JP2018060000A - Manufacturing method of toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of toner in which a release agent in a release agent dispersion liquid is finely dispersed to a small particle diameter that is sufficient to be included in toner.SOLUTION: A manufacturing method of toner includes a dispersion step for obtaining a release agent dispersion liquid in which a release agent is dispersed in a resin solution or polymerizable monomer. The dispersion step is the step for obtaining the release agent dispersion liquid by repeatedly executing the steps of: (i) discharging the mixture from a tank storing the mixture containing the resin solution or polymerizable monomer and release agent, and introducing the discharged mixture from a pump to a disperser; (ii) performing dispersion processing of the release agent by the disperser to obtain a dispersion processing liquid; (iii) returning the dispersion processing liquid to the tank; (iv) discharging the dispersion processing liquid in the tank and introducing the discharged dispersion processing liquid from the pump to the disperser. The manufacturing method of toner feeds the liquid by the pump and removes the gas conveyed together with the liquid.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing an electrostatic charge image developing toner.

As a method for producing resin particles such as an electrostatic charge image developing toner (hereinafter sometimes simply referred to as “toner”), it is easy to obtain a product having a reduced environmental burden during production, a small particle size and a sharp particle size distribution. A wet manufacturing method is often used because of its merit such as easy shape control and encapsulation.
The wet manufacturing method is a method for manufacturing resin particles in a liquid medium. Production methods such as a suspension polymerization method, an emulsion polymerization method, a dissolution suspension method, and a dispersion polymerization method are carried out depending on the material constituting the resin particles and the desired resin particle shape.
The toner obtained by these methods is developed on a photoreceptor and then a release agent or the like is added to the toner raw material in order to improve the fixability of the toner transferred to paper or the like.
In the pulverization method, the blending of about 5 parts by weight of the release agent is limited with respect to 100 parts by weight of the binder resin, whereas in the wet manufacturing method, it is possible to blend in a larger proportion. Further, the release agent can be reliably encapsulated, and good fixability and offset resistance can be obtained.
At this time, if a release agent having a low melting point is used, the plasticity of the toner at a low temperature increases, and the fixability in a low temperature region is improved. On the other hand, if a release agent having a high melting point is used, the releasability of the toner from the photoreceptor at a high temperature is increased, and the fixability in a high temperature region is improved.
In recent years, there has been a growing interest in the environment, and there is a demand for reducing the amount of toner-derived fine particles generated in a heat and pressure fixing machine. For this requirement, it is often advantageous to use a release agent having a high melting point.
When a release agent is added to the polymerized toner, if the melting point of the release agent is lower than the temperature during the polymerization step, it may be mixed with the raw material composition as it is. However, when the melting point of the release agent is higher than the temperature during the polymerization process, the release agent remains in a solid state, resulting in the formation of a coarse release agent mass and complete and even inclusion in the toner. Becomes difficult.
If the added release agent is not completely encapsulated in the toner and a part thereof is released from the toner as a release agent lump etc., the fluidity of the entire toner is significantly reduced even if it is small. . Alternatively, toner aggregation with the release agent block as a core is caused, and in any case, image quality is lowered when an image is formed.
Further, even when the release agent is completely encapsulated in the toner, if the distribution state is not uniform, the release agent content differs for each toner, and different properties are exhibited. When it is formed, it leads to deterioration of image quality.
If the domains of the release agent can be uniformly dispersed, the melting rate of the release agent at the time of heating is increased, which leads to improvement in fixability.
In order to completely and uniformly encapsulate the release agent having a melting point higher than the polymerization temperature in the toner,
It is preferable to use a high melting point release agent that is finely powdered or finely dispersed in a liquid medium.
Among these, from the viewpoint of ease of handling, it is more preferable to finely disperse it in a liquid medium. So far, proposals for producing fine dispersions of high melting point release agents have been actively made.

On the other hand, important elements of the colorant added to the toner include not only coloring power but also good transparency. In order to have good transparency, it is important that the dispersed particle diameter of the colorant is small and that the average particle diameter of the colorant in the toner is small.
However, in the step of dispersing the colorant in the polymerizable monomer using a disperser, the dispersion of the colorant increases as the colorant is finely dispersed.
In addition, as the viscosity of the dispersion increases, bubbles mixed in the dispersion become difficult to escape from the dispersion, thereby reducing the dispersion efficiency of the colorant.
Furthermore, if bubbles are mixed in the dispersion, the dispersion time increases with a decrease in dispersion efficiency, so that the colorant is likely to be overdispersed, and the colorant is likely to aggregate in the dispersion or in the toner. As a result, adverse effects such as a reduction in coloring power and transparency are likely to occur.
To date, proposals for producing a fine dispersion of a colorant have been actively made.

Patent Documents 1 to 4 disclose a method of finely dispersing a release agent or a colorant in a polymerizable monomer using a media disperser to obtain a fine dispersion of a high melting point release agent or a colorant. Yes.
According to the method described in Patent Document 1 or 2, a polymerized toner obtained by carrying out a polymerization reaction after dispersing a polymerizable monomer composition containing a release agent dispersion in an aqueous medium to form droplets. In the production method, the release agent dispersed in the release agent dispersion is not liberated. In addition, a polymerized toner having improved fixing properties can be produced by completely and uniformly encapsulating the release agent in the polymer fine particles.
Patent Documents 1, 3 and 4 also disclose a method in which a circulation line is assembled with a media disperser and the dispersion is passed through a plurality of times. Since this method has high dispersion efficiency and a large amount of processing with respect to the mill diameter, it can cope with scale-up, which is a problem of the batch method.
Further, in Patent Documents 3 and 4, since uneven distribution of beads is eliminated, the dispersibility of the colorant is remarkably excellent, the particle diameter distribution is uniform and sharp, and the toner characteristics such as image density and color tone are excellent. It is said that a polymerized toner can be produced efficiently.
In recent years, as the process speed of electrophotography increases, low temperature fixability of toner is required. Therefore, there is a need for the development of a technique capable of finely dispersing the release agent for the purpose of improving the uniform dispersibility of the release agent and further improving the heat transfer properties by making the domains finer.
On the other hand, high image quality is also required. Therefore, there is a need to develop a technique capable of finely dispersing the colorant for the purpose of improving the uniform dispersibility of the colorant and further improving the heat transfer properties by making the domains finer.
The method described above is effective as a method for obtaining a high-melting-point release agent or a fine dispersion of a colorant, but the problem is that the viscosity of the dispersion rises due to the incorporation of gas into the dispersion and the dispersion ability falls. was there. Therefore, there has been a limit to reducing the particle size of the dispersion.
Regarding removal of gas from the dispersion, Patent Document 5 discloses a rotary dispersion machine equipped with a mechanism that can disperse and concentrate the dispersion while reducing the pressure in the container forming the dispersion chamber in a rotary dispersion machine using media. A machine is disclosed.
As another example relating to the removal of gas from the liquid, Patent Document 6 discloses a twin-screw pump that can transfer a high-viscosity material while removing the gas from the transfer object. According to this pump, it was possible to prevent gas from being mixed during the transfer of food and industrial materials. Such a deaeration function is provided for the purpose of maintaining the quality of the final product, and has not been used for the purpose of improving the material dispersion process. In other words, the viscosity of the dispersion liquid is low at the beginning of the dispersion process, and if degassing is performed when the dispersion liquid has a low viscosity, the process liquid is contaminated at the degassing port, so that it is difficult to apply to the dispersion process. It was.

Japanese Patent No. 4336621 JP 2002-229251 A JP 2003-255605 A Japanese Patent No. 4085931 JP 11-314044 A JP2015-55179A

When the dispersion of the release agent or the colorant in the polymerizable monomer proceeds, many bubbles are taken into the dispersion as the viscosity increases. As a result, the viscosity of the dispersion increases rapidly, and the dispersion efficiency further decreases.
Therefore, it is necessary to sufficiently remove bubbles in the dispersion to finely disperse the release agent sufficiently and uniformly in the toner, and the colorant in the colorant dispersion. Is a problem in efficiently producing a toner having excellent dispersibility and excellent characteristics such as image density and OHP transparency.
According to the disperser shown in Patent Document 5, since dispersion can be performed while defoaming, an increase in the viscosity of the dispersion due to the incorporation of bubbles can be suppressed. Therefore, improvement in dispersion efficiency can be expected.
However, the circulation type disperser as shown in Patent Document 1 or 3 cannot be applied because it is essential to push the fluid into the dispersion chamber.
On the other hand, in the circulation type dispersion system, it is conceivable to remove bubbles while achieving the dispersion efficiency and scale-up which are the advantages of the circulation type by degassing the stirring tank.
However, since the liquid depth of the stirring tank is deep, when the viscosity of the dispersion liquid is high, the fluidity of the liquid in the tank is lowered, and the bubble removal efficiency is greatly reduced. In order to eliminate this, when the stirring speed of the liquid in the stirring tank is increased, the vortex becomes large and the amount of bubbles taken in increases. Further, when the degree of vacuum is excessively increased, volatilization of the dispersion medium in the stirring tank becomes a problem.
On the other hand, by installing an inner nozzle at the return port of the liquid and lowering the stirring speed of the stirring tank, the amount of bubbles taken in can be reduced, and the required degree of decompression can be suppressed. However, when the stirring speed is lowered, mixing in the stirring tank is weakened, and the efficiency of removing bubbles is lowered.

The present invention is to provide a toner production method that solves the above-described problems.
That is, the present invention relates to a method for producing a toner having a dispersion step of obtaining a release agent dispersion in which a release agent is dispersed in a resin solution or a polymerizable monomer, the release agent in the release agent dispersion. The present invention provides a method for producing a toner in which a mold is finely dispersed to a particle size small enough to be encapsulated in the toner.
The present invention also relates to a method for producing a toner having a dispersion step of obtaining a colorant dispersion in which a colorant is dispersed in a resin solution or a polymerizable monomer, and the dispersion of the colorant in the colorant dispersion It is an object of the present invention to provide a toner production method capable of efficiently producing a toner having excellent properties and excellent image density and OHP transparency.

