JP2019028158A - Stirring device and manufacturing method of agglomerated particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To introduce a first dispersion liquid containing first resin particles into a stirring tank, and in a state where the first dispersion liquid is stirred by a stirring blade, a second dispersion liquid containing second resin particles is mixed in the stirring tank. Provided is a stirring device in which the formation of coarse particles is suppressed as compared with the case where the particles are brought into contact with the inner wall and introduced into the stirring tank along the inner wall of the stirring tank. SOLUTION: A stirring device 1 has a stirring tank 10, a stirring shaft 12 rotatably mounted in the stirring tank 10, a stirring blade 14 mounted on the stirring shaft 12, and a wall surface of the stirring tank 10 in the tank. A heat transfer unit 16 for applying heat to the agitator tank 30 and an introduction unit 18 having a discharge port 30 for discharging the fluid from the discharge port 30 toward the inside of the agitation tank 10 and introducing the fluid into the agitation tank 10. The introduction unit 18 has a velocity component along the flow of the first dispersion liquid containing the first resin particles previously introduced into the stirring tank 10 and stirred by the stirring blade 14, and is on the inner wall of the stirring tank 10. A second dispersion containing the second resin particles is introduced without contact. [Selection diagram] Fig. 1

Description

  The present invention relates to a stirring device and a method for producing aggregated particles.

  There is a wet production method for producing aggregated particles such as toner particles. For example, the following methods are known.

  For example, in Patent Document 1, a metal salt-added resin dispersion containing a resin (2) and a metal salt is added to a dispersion containing core aggregated particles obtained by aggregating the binder resin (1), and the core is added. The resin (2) is adhered to the surface of the aggregated particles to form core-shell aggregated particles, and the core-shell aggregated particles are fused by heating to a temperature higher than the glass transition temperature of the binder resin (1) and the resin (2) ( A method for producing a core-shell toner is disclosed.

  By the way, in the production of the aggregated particles, for example, a stirring tank, a stirring shaft rotatably mounted in the stirring tank, a stirring blade attached to the stirring shaft, and a wall surface of the stirring tank into the tank. A stirring device is used that includes a heat transfer section that applies heat and an introduction section that introduces fluid into the stirring tank. Specifically, the first dispersion containing the first resin particles introduced into the stirring tank of the stirring device is stirred by a stirring blade, and the first resin particles are aggregated, and then the second dispersion containing the second resin particles. Is introduced into the agitation tank from the introduction part of the agitation device, and agglomerated particles in which the second resin particles adhere to the surface of the core agglomerated particles in which the first resin particles are agglomerated by stirring with the first dispersion in the agitation tank. Manufacturing.

  Here, normally, in order to suppress foaming of the liquid surface in the stirring tank when the second dispersion is introduced from the introduction part, the second dispersion is discharged from the introduction part toward the inner wall of the stirring tank, The dispersion may be brought into contact with the inner wall of the stirring tank and the second dispersion may be introduced along the inner wall. However, the inner wall of the stirring tank is a place where the liquid tends to stay. Further, the liquid that is in contact with the inner wall of the agitation tank or the liquid that is retained on the inner wall is likely to be heated by heat from the heat transfer section that applies heat from the wall surface of the agitation tank to the inside of the tank. As a result, excessive cohesive force may act on the resin particles in the second dispersion liquid that are brought into contact with the inner wall of the stirring tank and added along the inner wall of the stirring tank to form coarse particles. .

  Here, the coarse particle means a particle having a very large particle diameter as compared with the volume average particle diameter of the obtained aggregated particle, and particularly 2.5 times or more of the volume average particle diameter of the aggregated particle. A particle having a particle size.

JP 2011-8244 A

  An object of the present invention is to introduce a second dispersion containing second resin particles in a state where the first dispersion containing first resin particles is introduced into a stirring vessel and the first dispersion is stirred by a stirring blade. Compared to the case where it is brought into contact with the inner wall of the stirring tank and introduced into the stirring tank so as to be along the inner wall of the stirring tank, a stirrer in which formation of coarse particles is suppressed and a method for producing aggregated particles are provided. is there.

  The invention which concerns on Claim 1 gives heat in a tank from the stirring tank, the stirring shaft rotatably attached in the said stirring tank, the stirring blade attached to the said stirring shaft, and the wall surface of the said stirring tank A heat transfer section; and an introduction section that has a discharge port, discharges fluid from the discharge port into the stirring tank, and introduces the fluid into the stirring tank. A second component is introduced so as to have a velocity component along the flow of the first dispersion containing the first resin particles introduced in advance into the stirring tank and stirred by the stirring blade, and without contacting the inner wall of the stirring tank. A stirring device for introducing a second dispersion containing resin particles.

According to a second aspect of the present invention, an angle formed between a perpendicular to a straight line connecting the discharge port of the introduction part and the stirring shaft and a central axis of the discharge port of the introduction part is θ1, and the angle from the liquid level in the stirring tank The height from the introduction port to the discharge port is H, the angle formed by the extension line extending in the direction from which the second dispersion liquid is discharged from the discharge port of the introduction portion and the horizontal line is θ2, and the height from the discharge port of the introduction unit to the first port. 2. The stirring device according to claim 1, wherein d is a horizontal distance between the discharge port and the inner wall of the stirring tank in a direction in which the dispersion liquid is discharged, and satisfies the following (1) to (4).
-90 ° <θ1 <90 ° (1)
0.05m ≦ H ≧ 1.0m (2)
0 ° <θ2 <90 ° (3)
0.1 m ≦ d ≦ 2.5 m (4)

  The invention according to claim 3 uses the stirrer according to claim 1 or 2, and stirs the first dispersion liquid containing the first resin particles introduced into the stirring tank by the stirring blade, and Agglomeration step for agglomerating particles, and a speed component along the flow of the first dispersion liquid stirred by the stirring blade in the stirring tank, and without contacting the inner wall of the stirring tank; A second dispersion liquid containing two resin particles is introduced into the stirring tank from the introduction section, and a supplementary addition step of stirring the first dispersion liquid in the stirring tank is a method for producing agglomerated particles.

  In the invention according to claim 4, the difference (T2−T1) between the temperature T2 in the stirring tank after the introduction of the second dispersion and the temperature T1 in the stirring tank before the introduction of the second dispersion is obtained. It is a manufacturing method of the aggregated particle of Claim 3 made into the range of -5 degreeC or more and -1 degrees C or less.

In the invention according to claim 5, when the second dispersion liquid is introduced from the introduction part into the stirring tank, the liquid in the stirring tank is 0.5 kW / m ³ or more per unit volume of the liquid. It is the manufacturing method of the aggregated particle of Claim 3 or 4 stirred with the stirring power of 0 kW / m < ³ > or less.

  According to the first aspect of the present invention, the first dispersion liquid containing the first resin particles is introduced into the agitation tank, and the first dispersion liquid is contained in the state where the first dispersion liquid is stirred by the stirring blade. Compared with the case where the two dispersions are brought into contact with the inner wall of the stirring tank and introduced into the stirring tank along the inner wall of the stirring tank, a stirring device is provided in which the formation of coarse particles is suppressed.

  According to the invention which concerns on Claim 2, compared with the case where the said (1)-(4) is not satisfy | filled, the stirring apparatus by which formation of a coarse particle is suppressed is provided.

  According to the third aspect of the present invention, the first dispersion liquid containing the first resin particles is introduced into the agitation tank, and the first dispersion liquid is contained in the state where the first dispersion liquid is agitated by the agitation blade. 2 A method for producing agglomerated particles in which the formation of coarse particles is suppressed as compared with the case where the dispersion is brought into contact with the inner wall of the stirring tank and introduced into the stirring tank along the inner wall of the stirring tank is provided. .

  According to the invention which concerns on Claim 4, the difference (T2-T1) of temperature T2 in the stirring tank after introduction | transduction of a 2nd dispersion liquid and temperature T1 in the said stirring tank before introduction | transduction of the said 2nd dispersion liquid is carried out. There is provided a method for producing agglomerated particles in which the formation of coarse particles is suppressed as compared to the case of exceeding -1 ° C.

According to the invention which concerns on Claim 5, when introduce | transducing a 2nd dispersion liquid in the said stirring tank from the said introduction part, it is less than 0.5 kW / m < ³ > per unit volume of the said liquid with respect to the liquid in the said stirring tank. Compared with the case of stirring with the stirring power, a method for producing aggregated particles in which the formation of coarse particles is suppressed is provided.

It is a schematic sectional drawing which shows an example of a structure of the stirring apparatus which concerns on this embodiment. An example in which the second dispersion liquid is introduced from the introduction portion so as to have a velocity component along the flow of the first dispersion liquid being stirred by the stirring blade in the stirring tank and without contacting the inner wall of the stirring tank. It is a figure for carrying out, and is a top view of the stirring apparatus which concerns on this embodiment. (A) and (B) have a speed component along the flow of the first dispersion liquid stirred by the stirring blade in the stirring tank and are not brought into contact with the inner wall of the stirring tank, and the first part It is a figure for demonstrating the other example which introduces 2 dispersion liquid, and is a top view of the stirring apparatus which concerns on this embodiment. (A)-(B) is a figure for demonstrating the introduction form of the 2nd dispersion liquid which does not have a speed component along the flow of the 1st dispersion liquid stirred with the stirring blade in the stirring tank, and is stirred. It is a top view of an apparatus. (A)-(C) is a figure for demonstrating the introduction form of the 2nd dispersion liquid which does not have a speed component along the flow of the 1st dispersion liquid stirred with the stirring blade in the stirring tank, and is stirred. It is a top view of an apparatus. (A) is a top view of the stirring apparatus shown in FIG. 1, and (B) is an enlarged view of the introduction part shown in FIG.

  Embodiments of the present invention will be described below. This embodiment is an example for carrying out the present invention, and the present invention is not limited to this embodiment.

