JP2002229266A - Method for producing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method by which a toner having good developing performance and transferability even in an environment at a high temperature and a high humidity and in an environment at a low temperature and a low humidity and causing little fog and scattering can be produced in large quantities and in a high yield while further enhancing pulverizing efficiency. SOLUTION: A pulverizing means used is a mechanical pulverizer having at least a rotor 314 which is a body of rotation attached to a central rotating shaft 312 and a stator 310 disposed around the rotor while holding a uniform interval between it and the surface of the rotor in such a way that a circular space formed by holding the interval is kept airtight. Each of the rotor and the stator has a plurality of protrusions and depressions each formed between the adjacent protrusions, each of the depressions of at least one of the rotor and the stator has a flat face at the bottom and the surface of the rotor and/or the stator having the flat face is coated with a wear resistant plating film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a toner used in an image forming method such as an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or a toner jet recording method.

[0002]

2. Description of the Related Art In an image forming method such as an electrophotographic method, a toner for developing an electrostatic charge image is used. Toner production methods are roughly classified into pulverization methods and polymerization methods.
A simple and popular production method includes a pulverization method. As a general manufacturing method thereof, a binder resin for fixing to a transfer material, a colorant for giving a color as a toner is used, and a charge control agent for giving a charge to particles as necessary, Add a magnetic material for imparting transportability etc. to the toner itself, additives such as a release agent and a fluidity-imparting agent, mix, melt-knead, and solidify by cooling. If necessary, classify to a desired particle size distribution, or further add a fluidizing agent, etc.,
The toner used for image formation. In the case of a toner used in a two-component developing method, various magnetic carriers are mixed with the above-mentioned toner, and then the resultant is subjected to image formation.

As the pulverizing means, various pulverizing apparatuses are used, and a jet air flow type pulverizer using a jet air flow as shown in FIG. 11, particularly an impingement type air flow pulverizer is often used. The collision-type airflow pulverizer transports the powdery raw material with a high-pressure gas such as a jet stream, injects it from the outlet of the acceleration tube, and collides it with the collision surface of a collision member provided opposite to the opening surface of the acceleration tube outlet. Then, the powder raw material is pulverized by the impact force.

[0004] However, in the above-mentioned collision type air flow pulverizer, a large amount of air (high-pressure gas) is required to produce a toner having a small particle diameter. Therefore, power consumption is extremely large, and there is a problem in terms of energy cost. In particular, in recent years, energy saving of the apparatus has been demanded in response to environmental problems.

On the other hand, as a pulverizing apparatus which is more efficient than a jet air pulverizer in terms of energy, Japanese Patent Laid-Open No.
A rotary mechanical pulverizer as shown in FIG. 1 described in JP-A Nos. 4855, 59-105853, and JP-B-3-15489 is used. This mechanical pulverizer pulverizes powder by introducing powder material into an annular space formed between a rotor rotating at a high speed and a stator disposed around the rotor. According to the mechanical pulverizer, the pulverization can be performed with much less energy than the jet air pulverizer, and the pulverization
The generation of ultrafine powder is small, and the yield can be improved.

Focusing on the shape of the toner particles pulverized by these pulverizers, the toner particles pulverized by the jet air pulverizer have an irregular and angular shape, and the toner particles pulverized by the mechanical pulverizer. Is known to have rounded corners. This is believed to be due to differences in the grinding process. That is, in the pulverization method using a jet stream, most of the pulverization is performed by collision between particles or collision with a collision member,
This is because, in a mechanical pulverizer, most of the pulverization is performed by collision of particles against the walls of the rotor and the stator rotating at high speed. In addition, in mechanical pulverization, heat is generated by pulverization to a considerable extent, and there is also an effect due to thermal spheroidization,
It is considered that the shape of the pulverized toner particles is rounded.

For this reason, the toner particles pulverized by the mechanical pulverizer have a smaller specific surface area than the toner particles pulverized by the jet airflow pulverizer, so that the fluidity is improved.
In addition, since the voids are small, there is an advantage that the filling property is excellent and the addition amount of the external additive is small. In addition, there are also advantages in terms of quality, such as excellent chargeability and transferability. That is, according to the mechanical pulverizer, toner of excellent quality can be produced with energy saving and high yield.

In recent years, as the image quality and definition of copiers and printers have become higher, the performance required for toner as a developer has become more severe, the particle size of the toner has become smaller, and the particle size distribution of the toner has There has been a growing demand for sharp particles that do not contain coarse particles and have few ultrafine powders.

Normally, in a mechanical pulverizer such as a high-speed rotary pulverizer, in order to reduce the pulverized particle size, it is necessary to increase the peripheral speed of the rotor or to narrow the gap between the rotor and the stator. As a result, the grinding load also increases,
Eventually, the supply of the powder raw material to the pulverizer must be reduced. For this reason, the productivity has decreased, and the cost of the toner has increased.

In addition, the mechanical pulverizer wears down the pulverizing surface of the pulverizer during use or due to an inorganic substance contained in the toner, and the pulverizing ability is reduced or the quality of the pulverized material is changed. In addition, there has been a problem that reliability deteriorates due to mixing of abrasion materials. The crushing surfaces are the outer peripheral surface of the rotor and the inner peripheral surface of the stator, and if the surface is worn, it must be replaced.

The wear of the rotor and the stator is as follows.
This is remarkable when the rotational speed of the rotor is increased or the gap between the rotor and the stator is narrowed to obtain toner having a fine particle diameter.

Particularly, in recent years, magnetic toners have often been used as one-component developers because of their convenience. When the magnetic toner containing the magnetic particles is pulverized by the above-mentioned mechanical pulverizer, the surfaces of the rotor and the stator wear much faster than the toner containing no magnetic material. With the abrasion of the crushing surface, the particle shape is likely to be non-uniform, and stable production is difficult, the life of the rotor and the stator is short, the frequency of replacement is increased, and the cost of the product is increased.

In order to improve the wear resistance of the surfaces of the rotor and the stator, quenching, carburizing, and nitriding of the base material are performed. However, the surface hardness is not so high, and the abrasion resistance when crushing the magnetic toner is insufficient.

[0014] A ceramic material is spray-coated on the surface of the base material of the rotor and the stator.
The coating layer was easily peeled off and was insufficient in abrasion resistance.

Further, JP-A-7-155628 and JP-A-11-222480 disclose a method of improving the wear resistance by lining the surfaces of the base materials of the rotor and the stator with a titanium-based material. ing. Although this method has the advantage that the surface hardness is high, there is a problem that voids are easily generated during the lining treatment, peeling and cracks are easily generated, and there is also a problem that the cost of the surface treatment material is high.

[0016]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, to provide a method for producing a toner which can improve the pulverization efficiency, and can produce a high throughput and a high yield. .

It is a further object of the present invention to provide a method for producing a toner having good developability and transferability and having less fogging and scattering.

[0018]

Means for Solving the Problems The present inventor has made intensive studies to solve the above-mentioned problems of the prior art, and as a result, has found out the shapes of the uneven portions of the rotor and the stator in the mechanical pulverizer, and the surface treatment and resistance thereof. Knowing that there is a relationship between abrasion, crushing ability, and toner developability, they have invented a method for producing a toner.

That is, the present invention provides: (1) a mixture containing at least a binder resin and a colorant is melt-kneaded, and after cooling the obtained kneaded material, the cooled material is coarsely pulverized to obtain a coarsely pulverized material. In a method for producing a toner, the method comprises pulverizing a powder material by a pulverizing means and classifying the obtained pulverized material by a classifying means.
The pulverizing means includes a rotor that is a rotor that is attached to at least a central rotating shaft, and a stator that is arranged around the rotor while maintaining a constant interval from the rotor surface,
And is a mechanical pulverizer that is configured so that the annular space formed by maintaining the gap is in an airtight state, the rotor and the stator are both a plurality of convex portions,
A concave portion formed between the convex portion and the convex portion, wherein the concave portion of at least one of the rotor and the stator has a flat surface at a bottom and a flat surface at the bottom A method for producing a toner, wherein a surface of a rotor and / or a stator is coated with plating having wear resistance.