As a result of intensive studies on fine dispersion of a release agent or a colorant in a resin solution or a polymerizable monomer, the present inventors have found the following production method.
The present invention
A method for producing a toner having a dispersion step of obtaining a release agent dispersion in which a release agent is dispersed in a resin solution or a polymerizable monomer,
The dispersion step includes the following steps (i) to (iv):
A step of repeatedly performing the steps (i) to (iv) to obtain a release agent dispersion,
(I) The mixed solution is discharged from a tank containing a mixed solution containing the resin solution or the polymerizable monomer and the release agent, and the discharged mixed solution is dispersed by a pump. Introducing into the machine;
(Ii) performing a dispersion treatment of the release agent by the disperser to obtain a dispersion treatment liquid;
(Iii) returning the dispersion treatment liquid to the tank;
(Iv) discharging the dispersion treatment liquid in the tank and introducing the discharged dispersion treatment liquid into the disperser by the pump;
When the liquid is fed by the pump, the gas transported together with the liquid is removed.
The present invention also provides:
A method for producing a toner having a dispersion step of obtaining a colorant dispersion in which a colorant is dispersed in a resin solution or a polymerizable monomer,
The dispersion step includes the following steps (i) to (iv):
A step of repeatedly performing the steps (i) to (iv) to obtain a colorant dispersion,
(I) The mixed solution is discharged from a tank containing a mixed solution containing the resin solution or the polymerizable monomer and the colorant, and the discharged mixed solution is dispersed by a pump. Introducing into the process;
(Ii) a step of dispersing the colorant by the disperser to obtain a dispersion treatment liquid;
(Iii) returning the dispersion treatment liquid to the tank;
(Iv) discharging the dispersion treatment liquid in the tank and introducing the discharged dispersion treatment liquid into the disperser by the pump;
When the liquid is fed by the pump, the gas transported together with the liquid is removed.

  According to the present invention, it is possible to provide a method for producing a toner in which the release agent in the release agent dispersion is finely dispersed to a particle size small enough to be encapsulated in the toner. Further, it is possible to provide a toner production method capable of efficiently producing a toner excellent in the dispersibility of the colorant in the colorant dispersion and excellent in properties such as image density and OHP transparency.

Schematic showing an example of a distributed system Another schematic diagram showing an example of a distributed system

Hereinafter, the present invention will be described in detail.
In the present invention, the description of “XX or more and XX or less” or “XX to XX” representing a numerical range means a numerical range including a lower limit and an upper limit as endpoints unless otherwise specified.
The method for producing the toner of the present invention (hereinafter also referred to as the production method of the present invention)
A method for producing a toner having a dispersion step of obtaining a dispersion liquid in which a dispersion is dispersed in a resin solution or a polymerizable monomer,
The dispersion step includes the following steps (i) to (iv):
A step of repeatedly carrying out the steps (i) to (iv) to obtain a dispersion to be dispersed.
(I) The mixed solution is discharged from a tank containing a mixed solution containing the resin solution or the polymerizable monomer and the dispersion, and the discharged mixed solution is dispersed by a pump. Introducing into the machine;
(Ii) a step of performing a dispersion treatment of the material to be dispersed by the disperser to obtain a dispersion treatment liquid;
(Iii) returning the dispersion treatment liquid to the tank;
(Iv) discharging the dispersion treatment liquid in the tank and introducing the discharged dispersion treatment liquid into the disperser by the pump;
A method for producing a toner, wherein when the liquid is fed by the pump, the gas conveyed together with the liquid is removed.

The dispersion step can be applied to a wet manufacturing method including a step of preparing a dispersion in which a material to be dispersed is dispersed in a liquid dispersion medium.
Examples of the wet production method include a suspension polymerization method and a dissolution suspension method.
When the suspension polymerization method is used, for example, particles of the dispersion liquid in which the dispersion is dispersed in a polymerizable monomer are formed in an aqueous medium, and polymerization contained in the particles of the dispersion liquid is performed. The toner may be obtained through a step of polymerizing the polymerizable monomer.
When the dissolution suspension method is used, for example, a step of preparing a dispersion dispersion by dissolving or dispersing the dispersion in a resin solution obtained by dissolving a binder resin in an organic solvent, the dispersion The toner may be obtained through a granulation step of forming the particles of the dispersion liquid in an aqueous medium and a desolvation step of removing the organic solvent contained in the particles of the dispersion liquid to be dispersed to produce resin particles.
Hereinafter, examples in which the dispersion step is used in the suspension polymerization method will be described in more detail, but the present invention is not limited thereto. In addition, as a to-be-dispersed material, a mold release agent, a coloring agent, etc. can be mentioned.

(Rough dispersion preparation process)
Prior to the dispersion step of the dispersion, the mixed solution containing the polymerizable monomer and the dispersion or the mixed solution containing the resin solution and the dispersion is dispersed with a simple dispersion device. A coarse dispersion of the material to be dispersed may be prepared.
The preliminary coarse dispersion includes a turbine blade and an edged turbine blade having a large shearing force among ordinary stirring blades, Ultra Tarrax (manufactured by IKA), T.C. K. Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), T. K. Dispersing machines such as Fillmix (made by Special Machine Engineering Co., Ltd.) and Claremix (made by M Technique Co., Ltd.) can be used. Further, a continuous disperser such as Ebara Milder (manufactured by Ebara Corporation) or Cavitron (manufactured by Eurotech) may be used. These can be used in a single pass, or can be used by passing a plurality of times through a circulation line.

(Dispersion process)
A dispersion | distribution process is a process of obtaining the to-be-dispersed material dispersion liquid by which the to-be-dispersed material was disperse | distributed to the resin solution or the polymerizable monomer.
Specifically, it is a step of having the following steps (i) to (iv) and repeatedly performing the steps (i) to (iv) to obtain a dispersion liquid to be dispersed.
(I) A step of discharging the mixed solution from a tank in which a mixed solution containing a resin solution or a polymerizable monomer and a material to be dispersed is accommodated, and introducing the discharged mixed solution into a disperser by a pump. (Ii) A step of performing dispersion treatment of the object to be dispersed by a disperser to obtain a dispersion treatment liquid (iii) A step of returning the obtained dispersion treatment liquid to the tank (iv) A dispersion treatment liquid in the tank is discharged and discharged The step of introducing the dispersion treatment liquid into the disperser with a pump And, when the liquid is fed with the pump, the gas conveyed with the liquid is removed.

FIG. 1 shows an example of a dispersion system for a material to be dispersed, which incorporates a pump capable of removing the gas conveyed with the liquid when the liquid is fed, but the present invention is not limited to these.
The pump 7 shown in FIG. 1 has a function of feeding a liquid mixture containing a polymerizable monomer and a material to be dispersed in the holding tank 1 to a disperser and a function of extracting a gas contained in the liquid mixture. Have
Means for exerting the function of extracting the gas are not limited, and general means such as an air ejector type deaeration device, a piston / cylinder type or a centrifugal fan type decompression pump can be exemplified.

In the system including the pump 7, a coarse dispersion liquid to be dispersed, or a polymerizable monomer and the substance to be dispersed are charged into the holding tank 1.
Then, you may perform the pre-dispersion process of making it disperse | distribute or melt | dissolve for a predetermined time with the stirrer driven by the motor 2, and obtaining a liquid mixture. In the holding tank 1, temperature-controlled water adjusted in the jacket 3 may be introduced through the jacket inlet 4 and the jacket outlet 5 in order to adjust the temperature of the mixed liquid.
The obtained mixed liquid is supplied to the disperser 8 via the pump 7, and the disperse material is subjected to dispersion treatment by the disperser 8 to prepare a dispersion treatment liquid. Thereafter, the obtained dispersion treatment liquid is returned to the holding tank 1.
The dispersion processing liquid that has returned to the holding tank 1 is supplied to the disperser 8 through the pump 7 again. Then, while the circulation between the disperser 8 and the holding tank 1 is repeated, the object to be treated is uniformly and efficiently dispersed. By carrying out the dispersion process for a predetermined time, the object dispersion liquid is obtained. can get.

In the dispersion step, when the viscosity of the liquid led out from the pump 7 reaches a predetermined value, the gas may be extracted by the pump 7.
The degree of pressure reduction of the pump 7 may be adjusted so that the bulk specific gravity of the liquid derived from the pump 7 becomes a desired value. For example, in terms of gauge pressure, −0.01 MPa to −0.04 MPa is preferable from the viewpoint of achieving both degassing from the liquid and suppression of volatilization, but may be arbitrarily prepared depending on the physical properties of the liquid.
Since the pump has a function of extracting gas, the processing cross-sectional area of the liquid to be degassed is reduced, so that the depth of the liquid is higher than the degassing in the holding tank where the depth of the liquid is an issue. The time during which the mixture is exposed to reduced pressure can be shortened. Therefore, volatilization of the dispersion medium can be suppressed. In addition, since the liquid is immediately sent to the disperser after deaeration, the deaeration efficiency is high as a deaeration means in the dispersion system.

The degassed liquid is sent to the disperser 8, where it is dispersed. At this time, since the content of bubbles in the liquid is small, the dispersion efficiency of the dispersion is increased, and the dispersion of the dispersion can be performed in a shorter time than before. Furthermore, it becomes possible to finely disperse the object to be dispersed compared to the conventional case.
When a media-type disperser is used as the disperser 8, if bubbles are contained in the liquid, the collision energy due to the medium inside the disperser 8 is not easily imparted to the dispersion of the object to be dispersed. Similarly, even when a medialess disperser is used, if bubbles are contained in the liquid, it is difficult to efficiently apply mechanical energy to the dispersion of the object to be dispersed, and the dispersion efficiency tends to decrease.
When the bubble content in the liquid is small, the dispersion efficiency is increased and the treatment can be performed for a short time, so that the overdispersion of the object to be dispersed can be suppressed.
Therefore, for example, it is preferable because re-aggregation of the colorant can be suppressed in the toner. As a result, since a colorant having fine dispersion and sharp distribution can be present in the toner as compared with the conventional toner, a toner having high coloring power and excellent OHP transparency can be obtained.

