JP6671137B2 - Toner processing apparatus and toner manufacturing method - Google Patents

Description

  The present invention relates to a processing apparatus for toner (hereinafter, may be simply referred to as “toner”) used for developing an electrostatic latent image in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or the like. And a method for producing a toner using the processing apparatus.

Conventionally, in a toner in a general electrophotographic method, a surface of a colored particle is treated with a fluidity improver (external additive) to control desired fluidity and charging characteristics. As the external additive, those generally and widely used are fine particles made of an inorganic substance or an organic substance.
As such external additives, metal oxide particles, resin particles, and their surface-treated products have been widely used.

Among them, a large particle size external additive having a 50% particle diameter (D50) of about 80 nm or more and 300 nm or less based on volume distribution of primary particles, which has a function as spacer particles and is mainly added for the purpose of improving durability. There is.
Generally, external additives may be embedded in the surface of the toner due to stress with the carrier of the two-component developer, stress with the toner conveying member or the thinning blade in the one-component development, or the like.
On the other hand, this large particle size external additive is different from the small particle size external additive having a 50% particle size (D50) of less than 80 nm based on the volume distribution of the primary particles, and the external additive is embedded in the toner surface. hard.

On the other hand, however, the external additives having a large particle diameter are hard to adhere to the toner particles. Therefore, if the external additives are continuously stirred in a device such as a printer for a long time, the strong stress causes the transfer from the toner particles to a member in an image forming apparatus such as a printer. However, the function as spacer particles may be lost.
In particular, when a large number of sheets are printed by a printer or the like, there is a case where a transfer occurs to a functional component in the printer, and there is a concern that the surface of a charging roller, which is a charging member for charging a photosensitive member, is contaminated. .

In recent years, there has been a demand for a toner having a high stress resistance and a long life for high image quality and a long life of a device such as a printer, and a processing apparatus for a toner which suppresses migration of such a large particle size external additive. The following technology is disclosed.
Patent Document 1 discloses that in a powder processing apparatus in which rotating blades are provided at a lower portion in a processing container for processing powder, powder sowed by rotation of the rotating blades is lifted above the rotating blades in the processing container. A powder processing apparatus provided with a guide member for guiding downward is disclosed.

  Further, Patent Document 2 discloses a stirring tank having a stirring tank, a rotary drive shaft and a stirring blade, and a stirring blade fixed to a rotary drive shaft penetrating a bottom wall of the stirring tank is arranged at the bottom of the stirring tank. There is disclosed an apparatus in which a metal ring to which a plurality of regulating plates are fixed is suspended from an upper portion of a stirring tank.

JP-A-11-216348 JP 2012-212062 A

In the powder processing apparatus disclosed in Patent Document 1, although the migration of the small particle size external additive can be reduced to some extent, the processing in the processing region described later by the present inventors is insufficient, so It was difficult to reduce additive transfer.
Although the apparatus disclosed in Patent Document 2 can fix the large particle size external additive, the temperature of the material rises to the glass transition point (Tg) of the resin component contained in the toner during operation, There was a risk that fusion and coarse particles would occur in the machine.
In order to keep the material temperature during operation below the glass transition point (Tg) of the resin component contained in the toner, the amount of the charged material may be reduced or the rotational peripheral speed of the stirring blade may be reduced. If the value is reduced, the toner productivity (= product output per unit time) deteriorates.
In addition, if the rotational peripheral speed of the stirring blade is reduced, the above-mentioned adverse effects such as the transfer of the external additive having a large particle size over a long period of time cannot be solved. Therefore, there is room for further study on an apparatus for improving both toner productivity and external additive transfer reduction.
SUMMARY OF THE INVENTION An object of the present invention is to provide a toner processing apparatus and a toner manufacturing method which solve the above problems.
That is, an object of the present invention is to provide a toner processing apparatus and a toner manufacturing method capable of increasing the adhesion of a large particle size external additive to the surface of toner particles by increasing the processing energy of the toner processing apparatus. I do.
Still another object of the present invention is to provide a toner processing apparatus and a toner manufacturing method that suppress a rise in temperature of a material during processing even when processing energy is increased.

As a result of repeated studies, the present inventors have found that the above-described requirements can be satisfied by adopting the following configuration of the present invention, and have accomplished the present invention.
That is, the present invention
Processing of the object to be processed including the toner particles and the external additive is performed, has a cylindrical internal space, a processing tank installed such that the central axis of the cylindrical internal space is substantially vertical,
A cooling jacket provided on the outer peripheral surface of the processing tank,
Flow means provided at the bottom of the processing tank, for flowing the object to be processed contained in the processing tank upward from the bottom of the processing tank,
A rotatable member is provided above the fluidizing means, and the rotor body and the rotor body protrude radially outward from an outer peripheral surface of the rotor body, and collide with the workpiece to process the workpiece. A rotating body having a processing unit;
The rotating body is disposed above the, with the <br/> the regulating plate for regulating an object to be processed on the inner wall surface of the processing bath,
The regulating plate is provided with a gap with the inner wall surface of the processing tank,
In a plane perpendicular to the central axis of the processing tank,
A straight line connecting the end of the regulating plate on the central axis side and the end on the inner wall surface side,
An angle straight line and forms in contact with the inner wall surface at the point of intersection between the straight line and the inner wall surface, and when the angle of the upstream side in the rotational direction of the rotary member and .theta.1,
The regulating plate is attached such that the angle θ1 is always 30 degrees or more and 85 degrees or less in the entire region in the central axis direction ,
On a plane parallel to the central axis of the processing tank, an angle θ2 formed by a vertical line and a straight line connecting an upper end and a lower end of the regulating plate is not less than 8 degrees and not more than 45 degrees. A processing device for a toner characterized by the above-mentioned.
Furthermore, the present invention is a method for producing a toner including an external addition step of fixing an external additive to the surface of toner particles, wherein the external addition step is performed using the above-described toner processing apparatus. .

According to the present invention, it is possible to provide a processing apparatus for a toner and a method for manufacturing a toner which suppresses a rise in the temperature of a material being processed while increasing input energy for fixing a large particle size external additive. it can.
Further, it is possible to provide an electrostatic image developing toner processing apparatus and a toner manufacturing method capable of suppressing contamination of a charging member or the like due to transfer of a large particle size external additive even during long-term use.

FIG. 1 is a schematic configuration diagram of a toner processing apparatus of the present invention. FIG. 3 is a schematic view of a regulation plate according to the embodiment. The schematic diagram of the processing tank of an embodiment. FIG. 2 is a schematic view of a flow unit of the embodiment. FIG. 3 is an explanatory diagram of a rotating body according to the embodiment. FIG. 5 is an explanatory diagram of an angle θ1 of the regulating plate according to the embodiment. Explanatory drawing of Gap of the regulation plate of embodiment. FIG. 4 is an explanatory diagram of an angle θ2 of the regulating plate according to the embodiment. FIG. 4 is a schematic diagram of a toner processing device in Comparative Examples 1 and 2. FIG. 10 is an explanatory diagram of an angle θ1 of a regulating plate according to another embodiment.

Hereinafter, preferred embodiments of the toner processing apparatus and the toner manufacturing method of the present invention will be described in detail.
[Processing unit for toner]
FIG. 1 shows a schematic view of a toner processing apparatus to which the present invention can be applied.
The processing apparatus 100 for a toner includes a processing tank 110 as a processing chamber for storing an object to be processed including toner particles and an external additive, and a stirring blade 120 as a flow means rotatably provided at the bottom of the processing tank 110. ing.
Further, the processing blade 140 is configured as a rotating body provided rotatably above the stirring blade 120.
Further, a regulation plate 130 as a regulation plate which is a feature of the present invention is fixed to the treatment tank 110 above the treatment blade 140.

[Treatment tank]
FIG. 3 shows a schematic diagram of the processing tank 110.
The processing tank 110 is a cylindrical container having a flat bottom and a cylindrical internal space, and has a drive shaft 111 for attaching the stirring blade 120 and the processing blade 140 at substantially the center of the bottom. The drive shaft 111 is the central axis of the cylindrical internal space, and the processing tank 110 is installed so that the central axis is substantially vertical. The processing tank 110 is preferably made of a metal such as iron or SUS from the viewpoint of strength, and it is preferable to use a conductive material for the inner surface or to perform conductive processing on the inner surface.

