JP6849372B2 - Toner manufacturing method - Google Patents

Description

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

As a method for manufacturing resin particles such as toner for static charge image development (hereinafter, may be simply referred to as "toner"), it is easy to obtain a product having a small particle size and a sharp particle size distribution, which reduces the environmental load during manufacturing. Wet manufacturing methods are often used because of their merits such as shape control and easy encapsulation.
The wet production method is a method for producing 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 shape of the resin particles.
The toner obtained by these methods is developed on a photoconductor, and then a mold 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 release agent is limited to about 5 parts by mass with respect to 100 parts by mass of the binder resin, whereas in the wet production method, it can be added in a larger ratio. In addition, the release agent can be reliably encapsulated, and good fixability and offset resistance can be obtained.
At this time, if a mold release agent having a low melting point is used, the plasticity of the toner at a low temperature is increased, and the fixability in a low temperature region is improved. On the other hand, if a mold release agent having a high melting point is used, the mold release property of the toner from the photoconductor at a high temperature is increased, and the fixability in a high temperature region is improved.
Further, in recent years, there has been increasing interest in the environment, and it is required to reduce the amount of toner-derived fine particles generated in the heat-pressurizing fixing machine. To meet this requirement, it is often advantageous to use a mold release agent having a high melting point.
When the release agent is blended with the polymerized toner, when the melting point of the release agent is lower than the temperature at the time of 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 at the time of the polymerization step, the release agent remains in a solid state, so that a coarse release agent mass or the like is generated, and the toner is completely and uniformly encapsulated. Becomes difficult.
If the added release agent is not completely encapsulated in the toner and a part of the added release agent exists in a state of being released from the toner as a release agent mass or the like, even a small amount significantly reduces the fluidity of the entire toner. .. Alternatively, it causes agglomeration of the toner centered on the release agent mass, and in any case, it causes deterioration of the image quality when the image is formed.
Further, even if the release agent is completely encapsulated in the toner, if the distribution state is not uniform, the release agent content differs depending on the toner, and different properties are exhibited. When formed, it leads to deterioration of image quality.
Further, if the domain of the release agent can be uniformly dispersed, the melting rate of the release agent at the time of heating becomes high, which leads to improvement of 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 finely powdered or finely dispersed in a liquid medium.
Of these, from the viewpoint of ease of handling, it is more preferable that the medium is finely dispersed in a liquid medium. So far, proposals for producing a fine dispersion of a high melting point release agent have been actively made.

On the other hand, as an important element of the colorant added to the toner, not only the coloring power but also the transparency is good. For good transparency, it is important that the dispersed particle size of the colorant is small and that the average particle size of the colorant in the toner is small.
However, in the step of dispersing the colorant in the polymerizable monomer using a disperser, the more finely dispersed the colorant is, the higher the viscosity of the dispersion liquid is, so that further dispersion tends to be difficult.
Further, as the viscosity of the dispersion liquid increases, the bubbles mixed in the dispersion liquid become difficult to escape from the dispersion liquid, and the dispersion efficiency of the colorant is lowered.
Furthermore, when air bubbles are mixed in the dispersion liquid, the dispersion time increases as the dispersion efficiency decreases, so that the colorant tends to be overdispersed, and the colorant tends to aggregate in the dispersion liquid or the toner. As a result, adverse effects such as deterioration of coloring power and transparency are likely to occur.
With respect to this problem, proposals for producing a fine dispersion of a colorant have been actively made so far.

Patent Documents 1 to 4 disclose a method of obtaining a fine dispersion liquid of a high melting point release agent or a colorant by finely dispersing a mold release agent or a colorant in a polymerizable monomer by a media disperser. There is.
According to the method described in Patent Document 1 or 2, a polymerizable monomer composition containing a release agent dispersion is dispersed in an aqueous medium to form droplets, and then a polymerization reaction is carried out to obtain a polymerized toner. In the production method, the release agent dispersed in the release agent dispersion liquid does not release. Further, by completely and uniformly encapsulating the release agent in the polymer fine particles, it is possible to produce a polymerized toner having improved fixability.
Further, Patent Documents 1, 3 and 4 also disclose a method in which a circulation line is formed by a media disperser and the dispersion liquid is passed a plurality of times to be used. 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 batch type.
Further, in Patent Documents 3 and 4, since the uneven distribution of beads is eliminated, the dispersibility of the colorant is remarkably excellent, the particle size distribution is uniform and sharp, and the toner characteristics such as image density and color tone are excellent. It is said that polymerized toner can be produced efficiently.
In recent years, as the process speed of electrophotographic increases, low temperature fixability of toner is required. Therefore, it is necessary to develop a method 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 property by miniaturizing the domain.
On the other hand, higher image quality is also required. Therefore, it is necessary to develop a method capable of finely dispersing the colorant for the purpose of improving the uniform dispersibility of the colorant and further improving the heat transfer property by miniaturizing the domain.
The above-mentioned method is effective as a method for obtaining a fine dispersion liquid of a high melting point release agent or a colorant, but there is a problem that the viscosity of the dispersion liquid increases and the dispersion capacity decreases due to the inclusion of gas in the dispersion liquid. was there. Therefore, there is a limit to reducing the particle size of the dispersion.
Regarding the removal of gas in the dispersion liquid, Patent Document 5 describes rotary dispersion having a mechanism capable of dispersing and concentrating a dispersion while reducing the pressure inside the container forming the dispersion chamber in a rotary disperser using a medium. The machine is disclosed.
As another example relating to the removal of gas from a liquid, Patent Document 6 discloses a twin-screw pump capable of transferring a high-viscosity substance while removing the gas from the object to be transferred. With this pump, it was possible to prevent gas from entering during the transfer of food and industrial materials. Such a degassing function is provided for the purpose of maintaining the quality of the final product, and is not used for the purpose of improving the material dispersion process. That is, the viscosity of the dispersion liquid is low at the initial stage of the dispersion process, and if degassing is performed when the dispersion liquid has a low viscosity, the process liquid contaminates the degassing port, which makes it difficult to apply to the dispersion process. It was.

Japanese Patent No. 4336621 Japanese Unexamined Patent Publication No. 2002-229251 Japanese Unexamined Patent Publication No. 2003-255605 Japanese Patent No. 4085931 Japanese Unexamined Patent Publication No. 11-31404 JP-A-2015-55179

As the dispersion of the release agent or the colorant in the polymerizable monomer progresses, a large number of bubbles are incorporated into the dispersion liquid as the viscosity increases. As a result, the viscosity of the dispersion liquid rapidly increases, and the dispersion efficiency further decreases.
Therefore, sufficient removal of bubbles in the dispersion is sufficient to finely disperse the release agent sufficiently to be completely and uniformly encapsulated in the toner, and the colorant in the colorant dispersion. There 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, it is possible to suppress an increase in the viscosity of the dispersion due to the uptake of bubbles. Therefore, improvement in dispersion efficiency can be expected.
However, it cannot be applied to a circulation type disperser as shown in Patent Documents 1 or 3 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 air 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 efficiency of removing air bubbles is greatly lowered. In order to solve this problem, if the stirring speed of the liquid in the stirring tank is increased, the vortex increases and the amount of air bubbles taken in increases. Further, when the degree of decompression 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 reducing the stirring speed of the stirring tank, the amount of air bubbles taken in can be reduced and the required degree of decompression can be suppressed. However, when the stirring speed is reduced, the mixing in the stirring tank is weakened, and the efficiency of removing air bubbles is lowered.

The present invention is to provide a method for producing a toner that solves the above-mentioned problems.
That is, the present invention is 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, and the release in the release agent dispersion. It provides a method for producing a toner in which a mold agent is finely dispersed to a particle size small enough to be encapsulated in the toner.
Further, the present invention is 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, wherein the colorant is dispersed in the colorant dispersion. It is an object of the present invention to provide a method for producing a toner, which can efficiently produce a toner having excellent properties, image density, OHP transparency, and the like.

