JP2017215519A - Method for crushing external additive for toner and method for producing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a disintegrating method of toner external additive which stabilizes electrostatic propensity of the toner and decreases fogging when forming an image.SOLUTION: A disintegrating method of an external additive in which real density is 2,900 kg/mor more and 6,000 kg/mor less, and interparticle force is 15 pN or more and 200 pN or less comprises: a processing tank which is disposed so that a disintegrating device used in the disintegrating method includes a cylindrical internal space and a central axis of the internal space becomes approximately vertical; and a processing unit which collides with the external additive by rotation of a rotor body part and a rotor to disintegrate the external additive in which the processing unit includes the rotor arranged capable of horizontally rotating around almost the center of a horizontal section of the processing tank as a rotation center and the other rotor does not exist below the rotor. When height of the processing tank is L, height from the bottom of the processing tank to the lower limit of the processing unit is B, and height from the bottom of the processing tank to the upper limit of the processing unit is T, B is 20.0% of L or more and T is 50.0% of L or less. When inner diameter of the processing tank is D, L/D is 0.8 or more and 1.2 or less.SELECTED DRAWING: Figure 1

Description

The present invention relates to a toner used for developing an electrostatic latent image in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like (hereinafter, simply referred to as “toner”). The present invention relates to a method for crushing external additives.
Furthermore, the present invention relates to a method for producing a toner in which the external additive for toner crushed by the pulverizing method for external additive for toner is externally added to toner particles.

Conventionally, a toner in a general electrophotographic method has a surface of colored particles treated with a fluidity improver (external additive) to control desired fluidity and charging characteristics. As this external additive, what is generally widely used is fine particles made of inorganic or organic substances.
As the fine particles, metal oxide particles, resin particles, and surface treated products thereof have been conventionally used.
Among the fine particles, the volume average particle size of the primary particles has a function as a toner fluidizing agent and a charge imparting agent, and is added mainly for the purpose of improving developability (flight to the photoreceptor). There are external additives of 80 nm or more.

As the external additive, for example, strontium titanate, zinc stearate, zinc oxide, calcium carbonate or the like is used as an external additive for the toner in order to control the chargeability of the toner.
The external additive for toner is an external additive having a high true density of 2,900 kg / m ³ to 6,000 kg / m ³ and a high interparticle force of 15 pN to 200 pN.
The volume average particle diameter of the primary particles of the toner external additive is 80 nm or more, but since it has the characteristic that the force between the two particles is high as described above, it contains a lot of secondary aggregates of about several μm. Yes.

When a toner obtained by externally adding the toner additive to the toner particles is applied to an image forming apparatus, the toner charging characteristics may be insufficient if there are many secondary aggregates of the toner additive. .
The toner is charged by frictional charging between the charge applying member for applying charge to the toner and the toner.
Here, the charge imparting member is a carrier in the two-component development system, such as a regulating blade in the one-component development system.

It is the external additive for toner coated on the surface of the toner particles that comes into contact with the charging member and causes frictional charging.
In order for the external additive for toner to effectively cause triboelectric charging with the charge imparting member, the surface of the external additive sufficient for contacting the charge imparting member needs to be exposed. .
However, when there are many secondary aggregates of the toner external additive coated on the surface of the toner particles, the surface area per unit mass of the toner external additive is apparently reduced.
When the surface area of the external additive for toner relating to frictional charging is small, the charge amount (Q / M) per unit mass as the toner is also small, and the effect of the material added in anticipation of charging is sufficiently obtained. May not be obtained.
Alternatively, if the amount and size of secondary aggregates of the toner external additive are not constant, there is a risk that the charge amount of the toner will be uneven.

As a result, when an image is output by the image forming apparatus, a phenomenon called fogging may occur in which toner with insufficient charge amount adheres to a white background portion which is a non-image portion.
Therefore, in order to solve the above-described problems, the external additive for toner containing secondary aggregates is subjected to a crushing process before mixing with toner particles.
Several methods have heretofore been proposed as means for crushing the toner external additive containing secondary aggregates.
For example, a method of crushing using a jet crusher such as an IDS mill (manufactured by Nippon Pneumatic Industry Co., Ltd.) has been proposed (Patent Document 1).
Further, as another means, an external additive for toner containing a large amount of secondary aggregates of about several μm using a mixing / surface reformer such as COMPOSI (manufactured by Nippon Coke Industries Co., Ltd.). There is a method of crushing (Patent Document 2).

JP-A-8-254855 Japanese Patent No. 5575139

By using the apparatus disclosed in Patent Document 1, it is possible to crush secondary aggregates of about several μm. However, the crushing by the jet type pulverizer has a problem that the energy cost is high because high pressure air is used.
As another method, for example, an external additive for toner containing a large amount of secondary aggregates of about several μm using a mechanical pulverizer such as an atomizer mill (manufactured by Tokyo Atomizer Manufacturing Co., Ltd.). There is a way to crush.

The atomizer mill supplies external toner additives into the machine with a screw feeder, crushes in the gap between the rotor rotated at high speed and the liner installed on the outer periphery, and then crushed toner through a screen installed under the rotor This is an apparatus for obtaining external additives.
By using an atomizer mill, it is possible to pulverize the secondary aggregate of about several μm to some extent. However, in the atomizer mill, depending on the type of external additive for toner, the screen may be clogged, and thus the supplied external additive for toner may not be crushed.

COMPOSI rotates the turbine blades installed at the bottom of the processing tank at high speed to form a circulating flow of powder particles in the processing tank and is strongly compressed by the impingement plate installed in a part of the circulating flow. An external additive for toner is obtained by applying force and shearing force to the granular material.
By using COMPOSI, the secondary agglomerates of about several μm can be crushed to some extent, but such an apparatus stirs the material with a rotating stirring blade and causes the material to collide with a fixed impingement plate. Therefore, there are the following problems.

It is necessary to increase the rotating peripheral speed of the stirring blade in order to cause the material to strongly collide with the collision plate, but when the stirring blade attached to the position where the height from the bottom of the mixing tank is low is rotated at high speed In some cases, the material may be swollen up.
Since the toner external additive to which the crushing method of the present invention is applied has high true density and high interparticle force, when the toner external additive is swirled by a stirring blade, the toner external additive May adhere to the top lid in large quantities.

Further, in a configuration employing a fixed collision plate, the raised external additive for toner may adhere to and accumulate on the collision plate.
As a result, most of the external additive for toner adheres to and accumulates in the mixing tank and the collision plate, and the amount of external additive for toner to be crushed by the action of the stirring blade is substantially reduced. There is a risk that.
Therefore, the external additive for toner adhered or deposited on the inside of the mixing tank or the collision plate may be finished in a state where it is hardly crushed.

  It is an object of the present invention to provide a method for crushing an external additive for toner that solves the above-mentioned problems. Furthermore, another object of the present invention is to provide a toner manufacturing method in which the external additive for toner pulverized by the pulverization method is externally added to toner particles.