As the disperser 8, a general disperser that can be used a plurality of times or in one pass by forming a circulation line is used. This is not limited, but preferred examples include diamond fine mill (manufactured by Mitsubishi Heavy Industries), dyno mill (manufactured by Shinmaru Enterprise), apex mill (manufactured by Kotobuki Giken), SC mill (Nihon Coke Industries Co., Ltd.) Media dispersers such as the former Mitsui Miike Kako Co., Ltd.), Star Mill (manufactured by Ashizawa Finetech Co., Ltd.), OB Mill (manufactured by IVER BATTLLE), Super Mill (manufactured by Inoue Seisakusho Co., Ltd.), and the like.
On the other hand, medialess dispersers such as Sharp Flow Mill (manufactured by Taiheiyo Kiko Co., Ltd.), Claremix (manufactured by M Technique Co., Ltd.), and high shear mixer (manufactured by IKA Corporation) can also be used.
A media disperser is more preferable because it has high dispersion efficiency and can suppress overdispersion caused by local energy of cavitation.

Examples of media particles used in the media disperser include beads having excellent wear resistance. The diameter of the media particles is usually 0.3 mm or more, preferably 0.3 mm or more and 5 mm or less, more preferably 0.5 mm or more and 3 mm or less. The density of the beads is usually 3 g /
cm ³ or more, preferably 4.5 g / cm ³ or more. As the material of the beads, high-hardness ceramics such as zircon and zirconia; and high-hardness metals such as steel are preferably used. The filling amount of the media particles is usually 50 volume% or more and 90 volume% or less, preferably 70 volume% or more and 85 volume% or less.

  In order to reduce the amount of the dispersion medium recovered by deaeration, a cooling mechanism may be provided in the immediate vicinity of the pump of the deaeration line.

In the dispersion step, when the bulk specific gravity of the liquid before being introduced into the pump is A (kg / m ³ ) and the bulk specific gravity of the liquid after being led out from the pump is B (kg / m ³ ) It is preferable that A <B is satisfied.
The larger the volume of the gas contained in the liquid, the smaller the bulk specific gravity of the liquid. The smaller the volume of the gas contained in the liquid, the lower the viscosity of the liquid when the dispersion proceeds, and the more efficiently the dispersion can be performed.
If the bulk specific gravity B is a little larger than the bulk specific gravity A, the dispersion efficiency is improved, but the value obtained by subtracting the bulk specific gravity A from the bulk specific gravity B (ie, [B−A]) is 5 (kg / m ³ ) or more. Preferably, it is 10 (kg / m ³ ) or more. The upper limit is not particularly limited, but is preferably 80 (kg / m ³ ) or less. In order to adjust A and B to the above range, a method such as adjusting the suction pressure of a deaeration pump attached to the pump can be exemplified.

Further, in the dispersion step, the bulk specific gravity and viscosity of the liquid derived from the pump are B (kg / m ³ ) and D (Pa · s), respectively, and the resin solution or the polymerizable monomer And the true specific gravity of the mixed liquid containing the substance to be dispersed is C (kg / m ³ ),
It is preferable that 0.5 ≦ D is satisfied, 1.0 ≦ D is more preferable, and 1.5 ≦ D is more preferable. The upper limit is not particularly limited, but preferably D ≦ 4 (Pa · s).
On the other hand, it is preferable to satisfy 0.94 ≦ B / C ≦ 1.00, and it is more preferable to satisfy 0.97 ≦ B / C ≦ 0.99. In order to adjust D and [B / C] to the above range, a method of adjusting the deaeration start timing and the suction pressure of the deaeration pump attached to the pump can be exemplified.
By extracting the gas when the viscosity of the liquid is greater than 0.5 (Pa · s), excessive crushing is suppressed, and aggregation of a release agent, a colorant, and the like due to excessive crushing is prevented. Can do. In addition, contamination of the process liquid gas extraction line due to the low viscosity can be prevented. On the other hand, when [B / C] is 0.94 or more, the gas can be sufficiently removed from the liquid, and the dispersion efficiency is further improved.

Although it will not specifically limit if this pump can remove the gas conveyed with a liquid at the time of liquid feeding, The pump which has the following structures can illustrate suitably.
The pump includes a pair of pump screws that rotate in a non-contact manner and a housing chamber that accommodates the pair of pump screws in a non-contact manner, and the pair of pump screws and the storage chamber. A pump casing that forms a pump chamber, and a bearing portion that is connected to the pump casing and rotatably supports one end portion of the pair of pump screws in a cantilevered manner. The pump casing in the region is provided with an inlet for taking the mixed liquid or the dispersion processing liquid into the pump chamber, and the pump casing on the floating end side of the pair of pump screws has the mixing pump transferred from the pump chamber. A discharge port for discharging the liquid or the dispersion processing liquid, and the pair of the mixed liquid or the dispersion processing liquid taken into the pump chamber from the intake port. The gas in the storage chamber is transferred by the rotational drive of the pump screw, discharged from the discharge port, and upstream of the intake port in the transfer direction of the mixed liquid or dispersion treatment liquid and above the pump casing. In the twin screw pump provided with an outlet for extraction, it is preferable to have a structure in which a deaeration device for extracting the gas in the storage chamber is connected to the outlet.
The pump has a structure in which the liquid is pushed out by a pair of screws and fed, and the screw is not in contact, so that the liquid is not excessively sheared and aggregation due to overdispersion can be suppressed. Further, since the dispersion is performed only in the disperser portion, the dispersion balance is not lost, and the dispersion can be performed uniformly. Therefore, an increase in viscosity due to a decrease in the particle size distribution of the dispersion can be suppressed.
Specific examples of the pump having the above structure include a deforming pump (Fushitora Kogyo Co., Ltd.) and the like, but are not limited to the pump.

(Preparation process of polymerizable monomer composition)
If necessary, other toner materials may be added to the dispersion liquid in which the dispersion is dispersed in the polymerizable monomer obtained in the dispersion step to obtain a polymerizable monomer composition. .

(Granulation process)
The obtained polymerizable monomer composition is charged into an aqueous medium containing a dispersion stabilizer and dispersed to form particles of the polymerizable monomer composition. Get.
The granulation step can be performed, for example, in a vertical stirring tank provided with a stirrer having a high shearing force. Although it does not specifically limit as a stirrer which has high shear force, For example, a high shear mixer (made by IKA), T.C. K. Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), T. K. Commercially available products such as Philmix (made by Special Machine Industry Co., Ltd.) and Claremix (made by M Technique Co., Ltd.) can be exemplified.
Examples of the dispersion stabilizer include carbonates such as barium carbonate, calcium carbonate and magnesium carbonate; metal phosphates such as aluminum phosphate, magnesium phosphate, calcium phosphate, barium phosphate and zinc phosphate; barium sulfate and calcium sulfate And inorganic dispersion stabilizers such as calcium hydroxide, aluminum hydroxide, magnesium hydroxide, and ferric hydroxide metal hydroxide. These can be used alone or in combination of two or more. These exhibit functions as a dispersion stabilizer by being present as fine particles in an aqueous medium.

(Polymerization process)
A polymerization initiator is added to the polymerizable monomer composition dispersion obtained as described above to polymerize the polymerizable monomer. In the polymerization step, a general stirring tank capable of adjusting the temperature can be used.
The polymerization temperature is 40 ° C. or higher, generally 50 to 90 ° C. The polymerization temperature may be constant throughout, but may be raised in the latter half of the polymerization step for the purpose of obtaining a desired molecular weight distribution.
Any stirring blade may be used as long as it can float the polymerizable monomer composition dispersion without stagnation and keep the temperature in the tank uniform.
Stirring blades or stirring means include paddle blades, inclined paddle blades, three swept blades, propeller blades, disk turbine blades, and general stirring blades such as helical ribbon blades and anchor blades, and “full zone” (( "Shinko Environmental Solution Co., Ltd.", "Twin Star" (manufactured by Shinko Environmental Solution Co., Ltd.), "Max Blend" (manufactured by Sumitomo Heavy Industries), "Supermix" (manufactured by Satake Chemical Machinery Co., Ltd.) “Hi-F mixer” (manufactured by Soken Chemical Co., Ltd.) and the like.

(Distillation process)
If necessary, in order to remove volatile impurities such as unreacted polymerizable monomers and by-products, a part of the aqueous medium may be distilled off after the completion of the polymerization. The distillation step can be performed under normal pressure or reduced pressure.

(Washing process, solid-liquid separation process and drying process)
In order to remove the dispersion stabilizer adhering to the surface of the obtained resin particles, the resin particle dispersion may be treated with an acid or an alkali. Thereafter, the resin particles are separated from the liquid phase by a general solid-liquid separation method, but the resin particles may be washed again with water in order to completely remove the acid or alkali and the dispersion stabilizer component dissolved therein. This washing process is repeated several times, and after sufficient washing, solid-liquid separation is performed again to obtain toner particles. The obtained toner particles may be dried by a known drying means.

(Classification process)
The obtained toner particles have a sufficiently sharp particle size compared to conventional pulverized resin particles, but when a sharper particle size is required, by classifying with an air classifier or the like, Toner particles that deviate from the desired particle size distribution can be separated and removed.

(Polymerizable monomer)
Specific examples of the polymerizable monomer are as follows.
Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- Styrene derivatives such as n-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene; methyl acrylate , Ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, Acrylic polymerizable monomers such as n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl Methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-buty methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl Methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate Methacrylic polymerizable monomers such as ethyl methacrylate.
These polymerizable monomers can be used alone or in combination of two or more. Among these, styrene or a styrene derivative is preferably used alone or in combination, or in combination with other polymerizable monomers, from the viewpoint of the developing characteristics and durability of the toner.

<Colorant>
Examples of the colorant include known colorants used for toners such as organic pigments and oil-based dyes. Specific examples are shown below, but are not limited thereto.
As a pigment used for a cyan colorant, a copper phthalocyanine compound and a derivative thereof, an anthraquinone compound, and a basic dye lake compound can be used. Specific examples include the following. C. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3 and C.I. I. Pigment Blue 15: 4.
As the pigment used for the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds can be used. Specific examples include the following. C. I. Pigment violet 19, C.I. I. Pigment red 31, C.I. I. Pigment red 122, C.I. I. Pigment red 150 and C.I. I. Pigment Red 269.
As the pigment used for the yellow colorant, condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds can be used. Specific examples include the following. C. I. Pigment yellow 74, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 180 and C.I. I. Pigment Yellow 185.
As the black colorant, carbon black, a magnetic material, and a color tone adjusted to black using the yellow, magenta, and cyan colorants can be used.
The amount of the colorant added is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer or the resin component contained in the resin solution.