As a result of diligent studies on the fine dispersion of the release agent or the colorant in the resin solution or the polymerizable monomer, the present inventors have found the following production method.
The present invention
A method for producing a toner, which comprises 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 is a step of repeatedly carrying out the following steps (i) to ( iii) to obtain a release agent dispersion liquid.
(I) The mixed solution is discharged from the tank containing the resin solution or the mixed solution containing the polymerizable monomer and the release agent, and the discharged mixed solution is dispersed by a pump. Process to be introduced into the machine;
(Ii) A step of dispersing the release agent by the disperser to obtain the dispersed mixed solution;
(Iii) A step of returning the dispersed mixed solution to the tank;
The disperser is a media disperser.
The mixture in the process of the (i) when introduced into the dispersing machine from the tank by the pump, the gas contained in the mixture to be conveyed from the tank to the dispersing machine, the mixture is said After leaving the tank and before entering the disperser , remove from the mixture and
The pump
A pair of pump screws that rotate without contact with each other,
A storage chamber for accommodating a 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 accommodation chamber.
A bearing portion that is connected to the pump casing and rotatably supports one end of the pair of pump screws in a cantilever shape.
With
The pump casing in the region where the pump chamber is formed is provided with an intake for taking the mixed solution into the pump chamber.
The pump casing on the idle end side of the pair of pump screws is provided with a discharge port for discharging the mixed liquid transferred from the pump chamber.
The mixed liquid taken into the pump chamber from the intake port is transferred by rotational driving of the pair of pump screws, discharged from the discharge port, and
In a twin-screw pump in which an outlet for extracting gas in the accommodating chamber is provided on the upstream side of the inlet in the transfer direction of the mixture and above the pump casing.
A degassing device for extracting gas from the containment chamber is connected to the outlet.
This is a method for producing toner, which is characterized by the above.

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 liquid is finely dispersed to a particle size small enough to be encapsulated in the toner. Further, it is possible to provide a toner manufacturing method capable of efficiently producing a toner having excellent dispersibility of the colorant in the colorant dispersion liquid and excellent characteristics such as image density and OHP transparency.

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

Hereinafter, the present invention will be described in detail.
In the present invention, the description of "○○ or more and XX or less" and "○○ to XX" indicating a numerical range means a numerical range including a lower limit and an upper limit which are end points 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) is
A method for producing a toner, which comprises a dispersion step of obtaining a dispersion to be dispersed in a resin solution or a polymerizable monomer.
The dispersion step has the following steps (i) to (iv).
This is 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 the resin solution or the mixed solution containing the polymerizable monomer and the substance to be dispersed, and the discharged mixed solution is dispersed by a pump. Process to be introduced into the machine;
(Ii) A step of performing a dispersion treatment of the object to be dispersed by the disperser to obtain a dispersion treatment liquid;
(Iii) A step of returning the dispersion treatment liquid to the tank;
(Iv) A step of 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 toner, which comprises removing a gas conveyed together with the liquid when the liquid is sent by the pump.

The dispersion step can be applied to a wet production method including a step of preparing a dispersion liquid in which the object 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 to be dispersed in the polymerizable monomer are formed in an aqueous medium, and the polymerization contained in the particles of the dispersion to be dispersed is formed. It is preferable to obtain the toner through the step of polymerizing the sex monomer.
When the dissolution / suspension method is used, for example, a step of preparing a dispersion to be dispersed by dissolving or dispersing the dispersion in a resin dissolution solution in which a binder resin is dissolved in an organic solvent, the dispersion. It is preferable to obtain the toner 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, an example 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. Examples of the object to be dispersed include a mold release agent and a colorant.

(Coarse dispersion preparation process)
Before the step of dispersing the object to be dispersed, the mixed solution containing the polymerizable monomer and the object to be dispersed or the mixed solution containing the resin solution and the substance to be dispersed is dispersed by a simple dispersion device. A crude dispersion of the object to be dispersed may be prepared.
For the preliminary coarse dispersion, among ordinary stirring blades such as turbine blades and edged turbine blades, those having a large shearing force, Ultratarax (manufactured by IKA), T.I. K. Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), T.I. K. Dispersors such as Fillmix (manufactured by Tokushu Kagaku Kogyo Co., Ltd.) and Clairemix (manufactured by M-Technique) 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 one pass, or they can be used by forming a circulation line and passing the liquid multiple times.

(Dispersion process)
The dispersion step is a step of obtaining a dispersion to be dispersed solution in which the substance to be dispersed is dispersed in the resin solution or the polymerizable monomer.
Specifically, it is a step having the following steps (i) to (iv), and repeating the steps (i) to (iv) to obtain a dispersion to be dispersed liquid.
(I) Step of discharging the mixed liquid from the tank containing the mixed liquid containing the resin solution or the polymerizable monomer and the object to be dispersed, and introducing the discharged mixed liquid into the disperser by a pump. (Ii) A step of dispersing 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) Dispersing the dispersion treatment liquid in the tank is discharged and discharged. A step of introducing the dispersed dispersion treatment liquid into the disperser by a pump, and removing the gas conveyed together with the liquid when the liquid is sent by the pump.

FIG. 1 shows an example of a dispersion system of an object to be dispersed, which incorporates a pump capable of removing a gas conveyed together with the liquid when the liquid is sent, but the present invention is not limited thereto.
The pump 7 shown in FIG. 1 has a function of sending a mixed solution containing a polymerizable monomer and a substance to be dispersed in the holding tank 1 to a disperser and a function of extracting a gas contained in the mixed solution. Has.
The means for exerting the function of extracting gas is not limited, but general means such as an air ejector type degassing device, a piston / cylinder type or a centrifugal fan type decompression pump can be exemplified.

In the system including the pump 7, the crude dispersion liquid of the object to be dispersed, or the polymerizable monomer and the object to be dispersed are charged into the holding tank 1.
After that, a pre-dispersion step may be performed in which a mixed solution is obtained by dispersing or dissolving for a predetermined time with a stirrer driven by the motor 2. In order to control the temperature of the mixed solution, the temperature-controlled water adjusted in the jacket 3 may be introduced into the holding tank 1 via the jacket inlet 4 and the jacket outlet 5.
The obtained mixed liquid is supplied to the disperser 8 via the pump 7, and the disperser 8 performs a dispersion treatment of the object to be dispersed to prepare a dispersion treatment liquid. After that, the obtained dispersion treatment liquid is returned to the holding tank 1.
The dispersion treatment liquid returned to the holding tank 1 is supplied to the disperser 8 again via the pump 7. Then, while repeating circulation between the disperser 8 and the holding tank 1, the dispersion treatment of the object to be treated is uniformly and efficiently performed, and by carrying out the dispersion treatment for a predetermined time, the dispersion liquid to be processed is released. can get.

In the dispersion step, when the viscosity of the liquid drawn out from the pump 7 reaches a predetermined value, the gas may be extracted by the pump 7.
Further, the degree of decompression 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 it may be arbitrarily adjusted depending on the physical characteristics of the liquid.
Since the pump has a function to extract gas, the processing cross-sectional area of the degassed liquid becomes smaller, so in addition to higher degassing efficiency than degassing in a holding tank where the depth of the liquid is an issue. , The time the mixture is exposed to reduced pressure can be shortened. Therefore, the volatilization of the dispersion medium can be suppressed. Further, since the liquid is sent to the disperser immediately after degassing, the degassing efficiency is high as a degassing means in the dispersion system.