  A cooling jacket 112 is provided on the outer periphery of the processing tank 110. The cooling jacket 112 is hollow, and has a configuration in which a coolant such as cooling water can be introduced from the IN side and discharged from the OUT side. By passing a cooling medium through the cooling jacket 112, the temperature of the material heated during processing can be reduced.

[Flow means]
FIG. 4 shows a schematic view of the stirring blade 120. FIG. 4A is a top view, and FIG. 4B is a side view.
The stirring blade 120 causes the object to flow (up) in the processing tank 110.
The stirring blade 120 has a blade portion extending from the center to the outside, and has a shape in which the tip of the blade portion is flipped up so as to fly up the object to be processed.
The shape of the blade can be appropriately designed depending on the size and operating conditions of the toner processing apparatus, the amount of the material to be processed, and the specific gravity.
The stirring blade 120 is preferably made of a metal such as iron or SUS from the viewpoint of strength, and may be plated or coated for wear resistance as needed.
The stirring blade 120 is fixed to the drive shaft 111 at the bottom of the processing tank 110, and rotates clockwise as viewed from above. It is considered that the object to be processed rises while rotating clockwise in the processing tank 110 by the rotation of the stirring blade 120, and then descends due to gravity, so that the object to be processed can be uniformly mixed.

[Rotating body]
FIG. 5 shows a schematic diagram of the processing blade 140. FIG. 5A is a top view, and FIG. 5B is a side view.
The processing blade 140 collides with the flowing workpiece to process the workpiece.
The processing blade 140 includes an annular processing blade main body (rotary body main body) 141 and a processing unit 142 protruding radially outward from an outer peripheral surface of the processing blade main body 141.
The treatment blade 140 is preferably made of a metal such as iron or SUS from the viewpoint of strength, and may be plated or coated for wear resistance as needed.

[Regulation plate]
FIG. 2 is a schematic diagram in which a regulating plate (deflector) 130 is attached to the processing tank 110. 2A is a top view, and FIG. 2B is a perspective view.
In the present invention, the regulating plate is disposed above the rotating body. In the embodiment, the regulating plate 130 corresponding to the regulating plate is fixed to the upper lid of the processing tank 110 by the shaft 131.
The regulating plate 130 has a rectangular or fan-shaped plate shape, and is attached along the inner wall surface while having a gap with the inner wall surface of the processing tank 110.
The regulation plate 130 is preferably made of a metal such as iron or SUS from the viewpoint of strength, and may be plated or coated for wear resistance as needed.

The angle between the regulating plate 130 and the inner wall surface of the processing tank 110 will be described with reference to FIG. FIG. 6 is a horizontal sectional view showing a state in which the regulating plate 130 is attached to the processing tank 110. In this case, it is a cross-sectional view of the uppermost part of the regulating plate 130 at the position indicated by the dotted line A in FIG. 2B.
As shown in FIG. 6, the regulating plate 130 is formed on a plane perpendicular to the drive shaft 111 (center axis).
A straight line 601 connecting the end of the regulating plate 130 on the central axis side of the processing tank and the end of the regulating plate 130 on the inner wall surface side of the processing tank;
Attachment is made such that an angle θ1 between a straight line 601 and a straight line 602 contacting the inner wall surface of the processing tank 110 at the intersection of the inner wall surface is set to a predetermined angle.

The angle θ1 is an angle formed by the straight line 601 and the straight line 602, and is an angle on the upstream side in the rotation direction of the processing blade (rotary body) 140.
As shown in FIG.
The processing blade 140 rotates clockwise,
When the regulating plate 130 is located below the processing blade 140,
The position of the angle θ1 is on the right side of the regulating plate 130.
The restricting plate 130 is attached so that the angle θ1 is always less than 90 degrees in the entire region in the central axis direction.

The gap between the regulating plate 130 and the inner wall surface of the processing tank 110 will be described with reference to FIG. FIG. 7 is a horizontal sectional view showing a state where the regulating plate 130 is attached to the processing tank 110. In this case, it is a cross-sectional view of the uppermost part of the regulating plate 130 at the position indicated by the dotted line A in FIG. 2B. Note that the cooling jacket 112 is omitted in FIG. 2B for convenience of drawing.
In FIG. 7, the distance between the end of the regulating plate 130 on the side close to the inner wall surface of the processing tank 110 and the inner wall surface of the processing tank 110 is set with a predetermined gap (Gap) therebetween.

The inclination angle of the regulating plate 130 in the vertical direction will be described with reference to FIG. FIG. 8 is a vertical sectional view showing a state where the regulating plate 130 is attached to the processing tank 110. In this case, the positional relationship between the regulating plate 130 and the processing tank 110 when viewed from the direction indicated by the arrow B in FIG.
As shown in FIG. 8, on a plane parallel to the drive shaft 111 (center axis) of the processing tank 110, an angle formed by a vertical line and a straight line connecting the upper end and the lower end of the regulating plate 130. It is set and attached so that θ2 becomes a predetermined angle.
The specific angle of θ2 will be described later.

[Behavior of workpiece during toner processing]
The operation of the regulating plate will be described below.
In the processing tank 110 in the toner processing, an airflow swirling in the processing tank 110 is generated by the rotation of the stirring blade 120.
At this time, since the stirring blade 120 rotates at the bottom of the processing tank 110, the air current flows upward from the bottom along with the rotation.

It is considered that the temperature of the object to be processed such as the toner particles and the external additive during the processing increases with the progress of the processing due to the generation of frictional heat due to the collision or shear with the stirring blade 120 or the processing blade 140.
In order to maintain the quality of the processing target, it is necessary to perform the toner processing at a predetermined temperature or lower as described above. In the toner processing apparatus, the temperature of the object to be processed is maintained at a predetermined temperature or lower by passing cooling water through the cooling jacket 112.

However, when the processing energy of the toner processing apparatus is increased in order to increase the fixation of the large particle size external additive, the cooling of the object to be processed may be insufficient.
This is due to the fact that the object to be treated such as toner and external additives is fine particles and has a small mass. It is thought to be smaller.
Also, it is considered that when the fine particles having a small mass are swirled, the distribution of the object in the processing tank 110 may be segregated upward due to the object being swirled up.

Since the cooling jacket 112 is provided on the side wall (outer wall side) of the processing tank 110, the processing target that has been strongly processed and has increased in temperature is brought into contact with the inner wall surface, whereby the temperature of the processing target is lowered. is there.
However, if the amount of the object to be processed that contacts the inner wall surface is small, the cooling effect of the cooling jacket 112 may be weakened.
Also, when the object to be processed is segregated upward, the amount of the object to be processed below the inner wall surface may be reduced, and the effect of the cooling jacket 112 may be reduced.

In order to solve the above problem, it is desirable to segregate the object to be processed near the inner wall surface of the processing tank 110 and increase the amount of the object to be brought into contact with the cooling jacket.
Further, it is desirable that the segregation of the object to be processed is suppressed in the upward direction of the cooling jacket 112 while suppressing the segregation of the object to be processed upward.

[Function of restriction plate]
The function of the regulating plate 130 will be described.
The regulating plate 130 regulates the flow of the workpiece to be swirled in the processing tank 110.
In the processing apparatus for toner of the present invention, by setting the angle θ1 shown in FIG. 6 to less than 90 degrees, the rotating object is regulated on the inner wall surface side of the processing tank 110 when passing through the regulating plate 130. FIG. 6 shows the angle of θ1 at the position of the dotted line A in FIG. 2B. In the present invention, the restricting plate always has an angle θ1 of less than 90 degrees in the entire region in the central axis direction. It is attached so that it becomes.
The presence of a large amount of the object to be processed on the inner wall surface of the processing tank 110 can enhance the cooling effect of the cooling jacket 112.
If the angle of θ1 shown in FIG. 6 is 90 degrees or more, the turning object is likely to be regulated toward the center of the processing tank 110 when passing through the regulating plate 130. Therefore, the number of objects to be processed near the inner wall surface of the processing tank 110 is reduced, and the cooling effect of the cooling jacket 112 is reduced.

