JP2019095616A - Method for manufacturing toner - Google Patents

Abstract

To provide a manufacturing method with which in externally adding and mixing an external additive, the external additive can be firmly fastened to the surface of toner, and high fluidity can be maintained and cracks and chipping of toner can be prevented.SOLUTION: A method for manufacturing a toner includes a processing step of processing a mixture having toner particles containing a binder resin and colorant and an external additive. The external additive is inorganic fine particles or organic-inorganic composite fine particles; a processing device has a stirring member 31, a cylindrical container, and a driving unit 38; a plurality of stirring blades include a first stirring blade for feeding an introduced mixture in one direction and a second stirring blade for feeding the mixture in the other direction; the peripheral velocity V of the stirring blades 33 is 0.1 m/sec or more and 7.0 m/sec or less; in the processing step, the mixture is heated and mixed; an initial temperature T1 at the start of heating and mixing and the glass transition temperature T2 of the mixture satisfy the formula (1); the energy for heating and mixing processing E(Wh/g) satisfies the formula (2). (1) T2-10°C≤T1≤T2+10°C, and (2) 1.0×10Wh/g≤E≤1.5×10Wh/g.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method of producing a toner used in a recording method such as an electrophotographic method.

In recent years, electrophotographic apparatuses such as copying machines and printers have been widely spread worldwide, and are used in various environments indoors and outdoors. It is a time when longer life and smaller size are required while responding to such various environments.
In order to achieve long life, it is important to suppress changes in toner durability. Examples of means for suppressing the change in durability include adding inorganic fine particles having a large particle size as inorganic fine particles externally added to the surface of toner particles, or firmly fixing the inorganic fine particles.
Unlike the inorganic fine particles having a large particle size, the inorganic fine particles having a large particle size are unlikely to be embedded with an external additive on the toner surface, for example, due to stress with a toner conveyance member or a control blade. However, on the other hand, adhesion to toner particles tends to be insufficient, and when stirring is continued for a long time in an apparatus such as a printer, the toner particles move from one particle to another due to the strong stress and lose their function as spacer particles. There is.
The migration of such large particle size inorganic fine particles from the toner particles is caused by adhesion of the liberated inorganic fine particles on the developing roller after printing on a large number of sheets with a printer or the like in a high temperature and high humidity environment. There is a concern that the toner may be fused.
On the other hand, if a part of the large-diameter inorganic fine particles is buried and strongly fixed, there is a possibility that the fluidity imparting ability of the spacer particles, that is, the so-called bearing effect may be reversed. As a result, the fluidity of the toner is lowered, so that rubbing between the regulating member and the toner carrier can not be uniformly performed. Therefore, the phenomenon that the effective and uniform charging becomes insufficient in a high temperature and high humidity environment, the image density decreases, and a toner having a low charge amount is developed to a non-image area on the electrostatic latent image carrier So-called fog may occur.
Next, when focusing on miniaturization, miniaturization of the process cartridge containing the developer is effective for miniaturization. One of the effective means for miniaturizing the process cartridge is the use of a cleanerless system.
Most printers use a cleaner system, and in the transfer step, toner remaining on the electrostatic latent image carrier (hereinafter, transfer residual toner) is scraped off from the electrostatic latent image carrier by a cleaning blade. , Collected in the waste toner box.
On the other hand, since the cleanerless system does not have the cleaning blade and the waste toner box, it can greatly contribute to the downsizing of the main body.
However, in order to adopt a cleanerless system for a printer, the performance required for toner is also large. For example, since there is no cleaning blade, the transfer residual toner passes through the charging process, is collected in the toner container, and is sent to the developing process again. Therefore, the stress applied to the toner is greater than in a device having a cleaning blade, and the toner is more likely to be cracked or crushed, and further, problems associated with liberation or embedding of the inorganic fine particles and the like. The cracking and crushing of the toner occur notably in a condition in which members such as the toner carrier and the regulating blade become hard under a low temperature and low humidity environment, and in a contact development system. As a result, the particle size distribution is degraded, and the adhesion to the electrostatic latent image carrier or the like is increased, and the transfer efficiency may be degraded through long-term use.
Various methods for producing toners have been proposed as solutions to the above problems.
For example, in Patent Document 1, a mixing having a shaft-like member capable of rotating, a plurality of stirring members provided on the surface of the shaft-like member, and a casing capable of covering the plurality of stirring members A method has been proposed in which particles of 100 nm or more are uniformly coated and immobilized on the surface of toner particles using a method.
Further, Patent Document 2 proposes a manufacturing method in which adhesion of fine particles to the toner surface is controlled by controlling the amount of power per unit mass consumed when performing external additive mixing.
Further, in Patent Document 3, a stirring blade having a stirring tank, a rotation driving shaft and a stirring blade, and fixed to the rotation driving shaft penetrating the bottom wall of the stirring tank is disposed at the bottom of the stirring tank. There has been proposed an apparatus in which a metal ring on which a plurality of deflectors are fixed is arranged to be suspended from the top of a stirring vessel. It is described that this apparatus configuration can strongly fix large particle size external additives such as spacer particles.

JP, 2012-063636, A JP, 2013-029790, A JP 2012-212062 A

However, in the device configurations as described in Patent Documents 1 and 2 and in the device conditions, it may be insufficient to cause the inorganic particles of large particle diameter to be strongly fixed. There is a possibility that stress may build up and cracking may be promoted.
Moreover, although it is possible to fix the large particle size external additive under the apparatus configuration and the apparatus conditions as described in Patent Document 3, the glass transition point (Tg of the resin component contained in the toner at the material temperature during operation) As a result, there is a possibility that fusion and coarse particles may occur in the aircraft. In addition, since the inorganic fine particles are embedded in the toner strongly while being embedded at high speed because they collide with the stirring blade and the deflector at a high speed, there is a possibility that the flowability is deteriorated. In addition, the high-speed collision with the agitating blade and the deflector tends to cause residual stress to be stored, which may promote the breakage and breakage of the toner.
Therefore, there is still room for improvement in achieving both the fixation of the external additive and the maintenance of high fluidity and the resistance to cracking and chipping.
The object of the present invention is to allow the external additive to be firmly fixed to the toner surface without being buried in the toner surface when the external additive is added and mixed, and it is possible to achieve both high flowability and suppression of cracking of the toner It is to provide a manufacturing method.

The present invention relates to a method for producing a toner having toner particles containing a stirring binder resin and a colorant, and an external additive,
The external additive is inorganic fine particles or organic-inorganic composite fine particles,
Processing the mixture containing the toner particles and the external additive;
The processing apparatus used in the processing step is
A stirring member having a rotating body and a plurality of stirring blades provided on a surface of the rotating body;
A container whose inner peripheral surface accommodates the stirring member is cylindrical, and a driving unit for applying a rotational driving force to the rotating body to rotate the stirring member in the container,
Have
Each of the plurality of stirring blades is provided to have a gap with the inner circumferential surface of the container,
A plurality of stirring blades for causing the mixture introduced into the container by rotation of the stirring member to move in a first axial direction of the rotating body; And a second stirring blade for feeding in the other axial direction,
The circumferential velocity V of the plurality of stirring blades when rotating the stirring member in the treatment step is 0.1 m / sec or more and 7.0 m / or less,
In the processing step, the mixture is heated and mixed, and when the material temperature of the mixture at the start of the heating and mixing is T1 and the glass transition temperature of the toner particles is T2, the following formula (1) is satisfied:
The present invention relates to a method for producing a toner, which satisfies the following formula (2), where E (Wh / g) is the mixing treatment energy at the time of the heating and mixing.
T2-10 ° C. ≦ T1 ≦ T2 + 10 ° C. (1)
1.0 × 10 ⁻⁴ Wh / g ≦ E ≦ 1.5 × 10 ⁻² Wh / g (2)

  According to the present invention, it is possible to provide a manufacturing method capable of firmly holding the inorganic fine particles on the toner surface while externally adding and mixing the external additive, and maintaining high flowability and suppressing cracking of the toner. .

It is a schematic diagram which shows an example of the mixing processing apparatus which can be used for the external addition mixing of an external additive. It is a schematic diagram which shows an example of a structure of the stirring member used for a mixing treatment apparatus. It is the schematic which shows the mixing processing apparatus used by the heating and mixing process of Comparative Examples 6 and 7.

  As described above, in order to simultaneously achieve the long life and the miniaturization which are required for the printer in recent years, the strong fixing of the external additive (in particular, the large particle size inorganic fine particles) which functions as a spacer particle as a toner It is important to maintain high fluidity and improve crack and chip resistance. The present inventors first examined the strong fixation of the external additive.

  As a means for achieving strong adherence of external additives, the technology that has been advanced conventionally is mainly by improving the impact force and shear force between toner and agitating blades, toner and toner in an external additive mixing processing apparatus. It is a thing.

  As a result of investigations by the present inventors, it was found that adhesion due to collision or shear between the toner and the stirring blade and between the toner and the toner simultaneously causes detachment of the external additive from the toner surface. That is, it was found that the fixation of the external additive to the surface of the toner particle proceeds while repeating the fixation and the detachment.

  Therefore, in order to further promote the fixation, in order to increase the chance of collision with the stirring blade, it was studied to increase the external mixing time, to rotate the stirring blade at high speed, and to use an external heating means.

  As a result, even if the external mixing time was increased and the stirring blade was rotated at high speed, it was not changed that sticking and detachment occurred simultaneously. Therefore, it has been found that while the embedding significantly progresses in a part of the toner 1 particles, in some parts, the part which is insufficiently embedded exists due to the elimination step. As a result, although the fixing level is increased in the toner in the processing apparatus as a whole, when it is embedded, the fluidity may be reduced or the external additive state may be likely to be uneven. Furthermore, it was found that the residual stress was accumulated inside the toner particles as a result of the increase in the number of collisions and the strength between the toner and the agitating blade, and as a result, the problem of reduction in cracking resistance also occurred. .

  On the other hand, it was found that the surface of the toner particles was softened and fixation of the external additive proceeded by using a means for applying heat near the glass transition temperature (Tg) of the toner particles from the outside. However, due to the heat applied locally, in some cases, the embedding is greatly promoted, and the problem of a decrease in fluidity occurs.

  From the above, when it is attempted to strongly fix the external additive in the external addition mixing tank by the concept of adhering the conventional external additive, it is possible to achieve both the high fluidity and the improvement of the cracking resistance. Things have been difficult so far.

  Therefore, the present inventors diligently study a method for producing a toner in order to maintain high flowability and improve crack and chip resistance by strongly fixing without embedding external additives. Did. As a result, it has been found that the above problem can be solved by adopting the following configuration.

That is, the present invention is a method for producing a toner having toner particles containing a binder resin and a colorant, and an external additive,
The external additive is inorganic fine particles or organic-inorganic composite fine particles,
Processing the mixture containing the toner particles and the external additive;
The processing apparatus used in the processing step is
A stirring member having a rotating body and a plurality of stirring blades provided on a surface of the rotating body;
A container whose inner peripheral surface accommodates the stirring member is cylindrical, and a driving unit for applying a rotational driving force to the rotating body to rotate the stirring member in the container,
Have
Each of the plurality of stirring blades is provided to have a gap with the inner circumferential surface of the container,
A plurality of stirring blades for causing the mixture introduced into the container by rotation of the stirring member to move in a first axial direction of the rotating body; And a second stirring blade for feeding in the other axial direction,
The circumferential velocity V of the plurality of stirring blades when rotating the stirring member in the treatment step is 0.1 m / sec or more and 7.0 m / or less,
In the processing step, the mixture is heated and mixed, and when the material temperature of the mixture at the start of the heating and mixing is T1 and the glass transition temperature of the toner particles is T2, the following formula (1) is satisfied:
When the mixing process energy at the time of the heating and mixing is E (Wh / g), the following formula (2) is satisfied.
T2-10 ° C. ≦ T1 ≦ T2 + 10 ° C. (1)
1.0 × 10 ⁻⁴ Wh / g ≦ E ≦ 1.5 × 10 ⁻² Wh / g (2)

  The mixing and treating apparatus used in the present invention will be described with reference to FIGS. FIG. 1 is a schematic view showing an example of a mixing treatment apparatus used in the present invention, and FIG. 2 is a schematic view showing an example of a configuration of a stirring member used in the mixing treatment apparatus.