The degassed liquid is sent to the disperser 8 for dispersion processing. At this time, since the content of bubbles in the liquid is small, the dispersion efficiency of the object to be dispersed becomes high, and the fine dispersion treatment of the object to be dispersed can be performed in a shorter time than in the conventional case. Furthermore, the object to be dispersed can be finely dispersed as compared with the conventional case.
When a media type disperser is used for the disperser 8, if air bubbles are contained in the liquid, the collision energy by the media inside the disperser 8 is difficult to be efficiently applied to the dispersion of the object to be dispersed. Similarly, even when a medialess disperser is used, if air 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 content of bubbles in the liquid is small, the dispersion efficiency is high and the treatment can be performed for a short time, so that overdispersion of the object to be dispersed can be suppressed.
Therefore, for example, reaggregation of the colorant can be suppressed in the toner, which is preferable. As a result, a colorant having a fine dispersion and a sharp distribution can be present in the toner as compared with the conventional one, so that 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 suitable examples are Diamond Fine Mill (manufactured by Mitsubishi Heavy Industries), Dyno Mill (manufactured by Shinmaru Enterprise), Apex Mill (manufactured by Kotobuki Giken), SC Mill (manufactured by Nippon Coke Industries Co., Ltd.) Media dispersers such as the former Mitsui Miike Kakoki Co., Ltd., Star Mill (Ashizawa Finetech Co., Ltd.), OB Mill (ORIVER BATLLE), and Super Mill (Inoue Seisakusho Co., Ltd.) can be mentioned.
On the other hand, medialess dispersers such as Sharp Flow Mill (manufactured by Pacific Kiko Co., Ltd.), Claire Mix (manufactured by M Technique), and High Share Mixer (manufactured by IKA) 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 the 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, and more preferably 0.5 mm or more and 3 mm or less. The density of beads is usually 3 g /
It is 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% by volume or more and 90% by volume or less, preferably 70% by volume or more and 85% by volume or less.

Further, in order to reduce the amount of the dispersion medium recovered by degassing, a cooling mechanism may be provided in the immediate vicinity of the pump of the degassing 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 drawn 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 more the viscosity increase of the liquid can be suppressed when the dispersion progresses, and the dispersion can be efficiently performed.
If the bulk specific weight B is even slightly larger than the bulk specific weight A, the dispersion efficiency is improved, but the value obtained by subtracting the bulk specific weight A from the bulk specific weight B (that is, [BA]) is 5 (kg / m ³ ) or more. It is preferable that the weight 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 the A and B within the above range, a method such as adjusting the suction pressure of the degassing pump attached to the pump can be exemplified.

Further, in the dispersion step, the bulk specific gravity and viscosity of the liquid after being derived from the pump are set to B (kg / m ³ ) and D (Pa · s), respectively, and the resin solution or the polymerizable monomer is set. When the true specific gravity of the mixed solution containing the substance to be dispersed and the substance to be dispersed is C (kg / m ³ ),
It is preferable to satisfy 0.5 ≦ D, more preferably 1.0 ≦ D, and further preferably 1.5 ≦ D. The upper limit is not particularly limited, but is preferably D ≦ 4 (Pa · s).
On the other hand, it is preferable to satisfy 0.94 ≦ B / C ≦ 1.00, and more preferably 0.97 ≦ B / C ≦ 0.99. In order to adjust the D and [B / C] within the above range, a method such as adjusting the timing of starting degassing and the suction pressure of the degassing pump attached to the pump can be exemplified.
By extracting the gas when the viscosity of the liquid is larger than 0.5 (Pa · s), excessive pulverization is suppressed and aggregation of the release agent, colorant, etc. due to over pulverization is prevented. Can be done. In addition, it is possible to prevent contamination of the process liquid gas extraction line due to the low viscosity. 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.

The pump is not particularly limited as long as it can remove the gas conveyed together with the liquid when the liquid is sent, but a pump having the following structure can be preferably exemplified.
The pump has a pair of pump screws that rotate by being screwed together in a non-contact manner and a storage chamber for accommodating the pair of pump screws in a non-contact manner, and the pair of pump screws and the storage chamber are formed in the casing. The pump chamber is formed by providing a pump casing that forms a pump chamber and a bearing portion that is connected to the pump casing and rotatably supports one end of the pair of pump screws in a cantilever shape. The pump casing in the above region is provided with an intake for taking the mixed liquid or the dispersion treatment liquid into the pump chamber, and the pump casing on the idle end side of the pair of pump screws is the mixing transferred from the pump chamber. A discharge port for discharging the liquid or the dispersion treatment liquid is provided, and the mixed liquid or the dispersion treatment liquid taken into the pump chamber from the intake port is transferred by rotational driving of the pair of pump screws. An outlet for extracting gas from the storage chamber is provided on the upstream side of the inlet of the pump in the transfer direction of the mixed liquid or the dispersion treatment liquid and above the pump casing. The twin-screw pump preferably has a structure in which a degassing device for extracting gas in the accommodation chamber is connected to the outlet.
Since the pump has a structure in which the liquid is pushed out by a pair of screws and the liquid is sent out, and the screws are not in contact with each other, the liquid is not excessively sheared and aggregation due to overdispersion can be suppressed. Further, since the dispersion is performed only in the part of the disperser, the balance of the dispersion is not lost and the dispersion can be performed uniformly. Therefore, it is possible to suppress an increase in viscosity due to a decrease in the particle size distribution of the object to be dispersed.
Specific examples of the pump having the above structure include, but are not limited to, a deforming pump (Fushitora Metal Industry Co., Ltd.).

(Preparation step of polymerizable monomer composition)
If necessary, another toner material may be added to the dispersant dispersion liquid in which the dispersant is dispersed in the polymerizable monomer obtained in the above dispersion step to obtain a polymerizable monomer composition. ..

(Granulation process)
The obtained polymerizable monomer composition is put into an aqueous medium containing a dispersion stabilizer and dispersed to form particles of the polymerizable monomer composition, and the polymerizable monomer composition dispersion liquid is formed. To get.
The granulation step can be performed, for example, in a vertical stirring tank equipped with a stirrer having a high shearing force. The stirrer having a high shearing force is not particularly limited, but for example, a high share mixer (manufactured by IKA), T.I. K. Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), T.I. K. Commercially available products such as Philmix (manufactured by Tokushu Kagaku Kogyo Co., Ltd.) and Claremix (manufactured 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, calcium sulfate and the like. Inorganic dispersion stabilizers such as calcium hydroxide, aluminum hydroxide, magnesium hydroxide, and metal hydroxide of ferric hydroxide; can be mentioned. These can be used alone or in combination of two or more. These exhibit a function 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 whose temperature can be adjusted can be used.
The polymerization temperature is 40 ° C. or higher, generally 50 to 90 ° C. The polymerization temperature may be constant from beginning to end, but may be raised in the latter half of the polymerization step for the purpose of obtaining a desired molecular weight distribution.
Further, any stirring blade used for stirring may be used as long as the polymerizable monomer composition dispersion can be suspended without staying and the temperature in the tank can be kept uniform.
Stirring blades or means of stirring include common stirring blades such as paddle blades, tilted paddle blades, three swept blades, propeller blades, disc turbine blades, helical ribbon blades and anchor blades, and "full zone" ((( Kobelco Eco-Solutions Co., Ltd.), "Twin Star" (Kobelco Eco-Solutions Co., Ltd.), "Max Blend" (Sumitomo Heavy Machinery Co., Ltd.), "Super Mix" (Satake Chemical Machinery Co., Ltd.) and Examples include "Hi-F mixer" (manufactured by Soken Kagaku Co., Ltd.).

