in the presence of the polyester unit.
(4) After producing a vinyl polymer unit and a polyester unit, a vinyl monomer and / or a polyester monomer (alcohol, carboxylic acid) are reacted in the presence thereof.
(5) A vinyl monomer and a polyester monomer (alcohol, carboxylic acid, etc.) are mixed to perform addition polymerization and condensation polymerization reaction continuously.
In the production methods (1) to (5) above, the vinyl polymer unit and / or the polyester unit may have the same molecular weight and cross-linking degree, or may have a plurality of different molecular weights and cross-linking degrees. Polymer units can also be used.

  The release agent used in the toner of the present invention is not particularly limited as long as it is suitable for satisfying the physical property conditions of the toner of the present invention. Examples of the release agent include aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, olefin copolymers, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; aliphatic hydrocarbon waxes such as oxidized polyethylene wax. Oxides; block copolymers of aliphatic hydrocarbon waxes; waxes based on fatty acid esters such as carnauba wax, behenyl behenate and montanate wax; and partially or partially fatty acid esters such as deoxidized carnauba wax The thing which deoxidized all is mentioned.

  Examples thereof include a partially esterified product of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol; a methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils and the like. Particularly preferred waxes are aliphatic hydrocarbon waxes such as paraffin wax, polyethylene, and Fischer-Tropsch wax that have a short molecular chain and little steric hindrance and excellent fluidity.

  The molecular weight distribution of the release agent is preferably such that the main peak is in the region of molecular weight 350-2400, more preferably in the region of 400-2000. A toner containing a release agent having such a molecular weight distribution has favorable thermal characteristics. The addition amount of the release agent is 1 to 20 parts by mass, preferably 2 to 15 parts by mass with respect to 100 parts by mass of the binder resin.

  The colorant used for the toner particles constituting the toner of the present invention is not particularly limited as long as the physical properties of the toner of the present invention are satisfied, and known pigments and dyes can be used alone or in combination. Examples of the colorant include the following.

  Examples of the color pigment for magenta include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 202, 206, 207, 209, 238, C.I. I. Pigment violet 19, C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.

  Examples of the color pigment for cyan include C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 16, 17; I. Acid Blue 6; I. Examples thereof include Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.

  Examples of the color pigment for yellow include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 74, 83, 93, 97, 155, 180, 185, C.I. I. Bat yellow 1, 3, 20 etc. are mentioned.

  As the black pigment, for example, carbon black such as furnace black, channel black, acetylene black, thermal black, and lamp black is used. Also, magnetic powder such as magnetite and ferrite, or yellow / magenta / cyan shown above. / The thing etc. which were toned to black using a black coloring agent are mentioned.

  The content of the colorant is preferably 1 to 15 parts by mass, more preferably 3 to 12 parts by mass, and still more preferably 4 to 10 parts by mass with respect to 100 parts by mass of the binder resin. . When the content of the colorant is more than 15 parts by mass, the transparency is lowered, and in addition, the reproducibility of intermediate colors as typified by human skin color is likely to be lowered, and further, the chargeability of the toner is stabilized. And the low-temperature fixability becomes difficult to obtain. When the content of the colorant is less than 1 part by mass, the coloring power becomes low, and a large amount of toner must be used to obtain the density, which may be inferior in low-temperature fixability.

  The inorganic fine powder contained in the toner of the present invention is not particularly limited as long as the fluidity can be increased as compared with that before the addition by adding to the classified toner particles. For example, fluororesin powder such as vinylidene fluoride fine powder, polytetrafluoroethylene fine powder, titanium oxide fine powder, alumina fine powder, wet process silica, fine powder silica such as dry process silica, silane coupling agent, Any surface treated with a titanium coupling agent, silicone oil, etc. can be used.

For example, the dry process silica is a fine powder produced by vapor phase oxidation of a silicon halogen compound, which is called dry process silica or fumed silica, and is manufactured by a conventionally known technique. For example, a thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame is used, and the basic reaction formula is as follows.
SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl

  In this production process, it is also possible to obtain a composite fine powder of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride or titanium chloride together with silicon halogen compounds. . The average primary particle size is preferably in the range of 0.001 to 2 μm, particularly preferably silica fine powder in the range of 0.002 to 0.2 μm. .

  Further, it is more preferable to use a treated silica fine powder obtained by hydrophobizing a silica fine powder produced by vapor phase oxidation of the silicon halide compound.

  As a hydrophobizing method, it is applied by chemically treating with an organosilicon compound that reacts or physically adsorbs with silica fine powder. As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halogen compound is treated with an organosilicon compound.