<Agitator>
FIG. 1 is a schematic cross-sectional view showing an example of a configuration of a stirring device according to the present embodiment. The stirring device 1 shown in FIG. 1 includes a stirring tank 10, a stirring shaft 12 that is rotatably mounted in the stirring tank 10, a stirring blade 14 that is attached to the stirring shaft 12, and a wall of the stirring tank 10. The heat transfer part 16 which gives heat in 10 and the introducing | transducing part 18 which introduces a fluid in the stirring tank 10 are provided. The stirring device 1 may include a baffle plate 20 provided in the stirring tank 10.

  A driving source (not shown) (for example, a motor) is attached to the stirring shaft 12 shown in FIG. When the stirring shaft 12 is rotated (for example, rotated in the direction of arrow A shown in FIG. 1) by the driving source, the stirring blade 14 is rotated, and the fluid introduced into the stirring tank 10 is stirred. Although the shape of the stirring blade 14 is not specifically limited, For example, a paddle blade, a propeller blade, a turbine blade, etc. are mentioned. Among these, a paddle blade is preferable in terms of excellent fluid agitation.

  The heat transfer unit 16 is, for example, a heating jacket including a jacket portion 22 that covers at least a part of the outer wall of the stirring tank 10, a heat medium inlet 24 and a heat medium outlet 26 provided in the jacket portion 22, as shown in FIG. 1. is there. In the heat transfer part 16, a heat medium is introduced into the jacket part 22 from the heat medium inlet 24, and heat is given into the agitation tank 10 from the wall surface of the agitation tank 10 by the heat medium passing through the jacket part 22. The heat medium that has passed through the jacket portion 22 is discharged from the heat medium outlet 26. A heat medium is not specifically limited, A liquid phase heat medium, a gaseous-phase heat medium, a vapor | steam, etc. are mentioned. The heat transfer section 16 is not limited to a heating jacket as long as it provides heat from the wall surface of the stirring tank 10 into the tank, and may be, for example, an internal coil or an external heat exchange means.

  The baffle plate 20 shown in FIG. 1 is a plate-like member that is disposed, for example, in a vertical direction at a predetermined distance from the inner wall of the stirring tank 10, but the shape of the baffle plate 20 is limited to this. However, it may be appropriately selected from known modes as a baffle plate of the stirring device. By installing the baffle plate 20 in the agitation tank 10, for example, the fluid in the agitation tank 10 is agitated substantially uniformly compared to the case where the baffle plate 20 is not installed in the agitation tank 10.

  The introduction unit 18 illustrated in FIG. 1 includes an introduction port 28, a discharge port 30, and a fluid flow path 32 that connects the introduction port 28 and the discharge port 30. The fluid channel 32 shown in FIG. 1 extends, for example, linearly toward the liquid level L of the stirring tank 10, bends in the middle thereof, and is inclined with respect to the liquid level L of the stirring tank 10. The fluid (dispersion liquid or the like) supplied from the inlet 28 into the fluid channel 32 passes through the fluid channel 32, is discharged from the outlet 30, and is introduced into the agitation tank 10.

  The introduction part according to the present embodiment is not limited to the shape of the introduction part 18 shown in FIG. 1. For example, the entire fluid flow path 32 is linear and is inclined with respect to the liquid level L of the agitation tank 10. Alternatively, the fluid flow path 32 may be curved such that the discharge port 30 faces obliquely upward, or may have another shape. In any case, as will be described later, the introduction unit according to the present embodiment has a velocity component along the flow of the first dispersion liquid containing the first resin particles introduced in advance into the stirring tank and stirred by the stirring blade. Thus, the second dispersion liquid containing the second resin particles may be introduced into the stirring tank without contacting the inner wall of the stirring tank.

  Hereinafter, a method for producing aggregated particles using the stirring device 1 shown in FIG. 1 will be described, and the operation of the stirring device 1 shown in FIG. 1 and the velocity component along the flow of the first dispersion will be described in detail.

  In the method for producing agglomerated particles according to the present embodiment, the aggregating step of aggregating the first resin particles by agitating the first dispersion liquid containing the first resin particles introduced into the agitation tank 10 of the agitation device 1 with the agitation blade 14. And the second resin particles containing the second resin particles so as to have a velocity component along the flow of the first dispersion liquid stirred by the stirring blade 14 in the stirring tank 10 and without contacting the inner wall in the stirring tank 10. And a second addition step of introducing the two dispersion liquid into the stirring tank 10 from the introduction unit 18 and stirring the first dispersion liquid in the stirring tank 10. The method for producing agglomerated particles according to the present embodiment is suitably used, for example, for producing a toner for developing an electrostatic image.

  In the method for producing aggregated particles according to the present embodiment, for example, the second resin particles adhere to the surface of particles aggregated with the first resin particles (sometimes referred to as core aggregated particles) by the above-described aggregation step and additional addition step. Aggregated particles are obtained. The aggregated particles of the present embodiment include not only aggregated particles obtained by the above aggregation step and the additional addition step but also particles obtained by performing any subsequent step. For example, the particle | grains obtained by implementing a coalescence process after the said aggregation process and an additional addition process are also contained.

<Aggregation process>
In the stirring device 1 illustrated in FIG. 1, for example, the first dispersion liquid containing the first resin particles is introduced into the stirring tank 10 from the introduction unit 18 of the stirring device 1. The first dispersion may contain a release agent, a colorant, and the like, for example. In addition, when the first dispersion liquid containing the first resin particles is introduced into the stirring tank 10, a release agent dispersion liquid containing a release agent, a colorant dispersion liquid containing a colorant, and the like are introduced into the stirring tank 10. May be. The first dispersion liquid containing the first resin particles may be introduced from an introduction part provided separately from the introduction part 18.

  In the stirring device 1 shown in FIG. 1, the stirring shaft 12 is rotated, and the first dispersion liquid introduced into the stirring tank 10 is stirred by the rotation of the stirring blade 14 accompanying the rotation of the stirring shaft 12. The first resin particles therein are aggregated to obtain core aggregated particles. When aggregating the first resin particles, a heat medium is supplied from the heat medium inlet 24 into the jacket portion 22, and heat is applied from the outer wall of the agitation tank 10 to the agitation tank 10. It is preferable to heat the dispersion.

  In the aggregation step, the temperature in the stirring vessel 10 is preferably set to be lower than the glass transition temperature (Tg) of the first resin particles in the first dispersion. Compared to the case where the temperature in the stirring tank 10 is lower than the glass transition temperature of the first resin particles in the first dispersion by setting the temperature in the stirring tank 10 to be lower than the glass transition temperature of the first resin particles in the first dispersion, for example The excessive aggregation of the first resin particles is suppressed, and the formation of coarse particles is suppressed. Moreover, it is preferable that the temperature of the heat transfer part 16 (temperature of the heat medium supplied into the jacket part 22) is + 5 ° C. or less with respect to Tg of the first resin particles in the first dispersion. When the temperature of the heat transfer section 16 (the temperature of the heat medium supplied into the jacket section 22) is + 5 ° C. or less with respect to Tg of the first resin particles in the first dispersion, the first in the first dispersion Compared to the case where the temperature is higher than + 5 ° C. with respect to the Tg of one resin particle, for example, the fusion of the first resin particles on the inner wall surface of the stirring vessel 10 is suppressed, and the formation of coarse particles is suppressed. The lower limit of the temperature of the heat transfer section 16 (the temperature of the heat medium supplied into the jacket section 22) is not particularly limited. For example, for the Tg of the first resin particles in the first dispersion liquid It is −30 ° C. or higher.

In the coagulation step, the liquid containing the first dispersion liquid or the like introduced into the stirring tank 10 may be stirred with a stirring power of 0.5 kW / m ³ or more and 4.0 W / m ³ or less per unit volume of the liquid. Preferably, stirring is performed with a stirring power of 0.5 kW / m ³ or more and 3.0 kW / m ³ or less. Here, the stirring power is a value obtained by dividing the power (kW) required for stirring the liquid in the stirring tank 10 by the liquid amount (m ³ ) of the liquid in the stirring tank 10. In the stirring apparatus 1 shown in FIG. 1, the electric power used to rotate the stirring shaft 12 and the stirring blade 14 is the power required for stirring the liquid in the stirring tank 10.

When the stirring power in the aggregation process is 0.5 kW / m ³ or more, for example, the first dispersion liquid stays on the inner wall surface of the stirring tank 10 as compared with the case where the stirring power is less than 0.5 kW / m ^3. It becomes difficult and formation of coarse particles may be suppressed. In addition, when the stirring power in the aggregation process is 4.0 kW / m ³ or less, for example, the crushing of the core aggregated particles is suppressed compared to the case where the stirring power exceeds 4.0 kW / m ³ , and the core aggregation The particle size growth rate of the particles may be improved.

<Additional process>
Next, in the stirring apparatus 1 shown in FIG. 1, the second dispersion liquid containing the second resin particles is introduced into the stirring tank 10 from the introduction unit 18. The introduction unit 18 has the velocity component along the flow of the first dispersion liquid stirred by the stirring blade 14 in the stirring tank 10 and does not contact the inner wall of the stirring tank 10, and the second dispersion liquid is supplied. Introduce. In the stirring device 1 shown in FIG. 1, the first dispersion liquid and the second dispersion liquid in the stirring tank 10 are stirred by the rotation of the stirring blade 14 accompanying the rotation of the stirring shaft 12, and the second resin is formed on the surface of the core aggregated particles. Aggregated particles with particles attached are obtained.

  FIG. 2 shows that the second dispersion liquid is introduced from the introduction part so as to have a velocity component along the flow of the first dispersion liquid stirred by the stirring blade in the stirring tank and without contacting the inner wall of the stirring tank. It is a figure for demonstrating an example to do, and is a top view of the stirring apparatus which concerns on this embodiment. In FIG. 2, the heat transfer section 16 shown in FIG. 1 is omitted (the same applies to FIG. 3 and subsequent figures).