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

(Washing process, solid-liquid separation process and drying process)
The resin particle dispersion may be treated with an acid or an alkali for the purpose of removing the dispersion stabilizer adhering to the surface of the obtained resin particles. After that, 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 cleaning step is repeated several times, and after sufficient cleaning is performed, 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 as compared with the conventional pulverized resin particles, but when a sharper particle size is required, the toner particles are classified by a wind classifier or the like. Toner particles that deviate from the desired particle size distribution can also 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-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-phenylstyrene; 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, n -Acrylic polymerizable monomers such as 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. , Dibutyl phosphate ethyl methacrylate, Dibutyl phosphate ethyl methacrylate and other methacrylic polymerizable monomers.
The polymerizable monomer can be used alone or in combination of two or more. Among these, it is preferable to use styrene or a styrene derivative alone or in combination, or in combination with them and other polymerizable monomers from the viewpoint of toner development characteristics and durability.

<Colorant>
Examples of the colorant include known colorants used for toner such as organic pigments and oil dyes. Specific examples are shown below, but the present invention is not limited to these.
As the pigment used for the cyan-based colorant, a copper phthalocyanine compound and its derivative, an anthraquinone compound, and a basic dye lake compound can be used. Specifically, the following can be mentioned. 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, a condensed azo compound, a diketopyrrolopyrrole compound, an anthraquinone compound, a quinacridone compound, a basic dye lake compound, a naphthol compound, a benzimidazolone compound, a thioindigo compound and a perylene compound can be used. Specifically, the following can be mentioned. 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, a condensed azo compound, an isoindolinone compound, an anthraquinone compound, an azo metal complex, a methine compound and an allylamide compound can be used. Specifically, the following can be mentioned. 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 those colored black by using the above-mentioned 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 resin component contained in the polymerizable monomer or 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.
Known waxes include paraffin wax, polyolefin wax, microcrystalline wax, polymethylene wax such as Fishertropsh wax, amide wax, higher fatty acid, long chain alcohol, ester wax, graft compounds thereof, and block compounds thereof. It is possible to use wax. It is preferable that these have the low molecular weight component removed and the maximum endothermic peak of the endothermic curve obtained by the differential scanning calorimeter is sharp.
The amount of the release agent added 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 resin component contained in the polymerizable monomer or the resin solution. It is 30 parts by mass or less.

The peak temperature (hereinafter, also referred to as melting point) of the maximum endothermic peak measured by the 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 wax once finely dispersed 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. It can be prevented from becoming.
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 temperature rise rate is 10 ° C./min. In the measurement, the sample is once heated from 30 ° C. to 200 ° C. and then lowered to 200 ° C. to 30 ° C. After that, the temperature is raised again. The peak temperature of the maximum endothermic peak of the differential scanning calorimetry in the temperature range of 30 ° C. to 200 ° C. in the second temperature raising process is defined as the melting point [unit: ° C.].
Further, the release agent preferably has a needle insertion degree of 10 or less at 25 ° C. when measured according to the test method specified in JIS K 2235 (1991), and more preferably. The degree of needle insertion at 25 ° C. is 5 or less.
When the degree of needle insertion at 25 ° C. is 10 or less, the brittleness is not insufficient, and in the coarse dispersion step, coarse dispersion can be performed with a simple dispersion device such as a stirrer having a high shearing force, and the pressure is high. There is no need to use a large-scale device such as a disperser or a means that requires complicated operations such as an operation of heating and melting and then cooling.

Further, in order to increase the plasticity of the toner and improve the fixability in a low temperature region, a second mold release agent having a melting point of less 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 by the differential scanning calorimeter.
Examples of the second release agent include waxes of linear alkyl alcohols having 15 to 100 carbon atoms, linear fatty acids, linear acid amides, linear esters, and montane derivatives. Preferably, impurities such as liquid fatty acids have been removed from these waxes in advance.
A linear ester wax is preferably used as the second release agent in order to improve the translucency of the image fixed on the OHP.

<Charge control agent>
The toner may contain a charge control agent (internal addition) or a mixture (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 can be mentioned as the thing which controls the toner by the load electric property.
Organic metal compounds and chelate compounds are effective, and monoazo dye metal compounds, acetylacetone metal compounds; aromatic hydroxycarboxylic acids, aromatic mono and polycarboxylic acids and their metal salts, anhydrides thereof, esters thereof; bisphenol and the like. Phenolic derivatives.
In addition, the following can be mentioned. Sulfonic acid group-containing resins such as urea derivatives, metal-containing salicylic acid-based compounds, calix arene, silicon compounds, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, and styrene-acrylic-sulfonic acid copolymers, non-metals. Carboxylic acid-based compound.
Examples of controlling the toner to be positively charged include the following.
Modified products of niglosin and its fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate; onium salts such as phosphonium salts and lakes thereof. Pigments, triphenylmethane dyes and their lake pigments (as lake agents, phosphotung acid, phosphomolybdic acid, phosphotungene molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, or ferrosian), Metal salts of higher fatty acids; diorganosin oxides such as dibutyltin oxide, dioctyltinoxide, dicyclohexylstinoxide; diorganosinbolates such as dibutyltinborate, dioctylstinborate, dicyclohexylstinborate.
These charge control agents can be used alone or in combination of two or more.
The amount of the charge control agent added is preferably 0.01 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin component contained in the polymerizable monomer or the resin solution, and more preferably 0. It is 5 parts by mass or more and 10 parts by mass or less.

<Polymerization initiator>
In the above polymerization step, a polymerization initiator may be used. Examples of the polymerization initiator include azo-based polymerization initiators and organic peroxide-based initiators.
Examples of the azo-based 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, azobisisobutyronitrile.
Examples of the organic peroxide-based initiator include the following. Benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxy carbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, tert-butyl-peroxypivalate.
In addition, a redox-based initiator that combines an oxidizing substance and a reducing substance can also be used. Examples of the oxidizing substance include hydrogen peroxide, an inorganic peroxide of a persulfate (sodium salt, potassium salt, ammonium salt, etc.), and an oxidizing metal salt such as a tetravalent cerium salt.
Reducing substances include reducing metal salts (divalent iron salt, monovalent copper salt, trivalent chromium salt), ammonia, lower amines (amines having 1 to 6 carbon atoms such as methylamine and ethylamine), and the like. 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 like. Salts and their lower aldehydes (1-6 carbon atoms).
The polymerization initiator is selected with reference to the 10-hour half-life temperature, and is used alone or in combination.
The amount of the polymerization initiator added 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 cross-linking agents can also be used. Examples of the cross-linking agent include the following. Divinylbenzene, 4,4'-divinylbiphenyl, hexanediol diacrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycidyl (meth) acrylate, trimethylolpropane tri (meth) acrylate.

<Bundling resin>
The binder resin constituting the toner is not particularly limited, and known ones can be used.
Specific examples thereof 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-to-dispersion solution obtained by dissolving or dispersing the substance to be dispersed in a resin solution in which a binder resin is dissolved in an organic solvent in an aqueous medium is a suspension. It may be the same as the turbid polymerization method. Further, it is preferable to use known conditions as the conditions of the solvent removal step for removing the organic solvent contained in the granulated particles.
Specific examples of the organic solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichlorethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate and 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 facilitating the subsequent removal of the solvent.
When the resin to be dissolved or dispersed in the organic solvent is a resin having a polyester skeleton, it is preferable to use 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. .. A resin having a polyester skeleton is preferable because it has high solubility 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>
Further, a modified resin (hereinafter sometimes referred to as "prepolymer") may 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 and the like.
Examples thereof include polyol resins, polyacrylic resins, polyester resins, epoxy resins, and derivative resins thereof.
These may be used alone or in combination of two or more. Among these, polyester resin is particularly preferable in terms of high fluidity and transparency when melted.
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 and the like. For example, an isocyanate group, an epoxy group, a carboxylic acid and an acid can be selected. Chloride groups, etc. can be mentioned.
These may be contained individually by 1 type, and may contain 2 or more types. Of these, isocyanate groups are particularly preferred.