That is, according to one aspect of the present invention,
True density is less 2,900kg / ^{m 3} or more 6,000 kg / ^{m 3,} a toner external additive for the crushing method, which is than two inter-particle force is more than 15pN 200pN,
A crushing apparatus used in the crushing method,
A treatment tank having a cylindrical inner space, and installed so that the central axis of the inner space is substantially vertical;
A rotating body provided so as to be horizontally rotatable with the approximate center of the horizontal cross section of the processing tank as a rotation center, and below the rotating body, there is no other rotating body,
The rotating body includes a rotating body main body and a processing unit that collides with the external additive for toner by the rotation of the rotating body and crushes the external additive for toner,
When the height of the processing tank is L, the height from the bottom of the processing tank to the lower end of the processing unit is B, and the height from the bottom of the processing tank to the upper end of the processing unit is T, B is 20.0% or more with respect to L and T is 50.0% or less with respect to L;
There is provided a method for crushing an external additive for toner, wherein L / D is 0.8 or more and 1.2 or less, where D is the inner diameter of the treatment tank.

According to another aspect of the invention,
A toner manufacturing method including an external addition step of externally adding an external additive for toner to toner particles containing a binder resin and a colorant,
There is provided a method for producing a toner, wherein the external additive for toner is an external additive crushed by the method for pulverizing the external additive for toner.

According to the present invention, the true density of not more than 2,900kg / ^{m 3} or more 6,000 kg / ^{m 3,} be applicable to the external additive for toner force between two particles is less 200pN than 15 pN, solutions A crushing method capable of efficiently reducing the bulk density by crushing can be provided.
Further, according to the present invention, there is provided a method for producing a toner, in which an external additive for toner crushed by the pulverization method is externally added to toner particles, whereby a high-quality image free from image defects due to fog is obtained. Can be provided.

It is a schematic block diagram of the crushing apparatus applicable to the crushing method of this invention. It is the schematic of the processing tank of the crushing apparatus shown in FIG. It is a perspective view of the rotary body of the crushing apparatus shown in FIG. It is the schematic of the rotary body of the crushing apparatus shown in FIG. It is explanatory drawing of the process part of the crushing apparatus shown in FIG. It is explanatory drawing, such as the height of the process part of the crushing apparatus shown in FIG. It is explanatory drawing of the crushing apparatus used in Example 1, 2, 4, 5 etc. of this invention. It is explanatory drawing of the crushing apparatus used in Example 3 of this invention. It is explanatory drawing of the crushing apparatus used in Example 6 of this invention. It is explanatory drawing of the apparatus used for the external addition process in an Example, or the crushing process in the comparative example 1. FIG. It is explanatory drawing of the upper blade | wing and lower blade | wing of the processing apparatus shown in FIG.

Hereinafter, preferred embodiments of a method for pulverizing an external additive for toner and a method for producing a toner to which the present invention is applied will be described in detail.
[Crushing equipment]
FIG. 1 is a schematic diagram of a crusher for an external additive for toner to which the present invention can be applied.
The crushing apparatus 100 includes a processing tank 110 that stores an external additive for toner, and a processing blade 120 as a rotating body that is rotatably provided at the bottom of the processing tank 110. The external additive for toner to be accommodated, the true density of not more than 2,900kg / ^{m 3} or more 6,000 kg / ^{m 3,} force between the two particles is less 200pN than 15 pN. The processing blade 120 is provided so as to be horizontally rotatable with the approximate center of the horizontal section of the processing tank as the center of rotation.

[Treatment tank]
FIG. 2 shows a schematic diagram of the treatment tank 110.
The processing tank 110 is a cylindrical container having a cylindrical inner space and having a flat bottom, and is installed so that the central axis is substantially vertical. A processing blade 120 is provided at the approximate center of the bottom. A drive shaft 111 for mounting is provided.
The treatment tank 110 is preferably made of a metal such as iron or SUS from the viewpoint that high strength can be obtained, and the inner surface is preferably made of a conductive material or the inner surface is subjected to conductive processing.

The processing tank 110 is provided with a cooling jacket 112 on the outer peripheral portion thereof as necessary.
The cooling jacket 112 is hollow, and is configured such that a coolant such as cooling water can be introduced from the IN side and discharged from the OUT side.
By passing the coolant through the cooling jacket 112, the temperature of the material heated during the treatment can be adjusted.
In addition, it is preferable that the junction part of the bottom part and side wall of the processing tank 110 shown in FIG. 2 is made into a curved surface so that effective cleaning is easy.

In the cross-sectional view of the processing tank 110 shown in FIG. 6, when the inner diameter, which is the inner diameter of the processing tank 110, is D and the inner height of the processing tank 110 is L, in the present invention, L / D is 0. 8 or more and 1.2 or less.
When L / D is smaller than 0.8, that is, when the height L is low with respect to the inner diameter D, the distance between the processing blade 120 as a rotating body described later and the upper lid of the processing tank 110 becomes closer.
In this case, the external additive for toner that has been swollen by the rolling operation during the crushing process is likely to adhere to the upper lid or the like of the processing tank 110.

When L / D is larger than 1.2, that is, when the height L is higher than the inner diameter D, the surface area inside the processing tank 110 is relatively large.
In this case, although the distance between the processing blade 120 and the upper lid of the processing tank 110 is increased, the surface area inside the processing tank 110 is large, so that the external additive for the toner that has been lifted up is still inside the processing tank 110. The amount attached to the surface increases.
Therefore, the range of L / D in the present invention is 0.8 or more and 1.2 or less.

[Rotating body]
3 and 4 are schematic views of the processing blade 120. FIG. FIG. 3 is a perspective view showing the overall configuration of the processing blade 120, FIG. 4A is a plan view, and FIG. 4B is a front view.
In the present invention, the processing blade 120 collides with the external additive for toner inside the processing tank 110 and crushes the external additive for toner.
The processing blade 120 is configured by attaching an annular processing blade main body (rotary body main body) 121 and a plurality of processing units 122 protruding radially outward from the outer peripheral surface of the processing blade main body 121.
Further, a control member 123 that promotes the rolling of the toner external additive can be provided.
The processing blade 120 is preferably made of a metal such as iron or SUS from the viewpoint of obtaining high strength, and may be plated or coated for wear resistance as necessary.

[Processing unit shape]
The shape of the processing unit 122 will be described with reference to FIG.
As shown in FIG. 5A, the processing unit 122 is attached to the outer peripheral surface of the processing blade main body (rotating body main body) 121.
When the processing blade body 121 rotates in the direction of the arrow, the hatched portion becomes the processing surface 124 and collides with the toner external additive.

The processing surface 124 preferably has a certain area for the purpose of colliding with the toner external additive, but is not necessarily a flat surface, and is appropriately selected according to the workability of parts and the effect on the applied toner external additive. You can choose.
The shape of the processing unit 122 is not limited to the rectangle shown in FIG. 5A, and the corners may be chamfered as shown in FIG. 5B, as shown in FIG. 5C. A fan shape may be used.
Further, the shape is not limited to a plate shape, and the shape opposite to the processing surface 124 may be different from the processing surface 124 as shown in FIG.

[Processing section height]
The height of the processing unit 122 will be described.
FIG. 6 is a cross-sectional view showing a state where the processing blade 120 is attached to the processing tank 110.
As shown in FIG. 6, when the height inside the processing tank 110 is L, the height from the bottom of the processing tank 110 to the lower end of the processing unit 122 is B, and the height from the upper end to T is T in the present invention. , B / L is 0.2 or more and T / L is 0.5 or less.

When B / L is smaller than 0.2, that is, when B is lower than 20% with respect to L, the effect of raising the external additive for toner by the rotation of the processing unit 122 becomes strong, and the processing unit In some cases, the amount of the external additive for toner in the vicinity of 122 decreases.
When T / L is larger than 0.5, that is, when T is higher than 50% with respect to L, means for raising the external additive for toner to more than 50% is necessary. When the means for positively raising the external additive for toner is provided, there are the following problems.