(2) The rotor and / or the stator have a surface hardness of HV400 to 1300 (Vickers hardness of 4).
00 to 1300).

(3) A method for producing a toner, wherein the plating is chromium plating, preferably chromium alloy plating containing at least chromium carbide.

(4) The slope of the protrusion rising from the bottom face of the recess of the rotor on the rear side in the rotor rotation direction is a rotor first slope, and the rotor first slope is the center of the rotation shaft and the rotor first slope. With the line connecting the rising point (A) of the slope as a reference line, the inclination angle (α
1), and a slope of the projection rising from the bottom face of the recess of the stator on the front side in the rotor rotation direction is a stator first slope, and the stator first slope is the center of the rotation axis and the stator. With a line connecting the rising point (A ′) of the first slope as a reference line, an inclination angle (β
1) A method for producing a toner, characterized by having the following 1).

(5) The second inclined surface of the rotor that rises from the bottom surface of the concave portion of the rotor in the rotation direction of the rotor is defined as a second inclined surface of the rotor. A method for producing a toner, characterized by having a slope angle (α2) of less than 20 ° on the plus side with a line connecting the apex (C) of the slope as a reference line.

(6) The second slope of the stator is defined as a slope on the rear side in the rotor rotation direction of the projection rising from the bottom face of the recess of the stator. A method for producing a toner, characterized by having a slope angle (β2) of less than 20 ° on the minus side with respect to a line connecting a vertex (C ′) of a slope as a reference line.

(7) The second slope is the front slope of the projection rising from the bottom of the recess of the rotor in the rotor rotation direction, and the second slope is the center of the rotation shaft and the second rotor. With the line connecting the apex (C) of the slope as a reference line, it has an inclination angle (α2) of less than 20 ° on the plus side, and the rear of the protrusion rising from the bottom of the recess of the stator in the rotor rotation direction. Is the stator second slope, and the stator second slope is minus 20 ° with respect to a line connecting the rotation axis center and the top (C ′) of the stator second slope as a reference line. A toner having a tilt angle (β2) of less than 2.

(8) A method for producing a toner, characterized in that the bottom of the concave portion has curved surfaces at both ends of a flat surface.

(9) The rotor and / or the stator have a part or the whole of a convex portion formed with a curved surface, and the rotor and / or the stator has a concave portion formed with a flat bottom surface. A method for producing a toner.

(10) In the sectional view of the stator taken on a plane perpendicular to the direction of the rotation axis, the height H (mm) of the projection is 1.0 to 3.0 mm, and the length of the flat surface at the bottom of the recess is L1 (m
m) is from 1.0 to 3.0 mm.

(11) A method for producing a toner, characterized in that the height H of the convex portion and the length L1 of the flat surface at the bottom of the concave portion satisfy the following relationship: 0.25H ≦ L1 ≦ 2.5H. is there.

(12) When the length of the upper surface of the convex portion of the rotor and / or the stator is L2 and the length of the surface facing the upper surface of the convex portion is L3, L2 and L3 are as follows. The method for producing a toner according to the above, wherein the condition L2 <L3 is satisfied.

(13) A method for producing a toner, characterized in that the toner is a magnetic toner containing 40 to 200 parts by mass of a magnetic substance with respect to 100 parts by mass of a binder resin.

(14) Pulverization is performed by removing a worn or peeled plating component and using a rotor and / or a stator coated with the plating again and keeping the volume of the annular space within a certain range. Is a method for producing a toner.

(15) A method for producing a toner, comprising setting a minimum gap between the rotor and the stator to 0.5 to 10.0 mm and pulverizing a powder raw material.

(16) The plating layer has a thickness of 20 to 3
A method for producing a toner, characterized in that the thickness of the toner is 00 μm.

(17) A method for producing a toner, wherein the variation width of the minimum gap between the rotor and the stator is 0.5 mm or less.

(18) A method for producing a toner, characterized in that a powder raw material is introduced into a pulverizer together with air at + 30 ° C. or lower (preferably +20 to −40 ° C.).

(19) The mechanical pulverizer has a spiral chamber communicating with the powder inlet, and the room temperature T1 of the spiral chamber is + 20 ° C. or lower (preferably +10 to −30 ° C.). This is a method for producing a toner.

(20) The pulverized material generated in the mechanical pulverizer is discharged from the powder discharge port to the outside of the mechanical pulverizer through a rear chamber, and the room temperature T2 of the rear chamber is 30 to 60. ° C.

(21) The temperature difference ΔT (T2−T1) between the room temperature T2 and the room temperature T1 is 30 to 80 ° C. (preferably 3
(5 to 70 ° C.).

(22) Glass transition temperature T of the binder resin
g is 45 to 75 ° C., and the temperature is controlled so that the room temperature T1 of the spiral chamber of the mechanical pulverizer is + 20 ° C. or lower and 40 to 80 ° C. lower than Tg. is there.

(23) Glass transition temperature T of the binder resin
g is 45 to 75 ° C., and the temperature is adjusted so that the room temperature T2 in the rear chamber of the mechanical pulverizer is 0 to 30 ° C. lower than Tg.

(24) A method for producing a toner, characterized in that the mechanical pulverizer has a jacket for cooling the inside of the machine, and pulverizes the raw material powder while passing cooling water through the jacket.

[0043]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS First, an outline of a pulverizing method using a mechanical pulverizer used in the present invention will be described with reference to FIGS.

FIG. 1 shows an example of a pulverizing system incorporating a mechanical pulverizer used in the present invention, FIG. 2 shows a schematic sectional view taken along the line DD ′ in FIG. 1, and FIG. FIG. 1 is a perspective view of a rotor that rotates at a high speed.

FIG. 1 shows a schematic cross-sectional view of a horizontal type general mechanical pulverizer, but it may be a vertical type. Casing 313, Jacket 316 in casing 313 through which cooling water can flow, Casing 313
A rotor 314 in which a number of grooves are provided on a high-speed rotating surface composed of a rotating body attached to a central rotating shaft 312, and a surface arranged at a constant interval on the outer periphery of the rotor 314. Stator 310 having a large number of grooves formed therein, and a raw material inlet 3 for introducing a raw material to be processed.
11, a raw material discharge port 302 for discharging the powder after the treatment.

In the mechanical pulverizer constructed as described above, when a predetermined amount of the powdery raw material is supplied from the quantitative feeder 315 shown in FIG. 1 to the raw material input port 311 of the mechanical pulverizer,
The raw material is introduced into the pulverization processing chamber, and a rotor 314 provided with a number of grooves on a surface that rotates at a high speed in the pulverization processing chamber.
And instantaneous crushing due to the impact generated between the stator 310 having a large number of grooves formed on the surface thereof, the numerous super-high-speed vortices generated behind it, and the high-frequency pressure vibration generated thereby. . After that, it is discharged through the raw material discharge port 302. Air carrying particles (air)
Passes through the pulverization processing chamber, the raw material discharge port 302, the pipe 21
9, is discharged outside the system of the apparatus system through the collection cyclone 229, the bag filter 222, and the suction filter 224. In the present invention, since the powder raw material is pulverized in this manner, a desired pulverization treatment can be easily performed without increasing fine powder and coarse powder.

Examples of such a mechanical pulverizer include a pulverizer Inomaizer manufactured by Hosokawa Micron Corp., a crusher Cryptoline and Zepros manufactured by Kawasaki Heavy Industries, Ltd., a super rotor manufactured by Nisshin Engineering Co., Ltd., and Turbo Kogyo Co., Ltd. These can be used as they are or after being appropriately modified.

In the method of producing a toner by a pulverization method, a medium pulverization step may be inserted between a coarse pulverization step for obtaining a particle diameter of about 2 mm and a fine pulverization step for obtaining a desired particle diameter. The pulverizing process of the present invention may be a medium pulverizing step or a fine pulverizing step. Also, the pulverization process of the present invention may be connected in series or in parallel to two or more stages for pulverization. However, the process capable of maximizing the effect of the present invention is a process of directly reducing the particle size from a coarsely crushed toner in one pass.