  Examples of such organosilicon compounds are hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane. , Bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyl Dimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane 1,3-diphenyltetramethyldisiloxane, and dimethylpolysiloxane having 2 to 12 siloxane units per molecule and having one hydroxyl group in each of the terminal units of Si. These are used alone or in a mixture of two or more.

  As the inorganic fine powder used in the present invention, the above-described dry process silica treated with a coupling agent having an amino group or silicone oil may be used as necessary to achieve the object of the present invention. Absent. The fluidizing agent used in the present invention is used in an amount of 0.01 to 8 parts by weight, preferably 0.1 to 4 parts by weight, based on 100 parts by weight of toner particles.

  As described above, various inorganic fine powders can be used in the present invention. Among them, the fine powder surface is preferably treated with silicone oil, more preferably silica fine powder such as dry process silica. It is preferable to use a surface treated with silicone oil. This is because treatment with silicone oil enhances charge retention and makes it difficult for the charge to escape, so that a change in charge caused by leaving the toner is suppressed.

  Further, when using titanium oxide fine powder or alumina fine powder, which has a lower resistance than silica fine powder, it is desirable that these are preferably contained inside the toner outermost layer. This is because fine powder with low resistance is likely to release electric charge, and thus it is necessary to prevent electrification change caused by leaving the toner.

  As the inorganic fine powder, it is more preferable to use the above-mentioned silica fine powder in combination with a low-resistance titanium oxide fine powder and alumina fine powder. Charge-up etc. can be suppressed by using these together.

Further, a charge control agent can be further added to the toner of the present invention. Examples of the charge control agent include organometallic complexes, metal salts, and chelate compounds such as monoazo metal complexes, acetylacetone metal complexes, hydroxycarboxylic acid metal complexes, polycarboxylic acid metal complexes, and polyol metal complexes. Further, carboxylic acid derivatives such as metal salts of carboxylic acids, carboxylic acid anhydrides and esters, and condensates of aromatic compounds are also included. In addition, phenol derivatives such as bisphenols and calixarenes are also used. From the standpoint of charge rise, an aromatic carboxylic acid metal compound is preferably used. The addition amount of the charge control agent used in the toner of the present invention is 0.2 to 10 parts by mass, preferably 0.3 to 7 parts by mass with respect to 100 parts by mass of the binder resin. This is because if the amount is less than 0.2 parts by mass, it is difficult to sufficiently obtain the effect of improving the charge rise, and if the amount is more than 10 parts by mass, environmental fluctuation tends to increase.

  The toner of the present invention can be suitably used for nonmagnetic one-component development, but is more preferably used for a two-component developer. In this case, the toner is used by mixing with a magnetic carrier.

  Examples of the magnetic carrier include surface oxidized or unoxidized iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, rare earth metal particles, alloy particles thereof, oxide particles, ferrite and the like. A known carrier such as a resin carrier made by mixing these metals with a resin can be used without particular limitation. The coated carrier obtained by coating the surface of the magnetic carrier particles with a resin is particularly preferable in a developing method in which an AC bias is applied to the developing sleeve. As a coating method, a method in which a coating solution prepared by dissolving or suspending a coating material such as a resin in a solvent is adhered to the surface of the magnetic carrier core particle, and a method in which the magnetic carrier core particle and the coating material are mixed with powder. A conventionally known method can be applied.

  Examples of the coating material on the surface of the magnetic carrier core particle include silicone resin, polyester resin, styrene resin, acrylic resin, polyamide, polyvinyl butyral, and aminoacrylate resin. These are used alone or in plural. The treatment amount of the coating material is preferably 0.1 to 30% by mass (preferably 0.5 to 20% by mass) with respect to the carrier core particles. These carriers have an average particle diameter of 10 to 100 μm, preferably 20 to 70 μm.

  When a two-component developer is prepared by mixing the toner of the present invention and a magnetic carrier, the mixing ratio is usually 2 to 15% by mass, preferably 4 to 13% by mass, as the toner concentration in the developer. Good results are obtained. If the toner concentration is less than 2% by mass, the image density tends to decrease, and if it exceeds 15% by mass, fogging or in-machine scattering tends to occur.

Next, a method for producing the toner of the present invention will be described.
The toner of the present invention can be obtained using various methods. For example, as shown in Japanese Patent Application Laid-Open No. 2004-295100 by the present inventors, a method of increasing the circularity while preventing many release agents from existing on the surface is effective. In the present invention, a toner having the above physical properties was obtained by further improving the toner production method. Specifically, by reexamining the pulverization step in toner production, the toner having the above-mentioned aggregation degree can be obtained by making the fine irregularities on the toner surface uniform. However, this invention is not limited to the thing manufactured with this manufacturing method.