The gap (Gap shown in FIG. 7) between “the end of the regulating plate 130 and the end near the inner wall surface of the processing tank 110” and “the inner wall surface of the processing tank” is 1 mm or more and the processing tank 110 Is preferably 15% or less of the radius.
By doing so, it is considered that the object to be swirled can pass through the gap portion and swivel along the inner wall surface of the processing tank 110.

When the gap is 1 mm or more, the object to be processed can pass smoothly, and the object to be processed does not stay in the region surrounded by the inner wall surface of the processing tank 110 and the regulating plate 130. An object can sufficiently contact the cooling jacket 120.
When the gap is 15% or less of the radius of the processing tank 110, the effect of the control plate 130 is sufficient, and the object flows smoothly along the inner wall surface of the processing tank 110.

Further, as shown in FIG. 8, it is preferable that the regulating plate 130 is inclined downward in the rotation direction of the stirring blade 120 and the processing blade 140 from the upper side to the lower side of the processing tank 110.
It is considered that the object to be processed when reaching the regulation plate 130 also changes the flow in the vertical direction.
Since the airflow in the processing tank is a swirling flow from the bottom to the top, the object to be processed is easily segregated upward. However, the distribution in the downward direction is increased by inclining the regulating plate 130 as described above, and the cooling jacket 112 is cooled. This is preferable because the object to be processed in contact with can be made uniform in the vertical direction.

It is preferable that the inclination angle (the angle of θ2 in FIG. 8) of the regulating plate with respect to the vertical direction is not less than 8 degrees and not more than 45 degrees.
When θ2 is 8 degrees or more, upward segregation of the object can be sufficiently suppressed.
When θ2 is 45 degrees or less, there is no possibility that the object to be processed is prevented from rising too much, resulting in downward segregation.
Therefore, in order to uniformly rotate the amount of the object to be processed in contact with the cooling jacket 112 in the vertical direction, it is preferable to set the angle θ2 in FIG. It is more preferable to set the angle in the range of 10 degrees or more and less than 45 degrees because the amount of the object to be processed can be made more uniform in the vertical direction.

[Manufacture of toner]
Next, an example of a method for producing a toner using the toner processing apparatus of the present invention will be described.
The method for producing the toner particles is not particularly limited, and a conventionally known production method can be used, and the present invention can be applied to various toner particles such as a polymerization method, a pulverization method, an emulsion aggregation method, and a melt suspension method. .

[Production method of pulverized toner particles]
Here, a description will be given of a procedure for manufacturing a toner using a pulverization method.
In the raw material mixing step, a predetermined amount of a binder resin, a colorant, a wax, and, if necessary, other components such as a charge control agent are weighed and mixed as materials constituting the toner particles, and are mixed.
Examples of the mixing apparatus include a super mixer (manufactured by Kawata Corporation), an FM mixer, a mechano hybrid (manufactured by Nippon Coke Industry Co., Ltd.), a Nauta mixer (manufactured by Hosokawa Micron Corporation), and the like.

Next, the mixed materials are melt-kneaded to disperse wax and the like in the binder resin. In the melt kneading step, a batch kneader such as a pressure kneader or a Banbury mixer or a continuous kneader can be used.
A single- or twin-screw extruder has become mainstream because of its superiority in continuous production.
For example, a KTK type twin screw extruder (manufactured by Kobe Steel, Ltd.), a TEM type twin screw extruder (manufactured by Toshiba Machine Co., Ltd.), a PCM kneader (manufactured by Ikegai Co., Ltd.), Kneedex (Nihon Coke Industries Co., Ltd.).
Further, the resin composition obtained by melt-kneading may be rolled with two rolls or the like, and cooled with water or the like in a cooling step.

Next, the cooled product of the resin composition is pulverized to a desired particle size in a pulverizing step.
In the pulverizing step, after coarsely pulverizing with a pulverizer such as a crusher or a hammer mill, a fine pulverizer such as a Kryptron system (manufactured by Earth Technica Co., Ltd.) or a turbo mill (manufactured by Freund Turbo Co., Ltd.) And pulverize.
Then, if necessary, a classifier such as an inertial classification type elbow jet (manufactured by Nippon Mining Co., Ltd.), a centrifugal classification type TSP separator (manufactured by Hosokawa Micron Corp.), a faculty (hosokawa micron Corp.), or the like. Classification is performed using a sieving machine to obtain toner particles.

[Method for producing polymerized toner particles]
Examples of the polymerization method include a method of directly manufacturing a toner in a hydrophilic medium, such as a suspension polymerization method, an interfacial polymerization method, and a dispersion polymerization method.
Hereinafter, a procedure for producing a toner using the suspension polymerization method will be described.
The suspension polymerization method is a polymerization method in which toner base particles are produced through at least a granulation step and a polymerization step. The granulating step is a step of dispersing a polymerizable monomer composition having at least a polymerizable monomer, a colorant, and a wax in an aqueous medium to produce droplets of the polymerizable monomer composition. It is. The polymerization step is a step of polymerizing the polymerizable monomer in the droplet.
Then, when producing the toner of the present invention, it is preferable to include a low molecular weight resin in the polymerizable monomer composition.

  The toner of the present invention is preferably a toner having toner base particles having at least a core portion and a shell portion. The toner base particles have a shell portion so as to cover the core portion. By adopting such a structure, it is possible to prevent poor charging and blocking due to oozing of the toner particles on the surface of the core. Further, it is more preferable that a surface layer having a different resin composition from the shell is present on the surface of the shell. The presence of this surface layer can further improve environmental stability, durability, and blocking resistance.

  Preferred polymerizable monomers that can be used to produce the toner base particles of the present invention include vinyl polymerizable monomers. For example, 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-octyl, 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-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl Phosphate ethyl methacrylate, dibutyl phosphate Methacrylic polymerizable monomers such as methyl methacrylate; methylene aliphatic monocarboxylic esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl benzoate and vinyl formate; vinyl methyl ether; Vinyl ethers such as vinyl ethyl ether and vinyl isobutyl ether; and vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  The shell part is constituted by a vinyl polymer formed from these vinyl polymerizable monomers or an added vinyl polymer. Among these vinyl polymers, a styrene polymer, a styrene-acrylic copolymer, or a styrene-methacrylic copolymer is preferred from the viewpoint of efficiently covering the wax mainly forming the inner or central part.

Wax is preferred as the material constituting the core of the toner of the present invention.
Examples of the wax component usable in the toner according to the present invention include paraffin wax, microcrystalline wax, petroleum wax such as petrolatum and its derivatives, montan wax and its derivatives, Fischer-Tropsch hydrocarbon wax and its derivatives, polyethylene, Polyolefin wax such as polypropylene and its derivatives, natural wax such as carnauba wax and candelilla wax and its derivatives, etc. The derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. Furthermore, fatty acids such as higher aliphatic alcohols, stearic acid, and palmitic acid, or compounds thereof, acid amide waxes, ester waxes, ketones, hydrogenated castor oil and derivatives thereof, vegetable waxes, animal waxes, and silicone resins can also be used. .

[External processing]
The apparatus of the present invention shown in FIG. 1 is used as a processing apparatus for fixing an external additive to the surface of toner particles obtained in this manner. The processing blade 140 is located above the stirring blade 120, is fixed to the same drive shaft 111 as the stirring blade 120, and rotates clockwise as viewed from above. It is considered that the rotation of the processing blade 140 causes the processing target 142 to collide with the object to be processed, so that the toner particles and the external additive are processed, and the external additive is crushed or fixed to the toner particles.
The operation method is as follows.
The rotation peripheral speed of the processing blade 140 of the toner processing apparatus 100 shown in FIG. 1 is set within a predetermined range described later.

Next, the upper lid of the processing tank 110 is opened, and an object to be processed including the toner particles and the external additive that has been measured in advance is charged. After the charging, the upper lid is closed, and the processing blade 140 is rotated at a rotational peripheral speed described below.
Further, while the processing blade 140 is rotating, the cold water from the cold water generating means is supplied to the cooling jacket 112 so that the temperature of the material in the processing tank 110 falls below the glass transition point (Tg) of the resin component contained in the toner. adjust.