<Active hydrogen group-containing compound>
The active hydrogen group-containing compound acts as an extender, a cross-linking agent, or the like when a modified resin capable of reacting with the active hydrogen group-containing compound undergoes an extension reaction, a cross-linking reaction, or the like 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 depending on the intended purpose. For example, when the polymer capable of reacting with the active hydrogen group-containing compound is an isocyanate group-containing polyester prepolymer, the polymer can be increased in molecular weight by a reaction such as an elongation reaction or a cross-linking reaction with the isocyanate group-containing polyester prepolymer. Aamines are suitable.
The active hydrogen group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxy group and a mercapto group. These may be used alone or in combination of two or more. Of these, alcoholic hydroxyl groups are preferred.

<External agent>
An external additive may be added to the toner for the purpose of improving various powder properties.
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 Carbides such as silicon carbide; calcium sulfate, Inorganic metal salts such as barium sulfate, calcium carbonate; fatty acid metal salts such as zinc stearate, calcium stearate; carbon black, silica.
The amount of the external additive added 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. The external additive 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 substance.
The magnetic material 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 amount of the magnetic substance added is preferably 20 parts by mass or more and 200 parts by mass or less, and 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 less than a part by mass.

When a magnetic material is used, it is preferable to hydrophobize the surface of the magnetic material in order to improve the dispersibility of the magnetic material in the toner.
Coupling agents such as a silane coupling agent and a titanium coupling agent may be used for the hydrophobization treatment.
Of these, a silane coupling agent is preferable. Examples of the silane coupling agent include the following. Vinyl trimethoxysilane, vinyl triethoxysilane, 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 the dispersant in the dispersant dispersion>
The dispersibility of the object to be dispersed is determined by measuring the median diameter (standard deviation if necessary) based on the volume of the object to be dispersed using a laser diffraction / scattering particle size distribution measuring device LA-950 (manufactured by HORIBA, Ltd.). It was evaluated 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 resin dissolution) was added to such an extent that it filled 70 to 90% of the cell. The inside of the cell was stirred with a stirrer. The measurement sample (dispersion liquid to be dispersed) is charged therein so that the transmittance (R) of the cell is 70 to 98% and the transmittance (B) is 25 to 65%, and the relative refractive index is 0.95. The measurement was carried out under the conditions of.
(Evaluation criteria for mold release agent)
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 are some problems in image characteristics and fixability, but there is no practical problem. did. Further, it was judged that when the median diameter is 1.000 μm or more, the influence on the image is considerably severe and it is not preferable in terms of the product.
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 (evaluation criteria for colorants)
A: Very good less than 0.250 μm 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 toner 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 the measuring device, a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter Co., Ltd.) equipped with a 100 μm aperture tube by the pore electrical resistance method is used. For the setting of measurement conditions and the analysis of measurement data, the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter Co., Ltd.) is used. The measurement is performed with 25,000 effective measurement channels.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so that the concentration becomes about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter Co., Ltd.) can be used. ..
Before performing the 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 number in the control mode to 50,000 particles, measure once, and set the Kd value to "standard particles 10.0 μm" (Beckman Coulter). Set the value obtained using (manufactured by the company). By pressing the "threshold / noise level measurement button", the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check “Flash of aperture tube after measurement”.
On the "Pulse to particle size conversion setting" screen of the dedicated software, the bin spacing is set to logarithmic particle size, the particle size bin is set to 256 particle size bins, and the particle size range is set from 2 μm to 60 μm.
The specific measurement method is as follows.
(1) Put about 200 mL of the electrolytic aqueous solution in a glass 250 mL round bottom beaker dedicated to Multisizer 3, set it on a sample stand, and stir the stirrer rod counterclockwise at 24 rpm. Then, the dirt and air bubbles in the aperture tube are removed by the "aperture flash" function of the dedicated software.
(2) Put about 30 mL of the electrolytic aqueous solution in a 100 mL flat-bottomed beaker made of glass. Among them, as a dispersant, "Contaminone N" (a 10% by mass aqueous solution of a neutral detergent for cleaning a precision measuring instrument at pH 7 consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, Wako Pure Chemical Industries, Ltd. ) Is diluted with ion-exchanged water about 3 times by mass, and about 0.3 mL of the diluted solution is added.
(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 Tera150" (manufactured by Nikkaki Bios Co., Ltd.) with an electrical output of 120 W is prepared. To do. Approximately 3.3 L of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 mL of contaminationon N is added into 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. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.
(5) With the electrolytic aqueous solution in the beaker of (4) being irradiated with ultrasonic waves, about 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. In ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10 ° C. or higher and 40 ° C. or lower.
(6) Using a pipette, the electrolytic aqueous solution of (5) in which toner is dispersed is dropped onto the round bottom beaker of (1) installed in the sample stand, and the measured concentration is adjusted to about 5%. .. Then, the measurement is performed until the number of measurement particles reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the device, 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 and bulk specific gravity B>
The bulk specific gravity (kg / m ³ ) is measured by placing a sample in a 200 mL graduated cylinder and measuring its mass.

<Measurement of true specific gravity C>
The true specific gravity C is calculated by the following formula using the values of the polymerizable monomer (1) or the resin solution (2) and the known true specific gravities of the object to be dispersed.
(1) True specific gravity C =
{(True specific gravity of the polymerizable monomer) x (Mass part of the polymerizable monomer contained in the mixed solution containing the polymerizable monomer and the object to be dispersed) / (Mass part of the mixed solution)} + {(True specific gravity of the substance to be dispersed) × (Mass part of the substance to be dispersed contained in the mixed solution containing the polymerizable monomer and the substance to be dispersed) / (Parts by mass of the mixed solution)}
(2) True specific gravity C = {(true specific gravity of the resin solution) × (mass part of the resin solution contained in the mixed solution containing the resin solution and the object to be dispersed) / (mass part of the mixed solution)} + { (True specific gravity of the disperse) × (Mass part of the disperse contained in the mixture containing the resin solution and the disperse) / (Mass part of the mixture)}

When the known true specific gravity of the object to be dispersed (release agent or colorant) is unknown, it is advisable to actually measure it by the following method.
A dry automatic densitometer Accupic 1340 (manufactured by Shimadzu Corporation) is used to measure the true specific gravity.
First, the sample is ^{placed in a measurement cell (10 cm 3} ) at about 80% of the cell height, 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 into the main body and starting the measurement.
As the measurement condition of the automatic measurement, helium gas adjusted at 19.5 psig is used. After purging 5 times in the sample chamber, the equilibrium state is set when the pressure change in the sample chamber becomes 0.005 psig / min, and the helium gas is repeatedly purged until the equilibrium state is reached. Measure the pressure in the main body sample chamber in the equilibrium state. 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 sample (kg / m ³ ) = sample mass (kg) / sample volume (m ³ )
The average value of the values measured repeatedly 5 times by this automatic measurement is defined as the true specific gravity (kg / m ³ ) of the object to be dispersed.

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

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the embodiments of the present invention are not limited thereto. Unless otherwise specified, the number of copies and% of Examples and Comparative Examples are all based on mass.