  In order to obtain the toner of the present invention, it is preferable that the pulverizing step includes a step of performing multistage pulverization near the desired particle size instead of making the particle size desired at once. By including such a step, the power of the pulverizer can be used not only as pulverization energy but also as energy for uniforming the unevenness of the toner particle surface. Further, it is preferable to include a step of increasing the circularity by increasing the residence time between the rotor and the liner of the finely pulverized product (simultaneous granulation classification). Thereby, Et100 and Etd / Et100, which are essential requirements of the present invention, can be controlled within a preferable range.

Hereinafter, the method for producing the toner of the present invention will be specifically described. First, in the raw material mixing step, as a toner internal additive, at least a resin, a release agent, and a colorant are mixed by mixing a predetermined amount of a charge control agent if necessary. Examples of the mixing apparatus include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, and a Nauter mixer.
Further, the toner raw material mixed as described above is melt-kneaded to melt the resins and disperse the colorant and the like therein. For melt kneading, for example, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. In recent years, single-screw or twin-screw extruders have become mainstream due to the advantage of being capable of continuous production. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type twin screw extruder manufactured by Toshiba Machine In general, a twin-screw extruder manufactured by Kay Sea Kay, a co-kneader manufactured by Buss, or the like is used. Furthermore, the colored resin composition obtained by melt-kneading the toner raw material is melt-kneaded, rolled with two rolls, etc., and cooled by water cooling or the like.

Next, in order to obtain toner particles, the cooling material of the colored resin composition is pulverized. Generally, the cooling material is only pulverized to a desired particle size, but in order to obtain the toner of the present invention, this pulverizing step may include a step of increasing the circularity of the toner particles. preferable. In the pulverization process, it is common to first roughly pulverize the toner particle raw material to about 1 to 3 mm, but pulverize them with a crusher, hammer mill, feather mill, etc. For example, the same operation is further performed to make a coarsely pulverized product of about 0.3 mm. This coarsely pulverized product is produced with a kryptron system manufactured by Kawasaki Heavy Industries, Ltd., a super rotor manufactured by Nissin Engineering Co., Ltd., a turbo mill manufactured by Turbo Industry, etc., and a medium pulverized product larger than a desired toner particle size, for example, about 6 μm is prepared. .
Furthermore, turbo mill (equipment improved to RS rotor / RSS liner) manufactured by Turbo Industry
(FIG. 4) is used to obtain a finely pulverized product having a desired toner particle diameter, for example, about 5 μm.
Unlike a conventional turbo mill, an RS rotor (FIG. 5) / RSS liner is used. As shown in FIG. 6, the inter-tooth distance L (FIG. 6) is set to 3 mm and the time between the teeth is shortened by making the shape of the grinding surfaces of the rotor 314 and the stator 310 of the mechanical pulverizer 301 short. Is considered to be short, and the residence time between the rotor and the liner will be long. It is considered that this long residence time increases the establishment of contact with the rotor liner per unit time, and contributes to the preparation of particles having a uniform high degree of circularity.

  Furthermore, in order to make the unevenness of the toner particle surface uniform, a spherical particle is simultaneously classified by using a fascia made by Hosokawa Micron Co., Ltd., thereby obtaining toner particles having a desired toner particle size, for example, about 5.5 μm while further improving the circularity. be able to. Thus, Et100 and Etd / Et100, which are essential requirements of the present invention, can be controlled within a preferable range by adjusting the surface properties while making the pulverization process multistage, and increasing the circularity in the final process.

By mixing a predetermined amount of the toner particles and the inorganic fine powder obtained in this way, using a high-speed stirrer that gives shearing force to the powder of a Henschel mixer, a super mixer, etc. The toner of the present invention can be obtained. When silica fine powder, titanium oxide fine powder, and alumina fine powder are used in combination as inorganic fine powder, use a high-speed stirrer as an external additive to mix titanium oxide fine powder, alumina fine powder, etc. with low resistance first. Then, it is preferable to further mix silica fine powder.
In this way, after adding and mixing the inorganic fine powder, a sieving machine such as a wind-type sieve high voltor (manufactured by Shin Tokyo Machinery Co., Ltd.) may be used as necessary.

  A method for measuring the physical properties of the toner of the present invention, toner particles constituting the toner, and raw materials will be described.

<Measurement of number average particle diameter (D1) of fine particles>
The number average particle diameter of the fine particles is binarized after taking a photograph of the surface of the toner particles magnified 100,000 times with a scanning electron microscope FE-SEM (S-4700, manufactured by Hitachi, Ltd.), adjusting the contrast of the image. . Further, the binarized image is further enlarged, and for each particle, for example, the major axis of the particle is measured for 50 particles using a ruler, caliper, etc., and the number average particle size is measured. At that time, the composition determination of the fine particles is performed by detecting only the specified specific element with the X-ray microanalyzer of the apparatus.