  The mixing processing apparatus has a stirring member 31 mainly composed of a rotating body 32 on the surface of which at least a plurality of stirring blades 33 are installed, a drive unit 38 for rotationally driving the rotating body, a stirring blade 33 and a gap. And the main body casing 30 provided.

  As shown in FIG. 2, at least a part of the plurality of stirring blades 33 sends the toner in one axial direction of the rotating member as the rotating member 32 rotates (first stirring blade) It is formed as 33a. Further, at least a part of the plurality of stirring blades 33 is formed as a returning stirring blade (second stirring blade) 33 b for returning the toner in the other axial direction of the rotating member 32 as the rotating member 32 rotates. There is. Here, as shown in FIG. 1, when the raw material inlet 35 and the product outlet 36 are provided at both ends of the main casing, the direction from the raw material inlet 35 toward the product outlet 36 (right in FIG. 1) Direction) is called "feed direction".

  That is, as shown in FIG. 2, the plate surface of the first stirring blade 33 a is inclined to feed the toner in the feed direction 43. On the other hand, the plate surface of the second stirring blade 33 b is inclined to feed the toner in the return direction 42.

  Thus, the external additive mixing process is performed while repeatedly performing the feeding in the “feed direction” 43 and the feeding in the “return direction” 42. Further, in the stirring blades 33a and 33b, a plurality of members disposed at intervals in the circumferential direction of the rotating body 32 form one set. In the example shown in FIG. 2, the stirring blades 33a and 33b form a pair of two members at an interval of 180 degrees to the rotary body 32, but at an interval of 120 degrees, three members or at an interval of 90 degrees A large number of members, such as four, may be combined.

  By having the above-described configuration, as a result, heat is efficiently applied to the toner, and a minimum necessary share is uniformly given to the toner to loosen the external additive from the secondary particles to the primary particles. it can. As a result, the external additive can be uniformly fixed to the surface of the toner particles.

  In addition, a plurality of stirring blades of "feed direction" and "return direction" do not exist, for example, an apparatus configuration as shown in FIG. 3 (rotary body 53 having mixing processing unit 51, 52 in the figure, baffle plate 54). In the low power condition where the residual stress is not stored, it is not possible to ensure sufficient circulation of the toner in the processor, and the toner uniformity is insufficient, so that the image in a high temperature and high humidity environment can not be obtained. Causes a decrease in concentration.

In the apparatus configuration of FIG. 1 described above, in order to solve the problems described above, the peripheral velocity V of the plurality of stirring blades when rotating the stirring member in the processing step is 0.1 m / sec or more and 7.0 m or more. / S or less, the processing step is carried out by heating and mixing, and when the material temperature of the mixture at the start of the heating and mixing is T1 and the glass transition temperature of the toner particles is T2, the following formula (1) is satisfied: When the mixing treatment energy at the time of the heating and mixing is E (Wh / g), it is important to satisfy the following formula (2).
T2-10 ° C. ≦ T1 ≦ T2 + 10 ° C. (1)
1.0 × 10 ⁻⁴ Wh / g ≦ E ≦ 1.5 × 10 ⁻² Wh / g (2)

  As described above, when the agitating blade collides with the toner at high speed, the external additive is embedded on the surface of the toner particle, the flowability is deteriorated and the external additive state is generated, or the residual stress is generated inside the toner. As a result, toner breakage and chipping may be promoted.

  As a result of intensive investigations by the present inventors, when the circumferential speed of the plurality of stirring blades is 0.1 m / sec or more and 7.0 m / sec or less, residual stress can be obtained while securing the circulation property in the mixing treatment apparatus. It was found that the crack and chipping resistance did not decrease.

  When the peripheral velocity V of the plurality of stirring blades is lower than 0.1 m / sec, the toner circulation property is insufficient, and the uniformity of the external addition state of the toner particle surface is reduced, and an image in a high temperature and high humidity environment It causes a decrease in concentration. In addition, temperature distribution occurs in the raw material (mixture of toner particles and inorganic fine particles) in the processing apparatus, and the external additive tends to be in a non-uniformly fixed state. On the other hand, if it exceeds 7.0 m / sec, the impact of the agitating blade on the toner will accumulate residual stress and it will be easily broken. As a result, the transferability in a low temperature and low humidity (LL) environment is degraded. The circumferential velocity V of the stirring blade is 0.5 m / sec or more to 2.0 m / sec in order to achieve uniform temperature distribution in the processing apparatus, uniform coverage of the external additive on the surface of the toner 1 particle, and higher fluidity. Seconds or less are more preferable.

  Further, in the study of the present inventors, it is assumed that the material temperature of the mixture at the start of the heating and mixing in the processing step is T1 and the glass transition temperature of the toner particles is T2, while satisfying the above-mentioned circumferential speed conditions. When the mixing treatment is performed at T 2 -10 ° C. or more and T 2 + 10 ° C. or less, it is possible to achieve strong fixation while suppressing embedding, thereby confirming improvement in crack resistance while maintaining high flowability.

  When T1 falls below T2-10 ° C., the softening of the surface of the toner particles does not easily occur, and it becomes difficult to immobilize the large particle diameter external additive. As a result, during durability in a high temperature and high humidity environment, the external additive adheres to the developing roller, toner fusion occurs from that point, and white spots and streaks appear on the image. On the other hand, if T1 exceeds T2 + 10 ° C., fusion will occur in the processing apparatus because it will greatly exceed the glass transition temperature of the toner. Furthermore, the embedding of the external additive into the toner particles becomes remarkable, and the flowability decreases. As a result, the image density reduction and the fog after white in a high temperature and high humidity environment are deteriorated.

  When the product temperature of the mixture after completion of heating and mixing is T3, from the viewpoint of production stability, T3 is preferably T1-5 ° C. or more and T1 + 5 ° C. or less, and T1-2 ° C. or more and T1 + 2 ° C. or less More preferable.

  Note that “at the start of mixing” related to the material temperature T1 of the mixture means “after the raw material (mixture of toner particles and external additive) is introduced into the processing space in the processing Immediately after rotating, the temperature monitored by the thermocouple installed inside the raw material inlet is T1 as described later.

  In the present invention, it is also important to control the processing energy, the processing time, and the processing energy calculated from the processing amount in the mixing and processing apparatus in order to achieve the above-mentioned problems.

By setting the processing energy to 1.0 × 10 ⁻⁴ Wh / g or more and 1.5 × 10 ⁻² Wh / g or less, it is possible to achieve both the strong fixation of the external additive and the maintenance of high fluidity.

If it is less than 1.0 × 10 ⁻⁴ Wh / g, adhesion of the external additive will be insufficient, and white spots and streaks will occur in a high temperature and high humidity environment. If it exceeds 1.5 × 10 ⁻² Wh / g, the chance of collision between the toner and the agitating blade will increase, and residual stress will build up, making it easy for the toner to crack and chip. As a result, the transferability in a low temperature and low humidity environment is reduced.

  At this time, the filling ratio of toner particles in the mixing tank is preferably 40.0% by volume or more and 80.0% by volume or less. When it is 40.0% by volume or more, the collision of the toners is appropriately performed to such an extent that the crack and chipping resistance is not promoted. As a result, the adhesion rate of the external additive and the coverage rate can be easily improved, and the transferability is improved. On the other hand, by being 80.0% by volume or less, the mixing property is good even under the low power operation, the coverage with the external additive between the toners tends to be uniform, and the flowability is improved. Cheap. As a result, the image density and the suppression of fogging in a high temperature and high humidity environment can be easily improved.

  The heating time is not particularly limited, but is preferably 3 minutes to 30 minutes, and more preferably 3 minutes to 10 minutes.

  As described above, while maintaining the high fluidity of the toner, it is technically difficult to achieve both the strong fixation of the external additive on the toner particle surface and the improvement of the crack and chipping resistance of the toner, so far to achieve Was difficult. That is, in order to increase the fixing rate of the external additive, it is necessary to strike the external additive to the toner particle surface with a stronger force. When producing toner under such conditions, the toner accumulates residual stress (strain) inside. As a result, when the toner receives mechanical shear in the cartridge, cracking of the toner is likely to be promoted, starting from the residual stress accumulated therein. On the other hand, if the external additive is hit with a weak force so as not to cause distortion in order to increase the mechanical strength of the toner, the toner strength can be maintained, but it is difficult to achieve a high fixation rate. In addition, even if means for increasing the molecular weight is effective to increase the mechanical strength of the toner, the external additive similarly tends to be hard to fix, and the fixability also tends to deteriorate.

  Therefore, in the conventional toner manufacturing method, the idea itself to try to achieve both the improvement of the crack and chipping resistance of the toner and the strong fixation of the external additive in a state of maintaining high fluidity has hardly been seen.

  The greatest feature of the present invention lies in the coexistence of the improvement of the adhesion level under the "low power operating conditions" and the improvement of the uniformity of the external addition state and further the improvement of the crack resistance under "low power operating conditions", which has not been considered conventionally. As a result, it is possible to provide a toner having a good transferability through durability in a low temperature and low humidity environment. Furthermore, in a high temperature and high humidity environment, good image density and fog reduction can be achieved, and it has become possible for the first time to suppress contamination by external additives such as a development carrier through durability.

  Next, a preferred method of producing the toner of the present invention will be described with reference to FIGS. 1 and 2.

  In the present device, the diameter of the inner peripheral portion of the main body casing 30 is equal to or less than twice the diameter of the outer peripheral portion of the rotary body 32. In FIG. 1, an example is shown in which the diameter of the inner peripheral portion of the main body casing 30 is 1.7 times the diameter of the outer peripheral portion of the rotary body 32 (diameter of the body portion excluding the stirring member 33 from the rotary body 32). When the diameter of the inner peripheral portion of the main body casing 30 is not more than twice the diameter of the outer peripheral portion of the rotary body 32, the processing space in which the force acts on the toner particles is appropriately limited. It is possible to sufficiently disperse the external additives.

  Moreover, it is important to adjust the said clearance according to the magnitude | size of a main body casing. It is preferable to set the diameter to about 1% to 5% of the diameter of the inner peripheral portion of the main casing 30 in terms of efficiently applying heat to the toner particles. Specifically, when the diameter of the inner peripheral portion of the main body casing 30 is about 130 mm, the clearance is about 2 mm to 5 mm, and when the diameter of the inner peripheral part of the main body casing 30 is about 800 mm, 10 mm to 30 mm It should be a degree.

  In the example shown in FIG. 2, a total of 12 stirring blades 33a and 33b are formed at equal intervals.

  Further, in FIG. 2, D indicates the width of the stirring blade, and d indicates the interval indicating the overlapping portion of the stirring blade. From the viewpoint of efficiently feeding the toner in the feed direction and the return direction, D (D / L) relative to the length (L) of the rotating body 32 in FIG. 2 is about 0.2 or more and 0.3 or less. preferable. FIG. 2 shows an example of 0.23 (23%). Furthermore, it is preferable that the stirring blades 33a and 33b have an overlapping portion d of the stirring blade 33b and the stirring blade 33a to some extent when an extension line is drawn in the vertical direction from the end position of the stirring blade 33a.

  Thereby, the external additive on the surface of the toner particles can be dispersed efficiently. It is preferable that d (d / D) for D is 0.05 or more and 0.4 or less in terms of applying a share. More preferably, it is 0.1 or more and 0.3 or less.