  An arrow A shown in FIG. 2 indicates the rotation direction of the stirring shaft 12. Therefore, the first dispersion liquid introduced into the stirring tank 10 circulates in the arrow A direction. Further, an arrow B shown in FIG. 2 indicates a discharge direction of the second dispersion liquid discharged from the discharge port 30 of the introduction unit 18. Moreover, the point C shown in FIG. 2 has shown the liquid contact point of the 2nd dispersion liquid. The liquid contact point of the second dispersion is a portion where the second dispersion discharged from the discharge port 30 of the introduction unit 18 first comes into contact. Here, since the introduction unit 18 according to the present embodiment introduces the second dispersion liquid into the stirring tank 10 without contacting the inner wall of the stirring tank 10, the contact point of the second dispersion liquid is , Not the inner wall of the stirring tank 10 but the liquid level L of the first dispersion liquid introduced into the stirring tank 10.

  The second dispersion liquid discharged in the discharge direction B from the discharge port 30 of the introduction unit 18 contacts the liquid level L at the liquid contact point C, and the liquid surface L from the liquid contact point C on the liquid level L in the direction of arrow D (in top view). It tends to flow in the direction of extension of the discharge direction B). That is, the second dispersion liquid has a velocity component that flows on the liquid surface L along the direction of the arrow D at the liquid contact point C. The velocity component flowing along the direction of the arrow D on the liquid level L includes the velocity component E on the liquid level L along the straight line X connecting the liquid contact point C and the stirring shaft 12, and the liquid contact point C and the stirring shaft 12. And the velocity component F on the liquid level L along the vertical direction with respect to the straight line X. The velocity component F on the liquid surface L along the vertical direction with respect to the straight line X (hereinafter sometimes referred to as the velocity component F in the vertical direction) is relative to the velocity component in the vertical direction of the flow of the first dispersion. It is the same vector direction. Here, the velocity component F in the vertical direction, which is the same vector direction as the velocity component in the vertical direction of the flow of the first dispersion, is defined as the velocity component along the flow of the first dispersion.

  The second dispersion having a vertical velocity component F, which is the same vector direction as the vertical velocity component of the first dispersion flow, is the same as the vertical velocity component of the first dispersion flow. Compared to the case where there is no velocity component F in the vertical direction, which is the vector direction, it is considered that it is possible to suppress the gradual diffusion along the flow of the first dispersion and the immediate diffusion on the inner wall of the stirring tank. When the charged second dispersion does not have the vertical velocity component F which is the same vector direction as the vertical velocity component of the first dispersion flow, the flow of the first dispersion on the liquid surface Therefore, it is estimated that the liquid surface of the first dispersion liquid easily flows to the inner wall of the stirrer tank that tends to stay due to the centrifugal force of stirring. Therefore, the second dispersion liquid is introduced from the introduction portion into the stirring tank so as to have a velocity component along the flow of the first dispersion liquid that is stirred by the stirring blade in the stirring tank without being brought into contact with the inner wall of the stirring tank. As a result, the second dispersion is brought into contact with the inner wall of the stirring tank, and the second dispersion stays on the inner wall of the stirring tank as compared with the case where the second dispersion is introduced into the stirring tank along the inner wall of the stirring tank. This is considered to suppress the rapid temperature rise caused by the heat from the heat transfer section. Therefore, compared with the case where the second dispersion is brought into contact with the inner wall of the stirring tank and introduced into the stirring tank along the inner wall of the stirring tank, the second resin particles of the second dispersion introduced into the stirring tank. It is considered that excessive cohesive force hardly acts on the particles, and the formation of coarse particles is suppressed.

  3 (A) and 3 (B) show the introduction part so as to have a velocity component along the flow of the first dispersion liquid stirred by the stirring blade in the stirring tank and without contacting the inner wall of the stirring tank. It is a figure for demonstrating the other example which introduce | transduces a 2nd dispersion liquid from A, and is a top view of the stirring apparatus which concerns on this embodiment.

  In FIG. 3A, the discharge direction B of the second dispersion discharged from the discharge port 30 of the introduction unit 18 is a direction perpendicular to the straight line X connecting the liquid contact point C and the stirring shaft 12. Yes. In this case, the second dispersion discharged from the discharge port 30 of the introduction unit 18 contacts the liquid level L at the liquid contact point C, and is discharged from the liquid contact point C on the liquid level L in the direction indicated by the arrow D (in top view). It tries to flow in the direction of extension of direction B). That is, the second dispersion liquid has a velocity component that flows on the liquid surface L along the direction of the arrow D at the liquid contact point C. This velocity component is a velocity component F on the liquid surface along the direction perpendicular to the straight line X connecting the liquid contact point C and the stirring shaft 12. Since the velocity component F is in the same vector direction as the velocity component in the vertical direction of the flow of the first dispersion as described above, it is a velocity component along the flow of the first dispersion.

  In FIG. 3B, the discharge direction B of the second dispersion liquid discharged from the discharge port 30 of the introduction unit 18 is the diameter of the stirring tank 10 from the direction perpendicular to the straight line X connecting the liquid contact point C and the stirring shaft 12. It faces outward. In this case, the second dispersion discharged in the discharge direction B from the discharge port 30 of the introduction unit 18 has a velocity component that flows on the liquid level L along the direction of the arrow D at the liquid contact point C. The velocity component flowing along the direction of the arrow D on the liquid level L includes the velocity component E on the liquid level L along the straight line X connecting the liquid contact point C and the stirring shaft 12, and the liquid contact point C and the stirring shaft 12. And the velocity component F on the liquid level L along the vertical direction with respect to the straight line X. Since the velocity component F is in the same vector direction as the velocity component in the vertical direction of the flow of the first dispersion as described above, it is a velocity component along the flow of the first dispersion.

  In the case of FIGS. 3 (A) and 3 (B), it has a velocity component along the flow of the first dispersion liquid stirred by the stirring blade in the stirring tank, and without contacting the inner wall of the stirring tank. Since the second dispersion liquid is introduced into the stirring tank, as described above, the second dispersion liquid gradually diffuses along the flow of the first dispersion liquid and is prevented from immediately diffusing to the inner wall of the stirring tank. It is thought that it is done. Therefore, compared with the case where the second dispersion is brought into contact with the inner wall of the stirring tank and introduced into the stirring tank along the inner wall of the stirring tank, the second dispersion is prevented from staying on the inner wall of the stirring tank. Moreover, it is considered that rapid temperature rise due to heat from the heat transfer section is also suppressed. Therefore, compared with the case where the second dispersion is brought into contact with the inner wall of the stirring tank and introduced into the stirring tank along the inner wall of the stirring tank, the second resin particles of the second dispersion introduced into the stirring tank. It is considered that excessive cohesive force hardly acts on the particles, and the formation of coarse particles is suppressed.

  4 (A) to 4 (B) and FIGS. 5 (A) to 5 (C) show the second dispersion liquid having no velocity component along the flow of the first dispersion liquid being stirred by the stirring blade in the stirring tank. It is a figure for demonstrating an introduction form, and is a top view of a stirring apparatus.

  In FIG. 4A, the discharge direction B of the second dispersion liquid discharged from the discharge port 30 of the introduction unit 18 is on a straight line connecting the liquid contact point C and the stirring shaft 12 and is separated from the stirring shaft 12. It has become a direction. In this case, the second dispersion liquid has only the velocity component E on the liquid surface along the straight line X connecting the liquid contact point C and the stirring shaft 12 at the liquid contact point C. The velocity component E is not the same vector direction but the opposite vector direction with respect to the velocity component in the vertical direction of the flow of the first dispersion. In FIG. 4B, the discharge direction B of the second dispersion discharged from the discharge port 30 of the introduction unit 18 is on a straight line connecting the liquid contact point C and the stirring shaft 12 and approaches the stirring shaft 12 side. It has become a direction. In this case, as in FIG. 4A, the second dispersion has only the velocity component E on the liquid surface along the straight line X connecting the liquid contact point C and the stirring shaft 12 at the liquid contact point C. Therefore, the form of introduction of the second dispersion shown in FIGS. 4A and 4B does not have a velocity component along the flow of the first dispersion, but deviates from the scope of the present embodiment.

  In FIG. 5A, the discharge direction B of the second dispersion liquid discharged from the discharge port 30 of the introduction part 18 is a direction perpendicular to the straight line connecting the liquid contact point C and the stirring shaft 12, and It is in the opposite direction to the flow of 1 dispersion. In this case, at the liquid contact point C, the second dispersion liquid has only the velocity component F ′ on the liquid surface along the direction perpendicular to the straight line X connecting the liquid contact point C and the stirring shaft 12. The velocity component F ′ is not the same vector direction but the opposite vector direction with respect to the velocity component in the vertical direction of the flow of the first dispersion. Therefore, the form of introduction of the second dispersion shown in FIG. 5 (A) does not have a velocity component along the flow of the first dispersion, but deviates from the scope of the present embodiment.

  In FIG. 5B, the discharge direction B of the second dispersion discharged from the discharge port 30 of the introduction unit 18 is the radial direction of the stirring tank 10 from the direction perpendicular to the straight line connecting the liquid contact point C and the stirring shaft 12. It faces outward and is in the opposite direction to the flow of the first dispersion. In FIG. 5C, the discharge direction B of the second dispersion discharged from the discharge port 30 of the introduction unit 18 is greater than the direction perpendicular to the straight line connecting the liquid contact point C and the stirring shaft 12. It faces inward in the radial direction and is in the opposite direction to the flow of the first dispersion. In these cases, the second dispersion liquid has a velocity component that flows on the liquid surface L along the direction of the arrow D at the liquid contact point C, and this velocity component connects the liquid contact point C and the stirring shaft 12. It is decomposed into a velocity component E on the liquid surface L along the straight line X and a velocity component F ′ on the liquid surface L along the vertical direction with respect to the straight line X connecting the liquid contact point C and the stirring shaft 12. As described above, the velocity component E is not in the same vector direction as the velocity component in the vertical direction of the flow of the first dispersion, but in the opposite vector direction, and the velocity component F ′ is equal to that of the first dispersion. It is not the same vector direction but the reverse vector direction for the velocity component in the vertical direction of the flow. Therefore, the form of introduction of the second dispersion shown in FIGS. 5B and 5C does not have a velocity component along the flow of the first dispersion, but deviates from the scope of the present embodiment.