<Measurement of molecular weight of resin component of toner by GPC>
A solution obtained by dissolving the toner in tetrahydrofuran (THF) at room temperature for 24 hours is filtered through a solvent-resistant membrane filter having a pore diameter of 0.2 μm to obtain a sample solution, which is measured under the following conditions. In addition, sample preparation adjusts the quantity of THF so that the density | concentration of the component soluble in THF may be 0.4-0.6 mass%.
Equipment: High-speed GPC “HLC8120 GPC” (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: THF
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml

  In calculating the molecular weight of the sample, standard polystyrene resin (TSO standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F- manufactured by Tosoh Corporation) was used. 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500).

<Maximum endothermic peak measurement of toner>
Temperature curve: Temperature increase I (30 ° C. to 200 ° C., temperature increase rate 10 ° C./min)
Temperature drop I (200 ° C-30 ° C, temperature drop rate 10 ° C / min)
Temperature increase II (30 ° C. to 200 ° C., temperature increase rate 10 ° C./min)
The maximum endothermic peak of the toner is measured according to ASTM D3418-82 using a differential scanning calorimeter (DSC measuring device), DCS-7 (manufactured by Perkin Elmer) or DSC2920 (manufactured by TA Instruments Japan).
A measurement sample is accurately weighed in an amount of 5 to 20 mg, preferably 10 mg, and placed in an aluminum pan. Use an empty aluminum pan as a reference. The measurement is carried out at a temperature rise rate of 10 ° C./min at room temperature and humidity in the measurement range of 30 to 200 ° C. The maximum endothermic peak of the toner has the highest peak height from the baseline in the temperature range II in the temperature range equal to or higher than Tg of the measurement sample. When the endothermic peak of Tg overlaps with other endothermic peaks, and the maximum endothermic peak is difficult to distinguish, the endothermic peak including the overlapping endothermic peaks is the one with the highest peak height from the baseline as the maximum endothermic peak. To do.

<Measurement of molecular weight of release agent>
Apparatus: GPC-150C (Waters)
Column: GMH-HT 30 cm, 2 stations (manufactured by Tosoh Corporation)
Temperature: 135 ° C
Solvent: o-dichlorobenzene (0.1% by mass ionol added)
Flow rate: 1.0 ml / min
Sample: 0.4 ml injection of 0.15% by weight of mold release agent Measured under the above conditions, a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used for calculating the molecular weight of the mold release agent. Furthermore, the molecular weight of the release agent is calculated by converting to polyethylene based on a conversion formula derived from the Mark-Houwink viscosity formula.

<Method for measuring softening point of resin>
In JIS K 7210, it refers to that measured by an elevated flow tester. A specific measurement method is shown below. While heating a 1 cm ³ sample at a heating rate of 6 ° C./min using an elevated flow tester (manufactured by Shimadzu Corporation), 1960 N / m ² (
20 kg / cm ² ) is applied and a nozzle with a diameter of 1 mm and a length of 1 mm is pushed out, whereby a plunger drop (flow value) -temperature curve is drawn, and the height of the S-curve is h. In this case, the temperature corresponding to h / 2 (the temperature at which half of the resin flows out) is defined as the softening point (Tm) of the resin.

<Toner particle size distribution measurement>
In the present invention, the average particle size and particle size distribution of the toner use the Golter principle. As the measuring device, a Coulter counter TA-II type (manufactured by Coulter) is used, but a Coulter multisizer (manufactured by Coulter) can also be used. As the electrolytic solution, a 1% NaCl aqueous solution is prepared using primary sodium chloride. For example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used.
As a measuring method, 0.1 to 5 ml of a surfactant, preferably alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion process for about 1 to 3 minutes with an ultrasonic disperser, and the volume and the number of toners of 2.00 μm or more are measured by using the 100 μm aperture as the aperture by the measuring device. Distribution and number distribution are calculated. Then, the weight average particle diameter (D4) (the median value of each channel is used as a representative value for each channel) according to the present invention is obtained.

  As channels, 2.00 to 2.52 μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm; 4.00 to 5.04 μm; 5.04 to 6.35 μm; 6.35 to 8. 00 μm; 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 20.20 μm; 20.20 to 25.40 μm; 25.40 to 32.00 μm; 13 channels of 32.00-40.30 μm are used.

  The present invention will be described below with reference to examples, but the present invention is not limited to the examples. In addition, all the parts used in an Example show a mass part.