  With regard to the shape of the blade, in addition to the shape as shown in FIG. 2, the toner particles can be sent in the feed direction and the return direction, and if the clearance can be maintained, the shape having a curved surface or the tip blade portion It may be a paddle structure coupled to the rotating body 32 by a rod-like arm.

  The invention will now be described in more detail in accordance with the schematic views of the apparatus shown in FIGS. 1 and 2.

  The apparatus shown in FIG. 1 has a stirring member 31 mainly composed of a rotating body 32 on the surface of which at least a plurality of stirring blades 33 are installed, a drive unit 38 for rotationally driving the rotating body 32, a stirring blade 33 and a gap It has a main body casing 30 provided. Furthermore, a jacket 34 is provided on the inner side of the main body casing 30 and on the side surface 310 of the rotor for allowing a cooling medium to flow.

  Further, the apparatus shown in FIG. 1 has a raw material inlet 35 formed in the upper part of the main body casing 30 and a product discharge port 36 formed in the lower part of the main body casing 30. The raw material inlet 35 is used to introduce toner particles, and the product outlet 36 is used to discharge the externally mixed and treated toner from the main casing 30.

  Furthermore, in the apparatus shown in FIG. 1, the inner piece 316 for the raw material inlet is inserted into the raw material inlet 35, and the inner piece 317 for the product outlet is inserted into the product outlet 36.

  In the present invention, first, the inner piece 316 for the raw material inlet is taken out from the raw material inlet 35, toner particles are put into the processing space 39 from the raw material inlet 35, and the inner piece 316 for the raw material inlet is inserted. Next, the rotating body 32 is rotated by the drive unit 38 (41 indicates the direction of rotation), and the processing object introduced above is heated while being stirred and mixed by the stirring vanes 33 provided on the surface of the rotating body 32 Mix processing.

  In the present invention, heating is performed by passing warm water having a desired temperature through the jacket 34. The temperature is monitored by a thermocouple installed inside the raw material inlet inner piece 316. In order to obtain stable and required toner performance of the toner of the present invention, when T2 is a glass transition temperature of toner particles as a thermocouple temperature (T1) of the inner piece 316 for raw material inlet, T2-10. ° C or more and T2 + 10 ° C. or less. More preferably, it is T2-10 degreeC or more and T2 + 5 degreeC.

  Although it does not specifically limit as processing time depending on the temperature to heat, Preferably, they are 3 minutes or more and 10 minutes or less. By controlling to the said range, it becomes easy to make high flowability and fixation compatible. The glass transition temperature of the toner particles is preferably 45 ° C. or more and 65 ° C. or less from the viewpoint of storage stability.

  Further, from the viewpoint of manufacturing stability, the value obtained by multiplying T3 by the treatment time is 3000 (° C. · sec) or more and 100000 (° C. · sec) or less, and further, 8000 (° C. · sec) or more and 50000 (° C. · sec) Or less) is preferable. The present inventors believe that the value obtained by multiplying T3 by the processing time is synonymous with the amount of heat applied to the toner. By controlling this value within the above range, it is easy to achieve both strong fixation and high fluidity of the external additive, and it is also easy to obtain a toner with high quality stability.

  After completion of the mixing process, the product discharge port inner piece 317 in the product discharge port 36 is taken out, the rotating body 32 is rotated by the drive unit 38, and the toner is discharged from the product discharge port 36. In the obtained toner, coarse particles and the like are separated by a sieve such as a circular vibrating sieve as necessary to obtain a toner.

  In the toner of the present invention, it is preferable to provide a heating step after the external addition step, and the external addition and the heating treatment may be simultaneously carried out using the above heating and mixing treatment conditions, or the external addition step is completed. The above-described apparatus may heat the discharged toner.

  As a particularly preferred treatment method in the present invention, it is preferable to heat the mixture with the above-mentioned heating and mixing treatment apparatus after the toner particles and the external additive are mixed and externally added by a known mixer such as a Henschel mixer.

  The following may be mentioned as mixers. Mitsui Henschel Mixer (Mitsui Miike Kako Co., Ltd.); Super Mixer (Kawata Co., Ltd.); Ribocon (Ogawara Manufacturing Co., Ltd.); Nauta Mixer, Turbulizer, Cyclomix (Hosokawa Micron); Spiral Pin Mixer (Pacific Manufactured by Kiko Co., Ltd .; Loedige mixer (manufactured by Matsubo).

  The external additive of the present invention is inorganic fine particles or organic-inorganic composite fine particles. The inorganic fine particles used in the present invention preferably have a number average particle diameter (D1) of 40 nm or more and 200 nm or less, and more preferably 80 nm or more and 150 nm or less, in order to maintain performance through durability. By achieving the strong fixation state of the present invention using the inorganic fine particles having the above-mentioned particle size in the above range, an image free of white spots and streaks generated by stable and good transferability over a long period of time and sleeve fusion can be obtained. Is preferable because it becomes possible.

  Moreover, it is more preferable to use together with another inorganic fine particle with a small particle size separately from the inorganic fine particle whose number average particle diameter (D1) is 40 nm or more and 200 nm or less. Use of inorganic fine particles having different large and small particle sizes is preferable because the chargeability and the flowability can be easily controlled. When using the inorganic fine particles in combination, it is preferable to use the inorganic fine particles A of 40 nm to 200 nm and the inorganic fine particles B having a number average particle diameter (D1) of less than 40 nm.

  Examples of the inorganic fine particles used in the present invention include fine particles such as silica fine particles, alumina fine particles, titania fine particles, and composite oxide fine particles thereof, and organic-inorganic composite fine particles containing organic fine particles may be used.

  Among them, the inorganic fine particles are preferably silica fine particles. As a method for producing silica fine particles, a combustion method obtained by burning a silane compound (that is, a method for producing fumed silica), a deflagration method obtained by explosively burning metal silicon powder, sodium silicate and a mineral acid And sol-gel methods (so-called Stoeber methods) obtained by hydrolysis of alkoxysilanes such as hydrocarbyloxysilanes.

  The inorganic fine particles are preferably used by controlling the degree of hydrophobization by hydrophobization treatment. By controlling the degree of hydrophobicity, the inorganic fine particles are easily localized at the interface between the droplet and the hydrophobic dispersion medium, and the dispersion stability of the droplet can be easily improved. The method for hydrophobizing the inorganic fine particles is not particularly limited, and a known method can be used, but a method of treating the inorganic fine particles with a hydrophobizing agent is preferable.

  Specific examples of the hydrophobizing agent include chlorosilanes such as methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, t-butyldimethylchlorosilane and vinyltrichlorosilane; tetramethoxysilane, methyltrichlorosilane Methoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, o-methylphenyltrimethoxysilane, p-methylphenyltrimethoxysilane, n-butyltrimethoxysilane, i-butyltrimethoxysilane, hexyltrimethoxysilane , Octyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyl diele Xysilane, phenyltriethoxysilane, diphenyldiethoxysilane, i-butyltriethoxysilane, decyltriethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Glycidoxypropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyl Alkoxysilanes such as trimethoxysilane and γ- (2-aminoethyl) aminopropylmethyldimethoxysilane; hexamethyldisilazane, hexaethyldisilazane, hexapropyldisilazane, hexabutyl Disilazane, hexapentyldisilazane, hexahexyldisilazane, hexacyclohexyldisilazane, hexaphenyldisilazane, divinyltetramethyldisilazane, silazanes such as dimethyltetravinyldisilazane; dimethyl silicone oil, methyl hydrogen silicone oil, methyl phenyl Silicone oil, alkyl modified silicone oil, chloroalkyl modified silicone oil, chlorophenyl modified silicone oil, fatty acid modified silicone oil, polyether modified silicone oil, alkoxy modified silicone oil, carbinol modified silicone oil, amino modified silicone oil, fluorine modified silicone oil And, silicone oil of terminal reactive silicone oil; hexamethylcyclotrisiloxane And siloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, octamethyltrisiloxane, etc .; fatty acids and metal salts thereof such as undecylic acid, lauric acid, tridecylic acid, dodecylic acid, myristic acid, palmitic acid Long-chain fatty acids such as acid, pentadecyl acid, stearic acid, heptadecyl acid, arachic acid, montanic acid, oleic acid, linoleic acid, arachidonic acid, the above-mentioned fatty acids and metals such as zinc, iron, magnesium, aluminum, calcium, sodium, lithium And salt with

  Among these, alkoxysilanes, silazanes and straight silicone oils are preferably used because they are easy to carry out hydrophobization treatment. One of these hydrophobic treatment agents may be used alone, or two or more thereof may be used in combination.

  In the case of organic-inorganic composite fine particles, while maintaining good durability and chargeability as an inorganic material, at the time of fixing, it is difficult to inhibit the coalescence of toner particles due to the component of the organic material having a low heat capacity. Hard to produce Therefore, it is easy to achieve both durability and fixability.

  A preferable configuration of the organic-inorganic composite fine particles is composite fine particles composed of inorganic fine particles embedded in the surface of resin fine particles which are organic components. More preferably, it has a structure in which silica fine particles which are inorganic fine particles are exposed on the surface of the vinyl resin particle. More preferably, the surface of the vinyl resin particles has a convex portion derived from the inorganic fine particles.

  Moreover, in addition to the above-mentioned silica fine particles, for example, a lubricant such as fluorocarbon resin powder, zinc stearate powder, polyvinylidene fluoride powder; an abrasive such as cerium oxide powder, silicon carbide powder, strontium titanate powder, etc. good.

  Hereinafter, the constituent material of the toner particles according to the present invention will be described in more detail.

  Further, examples of the binder resin used for the toner particles of the present invention include the following. Vinyl resin, styrene resin, styrene copolymer resin, polyester resin, polyol resin, polyvinyl chloride resin, phenol resin, natural modified phenolic resin, natural resin modified maleic resin, acrylic resin, methacrylic resin, polyvinyl acetate, Silicone resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone indene resin, petroleum resin. Among them, a styrene-based copolymer resin, a polyester resin, a hybrid resin in which a polyester resin and a vinyl-based resin are mixed, or both are partially reacted as a resin to be preferably used.

  The toner particles according to the present invention may contain a release agent.

  As a mold release agent, waxes having fatty acid esters such as carnauba wax and montanic acid ester wax as the main components; and some or all of acid components from fatty acid esters such as deacidified carnauba wax and the like Methylated ester compounds having a hydroxyl group obtained by hydrogenation of vegetable oil and the like; saturated fatty acid monoesters such as stearyl stearate, stearyl stearate, behenyl behenate, dibehenyl sebacate, distearyl dodecanedioate, octadecanedioate Diester of a saturated aliphatic dicarboxylic acid such as distearyl and a saturated aliphatic alcohol; diester of a saturated aliphatic diol such as nonanediol dibehenate and dodecanediol distearate with a saturated fatty acid, low molecular weight polyethylene, low molecular weight Polypropylene Aliphatic hydrocarbon waxes such as microcrystalline wax, paraffin wax and Fischer-Tropsch wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; and aliphatic hydrocarbon waxes Waxes grafted with vinyl monomers such as styrene and acrylic acid, Saturated linear fatty acids such as palmitic acid, stearic acid and montanic acid; and unsaturated fatty acids such as brushic acid, eleostearic acid and parinaric acid Kinds; Saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, ceryl alcohol, and mesyl alcohol; polyhydric alcohols such as sorbitol; linoleic acid amide, oleic acid amide, Fatty acid amides such as uronic acid amide; Saturated fatty acid bisamides such as methylenebisstearic acid amide, ethylene biscapric acid amide, ethylene bis lauric acid amide, hexamethylene bisstearic acid amide; ethylene bis oleic acid amide, hexamethylene bis olein Unsaturated fatty acid amides such as acid amide, N, N'-dioleyl adipamide, N, N'-dioleyl sebacic acid amide; m-xylene bis-stearic amide, N, N'-distearyl isophthalic acid amide Aromatic bisamides such as: fatty acid salts of calcium stearate, calcium laurate, zinc stearate, magnesium stearate etc. (generally referred to as metal soaps); long-chain alkyl alcohols having 12 or more carbon atoms or Long chain al Quill carboxylic acid; and the like.