After performing the processing for a desired time, the discharge valve (not shown) is opened, and the toner is taken out of the processing tank 110. Thereafter, the mixture is passed through a mesh having an opening of about 35 μm to 75 μm to remove coarse particles, thereby obtaining a toner.
It is preferable that the rotation peripheral speed and the mixing time of the processing blade 140 be adjusted in a range where the material temperature during the processing is equal to or lower than the glass transition point (Tg) of the resin component contained in the toner.

Specifically, the maximum peripheral speed of the rotational speed of the processing blade 140 is preferably 10.0 m / sec or more and 150.0 m / sec or less, more preferably 30.0 m / sec or more and 70.0 m / sec. It is preferable to adjust in the range of seconds or less.
In particular, in consideration of the fixing process of the external additive, it is preferable to set the peripheral speed of the distal end of the processing unit 140 to 30 m / sec or more. If the speed is lower than 30 m / sec, it is necessary to fix the external additive to the toner particles insufficiently or to increase the processing time for fixing.

It is preferable to adjust the mixing time in a range from 0.5 minutes to 60 minutes.
The step of treating the toner particles and the external additive may be performed in one stage or in two or more stages, and the mixing conditions and the blending of the toner particles used in each stage are the same. May also be different.

[Binder resin]
Next, the toner used in the present invention will be described. As the toner used in the present invention, known toners can be used, and toners produced by any method such as a pulverization method, a polymerization method, an emulsion aggregation method, and a solution suspension method may be used.
As the binder resin constituting the toner, a resin that is usually used for a toner can be used. The following are mentioned.

In the toner suitably used in the present invention, examples of the binder resin include polystyrene; a styrene-substituted homopolymer such as poly-p-chlorostyrene and polyvinyltoluene; and a styrene-p-chlorostyrene copolymer.
Further, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, a styrene-acrylate copolymer, a styrene-methacrylate copolymer, and a styrene-α-chloromethyl methacrylate copolymer are exemplified. .

Further, a styrene-acrylonitrile copolymer, a styrene-vinyl methyl ether copolymer, a styrene-vinyl ethyl ether copolymer, a styrene-vinyl methyl ketone copolymer, and a styrene-butadiene copolymer are exemplified.
Further, styrene-based copolymers such as styrene-isoprene copolymer and styrene-acrylonitrile-indene copolymer; polyvinyl chloride, phenolic resin, naturally-modified phenolic resin, natural-resin-modified maleic acid resin, and acrylic resin.
Further, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral resin, terpene resin, cumarone indene resin and petroleum resin are exemplified.

Among the physical properties of the toner, those having a molecular weight distribution measured by gel permeation chromatography (GPC), which is soluble in tetrahydrofuran (THF), are preferably as follows.
That is, it is more preferable that at least one peak is present in a region having a molecular weight of 2,000 or more and 50,000 or less, and a component having a molecular weight of 1,000 or more and 30,000 or less is present at 50% to 90%.

The glass transition point (Tg) of the binder resin is preferably from 30 ° C to 60 ° C, more preferably from 40 ° C to 60 ° C.
When the glass transition point (Tg) is within the above range, the toner has excellent durability, and aggregation of toner particles in a high-temperature and high-humidity environment is suppressed.

[wax]
In the toner suitably used in the present invention, the following wax is used as a material of the toner particles from the viewpoint of improving the releasability from the fixing member at the time of fixing and improving the fixing property.
Examples of the wax include paraffin wax and its derivatives, microcrystalline wax and its derivatives, Fischer-Tropsch wax and its derivatives, polyolefin wax and its derivatives, and carnauba wax and its derivatives.

Derivatives of these waxes include oxides, block copolymers with vinyl monomers, and graft-modified products.
Other waxes include alcohols, fatty acids, acid amides, esters, ketones, hydrogenated castor oil and derivatives thereof, vegetable waxes, animal waxes, mineral waxes, and petrolactam.

[Charge control agent]
In the toner suitably used in the present invention, in order to control the charge amount and the charge amount distribution of the toner particles, a charge control agent is mixed (internally added) to the toner particles or mixed (externally added) with the toner particles. Preferably, it is used.
Examples of the negative charge control agent for controlling the toner to negative charge include organic metal complexes and chelate compounds. Examples of the organometallic complex include a monoazo metal complex, an acetylacetone metal complex, an aromatic hydroxycarboxylic acid metal complex, and an aromatic dicarboxylic acid metal complex.

Further, examples of the negative charge control agent include aromatic hydroxycarboxylic acid, aromatic monocarboxylic acid and aromatic polycarboxylic acid and metal salts thereof; and aromatic hydroxycarboxylic acid, aromatic monocarboxylic acid and aromatic polycarboxylic acid anhydride. Things.
Further, there may be mentioned ester compounds of aromatic hydroxycarboxylic acids, aromatic monocarboxylic acids and aromatic polycarboxylic acids, and phenol derivatives such as bisphenol.

Examples of the positive charge control agent for controlling the toner to have a positive charge include nigrosine and a modified product of nigrosine with a fatty acid metal salt; and tributylbenzylammonium-1-hydroxy-4-naphthosulfonate.
Further examples include quaternary ammonium salts such as tetrabutylammonium tetrafluoroborate and lake pigments thereof; and tributylbenzylphosphonium-1-hydroxy-4-naphthosulfonate.

Further, phosphonium salts such as tetrabutylphosphonium tetrafluoroborate and their lake pigments; triphenylmethane dyes and these lake pigments (as the lake-forming agent, phosphotungstic acid may be mentioned.
Furthermore, metal salts of phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids.

These charge control agents can be used alone or in combination of two or more. Further, a charge control resin can also be used, and can be used in combination with the above charge control agent.
The charge control agent described above is preferably used in the form of fine particles. When these charge control agents are internally added to the toner particles, it is preferable to add 0.1 to 20.0 parts by mass to the toner particles based on 100.0 parts by mass of the binder resin.

[Colorant]
In the toner suitably used in the present invention, conventionally known various colorants can be used as a material of the toner particles.
The colorant used in the present invention, as a black colorant, is magnetized, carbon black, a yellow colorant shown below, a magenta colorant and a chromatic colorant such as a cyan colorant are combined so as to be blackened. Is used. In particular, dyes and carbon black need to be carefully used because many of them have polymerization inhibitory properties.

As the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds and allylamide compounds are used.
Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111.
Furthermore, there are 120, 127, 128, 129, 147, 155, 162, 168, 174, 176, 180, 181, 185, 191.

As the magenta coloring agent, a condensed azo compound, a diketopyrrolopyrrole compound, an anthraquinone, a quinacridone compound, a basic dye lake compound, a naphthol compound, a benzimidazolone compound, a thioindigo compound, and a perylene compound are used.
Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 31, 48; 2, 48; 3, 48; 4, 57; 1, 81;
Further, there are 144, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, and 254.

As the cyan coloring agent, a copper phthalocyanine compound and its derivative, an anthraquinone compound, and a basic dye lake compound are used.
Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.
These colorants can be used alone or as a mixture or in the form of a solid solution.
In the present invention, the colorant is selected in consideration of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in a toner.
These chromatic non-magnetic coloring agents have a total amount of 1.0 to 20.0 parts by mass based on 100 parts by mass of the binder resin in the toner particles.

Further, the toner of the present invention can be made a magnetic toner by containing a magnetic material as a colorant.
In this case, the magnetic material can also serve as a colorant. Examples of the magnetic material include iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel, or aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, and the like. Alloys of metals such as calcium, manganese, selenium, titanium, tungsten, vanadium and mixtures thereof.

The magnetic material is more preferably a surface-modified magnetic material.
When a magnetic toner is prepared by a polymerization method, it is preferable that the magnetic toner is subjected to a hydrophobic treatment with a surface modifier which is a substance having no polymerization inhibition.
Examples of such a surface modifier include a silane coupling agent and a titanium coupling agent. These magnetic materials preferably have a number average particle size of 2 μm or less, more preferably 0.1 to 0.5 μm.
The amount to be contained in the toner particles is 20 to 200 parts by mass, particularly preferably 40 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the binder resin. good.