According to the present invention, a mixture containing at least a binder resin and a colorant is melt-kneaded, the obtained kneaded material is cooled, and then the cooled material is coarsely pulverized to pulverize a powder material comprising the coarsely pulverized material. Means for pulverizing the obtained pulverized product and classifying the obtained pulverized material by a classifying means, wherein the pulverizing means includes a rotor as a rotating body attached to at least a central rotating shaft; Mechanical grinding, comprising a surface and a stator arranged around the rotor at a constant distance, and configured so that an annular space formed by maintaining the distance is airtight. The rotor and the stator each have a plurality of protrusions and a recess formed between the protrusions and the protrusions, and at least one of the rotor and the stator The concave portion of Part has a flat surface, the rotor and / or the surface of the stator having a flat surface on the bottom portion, a method for producing a toner which is characterized in that it is coated with a plating having a wear resistance.

The first feature of the mechanical pulverizer used in the present invention is that, as shown in FIGS. 4 to 6 and 8, each of the rotor and the stator has a plurality of convex portions, the convex portions and the convex portions. A recess formed between the rotor and the stator, wherein the recess of at least one of the rotor and the stator has a flat surface at the bottom.

Since the concave portion of at least one of the rotor and the stator has a flat surface at the bottom, the sectional area of the concave portion, that is, the volume of the pulverizing chamber can be increased, and the pressure loss at this portion can be reduced. Since it is possible, more efficient pulverization can be performed as compared with the case where the concave portion does not have a flat surface at the bottom (FIGS. 7 and 9). The recess may have only a stator at the bottom (FIG. 4) or only the rotor (FIG. 5), or both recesses may have a flat surface at the bottom (FIGS. 6 and 5). 8).

That is, as compared with the shape of the crushing surface when the concave portion has no flat surface at the bottom (FIGS. 7 and 9), the shape of the crushing surface of the rotor and / or the stator used in the present invention (FIGS. 4 to 6). In FIG. 8), since the concave portion has a shape having a flat surface at the bottom, the entire portion has a trapezoidal or rectangular shape, so that the pressure loss at this portion can be reduced, and the rotor and the stator can be connected to each other. The impact generated between the two becomes stronger, and the pulverization efficiency is improved. However, the rotor and the stator are severely worn due to the strong impact as described above, and the abraded portion is not evenly distributed on the surface of the rotor and the stator, so that the pulverizing ability is liable to change, and the toner performance is deteriorated. Tended to vary easily.

As a base material of the rotor and the stator of these mechanical pulverizers, carbon steel such as S45C or chromium molybdenum steel such as SCM material is often used. There is a problem that the frequency of replacing the rotor and the stator is high, so the second feature of the mechanical crusher used in the present invention is that these surfaces are used by coating them with plating having wear resistance. That is.

By coating with plating having abrasion resistance, the surface hardness is increased, the abrasion resistance is increased, and a long-life rotor or stator is obtained. Plating makes it possible to finish the surface uniformly and smoothly, to reduce the coefficient of friction, and to improve wear resistance. After plating, a polishing process such as buffing or a blasting process such as shot blasting may be performed to adjust the surface roughness of the rotor and the stator.

The surface hardness of the rotor and / or the stator is preferably HV400 to 1300 (Vickers hardness 400 to 1300). A more preferred surface hardness is HV500 to 1250, particularly preferably HV900 to 1230. The surface hardness in the present invention was measured under the condition that a load of 0.4903 N was held for 30 seconds.

When the surface hardness is in the range of HV400 to 1300, the amount of wear of the crushed surface can be reduced as much as possible, and the frequency of replacing the rotor and the stator can be reduced. If the surface hardness is less than HV400, the wear resistance starts to decrease, and the pulverizing ability cannot be improved. If the surface hardness exceeds HV1300, the surface is too hard and brittle, so that peeling and cracking are likely to occur,
Rotor and stator replacement frequency begins to increase.

When the surface of the rotor and / or the stator is pulverized by a mechanical pulverizer coated with a wear-resistant plating as described above, the wear of the pulverized surface of the rotor and / or the stator is reduced. In addition to extending the life of the rotor, the surface is hard to pulverize to a desired particle size, so that the rotor can be rotated at a low peripheral speed and pulverized. The crushing capacity can be improved. At this time, by making the recesses of the rotor and / or the stator coated with abrasion-resistant plating have a flat surface at the bottom, the pulverization processing capacity (pulverization supply amount) is synergistically improved,
It is possible to further stabilize the toner quality.

Further, since the powder can be crushed to a desired particle diameter at a low peripheral speed, the amount of fine powder and ultrafine powder generated by over-pulverization is small, and the particle size distribution of the crushed material obtained is extremely sharp. In a classification step performed after the step, a toner classification powder having a desired particle size distribution can be obtained in a very high yield.

Further, since the powder can be pulverized to a desired particle size at a low peripheral speed, the calorific value at the time of pulverization is reduced, and the occurrence of fusion and coarse particles in the pulverizer, the thermal denaturation of the toner, and the mechanical roundness are suppressed. It is possible to produce toner particles having a tinged shape without variation in shape distribution. Therefore, the toner particles produced by the method of the present invention have less variation in chargeability and transferability, and are highly developable toner with less fogging and scattering.

A rotor and / or a stator coated with such wear-resistant plating is
By having a flat surface at the bottom of the recess, it is possible to increase the pressure vibration while enabling grinding at a low peripheral speed. It can be prevented from adhering to toner particles having a diameter. Therefore, in the classification process,
Ultrafine powder can be easily separated and removed, mixing in the toner is reduced as much as possible, and lowering of the developing property due to charging inhibition, particularly, low density in a solid black image is prevented.

The type of plating used in the present invention is not particularly limited as long as it has the abrasion resistance required to pulverize the toner powder raw material. For example, nickel plating, electroless nickel plating (plating solution) Composite plating in which fine powders such as diamond, silicon carbide, corundum, and tungsten carbide are added to the coating may be used), chromium plating, rhodium plating, ruthenium plating, and multilayer plating in which these are stacked in multiple layers.
Chromium plating (hard chromium plating) is preferable in terms of excellent wear resistance, and chromium alloy plating containing at least chromium carbide is particularly preferably used. Chromium carbide (Cr ₂₃ C ₆ ), which has a strong intermolecular bonding force, existing in the chromium alloy enhances the adhesion to the base material surface, and can reduce the frequency of occurrence of phenomena such as peeling and cracks.

It has already been mentioned that the rotor and / or the stator in the mechanical pulverizer used in the present invention may have a shape as shown in FIGS. 4 to 6 and FIG. 4, 5 and 6, it is preferable that the crushing surfaces of the rotor and the stator have an inclination angle in the rotation direction of the rotor from the viewpoint of improving the crushing efficiency.

Referring to FIG. 6, the preferred shape of the rotor and / or the stator in the mechanical crusher used in the present invention is more preferably the rotor rotation direction of the protrusion rising from the bottom of the recess of the rotor. The rear slope is a rotor first slope, and the rotor first slope is on the minus side with a line connecting the center of the rotation axis and the rising point (A) of the rotor first slope as a reference line. The stator has a slope angle (α1) of 10 ° or more and less than 80 °, and a first slope of the stator rising from the bottom of the recess in the rotor rotation direction is defined as a first slope of the stator. The slope has a shape having an inclination angle (β1) of 10 ° or more and less than 80 ° on the plus side with respect to a line connecting the center of the rotation axis and the rising point (A ′) of the stator first slope. is there.

As described above, the crushing surfaces of the rotor and the stator have an inclination angle in the rotation direction of the rotor, so that the rotor
Not only is the wear of the crushing surface of the stator reduced, but also a vortex is easily generated in the concave portion, and the crushing efficiency is improved.

Further, a slope on the front side in the rotor rotation direction of the projection rising from the bottom face of the recess of the rotor is defined as a rotor second slope, and the rotor second slope is the center of the rotation shaft and the rotor second slope. It is preferable that the shape has an inclination angle (α2) of less than 20 ° on the plus side with respect to a line connecting the apex (C) of the stator as a reference line. The slope on the rear side in the stator rotation direction is defined as a stator second slope, and the stator second slope is defined by using a line connecting the center of the rotation axis and the apex (C ′) of the stator second slope as a reference line. It is preferable that the shape has an inclination angle (β2) of less than 20 ° on the side, and it is more preferable that the inclination angle α2 of less than 20 ° on the plus side and the inclination angle β2 of less than 20 ° on the minus side are simultaneously satisfied.