  Among these releasing agents, monofunctional or difunctional ester waxes such as saturated fatty acid monoesters and diesters, and hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax are preferable.

  The melting point defined by the peak temperature of the maximum endothermic peak at the time of temperature rise measured with a differential scanning calorimeter (DSC) of the release agent is preferably 60 ° C. or more and 140 ° C. or less. The temperature is more preferably 60 ° C. or more and 90 ° C. or less. When the melting point is 60 ° C. or more, the storage stability of the toner of the present invention is improved. On the other hand, when the melting point is 140 ° C. or less, the low temperature fixability is easily improved, which is preferable.

  The content of the release agent is preferably 3 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin. When the content of the release agent is 3 parts by mass or more, the fixability tends to be improved. On the other hand, when the content of the release agent is 30 parts by mass or less, the toner is less likely to deteriorate during long-term use, and the image stability is likely to be improved.

  The toner particles according to the present invention preferably contain a charge control agent.

  Organic metal complex compounds and chelate compounds are effective as charge control agents for negative charge, and monoazo metal complex compounds; acetylacetone metal complex compounds; metal complex compounds of aromatic hydroxycarboxylic acid or aromatic dicarboxylic acid, etc. Be done. As specific examples of commercially available products, Spilon Black TRH, T-77, T-95 (Hodoya Chemical Industry Co., Ltd.), BONTRON (registered trademark) S-34, S-44, S-54, E-84, E -88, E-89 (Orient Chemical Industry Co., Ltd.).

  These charge control agents can be used alone or in combination of two or more. The amount of the charge control agent used is preferably 0.1 parts by mass or more and 10.0 parts by mass or less, and more preferably 0.1 parts by mass or more, per 100 parts by mass of the binder resin, from the viewpoint of the charge amount of the magnetic toner It is 5.0 parts by mass or less.

  The toner of the present invention can be used as any toner of magnetic one-component toner, nonmagnetic one-component toner, and nonmagnetic two-component toner.

  When used as a magnetic one-component toner, magnetic iron oxide particles are preferably used as the colorant. Examples of magnetic iron oxide particles contained in the magnetic one-component toner include magnetic iron oxide such as magnetite, maghemite and ferrite, and magnetic iron oxide containing other metal oxides; metals such as Fe, Co, Ni, or these Alloys of metals such as Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W, V, and mixtures thereof Can be mentioned.

  Among these, magnetite is preferably used, and the shape thereof includes polyhedrons, octahedrons, hexahedrons, spheres, needles, scaly shapes, etc., but is anisotropic such as polyhedrons, octahedrons, hexahedrons, spheres, etc. Less is preferable to increase the image density.

  The magnetic iron oxide particles preferably have a volume average particle size of 0.10 μm or more and 0.40 μm or less. When the volume average particle size is 0.10 μm or more, the magnetic iron oxide particles are less likely to aggregate, and the uniform dispersion of the magnetic iron oxide particles in the toner is improved. When the volume average particle diameter is 0.40 μm or less, the coloring power of the toner is preferably used.

  The volume average particle size of the magnetic iron oxide particles can be measured using a transmission electron microscope. Specifically, after the toner particles to be observed are sufficiently dispersed in the epoxy resin, a cured product obtained by curing for 2 days in an atmosphere at a temperature of 40 ° C. is obtained. The resulting cured product is used as a flaky sample by a microtome, and in a transmission electron microscope (TEM), the particle sizes of 100 magnetic iron oxide particles in the field of view are measured with a photograph at a magnification of 10,000 to 40,000. . Then, based on the equivalent diameter of the circle equal to the projected area of the magnetic iron oxide particles, the volume average particle diameter is calculated. It is also possible to measure the particle size with an image analysis device.

  As the black pigment, carbon black such as furnace black, channel black, acetylene black, thermal black, lamp black and the like are used, and magnetic powder such as magnetite and ferrite is also used.

  As a colorant suitable for yellow color, a pigment or dye can be used. As a pigment, C.I. I. Pigment yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 17, 23, 62, 65, 73, 74, 81, 83, 93, 94, 95, 97, 98, 109, 110, 111, 117, 120, 127, 128, 129, 137, 139, 147, 151, 154, 155, 167, 168, 173, 174, 176, 180, 181, 183, 183, 191, C.I. I. Bat Yellow 1, 3, 20 can be mentioned. As a dye, C.I. I. Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162 and the like. These may be used alone or in combination of two or more.

  As a colorant suitable for cyan color, a pigment or a dye can be used. As a pigment, C.I. I. Pigment blue 1, 7, 15, 15; 1, 15; 2, 15; 3, 15; 4, 16, 17, 60, 62, 66, etc., C.I. I. Bat Blue 6, C.I. I. Acid Blue 45 is mentioned. As a dye, C.I. I. Solvent Blue 25, 36, 60, 70, 93, 95 and the like. These may be used alone or in combination of two or more.

  As a colorant suitable for magenta color, a pigment or a dye can be used. As a pigment, 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, 23, 30, 31, 2, 48; 3, 48; 4, 49, 50, 51, 52, 53, 54, 55, 57, 57; 1, 58, 60, 32, 37, 38, 39, 40, 41, 48, 48; 63, 64, 68, 81, 81; 1, 83, 87, 88, 89, 90, 112, 122, 123, 144, 146, 150, 163, 166, 169, 177, 184, 185, 202, 206, 207, 209, 220, 221, 238, 254, etc., C.I. I. Pigment violet 19; C.I. I. Butt red 1, 2, 10, 13, 15, 23, 29, 35 may be mentioned. As dyes for magenta, C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 52, 58, 63, 81, 82, 83, 84, 100, 109, 111, 121, 122, etc., C.I. I. Disperse thread 9, C.I. I. Solvent violet 8, 13, 14, 21, 27 etc., C.I. I. Oil-soluble dyes such as disperse violet 1, C.I. I. Basic red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, etc., C.I. I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28 etc. may be mentioned. These may be used alone or in combination of two or more.

  In terms of mechanical strength of the toner, the magnetic toner using magnetic iron oxide particles as a coloring agent tends to be disadvantageous because the binding strength is weak at the interface between the binder resin and the magnetic iron oxide particles.

  The effects of the present invention can be obtained for both magnetic toners and non-magnetic toners, but particularly for magnetic toners whose mechanical strength is disadvantageous, it is easy to obtain great effects.

  Hereinafter, the method for producing toner particles according to the present invention will be exemplified, but the production method is not particularly limited, and it is possible to produce by a pulverizing method, but a dispersion polymerization method, association aggregation method, dissolution suspension method, It is preferable to produce toner particles in an aqueous medium such as suspension polymerization method and emulsion aggregation method, and in particular, suspension polymerization method is very preferable because toner particles satisfying the preferable physical properties of the present invention can be easily obtained.

  In the suspension polymerization method, first, a colorant (more optionally, a polymerization initiator, a crosslinking agent, a charge control agent, and other additives) is uniformly dispersed in the polymerizable monomer to obtain a polymerizable unit amount. The body composition is obtained. Thereafter, the obtained polymerizable monomer composition is dispersed in a continuous layer (for example, aqueous phase) containing a dispersion stabilizer using a suitable stirrer, and a polymerization reaction is performed using a polymerization initiator. To obtain toner particles having a desired particle size.

  The toner particles obtained by this suspension polymerization method (hereinafter, also referred to as “polymerized toner particles”) have substantially uniform spherical individual toner particle shapes, so that toner particles satisfying physical property requirements suitable for the present invention can be obtained. easy.

  Examples of the polymerizable monomer include the following.

  Styrene-based monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene, etc .; methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid Isobutyl, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, acrylic esters such as phenyl acrylate, methyl methacrylate, methacrylic acid Ethyl, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethyl methacrylate Aminoethyl, methacrylic acid esters such as diethylaminoethyl methacrylate; and other acrylonitrile, methacrylonitrile, and monomers such as acrylamide. These monomers may be used alone or in combination. Among the above-mentioned monomers, it is preferable to use styrene or a styrene derivative alone or in combination with other monomers from the viewpoint of controlling the toner structure and easily improving the developing characteristics and the durability of the toner. . In particular, it is more preferable to use styrene and alkyl acrylate or styrene and alkyl methacrylate as main components.

  As the polymerization initiator used in the production of the toner particles according to the present invention by the polymerization method, one having a half life of 0.5 hours or more and 30 hours or less at the time of the polymerization reaction is preferable. In addition, when the polymerization reaction is performed using an addition amount of 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer, it has a maximum between a molecular weight 5,000 and 50,000 or less Polymers can be obtained to provide the toner particles with desirable strength and suitable melt characteristics.

  In the present invention, the peak molecular weight Mp is preferably 10,000 or more and 35,000 or less, more preferably 15,000 or more and 30,000 or less, from the viewpoint of fixability and mechanical strength.

  Specific polymerization initiators include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbo) Azo or diazo polymerization initiators such as nitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxy Carbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, t-butylperoxy 2-ethylhexanoate, t-butylperoxypivalate, di (2-ethylhexyl) peroxydicarbonate , Di (secondary butyl) peroxy Peroxide polymerization initiators such as carbonate. Among these, peroxydicarbonate type di (2-ethylhexyl) peroxydicarbonate and di (secondary butyl) peroxydicarbonate are binder resins having a low molecular weight and linear type molecular structure as described above. It is preferably used because it is easy to manufacture.

  When the toner particles according to the present invention are produced by a polymerization method, a crosslinking agent may be added, and a preferable addition amount is 0.001 parts by mass or more and 15 parts by mass with respect to 100 parts by mass of the polymerizable monomer. It is below.

  Here, compounds having two or more polymerizable double bonds are mainly used as the crosslinking agent, and examples thereof include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; for example, ethylene glycol diacrylate and ethylene glycol di A carboxylic acid ester having two double bonds such as methacrylate, 1,3-butanediol dimethacrylate and the like; a divinyl compound such as divinyl aniline, divinyl ether, divinyl sulfide and divinyl sulfone; and three or more vinyl groups The compounds are used alone or as a mixture of two or more.

  Preferably, the polymerizable monomer composition contains a polar resin. In the suspension polymerization method, in order to produce magnetic toner particles in an aqueous medium, a layer of polar resin can be formed on the surface of toner particles by containing polar resin, and toner particles having a core / shell structure You can get

  Having a core / shell structure increases the freedom of core and shell design. For example, by raising the glass transition temperature of the shell, it is possible to suppress durability deterioration (degradation during long-term use) such as embedding of an external additive. Further, by providing the shell with a shielding effect, the composition of the shell can be easily made uniform, so that uniform charging can be performed.

  Examples of polar resins for the shell layer include polystyrene, homopolymers of styrene such as polyvinyl toluene and their substituted products; styrene-propylene copolymers, styrene-vinyl toluene copolymers, styrene-vinyl naphthalene copolymers, Styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl dimethylamino copolymer, styrene-meta Methyl acrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl Ethyl ether copolymer, Styrene -Styrene-based copolymers such as vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethyl methacrylate, Polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyester resin, styrene-polyester copolymer, polyacrylate-polyester copolymer, polymethacrylate-polyester copolymer, polyamide resin, epoxy resin, There are polyacrylic resin, terpene resin, phenol resin and the like, and these can be used alone or in combination of two or more. In addition, functional groups such as amino group, carboxyl group, hydroxyl group, sulfonic acid group, glycidyl group and nitrile group may be introduced into these polymers. Among these resins, polyester resins are preferred.