[External additives]
In the toner suitably used in the present invention, an external additive as fine particles is fixed to the surface of the toner particles. By fixing the fine particles, the fluidity and transferability of the toner particles can be improved.
The external additive fixed to the surface of the toner particles preferably contains any one of titanium oxide, alumina oxide, and silica fine particles.

The surface of the fine particles contained in the external additive is preferably subjected to a hydrophobic treatment.
The hydrophobizing treatment is preferably performed by a coupling agent such as various titanium coupling agents and silane coupling agents; fatty acids and metal salts thereof; silicone oil; or a combination thereof.
Among various combinations, it is preferable to add a large particle size external additive having a number average particle diameter of 80 nm or more and 300 nm or less as one of the fine particles. The reason is that it has a function as a spacer particle and can mainly improve transferability.

Examples of the material include silica, alumina, titanium oxide, cerium oxide and the like.
In the case of the silica, for example, any silica produced by a conventionally known technique such as a gas phase decomposition method, a combustion method, and a deflagration method can be used. Among them, silica particles obtained by a sol-gel method capable of sharpening the particle size distribution are preferable.
The content of the external additive in the toner is preferably from 0.1% by mass to 10.0% by mass, and more preferably from 0.5% by mass to 8.0% by mass. Further, the external additive may be a combination of plural kinds of fine particles.

When a toner and a magnetic carrier according to the present invention are mixed to prepare a two-component developer, the mixing ratio is 2% by mass or more and 15% by mass or less, preferably 4% by mass or more, as the toner concentration in the developer. When the content is 13% by mass or less, usually good results are obtained.
Hereinafter, methods for measuring various physical properties of the toner and the like in the present invention will be described.

[Method of Measuring Weight Average Particle Diameter (D4) of Toner]
The weight average particle diameter (D4) of the toner is calculated as follows.
As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube by a pore electric resistance method is used.

For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.
As the electrolytic aqueous solution used for the measurement, one prepared by dissolving a special grade sodium chloride in ion-exchanged water so as to have a concentration of 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter, Inc.) can be used.
Before performing the measurement and analysis, the dedicated software is set as follows.

On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count number in the control mode to 50,000 particles, set the number of measurements to 1, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter ( The value obtained using the above method is set.
By pressing the “threshold / noise level measurement button”, the threshold and the noise level are automatically set. Also, the current is set to 1600 μA, the gain is set to 2, and the electrolytic solution is set to ISOTON II, and a check is made in “Flush aperture tube after measurement”.
In the “pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to a logarithmic particle size, the particle size bin is set to a 256 particle size bin, and the particle size range is set from 2 μm to 60 μm.
The specific measuring method is as follows.

(1) 200 mL of the electrolytic aqueous solution is placed in a 250-mL round bottom beaker made of glass exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 revolutions / second.
Then, the dirt and air bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) 30 mL of the aqueous electrolytic solution is placed in a 100 mL flat bottom glass beaker.
A 10% by mass aqueous solution of a neutral detergent for cleaning a precision measuring instrument having a pH of 7 consisting of a nonionic surfactant, an anionic surfactant and an organic builder was used as a dispersant in the product, Wako Pure Chemical Industries, Ltd. ) Is diluted by 3 times with ion-exchanged water, and 0.3 mL of a diluent is added.

(3) An ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikkaki Bios Co., Ltd.) having two oscillators having an oscillation frequency of 50 kHz and having a phase shift of 180 degrees and having an electrical output of 120 W is prepared. I do.
3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and 2 mL of contaminone N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the electrolyte solution level in the beaker is maximized.

(5) While irradiating the aqueous solution in the beaker of (4) with ultrasonic waves, 10 mg of toner is added little by little to the aqueous solution and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds.
The ultrasonic dispersion is appropriately adjusted so that the water temperature of the water tank is 10 ° C. or more and 40 ° C. or less.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte aqueous solution of (5) in which toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to 5%. Then, measurement is performed until the number of particles to be measured reaches 50,000.

(7) Analyze the measured data with the dedicated software attached to the device, and calculate the weight average particle size (D4). The “average diameter” on the “analysis / volume statistical value (arithmetic average)” screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

[Measurement of BET specific surface area of toner]
The BET specific surface area of the toner is measured according to JIS Z8830 (2001). The specific measuring method is as follows.
As the measuring device, an "automatic specific surface area / pore distribution measuring device TriStar 3000 (manufactured by Shimadzu Corporation)" employing a gas adsorption method by a constant volume method as a measuring method is used. The setting of the measurement conditions and the analysis of the measurement data are performed using dedicated software “TriStar 3000 Version 4.00” attached to the apparatus, and a vacuum pump, a nitrogen gas pipe, and a helium gas pipe are connected to the apparatus. The value calculated by the BET multipoint method using nitrogen gas as the adsorption gas is defined as the BET specific surface area in the present invention.

The BET specific surface area is calculated as follows.
First, nitrogen gas is adsorbed on the toner, and the equilibrium pressure P (Pa) in the sample cell and the nitrogen adsorption amount Va (mol · g ⁻¹ ) of the toner at that time are measured. The relative pressure Pr, which is a value obtained by dividing the equilibrium pressure P (Pa) in the sample cell by the saturated vapor pressure Po (Pa) of nitrogen, is plotted on the horizontal axis, and the nitrogen adsorption amount Va (mol · g ⁻¹ ) is plotted on the vertical axis. Is obtained. Next, a monomolecular layer adsorption amount Vm (mol · g ⁻¹ ), which is an adsorption amount necessary for forming a monomolecular layer on the surface of the toner, is determined by applying the following BET formula.

Pr / Va (1-Pr) = 1 / (Vm * C) + (C-1) * Pr / (Vm * C)
(Here, C is a BET parameter, which is a variable that varies depending on the type of sample to be measured, the type of adsorption gas, and the adsorption temperature.)
When the X axis is Pr and the Y axis is Pr / Va (1-Pr), the BET equation is interpreted as a straight line having a slope of (C-1) / (Vm × C) and an intercept of 1 / (Vm × C). (This straight line is called a BET plot).
Straight line slope = (C-1) / (Vm × C)
Intercept of straight line = 1 / (Vm × C)

When the measured value of Pr and the measured value of Pr / Va (1-Pr) are plotted on a graph and a straight line is drawn by the least square method, the slope and intercept of the straight line can be calculated. By solving the above-described simultaneous equation of the slope and the intercept using these values, Vm and C can be calculated.
Further, the BET specific surface area S (m ² · g ⁻¹ ) of the toner is calculated from Vm and the molecular occupied cross-sectional area (0.162 nm ² ) of nitrogen molecules based on the following equation.
S = Vm × N × 0.162 × 10 ⁻¹⁸
(Here, N is Avogadro's number (mol- ¹ ).)

The measurement using this apparatus is in accordance with the “TriStar 3000 Instruction Manual V4.0” attached to the apparatus. Specifically, the measurement is performed according to the following procedure.
The tare of a thoroughly washed and dried glass sample cell (3/8 inch in stem diameter, about 5 mL in volume) is precisely weighed. Then, about 1.5 g of toner is put into this sample cell using a funnel.

  The sample cell containing the toner was set in "Pretreatment device VacuPrep 061 (manufactured by Shimadzu Corporation)" in which a vacuum pump and a nitrogen gas pipe were connected, and vacuum degassing was continued at a temperature of 23 ° C. for about 10 hours. I do. During vacuum degassing, the valve is gradually degassed while adjusting the valve so that the toner is not sucked into the vacuum pump. The pressure in the cell gradually decreases with degassing, and finally reaches about 0.4 Pa (about 3 mTorr). After completion of the vacuum deaeration, the inside of the sample cell is returned to atmospheric pressure by gradually injecting nitrogen gas, and the sample cell is removed from the pretreatment device. Then, the mass of the sample cell is precisely weighed, and the accurate mass of the toner is calculated from the difference from the tare. At this time, the sample cell is covered with a rubber stopper during weighing so that the toner in the sample cell is not contaminated by moisture in the atmosphere or the like.