  Although not shown in the figure, when the second dispersion is discharged in the direction perpendicular to the liquid level L in the agitation tank 10 and introduced perpendicular to the liquid level L, the second dispersion In the liquid contact point C, the velocity component flowing on the liquid level L is not given. Therefore, the form of introduction of the second dispersion in which the second dispersion is introduced perpendicularly to the liquid surface L does not have a velocity component along the flow of the first dispersion, and deviates from the scope of the present embodiment. Is.

  The second dispersion liquid having no velocity component along the flow of the first dispersion liquid stirred by the stirring blade in such a stirring tank is the second dispersion liquid having the velocity component along the flow of the first dispersion liquid. Compared to the flow of the first dispersion, it is considered that it diffuses over a wide range and tends to stay on the inner wall of the stirring tank. As described above, this is because, when the charged second dispersion does not have the vertical velocity component F which is the same vector direction as the vertical velocity component of the flow of the first dispersion, This is presumably because the vortex flow at the liquid surface of the dispersion is disturbed and is not easily drawn into the liquid in a sufficiently fluid state. Therefore, even if the second dispersion is introduced into the stirring tank without contacting the inner wall of the stirring tank, it does not have a velocity component along the flow of the first dispersion that is stirred by the stirring blade in the stirring tank. When the second dispersion liquid is introduced as described above, it has a velocity component along the flow of the first dispersion liquid stirred by the stirring blade in the stirring tank, and without contacting the inner wall of the stirring tank, Compared to the case where the second dispersion liquid is introduced into the stirring tank, it is considered that excessive cohesive force acts on the second resin particles of the second dispersion liquid introduced into the stirring tank and coarse particles are easily formed. It is done.

  Below, the second dispersion liquid is introduced into the stirring tank so as to have a velocity component along the flow of the first dispersion liquid being stirred by the stirring blade in the stirring tank and without contacting the inner wall of the stirring tank. Preferred parameters for doing so will be described.

6A is a top view of the stirring apparatus shown in FIG. 1, and FIG. 6B is an enlarged view of the introduction part shown in FIG. An angle formed by a perpendicular line Y2 with respect to a straight line Y1 connecting the discharge port 30 (the central portion of the discharge port 30) of the introduction unit 18 and the stirring shaft 12 and the central axis Y3 of the discharge port 30 of the introduction unit 18 shown in FIG. Θ1, the height from the liquid level L in the agitation tank 10 shown in FIG. 6B to the discharge port 30 (the lowest point of the discharge port 30) of the introduction portion 18 is H, and the introduction shown in FIG. 6B. The angle formed by the extension line Z1 extending in the direction in which the second dispersion liquid is discharged from the discharge port 30 of the section 18 and the horizontal line Z2 is θ2, and the second dispersion liquid is discharged from the discharge port 30 of the introduction section 18 shown in FIG. When the horizontal distance between the discharge port 30 and the inner wall of the stirring tank 10 in the discharge direction is d, it is preferable to satisfy the following (1) to (4).
-90 ° <θ1 <90 ° (1)
0.05m ≦ H ≦ 1.0m (2)
0 ° <θ2 <90 ° (3)
0.1 m ≦ d ≦ 2.5 m (4)

  An angle formed by a perpendicular line Y2 with respect to a straight line Y1 connecting the discharge port 30 (the central portion of the discharge port 30) of the introduction unit 18 and the stirring shaft 12 and the central axis Y3 of the discharge port 30 of the introduction unit 18 shown in FIG. θ1 is preferably more than −90 ° and less than 90 ° of (1) above, and more preferably −30 ° to 60 °. When θ1 is −90 ° or less and 90 ° or more, for example, it becomes difficult to introduce the second dispersion so as to have a velocity component along the flow of the first dispersion in the stirring tank 10, and the above (1) Compared with the case where the above range is satisfied, the effect of suppressing the formation of coarse particles may be reduced.

  The height H from the liquid level L in the stirring tank 10 shown in FIG. 6 (B) to the discharge port 30 (the lowest point of the discharge port 30) of the introduction unit 18 is 0.05 m or more in the above (2). It is preferably 0 m or less, and more preferably 0.1 m or more and 0.6 m or less. When H is less than 0.05 m, for example, the flow rate of the second dispersion discharged from the discharge port 30 of the introduction unit 18 becomes lower than when H satisfies the range of (2). 2 Dispersion liquid becomes easy to diffuse to the inner wall of stirring tank 10, and the effect which controls formation of coarse particles may be reduced. In addition, when H is more than 1.0 m, for example, when the second dispersion comes into contact with the liquid level L, foaming is likely to occur compared to the case where H satisfies the range of (2) above. The effect of suppressing the formation of coarse particles may be reduced.

  The angle θ2 formed by the extension line Z1 extending in the direction in which the second dispersion liquid is discharged from the discharge port 30 of the introduction unit 18 shown in FIG. 6B and the horizontal line Z2 is more than 0 ° and less than 90 ° in the above (3). It is preferable that the angle is 10 ° or more and 60 ° or less. When θ2 is 0 ° or less, compared to the case where the range of (3) is satisfied, for example, when the second dispersion is in contact with the liquid surface L, foaming is likely to occur, and formation of coarse particles is caused. The suppression effect may be reduced. Further, when θ2 is 90 ° or more, for example, it becomes difficult to introduce the second dispersion so as to have a velocity component along the flow of the first dispersion in the stirring tank 10, and the range of (3) above is satisfied. Compared to the case of satisfying, the effect of suppressing the formation of coarse particles may be reduced.

The horizontal distance d between the discharge port 30 and the inner wall of the stirring tank 10 in the direction in which the second dispersion liquid is discharged from the discharge port 30 of the introduction unit 18 shown in FIG. 6A is 0.1 m of the above (4). It is preferably 2.5 m or less and more preferably 0.5 m or more and 2 m or less. When d is less than 0.1 m, compared with the case where d satisfies the range of (4) above, for example, the second dispersion is introduced at a position closer to the inner wall of the agitation tank 10, so that the second dispersion However, the effect of suppressing the formation of coarse particles may be reduced. When d is more than 2.5 m, compared with the case where d satisfies the range of (4) above, for example, the tank diameter of the stirring tank becomes excessively large. The flow flowing to the inner wall of the stirring tank that tends to stay due to centrifugal force becomes more dominant than the flow drawn into, and the effect of suppressing the formation of coarse particles may be reduced.

  The introduction time when the second dispersion is introduced from the introduction unit 18 into the stirring tank 10 is preferably 3 minutes or more and 60 minutes or less. When the introduction time of the second dispersion is less than 3 minutes, compared to the case where the introduction time of the second dispersion satisfies the above range, foaming of the second dispersion occurs and the formation of coarse particles is suppressed. The effect may be reduced. Further, if the introduction time of the second dispersion is more than 60 minutes, the agglomeration progresses too much compared to the case where the introduction time of the second dispersion satisfies the above range, and the agglomerated particles having a desired volume average particle diameter May not be obtained.

  The difference (T2-T1) between the temperature T2 in the stirring tank 10 after the introduction of the second dispersion and the temperature T1 in the stirring tank 10 before the introduction of the second dispersion is −5 ° C. or more and −1 ° C. or less. It is preferable to set it as a range, and it is preferable to set it as the range of -3 degreeC or more and -1 degrees C or less. When T2-T1 is higher than −1 ° C., for example, the cohesive force of the second resin particles may be increased and coarse particles may be easily formed as compared with the case where T2-T1 satisfies the above range. Further, when T2-T1 is less than −5 ° C., for example, the cohesive force on the surface of the core aggregated particles (aggregated first resin particles) is considered to be lower than when T2-T1 satisfies the above range. In some cases, the yield (yield) of the aggregated particles in which the second resin particles adhere to the surface of the core aggregated particles may decrease. In the stirring apparatus 1 shown in FIG. 1, for example, when introducing the second dispersion liquid, it is preferable to raise the temperature of the heat transfer section 16 so that T2−T1 is within the above range. Further, in the stirring device 1 shown in FIG. 1, for example, after the temperature of the second dispersion before being introduced into the stirring tank 10 is raised, the heated second dispersion is introduced into the stirring tank 10, and T2 -T1 may be within the above range, or may be combined with a method of increasing the temperature of the heat transfer section 16 when the second dispersion described above is introduced.

  The temperature of the heat transfer section 16 when introducing the second dispersion (the temperature of the heat medium supplied into the jacket section 22) is preferably, for example, + 5 ° C. or less with respect to the temperature in the stirring tank 10. When the temperature of the heat transfer section 16 when introducing the second dispersion (temperature of the heat medium supplied into the jacket section 22) is + 5 ° C. or less with respect to the temperature in the stirring tank 10, the inside of the stirring tank 10 Compared with the case where the temperature is higher than + 5 ° C., the increase in the cohesive force of the resin particles on the inner wall surface of the stirring vessel 10 is suppressed, and the formation of coarse particles is further suppressed.

When introducing the second dispersion, to a liquid containing the first dispersion or the like in the stirring tank 10 and stirred at per unit volume of the liquid 0.5 kW / ^{m 3} or more 4.0 kW / ^{m 3} or less of the stirring power It is preferable that stirring is performed with a stirring power of 0.5 kW / m ³ or more and 3.0 kW / m ³ or less. When the stirring power is less than 0.5 kW / m ³ , compared to the case where the stirring power satisfies the above range, the amount of the second resin particles aggregated before adhering to the surface of the core aggregated particles increases, The effect of suppressing the formation of coarse particles may be reduced. In addition, when the stirring power is more than 4.0 kW / m ³ , compared to the case where the stirring power satisfies the above range, the shearing force by stirring is higher than the cohesive force of the core aggregated particle surface, and the surface of the core aggregated particle is increased. The second resin particles may be difficult to adhere.

<Other processes>
It is preferable that the manufacturing method of the aggregated particle of this embodiment includes the coalescing process which unites (fuses) the aggregated particle obtained by the said aggregation process and the additional addition process. The coalescence of the agglomerated particles obtained by the agglomeration step and the additional addition step heats the agglomerated particles under a temperature condition equal to or higher than the melting point or glass transition temperature of the first resin particles and the second resin particles contained in the agglomerated particles. Is preferably performed. The agglomerated particles change from an irregular shape to a more spherical shape, for example, by a coalescing process. The coalescence process may be performed by the stirring device of the present embodiment, but may be performed by another stirring device.