By providing the inclined surface on the back side of the crushing surface, a vortex is more likely to be generated in the concave portion, and the crushing efficiency is improved.

It is preferable that the bottom of the concave portion has curved surfaces at both ends of the flat surface. With such a shape, a vortex is more likely to be generated in the concave portion, and the pulverization efficiency is improved.

Further, the rotor and / or the stator may be formed such that a part or the whole of the convex portion is formed with a curved surface, and the rotor and / or the stator is formed with a flat bottom surface of the concave portion. Preferably, by having such a shape, the impact force on the toner is further increased, and the pulverization efficiency is improved.

The dimensions of the rotor and the stator having the above-described configuration are such that the height H (mm) of the projection is 1.0 to 3 in the cross-sectional view of the stator on a plane perpendicular to the rotation axis direction. .0
mm, and the length L1 (mm) of the flat surface at the bottom of the concave portion is preferably 1.0 to 3.0 mm, and more preferably the following relationship: 0.25H ≦ L1 ≦ 2.5H.

When the length of the upper surface of the protrusion of the rotor and / or the stator is L2 and the length of the surface facing the upper surface of the rotor is L3, L2 and L3 satisfy the following condition: L2 It is still more preferable that <L3 is satisfied.

By satisfying the above rules and relationships, the particle size distribution obtained by the conventional mechanical pulverizer having the rotor and the stator having the shapes shown in FIGS. 7 and 9 can be obtained at a higher pulverization supply rate. As a result, the toner production efficiency can be improved.

The above-mentioned pulverization processing capacity (pulverization supply amount)
The improvement in the classification yield is more remarkable as the powder raw material to be pulverized becomes harder, and is particularly remarkable in a magnetic toner containing 40 to 200 parts by mass of a magnetic substance per 100 parts by mass of a binder resin.

However, as the hard powder material such as the magnetic toner is pulverized, and in particular the pulverization of the coarsely pulverized toner material to a fine particle size in one pass is continued, the conventional rotor or fixed rotor which has been subjected to abrasion treatment is used. A mechanical grinder with a rotor and / or stator coated to a lesser extent, but with wear-resistant plating, completely eliminates the possibility of micro-abrasion or delamination of the grinding surface. Cannot be denied.

In order to cope with such a situation, it is necessary to remove the worn or peeled plating component, coat the exposed rotor and / or stator base material surface again with the above-mentioned plating and grind it. preferable. According to such a method, the mother body of the rotor and / or the stator can be continuously used without being damaged, and the resources can be effectively used. Further, the volume of the annular space (pulverization processing chamber) formed between the rotor and the stator can be kept constant, there is no need to change the pulverization conditions, the toner quality is always stable, and a flat surface is maintained. Therefore, high pulverization processing capacity can be maintained.

The minimum space between the rotor and the stator, which determines the volume of the annular space (pulverizing chamber), is 0.5 to 1
0.0 mm, preferably 1.0 to 5.0 m
m is more preferable. The distance between the rotor and the stator is 0.5 to 10.0 mm, more preferably 1.0 mm
When the thickness is from 5.0 mm to 5.0 mm, insufficient pulverization and excessive pulverization of the toner can be suppressed, and the pulverized raw material can be efficiently pulverized. 10.0m between rotor and stator
If it is larger than m, short paths are likely to occur without being crushed. The distance between the rotor and the stator is 0.5mm
If it is smaller, the load on the apparatus itself increases, and at the same time, it is excessively pulverized at the time of pulverization, so that thermal deterioration of the toner and fusing in the machine are likely to occur, so that the productivity of the toner decreases.

The thickness of the plating layer is 20 to 300 μm.
m, more preferably 30 to 200 μm. If the plating thickness is less than 20 μm, the effect of improving the wear resistance is not sufficiently exhibited, and if it exceeds 300 μm, the volume of the annular space (pulverization processing chamber) formed between the rotor and the stator is reduced, and Load may increase, leading to over-crushing or in-machine fusion.

Further, it is preferable that the variation width of the minimum gap between the rotor and the stator is 0.5 mm or less,
More preferably, it is 0.4 mm or less. By setting the fluctuation width to 0.5 mm or less, an annular space (crushing chamber)
Can be reduced, and the toner can be pulverized stably without changing the pulverization conditions.

As a more preferred form of pulverizing the toner, it is preferable to blow air at + 30 ° C. or lower into the pulverizer, and the temperature of the air is more preferably +30 to −50 ° C., and +20 to −40 ° C. Is particularly preferred. By the above-mentioned cold air generating means, the room temperature T1 in the spiral chamber 212 communicating with the powder inlet in the mechanical pulverizer is set at + 20 ° C. or lower, more preferably +20 to −40 ° C., and still more preferably +10 to −30 ° C. This is preferable in terms of toner production and developing performance.

By setting the room temperature T1 of the spiral chamber in the pulverizer to + 20 ° C. or lower, more preferably +10 to −30 ° C., thermal deterioration of the toner can be suppressed, and the pulverized raw material can be efficiently pulverized. Variations in the shape distribution of toner particles are suppressed, and generation of fog is reduced. If the room temperature T1 of the vortex chamber in the pulverizer exceeds + 20 ° C., thermal deterioration of the toner and fusing in the pulverizer are likely to occur at the time of pulverization, which may cause problems in toner production and development / transfer performance.

The refrigerant used in the cold air generating means 321 is preferably a CFC substitute from the viewpoint of global environmental problems. As alternative Freon, R134A, R404
A, R407C, R410A, R507A, R717, etc., among which R404A is particularly preferred from the viewpoint of energy saving and safety.

The finely pulverized material generated in the mechanical pulverizer passes through the rear chamber 320 of the mechanical pulverizer to the powder discharge port 3.
02 is discharged outside the machine. At that time, the room temperature T2 of the rear chamber 320 of the mechanical pulverizer is preferably 30 to 60 ° C. in terms of toner production and development / transfer performance.

The room temperature T2 of the rear chamber 320 of the mechanical pulverizer is set to 3
By setting the temperature to 0 to 60 ° C., thermal deterioration of the toner can be suppressed, the pulverized raw material can be efficiently pulverized, the variation in the shape distribution of the toner particles is suppressed, and the generation of fog is reduced. When the temperature T2 of the mechanical crusher is lower than 30 ° C., there is a possibility that a short path is caused without crushing. On the other hand, when the temperature is higher than 60 ° C., there is a possibility that the toner is excessively pulverized during the pulverization, so that the toner is liable to be thermally deteriorated or fused in the apparatus, which may cause a problem in toner production and development / transfer performance.

When the pulverized raw material is pulverized by a mechanical pulverizer, the room temperature T1 of the spiral chamber 212 and the rear chamber 3
The temperature difference ΔT (T2−T1) of the room temperature T2 of 20 is preferably 30 to 80 ° C., and more preferably 35 to 70 ° C. in terms of toner production and development and transfer performance. ΔT between the temperature T1 and the temperature T2 of the mechanical pulverizer is 30
By setting the temperature to a temperature of from 80 to 80 ° C., more preferably from 35 to 70 ° C., the thermal deterioration of the toner can be suppressed, the pulverized raw material can be efficiently pulverized, the variation in the shape distribution of the toner particles can be suppressed, and the generation of fog can be suppressed. Less. When ΔT between the temperature T1 and the temperature T2 of the mechanical crusher is smaller than 30 ° C., there is a possibility that a short path is caused without crushing. On the other hand, when the temperature is higher than 80 ° C., there is a possibility that the toner is excessively pulverized at the time of pulverization.