<Release agent>
The release agent is not particularly limited, but a wax in a solid state at room temperature is preferable in terms of toner blocking resistance, multi-sheet durability, low-temperature fixability, and offset resistance.
Examples of the wax include known paraffin waxes, polyolefin waxes, microcrystalline waxes, polymethylene waxes such as Fischer-Tropsch waxes, amide waxes, higher fatty acids, long chain alcohols, ester waxes, these graft compounds, and these block compounds. Wax can be used. These are preferably removed from the low molecular weight component and have a sharp maximum endothermic peak in the endothermic curve obtained by a differential scanning calorimeter.
The addition amount of the release agent is preferably 1 part by mass or more and 40 parts by mass or less, more preferably 4 parts by mass with respect to 100 parts by mass of the polymerizable monomer or the resin component contained in the resin solution. The amount is 30 parts by mass or less.

The peak temperature (hereinafter also referred to as melting point) of the maximum endothermic peak measured with a differential scanning calorimeter of the wax is preferably 80 ° C. or higher and 170 ° C. or lower.
When the melting point is 80 ° C. or higher, the phenomenon that the finely dispersed wax once causes thermal aggregation is easily prevented depending on the polymerization temperature during the polymerization process, and the particle size of the release agent particles dispersed in the toner is large. Can be prevented.
The melting point can be measured using a differential scanning calorimeter (DSC) “MDSC-2920, manufactured by TA Instruments”.
The measurement temperature range is 30 ° C. to 200 ° C., and the measurement is performed at a heating rate of 10 ° C./min. In the measurement, the sample is once heated from 30 ° C. to 200 ° C., and subsequently lowered from 200 ° C. to 30 ° C. Thereafter, the temperature is raised again. The peak temperature of the maximum endothermic peak of the differential scanning calorimetry curve in the temperature range of 30 ° C. to 200 ° C. in the second temperature raising process is defined as the melting point [unit: ° C.].
The mold release agent preferably has a penetration of 10 or less at 25 ° C. when measured according to a test method defined in JIS K 2235 (1991), more preferably The penetration at 25 ° C. is 5 or less.
When the penetration at 25 ° C. is 10 or less, brittleness is not insufficient, and during the coarse dispersion step, coarse dispersion can be performed with a simple dispersion device such as a stirrer having high shearing force. There is no need to use a large-scale device such as a disperser or means requiring complicated operations such as an operation of cooling after heating and melting.

In order to increase the plasticity of the toner and improve the fixability in a low temperature region, a second release agent having a melting point lower than 80 ° C. can be used in combination. The melting point of the second release agent is also represented by the peak temperature of the maximum endothermic peak measured with the differential scanning calorimeter.
Examples of the second release agent include linear alkyl alcohols having 15 to 100 carbon atoms, linear fatty acids, linear acid amides, linear esters, and montan derivative waxes. Preferably, impurities such as liquid fatty acids have been previously removed from these waxes.
In order to improve the translucency of the image fixed on the OHP, a linear ester wax is preferably used as the second release agent.

<Charge control agent>
In the toner, a charge control agent may be blended (internal addition) or mixed (external addition) in order to control the charge amount of the toner to a desired value.
Known charge control agents can be used.
For example, the following are examples of toners that are negatively charged.
Organic metal compounds and chelate compounds are effective, monoazo dye metal compounds, acetylacetone metal compounds; aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters thereof; bisphenol, etc. Phenol derivatives.
Furthermore, the following are mentioned. Urea derivatives, metal-containing salicylic acid compounds, calixarenes, silicon compounds, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-acrylic-sulfonic acid copolymers and other non-metallic resins Carboxylic acid compounds.
Examples of controlling the toner to be positively charged include the following.
Modified products of nigrosine and its fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate; onium salts such as phosphonium salts and lakes thereof Pigments, triphenylmethane dyes and lake pigments thereof (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, or ferrocyanide), Metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyltin borate Diorgano tin borate such UNA.
These charge control agents can be used alone or in combination of two or more.
The addition amount of the charge control agent is preferably 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.00 parts by mass with respect to 100 parts by mass of the polymerizable monomer or the resin component contained in the resin solution. 5 parts by mass or more and 10 parts by mass or less.

<Polymerization initiator>
In the polymerization step, a polymerization initiator may be used. Examples of the polymerization initiator include azo polymerization initiators and organic peroxide initiators.
Examples of the azo polymerization initiator include the following. 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis -4-methoxy-2,4-dimethylvaleronitrile, azobismethylbutyronitrile.
The following are mentioned as an organic peroxide type | system | group initiator. Benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, tert-butyl-peroxypivalate.
A redox initiator in which an oxidizing substance and a reducing substance are combined can also be used. Examples of the oxidizing substance include inorganic peroxides such as hydrogen peroxide and persulfates (sodium salts, potassium salts, ammonium salts, etc.), and oxidizing metal salts such as tetravalent cerium salts.
Reducing substances include reducing metal salts (divalent iron salts, monovalent copper salts, trivalent chromium salts), ammonia, lower amines (amines having 1 to 6 carbon atoms such as methylamine and ethylamine), Amino compounds such as hydroxylamine, sodium thiosulfate, sodium hydrosulfite, sodium hydrogen sulfite, sodium sulfite, reducing sulfur compounds such as sodium formaldehyde sulfoxylate, lower alcohols (1-6 carbon atoms), ascorbic acid or its Salt and its lower aldehyde (C1-6).
The polymerization initiator is selected with reference to a 10-hour half-life temperature, and is used alone or in combination.
The addition amount of the polymerization initiator is generally 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.

<Crosslinking agent>
Various crosslinking agents can also be used. The following are mentioned as a crosslinking agent. Divinylbenzene, 4,4′-divinylbiphenyl, hexanediol diacrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycidyl (meth) acrylate, trimethylolpropane tri (meth) acrylate.

<Binder resin>
The binder resin constituting the toner is not particularly limited, and known ones can be used.
Specific examples include a styrene-methacrylic acid copolymer, a styrene-acrylic acid copolymer, a polyester resin, an epoxy resin, and a styrene-butadiene copolymer. These resins can be used alone or in combination of two or more.

<Organic solvent>
The organic solvent is not particularly limited as long as it can dissolve or disperse the binder resin to be used, and a known solvent can be used. Further, the granulation step of forming particles of the dispersion liquid to be dispersed obtained by dissolving or dispersing the dispersion in a resin solution in which the binder resin is dissolved in an organic solvent in the aqueous medium is performed as described above. It may be the same as the turbid polymerization method. Furthermore, it is good to use well-known conditions also about the conditions of the desolvation process which removes the organic solvent contained in the granulated particle | grains.
Specific examples of the organic solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate. , Methyl ethyl ketone, methyl isobutyl ketone and the like. These can be used alone or in combination of two or more.
Further, the boiling point is preferably less than 100 ° C. from the viewpoint of easy removal of the solvent later.
When the resin to be dissolved or dispersed in the organic solvent is a resin having a polyester skeleton, an ester solvent such as methyl acetate, ethyl acetate, or butyl acetate, or a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone may be used. . A resin having a polyester skeleton is preferably highly soluble in the solvent, and among them, methyl acetate, ethyl acetate, and methyl ethyl ketone, which have high solvent removability, are more preferable.

<Modified resin added to organic solvent>
A modified resin (hereinafter sometimes referred to as “prepolymer”) may also be used. The modified resin is not particularly limited as long as it has at least a site capable of reacting with the active hydrogen group-containing compound, and can be appropriately selected from known resins.
For example, a polyol resin, a polyacrylic resin, a polyester resin, an epoxy resin, a derivative resin thereof, and the like can be given.
These may be used individually by 1 type and may use 2 or more types together. Among these, a polyester resin is particularly preferable in terms of high fluidity and transparency during melting.
The site capable of reacting with the active hydrogen group-containing compound in the prepolymer is not particularly limited and may be appropriately selected from known substituents. Examples thereof include isocyanate groups, epoxy groups, carboxylic acids, and acids. A chloride group, and the like.
These may be contained singly or in combination of two or more. Among these, an isocyanate group is particularly preferable.

<Active hydrogen group-containing compound>
The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent, or the like when a modified resin capable of reacting with the active hydrogen group-containing compound undergoes an extension reaction or a crosslinking reaction in an aqueous medium.
The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected according to the purpose. For example, when the polymer capable of reacting with the active hydrogen group-containing compound is an isocyanate group-containing polyester prepolymer, it can be increased in molecular weight by a reaction such as an isocyanate group-containing polyester prepolymer and an extension reaction or a crosslinking reaction. Amines are preferred.
There is no restriction | limiting in particular as this active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxy group, a mercapto group etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, an alcoholic hydroxyl group is preferable.

<External additive>
An external additive may be added to the toner for the purpose of improving various powder characteristics.
Examples of the external additive include the following. Metal oxides such as aluminum oxide, titanium oxide, strontium titanate, cerium oxide, magnesium oxide, chromium oxide, tin oxide, zinc oxide; nitrides such as silicon nitride; carbides such as carbide silicon carbide; calcium sulfate, Inorganic metal salts such as barium sulfate and calcium carbonate; fatty acid metal salts such as zinc stearate and calcium stearate; carbon black and silica.
The addition amount of the external additive is preferably 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 0.05 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the toner particles. External additives may be used alone or in combination. Further, these external additives are more preferably hydrophobized.

<Magnetic material>
The toner may be a magnetic toner containing a magnetic material.
The magnetic substance contained in the toner can also serve as a colorant. Examples of the magnetic material include the following.
Iron oxides such as magnetite, hematite, ferrite; metals such as iron, cobalt, nickel or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese Alloys of metals such as selenium, titanium, tungsten, vanadium and mixtures thereof.
The addition amount of the magnetic substance is preferably 20 parts by mass or more and 200 parts by mass or less, more preferably 40 parts by mass or more and 100 parts by mass with respect to 100 parts by mass of the resin component contained in the polymerizable monomer or the resin solution. It is below mass parts.