(Example of hybrid resin production)
As monomers for forming a vinyl copolymer unit, styrene 2.0 mol, 2-ethylhexyl acrylate 0.21 mol, fumaric acid 0.14 mol, α-methylstyrene dimer 0.03 mol, dicumyl peroxide 0.05 mol In a dropping funnel. Moreover, as a monomer which forms a polyester resin unit, 7.0 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane (3.0 mol), terephthalic acid (3.0 mol), trimellitic anhydride (1.9 mol), fumaric acid (5.0 mol) and dibutyltin oxide (0.2 g) were placed in a glass 4-liter four-necked flask. A thermometer, a stirring rod, a condenser and a nitrogen introduction tube were attached and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually increased while stirring, and while stirring at a temperature of 145 ° C., the monomer of the vinyl resin, the crosslinking agent and the polymerization initiator were added from the previous dropping funnel. It was dripped over 4 hours. Next, the temperature was raised to 200 ° C. and reacted for 4 hours to obtain a hybrid resin (Tm = 110 ° C.). The results of molecular weight measurement by GPC are shown in Table 1.

(Example of polyester resin production)
3.6 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 1.6 mol of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 1.7 mol of terephthalic acid, 0.1 mol of trimellitic anhydride, 2.4 mol of fumaric acid and 0.12 g of dibutyltin oxide are placed in a 4-liter 4-neck flask made of glass, a thermometer, a stir bar, a condenser and a nitrogen inlet tube Was installed in a mantle heater. Under a nitrogen atmosphere, the mixture was reacted at 215 ° C. for 5 hours to obtain a polyester resin (Tm = 95 ° C.). The results of molecular weight measurement by GPC are shown in Table 1.

<Example 1>
Toner 1 was produced as shown below.
-60 mass parts of said hybrid resin * 40 mass parts of cyan pigments (PigmentBlue 15: 3) It melt-kneaded with the kneader mixer by said prescription, and produced the cyan masterbatch. -91 parts by mass of the above hybrid resin-Purified normal paraffin (maximum endothermic peak temperature 70 ° C, Mw = 450, Mn = 320)
5 parts by mass · Cyan masterbatch (40% by mass for coloring) 15 parts by mass

Preliminarily mixed with a Henschel mixer with the above formulation, melt-kneaded so that the kneaded product temperature becomes 150 ° C. with a twin screw extruder kneader, after cooling, coarsely pulverized to about 1 to 3 mm using a hammer mill, The hammer shape was changed again, and a coarsely pulverized product was made to about 0.3 mm using a hammer mill with fine mesh. Further, a medium pulverized product was made to about 11 μm using a turbo mill (RS rotor / SNB liner) manufactured by Turbo Industry. Further, a medium pulverized product was made to about 6 μm using a turbo mill (RSS rotor / RSS liner) manufactured by Turbo Industry. Using a turbo mill (RSS rotor / RSS liner) again, a finely pulverized product was made to about 5 μm. Next, cyan particles 1 (toner particles) were obtained by performing spheronization at the same time as classification using a factory made by Hosokawa Micron with an improved hammer shape and the like.

Based on 100 parts by mass of the cyan particles 1 (toner particles), 0.6 parts by mass of anatase-type titanium oxide fine powder (BET specific surface area = 100 m ² / g, treated with 12% by mass of isobutyltrimethoxysilane), based on the number distribution First, 1.5 parts by mass of hydrophobized silica having a maximum peak particle size of 100 nm was externally added by a Henschel mixer, and further oil-treated silica (BET specific surface area 200 m ² / g, treated with 18% by mass of silicone oil) 1.2 mass Toner 1 was added by external addition using a Henschel mixer. The toner 1 has a weight average diameter of 5.5 μm and has the physical properties shown in Table 2.

  Further, toner 1 and magnetic ferrite carrier particles (average particle size 38 μm: Mn—Mg ferrite) surface-coated with a silicone resin are mixed so that the toner concentration becomes 8.0% by mass, and a two-component developer. It was set to 1.

  Under the above conditions, an image with a printing ratio of 30% in a single color mode in a room temperature and low humidity environment (23 ° C./5%) is intermittently printed in a 1000-sheet intermittent mode (that is, every 1000 print-outs, the developer is stopped for 10 seconds. In this mode, 100000 sheets were printed out in a mode in which the amount of replenished toner was large and toner deterioration was confirmed during long-term use), and the following items were evaluated at the initial and 100,000 times. A cyan image that faithfully reproduces the original image without fogging even after durability was formed. In addition, the image density was stable and high even after the endurance. Also, the level of roughness of the HT image was good before and after endurance. The evaluation results are shown in Table 3.