Further, the powder raw material to be pulverized by the above-mentioned mechanical pulverizer contains a binder resin having a glass transition temperature Tg of 45 to 75 ° C., and the room temperature T of the spiral chamber 212 of the mechanical pulverizer.
1 is + 20 ° C. or lower and 40 to 80 than Tg.
It is preferable to control the temperature to be lower by ° C. in terms of toner production and development / transfer performance. Room temperature T1 of the spiral chamber 212 of the mechanical crusher
Less than + 20 ° C. and 40 to 80 ° C. higher than Tg
By lowering, the deterioration of the binder resin, which is a major factor of thermal deterioration, can be suppressed, the pulverized raw material can be efficiently pulverized, the variation in the shape distribution of the toner particles is suppressed, and the generation of fog is reduced. . Further, it is preferable to control the temperature such that the room temperature T2 of the rear chamber 320 of the mechanical pulverizer is lower by 0 to 30 ° C. than Tg. Rear chamber 3 of mechanical crusher
By lowering the room temperature T2 of T.sub.20 by 0.degree. To 30.degree. C. below Tg, thermal degradation of the toner can be suppressed, the pulverized raw material can be efficiently pulverized, the variation in the shape distribution of toner particles can be suppressed, and fog and Reduce the occurrence of scattering.

In the present invention, the glass transition temperature Tg of the binder resin is determined by a differential thermal analyzer (DSC measurement device),
The measurement was performed using SC-7 (manufactured by PerkinElmer) under the following conditions. Sample: 5 to 20 mg, preferably 10 mg Temperature curve: temperature rise I (20 ° C. → 180 ° C., temperature rise rate 10 ° C.)
/ Min. ) Cooling I (180 ° C → 10 ° C, cooling rate 10 ° C / mi
n. ) Heating II (10 ° C → 180 ° C, heating rate 10 ° C / mi)
n. ) Tg measured at the temperature rise II is defined as a measured value. Measurement method: A sample is placed in an aluminum pan, and an empty aluminum pan is used as a reference. The intersection of the line at the midpoint of the base line before and after the endothermic peak appeared and the differential heat curve was defined as the glass transition point Tg.

In order to control the room temperature T2 in the rear chamber of the pulverizer as described above, the mechanical pulverizer has a jacket structure 316 as a cooling means in the mechanical pulverizer main body. Preferably, an antifreeze such as ethylene glycol is passed through. According to this method, it is possible to control the room temperature T2 of the rear chamber of the above-mentioned mechanical pulverizer also by the water temperature and the amount of water passing therethrough.

The cooling water (preferably an antifreeze such as ethylene glycol) is supplied into the jacket from a cooling water supply port 317 and discharged from a cooling water discharge port 318.

As described above, the powder raw material is introduced together with the cool air into the mechanical pulverizer having the rotor and / or the stator coated with the chromium alloy plating containing at least chromium carbide, and When the pulverization is carried out while controlling the room temperature, a high-quality toner without heat denaturation can be obtained in a high yield with a high pulverization processing capacity not obtained conventionally.

The particle size distribution can be measured by various methods. In the present invention, the particle size distribution was measured using a Coulter counter multisizer.

As a measuring device, a Coulter counter Multisizer II or IIe type (manufactured by Coulter) was used, and an interface (manufactured by Nikkaki) for outputting the number distribution and volume distribution and a general personal computer were connected. As the electrolyte, a 1% NaCl aqueous solution is prepared using a special grade or primary grade sodium chloride. As a measuring method, 0.1 to 5 ml of a surfactant (preferably an alkylbenzene sulfonate) is added as a dispersing agent to 100 to 150 ml of the electrolytic aqueous solution, and the measurement sample is further measured for 2 to 20 m.
Add g. The electrolyte in which the sample is suspended is approximately 1
Dispersion treatment is carried out for up to 3 minutes, and the measurement is carried out using a Coulter Counter Multisizer II with a 100 μm aperture. The volume and number of the toner are measured, the volume distribution and the number distribution are calculated, and the weight-based weight average diameter determined from the volume distribution is determined.

Next, the toner constituent materials used in the method for producing a toner of the present invention will be described. As the binder resin used in the present invention, any resin commonly used for toner can be used, and examples thereof include the following.

For example, vinyl resins, phenol resins,
Natural resin-modified phenolic resin, natural resin-modified maleic resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumaroindene Resins, petroleum resins and the like. Among them, vinyl resins and polyester resins are preferable in terms of chargeability and fixability.

As the vinyl resin, for example, styrene; o
-Methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene,
p-ethylstyrene, 2,4-dimethylstyrene, p-
n-butylstyrene, p-tert-butylstyrene,
Styrene derivatives such as pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene;
Ethylene unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene; unsaturated polyenes such as butadiene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; vinyl acetate, vinyl propionate , Vinyl esters such as vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate;
Isobutyl methacrylate, n-octyl methacrylate,
Dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate,
Α-methylene aliphatic monocarboxylic esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate Acrylates such as dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl methyl ketone ,
Vinyl ketones such as vinylhexyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole and N-vinylpyrrolidone; vinylnaphthalenes;
Acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide; α,
Esters of β-unsaturated acid, diesters of dibasic acid; acrylic acid such as acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, cinnamic acid, vinylacetic acid, isocrotonic acid, angelic acid and α- or β-alkyl derivatives; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, alkenyl succinic acid, itaconic acid, mesaconic acid, dimethyl maleic acid and dimethyl fumaric acid, and monoester derivatives or anhydrides thereof. These vinyl monomers are used alone or in combination of two or more.

Among these, a combination of monomers that results in a styrene copolymer or a styrene-acrylic copolymer is preferred.

Further, if necessary, a polymer or a copolymer cross-linked with a cross-linkable monomer as exemplified below may be used.

Examples of the aromatic divinyl compound include divinylbenzene and divinylnaphthalene; examples of the diacrylate compound linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, and 1,4-butane. Diol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate and acrylates of the above compounds in place of methacrylate;
Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, and diethylene glycol diacrylate. Propylene glycol diacrylate and acrylates of the above compounds in place of methacrylate; examples of diacrylate compounds linked by a chain containing an aromatic group and an ether bond include polyoxyethylene (2) -2,
2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4
(Hydroxyphenyl) propane diacrylate and acrylates of the above compounds in place of methacrylate; polyester-type diacrylates include, for example, MANDA (Nippon Kayaku).

As the polyfunctional crosslinking agent, pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate; Triallyl cyanurate and triallyl trimellitate;

These cross-linking agents are used alone or as a mixture, and are used with respect to 100 parts by mass of the other monomer components.
0.01 to 10 parts by mass (more preferably 0.03 to 5 parts by mass)
Parts by mass) can be used.

Among these crosslinkable monomers, those which are preferably used in toner resins from the viewpoint of fixability and offset resistance include aromatic divinyl compounds (particularly divinylbenzene), chains containing aromatic groups and ether bonds. Diacrylate compounds tied together.

In the present invention, a homopolymer or copolymer of a vinyl monomer, polyester, polyurethane, epoxy resin, polyvinyl butyral, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, An aromatic petroleum resin or the like can be used by mixing it with the binder resin described above, if necessary.

When two or more resins are mixed and used as a binder resin, as a more preferred form, those having different molecular weights are preferably mixed at an appropriate ratio.

The glass transition temperature of the binder resin is preferably 4
The temperature is 5 to 80C, more preferably 55 to 70C, the number average molecular weight (Mn) is 2,500 to 50,000, and the weight average molecular weight (Mw) is 10,000 to 1,000,000.
It is preferred that

As a method for synthesizing a binder resin comprising a vinyl polymer or a copolymer, polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used. When a carboxylic acid monomer or an acid anhydride monomer is used, it is preferable to use a bulk polymerization method or a solution polymerization method due to the nature of the monomer.

In the bulk polymerization method, a polymer having a low molecular weight can be obtained by increasing the termination reaction rate by polymerizing at a high temperature, but there is a problem that the reaction is difficult to control.

In the solution polymerization method, a low molecular weight polymer can be easily obtained under mild conditions by utilizing the difference in radical chain transfer depending on the solvent and by adjusting the amount of the polymerization initiator and the reaction temperature. It is preferable to obtain a low molecular weight compound in the resin composition used in the present invention.