When the toner external additive having a high true density and high interparticle force as applied to the present invention is positively raised, the toner external additive adheres to the upper side wall of the processing tank 110 or the upper lid. It will accumulate.
As a result, the amount of the external additive for toner to be crushed by colliding with the processing unit 122 is substantially reduced, and the effect cannot be obtained.
As described above, in order to achieve the object of the present invention, it is necessary that B / L is 0.2 or more and T / L is 0.5 or less, and B / L is 0.2% or more. And it is preferable that T / L is 0.32 or less.

[Area of treated surface]
The total area of the processing surfaces in the present invention is an area obtained by adding the areas of the processing surfaces 124 as shown in FIG. For example, when the area of the processing surface 124 illustrated in FIG. 5A is Sa and the processing blade body 121 includes eight processing units 122,
Total area of treated surface = 8 × Sa
It becomes.
There is a suitable range for the ratio of the total area of the processing surface 124 to the area of the cross section in the vertical direction passing through the central axis of the processing tank 110.
If the ratio of the total area of the processing surface 124 is 3% or more, the effect that the processing surface 124 collides with the external additive for toner and is crushed is sufficiently obtained.
If the ratio of the total area of the processing surface 124 is 20% or less, the effect of raising the external additive for toner by the operation of the processing surface 124 does not become too strong, and the crushing effect is small for the above-mentioned reason. It will never be.
In order to achieve the object of the present invention, the ratio of the total area of the treatment surface 124 to the area of the vertical cross section passing through the central axis of the treatment tank 110 is preferably 3% or more and 20% or less, 7% More preferably, it is 15% or less.

[Control member that promotes rolling]
In the present invention, in order to cause the toner external additive to collide with the processing unit 122, it is effective to promote the rolling of the toner external additive inside the processing tank 110 and repeatedly collide with the processing unit 122.
The control member 123 shown in FIG. 4 is attached to the processing blade 120 and is provided below the processing unit 122.
The control member 123 is provided on the upper side of the processing blade 120 on the side far from the drive shaft 111. On the lower side of the processing blade 120, that is, on the side close to the bottom of the processing tank 110, the control member 123 is preferably provided on the side close to the drive shaft 111 and is attached obliquely as shown in FIG.

The behavior of the external additive for toner inside the processing tank 110 basically turns as the processing blade 120 rotates, but the bottom part of the processing tank 110 in the high-density toner external additive. The closer to, the slower the turning speed.
By adopting the configuration of the control member 123 as in the present invention, the swirl speed of the external toner additive is not increased more than necessary in an area close to the processing unit 122.
Further, the effect of pushing the external additive for toner in the region near the bottom of the processing tank 110 outward from the center can be increased.
As a result, it is possible to promote the rolling of the toner external additive.
The shape of the control member 123 can be selected from a columnar shape, a blade shape, and the like according to the characteristics of the applied external additive for toner, and the number of the control members 123 can be selected from 2, 4 or 6 pieces. is there.

[Other parts]
As other members, it is preferable not to provide a member that prevents rolling of the toner external additive above the processing blade 120. When a member that prevents rolling of the external additive for toner is provided, the external additive for toner adheres to or accumulates on the member.
As a result, the amount of the external additive for toner to be crushed by colliding with the processing unit 122 may be substantially reduced and the effect may be reduced.
Examples of the member that prevents rolling include a deflector (regulation plate) in FM mixer (manufactured by Nippon Coke Industries, Ltd.) and a collision plate in COMPOSI (manufactured by Nippon Coke Industries, Ltd.).

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

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

Next, the mixed material is melt-kneaded to disperse wax or 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.
Due to the advantage of continuous production, single-screw or twin-screw extruders are the mainstream.
For example, KTK type twin screw extruder (manufactured by Kobe Steel, Ltd.), TEM type twin screw extruder (manufactured by Toshiba Machine Co., Ltd.), PCM kneader (manufactured by Ikekai Co., Ltd.), Nidex (Nippon Coke Industries, Ltd.) Product).

Furthermore, the resin composition obtained by melt-kneading may be rolled with two rolls or the like and cooled with water or the like in the cooling step.
Next, the cooled product of the resin composition is pulverized to a desired particle size in the pulverization step.
In the pulverization process, after coarse pulverization with a crusher such as a crusher or hammer mill, a fine pulverizer using a kryptron system (manufactured by Earth Technica), turbo mill (manufactured by Freund Turbo), etc. Crush finely.
After that, if necessary, classifiers such as inertial class elbow jet (manufactured by Nippon Steel Mining Co., Ltd.), centrifugal classifier TSP separator (manufactured by Hosokawa Micron Co., Ltd.), Faculty (manufactured by Hosokawa Micron Co., Ltd.) 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 producing a toner in a hydrophilic medium such as a suspension polymerization method, an interfacial polymerization method, and a dispersion polymerization method.
A procedure for producing a toner using the suspension polymerization method will be described below.
The suspension polymerization method is a granulation step in which a polymerizable monomer composition having a polymerizable monomer, a colorant and the like is dispersed in an aqueous medium to produce droplets of the polymerizable monomer composition. In this polymerization method, toner base particles are produced through at least a polymerization step of polymerizing the polymerizable monomer in the droplets.
And when manufacturing the toner of this invention, it is preferable to contain low molecular weight resin in a polymerizable monomer composition.

  The toner of the present invention is preferably a toner having toner base particles having at least a core part and a shell part. 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 leaching of the core part to the toner particle surface. Further, it is more preferable that a surface layer portion having a resin composition different from that of the shell portion is present on the surface of the shell portion. The presence of this surface layer portion can further improve environmental stability, durability, and blocking resistance.

  Preferred examples of the polymerizable monomer that can be used to produce the toner base particles of the present invention include a vinyl polymerizable monomer. 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-hexyl styrene, pn-octyl, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene; methyl acrylate, Ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, 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 acid esters; vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether; And vinyl ethers such as vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  The shell portion is composed of 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 preferable from the viewpoint of efficiently covering the wax mainly forming the inside or the central portion.

The material constituting the core of the toner of the present invention is preferably wax.
The wax component usable in the toner according to the present invention includes paraffin wax, microcrystalline wax, petroleum wax such as petrolatum and derivatives thereof, montan wax and derivatives thereof, hydrocarbon wax and derivatives thereof according to the Fischer-Tropsch method, polyethylene, Polyolefin waxes such as polypropylene and derivatives thereof, natural waxes such as carnauba wax and candelilla wax and derivatives thereof, and the like 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, plant-based waxes, animal waxes, and silicone resins can also be used. .

[Crushing of external additive for toner]
The external crushing apparatus 100 of the present invention shown in FIG. 1 as an apparatus for performing a crushing process on the toner external additive prior to externally adding the external additive to the surface of the toner particles thus obtained. Is used.
In the crushing apparatus 100, a cylindrical processing tank 110 is installed substantially vertically, and a processing blade 120 is attached to a drive shaft 111 provided at substantially the center of the bottom of the processing tank 110.
No other rotating member is attached below the processing blade 120.
The mounting height of the processing unit 122 is such that the lower end height B of the processing unit 122 is 20.0% or more with respect to the height L of the processing tank 110,
The height T of the upper end of the processing unit 122 is set to 50.0% or less.