  After completion of the coalescence process, a washing process, a solid-liquid separation process, a drying process, and the like may be performed. Although there is no restriction | limiting in particular in a washing | cleaning process, For example, it is the process of carrying out substitution washing | cleaning with the ion-exchange water etc. for the dispersion liquid containing the aggregated particle after a coalescence process. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, and the like are preferable from the viewpoint of productivity. The drying process is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferable from the viewpoint of productivity.

  Hereinafter, the raw material used for the manufacturing method of the aggregated particle which concerns on this embodiment is demonstrated.

  The first dispersion containing the first resin particles and the second dispersion containing the second resin particles are obtained by, for example, an emulsion polymerization method and a polymerization method in a heterogeneous dispersion system similar thereto. In addition, the first dispersion containing the first resin particles and the second dispersion containing the second resin particles are prepared by adding a polymer previously polymerized by a solution polymerization method or a cage polymerization method into a solvent in which the polymer does not dissolve. Alternatively, it may be added with a stabilizer and mechanically mixed and dispersed.

  The resins constituting the first resin particles and the second resin particles may be the same or different. The resin constituting the first resin particles and the second resin particles is not particularly limited, and examples thereof include known binder resins used for electrostatic charge image developing toners.

  Examples of the binder resin include homopolymers or copolymers of styrenes such as styrene, parachlorostyrene, and α-methylstyrene (styrene resin); methyl acrylate, ethyl acrylate, n-propyl acrylate, Single weight of esters having vinyl group such as n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate Polymers or copolymers (acrylate resins); Homopolymers or copolymers of vinyl nitriles such as acrylonitrile and methacrylonitrile (vinyl nitrile resins); Homopolymers of vinyl ethers such as vinyl ethyl ether and vinyl isobutyl ether Or copolymer (vinyl Homopolymer or copolymer of vinyl methyl ketone, vinyl ethyl ketone, or vinyl isopropenyl ketone (vinyl ketone resin); Homopolymer or copolymer of olefins such as ethylene, propylene, butadiene, or isoprene Combined (olefin resin); non-vinyl condensation resins such as epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, and graft polymers of these non-vinyl condensation resins and vinyl monomers Etc. These resins may be used alone or in combination of two or more. Among these, polyester resins and various vinyl resins are preferable, and polyester resins are particularly preferable.

  When the binder resin is a polyester resin, it can be obtained, for example, by condensation polymerization of a polymerizable monomer. Examples of the polymerizable monomer include polycarboxylic acids and esters or acid anhydrides thereof, and polyols, and may be appropriately selected from known compounds as raw materials for polyester resins. Moreover, as a polyester resin, any of a crystalline polyester resin and an amorphous polyester may be used, and it is not particularly limited, but it is preferable to contain at least an amorphous polyester resin. “Crystallinity” means that in differential scanning calorimetry (DSC), it has a clear endothermic peak, not a stepwise endothermic change. Specifically, the rate of temperature increase is 10 (° C./min. ) Indicates that the half-value width of the endothermic peak is 10 ° C. or less. On the other hand, “amorphous” means that the half width exceeds 10 ° C., shows a step-like change in endothermic amount, or that no clear endothermic peak is observed.

  When the binder resin is a vinyl resin, for example, it can be obtained by radical polymerization of a polymerizable monomer. The polymerizable monomer may be appropriately selected from known compounds having an ethylenically unsaturated bond, preferably a vinyl group.

  The first dispersion liquid, the second dispersion liquid, and the like may contain a surfactant or the like. Examples of the surfactant include anionic surfactants such as sulfate ester-based, sulfonate-based, phosphate ester-based, and soap-based surfactants, and cationic surfactants such as amine salt type and quaternary ammonium salt type, Nonionic surfactants such as polyethylene glycol, alkylphenol ethylene oxide adducts, alkyl alcohol ethylene oxide adducts, and polyhydric alcohols, and various graft polymers may be mentioned.

  Examples of the release agent contained in the first dispersion, the second dispersion, or the release agent dispersion include known release agents used in the production of toner for developing electrostatic images, such as polyethylene. Low molecular weight polyolefins such as polypropylene, polybutene; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide; carnauba wax, rice wax, candelilla wax, wood wax, jojoba oil, etc. Plant waxes; animal waxes such as beeswax; mineral waxes such as montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, and Fischer-Tropsch wax, petroleum waxes, and modified products thereof. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the colorant contained in the first dispersion, the second dispersion, or the colorant dispersion include carbon black, chrome yellow, hansa yellow, benzidine yellow, sren yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, Vulcan Orange, Watch Young Red, Permanent Red, Brilliantamine 3B, Brilliantamine 6B, DuPont Oil Red, Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C, Rose Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Various pigments such as methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxalate, acridine, xanthene, azo, benzox Various dyes such as benzene, azine, anthraquinone, thioindico, dioxazine, thiazine, azomethine, indico, phthalocyanine, aniline black, polymethine, triphenylmethane, diphenylmethane, and thiazole Can be mentioned. These may be used individually by 1 type and may use 2 or more types together.

  Further, as the colorant, for example, a colorant that has been surface-modified with rosin, polymer, or the like is also used. Examples of the polymer used for the surface treatment of the colorant include acrylonitrile polymer and methyl methacrylate polymer. As the surface modification treatment, for example, a polymerization method in which a monomer is polymerized in the presence of a colorant (pigment), a colorant (pigment) is dispersed in a polymer solution, and the solubility of the polymer is lowered to reduce the colorant (pigment). Examples thereof include a phase separation method for precipitation on the surface.

  The first dispersion, the second dispersion, and the like may further contain various additives. For example, when the toner for developing an electrostatic charge image is produced using the method for producing aggregated particles according to this embodiment. In addition, additives such as known internal additives, charge control agents, inorganic particles, organic particles, lubricants, and abrasives may be included.

  Hereinafter, although an example and a comparative example are given and the present invention is explained more concretely in detail, the present invention is not limited to the following examples. In the following examples and comparative examples, “%” and “part” mean “% by mass” and “part by mass” unless otherwise specified.

<Synthesis of polyester resin>
In a stainless steel container with a jacket, 60 mol parts of polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, 30 mol parts of ethylene glycol, 20 mol parts of cyclohexanediol, and 70 mol of terephthalic acid , 10 mol parts of isophthalic acid, and 8 mol parts of n-dodecenyl succinic acid as raw materials, dibutyltin oxide was added as a catalyst, nitrogen gas was introduced into the apparatus, and the temperature was raised to 150 ° C. while maintaining an inert atmosphere. A copolycondensation reaction was performed at 230 ° C. or lower for about 12 hours, and then the pressure was gradually reduced at 210 ° C. or higher and 250 ° C. or lower to synthesize a polyester resin.

  The weight average molecular weight (Mw) of the obtained polyester resin was 17,100. The weight average molecular weight (Mw) (polystyrene conversion) of the polyester resin was measured using GPC (manufactured by Tosoh Corporation: HLC-8120). The column used was Tosoh TSKgel SuperHM-M (15 cm), and the GPC spectrum was measured with a THF solvent. The molecular weight of the polyester resin was calculated using a molecular weight calibration curve created with a monodisperse polystyrene standard sample.

  The acid value of the obtained polyester resin was 11.0 mgKOH / g. The acid value was measured using a neutralization titration method according to JIS K0070. That is, an appropriate amount of sample was taken, 100 ml of a solvent (diethyl ether / ethanol mixed solution) and a few drops of an indicator (phenolphthalein solution) were added, and the mixture was thoroughly shaken until the sample was completely dissolved in a water bath. . This was titrated with a 0.1 mol / L potassium hydroxide ethanol solution, and the end point was when the indicator was light red for 30 seconds. When the acid value is A, the sample amount is S (g), the 0.1 mol / l potassium hydroxide ethanol solution used for the titration is B (ml), and f is the factor of the 0.1 mol / L potassium hydroxide ethanol solution. , A = (B × f × 5.611) / S.

  The glass transition temperature of the obtained polyester resin was measured using a differential scanning calorimeter (DSC) and analyzed according to JIS standards (see JIS K-7121). As a result, a stepwise endothermic change was observed without showing a clear peak. The glass transition temperature (Tg) at the midpoint of the stepwise endothermic change was 56 ° C.

<Preparation of First Dispersion Containing Polyester Resin Particles>
-100 parts by weight of the above polyester resin-70 parts by weight of ethyl acetate-15 parts by weight of isopropyl alcohol A mixed solvent of the above ethyl acetate and the above isopropyl alcohol is put into a jacketed stainless steel container, and the above polyester resin is gradually put into this. The oil phase was obtained by complete dissolution with stirring. A 10% by mass aqueous ammonia solution is gradually added dropwise to the stirred oil phase by a pump so that the total amount becomes 3 parts by mass, and 230 parts by mass of ion-exchanged water is gradually added dropwise at a rate of 10 L / min. Phase emulsified. Then, the 1st dispersion liquid (solid content concentration: 40 mass%) containing a polyester resin particle was obtained by implementing vacuum distillation. The solid content concentration was measured using a moisture meter MA35 (manufactured by Sartorius Mechatronics Japan Co., Ltd.). The measurement of the solid content concentration of each sample below is the same.

  The volume average particle diameter (D50v) of the polyester resin particles in the obtained first dispersion was 180 nm. The volume average particle size of the polyester resin particles was measured using a laser diffraction particle size distribution measuring device (LA-700: manufactured by Horiba, Ltd.). As a measuring method, a sample in a dispersion state is adjusted so as to have a solid content of about 2 g, and ion-exchanged water is added thereto to make about 40 ml, which becomes an appropriate concentration in the cell. Until the concentration in the cell was almost stable. The obtained volume average particle size for each particle size range (channel) was accumulated from the smaller volume average particle size, and the volume average particle size (D50v) was determined to be 50%.