  As polyester resin, it is possible to select and use a saturated polyester resin, unsaturated polyester resin, or both suitably.

  As the polyester resin used in the present invention, conventional ones composed of an alcohol component and an acid component can be used, and both components are exemplified below.

  Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, cyclohexanedimethanol, butenediol, octenediol, cyclohexene dimethanol, hydrogenated bisphenol A, and a bisphenol derivative represented by the formula (A) ;

（式中、Ｒはエチレンまたはプロピレン基であり、ｘ，ｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値は２以上１０以下である。）
あるいは、式（Ａ）の化合物の水添物、また、式（Ｂ）で示されるジオール；

(In the formula, R is ethylene or propylene, x and y are each an integer of 1 or more, and the average value of x + y is 2 or more and 10 or less.)
Alternatively, a hydrogenated product of a compound of the formula (A), and a diol represented by the formula (B);

あるいは、式（Ｂ）の化合物の水添物のジオールが挙げられる。

Or the diol of the hydrogenated substance of the compound of Formula (B) is mentioned.

  As the dihydric alcohol component, the above-mentioned alkylene oxide adduct of bisphenol A which is excellent in charging characteristics and environmental stability and is well balanced in other electrophotographic characteristics is particularly preferable. In the case of this compound, the average addition mole number of alkylene oxide is preferably 2 or more and 10 or less in terms of fixability and toner durability.

  Examples of the divalent acid component include benzenedicarboxylic acid such as phthalic acid, terephthalic acid, isophthalic acid and phthalic anhydride or anhydride thereof; alkyldicarboxylic acid such as succinic acid, adipic acid, sebacic acid and azelaic acid or its acid Anhydride, or succinic acid or an anhydride thereof further substituted with an alkyl or alkenyl group having 6 to 18 carbon atoms; fumaric acid, maleic acid, citraconic acid, unsaturated dicarboxylic acid such as itaconic acid, or an anhydride thereof Can be mentioned.

  Furthermore, as the alcohol component of trivalent or higher, glycerin, pentaerythritol, sorbite, sorbitan, oxyalkylene ether of novolac type phenol resin can be exemplified, and as the acid component of trivalent or higher, trimellitic acid, pyromellitic acid can be exemplified. An acid, 1,2,3,4-butane tetracarboxylic acid, benzophenone tetracarboxylic acid, its anhydride, etc. can be illustrated.

  It is preferable that 45 mol% or more and 55 mol% or less of the polyester resin in this invention is an alcohol component, when the sum total of an alcohol component and an acid component is 100 mol%.

  The polyester resin in the present invention can be produced using any catalyst such as a tin-based catalyst, an antimony-based catalyst, and a titanium-based catalyst, but it is preferable to use a titanium-based catalyst.

  The polar resin for the shell preferably has a number average molecular weight of 2,500 or more and 25,000 or less from the viewpoint of developability, blocking resistance, and durability. The number average molecular weight can be measured by GPC.

  The polar resin for the shell preferably has an acid value of 1.0 mg KOH / g or more and 15 mg KOH / g or less, more preferably an acid value of 2 mg KOH / g or more and 10 mg KOH / g or less. By controlling the acid value in the above range, it is easy to form a uniform shell.

  The polar resin for the shell layer is preferably contained in an amount of 2 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin from the viewpoint of sufficiently obtaining the effect of the shell layer.

  A dispersion stabilizer is contained in the aqueous medium in which the polymerizable monomer composition is dispersed, but as the dispersion stabilizer, known surfactants, organic dispersants and inorganic dispersants can be used. Among them, the inorganic dispersant is preferably used because it has high dispersion stability due to its steric hindrance, so that the stability does not easily deteriorate even if the reaction temperature is changed, the washing is easy, and the toner is not adversely affected.

  Examples of such inorganic dispersants include tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, polyvalent metal salts of phosphate such as hydroxyapatite, carbonates such as calcium carbonate and magnesium carbonate, calcium metasilicate And inorganic salts such as calcium sulfate and barium sulfate; and inorganic compounds such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide.

  It is preferable to use 0.2 parts by mass or more and 20 parts by mass or less of these inorganic dispersants with respect to 100 parts by mass of the polymerizable monomer. Also, the dispersion stabilizer may be used alone or in combination of two or more. Furthermore, 0.001 mass part or more and 0.1 mass part or less of surfactant may be used together. When these inorganic dispersants are used, they may be used as they are, but in order to obtain finer particles, the inorganic dispersant particles can be formed and used in an aqueous medium.

  For example, in the case of tricalcium phosphate, a water-insoluble calcium phosphate can be produced by mixing an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high-speed stirring, and more uniform and finer dispersion becomes possible. At this time, a water-soluble sodium chloride salt is also by-produced at the same time, but when the water-soluble salt is present in the aqueous medium, the dissolution of the polymerizable monomer in water is suppressed and the ultrafine toner is generated by emulsion polymerization. It is more convenient because it becomes difficult to do.

  Examples of the surfactant include sodium dodecyl benzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium stearate, potassium stearate and the like.

  In the step of polymerizing the polymerizable monomer, the polymerization temperature is set to a temperature of 40 ° C. or more, generally 50 ° C. to 90 ° C. When polymerization is carried out in this temperature range, the release agent to be sealed inside is precipitated by phase separation, and the encapsulation is more complete. Then, it cools from reaction temperature about 50 degreeC or more and 90 degrees C or less, and there exists a cooling process which terminates a polymerization reaction process. At that time, it is preferable to gradually cool so as to maintain the compatible state of the release agent and the binder resin.

  After completion of the polymerization of the polymerizable monomer, the obtained polymer particles are filtered, washed and dried by a known method to obtain toner particles. The toner of the present invention can be obtained by mixing inorganic particles such as silica fine particles with the toner particles as described above and adhering them to the surface of the toner particles. In addition, it is possible to put a classification step in the manufacturing process and to cut coarse powder and fine powder contained in toner particles.

  Next, the measuring method of each physical property in connection with this invention is described.

<Method of measuring adhesion rate of external additive>
A silica particle is demonstrated to an example.

  Weigh 20 g of a 10 wt% aqueous solution of neutral detergent for pH 7 precision measuring instrument cleaning consisting of nonionic surfactant, anionic surfactant and organic builder into a 50 mL capacity vial, and use 1 g of toner Mix.

  Set to "KM Shaker" (model: V.SX) manufactured by Iwaki Sangyo Co., Ltd., and set the speed to 50 and shake for 30 seconds. Thereby, depending on the fixed state of the silica fine particles, the silica fine particles move from the surface of the toner particle to the dispersion liquid side.

  After that, in the case of magnetic toner, while the toner particles are restrained using a neodymium magnet, the supernatant liquid is separated, and the precipitated toner is dried by vacuum drying (40 ° C./1 day), It will be a sample.

  In the case of non-magnetic toner, the toner and the transferred silica fine particles are separated by a centrifuge (H-9R; manufactured by Kokusan Co., Ltd.) (1000 rpm, for 5 minutes).

  With respect to the sample before and after the above treatment, the silica fine particles are quantified by using the intensity of Si by wavelength dispersive fluorescent X-ray analysis (XRF) described below. Then, the amount of the silica fine particles remaining on the surface of the toner particle without being transferred to the supernatant side by the above-mentioned processing is obtained from the following equation, and is defined as the fixation rate. The arithmetic mean value of 100 samples is adopted.

(I) Example of device used X-ray fluorescence analyzer 3080 (RIKEN ELECTRIC CO., LTD.)

(Ii) Sample Preparation For sample preparation, a sample press molding machine MAEKAWA Testing Machine (manufactured by MFG Co, LTD.) Is used. 0.5 g of toner is put in an aluminum ring (model number: 3481 E1), set to a load of 5.0 tons, and pressed for 1 min to pelletize.

(Iii) Measurement conditions Measuring diameter: 10φ
Measurement potential, voltage 50kV, 50-70mA
2θ angle 25.12 °
Crystal plate LiF
Measurement time 60 seconds

(Iii) Calculation Method of Fixation Rate of Silica Fine Particles [Formula] Fixation rate (%) of silica fine particles = (After-treatment toner Si strength / pre-treatment toner Si strength) × 100

<Method of measuring number average particle diameter (D1) of primary particles of external additive>
As a method of determining the number average particle diameter of primary particles of external additive from toner, the surface of toner particles photographed with Hitachi ultra-high resolution field emission scanning electron microscope S-4800 (Hitachi High Technologies Co., Ltd.) It is calculated from the external additive image. The image shooting conditions of S-4800 are as follows.

(1) Sample Preparation A conductive paste is thinly applied to a sample stand (aluminum sample stand 15 mm × 6 mm), and a toner is sprayed thereon. Furthermore, air is blown to remove excess toner from the sample table and allow it to dry sufficiently. The sample stage is set to the sample holder, and the sample stage height is adjusted to 36 mm by the sample height gauge.

(2) Setting of S-4800 observation conditions Calculation of the number average particle diameter of primary particles of the external additive is performed using an image obtained by observation of a backscattered electron image of S-4800. Since the reflection electron image has less charge up of the external additive as compared with the secondary electron image, the particle diameter of the external additive can be measured with high accuracy.

  Inject the liquid nitrogen into the anticontamination trap attached to the S-4800 housing until it overflows, and place for 30 minutes. The "PC-SEM" of S-4800 is activated to perform flushing (cleaning of the FE chip as an electron source). Click the acceleration voltage display part of the control panel on the screen and press the [Flushing] button to open the flushing execution dialog.

  Confirm that the flushing strength is 2 and execute. Confirm that the emission current by flushing is 20 to 40 μA. Insert the sample holder into the sample chamber of the S-4800 chassis. Press [Origin] on the control panel to move the sample holder to the observation position.

  Click the acceleration voltage display to open the HV setting dialog, and set the acceleration voltage to [0.8 kV] and the emission current to [20 μA]. In the [Basic] tab of the operation panel, set the signal selection to [SE], select [Up (U)] and [+ BSE] for the SE detector, select [+ BSE] in the selection box to the right L. A. 100], and set it to the mode to observe in the reflection electron image.

  Similarly, in the [Basic] tab of the operation panel, set the probe current of the electron optical system condition block to [Normal], the focus mode to [UHR], and WD to [3.0 mm]. Press the [ON] button on the acceleration voltage display on the control panel to apply an acceleration voltage.

(3) Calculation of the number average particle diameter (D1) ("da" used when calculating the theoretical coverage) of the external additive Drag the inside of the magnification display portion of the control panel to set the magnification to 100000 (100 k) times Do. Rotate the focus knob [COARSE] on the operation panel and adjust the aperture alignment when the camera is in focus. Click [Align] on the control panel to display the alignment dialog and select [Beam]. Rotate the STIGMA / ALIGNMENT knob (X, Y) on the operation panel to move the displayed beam to the center of the concentric circle.

  Next, select [Aperture] and turn the STIGMA / ALIGNMENT knobs (X, Y) one by one to stop the movement of the image or adjust it so as to minimize movement. Close the aperture dialog and focus on the auto focus. Repeat this operation two more times to focus.

  Thereafter, the particle diameter of at least 300 external additives having a particle diameter of 30 nm or more on the surface of the toner particles is measured to determine the average particle diameter. Here, since some external additives exist as agglomerates, the maximum diameter of particles that can be identified as primary particles is determined, and the resulting maximum diameter is arithmetically averaged to obtain a number average particle size of primary particles of the external additive. Obtain the diameter (D1).

  When plural kinds of external additives are used, elemental analysis is performed beforehand by an energy dispersive X-ray analyzer (EDAX) to identify the types of external additives on the toner surface, and then each external additive is selected. The number average particle size of primary particles was determined.

  When calculation of the number average particle diameter by the surface observation method is difficult, the number average particle diameter of each external additive measured in advance may be adopted. In that case, the external additive alone is observed with a transmission electron microscope, and the major diameter of 100 particles is measured to determine the number average particle diameter.