As the solvent used in the solution polymerization, xylene, toluene, cumene, cellosolve acetate, isopropyl alcohol or benzene is used. When a styrene monomer is used, xylene, toluene or cumene is preferred. The solvent is appropriately selected depending on the polymer to be polymerized. The reaction temperature varies depending on the solvent used, the polymerization initiator, and the polymer to be polymerized.
It is better to carry out at 30 ° C. In solution polymerization, solvent 100
It is preferable to carry out with 30 to 400 parts by mass of the monomer with respect to parts by mass. Further, it is also preferable to mix another polymer in the solution at the end of the polymerization, and several types of polymers can be mixed well.

As a polymerization method for obtaining a high molecular weight component or a gel component, an emulsion polymerization method or a suspension polymerization method is preferable.

Among them, the emulsion polymerization method is a method in which a monomer almost insoluble in water is dispersed in an aqueous phase as small particles with an emulsifier, and polymerization is carried out using a water-soluble polymerization initiator. In this method, the reaction heat can be easily controlled, and the termination reaction rate is low because the phase in which the polymerization is performed (the oil phase composed of the polymer and the monomer) and the aqueous phase are different. As a result, the polymerization rate is high. , With a high degree of polymerization. Furthermore, because the polymerization process is relatively simple, and because the polymerization product is fine particles, it is easy to mix with colorants and charge control agents and other additives in the production of toner. This is advantageous as compared with other methods as a method for producing a binder resin for a toner.

However, the resulting polymer tends to be impure due to the added emulsifier, and an operation such as salting out is required to remove the polymer. Therefore, suspension polymerization is a simpler method.

In the suspension polymerization, 100 parts by mass or less of the monomer (preferably 10 parts by mass) is added to 100 parts by mass of the aqueous medium.
To 90 parts by mass). As a dispersant that can be used, polyvinyl alcohol, partially saponified polyvinyl alcohol or calcium phosphate is used. Generally, 0.05 to 1 part by mass of a dispersant is used per 100 parts by mass of the aqueous medium. The polymerization temperature is suitably from 50 to 95 ° C, but should be appropriately selected depending on the polymerization initiator used and the target polymer. As the polymerization initiator, any one which is insoluble or hardly soluble in water can be used.

Examples of the polymerization initiator include t-butylperoxy-2-ethylhexanoate, cumin perpivalate, t-butylperoxylaurate, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, t-butyl peroxide, t-
Butylcumyl peroxide, dicumyl peroxide, 2,2′-azobisisobutyronitrile, 2,2 ′
-Azobis (2-methylbutyronitrile), 2,2'-
Azobis (2,4-dimethylbutyronitrile), 2,
2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1-bis (t-butylperoxy)
-3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,4-
Bis (t-butylperoxylcarbonyl) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (t -Butylperoxy) butane, 1,3-bis (t-butylperoxy-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2 , 5-di (benzoylperoxy) hexane, di-
t-butylperoxyisophthalate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl)
Propane, di-t-butylperoxy α-methylsuccinate, di-t-butylperoxydimethylglutarate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, diethylene glycol-bis (T-butylperoxycarbonate), di-t-butylperoxytrimethyladipate, tris (t-butylperoxy) triazine, vinyltris (t-butylperoxy) silane, and the like. These may be used alone or in combination. Can be used. The amount used is 0.05 parts by mass or more (preferably 0.1 to 15 parts by mass) with respect to 100 parts by mass of the monomer.

As the binder resin, the following polyester resins are also preferable.

The polyester resin contained 45 to 55 of all components.
mol% is the alcohol component, 55 to 45 mol%
Is an acid component.

The dihydric alcohol component includes ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol and 1,5-pentanediol. , 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-
Hexanediol, hydrogenated bisphenol A, bisphenol represented by the following formula (A) and derivatives thereof;

[0115]

Embedded image (In the formula, R is an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10.) Further, diols represented by the formula (B);

[0116]

Embedded image

Examples of the divalent acid component include phthalic acid,
Benzenedicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic anhydride or anhydrides thereof, lower alkyl esters; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid or anhydrides thereof, lower alkyl esters; Alkenyl succinic acids such as dodecenyl succinic acid, n-dodecyl succinic acid or alkyl succinic acids or anhydrides, lower alkyl esters;
Examples thereof include unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, and itaconic acid or anhydrides thereof, dicarboxylic acids such as lower alkyl esters, and derivatives thereof.

It is preferable to use a trivalent or higher valent alcohol component and a trivalent or higher valent acid component which also function as a crosslinking component.

As the polyhydric alcohol component having three or more valences,
For example, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol,
1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropynetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,
3,5-trihydroxybenzene and the like.

Examples of the trivalent or higher polycarboxylic acid component include:
For example, trimellitic acid, pyromellitic acid, 1,2,4-
Benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid,
1,2,4-naphthalenetricarboxylic acid, 1,2,4-
Butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid , Empole trimer acid, and their anhydrides and lower alkyl esters; the following formula (C)

[0121]

Embedded image (Wherein X is an alkylene group or alkenylene group having 5 to 30 carbon atoms having at least one side chain having 3 or more carbon atoms), and polyvalent such as anhydrides and lower alkyl esters thereof. Carboxylic acids and their derivatives are mentioned.

The alcohol component of the polyester resin is particularly preferably a bisphenol derivative represented by the above formula (A), and the acid component is phthalic acid, terephthalic acid, isophthalic acid or its anhydride, succinic acid, n-dodecenylsuccinic acid. And dicarboxylic acids such as anhydrides, fumaric acid, maleic acid and maleic anhydride; and trimellitic acids or tricarboxylic acids of anhydrides thereof.

This is because the toner for fixing with a heat roller using the polyester resin obtained from the acid component and the alcohol component as a binder resin has good fixability and excellent offset resistance.

The acid value of the polyester resin is preferably 90
mgKOH / g or less, more preferably 50 mgKOH / g
g, and the OH value is preferably 50 mg KOH / g.
Below, it is more preferable that it is 30 mgKOH / g. This is because the environmental dependence of the charging characteristics of the toner increases as the number of terminal groups in the molecular chain increases.

The glass transition temperature of the polyester resin is preferably 50 to 75 ° C., more preferably 55 to 65 ° C., and the number average molecular weight (Mn) is preferably 1,500.
~ 50,000, more preferably 2,000 ~ 20,000.
And the weight average molecular weight (Mw) is preferably 6,
000 to 100,000, more preferably 10,000
It is better to be ~ 90,000.

The toner particles used in the present invention contain a coloring agent together with the above-mentioned binder resin. As the coloring agent, any pigments and / or dyes other than carbon black and titanium white can be used. .

As the nonmagnetic colorant that can be used in the toner of the present invention, any suitable pigment or dye can be used.
For example, examples of pigments include carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizaren lake, bengara, phthalocyanine blue, and indanthrene blue. These are 0.1 to 100 parts by mass of the binder resin.
The addition amount of 20 parts by mass, preferably 1 to 10 parts by mass is good. Similarly, dyes are used, for example, anthraquinone dyes, xanthene dyes, methine dyes,
The addition amount is 0.1 to 20 parts by mass, preferably 0.3 to 10 parts by mass, based on 100 parts by mass of the binder resin.

In the method of producing a toner of the present invention, when producing a magnetic toner using a magnetic substance as a colorant, the following magnetic substances can be used. In this case, the magnetic material also functions as a colorant. Examples of the magnetic material contained in the magnetic toner include iron oxides such as magnetite, maghemite, and ferrite, and iron oxides containing other metal oxides; metals such as Fe, Co, and Ni; or metals such as Al and Co. , Cu, Pb, Mg, Ni, S
n, Zn, Sb, Be, Bi, Cd, Ca, Mn, S
e, alloys with metals such as Ti, W and V, and mixtures thereof.

Specifically, examples of the magnetic material include iron tetroxide (Fe ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), and yttrium iron ( Y ₃ Fe ₅
O ₁₂ ), cadmium iron oxide (CdFe ₂ O ₄ ), gadolinium iron oxide (Gd ₃ Fe ₅ O ₁₂ ), copper iron oxide (CuFe ₂
O ₄ ), lead iron oxide (PbFe ₁₂ O ₁₉ ), nickel iron oxide (NiFe ₂ O ₄ ), iron oxide niodymium (NdFe ₂ O ₃ ),
Barium iron oxide (BaFe ₁₂ O ₁₉ ), magnesium iron oxide (MgFe ₂ O ₄ ), lanthanum iron oxide (LaFe
O ₃ ), iron powder (Fe), cobalt powder (Co), nickel powder (Ni) and the like. The above-mentioned magnetic materials are used alone or in combination of two or more. Particularly preferred magnetic materials are fine powders of triiron tetroxide or gamma-iron sesquioxide.