When using a magnetic material, it is preferable to hydrophobize the surface of the magnetic material in order to improve the dispersibility of the magnetic material in the toner.
For the hydrophobizing treatment, coupling agents such as a silane coupling agent and a titanium coupling agent may be used.
Of these, a silane coupling agent is preferable. The following are mentioned as a silane coupling agent. Vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxy Silane, hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane.

Hereinafter, the measurement method or evaluation method used in the present invention will be described.
<Evaluation of Dispersibility of Dispersed Substance in Dispersed Dispersion>
The dispersibility of the dispersion is measured using a laser diffraction / scattering particle size distribution analyzer LA-950 (manufactured by Horiba Seisakusho), and the volume-based median diameter (standard deviation as necessary) of the dispersion is measured. Evaluation was made by the following method.
For the preparation of the dispersion medium at the time of measurement, a batch type cell was used, and a polymerizable monomer (or an organic solvent used for dissolving the resin) was added to such an extent that 70 to 90% of the cell was satisfied. The cell was stirred with a stir bar. Here, a measurement sample (dispersed dispersion) was introduced so that the transmittance (R) of the cell was 70 to 98% and the transmittance (B) was 25 to 65%, and the relative refractive index was 0.95. The measurement was performed under the following conditions.
(Evaluation criteria for release agents)
If the volume-based median diameter is less than 0.250 μm, it is judged that the dispersibility is good, and if it is 0.250 μm or more and less than 1.000 μm, there is a slight problem in image characteristics and fixability, but there is no practical problem. did. Further, when the median diameter is 1.000 μm or more, it is judged that the influence on the image is so severe that the product is not preferable.
A: Less than 0.250 μm Good B: 0.250 μm or more and less than 1.000 μm Slightly inferior C: 1.000 μm or more Inferior (colorant evaluation criteria)
A: Less than 0.250 μm Very good B: 0.250 μm or more and less than 0.500 μm Good C: 0.500 μm or more and less than 1.000 μm Slightly inferior D: 1.000 μm or more Inferior

<Measurement of Volume-Based Median Diameter (Dv50) and Number-Based Median Diameter (Dn50)>
The volume-based median diameter (Dv50) and the number-based median diameter (Dn50) of the toner are calculated as follows.
As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method provided with a 100 μm aperture tube is used. For setting of measurement conditions and analysis of measurement data, attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.
As the electrolytic aqueous solution used for the measurement, a special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used. .
Prior to measurement and analysis, the dedicated software was set as follows.
On the “Change Standard Measurement Method (SOMME)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter) Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.
In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.
The specific measurement method is as follows.
(1) About 200 mL of the electrolytic solution is placed in a glass 250 mL round-bottom beaker dedicated to Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30 mL of the electrolytic solution is placed in a glass 100 mL flat bottom beaker. As a dispersant, “Contaminone N” (a nonionic surfactant, an anionic surfactant, a 10% by weight aqueous solution of a neutral detergent for washing a pH 7 precision measuring instrument comprising an organic builder, Wako Pure Chemical Industries, Ltd. About 0.3 mL of a diluted solution obtained by diluting (made in ()) with ion-exchanged water about 3 times by mass.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispersion System Tetra 150” (manufactured by Nikki Bios Co., Ltd.) with an electrical output of 120 W is prepared. To do. About 3.3 L of ion exchange water is placed in the water tank of the ultrasonic disperser, and about 2 mL of Contaminone N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker (1) installed in the sample stand, the electrolytic solution (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the volume-based median diameter (Dv50) and the number-based median diameter (Dn50) are calculated.
The closer the ratio of Dv50 to Dn50 (Dv50 / Dn50) is to 1.00, the sharper the particle size distribution.

<Measurement of bulk specific gravity A, bulk specific gravity B>
The bulk specific gravity (kg / m ³ ) is measured by putting a sample into a 200 mL measuring cylinder and measuring its mass.

<Measurement of true specific gravity C>
The true specific gravity C is calculated by the following formula using the polymerizable monomer (1) or the resin solution (2) and a known true specific gravity value of the dispersion.
(1) True specific gravity C =
{(True specific gravity of polymerizable monomer) × (mass part of polymerizable monomer contained in mixed liquid containing polymerizable monomer and dispersion) / (mass part of the mixed liquid)} + {(True specific gravity of the material to be dispersed) × (mass part of the material to be dispersed contained in the mixed liquid containing the polymerizable monomer and the material to be dispersed) / (mass part of the liquid mixture)}
(2) True specific gravity C = {(true specific gravity of resin solution) × (mass part of resin solution contained in mixed solution containing resin solution and dispersion) / (mass part of mixed solution)} + { (True specific gravity of the dispersion) × (mass part of the dispersion contained in the mixed solution containing the resin solution and the dispersion) / (mass part of the mixture)}

If the known true specific gravity of the material to be dispersed (release agent or colorant) is unknown, it may be measured by the following method.
For the measurement of true specific gravity, a dry automatic densimeter Accupic 1340 (manufactured by Shimadzu Corporation) is used.
First, about 80% of the cell height is put in a measurement cell (10 cm ³ ), the sample mass is recorded, and the sample is inserted into the main body sample chamber.
The measurement can be automatically performed by inputting the sample mass to the main body and starting the measurement.
As the measurement conditions for automatic measurement, helium gas adjusted at 19.5 psig is used. After purging the sample chamber five times, the state in which the pressure change in the sample chamber becomes 0.005 psig / min is made an equilibrium state, and helium gas is repeatedly purged until the equilibrium state is reached. Measure the pressure in the main sample chamber when in equilibrium. The sample volume can be calculated from the pressure change when the equilibrium state is reached.
Since the sample volume can be calculated, the true specific gravity of the sample can be calculated by the following formula.
True specific gravity of the sample (kg / m ³ ) = sample mass (kg) / sample volume (m ³ )
The average of the values measured five times by this automatic measurement is defined as the true specific gravity (kg / m ³ ) of the dispersion.

<Measurement of viscosity D>
A sample whose liquid temperature is adjusted to 20 ± 1 ° C. is measured under the following conditions using a Salle-type rotary viscometer (Viscotester VT550, manufactured by HAAKE).
Measurement software: HAAKE RheoWin job Manager
Rheometer: VT550
Sensor: SV-DIN
Shear rate: Time dependent measurement 1066 (1 / s) <1 min># 10
Time-dependent measurement 0.0 (1 / s) <1 min># 5
Step measurement 1.290 (1 / s) to 725.4 (1 / s) lin # 12 <1 min>
Step retention time: 0.5 min, integration time: 0.05 min
In the step measurement, the measured value when 0.5 min has passed at a shear rate of 1.290 (1 / s) is taken as the viscosity.

  Hereinafter, although this invention is demonstrated further in detail using an Example and a comparative example, the aspect of this invention is not limited to these. In addition, all the parts and% of an Example and a comparative example are mass references | standards unless there is particular notice.

A production example of the release agent dispersion will be described below.
(Production Example of Release Agent Dispersion 1)
As preliminary dispersion, the following components are charged into a temperature-controllable container, and using Ultra Turrax T-50 (manufactured by IKA), the liquid temperature is always 50 ° C. or lower, and stirring is performed at 10,000 rpm for 40 minutes to rough the release agent. A dispersion was obtained. The volume-based median diameter of the release agent particles in the release agent coarse dispersion was 64 μm.

-Styrene 30.00 parts by mass-Fischer-Tropsch wax 8.18 parts by mass (molecular weight: 1300, melting point: 105 ° C)
Fischer-Tropsch wax (release agent) was dispersed using the dispersion system shown in FIG. As the pump 7, a deforming pump (manufactured by Futoko Metal Industry Co., Ltd.) was used.
Further, as the disperser 8, an OB mill (manufactured by IVER BATLLE) was used.
First, the entire amount of the release agent crude dispersion (30 L) was charged into the holding tank 1 (10 ° C. cooling water passed through the jacket 3).
Next, the release agent was dispersed under the following conditions to obtain a release agent dispersion 1.
Bead material: Zirconia bead diameter: 0.5mm
Circulating flow rate: 5L / min
Rotating body peripheral speed: 13m / s
Dispersion time: 180 minutes In the dispersion step, when the viscosity of the liquid led out from the pump 7 reaches 2.0 (Pa · s), the deaeration device 6 attached to the pump 7 is operated to increase the volume. The suction pressure is set so that the value obtained by subtracting the bulk specific gravity A from the specific gravity B (ie, [B−A]) is 48 (kg / m ³ ), and the ratio of the bulk specific gravity B to the true specific gravity C is 0.99. It was adjusted. Moreover, the temperature rise of the mold release agent dispersion was suppressed by flowing cooling water of 10 ° C. through the jacket 3. Further, the temperature of the release agent dispersion after the completion of the dispersion step was 15 ° C. The volume-based median diameter of the release agent in the release agent dispersion after completion of the dispersion step was 0.180 μm. Further, the true specific gravity of the release agent crude acid solution was 917 (kg / m ³ ) as a result of calculation from a known value.

(Production Example of Release Agent Dispersion 2)
In the production example of the release agent dispersion 1, the deforming pump (Fushitora Kogyo Co., Ltd.) is changed to the defoaming / deaeration pump ASP type (Yokota Seisakusho Co., Ltd.) as the pump 7. Produced release agent dispersion 2 in the same manner as in the production example of release agent dispersion 1.

(Production Example of Release Agent Dispersion 3)
In the production example of the release agent dispersion 1, except that the suction pressure was adjusted so that [B-A] was 39 (kg / m ³ ) and the ratio of the bulk specific gravity B to the true specific gravity C was 0.97. Produced release agent dispersion 3 in the same manner as in the production example of release agent dispersion 1.

(Production Example of Release Agent Dispersion 4)
In the production example of the release agent dispersion liquid 1, when the viscosity of the liquid reaches 1.0 (Pa · s), the deaeration device 6 attached to the pump 7 is operated, and [B−A] is 58 ( kg / m ³ ) and the release agent in the same manner as in the production example of the release agent dispersion 1 except that the suction pressure was adjusted so that the ratio of the bulk specific gravity B to the true specific gravity C was 0.99. Dispersion 4 was produced.