An example of production of the release agent dispersion liquid will be described below.
(Production example of release agent dispersion 1)
As pre-dispersion, the following components are placed in a temperature-adjustable container, and the liquid temperature is always kept at 50 ° C. or lower using Ultratarax T-50 (manufactured by IKA), and the mixture is stirred at 10000 rpm for 40 minutes to coarsely release the release agent. A dispersion was obtained. The volume-based median diameter of the release agent particles in the release agent crude 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 Fushitora Metal Industry Co., Ltd.) was used.
Further, as the disperser 8, an OB mill (manufactured by ORIVER BATLLE) was used.
First, the entire amount of the release agent crude dispersion (30 L) was charged into the holding tank 1 (cooling water at 10 ° C. passed through the jacket 3).
Next, the release agent was dispersed under the following conditions to obtain a release agent dispersion liquid 1.
Bead material: Zirconia Bead diameter: 0.5 mm
Circulating flow rate: 5 L / min
Peripheral speed of rotating body: 13 m / 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 degassing 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 (that is, [BA]) 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. Further, the temperature rise of the release agent dispersion was suppressed by flowing cooling water at 10 ° C. through the jacket 3. The temperature of the release agent dispersion liquid after the completion of the dispersion step was 15 ° C. The volume-based median diameter of the release agent in the release agent dispersion liquid after the completion of the dispersion step was 0.180 μm. The true specific gravity of the release agent crude acid solution was 917 (kg / m ³ ) as a result of calculation from known values.

(Production example of release agent dispersion 2)
In the production example of the release agent dispersion 1, the deforming pump (manufactured by Fushitora Metal Industry Co., Ltd.) was changed to the defoaming / degassing pump ASP type (manufactured by Yokota Seisakusho Co., Ltd.) as the pump 7. Produced the release agent dispersion 2 by the same method as in the production example of the release agent dispersion 1.

(Production example of release agent dispersion liquid 3)
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 0.97. 3 produced the release agent dispersion liquid 3 in the same manner as in the production example of the release agent dispersion liquid 1.

(Production example of release agent dispersion liquid 4)
In the production example of the release agent dispersion liquid 1, when the viscosity of the liquid reaches 1.0 (Pa · s), the degassing device 6 attached to the pump 7 is operated, and [BA] is 58 (BA). The release agent was prepared in the same manner as in the production example of the release agent dispersion liquid 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 kg / m ^3). The dispersion liquid 4 was produced.

(Production example of release agent dispersion liquid 5)
In the production example of the release agent dispersion liquid 1, when the viscosity of the liquid reaches 1.0 (Pa · s), the degassing device 6 attached to the pump 7 is operated, and [BA] is 57 (. The mold release agent was prepared in the same manner as in the production example of the release agent dispersion liquid 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 kg / m ^3). The dispersion liquid 5 was produced.

(Production example of release agent dispersion liquid 6)
In the production example of the release agent dispersion liquid 1, when the viscosity of the liquid reaches 1.0 (Pa · s), the degassing device 6 attached to the pump 7 is operated, and [BA] is 39 (BA). kg / m ^3), and, except that the ratio of the bulk density B for a true specific gravity of C is adjusted a suction pressure so that 0.97, releasing agent dispersion 1 of preparation the same method with a release agent The dispersion liquid 6 was produced.

(Production example of release agent dispersion 7)
In the production example of the release agent dispersion liquid 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 the release agent dispersion 7 by the same method as in the production example of the release agent dispersion 1.

(Production example of release agent dispersion liquid 8)
In the production example of the release agent dispersion liquid 1, when the viscosity of the liquid reaches 0.5 (Pa · s), the degassing device 6 attached to the pump 7 is operated, and [BA] is 56 (BA). The release agent was prepared in the same manner as in the production example of the release agent dispersion liquid 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 kg / m ^3). The dispersion liquid 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. Is a release agent dispersion 1
The release agent dispersion liquid 9 was produced in the same manner as in the production example of.

(Production example of release agent dispersion liquid 10)
In the production example of the release agent dispersion liquid 1, the OB mill (manufactured by ORIVER BATLLE) was changed to a sharp flow mill (manufactured by Pacific Kiko Co., Ltd.) as the disperser 8, and the dispersion conditions were changed to the following. The suction pressure was adjusted so that [BA] was 12 (kg / m ³ ) and 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 liquid 10 was produced in the same manner as in the production example of the release agent dispersion liquid 1.
Circulating flow rate: 5 L / min
Peripheral speed of rotating body: 60 m / s
Back pressure: 0.2 MPa
Dispersion time: 180 min

(Production example of release agent dispersion liquid 11)
In the production example of the release agent dispersion liquid 1, the deforming pump (manufactured by Fushitora Metal Industry Co., Ltd.) was changed to the defoaming / degassing pump ASP type (manufactured by Yokota Seisakusho Co., Ltd.) as the pump 7. As the disperser 8, the OB mill (manufactured by ORIVER BATLLE) was changed to a sharp flow mill (manufactured by Pacific 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 liquid 11 was produced in the same manner as in the production example of the release agent dispersion liquid 1. Circulating flow rate: 5 L / min
Peripheral speed of rotating body: 60 m / s
Back pressure: 0.2 MPa
Dispersion time: 180 min

(Production example of release agent dispersion liquid 12)
In the production example of the release agent dispersion liquid 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 (manufactured by Nippon Coke Industries Co., Ltd., formerly Mitsui Miike Kakoki Co., Ltd.) was used, and batch-type release agent dispersion was performed under the following conditions.
At this time, cooling water at 10 ° C. was passed through the jacket 3 of the handy mill. Further, 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 with the parts other than the degassing port 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 liquid 1, but the release agent dispersion liquid contained in the holding tank 1 had a high viscosity and a liquid depth. Since it was deep, no degassing action was observed, and the bulk specific gravity of the liquid could not be adjusted. A release agent dispersion liquid 12 was obtained in the same manner as in the production example of the release agent dispersion liquid 1 except for the above.
Bead material: Zirconia Bead diameter: 3 mm
Peripheral speed of rotating body: 8.4 m / s
Dispersion time: 180 minutes

(Production example of release agent dispersion liquid 13)
In the production example of the release agent dispersion liquid 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 The degassing device 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 liquid 1, but the release agent dispersion liquid contained in the holding tank 1 had a high viscosity and a liquid depth. Since it was deep, no degassing action was observed, and the bulk specific gravity B could not be adjusted. Except for the above, the release agent dispersion liquid 13 was produced in the same manner as in the production example of the release agent dispersion liquid 1.

(Production example of release agent dispersion liquid 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 is used except that the degassing port of the pump 7 is fully closed and the degassing device 6 is not activated. The release agent dispersion liquid 14 was produced.

[Example A1]
Toner was manufactured by the following procedure.
(Preparation of pigment dispersion composition)
23.0 parts by mass of styrene, 1.88 parts by mass of C.I. I. Pigment Yellow 155 and 0.58 parts by mass of charge control agent (Bontron E88; manufactured by Orient Chemical Industry Co., Ltd.) were introduced into Attrita (Nippon Coke Industry Co., Ltd., formerly manufactured by Mitsui Miike Machinery Co., Ltd.). Using zirconia beads 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)
Put the following ingredients in the same container, and T.I. K. Using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), mixing and dispersion were performed at a peripheral speed of 20 m / s.
-Release agent dispersion 1 19.52 parts by mass-Pigment dispersion composition 25.02 parts by mass-n-butyl acrylate 9.59 parts by mass-Polyester resin 1.92 parts by mass [propylene oxide-modified bisphenol A (2 mol added) (Product) and terephthalic acid polycondensate (polymerization molar ratio: 10:12), glass transition temperature (Tg): 68 ° C., weight average molecular weight (Mw): 10000, weight average molecular weight (Mw) / number average molecular weight (Mw) Mn): 5.12]
-Styline-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 mgKOH / g, weight average molecular weight (Mw) / number average molecular weight (Mn): 2.1) 5.75 parts by mass, 0.05 parts by mass of sulfonic acid group-containing resin (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 Seiko Co., Ltd.) was added, and dispersion and mixing were carried out for 30 minutes, and the polymerization initiators 2 and 2 were added. 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 of hydrochloric acid were added to prepare an aqueous sodium phosphate solution. It was heated 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. An aqueous solution of calcium chloride was added to the above-mentioned aqueous solution of sodium phosphate, and T.I. 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.I. K. A dispersion of a polymerizable monomer composition was obtained by stirring with a homomixer (manufactured by Tokushu Kagaku Kogyo Co., Ltd.) at a peripheral speed of 25 m / s for 20 minutes.
(Polymerization reaction step)
The dispersion liquid 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 the reaction was carried out for 4 hours. Then, 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. Then, after filtering and washing with water, it was dried at a temperature of 40 ° C. for 48 hours to obtain toner particles.
(External 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 (mean number of primary particles: 7 nm) were mixed with FM mixer (Nippon Coke Industries Co., Ltd., formerly Mitsui Miike Machinery Co., Ltd.)) mixed for 10 minutes to obtain toner A1.
The fixability of the obtained toner was evaluated by the method shown below.