The shapes of these magnetic materials include octahedron,
There are a hexahedron, a sphere, a needle shape, a scale shape and the like, but an octahedron, a hexahedron and a sphere having little anisotropy are preferable. This is because those having an isotropic shape can achieve good dispersibility even in the binder resin and wax used in the present invention.

Further, these ferromagnetic materials have an average particle size of 0.1.
BET specific surface area by nitrogen gas adsorption method is 1 to 40 m ² / g, and more preferably ^{2 to} 301 to ⁴ μm.
0 m ² / g, and the magnetic properties when 795.8 kA / m was applied showed a coercive force of 1.6 to 12.0 kA / m and a saturation magnetization of 50 to
200 Am ² / kg (preferably 50-100 Am ² / k
g), those having a residual magnetization of ^{2 to 20} Am ² / kg are preferable.

These magnetic materials are used in an amount of 40 to 200 parts by mass, preferably 60 to 200 parts by mass, based on 100 parts by mass of the binder resin.
It is preferable to contain 150 parts by mass. If the amount is less than 40 parts by mass, the toner transportability is insufficient, and the developer layer on the developer carrier becomes uneven, which tends to cause image unevenness. The drop is likely to occur. On the other hand, when the amount exceeds 200 parts by mass, the developer cannot be sufficiently charged, so that the image density tends to decrease.

In the toner of the present invention, a charge control agent can be used if necessary in order to further stabilize the chargeability. As a method of incorporating the charge control agent into the toner, there are a method of adding the toner inside the toner and a method of externally adding the toner,
It is preferable to use 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass per 100 parts by mass of the binder resin.

Examples of the charge control agent include the following.

As the negative charge controlling agent for making the toner negatively chargeable, for example, an organometallic complex or a chelate compound is effective. Examples thereof include a monoazo metal complex, a metal complex of an aromatic hydroxycarboxylic acid, and a metal complex of an aromatic dicarboxylic acid. As metal complex type monoazo compounds,
-20153, 42-27596, 4
There are metal complexes of monoazo dyes described in JP-A-4-6397 and JP-A-45-26478. In particular, from the viewpoint of dispersibility, chargeability, and the like, a metal complex-type monoazo compound represented by the following general formula (D) is preferable, and a metal complex-type monoazo compound in which the central metal is iron is particularly preferable.

[0136]

Embedded image (Wherein, M represents a coordination center metal, and Cr, Co, Ni,
Mn, Fe, Ti or Al. . Ar is an aryl group, is a phenyl group or a naphthyl group, and may have a substituent. In this case, the substituent includes a nitro group, a halogen group, a carboxyl group, an anilide group and a group having 1 to 1 carbon atoms.
8 is an alkyl group or an alkoxy group. X, X ', Y,
Y 'is -O-, -CO-, -NH-, -NR- (R is an alkyl group having 1 to 4 carbon atoms). A ⁺ is a hydrogen ion,
It represents a sodium ion, a potassium ion, an ammonium ion or an aliphatic ammonium ion. )

Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts thereof, anhydrides or esters thereof, and phenol derivatives of bisphenol.

Examples of the positive charge controlling agent for making the toner positively charged include nigrosine and denatured products of nigrosine with a fatty acid metal salt; tributylbenzylammonium-1-hydroxy-4-naphthosulfonate; Quaternary ammonium salts such as borate, and onium salts such as phosphonium salts and their lake pigments; triphenylmethane dyes and these lake pigments (phosphor tungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, Tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), metal salts of higher fatty acids;
Dibutyltin oxide, dioctyltin oxide,
Diorganotin oxides such as dicyclohexyltin oxide; diorganotin borates such as dibutyltin borate, dioctyltin borate, dicyclohexyltin borate; guanidine compounds, imidazole compounds, and the like. These may be used alone or in combination of two or more. it can. Among these, a triphenylmethane compound and a quaternary ammonium salt whose counter ion is not halogen are preferably used.

In the case where the toner produced by the toner production method of the present invention is a color toner, a charge control agent which is colorless, has a high charge speed of the toner and can stably maintain a constant charge amount is particularly preferable. Specific examples of such compounds include salicylic acid, naphthoic acid, dicarboxylic acid, metal compounds of their derivatives, sulfonic acid,
Examples thereof include a high molecular compound having a carboxylic acid in a side chain, a boron compound, a urea compound, a silicon compound, and carricks arene. Positive compounds include quaternary ammonium salts, polymer compounds having the quaternary ammonium salt in the side chain, guanidine compounds, imidazole compounds and the like.

These charge control agents are preferably used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin. However, in the present invention, the addition of the charge control agent is not essential. For example, the toner used in the image forming method of the two-component developing method uses frictional charging with a carrier to charge the toner, and the toner used in the non-magnetic one-component blade coating developing method also Since the toner is charged by positively utilizing frictional charging with the blade member and the sleeve member, it is not always necessary to include a charge control agent in the toner.

In the toner production method of the present invention, one or more waxes may be used as necessary as a constituent material of the toner. In this case, the following waxes can be used. For example,
Low-molecular-weight polyethylene, low-molecular-weight polypropylene, microcrystalline wax, aliphatic hydrocarbon wax such as paraffin wax, or an oxide of an aliphatic hydrocarbon wax such as oxidized polyethylene wax, or
Block copolymers thereof; waxes mainly containing fatty acid esters such as carnauba wax, sasol wax, montanic acid ester wax, and fatty acid esters such as deoxidized carnauba wax partially or wholly deoxidized. And the like.

Further, saturated straight-chain fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and barinanoic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol Saturated alcohols such as glycerol, seryl alcohol and melisyl alcohol; polyhydric alcohols such as sorbitol; linoles amides;
Fatty acid amides such as oleic acid amide and lauric acid amide; saturated fatty acid bisamides such as methylenebisstearic acid amide, ethylenebiscapramide, ethylenebislauric acid amide, hexamethylenebisstearic acid amide; ethylenebisoleic acid amide; Unsaturated fatty acid amides such as hexamethylenebisoleic acid amide, N, N'-dioleyladipamide, N, N'-dioleylsebacic acid amide; m-xylenebisstearic acid amide, N, N'-diamide Aromatic bisamides such as stearyl isophthalic acid amide; calcium stearate, calcium laurate, zinc stearate,
Aliphatic metal salts such as magnesium stearate (commonly referred to as metal soaps), waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid, And a partially esterified product of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol, and a methyl ester compound having a hydroxyl group obtained by hydrogenation of a vegetable oil or the like.

The waxes that can be preferably used include:
Paraffin wax, microcrystalline wax,
Petroleum waxes and derivatives thereof such as petrolactam, montan waxes and derivatives thereof, hydrocarbon waxes and derivatives thereof by the Fischer-Tropsch method, polyolefin waxes and derivatives thereof represented by polyethylene, carnauba wax, candelilla wax, and natural waxes. Derivatives such as oxides,
Also includes a block copolymer with a vinyl monomer and a graft-modified product. Alcohols such as higher aliphatic alcohols; fatty acids such as stearic acid and palmitic acid or compounds thereof; acid amides, esters, ketones, hydrogenated castor oil and derivatives thereof, vegetable waxes, animal waxes and the like.

Among these, it is particularly preferable to use a hydrocarbon wax, a petroleum wax or a higher aliphatic alcohol by a polyolefin, a Fischer-Tropsch method, or a higher aliphatic alcohol as a constituent material of the toner, and to manufacture a toner containing these. In the toner production method of the present invention, among the above, it is preferable to further use a polyolefin or a hydrocarbon wax or a petroleum wax obtained by a Fischer-Tropsch method as a constituent material of the toner.

In the present invention, when these waxes are used, the amount is 0.1 to 4 parts by weight per 100 parts by weight of the binder resin.
5 parts by weight is desirable.