<Preparation of release agent dispersion>
-Paraffin wax (Nippon Seiwa Co., Ltd., FNP92, melting point 92 ° C) 45 parts-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK) 5 parts-Ion-exchanged water 200 parts or more The mixture was then heated to 95 ° C. and dispersed using a homogenizer (manufactured by IKA, Ultra Turrax T50). Thereafter, a dispersion treatment (solid content concentration: 20% by mass) was prepared by dispersing with a Manton Gorin high-pressure homogenizer (Gorin Co., Ltd.) and dispersing the release agent.

  The volume average particle size of the release agent particles in the release agent dispersion was 0.19 μm. The method for measuring the volume average particle size of the release agent particles is the same as the method for measuring the volume average particle size of the polyester resin particles.

<Preparation of second dispersion containing polyester resin particles>
-200 parts of first dispersion containing polyester resin particles-100 parts of ion-exchanged water-1.0 part of anionic surfactant (Kao Co., Ltd., Demol SN-B)
The above raw materials were put into a stainless steel stirring tank, and 20 parts of 0.3 M nitric acid aqueous solution was added to adjust the pH to 3.0 to obtain a second dispersion liquid (solid content concentration: 25% by mass) containing polyester resin particles. .

(Example 1: Production of aggregated particles (1))
The stirring apparatus shown in FIG. 1 was prepared. In Example 1, θ1 shown in FIG. 6A was set to 30 °, d was set to 1.0 m, and θ2 shown in FIG. 6B was set to 60 °.

-First dispersion containing polyester resin particles 300 parts-Release agent dispersion 40 parts-Anionic surfactant (Kao Co., Ltd., Demol SN-B) 2.0 parts In the stirring tank of the prepared stirring device After the raw materials were charged, 12 parts of 0.3 M nitric acid aqueous solution was added to adjust the pH to 4.0. While circulating the mixed dispersion in the stirring tank through a disperser (Caitron, manufactured by Taihei Koki Co., Ltd.) installed outside the stirring tank, 150 parts of a 10% aqueous solution of aluminum sulfate as a flocculant was dropped into the stirring tank. did. In addition, since the viscosity of the raw material mixture increases during the dropping of the flocculant, the dropping speed was reduced when the viscosity increased, so that the flocculant was not biased to one place. The temperature of the mixed dispersion obtained after the dropping was 30 ° C. Subsequently, the obtained mixed dispersion was stirred at 500 rpm (circulation through the disperser was stopped), and the temperature was raised under a temperature rising condition of a jacket temperature of 55 ° C., and the temperature in the stirring vessel was maintained at 48 ° C. Aggregation was advanced until the particle diameter of the polyester resin particles reached 5.0 μm (aggregation step). The particle diameter of the polyester resin particles was measured by the method described later.

  After the agglomeration step, the second dispersion liquid containing the polyester resin particles is introduced from the introduction portion in 10 minutes in the form of introduction of the second dispersion liquid shown in FIG. 3 (A), and 15 minutes while stirring at a stirring rotational speed of 50 rpm. Retained (addition step). That is, the second dispersion was introduced into the agitation tank so as to have a velocity component along the flow of the first dispersion and without contacting the inner wall of the agitation tank. When the second dispersion was introduced from the introduction part, H shown in FIG. 6 (B) was 0.2 m.

  After stirring for 15 minutes, the pH was raised to 8, the stirring speed was reduced to 100 rpm, and aggregated particles in which polyester resin particles adhered to the surface of the core aggregated particles (aggregated polyester resin particles) were obtained. In order to coalesce the aggregated particles, the dispersion containing the aggregated particles was transferred to another stirring device, and the temperature was raised to 90 ° C. (a coalescence step). After cooling the dispersion containing aggregated particles after the coalescence step, the dispersion containing aggregated particles was washed and dried to obtain aggregated particles (1).

(Example 2: Production of aggregated particles (2))
In FIG. 6A, θ1 is 60 °, d is 1.8 m, θ2 shown in FIG. 6B is 60 °, and H is 0 when the second dispersion is introduced from the introduction portion in the additional addition step. 2m, and in the form of introduction of the second dispersion shown in FIG. 2, the second dispersion has a velocity component along the flow of the first dispersion and does not contact the inner wall of the stirring tank. Aggregated particles were produced in the same manner as in Example 1 except that the liquid was introduced to obtain aggregated particles (2).

(Example 3: Production of aggregated particles (3))
6 (A) is 0 °, d is 0.6 m, θ2 is 60 ° shown in FIG. 6 (B), and FIG. H) shown in B) is 0.5 m, and the second dispersion liquid is introduced as shown in FIG. 3B so as to have a velocity component along the flow of the first dispersion liquid, and in the stirring tank. Aggregated particles were produced in the same manner as in Example 1 except that the second dispersion was introduced without contacting the inner wall, and aggregated particles (3) were obtained.

(Example 4: Production of aggregated particles (4))
FIG. 6A shows a case where θ1 is −30 °, d is 0.1 m, θ2 is 80 ° shown in FIG. 6B, and the second dispersion is introduced from the introduction part in the additional addition step. The H shown in (B) is 0.5 m, and the second dispersion shown in FIG. 3 (B) has a velocity component along the flow of the first dispersion, and a stirring tank. Agglomerated particles were produced in the same manner as in Example 1 except that the second dispersion was introduced without contacting the inner wall of the material to obtain agglomerated particles (4).

(Example 5: Production of aggregated particles (5))
6 (A) is 60 °, d is 1.8 m, θ2 is 10 ° shown in FIG. 6 (B), and FIG. H) shown in B) is 0.3 m, and the second dispersion liquid is introduced as shown in FIG. 3B so as to have a velocity component along the flow of the first dispersion liquid and in the stirring tank. Aggregated particles were produced in the same manner as in Example 1 except that the second dispersion was introduced without contacting the inner wall, and aggregated particles (5) were obtained.

(Example 6: Production of aggregated particles (6))
6A, when θ1 is 80 °, d is 2.3 m, θ2 is 5 ° shown in FIG. 6B, and the second dispersion is introduced from the introduction portion in the additional addition step. B) was set to 0.2 m, and in the introduction form of the second dispersion shown in FIG. 3 (B), so as to have a velocity component along the flow of the first dispersion, Aggregated particles were produced in the same manner as in Example 1 except that the second dispersion was introduced without contacting the inner wall, and aggregated particles (6) were obtained.

(Comparative Example 1: Production of agglomerated particles (7))
Using the introduction part linearly extending toward the liquid level of the stirring tank (that is, θ2 shown in FIG. 6B is 90 °), the second dispersion is introduced from the introduction part in the additional addition step. H was 0.03, and the second dispersion was discharged in a direction perpendicular to the liquid level in the stirring tank and introduced perpendicular to the liquid level (that is, the inner wall of the stirring tank) The agglomerated particles are produced in the same manner as in Example 1 except that the second dispersion is introduced so as not to have a velocity component along the flow of the first dispersion, but the agglomerated particles (7) are obtained. It was.

(Comparative Example 2: Production of aggregated particles (8))
6 when the second dispersion is introduced from the introduction part in the additional addition step, θ1 shown in FIG. 6A is −90 °, d is 0.1 m, θ2 is 60 ° shown in FIG. The H shown in (B) is set to 0.8 m, and the second dispersion liquid introduction mode shown in FIG. 4 (A) is set so as not to have a velocity component along the flow of the first dispersion liquid. Aggregated particles were produced in the same manner as in Example 1 except that the dispersion was introduced (provided that the second dispersion was brought into contact with the inner wall of the stirring tank) to obtain aggregated particles (8).

(Comparative Example 3: Production of Aggregated Particle (9))
6 (A) is 90 °, d is 2.6 m, θ2 is 30 ° shown in FIG. 6 (B), and in the additional addition step, FIG. B) is set to 1.5 m, and the second dispersion shown in FIG. 4B is introduced so as not to have a velocity component along the flow of the first dispersion. Aggregated particles were produced in the same manner as in Example 1 except that the liquid was introduced (however, the second dispersion was brought into contact with the stirring shaft) to obtain aggregated particles (9).

(Comparative Example 4: Production of Aggregated Particle (10))
6 (A) is 135 °, d is 2.0 m, θ2 is 60 ° shown in FIG. 6B, and the second dispersion is introduced from the introduction portion in the additional addition step. B) was set to 1.2 m, and the second dispersion liquid was introduced as shown in FIG. 5 (A) so as not to have a velocity component along the flow of the first dispersion liquid and stirring. Aggregated particles were produced in the same manner as in Example 1 except that the second dispersion was introduced without contacting the inner wall of the tank, and aggregated particles (10) were obtained.

(Comparative Example 5: Production of agglomerated particles (11))
6 (A) is 90 °, d is 2.6 m, θ2 is 60 ° shown in FIG. 6 (B), and FIG. B) is set to 1.5 m, and the second dispersion liquid is introduced as shown in FIG. 5 (A) so that it does not have a velocity component along the flow of the first dispersion liquid and stirred. Aggregated particles were produced in the same manner as in Example 1 except that the second dispersion was introduced without contacting the inner wall of the tank, and aggregated particles (11) were obtained.

(Comparative Example 6: Production of agglomerated particles (12))
6 when the second dispersion is introduced from the introduction part in the additional addition step, θ1 shown in FIG. 6A is −90 °, d is 0.1 m, θ2 is 60 ° shown in FIG. The H shown in (B) is set to 0.15 m, and the second dispersion liquid is introduced as shown in FIG. 4 (A) so as not to have a velocity component along the flow of the first dispersion liquid. Aggregated particles were produced in the same manner as in Example 1 except that the dispersion was introduced to obtain aggregated particles (12).

<Measurement of Volume Average Particle Diameter (D50v) of Aggregated Particles (1) to (12) Obtained in Each Example and Comparative Example>
A Coulter Multisizer-II type (manufactured by Beckman Coulter, Inc.) was used as the measuring apparatus, and ISOTON-II (manufactured by Beckman-Coulter, Inc.) was used as the electrolyte. As a measurement method, 0.5 mg of a measurement sample is added to 2 ml of a 5% aqueous solution of a surfactant (sodium dodecylbenzenesulfonate) as a dispersant, and this is added to 100 ml of the electrolytic solution to suspend the measurement sample. A turbid electrolyte was prepared. The electrolytic solution in which the measurement sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 minute. Using the Coulter Multisizer II type, an aperture having an aperture diameter of 100 μm is used, and the particle diameter is 2.0 to 60 μm. The particle size distribution of the range of particles was measured. The number of particles measured was 50,000. For the measured particle size distribution, a cumulative distribution was drawn from the smaller diameter side with respect to the divided particle size range (channel), and the particle size at 50% cumulative was defined as D50v.