(Production example of release agent dispersion 5)
In the production example of the release agent dispersion 1, when the viscosity of the liquid reaches 1.0 (Pa · s), the deaeration device 6 attached to the pump 7 is operated, and [B−A] is 57 ( kg / m ³ ) and the release agent in the same manner as in the production example of the release agent dispersion 1 except that the suction pressure was adjusted so that the ratio of the bulk specific gravity B to the true specific gravity C was 1.00. Dispersion 5 was produced.

(Production Example of Release Agent Dispersion 6)
In the production example of the release agent dispersion 1, when the viscosity of the liquid reaches 1.0 (Pa · s), the deaeration device 6 attached to the pump 7 is operated, and [B-A] is 39 ( kg / m ³ ) and the release agent in the same manner as in the production example of the release agent dispersion 1 except that the suction pressure was adjusted so that the ratio of the bulk specific gravity B to the true specific gravity C was 0.97. Dispersion 6 was produced.

(Production example of release agent dispersion liquid 7)
In the production example of the release agent dispersion 1, the suction pressure was adjusted so that [BA] was 27 (kg / m ³ ) and the ratio of the bulk specific gravity B to the true specific gravity C was 0.95. Produced release agent dispersion 7 in the same manner as in the production example of release agent dispersion 1.

(Production Example of Release Agent Dispersion 8)
In the production example of the release agent dispersion 1, when the viscosity of the liquid becomes 0.5 (Pa · s), the deaeration device 6 attached to the pump 7 is operated, and [B−A] is 56 ( kg / m ³ ) and the release agent in the same manner as in the production example of the release agent dispersion 1 except that the suction pressure was adjusted so that the ratio of the bulk specific gravity B to the true specific gravity C was 0.99. Dispersion 8 was produced.

(Production Example of Release Agent Dispersion 9)
In the production example of the release agent dispersion 1, the suction pressure was adjusted so that [BA] was 39 (kg / m ³ ) and the ratio of the bulk specific gravity B to the true specific gravity C was 0.95. Release agent dispersion 1
A release agent dispersion 9 was produced in the same manner as in the above production example.

(Production Example of Release Agent Dispersion Liquid 10)
In the production example of the release agent dispersion 1, as the disperser 8, the OB mill (manufactured by IVER BATTLLE) is changed to a sharp flow mill (manufactured by Taiheiyo Kiko Co., Ltd.), and the dispersion conditions are changed to the following: B—A] was 12 (kg / m ³ ), and the suction pressure was adjusted so that the ratio of the bulk specific gravity B to the true specific gravity C was 0.94. Except for the above, the release agent dispersion 10 was produced in the same manner as in the production example of the release agent dispersion 1.
Circulating flow rate: 5L / min
Rotating body peripheral speed: 60m / s
Back pressure: 0.2 MPa
Dispersion time: 180 min

(Production Example of Release Agent Dispersion 11)
In the production example of the release agent dispersion 1, the deforming pump (Fushitora Kogyo Co., Ltd.) is changed to the defoaming / deaeration pump ASP type (Yokota Seisakusho Co., Ltd.) as the pump 7. As the disperser 8, the OB mill (manufactured by IVER BATTLLE) was changed to a sharp flow mill (manufactured by Taiheiyo Kiko Co., Ltd.), and the dispersion conditions were changed to the following, and [BA] was 7 (kg / m ^3). ) And the suction pressure was adjusted so that the ratio of the bulk specific gravity B to the true specific gravity C was 0.95. Except for the above, the release agent dispersion 11 was produced in the same manner as in the production example of the release agent dispersion 1. Circulating flow rate: 5L / min
Rotating body peripheral speed: 60m / s
Back pressure: 0.2 MPa
Dispersion time: 180 min

(Production Example of Release Agent Dispersion 12)
In the production example of the release agent dispersion 1, dispersion was performed using the dispersion system shown in FIG. 2 instead of the dispersion system shown in FIG. As a disperser 8, a handy mill (Nihon Coke Industries, Ltd., formerly Mitsui Miike Chemical Co., Ltd.) was used, and batch type release agent dispersion was performed under the following conditions.
At this time, 10 ° C. cooling water was passed through the jacket 3 of the handy mill. In addition, when the viscosity D reaches 2.0 (Pa · s), the holding tank degassing device 12 attached to the upper part of the holding tank 1 of the handy mill is operated in a state where the parts other than the degassing port are sealed. I let you. At this time, the suction pressure was adjusted so as to have a history similar to that in the production example of the release agent dispersion 1, but the release agent dispersion contained in the holding tank 1 had a high viscosity and the liquid depth was Since it was deep, no deaeration was observed, and the bulk specific gravity of the liquid could not be adjusted. Except for the above, a release agent dispersion 12 was obtained in the same manner as in the production example of the release agent dispersion 1.
Bead material: Zirconia Bead diameter: 3mm
Rotating body peripheral speed: 8.4 m / s
Dispersion time: 180 minutes

(Production Example of Release Agent Dispersion 13)
In the production example of the release agent dispersion 1, instead of completely closing the degassing port of the pump 7 and extracting the gas with the degassing device 6 provided in the pump 7, the holding tank provided in the holding tank 1 is used. The deaerator 12 was activated. At this time, the suction pressure was adjusted so as to have a history similar to that in the production example of the release agent dispersion 1, but the release agent dispersion contained in the holding tank 1 had a high viscosity and the liquid depth was Since it was deep, no deaeration action was observed, and the bulk specific gravity B could not be adjusted. Except for the above, the release agent dispersion 13 was produced in the same manner as in the production example of the release agent dispersion 1.

(Production Example of Release Agent Dispersion 14)
In the production example of the release agent dispersion liquid 1, the same method as in the production example of the release agent dispersion liquid 1 was used except that the deaeration port of the pump 7 was fully closed and the deaeration device 6 was not started. A release agent dispersion 14 was produced.

[Example A1]
A toner was manufactured according to the following procedure.
(Preparation of pigment dispersion composition)
23.0 parts by mass of styrene and 1.88 parts by mass of C.I. I. Pigment Yellow 155 and 0.58 parts by mass of a charge control agent (Bontron E88; manufactured by Orient Chemical Co., Ltd.) were introduced into Attritor (Nihon Coke Industries, Ltd., former Mitsui Miike Chemicals Co., Ltd.). Using a zirconia bead having a radius of 5.00 mm, the mixture was stirred at 200 rpm at 25 ° C. for 300 minutes to obtain a pigment dispersion composition.

(Preparation of polymerizable monomer composition)
The following materials are put in the same container. K. The mixture was mixed and dispersed at a peripheral speed of 20 m / s using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.).
-Release agent dispersion 1 19.52 parts by mass-Pigment dispersion composition 25.02 parts by mass-9.59 parts by mass of n-butyl acrylate-1.92 parts by mass of polyester resin [Propylene oxide modified bisphenol A (2 mol addition) Product) and terephthalic acid (condensation molar ratio is 10:12), glass transition temperature (Tg): 68 ° C., weight average molecular weight (Mw): 10,000, weight average molecular weight (Mw) / number average molecular weight ( Mn): 5.12]
Styrene-methacrylic acid-methyl methacrylate-α-methylstyrene copolymer (styrene / methacrylic acid / methyl methacrylate / α-methylstyrene (mass ratio) = 80.85 / 2.50 / 1.65 / 15.0, Peak molecular weight (Mp): 19,700, weight average molecular weight (Mw): 7,900, glass transition temperature (Tg): 96 ° C., acid value: 12.0 mg KOH / g, weight average molecular weight (Mw) / number average molecular weight (Mn): 2.1) 5.75 parts by mass / sulfonic acid group-containing resin 0.05 parts by mass (Acrybase FCA-1001-NS, manufactured by Fujikura Kasei)
Further, after heating to 60 ° C., 5.94 parts by mass of a hydrocarbon release agent (HNP-9; manufactured by Nippon Seiki Co., Ltd.) is added, and dispersion and mixing are performed for 30 minutes. 4.31 parts by mass of '-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

(Preparation of aqueous dispersion medium)
To the granulation tank, 129.98 parts by mass of ion-exchanged water, 2.51 parts by mass of sodium phosphate dodecahydrate, and 1.13 parts by mass of 10% by mass hydrochloric acid were prepared to prepare an aqueous sodium phosphate solution. Warmed to ° C.
1.46 parts by mass of calcium chloride dihydrate was dissolved in 10.24 parts by mass of ion-exchanged water to obtain an aqueous calcium chloride solution. A calcium chloride aqueous solution is added to the above-mentioned sodium phosphate aqueous solution, and T.C. K. The mixture was stirred for 30 minutes at a peripheral speed of 25 m / s using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.).
(Granulation process)
The polymerizable monomer composition was put into an aqueous dispersion medium, and T.C. K. The mixture was stirred for 20 minutes at a peripheral speed of 25 m / s with a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain a dispersion of a polymerizable monomer composition.
(Polymerization reaction process)
The dispersion of the polymerizable monomer composition was transferred to another tank, and the temperature was raised to 73 ° C. while stirring with a paddle stirring blade, and reacted for 4 hours. Thereafter, the temperature was further raised to 85 ° C. and reacted for 2 hours to obtain a dispersion of resin particles.
(Washing / filtration / drying process)
After cooling the obtained dispersion of resin particles, hydrochloric acid was added to adjust the pH to 1.4, and the mixture was stirred for 2 hours. Thereafter, after filtration and washing with water, the toner particles were obtained by drying at a temperature of 40 ° C. for 48 hours.
(External addition process)
100.0 parts by mass of toner particles and 1.0 part by mass of hydrophobic silica fine particles surface-treated with dimethyl silicone oil (number average diameter of primary particles: 7 nm) were mixed with an FM mixer (Nippon Coke Industries, Ltd., formerly The toner A1 was obtained by mixing for 10 minutes with Mitsui Miike Chemical Industries, Ltd.).
The toner obtained was evaluated for fixability by the following method.