The rotational peripheral speed of the processing blade 120 is set within a predetermined range described later.
Next, the upper lid of the processing tank 110 is opened, and the toner external additive weighed in advance is put in. After the charging, the upper lid is closed, and the processing blade 120 is rotated at the rotational peripheral speed described below.
After processing for a desired time, a discharge valve (not shown) is opened, and the toner external additive is taken out from the processing tank 110.

As for the rotational peripheral speed of the processing blade 120 and the mixing time, it is preferable to use a peripheral speed that is somewhat high in order to disintegrate the external additive for toner.
Specifically, the peripheral speed at the tip of the processing unit is preferably 30.0 m / second or more, and more preferably 40.0 m / second or more.
The mixing time is preferably adjusted in the range of 0.5 minutes to 60 minutes.

[External processing]
For example, a toner processing apparatus 200 shown in FIG. 10 is used as a processing apparatus for coating the surface of the toner particles with the pulverized external additive for toner.
The toner processing apparatus 200 includes a processing tank 210, a lower blade 220 that is rotatably attached to the bottom of the processing tank 210, an upper blade 230, and a regulation plate 240 that is fixed to the upper portion of the processing tank 210.
The control unit 260 includes a drive switch, a rotation speed adjuster, a temperature indicator, and the like, and the lower blade 220 and the upper blade 230 rotate at a rotation speed set by the motor 250 rotating by the drive switch. It is.

The operation method is as follows.
The rotational peripheral speeds of the lower blade 220 and the upper blade 230 shown in FIG. 10 are set within a predetermined range described later.
Next, the upper lid of the processing tank 210 is opened, and an object to be processed containing toner particles weighed in advance and the external additive for toner that has been crushed is charged. After the charging, the upper lid is closed, and the lower blade 220 and the upper blade 230 are rotated at the rotational peripheral speed described below.

Further, while the lower blade 220 and the upper blade 230 are rotating, the cold water from the cold water generating means is supplied to the cooling jacket 211, so that the material temperature in the processing tank 210 is changed to the glass transition point of the resin component contained in the toner ( Tg) Adjust to below.
After processing for a desired time, a discharge valve (not shown) is opened and the toner is taken out from the processing tank 210. Thereafter, the particles are passed through a mesh having an opening of about 35 μm to 75 μm to remove coarse particles, thereby obtaining a toner.

The rotational peripheral speed and mixing time of the lower blade 220 and the upper blade 230 are preferably adjusted in a range in which the material temperature during 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 peripheral speed of the lower blade 220 and the upper blade 230 is preferably 10.0 m / second or more and 150.0 m / second or less, preferably 30.0 m / second or more and 70.0 m. / Second or less is more preferable.
The mixing time is preferably adjusted in the range of 0.5 minutes to 60 minutes.
The process of treating the toner particles and the toner external additive may be performed in one step or in two or more steps, and the mixing conditions and the blending of the toner particles used in each step are the same. It can be different.

[Binder resin]
Next, the toner used in the present invention will be described. As the toner, a known toner can be used, and the toner may be produced by any method such as a pulverization method, a polymerization method, an emulsion aggregation method, and a dissolution suspension method.
As the binder resin constituting the toner, a resin that is usually used for toner can be used. The following are listed.
Polystyrene; homopolymer of styrene-substituted product such as poly-p-chlorostyrene and polyvinyltoluene; styrene-p-chlorostyrene copolymer.

Furthermore, a styrene-vinyl toluene copolymer, a styrene-vinyl naphthalene copolymer, a styrene-acrylic acid ester copolymer, a styrene-methacrylic acid ester copolymer, and a styrene-α-chloromethyl methacrylate copolymer are exemplified. .
Furthermore, 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 copolymers such as styrene-isoprene copolymer and styrene-acrylonitrile-indene copolymer; polyvinyl chloride, phenol resin, natural modified phenol resin, natural resin modified maleic acid resin, and acrylic resin.
Further examples include methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone indene resin, and petroleum resin.

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

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

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

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

[Charge control agent]
In the toner used in the present invention, in order to control the charge amount and charge amount distribution of the toner particles, a charge control agent is blended with the toner particles (internal addition) or mixed with the toner particles (external addition). Is preferred.
Examples of the negative charge control agent for controlling the toner to be negatively charged include organometallic 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, the negative charge control agent includes aromatic hydroxycarboxylic acid, aromatic monocarboxylic acid and aromatic polycarboxylic acid and metal salts thereof; anhydrous hydroxycarboxylic acid, aromatic monocarboxylic acid and aromatic polycarboxylic acid anhydride. Things.
Furthermore, ester compounds of aromatic hydroxycarboxylic acid, aromatic monocarboxylic acid and aromatic polycarboxylic acid, and phenol derivatives such as bisphenol are included.

Examples of the positive charge control agent for controlling the toner to be positively charged include nigrosine and a modified product of nigrosine by a fatty acid metal salt; tributylbenzylammonium-1-hydroxy-4-naphthosulfonate.
Further examples include quaternary ammonium salts such as tetrabutylammonium tetrafluoroborate and lake pigments thereof; tributylbenzylphosphonium-1-hydroxy-4-naphthosulfonate.
Furthermore, phosphonium salts such as tetrabutylphosphonium tetrafluoroborate and lake lake pigments thereof; triphenylmethane dyes and lake lake pigments (the rake agent includes phosphotungstic acid.
Furthermore, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); higher fatty acid metal salts.

These charge control agents can be used alone or in combination of two or more. Moreover, charge control resin can also be used and can also be used together with said charge control agent.
The above charge control agent 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 parts by mass or more and 20.0 parts by mass or less to the toner particles with respect to 100.0 parts by mass of the binder resin.

[Colorant]
In the toner used in the present invention, conventionally known various colorants can be used as the toner particle material.
As the black colorant, those combined so as to be adjusted to black by a chromatic colorant such as magnetite, carbon black, the following yellow colorant, magenta colorant and cyan colorant are used. In particular, since dyes and carbon black have many polymerization-inhibiting properties, care must be taken when using them.

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, 120, 127, 128, 129, 147, 155, 162, 168, 174, 176, 180, 181, 185, 191 may be mentioned.

As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used.
Specifically, C.I. I. Pigment red 2, 3, 5, 6, 7, 23, 31, 48; 2, 48; 3, 48; 4, 57; 1, 81;
Furthermore, 144, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254 may be mentioned.

As the cyan colorant, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds 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 in combination and further 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 the toner.
These chromatic non-magnetic colorants are contained in the toner particles in a total amount of 1.0 to 20.0 parts by mass with respect to 100 parts by mass of the binder resin.
Furthermore, the toner of the present invention may be a magnetic toner containing a magnetic material as a colorant.

In this case, the magnetic material can also serve as a colorant. Magnetic materials 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, Examples include 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 to apply a hydrophobic treatment with a surface modifier, which is a substance that does not inhibit polymerization.

Examples of such surface modifiers include silane coupling agents and titanium coupling agents. These magnetic materials preferably have a number average particle diameter 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 to 150 parts by mass with respect to 100 parts by mass of the binder monomer or the polymerizable monomer or binder resin. good.

[External additive]
In addition to the pulverized toner external additive in the present invention, any of titanium oxide, alumina oxide, and silica fine particles may be added.
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 oils; or a combination thereof.