Next, a dedicated “isothermal jacket” is attached to the stem of the sample cell containing the toner. Then, a special filler rod is inserted into the sample cell, and the sample cell is set in the analysis port of the apparatus. The isothermal jacket is a tubular member whose inner surface is made of a porous material and whose outer surface is made of an impermeable material, which can suck up liquid nitrogen to a certain level by capillary action.
Subsequently, the free space of the sample cell including the connection device is measured. The free space was measured at 23 ° C. using helium gas to measure the volume of the sample cell, followed by cooling the sample cell with liquid nitrogen and then measuring the volume of the sample cell using helium gas in the same manner. Calculated by converting from the difference in volume. Further, the saturated vapor pressure Po (Pa) of nitrogen is automatically measured separately using a Po tube built in the apparatus.

  Next, after performing vacuum degassing in the sample cell, the sample cell is cooled with liquid nitrogen while continuing vacuum degassing. Thereafter, nitrogen gas is introduced stepwise into the sample cell to cause the toner to adsorb nitrogen molecules. At this time, the above-mentioned adsorption isotherm is obtained by measuring the equilibrium pressure P (Pa) as needed, and this adsorption isotherm is converted into a BET plot. The points of the relative pressure Pr for collecting data are set to a total of 6 points of 0.05, 0.10, 0.15, 0.20, 0.25, and 0.30. A straight line is drawn from the obtained measurement data by the least squares method, and Vm is calculated from the slope and intercept of the straight line. Further, using the value of Vm, the BET specific surface area of the toner is calculated as described above.

[Measurement of glass transition point (Tg) of resin component contained in toner]
The glass transition point (Tg) of the resin component contained in the toner is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the heat quantity correction uses the heat of fusion of indium.

Specifically, about 10 mg of the toner is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference. The temperature is raised at a rate of 10 ° C./min between 30 and 200 ° C. Perform the measurement with.
During this heating process, a specific heat change is obtained in the temperature range of 40 ° C to 100 ° C. The intersection between the line at the midpoint of the baseline and the differential heat curve before and after the change in specific heat at this time is defined as the glass transition temperature Tg of the resin component contained in the toner.

The peak temperature of the maximum endothermic peak of the wax and the toner is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the heat quantity correction uses the heat of fusion of indium.
Specifically, about 10 mg of the toner is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference. The temperature is raised at a rate of 10 ° C./min between 30 and 200 ° C. Perform the measurement with.
During this heating process, a specific heat change is obtained in the temperature range of 40 ° C to 100 ° C. The intersection between the line at the midpoint of the baseline before and after the specific heat change and the differential heat curve at this time is defined as the glass transition temperature Tg of the binder resin.

[Method for measuring 50% particle size (D50) based on volume distribution of external additive]
The particle size distribution of the large particle size external additive is measured by a laser diffraction / scattering type particle size distribution analyzer “Microtrack MT3300EX” (manufactured by Nikkiso Co., Ltd.).
The measurement of the 50% particle size (D50) based on the volume distribution of the large particle size external additive is performed by attaching a sample supply device for dry measurement.
In addition, as the above-mentioned sample supply device, there is a "one-shot dry type sample conditioner Turbotrac" (manufactured by Nikkiso Co., Ltd.).

Turbotrac was supplied under the conditions of a dust collector as a vacuum source, an air volume of about 33 liters / second, and a pressure of about 17 kPa. Control is performed automatically on software.
As the particle size, a 50% particle size (D50) which is a cumulative value on a volume basis is obtained. Control and analysis are performed using attached software (version 10.3.3-202D).
The measurement conditions are as follows: Set Zero time 10 seconds, measurement time 10 seconds, number of measurements once, particle refractive index 1.81, particle shape non-spherical, upper measurement limit 1408 μm, lower measurement limit 0.243 μm. The measurement is performed under normal temperature and normal humidity (temperature 23 ° C., relative humidity 50%).

[Measurement method of fixation rate of large particle size external additive]
160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water and dissolved in a water bath to prepare a concentrated sucrose solution.
In a tube for centrifugation, 31 g of the sucrose concentrate was added to a contaminone N (a 10% by mass aqueous solution of a neutral detergent for washing a precision measuring instrument having a pH of 7 comprising a nonionic surfactant, an anionic surfactant and an organic builder, 6 mL of Wako Pure Chemical Industries, Ltd.) is added to prepare a dispersion.
1 g of the toner is added to the dispersion, and the lump of the toner is loosened with a spatula or the like.

The tube for centrifugation is shaken on a shaker at 350 rpm for 20 minutes. After shaking, the solution is replaced with a swing rotor glass tube (50 mL), and separated by a centrifuge at 3500 rpm for 30 minutes.
It is visually confirmed that the toner and the aqueous solution are sufficiently separated, and the toner separated in the uppermost layer is collected with a spatula or the like. The collected aqueous solution containing the toner is filtered with a vacuum filter, and then dried with a dryer for 1 hour or more.
The dried product is disintegrated with a spatula, and the amount of the external additive is measured by fluorescent X-rays (diameter aluminum ring: 10 mm). The liberation ratio is calculated from the amount of the external additive of the toner after washing and the initial amount of the toner.

The measurement of the fluorescent X-ray of each element conforms to JIS K 0119-1969, and is specifically as follows.
As a measuring device, a wavelength-dispersive X-ray fluorescence analyzer "Axios" (manufactured by PANalytical) and an attached dedicated software "SuperQ ver. 4.0F" (manufactured by PANalytical) for setting measurement conditions and analyzing measurement data are used. ) Is used.
Note that Rh (rhodium) is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 10 mm, and the measurement time is 10 seconds.
When a light element is measured, a proportional counter (PC) is used, and when a heavy element is measured, a scintillation counter (SC) is used.

As a measurement sample, about 1 g of the toner after washing and the initial toner were put into a dedicated aluminum ring for press and leveled, and the tableting and compression machine "BRE-32" (Maekawa Testing Machine Co., Ltd.) ) Into pellets.
Pelletization conditions include a pellet molded to a thickness of about 2 mm by applying a pressure of 20 MPa and a time of 60 seconds.
The measurement is performed under the above conditions, the element is identified based on the obtained X-ray peak position, and its concentration is calculated from the count rate (unit: cps) which is the number of X-ray photons per unit time.
As a method of quantifying SiO _{2 in} the toner, a fine powder of silica (SiO ₂ ) is added to 100 parts by mass of toner particles so as to be 0.10 parts by mass, and sufficiently mixed using a coffee mill.

Similarly, 0.20 parts by mass and 0.50 parts by mass of the silica fine powder are respectively mixed with the toner particles, and these are used as a sample for a calibration curve.
For each sample, a pellet for a calibration curve sample was prepared using a tablet molding compressor as described above, and when PET was used for the spectral crystal, the diffraction angle (2θ) was observed at 109.08 °. The counting rate (unit: cps) of the Si-Kα ray is measured.
At this time, the acceleration voltage and the current value of the X-ray generator are set to 24 kV and 100 mA, respectively. A calibration curve of a linear function is obtained with the obtained X-ray count rate on the vertical axis and the added amount of SiO ₂ in each calibration curve sample on the horizontal axis.

Next, the toner to be analyzed is formed into pellets by using a tablet molding compressor as described above, and the counting rate of the Si-Kα ray is measured. Then, the content of SiO ₂ in the toner is determined from the above calibration curve.
With respect to the initial amount of the external additive of the toner calculated by the above method, the rate of decrease in the amount of the external additive of the toner after washing was subtracted from 1 to obtain the fixation rate of the external additive having a large particle diameter.

[Evaluation method for contamination of charging member]
In the present invention, the contamination of the charging member is evaluated by the following method.
When the particles of the external additive adhere to the surface of the charging member, the color of the surface of the charging member becomes cloudy.
The brightness value of the clouded area was quantified, and the difference from the value of the unused product was defined as the contamination amount.
The charging member subjected to the repeated use test is taken out of the image forming apparatus.
Using an image scanner, the reading resolution is set to 600 dpi and the bit depth is set to 8 bits, and the surface of the charging member is read.
A luminance value (0 to 255) of the surface of the charging member is obtained from the read image.