<Evaluation of fixability>
The toner was loaded into a modified iRC3220N (Canon) machine from which the fixing roller was removed, and an unfixed image with a toner loading amount of 0.55 mg / cm ² on the paper was output.
The obtained unfixed image was fixed using an external fixing device under the conditions of paper feed speed: 100 mm / s and roller load: 294N. As the external fixing device, an iRC3220N (Canon) fixing device was removed to the outside so that it can be operated outside the laser beam printer.
In the evaluation, 9 points were swung every 10 ° C. within the range of 140 ° C. to 220 ° C., and the state of offset when the unfixed image was fixed was visually evaluated (the fixing temperature at which no offset occurs is 140 ° C. to It was evaluated how many points existed in all 9 points at 220 ° C.). For the evaluation, 64 g / m ² plain paper was used.
A: 5 points or more Quite good B: 4 points Good C: 2 to 3 points Slightly inferior D: 1 point or less Inferior

[Examples A2 to A11 and Comparative Examples A1 to A3]
Toners A2 to A11 and comparative toners A1 to A3 are obtained in the same manner as in Example A1 except that the releasing agent dispersions 2 to 14 listed in Table 1 are used instead of the releasing agent dispersion 1. It was. In addition, the fixing property was evaluated in the same manner as the toner A1.
Table 1 shows the following results. In the table, (1), (2), (3), (4), (5), (6-1), (6-2) and (6-3) mean the following descriptions.
(1) Conditions of dispersion process related to release agent dispersions 1 to 14 (2) Volume-based median diameter of release agent in release agent dispersion (μm)
(3) Evaluation of dispersibility based on volume-based median diameter (μm) of release agent (4) Volume-based median diameter of toner (Dv50) (μm)
(5) Toner particle size distribution (Dv50) / (Dn50)
(6) Evaluation of fixability (6-1) Fixing temperature range in which no offset occurs (6-2) Fixing temperature score that does not generate offset present in all nine points of 140 ° C. to 220 ° C. (6-3) ) Evaluation results based on the fixing temperature score without offset

A production example of the colorant dispersion will be described below.
(Production Example of Colorant Dispersion 1)
As pre-dispersion, the following components are charged into a temperature-controllable container, and using Ultra Turrax T-50 (manufactured by IKA), the liquid temperature is always 50 ° C. or less, and stirring is performed at 10,000 rpm for 40 minutes to coarsely disperse the colorant. A liquid was obtained. The volume-based median diameter of the colorant particles in the colorant coarse dispersion was 10.5 μm.

Styrene 44.0 parts by mass Colorant 8.0 parts by mass (CI Pigment Red 122, manufactured by Clariant)
・ 1.0 parts by mass of charge control agent (Bontron E88; manufactured by Orient Chemical Co., Ltd.)
-0.5 part by mass of sulfonic acid group-containing resin (Acrybase FCA-1001-NS, manufactured by Fujikura Kasei)
Next, the colorant was dispersed using the dispersion system shown in FIG. As the pump 7, a deforming pump (manufactured by Futoko Metal Industry Co., Ltd.) was used.
Further, as the disperser 8, an OB mill (manufactured by IVER BATLLE) was used.
First, the entire amount of the colorant coarse dispersion (30 L) was charged into the holding tank 1 (10 ° C. cooling water passed through the jacket 3).
Next, the colorant was dispersed under the following conditions to obtain a colorant dispersion 1.
Bead material: Zirconia bead diameter: 0.5mm
Circulating flow rate: 5L / min
Rotating body peripheral speed: 13m / s
Dispersion time: 180 minutes In the dispersion step, when the viscosity of the liquid led out from the pump 7 reaches 2.0 (Pa · s), the deaeration device 6 attached to the pump 7 is operated to increase the volume. The suction pressure is adjusted so that the value obtained by subtracting the bulk specific gravity A from the specific gravity B (ie, [B−A]) is 58 (kg / m ³ ), and the ratio of the bulk specific gravity B to the true specific gravity C is 0.99. It was adjusted. Moreover, the temperature increase of the colorant dispersion was suppressed by flowing cooling water of 10 ° C. through the jacket 3. Further, the temperature of the colorant dispersion after the dispersion step was 15 ° C. The volume-based median diameter of the colorant in the colorant dispersion after completion of the dispersion step was 0.172 μm. Moreover, the true specific gravity of the colorant crude dispersion was 1018.4 (kg / m ³ ) as a result of calculation from known values.

(Production Example of Colorant Dispersion 2)
In the production example of the colorant dispersion 1, except that the deforming pump (manufactured by Futoko Metal Industry Co., Ltd.) is changed to the defoaming / degassing pump ASP type (manufactured by Yokota Manufacturing Co., Ltd.) as the pump 7. The colorant dispersion 2 was produced in the same manner as in the production example of the colorant dispersion 1.

(Production Example of Colorant Dispersion 3)
In the production example of the colorant dispersion 1, except that [BA] is 47 (Kg / m ³ ) and the suction pressure is adjusted so that the ratio of the bulk specific gravity B to the true specific gravity C is 0.97. The colorant dispersion 3 was produced in the same manner as in the production example of the colorant dispersion 1.

(Production Example of Colorant Dispersion 4)
In the production example of the colorant dispersion 1, when the viscosity of the liquid reaches 1.0 (Pa · s), the deaeration device 6 attached to the pump 7 is activated, and [B−A] is 68 (Kg). / M ³ ) and the colorant dispersion 4 in the same manner as in the production example of the colorant dispersion 1 except that the suction pressure was adjusted so that the ratio of the bulk specific gravity B to the true specific gravity C was 0.99. Manufactured.

(Production Example of Colorant Dispersion Liquid 5)
In the production example of the colorant dispersion 1, when the viscosity of the liquid reaches 1.0 (Pa · s), the deaeration device 6 attached to the pump 7 is activated, and [B−A] is 68 (Kg). / M ³ ) and colorant dispersion 5 in the same manner as in the production example of colorant dispersion 1 except that the suction pressure was adjusted so that the ratio of bulk specific gravity B to true specific gravity C was 1.00. Manufactured.

(Production Example of Colorant Dispersion 6)
In the production example of the colorant dispersion 1, when the viscosity of the liquid reaches 1.0 (Pa · s), the deaeration device 6 attached to the pump 7 is operated, and [B−A] is 47 (Kg). / M ³ ) and the colorant dispersion 6 in the same manner as in the production example of the colorant dispersion 1 except that the suction pressure was adjusted so that the ratio of the bulk specific gravity B to the true specific gravity C was 0.97. Manufactured.

(Production Example of Colorant Dispersion 7)
In the production example of the colorant dispersion 1, except that [BA] is 33 (Kg / m ³ ) and the suction pressure is adjusted so that the ratio of the bulk specific gravity B to the true specific gravity C is 0.95. A colorant dispersion 7 was produced in the same manner as in the production example of the colorant dispersion 1.

(Production Example of Colorant Dispersion 8)
In the production example of the colorant dispersion 1, when the viscosity of the liquid becomes 0.5 (Pa · s), the deaeration device 6 attached to the pump 7 is operated, and [B−A] is 66 (Kg). / M ³ ) and the colorant dispersion 8 in the same manner as in the production example of the colorant dispersion 1 except that the suction pressure was adjusted so that the ratio of the bulk specific gravity B to the true specific gravity C was 0.99. Manufactured.

(Production Example of Colorant Dispersion 9)
In the production example of the colorant dispersion 1, as the disperser 8, the OB mill (manufactured by IVER BATLLE) is changed to a sharp flow mill (manufactured by Taiheiyo Kiko Co., Ltd.), and the dispersion conditions are changed to the following: -A] was 17 (Kg / m ³ ), and the suction pressure was adjusted so that the ratio of bulk specific gravity B to true specific gravity C was 0.94. Except for the above, the colorant dispersion 9 was produced in the same manner as in the production example of the colorant dispersion 1.
Circulating flow rate: 5L / min
Rotating body peripheral speed: 60m / s
Back pressure: 0.2 MPa
Dispersion time: 180 min

(Production Example of Colorant Dispersion Liquid 10)
In the production example of the colorant dispersion 1, the deforming pump (Fushitora Kogyo Co., Ltd.) is changed to the defoaming / degassing pump ASP type (Yokota Seisakusho Co., Ltd.) as the pump 7 and dispersed. As machine 8, OB mill (manufactured by IVER BATTLLE) was changed to Sharp Flow Mill (manufactured by Taiheiyo Kiko Co., Ltd.) and the dispersion conditions were changed to the following, and [BA] was 12 (Kg / m ³ ) The suction pressure was adjusted so that the ratio of the bulk specific gravity B to the true specific gravity C was 0.95. Except for the above, the colorant dispersion 10 was produced in the same manner as in the production example of the colorant dispersion 1.
Circulating flow rate: 5L / min
Rotating body peripheral speed: 60m / s
Back pressure: 0.2 MPa
Dispersion time: 180 min

(Production Example of Colorant Dispersion 11)
In the production example of the colorant dispersion 1, dispersion was performed using the dispersion system shown in FIG. 2 instead of the dispersion system shown in FIG. As the disperser 8, a handy mill (Nihon Coke Industries, Ltd., formerly Mitsui Miike Chemical Co., Ltd.) was used, and the batch colorant was dispersed under the following conditions.
At this time, 10 ° C. cooling water was passed through the jacket 3 of the handy mill. In addition, when the viscosity D reaches 2.0 (Pa · s), the holding tank degassing device 12 attached to the upper part of the holding tank 1 of the handy mill is operated in a state where the parts other than the degassing port are sealed. I let you. At this time, the suction pressure was adjusted so as to have a history similar to that of the production example of the colorant dispersion 1, but the colorant dispersion contained in the holding tank 1 had high viscosity and a deep liquid depth. Thus, no deaeration action was observed, and the bulk specific gravity of the liquid could not be adjusted. Except for the above, a colorant dispersion 11 was obtained in the same manner as in the production example of the colorant dispersion 1.
Bead material: Zirconia Bead diameter: 3mm
Rotating body peripheral speed: 8.4 m / s
Dispersion time: 180 minutes

(Production Example of Colorant Dispersion 12)
In the production example of the colorant dispersion 1, instead of completely closing the degassing port of the pump 7 and extracting the gas with the degassing device 6 provided in the pump 7, the holding tank 1 provided for the holding tank 1 is used. The deaerator 12 was activated. At this time, the suction pressure was adjusted so as to have a history similar to that of the production example of the colorant dispersion 1, but the colorant dispersion contained in the holding tank 1 had high viscosity and a deep liquid depth. No degassing action was observed, and the bulk specific gravity B could not be adjusted. Except for the above, the colorant dispersion 12 was produced in the same manner as in the production example of the colorant dispersion 1.