(1) Fog measurement
Using an IRC-3200 (Canon copier), 1000 sheets of printing durability test is evaluated using an original document with an image area ratio of 5% in a single color mode in a normal temperature and low humidity environment (23 ° C./5%). In the durability test, the method for measuring fog is as follows. First, in the case of a cyan image, the average reflectance Dr (%) of plain paper before image printing is measured with a reflectometer (“REFECTOMETER MODEL TC-6DS” manufactured by Tokyo Denshoku Co., Ltd.) equipped with an amber filter. . On the other hand, a solid white image is drawn on plain paper, and then the reflectance Ds (%) of the solid white image is measured. Using these measured values, fog (Fog [%]) is obtained by the following formula (2).
Fog [%] = Dr [%] − Ds [%] (2)
(Evaluation criteria)
A: Less than 0.7% and excellent B: 0.7% or more, less than 1.2%, good C: 1.2% or more, less than 1.5%, no practical problem D: 1.5% or more, Less than 2.0% has practical problems E: Poor at 2.0% or more

(2) Image density
IRC-3200 (manufactured by Canon Inc.) was used to output a solid image at the end of the durability evaluation in the image output test using a normal copying machine plain paper (75 g / m ² ) transfer material and measure its density. It was evaluated by doing. The image density was measured by using a “Macbeth reflection densitometer RD918” (manufactured by Macbeth Co., Ltd.) to measure the relative density with respect to an image of a white background portion having a document density of 0.00.
(Evaluation criteria)
A: Very good 1.40 or more B: Good 1.35 or more, less than 1.40 C: No problem in practical use 1.00 or more, less than 1.35 D: Somewhat difficult Less than 1.00

(3) Roughness of halftone image In order to evaluate the balance between fluidity and chargeability of the toner, the uniformity of the halftone image output after printing three solid images was visually determined.
(Evaluation criteria)
A: Very good Image uniformity is very excellent and extremely clear image B: Good Image uniformity is excellent and good image C: No problem in practical use Image quality D: no problem in practical use Image uniformity is poor and is not practically desirable

<Example 2>
In Example 1, a toner 2 was obtained in the same manner as in Example 1 except that a turbo mill (RSS rotor / RSS liner) was used to obtain a medium pulverized product of about 11 μm. Various evaluations were made in the same manner as in Example 1. As shown in Table 3, although fog was slightly inferior, it was a favorable result.

<Example 3>
In Example 1, as a fine powder to be processed to 100 parts by weight of toner particles, 2.0 parts by mass of hydrophobized silica having an average particle size of 100 nm was added to oil-treated silica (BET specific surface area 200 m ² / g, silicone oil 18). Toner 3 was obtained in the same manner as in Example 1 except that (mass% treatment) was changed to 1.5 parts by mass. Various evaluations were made in the same manner as in Example 1. As shown in Table 3, although the HT image was slightly inconsistent, the result was good.

<Example 4>
In Example 1, when a medium pulverized product of about 6 μm is obtained, the toner 4 is changed in the same manner as in Example 1 except that it is changed to a turbo mill (RS rotor / SNB liner) manufactured by Turbo Industries.
Got. Various evaluations were made in the same manner as in Example 1. As shown in Table 3, although fog was slightly inferior, it was a favorable result.

<Example 5>
In Example 1, a toner 5 was obtained in the same manner as in Example 1 except that the spheronization treatment was performed three times with the Faculty of Hosokawa Micron having an improved hammer shape and the like. Various evaluations were made in the same manner as in Example 1. As shown in Table 3, although the HT image was slightly inconsistent, the result was good.

<Example 6>
In Example 1, a toner 6 was obtained in the same manner as in Example 1 except that the hybrid resin was changed to the polyester resin. When various evaluations were made in the same manner as in Example 1, as shown in Table 3, all results were satisfactory with respect to fogging, image density, and roughness of the HT image.

<Example 7>
In Example 1, Toner 7 was obtained in the same manner as in Example 1 except that the hydrophobized silica having a maximum peak particle size of 100 nm based on the number distribution was changed to a maximum peak particle size of 82 nm based on the number distribution. . Various evaluations were made in the same manner as in Example 1. As shown in Table 3, the results were good as in Example 1.

<Example 8>
In Example 1, a toner 8 was obtained in the same manner as in Example 1 except that the hydrophobically treated silica having a maximum peak particle size of 100 nm based on the number distribution was changed to a maximum peak particle size of 165 nm based on the number distribution. . Various evaluations were made in the same manner as in Example 1. As shown in Table 3, although fog and image density were slightly inferior, they were good results.

<Comparative Example 1>
In Example 1, after obtaining toner particles without performing the process of obtaining a medium pulverized product, anatase-type titanium oxide fine powder (BET specific surface area = 100 m ² ) with respect to 100 parts by mass of the cyan particles 1 (toner particles). / G, 12 parts by mass of isobutyltrimethoxysilane) and 1.0 part by mass of hydrophobized silica having an average particle size of 100 nm were first externally added using a Henschel mixer, and further oil-treated silica (BET ratio) Toner 9 was obtained by adding 2.0 parts by mass of a surface area of 200 m ² / g and a treatment of 18% by mass of silicone oil, and externally adding it using a Henschel mixer. The toner 9 had a weight average diameter of 7.2 μm and had physical properties as shown in Table 2.
When various evaluations were made in the same manner as in Example 1, the fog was poor as shown in Table 3, and the image density and the level of HT roughness were inferior.