The luminance value of the surface of the unused charging member is obtained in the same procedure.
Since the brightness value becomes higher as the surface of the charging member becomes more cloudy, the difference between the brightness value of the unused product and the brightness value of the durability evaluation product is calculated, and the arithmetic average value over the entire area in the longitudinal direction of the charging member is defined as the contamination amount.
CanoScan 5600F (manufactured by Canon Inc.) was used for the image scanner.

Hereinafter, the present invention will be described with reference to examples and comparative examples of a specific configuration and manufacturing method of a toner processing apparatus, but the present invention is not limited to only these examples.
[Production example of toner particles]
710 parts by mass of ion-exchanged water and 850 parts by mass of a 0.1 mol / L aqueous solution of Na ₃ PO ₄ are added to a four-necked container, and a high-speed stirrer TK homomixer (manufactured by Primix Industry Co., Ltd.) is used. And maintained at a temperature of 60 ° C. while stirring at 12,000 rpm. 68 parts by mass of 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added thereto to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

Styrene 124 parts by mass n-butyl acrylate 36 parts by mass Copper phthalocyanine pigment (Pigment Blue 15: 3) 13 parts by mass styrene resin (1) 40 parts by mass polyester resin (1)
(Terephthalic acid-propylene oxide-modified bisphenol A (2 mol adduct) (molar ratio = 51: 50), acid value = 10 mgKOH / g, glass transition point = 70 ° C., Mw = 10500, Mw (weight average molecular weight) / Mn (Number average molecular weight) = 3.20) 10 parts by mass negative charge control agent (aluminum compound of 3,5-di-tert-butylsalicylic acid)
0.8 parts by mass wax (Fischer-Tropsch wax; endothermic main peak temperature = 78 ° C)
15 parts by mass

  The above materials were stirred for 3 hours using an attritor (manufactured by Nippon Coke Industry Co., Ltd. (formerly Mitsui Miike Kakoki Co., Ltd.)) to disperse each component in the polymerizable monomer, and the monomer mixture was dispersed. Prepared. To the monomer mixture, 20.0 parts by mass of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (a 50% toluene solution) as a polymerization initiator was added, and a polymerizable monomer was added. A composition was prepared. The polymerizable monomer composition was charged into an aqueous dispersion medium, and granulated for 5 minutes while maintaining the rotation speed of the stirrer at 10,000 rpm. Thereafter, the high-speed stirrer was changed to a propeller stirrer, the internal temperature was raised to 70 ° C., and the reaction was carried out for 6 hours while stirring slowly.

Next, the inside of the container was heated to 80 ° C. and maintained for 4 hours, and then gradually cooled to 30 ° C. at a cooling rate of 1 ° C. per minute to obtain a slurry 1. Dilute hydrochloric acid was added to the container containing the slurry 1 to remove the dispersion stabilizer. The polymer particles were further filtered, washed and dried to obtain polymer particles (toner mother particles 1) having a weight average particle diameter (D4) of 6.2 μm. The true density of the toner particles was 1.1 g / cm ³ .

[Example 1]
FIG. 1 is a schematic configuration diagram of a toner processing apparatus according to the first embodiment.
The toner processing apparatus 100 includes a processing tank 110 that stores an object to be processed including toner particles and an external additive, a drive motor 150, and a control unit 160.
The processing tank 110 is a cylindrical container having an inner height of 250 mm, an inner diameter of 230 mm, and an effective volume of 10 L as shown in FIG. 3, and has a drive shaft 111 at the center of a flat bottom. The drive of the drive motor 150 is transmitted to the drive shaft 111 via a drive belt.
Since the radius of the processing tank is 115 mm, 15% of the radius is 17.25 mm.
The control unit 160 includes a power switch, a drive ON switch, a drive stop switch, a rotation speed adjustment volume, a rotation speed display unit, a product temperature display unit, and the like, and controls the operation of the toner processing apparatus 100.

In the processing tank 110, a stirring blade 120 shown in FIG. 4 was attached to a drive shaft 111 as a flow means for flowing an object to be processed upward from the bottom of the processing tank. The stirring blade 120 used was S-shaped and the tip was flipped up.
Further, a processing blade 140 shown in FIG. 5 is attached to the same drive shaft 111 as a rotating body above the stirring blade 120. The processing blade 140 has an annular processing blade main body (rotary body main body) 141 and a processing unit 142 that protrudes radially outward from the outer peripheral surface of the processing blade main body 141.
The shape of the processing section 142 was such that the distance from the center of rotation to the outermost end in the radial direction was 96% of the inner diameter of the processing tank 110, and the thickness was 4 mm.

Further, a regulating plate 130 is attached above the processing blade 140 as shown in FIG.
The thickness of the regulating plate 130 is not particularly limited, as long as the strength can be ensured. In this embodiment, the thickness is 3 mm.
The length of the regulating plate 130 is preferably at least half the height of the processing tank 110 in order to obtain a regulating effect on the object to be treated. In this embodiment, the length is 130 mm.

When the processing tank is viewed from above as shown in FIG. 7, the width of the regulating plate 130 is such that the end near the center of the regulating plate 130 substantially overlaps with the part where the processing section 142 protrudes from the processing blade body 141. .
The end near the outer periphery of the regulating plate 130 was set so that the gap was 1 mm, and the width of the regulating plate 130 in this embodiment was 40 mm.
A fan-shaped plate-shaped regulating plate having the above dimensions was attached under the following conditions.

The angle θ1 shown in FIG. 6 was always set to 60 degrees in the entire region in the center direction, the gap shown in FIG. 7 was set to 1 mm, and the angle θ2 shown in FIG. 8 was set to 30 degrees.
The upper part of the regulating plate 130 was fixed to the upper lid of the processing tank 110 by a shaft 131.

The distance L1 between the upper end of the regulating plate 130 and the ceiling of the processing tank 110 shown in FIG. 8 may be close to or apart from each other, but if the distance L1 is too far, the material near the ceiling of the processing tank 110 is regulated. Since it is difficult to obtain the effect of the above, the thickness is set to 25 mm.
If the distance L2 between the lower end of the regulating plate 130 and the processing blade 140 shown in FIG. 8 is too large, it is considered that the effect of restricting the processing object above the processing blade 140 becomes insufficient. L2 was 35 mm.
A temperature sensor is attached to the lower end of the regulating plate 130 so that the temperature in the processing tank 110 during the toner processing can be monitored.

In the present embodiment, a two-stage external addition process was performed. First, the toner particles and the first external additive were added to perform a first external addition process, and then a second external additive was added to perform a second external addition process.
With respect to the toner processing apparatus having the above configuration, 100 parts by mass of the toner particles 1 and a sol-gel silica particle having a 50% particle size (D50) of 100 nm as a first external additive having a BET specific surface area of 28.55 m ^{2 /} g) 1.0 part by mass was introduced for 8% of the effective volume of the processing tank 110. By controlling the rotation speed of the processing blade 140 to be 4,000 rpm and operating for 8 minutes, the first externally added processing toner is obtained. A part of the first externally added product was recovered and the fixation ratio of the large-diameter external additive was measured.
Table 1 shows the measurement results of the power of the toner processing apparatus, the temperature in the processing tank, and the sticking ratio at this time.

Further, as a second external additive to the first-stage toner, 0.5% silica particles having a 50% particle size based on a volume distribution of primary particles of 18 nm (oil treatment amount: 3%, BET specific surface area: 90.5 m ^{2 /} g) Parts by weight were introduced.
After operating for 5 minutes while controlling the rotation speed of the processing blade 140 to be 4,000 rpm, coarse particles were removed by sieving with a mesh having an opening of 100 μm to obtain a second externally added toner.
Using this toner, image evaluation was performed using a full color laser printer LBP9510C (hereinafter, printer) manufactured by Canon Inc.