(Production Example of Colorant Dispersion 13)
In the production example of the colorant dispersion 1, the colorant was produced in the same manner as in the production example of the colorant dispersion 1 except that the deaeration port of the pump 7 was fully closed and the deaeration device 6 was not started. Dispersion 13 was produced.

[Example B1]
A toner was manufactured according to the following procedure.
(Preparation of polymerizable monomer composition)
The following materials are put in the same container. K. The mixture was mixed and dispersed at a peripheral speed of 20 m / s using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.).
-Colorant dispersion 1 53.5 parts by mass-Styrene 28.0 parts by mass-N-butyl acrylate 28.0 parts by mass-Polyester resin 4.0 parts by mass [Propylene oxide modified bisphenol A (2 mol adduct) and terephthalate Polycondensate with acid (polymerization molar ratio 10:12), glass transition temperature (Tg): 68 ° C., weight average molecular weight (Mw): 10,000, weight average molecular weight (Mw) / number average molecular weight (Mn): 5 .12]
-Polar resin 12.0 parts by mass [styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization mass ratio is 94.0: 3.5: 2.5), peak molecular weight (Mp): 15,500, glass Transition temperature (Tg): 90 ° C., acid value: 21 mg KOH / g, weight average molecular weight (Mw) / number average molecular weight (Mn): 2.1]
Further, after heating to 60 ° C., 10.0 parts by mass of a hydrocarbon release agent (HNP-9; manufactured by Nippon Seiki Co., Ltd.) is added, and dispersion and mixing are performed for 30 minutes. 9.0 parts by mass of '-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

(Preparation of aqueous dispersion medium)
To the granulation tank, 300.0 parts by mass of ion-exchanged water, 5.3 parts by mass of sodium phosphate 12 hydrate, and 2.2 parts by mass of 10% by mass hydrochloric acid were prepared to prepare a sodium phosphate aqueous solution, Warmed to.
In 25.0 parts by mass of ion-exchanged water, 3.1 parts by mass of calcium chloride dihydrate was dissolved to obtain an aqueous calcium chloride solution. A calcium chloride aqueous solution is added to the above-mentioned sodium phosphate aqueous solution, and T.C. K. The mixture was stirred for 30 minutes at a peripheral speed of 25 m / s using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.).
(Granulation process)
The polymerizable monomer composition was put into an aqueous dispersion medium, and T.C. K. The mixture was stirred for 20 minutes at a peripheral speed of 25 m / s with a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain a dispersion of a polymerizable monomer composition.
(Polymerization reaction process)
The dispersion of the polymerizable monomer composition was transferred to another tank, and the temperature was raised to 70 ° C. while stirring with a paddle stirring blade, and reacted for 4 hours. Thereafter, the temperature was further raised to 85 ° C. and reacted for 2 hours to obtain a dispersion of resin particles.
(Washing / filtration / drying process)
After cooling the obtained dispersion of resin particles, hydrochloric acid was added to adjust the pH to 1.4, and the mixture was stirred for 2 hours. Thereafter, after filtration and washing with water, the toner particles were obtained by drying at a temperature of 40 ° C. for 48 hours.
(External addition process)
100.0 parts by mass of toner particles and 1.0 part by mass of hydrophobic silica fine particles surface-treated with dimethylsilicone oil (number average diameter of primary particles: 7 nm) were mixed with an FM mixer (Nippon Coke Industries, Ltd.). The toner B1 was obtained by mixing for 10 minutes.
The performance of the obtained toner was evaluated by the following method.

<Evaluation of toner performance>
(1) Coloring power A modified machine of a commercially available laser beam printer LBP-5400 (manufactured by Canon) was used as the image forming apparatus. The evaluator was modified so that the process speed was 270 mm / sec by changing the gear and software of the evaluator main body.
Normal temperature and normal humidity (N / N; 23.5 ℃, 60% RH) under the environment, on the CLC color copy paper (manufactured by Canon Inc.), from 0.1 mg / cm ² of 1.0 mg / cm ² Several types of solid images with different toner amount in the range were created. The image density of the obtained solid image was measured using “Macbeth reflection densitometer RD918” (manufactured by Macbeth Co., Ltd.), and the relationship between the toner amount on the transfer paper and the image density was determined. The coloring power was relatively evaluated at an image density corresponding to the case of ³ mg / cm ² .
A: Image density is 1.20 or more, very good. B: Image density is 1.10 or more, but less than 1.20. C: Image density is 1.00 or more, but less than 1.10. D: The image density is less than 1.00.

(2) OHP transparency A modified machine of a commercially available laser beam printer LBP-5400 (manufactured by Canon) was used as an image forming apparatus. The evaluator was modified so that the process speed was 270 mm / sec by changing the gear and software of the evaluator main body.
An image was output to an OHP sheet “CG3700” (manufactured by 3M) in a normal temperature and normal humidity (N / N; 23.5 ° C., 60% RH) environment. The obtained image on the OHP sheet was converted into a transmission image using OHP “9550” (manufactured by 3M), projected onto a white wall surface, and visually evaluated in five stages as follows.
A: Transparency is extremely high and good B: Transparency is good C: Slightly dull D: Pretty dull

[Examples B2 to B10 and Comparative Examples B1 to B3]
Toners B2 to B10 and comparative toners B1 to B3 were obtained in the same manner as in Example B1, except that the colorant dispersions 2 to 13 listed in Table 2 were used instead of the colorant dispersion 1. Further, toner performance evaluation was performed in the same manner as the toner B1.
Table 2 shows the following results. In the table, (1), (2), (3), (4), (5), (6), (7-1) and (7-2) mean the following descriptions.
(1) Dispersion process conditions relating to colorant dispersions 1 to 13 (2) Volume-based median diameter (μm) of colorant in colorant dispersion
(3) Standard deviation (μm) in the volume-based particle size distribution of the colorant in the colorant dispersion.
(4) Evaluation of dispersibility based on volume-based median diameter (μm) of colorant (5) Volume-based median diameter of toner (Dv50) (μm)
(6) Toner particle size distribution (Dv50) / (Dn50)
(7) Toner performance evaluation (7-1) Toner coloring power (7-2) OHP transparency

1: Holding tank, 2: Motor, 3: Jacket, 4: Jacket inlet, 5: Jacket outlet, 6: Deaerator, 7: Pump, 8: Disperser, 9: Back pressure valve, 10: Strainer, 11: Three-way Valve, 12: Degassing device for holding tank

Claims (6)

A method for producing a toner having a dispersion step of obtaining a release agent dispersion in which a release agent is dispersed in a resin solution or a polymerizable monomer,
The dispersion step includes the following steps (i) to (iv):
A step of repeatedly performing the steps (i) to (iv) to obtain a release agent dispersion,
(I) The mixed solution is discharged from a tank containing a mixed solution containing the resin solution or the polymerizable monomer and the release agent, and the discharged mixed solution is dispersed by a pump. Introducing into the machine;
(Ii) performing a dispersion treatment of the release agent by the disperser to obtain a dispersion treatment liquid;
(Iii) returning the dispersion treatment liquid to the tank;
(Iv) discharging the dispersion treatment liquid in the tank and introducing the discharged dispersion treatment liquid into the disperser by the pump;
A method for producing a toner, wherein when the liquid is fed by the pump, the gas conveyed together with the liquid is removed. A method for producing a toner having a dispersion step of obtaining a colorant dispersion in which a colorant is dispersed in a resin solution or a polymerizable monomer,
The dispersion step includes the following steps (i) to (iv):
A step of repeatedly performing the steps (i) to (iv) to obtain a colorant dispersion,
(I) The mixed solution is discharged from a tank containing a mixed solution containing the resin solution or the polymerizable monomer and the colorant, and the discharged mixed solution is dispersed by a pump. Introducing into the process;
(Ii) a step of dispersing the colorant by the disperser to obtain a dispersion treatment liquid;
(Iii) returning the dispersion treatment liquid to the tank;
(Iv) discharging the dispersion treatment liquid in the tank and introducing the discharged dispersion treatment liquid into the disperser by the pump;
A method for producing a toner, wherein when the liquid is fed by the pump, the gas conveyed together with the liquid is removed.   The toner manufacturing method according to claim 1, wherein the disperser is a media disperser. In the dispersing step,
The bulk specific gravity of the liquid before being introduced into the pump is A (kg / m ³ ),
When the bulk specific gravity of the liquid after being derived from the pump is B (kg / m ³ ),
A <B is satisfied,
The method for producing a toner according to claim 1. In the dispersing step,
The bulk specific gravity and viscosity of the liquid derived from the pump are B (kg / m ³ ) and D (Pa · s), respectively, and the resin solution or the polymerizable monomer and the release agent or When the true specific gravity of the liquid mixture containing the colorant is C (kg / m ³ ), 1.0 ≦ D and 0.97 ≦ B / C ≦ 1.00 are satisfied.
The method for producing a toner according to claim 1. The pump is
A pair of pump screws that rotate in a non-contacting manner,
A housing for accommodating the pair of pump screws in a non-contact manner is formed in the casing, and the pump casing forming the pump chamber by the pair of pump screws and the housing;
A bearing portion connected to the pump casing and rotatably supporting one end portion of the pair of pump screws in a cantilevered manner;
The pump casing in the region where the pump chamber is formed is provided with an intake for taking the mixed liquid or the dispersion processing liquid into the pump chamber,
The pump casing on the floating end side of the pair of pump screws is provided with a discharge port for discharging the mixed liquid or dispersion treatment liquid transferred from the pump chamber,
The mixed liquid or dispersion processing liquid taken into the pump chamber from the intake port is transferred by rotating the pair of pump screws and discharged from the discharge port; and
In the twin screw pump provided with an outlet for extracting the gas in the storage chamber upstream of the inlet in the transfer direction of the mixed liquid or dispersion treatment liquid and at the top of the pump casing,
A degassing device for extracting gas in the accommodation chamber is connected to the outlet.
The method for producing a toner according to claim 1.