<Evaluation of fixability>
The toner was loaded into an iRC3220N (manufactured by Canon) remodeling machine from which the fixing roller was removed, and an unfixed image in which the ^{amount of toner loaded on the paper was 0.55 mg / cm 2 was output.}
The obtained unfixed image was fixed using an external fixing device under the conditions of a paper feed rate of 100 mm / s and a roller load of 294N. As the external fuser, an iRC3220N (manufactured by Canon) fuser was removed to the outside so that it could operate outside the laser beam printer.
In the evaluation, 9 points were shaken every 10 ° C. in 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 220 ° C.). It was evaluated by how many points were present in all 9 points at 220 ° C.). A plain paper of 64 g / m ² was used for the evaluation.
A: 5 points or more Very good B: 4 points Good C: 2-3 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 were obtained in the same manner as in Example A1 except that the release agent dispersions 2 to 14 shown in Table 1 were used instead of the release agent dispersion 1. It was. Moreover, the fixability was evaluated in the same manner as the toner A1.
Table 1 shows the following results. In addition, (1), (2), (3), (4), (5), (6-1), (6-2) and (6-3) in the table mean the following description.
(1) Conditions of the dispersion step according to the release agent dispersions 1 to 14 (2) The median diameter (μm) based on the volume of the release agent in the release agent dispersion.
(3) Evaluation of dispersibility based on the volume-based median diameter (μm) of the release agent (4) Toner volume-based median diameter (Dv50) (μm)
(5) Toner particle size distribution (Dv50) / (Dn50)
(6) Evaluation of fixability (6-1) Fixing temperature range where offset does not occur (6-2) Number of fixing temperature points where offset does not occur, which exists in all 9 points from 140 ° C to 220 ° C (6-3) ) Evaluation result based on the fixing temperature score without offset
Further, Example A2, Example A10 and Example A11 are referred to as Reference Example A2, Reference Example A10 and Reference Example A11, respectively.

An example of producing the colorant dispersion liquid will be described below.
(Production example of colorant dispersion 1)
As pre-dispersion, the following components are placed in a temperature-adjustable container, and using Ultratarax T-50 (manufactured by IKA), the liquid temperature is always kept at 50 ° C. or lower, and the mixture is stirred at 10000 rpm for 40 minutes to roughly disperse the colorant. Obtained liquid. The volume-based median diameter of the colorant particles in the colorant crude dispersion was 10.5 μm.

-Styrene 44.0 parts by mass-Colorant 8.0 parts by mass (CI Pigment Red 122, manufactured by Clariant AG)
-Charge control agent 1.0 part by mass (Bontron E88; manufactured by Orient Chemical Industry Co., Ltd.)
-Sulfonic acid group-containing resin 0.5 parts by mass (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 Fushitora Metal Industry Co., Ltd.) was used.
Further, as the disperser 8, an OB mill (manufactured by ORIVER BATLLE) was used.
First, the entire amount of the crude colorant dispersion (30 L) was charged into the holding tank 1 (cooling water at 10 ° C. passed through the jacket 3).
Next, the colorant was dispersed under the following conditions to obtain a colorant dispersion liquid 1.
Bead material: Zirconia Bead diameter: 0.5 mm
Circulating flow rate: 5 L / min
Peripheral speed of rotating body: 13 m / 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 degassing 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 (that is, [BA]) 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. Further, the temperature rise of the colorant dispersion was suppressed by flowing cooling water at 10 ° C. through the jacket 3. The temperature of the colorant dispersion liquid after the completion of the dispersion step was 15 ° C. The volume-based median diameter of the colorant in the colorant dispersion after the completion of the dispersion step was 0.172 μm. The true specific gravity of the crude colorant 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 liquid 1, except that the deforming pump (manufactured by Fushitora Metal Industry Co., Ltd.) was changed to the defoaming / degassing pump ASP type (manufactured by Yokota Seisakusho 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 liquid 1 ^{, the suction pressure was adjusted so that [BA] was 47 (Kg / m 3} ) and the ratio of the bulk specific gravity B to the true specific gravity C was 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 liquid 1, when the viscosity of the liquid reaches 1.0 (Pa · s), the degassing device 6 attached to the pump 7 is operated, and [BA] is 68 (Kg). / M ³ ) and the colorant dispersion liquid 4 was adjusted in the same manner as in the production example of the colorant dispersion liquid 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 5)
In the production example of the colorant dispersion liquid 1, when the viscosity of the liquid reaches 1.0 (Pa · s), the degassing device 6 attached to the pump 7 is operated, and [BA] is 68 (Kg). / M ³ ), and the colorant dispersion liquid 5 was prepared in the same manner as in the production example of the colorant dispersion liquid 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. Manufactured.

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

(Production example of colorant dispersion 7)
In the production example of the colorant dispersion liquid 1 ^{, the suction pressure was adjusted so that [BA] was 33 (Kg / m 3} ) and the ratio of the bulk specific gravity B to the true specific gravity C was 0.95. , The colorant dispersion 7 was produced in the same manner as in the production example of the colorant dispersion 1.

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

(Production Example of Colorant Dispersion Solution 9)
In the production example of the colorant dispersion liquid 1, the OB mill (manufactured by ORIVER BATLLE) was changed to a sharp flow mill (manufactured by Pacific Kiko Co., Ltd.) as the disperser 8, and the dispersion conditions were changed to the following, [B The suction pressure was adjusted so that −A] was 17 (Kg / m ³ ) and the ratio of the bulk specific gravity B to the 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: 5 L / min
Peripheral speed of rotating body: 60 m / 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 liquid 1, the deforming pump (manufactured by Fushitora Metal Industry Co., Ltd.) was changed to the defoaming / degassing pump ASP type (manufactured by Yokota Seisakusho Co., Ltd.) as the pump 7 to disperse. As the machine 8, the OB mill (manufactured by ORIVER BATLLE) was changed to a sharp flow mill (manufactured by Pacific Kiko Co., Ltd.), and the dispersion conditions were changed to the following, and [BA] was 12 (Kg / m ³ ). Moreover, 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: 5 L / min
Peripheral speed of rotating body: 60 m / s
Back pressure: 0.2 MPa
Dispersion time: 180 min

(Production example of colorant dispersion liquid 11)
In the production example of the colorant dispersion liquid 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 (manufactured by Nippon Coke Industries Co., Ltd., formerly Mitsui Miike Kakoki Co., Ltd.) was used to disperse the colorant in a batch under the following conditions.
At this time, cooling water at 10 ° C. was passed through the jacket 3 of the handy mill. Further, 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 with the parts other than the degassing port 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 colorant dispersion liquid 1, but the colorant dispersion liquid contained in the holding tank 1 had a high viscosity and a deep liquid depth. No degassing action was observed, and the bulk specific gravity of the liquid could not be adjusted. A colorant dispersion 11 was obtained in the same manner as in the production example of the colorant dispersion 1 except for the above.
Bead material: Zirconia Bead diameter: 3 mm
Peripheral speed of rotating body: 8.4 m / s
Dispersion time: 180 minutes

(Production example of colorant dispersion liquid 12)
In the production example of the colorant dispersion liquid 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, for the holding tank provided in the holding tank 1. The degassing device 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 colorant dispersion liquid 1, but the colorant dispersion liquid contained in the holding tank 1 had a 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 liquid 12 was produced in the same manner as in the production example of the colorant dispersion liquid 1.