  The D50v of the aggregated particles (1) obtained in Example 1 was 5.90 μm. The D50v of the aggregated particles (2) obtained in Example 2 was 5.86 μm. The D50v of the aggregated particles (3) obtained in Example 3 was 6.02 μm. The D50v of the agglomerated particles (4) obtained in Example 4 was 6.04 μm. D50v of the aggregated particles (5) obtained in Example 5 was 5.92 μm. The D50v of the agglomerated particles (6) obtained in Example 6 was 5.98 μm. The D50v of the agglomerated particles (7) obtained in Comparative Example 1 was 6.02 μm. The D50v of the aggregated particles (8) obtained in Comparative Example 2 was 6.30 μm. The D50v of the aggregated particles (9) obtained in Comparative Example 3 was 6.11 μm. The D50v of the aggregated particles (10) obtained in Comparative Example 4 was 5.98 μm. The D50v of the aggregated particles (11) obtained in Comparative Example 5 was 5.97 μm. The D50v of the aggregated particles (12) obtained in Comparative Example 6 was 6.18 μm.

<Measurement of ratio of coarse particles in aggregated particles (1) to (12) obtained in each of Examples and Comparative Examples>
In the particle size distribution measured by Coulter Multisizer-II, the cumulative distribution is drawn from the small diameter side with respect to the divided particle size range (channel), and particles of 15 μm or more are defined as coarse particles. The ratio (volume%) of coarse particles was determined.

  The ratio of coarse particles in the aggregated particles (1) obtained in Example 1 was 0.6% by volume. The ratio of coarse particles in the aggregated particles (2) obtained in Example 2 was 0.2% by volume. The ratio of coarse particles in the aggregated particles (3) obtained in Example 3 was 1.5% by volume. The ratio of coarse particles in the agglomerated particles (4) obtained in Example 4 was 1.8% by volume. The proportion of coarse particles in the agglomerated particles (5) obtained in Example 5 was 0.8% by volume. The ratio of coarse particles in the agglomerated particles (6) obtained in Example 6 was 1.4% by volume. The ratio of coarse particles in the aggregated particles (7) obtained in Comparative Example 1 was 2.5% by volume. The ratio of coarse particles in the aggregated particles (8) obtained in Comparative Example 2 was 3.5% by volume. The ratio of coarse particles in the aggregated particles (9) obtained in Comparative Example 3 was 2.4% by volume. The ratio of coarse particles in the aggregated particles (10) obtained in Comparative Example 4 was 3.0% by volume. The ratio of coarse particles in the aggregated particles (11) obtained in Comparative Example 5 was 2.1% by volume. The ratio of coarse particles in the aggregated particles (12) obtained in Comparative Example 6 was 3.1% by volume.

Moreover, the ratio of the coarse particle in aggregated particle (1)-(7) was evaluated with the following criteria. The practical acceptable range when the aggregated particles are used as a toner for developing an electrostatic image is Δ or more.
○: Less than 0.5% by volume Δ: Less than 2.0% by volume ×: 2.0% by volume or more

  Table 1 summarizes θ1, θ2, d, and H of the stirring devices used in each example and each comparative example. Further, in Table 1, the liquid contact point (first contacted portion) of the second dispersion in each example and each comparative example, and the velocity component along the flow of the first dispersion when the second dispersion is introduced. Whether or not to have. Furthermore, the determination results of the volume average particle diameter (D50v) of the aggregated particles obtained in each Example and each Comparative Example, the ratio of coarse particles in the aggregated particles, and the ratio of coarse particles in the aggregated particles are summarized.

  As can be seen from the results in Table 1, in Examples 1 to 6, compared to Comparative Examples 1 to 6, the ratio of coarse particles in the aggregated particles was a low value, and the formation of coarse particles was suppressed. The ratio of coarse particles in the aggregated particles of Examples 1 to 6 was 2.0% by volume or less, satisfying the practically acceptable range when used as an electrostatic image developing toner. From these facts, it has a velocity component along the flow of the first dispersion liquid containing the first resin particles introduced in advance into the stirring tank and stirred by the stirring blade, and without contacting the inner wall of the stirring tank. It can be said that the formation of coarse particles is suppressed by introducing the second dispersion liquid containing the second resin particles into the stirring tank from the introduction part to produce the aggregated particles.

<Preparation of dispersion containing amorphous polyester resin particles>
In a heat-dried stirring tank, 10 mol parts of polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene (2,2) -2,2-bis (4- Hydroxyphenyl) propane 90 mol part, terephthalic acid 10 mol part, fumaric acid 67 mol part, n-dodecenyl succinic acid 3 mol part, trimellitic acid 20 mol part, and these acid components (terephthalic acid, n- After adding 0.05 mol part of dibutyltin oxide to the total number of moles of dodecenyl succinic acid, trimellitic acid and fumaric acid), introducing nitrogen gas into the tank and keeping the inert atmosphere, the temperature is increased. A copolycondensation reaction was carried out at a temperature of not lower than 230 ° C. and not higher than 230 ° C. for 12 to 20 hours. This resin had a weight average molecular weight Mw of 55000 and a glass transition temperature Tg of 55 ° C. Next, 3000 parts of the obtained amorphous polyester resin, 10000 parts of ion-exchanged water and 90 parts of surfactant sodium dodecylbenzenesulfonate were charged into the emulsification tank of the high-temperature / high-pressure emulsifier, and then heated and melted to 130 ° C. , Dispersed at 10000 rpm for 30 minutes at a flow rate of 3 L / m at 110 ° C., passed through a cooling tank to recover a dispersion containing amorphous polyester resin particles, and an amorphous having a volume average particle diameter (D50v) of 150 nm A dispersion containing solid polyester resin particles (solid content concentration: 40% by mass) was obtained (hereinafter sometimes referred to as amorphous polyester resin particle dispersion). In addition, the measuring method of the weight average molecular weight and glass transition temperature of an amorphous polyester resin is as having mentioned above. The method for measuring the volume average particle size of the amorphous polyester resin particles in the amorphous polyester resin particle dispersion is the same as the method for measuring the volume average particle size of the polyester resin particles in the first dispersion described above. is there.

<Preparation of dispersion containing crystalline polyester resin particles>
Pentanediol 52 mol%, succinic acid 48 mol%, dibutyltin oxide 0.08 mol% as a catalyst was charged into a stirring tank, mixed, heated to 220 ° C. under reduced pressure, and subjected to a dehydration condensation reaction for 6 hours. A crystalline polyester resin was obtained. Subsequently, 80 parts by mass of the crystalline polyester resin and 720 parts by mass of deionized water were heated to 55 ° C. When the crystalline polyester resin was melted, it was stirred using a homogenizer. Then, an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK; 20% by mass) was added dropwise with emulsification and dispersion, and a crystal having a volume average particle size (D50v) of 0.160 μm. A dispersion containing solid polyester resin particles (solid content concentration: 10% by mass) was obtained (hereinafter sometimes referred to as crystalline polyester resin particle dispersion). The method for measuring the volume average particle size of the crystalline polyester resin particles in the crystalline polyester resin particle dispersion is the same as the method for measuring the volume average particle size of the polyester resin particles in the first dispersion described above.

<Preparation of pigment dispersion>
・ Carbon black (Cabot Co., Mogal L) 50 parts ・ Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK) 6 parts ・ Ion-exchanged water 200 parts And a pigment dispersion liquid (solid content concentration: 20% by mass) having a volume average particle diameter (D50v) of 160 nm was obtained. The method for measuring the volume average particle size is the same as the method for measuring the volume average particle size of the polyester resin particles in the first dispersion described above.

<Preparation of release agent dispersion>
・ 50 parts of paraffin wax (Nippon Seiwa Co., Ltd., HNP0190, melting point 85 ° C.) 3 parts of anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R) 150 parts of ion-exchanged water Then, the dispersion is passed through a pressure discharge type homogenizer (manufactured by Gorin, high pressure homogenizer), and a release agent dispersion liquid (solid content concentration: 20% by mass) having a volume average particle size (D50v) of 200 nm is obtained. Obtained. The method for measuring the volume average particle size is the same as the method for measuring the volume average particle size of the polyester resin particles in the first dispersion described above.

(Example 7: Production of aggregated particles (13))
-Amorphous polyester resin particle dispersion 200 parts-Crystalline polyester resin particle dispersion 50 parts-Pigment dispersion 50 parts-Release agent dispersion 45 parts-Polyaluminum chloride 1 part-Ion exchange water 300 parts The mixture was put into a stirring tank having a jacket capable of heating and cooling, adjusted to pH 4.0, and mixed and dispersed using a disperser to obtain a mixed dispersion.

The stirring apparatus shown in FIG. 1 was prepared. In Example 7, θ1 shown in FIG. 6 (A) was set to 30 °, d was set to 1.0 m, and θ2 shown in FIG. 6 (B) was set to 60 °. The mixed dispersion was put into the stirring tank of the prepared stirring apparatus. In this state, stirring was performed with a stirring power of 1.5 kW / m ^{3, and} the temperature was raised under the condition of a heating medium inlet temperature of 48 ° C. (aggregation step). The temperature in the tank 120 minutes after the start of temperature increase was 47.5 ° C. Next, the heating medium inlet temperature was maintained at 48 ° C., the stirring power was set to 0.8 kW / m ³ , and as shown in FIG. 3 (A), the amorphous polyester resin dispersion liquid heated to 40 ° C. ( 150 parts of the second dispersion liquid was added from the introduction part over 20 minutes (additional addition step). That is, the second dispersion was introduced into the stirring tank so as to have a velocity component along the flow of the first dispersion (mixed dispersion) and without contacting the inner wall of the stirring tank. In the additional addition step, H when the second dispersion was introduced from the introduction portion was 0.2 m.