<Method of measuring weight average particle diameter (D4)>
The weight average particle diameter (D4) of the toner particles is measured with a Coulter Counter Multisizer 3 (registered trademark, manufactured by Beckman Coulter, Inc.), a precise particle size distribution measuring device by a pore electrical resistance method equipped with an aperture tube of 100 μm. Measurement data is measured using 25,000 channels of effective measurement channels using the dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter Inc.) for condition setting and measurement data analysis. Was analyzed and calculated.

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

  In addition, before performing measurement and analysis, setting of dedicated software was performed as follows.

  Set the total count number in the control mode to 50000 particles, set the number of measurements once, and the Kd value is “10.0 μm standard particle” (Beckman Coulter Co., Ltd.) Make the obtained value. By pressing the threshold / noise level measurement button, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check the flush of the aperture tube after measurement.

  In the dedicated software “pulse to particle size conversion setting screen”, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

The specific measurement method is as follows.
(1) Put about 200 ml of the electrolytic aqueous solution in a 250 ml round bottom beaker for exclusive use of ultisizer 3 and set it on a sample stand, and stir the stirrer rod at 24 rotations / sec counterclockwise. Then, dirt and air bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
(2) About 30 ml of the above-mentioned electrolytic aqueous solution is placed in a 100 ml flat bottom beaker made of glass, and "contaminone N" (a nonionic surfactant, an anionic surfactant, an organic builder precisely measured in pH 7 as a dispersant) Add about 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for cell washing (manufactured by Wako Pure Chemical Industries, Ltd.) with ion-exchanged water three times by mass.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated 180 degrees out of phase, and an electric output of 120 W is placed in a water tank of an ultrasonic dispersion “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikkaki Bios Co., Ltd.) Add a fixed amount of ion-exchanged water, and add about 2 ml of the Contaminone N to the water tank.
(4) The beaker of said (2) is set to the beaker fixing hole of the said ultrasonic dispersion device, and an ultrasonic dispersion device is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid surface of the electrolytic aqueous solution in the beaker is maximized.
(5) While the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, ultrasonic dispersion processing is continued for another 60 seconds. In addition, in ultrasonic dispersion, the water temperature of the water tank is appropriately adjusted so as to be 10 ° C. or more and 40 ° C. or less.
(6) In the (1) round bottom beaker placed in the sample stand, the (5) electrolyte aqueous solution in which the toner is dispersed using a pipette is dropped to adjust the measurement concentration to about 5%. Then, measurement is performed until the number of measurement particles reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the device to calculate the weight average particle diameter (D4). The "arithmetic diameter" on the analysis / volume statistical value (arithmetic mean) screen when the graph / volume% is set by dedicated software is the weight average particle size (D4).

<Method of Measuring Average Circularity of Toner Particles>
The average circularity of the toner particles is measured by a flow type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) under the measurement and analysis conditions at the time of the calibration operation.

  The specific measurement method is as follows. First, about 20 mL of ion-exchanged water from which impure solids and the like have been previously removed is placed in a glass container. Among them, “contaminone N” (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH 7 precision measuring instrument cleaning consisting of organic builders as a dispersant, Wako Pure Chemical Industries, Ltd. 2.) add about 0.2 mL of a diluted solution diluted about 3 times by volume with deionized water.

  Further, about 0.02 g of a measurement sample is added, and dispersion treatment is performed for 2 minutes using an ultrasonic dispersion device to obtain a dispersion for measurement. At that time, the dispersion is suitably cooled so that the temperature of the dispersion becomes 10 ° C. or more and 40 ° C. or less. As an ultrasonic disperser, a table-top ultrasonic cleaner disperser with an oscillation frequency of 50 kHz and an electrical output of 150 W (for example, "VS-150" (manufactured by VERVO CREER)) is used. Add a fixed amount of ion exchange water, and add about 2 mL of the Contaminone N into the water bath.

  For measurement, use the flow type particle image analyzer equipped with “UPlanApro” (10 × magnification, 0.40 numerical aperture) as the objective lens, and for the sheath liquid, use the particle sheath “PSE-900A” (Sysmex Corp.) Made). The dispersion prepared according to the above procedure is introduced into the flow type particle image analyzer, and 3,000 toner particles are measured in the total count mode in the HPF measurement mode. Then, the binarization threshold value at the time of particle analysis is set to 85%, and the diameter of an analysis particle is limited to not less than 1.985 μm and less than 39.69 μm, and the average circularity of toner particles is determined.

  In the measurement, automatic focusing is performed using standard latex particles (for example, “RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A” manufactured by Duke Scientific Inc. diluted with ion exchange water) before the start of the measurement. After that, it is preferable to perform focusing every two hours from the start of measurement.

  In the present invention, a flow type particle image measuring device which has been subjected to a calibration work by Sysmex Corporation and which has been issued a calibration certificate issued by Sysmex Corporation is used. The measurement is performed under the measurement and analysis conditions at the time of receiving the proof of calibration except that the analysis particle diameter is limited to the circle equivalent diameter of 1.985 μm or more and less than 39.69 μm.

  The measurement principle of the flow type particle image measurement apparatus "FPIA-3000" (manufactured by Sysmex Corporation) is to perform image analysis by imaging flowing particles as a still image. 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 cell is sandwiched by the sheath fluid to form a flat flow.

  The sample passing through the flat sheath flow cell is irradiated with strobe light at intervals of 1/60 seconds, and it is possible to capture flowing particles as a still image. Also, since the flow is flat, the image is captured in focus. The particle image is imaged by a CCD camera, and the imaged image is subjected to image processing with an image processing resolution of 512 × 512 pixels (0.37 × 0.37 μm per pixel), and the outline of each particle image is extracted, and the particle image The projected area S, the perimeter L, etc. of the

Next, the equivalent circle diameter and the degree of circularity are determined using the area S and the perimeter L. The equivalent circle 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 perimeter of the circle determined from the equivalent circle diameter by the perimeter of the particle projection image It is defined and calculated by the following equation.
Circularity = 2 × (π × S) ^1/2 / L

  When the particle image is circular, the degree of circularity is 1.000, and the degree of circularity becomes smaller as the degree of unevenness on the outer periphery of the particle image becomes larger. After calculating the degree of circularity of each particle, the range of degree of circularity 0.200 to 1.000 is divided into 800, the arithmetic mean value of the obtained degree of circularity is calculated, and the value is defined as the average degree of circularity.

<Method of measuring coverage of external additive>
The coverage (X1) of the surface of the toner particles with the external additive is calculated as follows.

The following apparatus is used under the following conditions to conduct elemental analysis of the toner surface.
Measurement device: Quantum 2000 (trade name, manufactured by ULVAC-PHI, Inc.)
・ X-ray source: Monochrome Al K α
・ Xray Setting: 100 μmφ (25 W (15 KV))
Photoelectron delivery angle: 45 degrees Neutralization condition: Combination of neutralization gun and ion gun Analysis area: 300 μm × 200 μm
・ Pass Energy: 58.70 eV
Step size: 1.25 eV
Analysis software: Multipak (PHI)

  For example, when the coverage of silica fine particles is to be determined, the peaks of C 1c (B.E. 280 to 295 eV), O1s (B.E. 525 to 540 eV) and Si 2p (B.E. 95 to 113 eV) are used Calculate the quantitative value of Si atom. The quantitative value of the Si atom obtained here is Y1.

  Next, the elemental analysis of the silica fine particle alone is performed in the same manner as the elemental analysis of the surface of the toner described above, and the quantitative value of the Si atom obtained here is taken as Y2.

The coverage X1 of the toner surface with the silica fine particles is defined as the following equation using the above Y1 and Y2.
X1 (area%) = (Y1 / Y2) x 100

  The measurement is performed 100 times on the same sample, and their arithmetic mean value is adopted.

  Moreover, when using multiple types of external additives, the said coverage X1 is calculated | required about each external additive, and let the value which added them be X1.

  When obtaining the quantitative value Y2, if it is possible to obtain an external additive used for external addition, measurement may be performed using it.

  When the external additive separated from the surface of the toner particles is used as a measurement sample, the external additive is separated from the toner particles according to the following procedure.

1) In the case of magnetic toner First, in 100 mL of ion-exchanged water, Contaminone N (a 10% by weight aqueous solution of a neutral detergent for cleaning a pH 7 precision measuring instrument consisting of a nonionic surfactant, an anionic surfactant and an organic builder, 6 mL of Wako Pure Chemical Industries, Ltd. is added to prepare a dispersion medium. To this dispersion medium, 5 g of toner is added, and dispersed for 5 minutes with an ultrasonic dispersion machine (As One Corp. VS-150). Then, it sets in Iwaki Sangyo Co., Ltd. "KM Shaker" (model: V.SX), and shakes for 20 minutes on the conditions of 350 reciprocations per minute.

  Thereafter, the toner particles are restrained using a neodymium magnet, and the supernatant is collected. The external additive is collected by drying the supernatant. Repeat this process if it is not possible to collect a sufficient amount of external additive.

  When a plurality of types of external additives are used, the external additives may be sorted from the collected external additives using centrifugation or the like.

2) In the case of non-magnetic toner 160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water, and the mixture is dissolved in water to prepare a sucrose concentrate. Into a tube for centrifugation, 31 g of the sucrose concentrate and 6 mL of contaminone N are added to prepare a dispersion. 1 g of toner is added to this dispersion, and a toner is loosened with a spatula or the like.

  The centrifuge tube is shaken on the shaker for 20 minutes at 350 reciprocations per minute. After shaking, the solution is replaced with a glass tube for swing rotor (50 mL), and centrifugation is performed using a centrifuge (H-9R; manufactured by Kokusan Co., Ltd.) under conditions of 3500 rpm for 30 minutes. In the glass tube after centrifugation, the toner is present in the uppermost layer, and the external additive is present on the aqueous solution side of the lower layer. The lower layer aqueous solution is collected and centrifuged to separate sucrose and external additives and collect external additives. If necessary, repeat centrifugation repeatedly, and after sufficient separation, dry the dispersion and collect external additives.

  As in the case of the magnetic toner, when a plurality of external additives are used, the external additives are sorted from the collected external additives by using a centrifugal separation method or the like.

<Method of measuring true density of toner particles and external additive>
The true density of the toner particles is measured according to the operation manual of the apparatus using a dry automatic densitometer "Accupick 1330" manufactured by Shimadzu Corporation.

<Measurement of Tg of Toner Particles>
The Tg of toner particles is measured according to ASTM D3418-82 using a differential scanning calorimeter "Q2000" (manufactured by TA Instruments). The temperature correction of the device detection unit uses the melting points of indium and zinc, and the heat of fusion uses the heat of fusion of indium. Specifically, approximately 2 mg of the sample is precisely weighed, and placed in an aluminum pan, using an empty aluminum pan as a reference, with a temperature rising rate of 10 between the measurement temperature range of 30 to 200 ° C. Measure at ° C / min. In the measurement, the temperature is once raised to 200 ° C., then the temperature is lowered to 30 ° C., and then the temperature is raised again. The specific heat change is obtained in the temperature range of 40 ° C. to 100 ° C. in the second temperature raising process. The intersection point of the line at the midpoint of the baseline before and after the specific heat change at this time and the differential thermal curve is taken as the glass transition temperature Tg of the toner particles.

  Hereinafter, the present invention will be specifically described by way of production examples and examples, but the present invention is not limited at all. All parts in the following formulation are parts by mass.

<Production example of treated magnetic material>
In aqueous ferrous sulfate solution, sodium hydroxide solution of 1.00 to 1.10 equivalent to iron element, P ₂ O _{5 in} an amount of 0.15 mass% in terms of phosphorus element to iron element, iron SiO ₂ was mixed in an amount of 0.50% by mass in terms of silicon element with respect to the element to prepare an aqueous solution containing ferrous hydroxide. The pH of the aqueous solution was adjusted to 8.0, and oxidation reaction was carried out at 85 ° C. while blowing in air to prepare a slurry liquid having seed crystals.