<Comparative example 2>
560 parts by mass of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 250 parts by mass of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 300 parts by mass of terephthalic acid and 2 parts by mass of dibutyltin oxide were placed in a 4-liter four-necked flask made of glass. A thermometer, a stirring rod, a condenser and a nitrogen introducing tube were attached to this four-necked flask and placed in a mantle heater. The reaction was carried out at 230 ° C. for 7 hours under a nitrogen atmosphere. Then, it cooled to 160 degreeC, 30 mass parts of phthalic anhydride was added, and it was made to react for 2 hours.
It was then cooled to 80 ° C. A solution prepared by dissolving 180 parts by mass of isophorone diisocyanate in 1000 parts by mass of ethyl acetate (preliminarily heated to 80 ° C.) was put into the above solution and reacted for 2 hours.
Furthermore, it cooled to 50 degreeC, 70 mass parts of isophoronediamine was added, and it was made to react for 2 hours, and the urea modified polyester resin was obtained. The urea-modified polyester resin had a weight average molecular weight of 60,000 and a number average molecular weight of 5,500.
-Urea-modified polyester resin 100 parts by mass-Ester wax (maximum endothermic peak temperature 72 ° C) 7 parts by mass-Aluminum compound 3,5-di-t-butylsalicylate 1 part by mass-C.I. I. Pigment Blue 15: 3 5 parts by mass The above materials are added to 100 parts by mass of ethyl acetate, heated to 60 ° C., and uniformly dissolved and dispersed at 12,000 rpm using a TK homomixer (manufactured by Special Machine Industries). did.
On the other hand, 450 parts by mass of 0.12M-Na ₃ PO ₄ aqueous solution was added to 710 parts by mass of ion-exchanged water, heated to 60 ° C., and then TK-type homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), 15, Stir at 000 rpm. To the obtained aqueous solution, 68 parts by mass of 1.2M-CaCl ₂ aqueous solution was gradually added to prepare an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .
The above-mentioned dispersion liquid was put into the obtained aqueous medium, and the obtained liquid mixture was granulated by stirring at 15,000 rpm for 10 minutes at 60 ° C. using a TK homomixer. Thereafter, the temperature was raised to 98 ° C. while stirring with a paddle stirring blade, the solvent was removed, and after cooling, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ . The resulting mixture was filtered, and the filtered product was washed with water and dried to obtain particles. The obtained particles were classified by wind to obtain cyan particles.
The resulting cyan particles were subjected to the same external addition treatment as in Example 1 to obtain toner 10. When various evaluations were made in the same manner as in Example 1, the image density deteriorated as shown in Table 3, and toner spent was observed on the carrier surface.