  The temperature in the stirring tank after the introduction of the second dispersion is 44 ° C., and the difference between the temperature in the stirring tank after the introduction of the second dispersion (T2) and the temperature in the stirring tank before the introduction of the second dispersion (T1) is -3.5 ° C.

The heating medium inlet temperature was set to 45 ° C., the stirring power was lowered to 0.3 kW / m ³ while raising the pH to 8 after stirring for 3 minutes, and the core aggregated particles (aggregated crystalline and amorphous polyester resin particles) Agglomerated particles having amorphous polyester resin particles adhered to the surface were obtained. In order to coalesce the aggregated particles, the dispersion containing the aggregated particles was transferred to another stirring device, and the temperature was raised to 90 ° C. (a coalescence step). After cooling the dispersion containing aggregated particles after the coalescence step, the dispersion containing aggregated particles was washed and dried to obtain aggregated particles (13). The recovery rate of the agglomerated particles (13) with respect to the input raw material was 99%. The ratio of coarse particles in the aggregated particles (13) obtained in Example 4 was 0.4% by volume. The method for measuring the ratio of coarse particles is the same as that described above, and the following examples are also the same measurement method. The input raw materials are amorphous polyester resin particle dispersion, crystalline polyester resin particle dispersion, pigment dispersion, release agent dispersion, polyaluminum chloride, ion exchange water, amorphous polyester resin dispersion (second The recovery rate with respect to the input raw material is (input raw material−coarse particles−non-attached amorphous polyester resin particles) ÷ input raw material [%].

(Example 8)
Aggregated particles were produced in the same manner as in Example 7 except that the temperature in the stirring tank (T2) after introduction of the second dispersion was 46 ° C. and T2-T1 was −1.5 ° C. ) The recovery rate of the agglomerated particles (14) with respect to the input raw material was 97%. The ratio of coarse particles in the agglomerated particles (9) obtained in Example 8 was 0.8% by volume.

Example 9
Aggregated particles were produced in the same manner as in Example 7 except that the temperature in the stirring tank (T2) after the introduction of the second dispersion was 43 ° C. and T2-T1 was −4.5 ° C. ) The recovery rate of the agglomerated particles (15) with respect to the input raw material was 97%. The ratio of coarse particles in the agglomerated particles (10) obtained in Example 9 was 0.3% by volume.

(Example 10)
Aggregated particles were produced in the same manner as in Example 7 except that the stirring power during the introduction of the second dispersion was changed from 0.8 kW / m ³ to 0.6 kW / m ³ to obtain agglomerated particles (16). . The recovery rate of the agglomerated particles (16) with respect to the input raw material was 97%. The ratio of coarse particles in the aggregated particles (16) obtained in Example 10 was 0.5% by volume.

(Example 11)
Aggregated particles were produced in the same manner as in Example 7 except that the stirring power during introduction of the second dispersion was changed from 0.8 kW / m ³ to 3.5 kW / m ³ to obtain agglomerated particles (17). . The recovery rate of the agglomerated particles (17) with respect to the input raw material was 98%. The proportion of coarse particles in the aggregated particles (17) obtained in Example 11 was 0.3% by volume.

(Example 12)
Aggregated particles were produced in the same manner as in Example 7 except that the stirring power during introduction of the second dispersion was changed from 0.8 kW / m ³ to 0.4 kW / m ³ to obtain aggregated particles (18). . The recovery rate of the agglomerated particles (18) with respect to the input raw material was 96%. The ratio of coarse particles in the aggregated particles (18) obtained in Example 12 was 1.2% by volume.

(Example 13)
Aggregated particles were produced in the same manner as in Example 7 except that the stirring power during the introduction of the second dispersion was changed from 0.8 kW / m ³ to 4.5 kW / m ³ to obtain agglomerated particles (19). . The recovery rate of the agglomerated particles (19) with respect to the input raw material was 96%. The ratio of coarse particles in the aggregated particles (19) obtained in Example 13 was 0.2% by volume.

(Example 14)
Example 7 except that the temperature of the second dispersion introduced from the introduction part was changed from 40 ° C. to 20 ° C., and the heat medium inlet temperature when the second dispersion was introduced was changed from 48 ° C. to 52 ° C. Aggregated particles were produced in the same manner as described above to obtain agglomerated particles (20). The recovery rate of the agglomerated particles (20) with respect to the input raw material was 97%. The ratio of coarse particles in the aggregated particles (20) obtained in Example 14 was 1.0% by volume.

(Example 15)
Aggregated particles were produced in the same manner as in Example 7 except that the temperature in the stirring tank (T2) after the introduction of the second dispersion was 42 ° C. and T2-T1 was −5.5 ° C. ) The recovery rate of the aggregated particles (20) with respect to the input raw material was 90%. The ratio of coarse particles in the aggregated particles (20) obtained in Example 15 was 0.2% by volume.

(Example 16)
Aggregated particles were produced in the same manner as in Example 7 except that the stirring power during the introduction of the second dispersion was changed from 0.8 kW / m ³ to 4.0 kW / m ³ to obtain aggregated particles (22). . The recovery rate of the agglomerated particles (22) with respect to the input raw material was 97%. The ratio of coarse particles in the aggregated particles (22) obtained in Example 16 was 0.3% by volume.

  Table 2 shows the temperature (T1) in the agitation tank before the introduction of the second dispersion in Examples 7 to 16, the temperature of the second dispersion introduced from the introduction part, and the inlet temperature of the heat medium when the second dispersion is introduced. , Stirring power during introduction of second dispersion, temperature in stirring tank after introduction of second dispersion (T2), difference between T2 and T1 (T2-T1), ratio of coarse particles in aggregated particles, and aggregated particles The recovery rate was summarized.

As can be seen from the results in Table 2, the difference between the temperature in the stirring tank before introducing the second dispersion (T1) and the temperature in the stirring tank after introducing the second dispersion (T2) is -5 ° C or higher and -1 ° C or lower. In Examples 7 to 14 and 16, the difference between the temperature in the stirring tank before introducing the second dispersion (T1) and the temperature in the stirring tank after introducing the second dispersion (T2) is less than −5 ° C. Compared with Example 15 that is, the proportion of coarse particles in the aggregated particles is similar, but the recovery rate of the aggregated particles is greatly increased. Furthermore, in the embodiment 7-14 and 16, Examples 7～11,14 and 16 and the stirring power of the second dispersion introduced with 0.5 kW / ^{m 3} or more 4.0 kW / ^{m 3} or less of the range ^3. Compared with Example 12 in which the stirring power during the introduction of the second dispersion was less than 0.5 kW / m ³ , the ratio of coarse particles in the aggregated particles was low, and the recovery rate of the aggregated particles was increased. Compared with Example 13 which is more than 0 kW / m ³ , the ratio of coarse particles in the aggregated particles is similar, but the recovery rate of the aggregated particles is increased.

  As described above, the first dispersion liquid containing the first resin particles is introduced into the stirring tank by the method of the embodiment, and the first dispersion liquid containing the second resin particles is stirred with the stirring blade. Compared with the case where the 2 dispersion was brought into contact with the inner wall of the stirring tank and introduced into the stirring tank along the inner wall of the stirring tank, the formation of coarse particles was suppressed.

  DESCRIPTION OF SYMBOLS 1 Stirrer, 10 Stirrer tank, 12 Stirrer shaft, 14 Stirrer blade, 16 Heat transfer part, 18 Introduction part, 20 Baffle plate, 22 Jacket part, 24 Heat medium inlet, 26 Heat medium outlet, 28 Inlet, 30 Discharge port 32 Fluid flow path.

Claims (5)

A stirring tank, a stirring shaft rotatably mounted in the stirring tank, a stirring blade attached to the stirring shaft, a heat transfer section for applying heat from the wall surface of the stirring tank to the tank, and a discharge port; Having an introduction part that discharges fluid from the discharge port into the stirring tank and introduces the fluid into the stirring tank;
The introduction part has a velocity component along the flow of the first dispersion liquid including the first resin particles introduced in advance into the stirring tank and stirred by the stirring blade, and contacts the inner wall of the stirring tank A stirrer characterized by introducing the second dispersion containing the second resin particles without introducing the second resin particles. An angle formed between a perpendicular to a straight line connecting the discharge port of the introduction part and the stirring shaft and the central axis of the discharge port of the introduction part is θ1, and a high level from the liquid level in the stirring tank to the discharge port of the introduction part H is an angle formed by an extension line extending in a direction in which the second dispersion liquid is discharged from the discharge port of the introduction part and a horizontal line is θ2, and in a direction in which the second dispersion liquid is discharged from the discharge port of the introduction part 2. The stirring device according to claim 1, wherein the following (1) to (4) are satisfied, where d is a horizontal distance between the discharge port and the inner wall of the stirring tank.
-90 ° <θ1 <90 ° (1)
0.05m ≦ H ≧ 1.0m (2)
0 ° <θ2 <90 ° (3)
0.1 m ≦ d ≦ 2.5 m (4) Aggregation step of using the stirring device according to claim 1 or 2 to stir the first dispersion containing the first resin particles introduced into the stirring tank with the stirring blade, and agglomerate the first resin particles;
A second dispersion containing second resin particles so as to have a velocity component along the flow of the first dispersion liquid being stirred by the stirring blade in the stirring tank and without contacting the inner wall of the stirring tank. A method for producing agglomerated particles, comprising: a step of introducing a liquid from the introduction part into the stirring tank and stirring the first dispersion in the stirring tank.   The difference (T2-T1) between the temperature T2 in the stirring tank after the introduction of the second dispersion and the temperature T1 in the stirring tank before the introduction of the second dispersion is −5 ° C. or more and −1 ° C. or less. The method for producing aggregated particles according to claim 3, wherein When introducing the second dispersion liquid to the agitation tank from the inlet portion, the relative liquid stirring tank, per unit volume 0.5 kW / m ³ or more 4.0 kW / m ³ or less of the stirring power of the liquid The method for producing aggregated particles according to claim 3 or 4, wherein the agglomerated particles are agitated.

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