[Evaluation of charging member contamination]
The obtained second externally added toner was filled in a predetermined process cartridge.
Next, the printer was installed in a JIS environment (temperature: 23 ° C., relative humidity: 50%), a test pattern with an image area ratio of 2% was continuously printed, and a repeated use test of 10,000 sheets of A4 size was performed.
After the repeated use test, the charging member was recovered from the process cartridge, and the amount of contamination was evaluated.
If the amount of contamination is less than 6.0, the density of the printed image is uniform, but if it is more than 6.0, density unevenness of the printed image is visually confirmed. The amount of contamination was measured by the method described above.
The evaluation rank was assigned to the amount of contamination as follows:

A: Less than 2.5. Uneven density cannot be confirmed.
B: 2.5 or more and less than 4.0. Very slight concentration unevenness is observed.
C: 4.0 or more and less than 6.0. Density unevenness is confirmed but acceptable level.
D: 6.0 or more. Remarkable density unevenness was confirmed, and the level was unacceptable.
E: Cannot be evaluated.
GF-C081 sold by Canon Marketing Japan was used as print paper. Table 1 shows the evaluation results.

[Examples 2 to 13]
In Examples 2 to 13, the same effective volume as in Example 1 was used in the treatment tank having a volume of 10 L.
The configuration of the regulating plate 130 is as shown in Table 1.
In Examples 2 to 4, the same conditions as in Example 1 were used except that the angle of θ1 was changed.
In Examples 5 to 8, the same conditions as in Example 4 were used except that Gap was changed.
In Examples 9 to 13, the conditions were the same as in Example 8 except that the angle θ2 was changed.
In each of the examples, a toner was manufactured by introducing an object to be processed by 8% of the effective volume in the same manner as in the example 1, and the physical properties of the toner and the contamination of the charging member were evaluated. Table 1 shows the evaluation results.

[Comparative Example 1]
In Comparative Example 1, an FM mixer (Model FM10C manufactured by Nippon Coke Industry Co., Ltd.) was used.
FIG. 9 shows a schematic configuration diagram of the used apparatus.
This apparatus includes a processing tank 210, a stirring blade 220, a processing blade 230, and a regulating plate 240.
The regulating plate 240 sets θ1 to 135 degrees, sets the distance Gap to the inner wall surface to 1 mm, does not tilt in the vertical direction, and sets θ2 to 0 degrees.
In the same manner as in Example 1, an object to be processed was introduced by 8% of the effective volume, a toner was manufactured at a rotation speed of the processing blade 230 of 4,000 rpm, and evaluation of physical properties of the toner and evaluation of contamination of the charging member were performed. Table 2 shows the operating conditions and evaluation results.

[Comparative Example 2]
In Comparative Example 2, the same conditions as in Comparative Example 1 were adopted except that the object to be treated was introduced by 16% of the effective volume. In Comparative Example 2, the operation was stopped because the temperature inside the processing tank 210 exceeded 40 ° C. during the operation. Image evaluation by printer was not performed. Table 2 shows the operating conditions and evaluation results.

[Comparative Example 3]
In Comparative Example 3, the same conditions as in Example 1 were used except that the angle θ1 was set to 100 degrees. Table 2 shows the evaluation results.
[Comparative Example 4]
In Comparative Example 4, the regulating plate 130 was brought into close contact with the inner wall surface of the processing tank 110, and the gap was set to 0 mm. Other conditions were the same as in Example 4.

As shown in Tables 1 and 2, in the toners of Examples 1 to 13 employing the configuration of the present invention, the power of the toner processing device during the toner processing is high, and accordingly, large power is applied to the toner particles. The value of the sticking rate of the external additive is high.
As a result, the contamination of the charging member after the repeated use test is reduced.
On the other hand, the toners of Comparative Examples 1 and 3 which do not employ the configuration of the present invention have low values of the fixation ratio. As a result, it is found that the charging member after the repeated use test is much soiled.
Further, when the amount of the object to be processed is increased as in Comparative Example 2, it is not practical because the power to be applied can be increased, but the temperature of the object to be processed during processing increases.
When the gap is set to 0 mm as in Comparative Example 4, the object to be processed stays in the region surrounded by the inner wall surface of the processing tank 110 and the regulating plate 130. As a result, the toner is mixed with an object to be processed which is not sufficiently fixed, and the charging member becomes more soiled after the repeated use test.

[Other Embodiments]
As described above, the regulating plate 130 is attached so that the angle θ1 is always less than 90 degrees in the entire region in the central axis direction. The angle θ1 only needs to be always less than 90 degrees in the entire area in the central axis direction, and the angle θ1 does not need to be always the same angle in the entire area in the central axis direction.

An example will be described with reference to FIG. 10 in which the angle θ1 is always less than 90 degrees in the entire region in the central axis direction, but the angle θ1 changes depending on the height.
θ1-1 is the height indicated by the dotted line A11.
In a plane perpendicular to the central axis of the processing tank,
A straight line 1011 connecting the end on the central axis side and the end on the inner wall surface side of the regulating plate,
This is the angle between the straight line 1011 and the straight line 1012 contacting the inner wall surface at the intersection of the inner wall surface and the upstream angle in the rotation direction of the rotating body.

θ1-2 is the height indicated by the dotted line A12.
In a plane perpendicular to the central axis of the processing tank,
A straight line 1021 connecting the end of the regulating plate on the central axis side and the end on the inner wall surface side;
This is the angle between the straight line 1021 and the straight line 1022 contacting the inner wall surface at the intersection of the inner wall surface and the upstream angle in the rotation direction of the rotating body.
θ1-3 is at the height indicated by the dotted line A13.
In a plane perpendicular to the central axis of the processing tank,
A straight line 1031 connecting the end of the regulating plate on the central axis side and the end on the inner wall surface side;
This is the angle between the straight line 1031 and the straight line 1032 that is in contact with the inner wall surface at the intersection of the inner wall surface and the upstream angle in the rotation direction of the rotating body.
For example, the configuration may be such that θ1-1 is 60 degrees, θ1-2 is 66 degrees, and θ1-3 is 68 degrees.

100 {toner processing apparatus 110} processing tank 111 {drive shaft 120} stirring blade 130} regulating plate 140} processing blade 142} processing unit 150} drive motor 160 {control unit 210} Processing tank (comparative example)
220 ° stirring blade (comparative example)
230 ‥‥ processing blade (comparative example)
240 ° regulation plate (comparative example)

Claims (4)

Processing of the object to be processed including the toner particles and the external additive is performed, has a cylindrical internal space, a processing tank installed such that the central axis of the cylindrical internal space is substantially vertical,
A cooling jacket provided on the outer peripheral surface of the processing tank,
Flow means provided at the bottom of the processing tank, for flowing the object to be processed contained in the processing tank upward from the bottom of the processing tank,
A rotatable member is provided above the fluidizing means, and the rotor body and the rotor body protrude radially outward from an outer peripheral surface of the rotor body, and collide with the workpiece to process the workpiece. A rotating body having a processing unit;
The rotating body is disposed above the, with the <br/> the regulating plate for regulating an object to be processed on the inner wall surface of the processing bath,
The regulating plate is provided with a gap with the inner wall surface of the processing tank,
In a plane perpendicular to the central axis of the processing tank,
A straight line connecting the end of the regulating plate on the central axis side and the end on the inner wall surface side,
An angle straight line and forms in contact with the inner wall surface at the point of intersection between the straight line and the inner wall surface, and when the angle of the upstream side in the rotational direction of the rotary member and .theta.1,
The regulating plate is attached such that the angle θ1 is always 30 degrees or more and 85 degrees or less in the entire region in the central axis direction ,
On a plane parallel to the central axis of the processing tank, an angle θ2 between a straight line connecting the upper end and the lower end of the regulating plate and the vertical direction is 8 degrees or more and 45 degrees or less. A toner processing apparatus characterized by the above-mentioned. And the side of the end portion closer to the inner wall surface of the processing tank comprising an end portion of the regulation plate, the gap between the inner wall surface of the processing tank, claim is 1mm or more but less than 15% of the radius of the processing bath 2. The processing device for a toner according to 1.   3. The toner processing apparatus according to claim 1, wherein the regulating plate is inclined downward in the rotation direction as it goes downward. 4. In a method for producing a toner including an external addition step of fixing an external additive to the surface of the toner particles,
The toner manufacturing method which is characterized in that the external addition step using the toner processing device according to any one of claims 1-3.