<Comparative Example 3>
The following materials were mixed and dissolved to obtain an organic solution.
Styrene 87 parts by mass nbutyl acrylate 13 parts by mass acrylic acid 3 parts by mass dodecanethiol 6 parts by mass carbon tetrabromide 1 part by mass Nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd .: Nonipol 400) ) 1.5 parts by mass and 2.5 parts by mass of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) were dissolved in 140 parts by mass of ion-exchanged water in a flask. The organic solution was added to the obtained aqueous solution, dispersed and emulsified, and slowly mixed for 10 minutes.
To the obtained mixture, 10 parts by mass of ion-exchanged water in which 1 part by mass of ammonium persulfate was dissolved was added to perform nitrogen substitution. While stirring the inside of the flask, the contents were heated in an oil bath until the temperature reached 70 ° C., and emulsion polymerization was continued as it was for 5 hours to prepare a resin particle dispersion 1. The number average particle diameter of the particles contained in the resin particle dispersion 1 was 0.15 μm.
The following materials were mixed and dissolved to obtain an organic solution.
-Styrene 75 parts by mass-n-butyl acrylate 25 parts by mass-Acrylic acid 3 parts by mass On the other hand, 1.5 parts by mass of a nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd .: Nonipol 400) and an anionic surfactant ( 3 parts by mass of Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) was dissolved in 150 parts by mass of ion-exchanged water in a flask to obtain an aqueous solution. The organic solution was added to the obtained aqueous solution, dispersed and emulsified, and slowly mixed for 10 minutes.
While mixing, 10 parts by mass of ion-exchanged water in which 0.8 part by mass of ammonium persulfate was further dissolved was added to perform nitrogen substitution. While stirring the inside of the flask, the content was heated in an oil bath until the temperature reached 70 ° C., and emulsion polymerization was continued for 5 hours to prepare a resin particle dispersion 2. The number average particle diameter of the particles contained in the resin particle dispersion 2 was 0.12 μm.
The following materials are mixed, heated to 97 ° C., dispersed using a homogenizer (IKA: Ultra Turrax T50), and further dispersed using a pressure discharge homogenizer to prepare a release agent particle dispersion. did.
Paraffin wax (melting point 95 ° C.) 45 parts by mass Anionic surfactant 5 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
-Ion-exchanged water The number average particle size of the release agent particles in the 200 parts by mass dispersion was 0.42 µm.
A colorant dispersion was prepared by dispersing the following materials using a sand grinder mill.
・ C. I. Pigment Blue 15: 3 12 parts by mass / Anionic surfactant 2 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
-Ion-exchange water 78 mass parts The following material obtained by processing as mentioned above was thrown into the reaction container equipped with the stirring apparatus, the cooling tube, and the thermometer, and was stirred.
-150 parts by weight of the resin particle dispersion 1-210 parts by weight of the resin particle dispersion 2-40 parts by weight of the colorant dispersion-70 parts by weight of the release agent dispersion 70 parts by weight of this mixture using 1N potassium hydroxide The pH was adjusted to 5.5.
150 parts by mass of a 10% sodium chloride aqueous solution as a flocculant was dropped into the obtained mixed liquid, and the flask was heated to 70 ° C. while stirring in the heating oil bath. While maintaining this temperature, 3 parts by mass of the resin particle dispersion 2 was further added. After maintaining the obtained solution at 60 ° C. for 1 hour, after adding 3 parts by mass of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC), the stainless steel reaction vessel was sealed, The mixture was heated to 90 ° C. while continuing stirring using a magnetic seal and held for 3 hours.
After cooling, the reaction product was filtered, and the resulting filtered product was sufficiently washed with ion-exchanged water and then dried to obtain cyan particles.
Thereafter, external addition treatment was performed in the same manner as toner 1 to obtain toner 11. Various evaluations were made in the same manner as in Example 1. As shown in Table 3, the fog was bad.

It is a front view of the 48 mm diameter blade only for powder fluidity analyzer RH-4 powder rheometer measurement (photo). It is a side view of a 48 mm diameter blade for exclusive use of powder rheometer FT-4 measurement (powder). It is a graph of Etd / Et100 relationship between the number of Et100 measurements after aeration stop. 1 is a schematic cross-sectional view of an example of a mechanical pulverizer used in a toner pulverization step of the present invention. It is a perspective view of the rotor shown in FIG. It is an enlarged view of the rotor shown in FIG.

Explanation of symbols

212: Swirl chamber 219: Pipe 220: Distributor 222: Bag filter 224: Suction blower 229: Collection cyclone 301: Mechanical pulverizer 302: Powder discharge port 310: Stator 311: Powder input port 312: Rotation Shaft 313: Casing 314: Rotor 315: First metering feeder 316: Jacket 317: Cooling water supply port 318: Cooling water discharge port 320: Rear chamber L: Interdental distance

Claims (1)

And at least a binder resin to obtain a colored resin composition a release agent及 beauty colorant are melt-kneaded, and the toner particles obtained through the step of pulverizing the colored resin composition,
A toner for organic and inorganic fine powder,
The number average particle diameter (D1) of the inorganic fine powder is 80 nm or more and 200 nm or less,
Obtained by analyzing the circularity of toner particles measured by a flow type particle image measuring apparatus with an equivalent circle diameter of 2.00 μm or more and 200.00 μm or less divided into 800 in a circularity range of 0.2 to 1.0. The toner particles have an average circularity of 0.950 or more and 0.987 or less,
The toner has a weight average particle diameter of 4.0 μm or more and 6.5 μm or less,
The toner satisfying the following relational expressions (1) and (2):
100 ≦ Et100 (mJ) ≦ 350 (1)
0.10 ≦ Etd / Et100 ≦ 0.50 (2)
(Et100 in the formula (1) and (2) (mJ) is powder flowability analyzing outermost edge of the propeller blade peripheral speed 1 while rotating at 300 mm / sec toner powder layer in the container in the device The measurement is started from a position 100 mm from the bottom surface of the powder layer, and the sum of the rotational torque and the vertical load obtained when the measurement is entered to a position 10 mm from the bottom surface, Etd in 2) is placed a porous plate in the container bottom, after the measurement of the Et100 while venting the dry air from which the flow rate 0.48 (m m / sec), to stop the aeration, the The measurement is repeated four times in the manner of measuring Et100, and represents the sum of the rotational torque and the vertical load obtained by the fourth measurement.)

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