  Next, an aqueous ferrous sulfate solution is added to the slurry liquid so as to be 0.90 to 1.20 equivalents with respect to the initial alkali amount (sodium component of sodium hydroxide), and then the slurry liquid is maintained at pH 7.6. Then, while introducing air, the oxidation reaction was promoted to obtain a slurry containing magnetic iron oxide.

  The obtained slurry was filtered and washed, and the water-containing slurry was once taken out. At this time, a small amount of water-containing slurry was collected and the water content was measured.

  Next, this water-containing slurry was put into another aqueous medium without drying, and was re-dispersed with a pin mill while stirring and circulating the slurry, and the pH of the re-dispersion was adjusted to about 4.8.

  Then, while stirring, 1.6 parts (the amount of magnetic iron oxide was calculated as a value obtained by subtracting the water content from the water-containing slurry) with respect to 100 parts of the magnetic iron oxide with n-hexyltrimethoxysilane coupling agent added It was disassembled. Thereafter, the mixture was sufficiently stirred, and the pH of the dispersion was adjusted to 8.6 to perform surface treatment. The formed hydrophobic magnetic material is filtered by a filter press, washed with a large amount of water and then dried at 100 ° C. for 15 minutes and 90 ° C. for 30 minutes, and the resulting particles are crushed to obtain a volume average particle diameter of A 0.21 μm processed magnetic material was obtained.

<Production Example of External Additive 1>
In a stirrer-equipped autoclave, a silica bulk (a number average particle diameter of primary particles = 12 nm of fumed silica) was charged, and heated to 200 ° C. in a fluidized state by stirring.

  The inside of the reactor was replaced with nitrogen gas to seal the reactor, and 25 parts of hexamethyldisilazane was sprayed to the inside with respect to 100 parts of the silica raw material to perform silane compound treatment in a fluidized state of silica. The reaction was continued for 60 minutes and then terminated. After completion of the reaction, the autoclave was depressurized and washed with a nitrogen gas stream to remove excess hexamethyldisilazane and by-products from the hydrophobic silica.

Further, 10 parts of dimethyl silicone oil (viscosity = 100 mm ² / sec) was sprayed onto 100 parts of the silica base while stirring the hydrophobic silica in the reaction vessel, and the stirring was continued for 30 minutes. Thereafter, the temperature was raised to 300 ° C. while stirring, and stirring was further performed for 2 hours. Thereafter, it was taken out and subjected to crushing treatment to obtain an external additive 1 which is silica fine particles. Physical properties are shown in Table 1.

<Production example of external additive 2>
In the production of the external additive 2, the combustion furnace used a double tube hydrocarbon-oxygen mixed burner capable of forming an inner flame and an outer flame. The two-fluid nozzle for slurry injection is grounded at the center of the burner, and the silicon compound of the raw material is introduced. A hydrocarbon-oxygen combustible gas is injected from the periphery of the two-fluid nozzle to form an inner flame and an outer flame which are reducing atmospheres. By controlling the amount and flow rate of the flammable gas and oxygen, the atmosphere, temperature, flame length, etc. are adjusted. In the flame, silica fine particles are formed from the silicon compound and are further fused until the desired particle size is obtained. Then, after cooling, it is obtained by collecting with a bag filter etc. Silica fine particles were manufactured using hexamethyl cyclotrisiloxane as a raw material silicon compound, and 99.6% by mass of the obtained silica fine particles were surface-treated with 0.4% by mass of hexamethyldisilazane. Physical properties are shown in Table 1.

<Production example of external additive 3>
687.9 g of methanol, 42.0 g of pure water, and 47.1 g of 28% by mass aqueous ammonia were added to and mixed with a 3 L glass reactor equipped with a stirrer, a dropping funnel, and a thermometer. The resulting solution was adjusted to 35 ° C., and 1100.0 g (7.23 mol) of tetramethoxysilane and 395.2 g of 5.4% by mass aqueous ammonia were started to be added simultaneously while stirring. The tetramethoxysilane was dropped over 5 hours, and the ammonia water was dropped over 4 hours.

  After completion of the dropwise addition, stirring was further continued for 0.2 hours to conduct hydrolysis to obtain a methanol-water dispersion liquid of hydrophilic spherical sol-gel silica fine particles. Then, an ester adapter and a cooling pipe were attached to a glass reactor, and the dispersion was heated to 65 ° C. to distill off methanol. Thereafter, the same amount of pure water as the distilled off methanol was added. The dispersion was thoroughly dried at 80 ° C. under reduced pressure. The obtained silica particles were heated at 400 ° C. for 10 minutes in a thermostat. The above process was carried out 20 times, and the obtained silica fine particles were subjected to crushing treatment with a Pulverizer (manufactured by Hosokawa Micron Ltd.).

  Thereafter, 500 g of the silica particles were charged into a polytetrafluoroethylene inner cylinder type stainless steel autoclave having an inner volume of 1000 mL. After replacing the inside of the autoclave with nitrogen gas, 0.5 g of HMDS (hexamethyldisilazane) and 0.1 g of water are atomized with a two-fluid nozzle while rotating the stirring blade attached to the autoclave at 400 rpm. The silica powder was sprayed uniformly. After stirring for 30 minutes, the autoclave was sealed and heated at 200 ° C. for 2 hours. Subsequently, while heating, the system was depressurized to remove ammonia, whereby an external additive 3 was obtained. Physical properties are shown in Table 1.

<Production example of external additive 4>
The external additive 4 was prepared according to Example 1 of WO 2013/063291. Physical properties are shown in Table 1.

<Production example of external additive 5>
The external additive 5 used commercially available strontium titanate (made by Fuji titanium industry Co., Ltd.). Physical properties are shown in Table 1.

<Production Example of Amorphous Polyester 1>
In a reaction vessel equipped with a nitrogen introducing pipe, a dewatering pipe, a stirrer and a thermocouple, as shown in Table 2, the carboxylic acid component and the alcohol component are adjusted as raw material monomers, and then put into an esterification catalyst (octylic acid 1.5 parts of tin) was added to 100 parts of total monomers.

  Next, the temperature was raised quickly to 180 ° C. under normal pressure under a nitrogen atmosphere, and then water was distilled off while heating from 180 ° C. to 210 ° C. at a rate of 10 ° C./hour to carry out polycondensation.

  After reaching 210 ° C., the pressure in the reaction vessel was reduced to 5 kPa or less, and polycondensation was performed under the conditions of 210 ° C. and 5 kPa or less to obtain amorphous polyester 1.

  In addition, the physical properties which adjusted superposition | polymerization time so that the peak molecular weight of amorphous polyester 1 might become a value of Table 2 are shown in Table 1.

<Production Example of Amorphous Polyester 2>
Amorphous polyester 2 was obtained in the same manner as amorphous polyester 1 except that the raw material monomers and the amount used were changed to those described in Table 2. Physical properties are shown in Table 2.

<Production Example of Toner Particles 1>
After adding 450 parts of 0.1 mol / L Na ₃ PO ₄ aqueous solution to 720 parts of ion exchange water and heating to 60 ° C., 67.7 parts of 1.0 mol / L CaCl ₂ aqueous solution is added An aqueous medium containing a dispersant was obtained.

Styrene 75.0 parts n-butyl acrylate 25.0 parts amorphous polyester 1 10.0 parts divinylbenzene 0.6 part iron complex of monoazo dye (T-77: manufactured by Hodogaya Chemical Co., Ltd.) 1. 5 parts and 65.0 parts of treated magnetic material The above-mentioned formulation was uniformly dispersed and mixed using an attritor (Mitsui Miike Kako Co., Ltd.) to obtain a monomer composition. This monomer composition was heated to 63 ° C., to which 15.0 parts of paraffin wax (melting point: 78 ° C.) were added and mixed, and dissolved. Thereafter, 6.0 parts of a polymerization initiator tert-butyl peroxypivalate was dissolved.

  The above monomer composition is charged into the above aqueous medium, and T.V. K. The mixture was granulated by stirring with a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 12000 rpm for 10 minutes.

  Then, it was made to react at 70 degreeC for 4 hours, stirring with a paddle stirring blade. After completion of the reaction, colored resin particles were dispersed in the aqueous medium obtained here, and it was confirmed that calcium phosphate was adhered to the surface of the colored resin particles as an inorganic dispersant.

  Subsequently, the aqueous medium in which the colored resin particles were dispersed was heated to 100 ° C. and held for 120 minutes. Thereafter, the mixture was cooled to room temperature at 3 ° C./minute, and hydrochloric acid was added to dissolve the dispersant, followed by filtration, washing with water and drying to obtain toner particles 1. Physical properties of the obtained toner particles 1 are shown in Table 3.

<Production Example of Toner Particles 2>
After adding 450 parts of 0.1 mol / L Na ₃ PO ₄ aqueous solution to 720 parts of ion exchange water and heating to 60 ° C., 67.7 parts of 1.0 mol / L CaCl ₂ aqueous solution is added An aqueous medium containing a dispersant was obtained.

Styrene 74.0 parts n-butyl acrylate 26.0 parts Amorphous polyester 2 10.0 parts divinylbenzene 0.4 parts Iron complex of monoazo dye (T-77: manufactured by Hodogaya Chemical Co., Ltd.) 1. 5 parts of carbon black (MA 100: manufactured by Mitsubishi Chemical Co., Ltd.) 7.0 parts The above-described formulation was uniformly dispersed and mixed using an attritor (Mitsui Miike Kako Co., Ltd.) to obtain a monomer composition. This monomer composition was heated to 63 ° C., and 10.0 parts of paraffin wax (melting point: 78 ° C.) and 5.0 parts of ester wax (melting point: 72 ° C.) were added thereto and mixed and dissolved. Thereafter, 6.0 parts of a polymerization initiator tert-butyl peroxypivalate was dissolved.

  The above monomer composition is charged into the above aqueous medium, and T.V. K. The mixture was granulated by stirring with a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 12000 rpm for 10 minutes.

  Then, it was made to react at 70 degreeC for 4 hours, stirring with a paddle stirring blade. After completion of the reaction, colored resin particles were dispersed in the aqueous medium obtained here, and it was confirmed that calcium phosphate was adhered to the surface of the colored resin particles as an inorganic dispersant.

  Subsequently, the aqueous medium in which the colored resin particles were dispersed was heated to 100 ° C. and held for 120 minutes. Thereafter, the mixture was cooled to room temperature at 3 ° C./minute, and hydrochloric acid was added to dissolve the dispersant, followed by filtration, washing with water and drying to obtain toner particles 2. Physical properties of the obtained toner particles 2 are shown in Table 3.

<Production Example of Toner Particles 3>
71.0 parts of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 28.0 parts of terephthalic acid, 1.0 parts of trimellitic anhydride and 0.5 parts of titanium tetrabutoxide Place it in a glass 4-liter four-necked flask, attach a thermometer, a stirrer, a condenser and a nitrogen inlet tube, and place it in a mantle heater. Next, the inside of the flask is replaced with nitrogen gas, and the temperature is gradually raised while stirring, and reaction is performed for 4 hours while stirring at a temperature of 200 ° C. to obtain polyester resin 1-1. Physical properties of this polyester resin 1-1 are weight average molecular weight (Mw) 80000, number average molecular weight (Mn) 3500, and peak molecular weight (Mp) 5700.