(Production Example of Colorant Dispersion Solution 13)
In the production example of the colorant dispersion liquid 1, the colorant was used in the same manner as in the production example of the colorant dispersion liquid 1 except that the degassing port of the pump 7 was completely closed and the degassing device 6 was not activated. The dispersion liquid 13 was produced.

[Example B1]
Toner was manufactured by the following procedure.
(Preparation of polymerizable monomer composition)
Put the following ingredients in the same container, and T.I. K. Using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), mixing and dispersion were performed at a peripheral speed of 20 m / s.
-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 terephthal Polycondensate with acid (polymerization molar ratio 10:12), glass transition temperature (Tg): 68 ° C., weight average molecular weight (Mw): 10000, weight average molecular weight (Mw) / number average molecular weight (Mn): 5 .12]
12.0 parts by mass of polar resin [styrene-methacrylic acid-methyl methacrylate copolymer (copolymerization mass ratio 94.0: 3.5: 2.5), peak molecular weight (Mp): 15,500, glass Transition temperature (Tg): 90 ° C., acid value: 21 mgKOH / 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 Seiko Co., Ltd.) was added, and dispersion and mixing were carried out for 30 minutes, and the polymerization initiators 2 and 2 were added. 9.0 parts by mass of'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

(Preparation of aqueous dispersion medium)
300.0 parts by mass of ion-exchanged water, 5.3 parts by mass of sodium phosphate dodecahydrate, and 2.2 parts by mass of 10% by mass hydrochloric acid were added to the granulation tank to prepare an aqueous sodium phosphate solution at 60 ° C. Was heated to.
3.1 parts by mass of calcium chloride dihydrate was dissolved in 25.0 parts by mass of ion-exchanged water to obtain an aqueous calcium chloride solution. An aqueous solution of calcium chloride was added to the above-mentioned aqueous solution of sodium phosphate, and T.I. 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.I. K. A dispersion of a polymerizable monomer composition was obtained by stirring with a homomixer (manufactured by Tokushu Kagaku Kogyo Co., Ltd.) at a peripheral speed of 25 m / s for 20 minutes.
(Polymerization reaction step)
The dispersion liquid 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 the reaction was carried out for 4 hours. Then, 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. Then, after filtering and washing with water, it was dried at a temperature of 40 ° C. for 48 hours to obtain toner particles.
(External 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 (average number of primary particles: 7 nm) were mixed with an FM mixer (Nippon Coke Industries Co., Ltd.). Mixing for 10 minutes gave toner B1.
The performance evaluation of the obtained toner was carried out by the method shown below.

<Toner performance evaluation>
(1) Coloring power As an image forming apparatus, a modified machine of a commercially available laser beam printer LBP-5400 (manufactured by Canon) was used. The evaluation machine was modified so that the process speed was 270 mm / sec by changing the gear and software of the evaluation machine 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 amounts of toner applied within the range were created. The image density of the obtained solid image was measured using "Macbeth Reflection Densitometer RD918" (manufactured by Macbeth), and after determining the relationship between the amount of toner on the transfer paper and the image density, the amount of toner glued on the transfer paper was 0. The tinting strength was evaluated relatively at the corresponding image density in the case of .3 mg / cm ^2.
A: Image density is 1.20 or more and very good B: Image density is 1.10 or more and less than 1.20 Excellent C: Image density is 1.00 or more and less than 1.10 There is no problem in actual use. D: Image density is less than 1.00 It causes a problem in actual use.

(2) As the OHP transparency image forming apparatus, a modified machine of a commercially available laser beam printer LBP-5400 (manufactured by Canon) was used. The evaluation machine was modified so that the process speed was 270 mm / sec by changing the gear and software of the evaluation machine main body.
An image was output on an OHP sheet "CG3700" (manufactured by 3M) under a normal temperature and humidity (N / N; 23.5 ° C., 60% RH) environment. The image on the obtained OHP sheet was made into a transparent image by OHP "9550" (manufactured by 3M), projected onto a white wall surface, and visually evaluated in 5 stages as described below.
A: Remarkably high transparency and good B: Good transparency C: Slightly dull D: Very 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 shown in Table 2 were used instead of the colorant dispersion 1. Moreover, the performance evaluation of the toner was carried out in the same manner as the toner B1.
Table 2 shows the following results. In addition, (1), (2), (3), (4), (5), (6), (7-1) and (7-2) in the table mean the following description.
(1) Conditions of the dispersion step according to the colorant dispersions 1 to 13 (2) The median diameter (μm) based on the volume of the colorant in the 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 the volume-based median diameter (μm) of the colorant (5) Toner volume-based median diameter (Dv50) (μm)
(6) Toner particle size distribution (Dv50) / (Dn50)
(7) Toner performance evaluation (7-1) Toner coloring power (7-2) OHP transparency
Further, Examples B1 to B10 are referred to as Reference Examples B1 to B10, respectively.

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

Claims (3)

A method for producing a toner, which comprises 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 is a step of repeatedly carrying out the following steps (i) to ( iii) to obtain a release agent dispersion liquid.
(I) The mixed solution is discharged from the tank containing the resin solution or the mixed solution containing the polymerizable monomer and the release agent, and the discharged mixed solution is dispersed by a pump. Process to be introduced into the machine;
(Ii) A step of dispersing the release agent by the disperser to obtain the dispersed mixed solution;
(Iii) A step of returning the dispersed mixed solution to the tank;
The disperser is a media disperser.
The mixture in the process of the (i) when introduced into the dispersing machine from the tank by the pump, the gas contained in the mixture to be conveyed from the tank to the dispersing machine, the mixture is said After leaving the tank and before entering the disperser , remove from the mixture and
The pump
A pair of pump screws that rotate without contact with each other,
A storage chamber for accommodating a 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 accommodation chamber.
A bearing portion that is connected to the pump casing and rotatably supports one end of the pair of pump screws in a cantilever shape.
With
The pump casing in the region where the pump chamber is formed is provided with an intake for taking the mixed solution into the pump chamber.
The pump casing on the idle end side of the pair of pump screws is provided with a discharge port for discharging the mixed liquid transferred from the pump chamber.
The mixed liquid taken into the pump chamber from the intake port is transferred by rotational driving of the pair of pump screws, discharged from the discharge port, and
In a twin-screw pump in which an outlet for extracting gas in the accommodating chamber is provided on the upstream side of the inlet in the transfer direction of the mixture and above the pump casing.
A degassing device for extracting gas from the containment chamber is connected to the outlet.
A method for producing toner, which is characterized by the fact that. In the dispersion step
The bulk specific gravity of the liquid before it was introduced into the pump was A (kg / m ³ ).
When the bulk specific gravity of the liquid after being derived from the pump is B (kg / m ³ ),
Satisfy A <B,
The method for producing toner according to claim 1. In the dispersion step
The bulk specific gravity and viscosity of the liquid after being 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 the mold release agent or When the true specific gravity of the mixed solution containing the colorant is C (kg / m ³ ), 1.0 ≦ D and 0.97 ≦ B / C ≦ 1.00.
Meet,
The method for producing toner according to claim 1 or 2.

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