In the present invention, the content of the external additives including the external additive for the toner crushed in the toner is preferably 0.1 parts by mass or more and 10.0 parts by mass or less, and 0.5 parts by mass or more. It is more preferably 8.0 parts by mass or less. The external additive may be a combination of a plurality of types of fine particles.
When a two-component developer is prepared by mixing the toner to which the present invention is applied and a magnetic carrier, 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, good results are usually obtained.
Hereinafter, methods for measuring various physical properties of the toner and the like in the present invention will be described.

[Method for Measuring Weight Average Particle Size (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.) using a pore electrical resistance method provided with a 100 μm aperture tube is used.
For setting of measurement conditions and analysis of measurement data, attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.
As the electrolytic aqueous solution used for the measurement, a special grade sodium chloride is dissolved in ion-exchanged water so that the concentration becomes 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) is used. it can.

Prior to 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 in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman The value obtained using Coulter Co.) is set.
By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.
In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

The specific measurement method is as follows.
(1) Put 200 mL of the electrolytic 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 bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) Put 30 mL of the electrolytic aqueous solution into a glass 100 mL flat bottom beaker.
As a dispersant, “Contaminone N” (a nonionic surfactant, an anionic surfactant, a 10% by weight aqueous solution of a neutral detergent for washing a pH 7 precision measuring instrument comprising an organic builder, Wako Pure Chemical Industries, Ltd. 0.3) of a diluted solution obtained by diluting 3) with ion-exchanged water is added.

(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispersion System Tetora150” (manufactured by Nikki Bios Co., Ltd.) with an electrical output of 120 W is prepared. To do.
Put 3.3 L of ion exchange water in the water tank of the ultrasonic disperser, and add 2 mL of Contaminone N into this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the electrolyte solution liquid surface in a beaker may become the maximum.

(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds.
In ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in a sample stand, the electrolyte aqueous solution of (5) in which toner is dispersed is dropped using a pipette, and the measured concentration is adjusted to 5%. The measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the “analysis / volume statistic (arithmetic average)” screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

[Measurement method of BET specific surface area of toner]
The BET specific surface area of the toner is measured according to JIS Z8830 (2001). A specific measurement method is as follows.
As the measuring device, an “automatic specific surface area / pore distribution measuring device TriStar 3000 (manufactured by Shimadzu Corporation)” which employs a gas adsorption method based on a constant volume method as a measuring method is used. Setting of measurement conditions and analysis of measurement data are performed using dedicated software “TriStar3000 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 to the toner, and then the equilibrium pressure P (Pa) in the sample cell and the nitrogen adsorption amount Va (mol · g ⁻¹ ) of the toner 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. The adsorption isotherm 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 obtained by applying the following BET equation.
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 measurement sample, the type of adsorption gas, and the adsorption temperature.)

The BET equation is interpreted as a straight line with an inclination of (C-1) / (Vm × C) and an intercept of 1 / (Vm × C), where Pr is X axis and Pr / Va (1-Pr) is Y axis. Yes (this line is called a BET plot).
Straight line slope = (C-1) / (Vm × C)
Straight line intercept = 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 value of the straight line can be calculated. Vm and C can be calculated by solving the above slope and intercept simultaneous equations using these values.
Furthermore, the BET specific surface area S (m ² · g ⁻¹ ) of the toner is calculated from the calculated Vm and the molecular occupation cross-sectional area (0.162 nm ² ) of the nitrogen molecule based on the following formula.
S = Vm × N × 0.162 × 10 ⁻¹⁸
(N is Avogadro's number (mol- ¹ ).)

The measurement using this apparatus follows the “TriStar 3000 Instruction Manual V4.0” attached to the apparatus, and specifically, the measurement is performed according to the following procedure.
Thoroughly weigh the tare of a dedicated glass sample cell (stem diameter 3/8 inch, volume about 5 mL) that has been thoroughly washed and dried. Then, about 1.5 g of toner is put into the sample cell using a funnel.
The sample cell containing the toner is set in a “pretreatment device Bacrepprep 061 (manufactured by Shimadzu Corporation)” connected to a vacuum pump and a nitrogen gas pipe, and vacuum degassing is continued at 23 ° C. for about 10 hours. . In vacuum degassing, the toner 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 deaeration and finally becomes about 0.4 Pa (about 3 mTorr). After completion of vacuum degassing, nitrogen gas is gradually injected to return the inside of the sample cell to atmospheric pressure, and the sample cell is removed from the pretreatment device. Then, the mass of the sample cell is precisely weighed, and the accurate toner mass 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.

  Next, a dedicated “isothermal jacket” is attached to the stem portion of the sample cell containing the toner. Then, a dedicated 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 cylindrical member having an inner surface made of a porous material and an outer surface made of an impervious material capable of sucking liquid nitrogen to a certain level by capillary action.

  Subsequently, the free space of the sample cell including the connection tool is measured. Free space is measured by measuring the volume of the sample cell with helium gas at 23 ° C., and then measuring the volume of the sample cell after cooling the sample cell with liquid nitrogen in the same manner using helium gas. Calculated from the difference in volume. The saturated vapor pressure Po (Pa) of nitrogen is automatically measured separately using a Po tube built in the apparatus.

  Next, after performing vacuum deaeration in the sample cell, the sample cell is cooled with liquid nitrogen while continuing the vacuum deaeration. Thereafter, nitrogen gas is gradually introduced into the sample cell to adsorb nitrogen molecules to the toner. At this time, the adsorption isotherm is obtained by measuring the equilibrium pressure P (Pa) as needed, and the adsorption isotherm is converted into a BET plot. Note that the points of 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 square 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 in accordance with 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 correction of heat uses the heat of fusion of indium.

Specifically, about 10 mg of toner is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the temperature rising rate is 10 ° C./min between a measurement range of 30 to 200 ° C. Measure with.
In this temperature raising process, a specific heat change is obtained in the temperature range of 40 ° C to 100 ° C. At this time, a straight line obtained by extending the base line before the change in specific heat appears as the first straight line, a straight line obtained by extending the base line after the change in specific heat occurs as the second straight line, and the first straight line and the second straight line. A straight line that is equidistant from the straight line in the vertical axis direction is taken as a third straight line. The temperature at the intersection of the third straight line and the differential heat curve (so-called midpoint glass transition temperature) 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 correction of heat uses the heat of fusion of indium.

Specifically, about 10 mg of toner is precisely weighed, put in an aluminum pan, an empty aluminum pan is used as a reference, and the temperature rising rate is 10 ° C./min between a measurement range of 30 to 200 ° C. Measure with.
In this temperature raising process, a specific heat change is obtained in the temperature range of 40 ° C to 100 ° C. The so-called midpoint glass transition temperature at this time is defined as the glass transition temperature Tg of the binder resin.

[Measurement Method of Volume Distribution Standard 50% Particle Size (D50) of External Additive for Toner]
The volume-based median diameter (D50) of the toner external additive used in the present invention is measured according to JIS Z8825-2 (2001), and is specifically as follows.
As a measuring device, a laser diffraction / scattering particle size distribution measuring device “LA-920” (manufactured by Horiba, Ltd.) is used.
The dedicated software “HORIBA LA-920 for Windows WET (LA-920) Ver. 2.02” attached to LA-920 is used for setting measurement conditions and analyzing measurement data.
As the measurement solvent, ion-exchanged water from which impure solids are removed in advance is used.