  Also, 70.0 parts of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 20.0 parts of terephthalic acid, 3.0 parts of isophthalic acid, and 7.0 parts of trimellitic anhydride Then, 0.5 parts of titanium tetrabutoxide is placed in a 4-liter, four-neck glass flask, and a thermometer, a stirrer, a condenser and a nitrogen inlet tube are attached and placed in a mantle heater. Next, the inside of the flask is replaced with nitrogen gas, and the temperature is gradually raised with stirring, and reaction is performed for 6 hours while stirring at a temperature of 220 ° C. to obtain polyester resin 1-2. Physical properties of the polyester resin 1-2 are weight average molecular weight (Mw) 120000, number average molecular weight (Mn) 4000, and peak molecular weight (Mp) 7800.

The above polyester resin 1-1: 70 parts and polyester resin 1-2: 30 parts are preliminarily mixed with Mitsui Henschel mixer (made by Mitsui Miike Koki Co., Ltd.), and melt kneader (PCM-30 type, Ikegai Iron Works Co., Ltd.) C., and melt-blended under the conditions of a rotation speed of 3.3 s.sup.- ¹ and a kneading resin temperature of 100.degree. C. to obtain a binder resin 1.

next,
・ Low density polyethylene (Mw 1400, Mn 850, maximum endothermic peak by DSC 100 ° C) 20.0 parts ・ Styrene 64.0 parts ・ n-butyl acrylate 13.5 parts ・ Acrylonitrile 2.5 parts or more are charged in an autoclave, After the interior is purged with N ₂ , the temperature is maintained at 180 ° C. while being heated and stirred. Into the system, 50 parts of a 2% by mass solution of t-butyl hydroperoxide in xylene is continuously added dropwise for 5 hours, and after cooling, the solvent is separated and removed to obtain a polymer A. When the molecular weight of the polymer A was measured, the weight average molecular weight (Mw) was 7,000, and the number average molecular weight (Mn) was 3,000.

next,
Binder resin 1 100 parts Polymer A 5 parts Fischer Tropsch wax 5 parts (peak temperature of maximum endothermic peak 78 ° C.)
C. I. Pigment Blue 15: 3: 8 parts by Dainichi Seisei Co., Ltd. Negative charge control agent (aluminum compound of 3,5-di-tert-butylsalicylic acid)
0.5 part After mixing the above-mentioned prescription with Mitsui Henschel mixer (made by Mitsui Miike Kako Co., Ltd.), it knead | mixes with the twin-screw kneader (PCM-30 type, Ikegai Iron Works Co., Ltd. product) set to temperature 130 ° C. Do. The mixture is cooled and roughly crushed to 1 mm or less with a hammer mill to obtain a crushed material. The obtained crushed material is crushed by a mechanical grinder (T-250, manufactured by Turbo Kogyo Co., Ltd.). Further, classification is performed by a multi-division classifier utilizing the Coanda effect to obtain resin particles.

The resin particles thus obtained are passed through a mechanical type classification and simultaneous spheronizing device (facialty, manufactured by Hosokawa Micron Corporation) to remove fine particles at a classification rotor rotation speed of 120 s ⁻¹ while the dispersion rotor rotation speed is 100 s ⁻¹ (rotation circumference The surface treatment was performed at a speed of 130 m / sec) for 60 seconds to obtain toner particles 3. Physical properties of the obtained toner particles 3 are shown in Table 3.

<Production Example of Toner 1>
100 parts of toner particles 1, 0.3 parts of external additive 1, 1.5 parts of external additive 2 and 0.3 parts of external additive 5 were prepared using Mitsui Henschel Mixer (manufactured by Mitsui Miike Kako Co., Ltd.). It mixed for 5 minutes at 42 m / sec in speed (1st step; Table 4-1). Thereafter, a heating and mixing process was performed using the apparatus shown in FIG. 1 (second stage; Table 4-2).

  The apparatus shown in FIG. 1 uses the apparatus of 130 mm in diameter of the inner peripheral part of the main body casing 30, and further has the apparatus configuration conditions shown in Table 4-2. Hot water was passed through the jacket so that the temperature (T1) inside the inner piece for raw material inlet 316 was 55 ° C.

  After the external additive toner is charged into the apparatus shown in FIG. 1 and configured as described above, the peripheral velocity (1.0 m / m) of the outermost end of the agitating blade 33 is constant so that the effective operating power shown in Table 4-2 is constant. It heat-processed for 10 minutes, adjusting sec).

  After the heat treatment, the toner 1 was obtained by sieving with a mesh of 75 μm. Various physical properties of Toner 1 are shown in Table 5.

<Production Example of Toner 2 to Toner 37>
Toners 2 to 37 were obtained in the same manner as in the production example of the toner 1 except that the formulations shown in Tables 4-1 and 4-2 and the production conditions in the production example of the toner 1 were used. Table 5 shows physical properties of Toner 2 to Toner 37 obtained.

Example 1
<Image forming apparatus>
150 g of the toner 1 was filled in a cartridge (CF230X) for an HP printer (LaserJet Pro M203 dw), and the following evaluation was performed in each of a high temperature and high humidity environment and a low temperature and low humidity environment.

  First, the main body and the cartridge are left for 5 days in a high temperature and high humidity environment (32.5 ° C., 80% RH). After leaving, perform the following evaluation.

<Image density>
The image density was such that a solid black image was formed entirely in a high temperature and high humidity environment (32.5 ° C. 80% RH), and the density of this solid image was measured with a Macbeth densitometer (manufactured by Macbeth) using a SPI filter. The evaluation timing was carried out immediately after the toner was put into the cartridge. The results are shown in Table 6. The judgment criteria are as follows. It is judged that C or more is good.
A: 1.45 or more B: 1.40 or more and less than 1.45 C: 1.35 or more and less than 1.40 D: less than 1.35

<Dr upper white after fog>
The measurement of fog is measured using REFLECTMETER MODEL TC-6DS manufactured by Tokyo Denshoku Co., Ltd. The filter uses a green filter. After black on the drum, the white image immediately after outputting a solid black image is taped on the drum (electrostatic latent image carrier) with mylar tape, and the reflectance of the mylar tape pasted on the paper is directly on the paper. It calculated by deducting the Macbeth density | concentration of the pasted mylar tape, and evaluated by the following judgment criteria.
Fog (reflectance) (%) = reflectance of tape taped on drum (%)-reflectance of tape directly applied to paper (%)

The evaluation timing is immediately after the image density evaluation is performed. The results are shown in Table 6. The judgment criteria are as follows. It is judged that C or more is good.
A: less than 5% B: 5% or more and less than 10% C: 10% or more and less than 15% D: 15% or more

<Sleeve fusion>
After the repeated use test, the sleeve surface was visually observed, and the degree of toner contamination was evaluated according to the following criteria. It is judged that C or more is good.
A: no contamination observed B: slight contamination observed C: partial contamination observed D: significant contamination observed

Then, the evaluation in a low temperature and low humidity environment is performed. After charging the toner into the cartridge again, leave the main unit and the cartridge in a low temperature and low humidity environment (15.0 ° C, 10.0% RH) for 5 days. After standing, repeat the use test. In the repeated use test, as in the evaluation under the high-temperature and high-humidity environment, a horizontal line image with a printing rate of 1% was printed on a total of 5000 sheets (5 days), 1000 sheets a day by intermittent sheet passing. In addition, it carries out using the Vitality (made by Xerox Co., Ltd.) whose basis weight is 75 g / m < ² > as evaluation paper used for a repeated use test.

  In addition, in anticipation of speeding up in the future, a modification was made to change the process speed of the main unit, and the speed was increased from 30 sheets / minute to 33 sheets / minute.

<Evaluation of transferability>
In the low temperature and low humidity environment (15.0 ° C, 10.0% RH), electrostatics at the time of solid image formation when the transfer current is adjusted to 8.0 μA immediately after charging the toner into the cartridge and after printing 5000 sheets The transfer residual toner on the latent image carrier was taped off with a transparent polyester adhesive tape (trade name: polyester tape No. 5511, supplied to: Nichiban Co., Ltd.). The density difference of what peeled off the pressure-sensitive adhesive tape on paper was calculated by subtracting the density difference of the pressure-sensitive adhesive tape only on the paper.

The concentration was measured using REFLECTMETER MODEL TC-6DS manufactured by Tokyo Denshoku Co., Ltd. The filter used was a green filter.
A: The concentration difference is very good at less than 5.0 B: The concentration difference is good at 5.0 or more and less than 10.0 C: The concentration difference is 10.0 or more and less than 15.0 D: The concentration The difference is 15.0 or more

[Examples 2 to 30, Comparative Examples 1 to 7]
The toners shown in Table 6 were evaluated in the same manner as in Example 1. The results are shown in Table 6.

  30: Body casing, 31: stirring member, 32: rotating body, 33: stirring blade, 33a: first stirring blade (feeding stirring blade), 33b: second stirring blade (returning stirring blade), 34: Jacket, 35: Raw material inlet, 36: Product outlet, 37: Central axis, 38: Drive part, 39: Processing space, 310: Rotor end side, 41: Rotation direction, 42: Return direction, 43: Feed Direction, 316: Inner piece for raw material inlet, 317: Inner piece for product outlet, d: Interval showing overlapping portion of stirring members, D: Width of stirring members

Claims (8)

A method for producing a toner comprising toner particles containing a binder resin and a colorant, and an external additive,
The external additive is inorganic fine particles or organic-inorganic composite fine particles,
Processing the mixture containing the toner particles and the external additive;
The processing apparatus used in the processing step is
A stirring member having a rotating body and a plurality of stirring blades provided on a surface of the rotating body;
A container whose inner peripheral surface accommodates the stirring member is cylindrical, and a driving unit for applying a rotational driving force to the rotating body to rotate the stirring member in the container,
Have
Each of the plurality of stirring blades is provided to have a gap with the inner circumferential surface of the container,
A plurality of stirring blades for causing the mixture introduced into the container by rotation of the stirring member to move in a first axial direction of the rotating body; And a second stirring blade for feeding in the other axial direction,
The circumferential velocity V of the plurality of stirring blades when rotating the stirring member in the treatment step is 0.1 m / sec or more and 7.0 m / or less,
In the processing step, the mixture is heated and mixed, and when the material temperature of the mixture at the start of the heating and mixing is T1 and the glass transition temperature of the toner particles is T2, the following formula (1) is satisfied:
A toner manufacturing method characterized in that the following formula (2) is satisfied, where E (Wh / g) is the mixing processing energy at the time of the heating and mixing.
T2-10 ° C. ≦ T1 ≦ T2 + 10 ° C. (1)
1.0 × 10 ⁻⁴ Wh / g ≦ E ≦ 1.5 × 10 ⁻² Wh / g (2)   2. The method according to claim 1, wherein a peripheral velocity V of the plurality of stirring blades when rotating the stirring member in the processing step is 0.5 m / sec or more and 2.0 m / sec or less.   When an extension line is drawn from the end position of the first stirring blade in a direction perpendicular to the rotation axis of the rotating body, there is a portion overlapping the second stirring blade, and its width is d, 3. The method according to claim 1, wherein d / D is 0.1 or more and 0.3 or less, where D is a width of the second stirring blade.   The method for producing a toner according to any one of claims 1 to 3, wherein the gaps are respectively 1% or more and 5% or less of the diameter of the inner peripheral surface of the container. The toner according to any one of claims 1 to 4, wherein D / L is 0.2 or more and 0.3 or less, where D is a width of the plurality of stirring blades and L is a length of the rotating body. Manufacturing method.
  The method for producing a toner according to any one of claims 1 to 5, wherein the external additive is inorganic fine particles, and the number average particle diameter of the inorganic fine particles is 40 nm or more and 200 nm or less.   The method for producing a toner according to any one of claims 1 to 6, wherein the inorganic fine particles are silica fine particles. Let T3 be the temperature of the mixture after completion of the heating and mixing,
The method for producing a toner according to any one of claims 1 to 7, wherein a value obtained by multiplying T3 by a processing time of the processing step is 3000 (° C · sec) or more and 100,000 (° C · sec) or less. .

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