The measurement procedure is as follows.
(1) A batch type cell holder is attached to LA-920.
(2) A predetermined amount of ion-exchanged water is put into a batch type cell, and the batch type cell is set in a batch type cell holder.
(3) The inside of the batch cell is stirred using a dedicated stirrer chip.
(4) Press the “refractive index” button on the “display condition setting” screen and select the file “110A000I” (relative refractive index 1.10).
(5) In the “display condition setting” screen, the particle diameter reference is set as the volume reference.

(6) After performing warm-up operation for 1 hour or more, optical axis adjustment, optical axis fine adjustment, and blank measurement are performed.
(7) About 60 mL of ion exchange water is put into a glass 100 mL flat bottom beaker.
About 0.3 mL of the following diluent is added as a dispersant.
-Diluent: "Contaminone N" (Nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for cleaning precision measuring instruments with pH 7 consisting of organic builder, manufactured by Wako Pure Chemical Industries, Ltd. ) Diluted with ion-exchanged water about 3 times mass (8) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System” with an electrical output of 120 W Tetora 150 "(manufactured by Nikka Ki Bios Co., Ltd.) is prepared.
About 3.3 L of ion exchange water is placed in the water tank of the ultrasonic disperser, and about 2 mL of Contaminone N is added to the water tank.

(9) The beaker of (7) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the aqueous solution in a beaker may become the maximum.
(10) In a state where the aqueous solution in the beaker of (9) is irradiated with ultrasonic waves, about 1 mg of a fatty acid metal salt is added to the aqueous solution in the beaker little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds.
In this case, the fatty acid metal salt may solidify and float on the liquid surface. In that case, ultrasonic dispersion is performed for 60 seconds after the mass is submerged by shaking the beaker. Moreover, in ultrasonic dispersion, it adjusts suitably so that the water temperature of a water tank may become 10 to 40 degreeC.

(11) The aqueous solution in which the fatty acid metal salt prepared in the above (10) is dispersed is immediately added little by little to a batch type cell, taking care not to enter bubbles, and the transmittance of the tungsten lamp is 90% to 95%. Adjust so that
Then, the particle size distribution is measured. The volume-based median diameter (D50) is calculated based on the obtained volume-based particle size distribution data.

[Method for Measuring BET Specific Surface Area of External Additive for Toner]
The BET specific surface area of the toner external additive is measured according to JIS Z8830 (2001). A specific measuring method is the same as the above-mentioned [Method for measuring BET specific surface area of toner].

[Method for measuring bulk density of external additive for toner]
In the present invention, the crushability of the toner external additive was evaluated by measuring the bulk density of the toner external additive before and after crushing. The bulk density is measured using a graduated cylinder. Specifically, it is as follows.
(1) Weigh 1.0 g of the external additive for toner before and after crushing with an accuracy of ± 0.02%. The weighing result is m [g].
(2) The weighed external additive for toner is gently put into a dry 200 mL graduated cylinder (minimum scale unit: 2 mL) without being compacted.
(3) If necessary, the upper surface of the added toner external additive is carefully leveled without being compacted, and after a certain period of time, the loose bulk volume is read to the minimum scale unit. The read value is V ₀ [cm ³ ].
(4) The bulk density is calculated by m / V ₀ .

[Method for measuring force between two particles of external additive]
In the present invention, the force between two particles of the toner external additive is measured using AGGROBOT sold by Hosokawa Micron Co., Ltd., which can measure the tensile properties of the powder layer.
As a measuring device, the powder to be measured is placed in a predetermined container and pressed to form a powder layer, and then the tensile powder layer is broken at a predetermined speed to obtain the adhesive force. The specific procedure is as follows.

(1) The powder to be measured is put into a cell having an inner diameter of 25 mm, and the put mass is weighed.
(2) The covered cell is placed on the tapping device and tapped 10 times.
(3) Place the tapped cell on the measuring instrument body.
(4) Test item: Compression / tensile test is selected by application software dedicated to AGGROBOT. Compression speed: 0.1 (mm / s)
Maximum compression force setting value: 8 (kgf)
Tensile speed: 0.4 (mm / s)
Measurement is started after inputting the powder charge mass, the true density of the powder, and the volume average particle diameter of the powder.
(5) When the measurement is completed, the value of the force between two particles (Fp) is read.

Hereinafter, the present invention will be described with reference to examples and comparative examples regarding specific methods for crushing external additives for toner and methods for producing toner, but the present invention is not limited to 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 / liter Na ₃ PO ₄ aqueous solution are added to a four-necked container, and a high-speed stirring device TK Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Was kept at 60 ° C. while stirring at 12,000 rpm. To this, 68 parts by mass of a 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added 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 mole adduct) (molar ratio = 51: 50), acid value = 10 mg KOH / g, glass transition point = 70 ° C., Mw = 10,500, Mw / Mn = 3. 20) 10 parts by mass Negative charge control agent (aluminum compound of 3,5-di-tert-butylsalicylic acid)
0.8 parts by weight 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 Kogyo Co., Ltd.), and each component was dispersed in the polymerizable monomer to prepare a monomer mixture. To the monomer mixture, 20.0 parts by mass of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (50% toluene solution) as a polymerization initiator was added, and a polymerizable monomer was added. A composition was prepared. The polymerizable monomer composition was put into an aqueous dispersion medium, and granulated for 5 minutes while maintaining the rotational 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 allowed to proceed for 6 hours with slow stirring.

Next, the temperature in the container was raised 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 slurry 1. Dilute hydrochloric acid was added to the container containing the slurry 1 to remove the dispersion stabilizer. Further, filtration, washing and drying were performed 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 base particles 1 was 1.1 g / cm ³ .

[Example of external additive for toner]
Examples of the external additive for toner to which the crushing method of the present invention can be applied include inorganic fine particles containing one or more elements selected from magnesium, calcium, strontium, barium, zinc and cerium. The toner external additives listed in Table 1 were used.

一次粒子径：一次粒子の体積平均粒径

Primary particle size: Volume average particle size of primary particles

[Example of crushing equipment]
The structure shown in Table 2 is used as a crushing apparatus applied to the crushing method of the present invention.

[Example 1]
[Crushing process]
Table 2 shows the configuration of the external additive crushing apparatus 1 for the toner according to Example 1, and FIGS. 1 and 7 show schematic configuration diagrams. FIG. 7A is a plan view, and FIG. 7B is a front view.
The crushing apparatus 100 includes a processing tank 110 that stores an external additive for toner, a drive motor 130, and a control unit 140.
The processing tank 110 is a cylindrical container as shown in FIG. 2 (inner height L: 250 mm, inner diameter D: 232 mm, effective volume: about 10 L), and includes a drive shaft 111 at the center of a flat bottom. Yes. The L / D of the processing tank 110 is 1.08.

The drive of the drive motor 130 is transmitted to the drive shaft 111 via the drive belt.
The control unit 140 includes a power switch, a drive ON switch, a drive stop switch, a rotation speed adjustment volume, a rotation speed display section, a product temperature display section, and the like, and controls the operation of the crushing apparatus 100.
The processing blade 120 shown in FIGS. 3 and 4 is attached to the drive shaft 111 as a rotating body that disintegrates the object to be processed inside the processing tank 110.

The processing blade 120 is provided with eight processing portions 122 protruding radially outward from the outer peripheral surface of the annular processing blade main body 121.
The shape of the processing unit 122 is such that the radial width W shown in FIG. 3 is 33 mm and the height H is 28 mm.
The height B of the lower end of the processing unit 122 shown in FIG. 6 was 52 mm, and the height T of the upper end of the processing unit 122 was 80 mm.
Therefore, B with respect to the height L of the processing tank 110 is 20.8%, and T with respect to L is 32.0%.

Further, a control member 123 is provided below the processing unit 122 to promote the rolling of the toner external additive. As shown in FIG. 4, the control member 123 has four columnar portions 123a. As shown in the figure, the upper portion of the columnar portion 123 a is disposed near the processing blade main body 121, and the lower portion of the columnar portion 123 a is disposed near the drive shaft 111. As a result, the columnar part 123a is separated from the drive shaft 111 as it goes from the lower part to the upper part, and the upper part is farthest from the drive shaft 111 in the radial direction.
1.0 kg of external additive 1 for toner was introduced into the pulverization apparatus having the above-described configuration, and pulverized under the conditions shown in Table 3 to obtain pre-crushing external additive 1.
A part of the pre-ground external additive 1 was recovered and the bulk density was measured.

[Evaluation-1: Evaluation of bulk density of external additive for toner]
The bulk density [g / cm ³ ] of the pre-ground external additive 1 obtained above was measured and evaluated according to the following criteria. The evaluation criterion is to evaluate the percentage of the bulk density (B) of the pre-crushing external additive with respect to the bulk density (A) of the external additive for the toner before crushing as the crushing index, and the lower the crushing index, the better. He said.
Crushing index = (B / A) × 100

A: Less than 65 B: 65 or more and less than 75 C: 75 or more and less than 85 D: 85 or more Table 3 shows the evaluation results.

[External processing]
Next, the toner particles and the pre-ground external additive were processed by the toner processing apparatus 200 shown in FIG.
As shown in FIG. 10, the toner processing apparatus 200 includes a processing tank 210 that stores an object to be processed including toner particles and an external additive, a drive motor 250, and a control unit 260.
The processing tank 210 is a cylindrical container having an inner height of 250 mm, an inner diameter of 232 mm, and an effective volume of about 10 L, and includes a drive shaft 221 at the center of a flat bottom. The drive of the drive motor 250 is transmitted to the drive shaft 221 through a drive belt.
The control unit 260 includes a power switch, a drive ON switch, a drive stop switch, a rotation speed adjustment volume, a rotation speed display section, a product temperature display section, and the like, and controls the operation of the toner processing apparatus 200.

A lower blade (agitating blade) 220 shown in FIG. 11A is attached to the drive shaft 221 as a flow means for flowing an object to be processed upward from the bottom of the processing tank 210. As shown in FIG. 11A, a lower blade (stirring blade) 220 having an S-shape and a tip-up shape was used.
Further, an upper blade (processing blade) 230 shown in FIG. 11B is attached to the same drive shaft 221 as the rotating body above the lower blade (stirring blade) 220. The upper blade (processing blade) 230 was provided with two processing portions protruding outward in the radial direction from the outer peripheral surface of the annular main body.

Further, a regulating plate 240 is attached above the upper blade (processing blade) 230.
To the toner processing apparatus 200 having the above-described configuration, 100 parts by mass of the toner base particles 1 and 0.1 part by mass of the pre-pulverized external additive 1 were introduced by 8% of the effective volume of the processing tank 210.
After controlling the peripheral speed at the tip of the upper blade (processing blade) 230 to be 47 m / s and operating for 8 minutes, the coarse particles were removed by sieving with a mesh having a mesh size of 100 μm to obtain a toner.

[Image evaluation]
Image evaluation was performed using the obtained toner using a full color laser printer LBP9510C (hereinafter referred to as a printer) manufactured by Canon Inc.
The printing paper uses CS-680 sold by Canon Marketing Japan.
The evaluation of toner fog was performed as follows.
The obtained toner 1 was filled in a predetermined process cartridge. Next, install the printer in a JIS environment (temperature 23 ° C., relative humidity 50%), adjust the printer body so that the toner loading on the photoconductor is 0.4 mg / cm ^2, and output a test pattern did.

The absolute value of the difference between the whiteness of the unused paper on which the test pattern was not printed and the whiteness of the white background portion of the paper on which the test pattern was output was obtained as the fog amount. For example, when the whiteness of the print paper is 83.0 and the whiteness of the paper on which the test pattern is output is 81.0, the fog amount is set to 2.0.
For the measurement of whiteness, a white photometer TC-6DS (manufactured by Tokyo Denshoku) corresponding to the JIS P 8148 paper pulp test method was used.

The evaluation rank was given as follows with respect to the amount of fog A: Less than 1.0.
B: 1.0 or more and less than 2.0.
C: 2.0 or more and less than 4.0.
D: 4.0 or more.
The evaluation results are shown in Table 4.

In Examples 2 to 12, the crushing apparatus shown in Table 3 and the external additive for toner were used.
[Example 2]
The crushing apparatus 2 shown in FIG. 7 was used. The detailed configuration of the crushing apparatus 2 is shown in Table 2.
The operating conditions were the same as in Example 1, and a pre-ground external additive 2 was obtained.
The evaluation results of the pre-crushing external additive 2 are shown in Table 3, and the evaluation results of the images obtained using the toner obtained by externally treating the pre-crushing external additive 2 are shown in Table 4.

[Example 3]
Table 2 shows the configuration of the external additive crushing device 3 for the toner according to Example 3, and FIG. FIG. 8A is a plan view and FIG. 8B is a front view.
The operating conditions were the same as in Example 1, and a pre-ground external additive 3 was obtained.
The evaluation results of the pre-crushing external additive 3 are shown in Table 3, and the evaluation results of images obtained using the toner obtained by externally treating the pre-crushing external additive 3 are shown in Table 4.

[Example 4]
The crushing apparatus 4 shown in FIG. 7 was used. The detailed configuration of the crushing device 4 is shown in Table 2.
The operating conditions were the same as in Example 1, and a pre-ground external additive 4 was obtained.
The evaluation results of the pre-crushing external additive 4 are shown in Table 3, and the evaluation results of images obtained using the toner obtained by externally treating the pre-crushing external additive 4 are shown in Table 4.

[Example 5]
The crushing apparatus 5 which attached the control board to the upper part of the processing tank 110 of the crushing apparatus shown in FIG. 7 was used. The detailed configuration of the crushing device 5 is shown in Table 2. The operating conditions were the same as in Example 1, and a pre-ground external additive 5 was obtained.
The evaluation results of the pre-crushing external additive 5 are shown in Table 3, and the evaluation results of images obtained using the toner obtained by externally treating the pre-crushing external additive 5 are shown in Table 4.

[Example 6]
Table 2 shows the configuration of the external additive crushing device 6 for the toner in Example 6, and FIG. 9 shows a schematic configuration diagram. FIG. 9A is a plan view and FIG. 9B is a front view.
As shown in FIG. 9, the crushing device 6 is configured not to include a member (control member 123) that promotes rolling. The operating conditions were the same as in Example 1, and a pre-ground external additive 6 was obtained.
The evaluation results of the pre-crushing external additive 6 are shown in Table 3, and the evaluation results of the images obtained using the toner obtained by externally treating the pre-crushing external additive 6 are shown in Table 4.

[Example 7]
The configuration of the crushing apparatus used in Example 7 was the same as the configuration of the crushing apparatus 1 of Example 1, and the operating conditions were such that the peripheral speed of the treatment blade was 33 mm / s, and a pre-crushing external additive 7 was obtained. .
The evaluation results of the pre-crushing external additive 7 are shown in Table 3, and the evaluation results of images obtained using the toner obtained by externally treating the pre-crushing external additive 7 are shown in Table 4.

[Example 8]
The configuration of the crushing apparatus used in Example 8 was the same as the configuration of the crushing apparatus 1 of Example 1, and the operating conditions were such that the peripheral speed of the treatment blade was 22 mm / s, and a pre-crushing external additive 8 was obtained. .
The evaluation results of the pre-crushing external additive 8 are shown in Table 3, and the evaluation results of images obtained using the toner obtained by externally adding the pre-crushing external additive 8 are shown in Table 4.

[Example 9]
The configuration of the crushing device 7 used in Example 9 is the same as the configuration of the crushing device 1 of Example 1 except that the shape (height: L) of the treatment tank 110 is changed, and the operating conditions are also the same as those of Example 1. The pre-crushing external additive 9 was obtained.
The evaluation results of the pre-crushing external additive 9 are shown in Table 3, and the evaluation results of images obtained using the toner obtained by externally treating the pre-crushing external additive 9 are shown in Table 4.

[Example 10]
In Example 10, a pre-ground external additive 10 was obtained under the same conditions as in Example 1 except that the toner external additive 2 was used.
The evaluation results of the pre-crushing external additive 10 are shown in Table 3, and the evaluation results of the images obtained using the toner obtained by externally treating the pre-crushing external additive 10 are shown in Table 4.

[Example 11]
In Example 11, a pre-ground external additive 11 was obtained under the same conditions as in Example 1 except that the toner external additive 3 was used.
The evaluation results of the pre-crushing external additive 11 are shown in Table 3, and the evaluation results of images obtained using the toner obtained by externally treating the pre-crushing external additive 11 are shown in Table 4.

[Example 12]
In Example 12, a pre-ground external additive 12 was obtained under the same conditions as in Example 1 except that the toner external additive 4 was used.
The evaluation results of the pre-crushing external additive 12 are shown in Table 3, and the evaluation results of images obtained using the toner obtained by externally treating the pre-crushing external additive 12 are shown in Table 4.

[Comparative Example 1]
In Comparative Example 1, a pre-ground external additive 13 was obtained under the same operating conditions as in Example 1 except that the apparatus shown in FIG. 10 (the apparatus used in the external addition process in Example 1) was used.
The evaluation results of the pre-crushing external additive 13 are shown in Table 3, and the evaluation results of the image obtained using the toner obtained by externally treating the pre-crushing external additive 13 using the apparatus shown in FIG. 4 shows.

[Comparative Example 2]
As shown in Table 2, a pre-crushing external additive 14 was obtained under the same conditions as in Example 4 except that the crushing apparatus 9 having a lower mounting height of the processing unit 122 was used.
The evaluation results of the pre-crushing external additive 14 are shown in Table 3, and the evaluation results of images obtained using the toner obtained by externally treating the pre-crushing external additive 14 are shown in Table 4.

[Comparative Example 3]
As shown in Table 2, a pre-crushing external additive 15 was obtained under the same conditions as in Example 4 except that the crushing apparatus 10 having a higher attachment height of the processing unit 122 was used.
The evaluation results of the pre-crushing external additive 15 are shown in Table 3, and the evaluation results of images obtained using the toner obtained by externally treating the pre-crushing external additive 15 are shown in Table 4.

[Comparative Example 4]
A pre-ground external additive 16 was obtained under the same conditions as in Example 1 except that the toner external additive 5 was used.
The evaluation results of the pre-crushing external additive 16 are shown in Table 3, and the evaluation results of the images obtained using the toner obtained by externally treating the pre-crushing external additive 16 are shown in Table 4.

As shown in Table 3, in Examples 1 to 12, the crushing index of the toner external additive was lower than that in Comparative Examples 1 to 3.
As a result, as shown in Table 4, the fog amount in the image evaluation of the printer was smaller in Examples 1 to 12 than in Comparative Examples 1 to 3.
Further, as shown in Table 3, when the true density of the toner additive 5 to be processed is low even if the crushing process is performed under the same conditions using the same apparatus as in Example 1, the toner external Additive 5 was swollen up and the crushing index was not sufficiently reduced.

100 ... Disintegrating device 110 ... Processing tank 111 ... Drive shaft 112 ... Jacket 120 ... Processing blade (rotating body)
121 ... Processing blade body (rotary body)
122 ... Processing section 123 ... Control member 130 ... Motor 140 ... Control section 200 ... Toner processing device 210 ... Processing tank 211 ... Jacket 220 ... Lower blade 221 ... Drive shaft 230 ... Upper blade 240 Control plate 250 Motor 260 Control unit

Claims (8)

True density is less 2,900kg / ^{m 3} or more 6,000 kg / ^{m 3,} a toner external additive for the crushing method, which is than two inter-particle force is more than 15pN 200pN,
A crushing apparatus used in the crushing method,
A treatment tank having a cylindrical inner space, and installed so that the central axis of the inner space is substantially vertical;
A rotating body provided so as to be horizontally rotatable with the approximate center of the horizontal cross section of the processing tank as a rotation center, and below the rotating body, there is no other rotating body,
The rotating body includes a rotating body main body, and a processing unit that collides with the toner external additive by the rotation of the rotating body and crushes the toner external additive,
When the height of the processing tank is L, the height from the bottom of the processing tank to the lower end of the processing unit is B, and the height from the bottom of the processing tank to the upper end of the processing unit is T, B is 20.0% or more with respect to L and T is 50.0% or less with respect to L;
When the inner diameter of the treatment tank is D, L / D is 0.8 or more and 1.2 or less,
A method for crushing an external additive for toner.   The said processing part has a processing surface, and the total area of the said processing surface with respect to the area of the cross section which gives the largest cross-sectional area is 3% or more and 20% or less regarding the cross section of the vertical direction of the said processing tank. Of crushing external toner additives.   3. The crushing of the external additive for toner according to claim 1, wherein the crushing device does not have a member that prevents the external additive from rolling within the processing tank above the processing unit. Method.   The method for crushing an external additive for toner according to claim 3, wherein the member that prevents rolling of the external additive is a regulating plate. The rotating body includes a control member that promotes rolling of the external additive,
The control member is at a lower position than the processing surface; and
5. The toner exterior according to claim 1, wherein the control member is installed so that a lower part of the control member is located closer to the central axis than an upper part of the control member. How to break up additives.   The method for crushing an external additive for toner according to any one of claims 1 to 5, wherein the rotating body is rotated so that a peripheral speed at a tip of the processing unit is 30.0 m / sec or more.   The external additive for toner is inorganic fine particles containing one or more elements selected from magnesium, calcium, strontium, barium, zinc and cerium. Method for crushing external additive for toner. A toner manufacturing method including an external addition step of externally adding an external additive for toner to toner particles containing a binder resin and a colorant,
A method for producing a toner, wherein the external additive for toner is an external additive crushed by the method for pulverizing an external additive for toner according to any one of claims 1 to 7.

Images