A fluidity improver may be added to the toner of the present invention. The fluidity improver can be added to the toner particles to increase the fluidity before and after the addition. For example, fluorine resin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; fine powder silica such as wet-process silica and dry-process silica, fine-powder titanium oxide, fine-powder alumina, and silane compounds thereof; Titanium coupling agents, treated silica surface-treated with silicone oil, and the like are available. These may be used alone or in combination.

Preferred fluidity improvers are fine powders produced by the vapor phase oxidation of silicon halides, and are produced from dry silica called so-called dry silica or fumed silica, water glass and the like. Although it is a so-called wet silica, dry silica having less silanol groups on the surface and in the inside and having less production residues such as Na ₂ O and SO ₃ ^2- is more preferable. In the case of fumed silica, for example, in the production process, by using aluminum chloride, titanium chloride, and other halogen compounds together with a silicon halide compound, it is also possible to obtain a composite fine powder of silica and other metal oxides. Is also included.

The particle size is defined as an average primary particle size of 0.1.
It is preferable to use a silica fine powder in a range of 001 to 2 μm, particularly preferably in a range of 0.002 to 0.2 μm.

As commercially available fine silica powder produced by the vapor phase oxidation of a silicon halide, there is, for example, one commercially available under the following trade names.

AEROSIL (Nippon Aerosil) 130 200 300 380 TT600 MOX170 MOX80 COK84 Ca-O-SiL (CABOT Co.) M-5 MS-7 MS-75 HS-5 EH-5 Wacker HDKN 20 (WACKER-) CHEMIE GMBH) V15 N20E T30 T40 DC Fine Silica (Dow Corning Co.) Fransol (Fransil)

Further, a treated silica fine powder obtained by subjecting a silica fine powder produced by vapor-phase oxidation of the silicon halide compound to a hydrophobic treatment is more preferable. It is particularly preferable that the treated silica fine powder is obtained by treating the silica fine powder such that the degree of hydrophobicity measured by a methanol titration test shows a value in the range of 30 to 80.

The method for imparting hydrophobicity is provided by chemically treating with an organic silicon compound or the like which reacts with or physically adsorbs silica fine powder. The preferred method is
After treating the dry silica fine powder generated by the vapor phase oxidation of the silicon halide with a silane coupling agent,
Alternatively, a method of treating with a silane coupling agent and at the same time with an organosilicon compound such as silicone oil may be used.

Examples of the silane coupling agent used in the hydrophobic treatment include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, and allylphenyldichlorosilane. , Benzyldimethylchlorosilane,
Bromometridimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan,
Triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and one molecule For example, dimethylpolysiloxane having 2 to 12 siloxane units per unit and having a hydroxyl group bonded to Si, one of each of the units located at the terminal.

Examples of the organosilicon compound include silicone oil. Preferred silicone oils are those having a viscosity of 30 to 1000 mm ² / s at 25 ° C., such as dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, and fluorine-modified silicone oil. Is particularly preferred. These are used alone or as a mixture of two or more.

As a method of treating the silicone oil, for example, the silica fine powder treated with the silane coupling agent may be directly mixed with the silicone oil using a mixer such as a Henschel mixer, or the silica fine powder serving as a base may be mixed. A method of spraying silicone oil on the surface may be used.

The fluidity improver has a specific surface area by nitrogen adsorption measured by the BET method of 30 m ² / g or more, preferably 5 m ² / g or more.
Those with 0 m ² / g or more give good results. Toner 1
0.01 to 8 parts by mass of the fluidity improver with respect to 00 parts by mass,
Preferably, 0.1 to 4 parts by mass is used.

If necessary, an external additive other than silica fine powder or titanium oxide fine powder may be added to the toner of the present invention. For example, there are resin fine particles and inorganic fine particles which function as a charge auxiliary agent, a conductivity imparting agent, an anti-caking agent, a release agent at the time of hot roll fixing, a lubricant, an abrasive, and the like.

For example, lubricants such as Teflon, stearic acid and polyvinylidene fluoride, among which polyvinylidene fluoride are preferred. Alternatively, abrasives such as cerium oxide, silicon carbide, and strontium titanate, among which strontium titanate is preferable. Alternatively, a fluidity-imparting agent such as titanium oxide and aluminum oxide, particularly a hydrophobic agent is preferred. A small amount of a caking inhibitor or a conductivity-imparting agent such as carbon black, zinc oxide, antimony oxide, or tin oxide, or white and black fine particles of opposite polarity can also be used as a developer improver.

The fine resin particles, inorganic fine powder, or hydrophobic inorganic fine powder mixed with the toner is used in an amount of 0.1 to 5 parts by mass, preferably 0.1 to 3 parts by mass, per 100 parts by mass of the toner.
It is good to use parts by mass.

The toner of the present invention can be used as a two-component developer in combination with a carrier. As the carrier used in the two-component developing method, conventionally known carriers can be used. Specifically, particles having an average particle diameter of 20 to 300 μm, such as a metal such as iron, nickel, cobalt, manganese, chromium, and rare earth, and an alloy or oxide thereof, which are not oxidized on the surface, are used.

[0161] Those having a carrier such as a styrene resin, an acrylic resin, a silicone resin, a fluorine resin, or a polyester resin adhered or coated on the surface of the carrier particles are preferably used.

Next, a procedure for producing a toner by the method for producing a toner of the present invention using the above-described toner particle forming material and external additives will be described.

First, in the raw material mixing step, at least a predetermined amount of a resin and a colorant are weighed and blended as additives in the toner, and they are mixed. An example of a mixing device is a double
There are a mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer and the like.

Next, the toner raw materials thus blended and mixed are melted and kneaded to melt the resins, and the colorant and the like are dispersed therein. In the melt-kneading step, for example, a batch kneader such as a pressure kneader or a Banbury mixer or a continuous kneader can be used. In recent years, single-screw or twin-screw extruders have become the mainstream due to their superiority such as continuous production. For example, KTK-type twin-screw extruders manufactured by Kobe Steel, TEM-type twin-screw extruders manufactured by Toshiba Machine Co., Ltd. A twin screw extruder manufactured by Kay Kay Co., Ltd., a PCM type twin screw extruder manufactured by Ikegai Iron Works,
A bus kneader or the like is generally used. Furthermore,
The colored resin composition obtained by melt-kneading the toner raw material is rolled by two rolls or the like after melt-kneading, and then cooled through a cooling step of cooling with water cooling or the like.

The cooled product of the colored resin composition obtained as described above is then pulverized to a desired particle size in a pulverizing step.
In the pulverization step, first, coarse pulverization is performed by a crusher, a hammer mill, a feather mill, or the like, and further pulverization is performed by the mechanical pulverizer described above. As the medium crusher, an ACM pulverizer, an MVM vertical mill, etc. manufactured by Hosokawa Micron Corp. can be used, and the crushing process of the present invention may be used as a medium crusher. In the pulverizing step, the toner is pulverized stepwise to a predetermined toner particle size. Further, after pulverization, the toner is classified using a classifier such as an inertial classification type elbow jet, a centrifugal force classification type microplex, or a DS separator to obtain a toner having an average particle diameter of 3 to 15 μm. Among these, a multi-split airflow classifier is particularly preferred as the classifier.

As a preferred example of a multi-split air flow classifier, an apparatus of the type shown in FIG. 10 (cross-sectional view) is illustrated as a specific example.

In FIG. 10, the side wall 22 and the G block 23 form a part of the classification chamber, and the classification edge block 24
And 25 have classification edges 17 and 18. G
The position of the block 23 can be slid right and left. The classification edges 17 and 18 are
It is rotatable around a and 18a, and the classification edge can be rotated to change the classification edge tip position. Each of the classification edge blocks 24 and 25 can be slid left and right, and accordingly, the respective knife edge type classification edges 17 and 18 can be slid.
Also slide left and right. The classification area 30 of the classification chamber 32 is divided into three by the classification edges 17 and 18.

Raw material supply port 40 for introducing raw material powder
At the rear end of the material supply nozzle 16, a high pressure air supply nozzle 41 and a material powder introduction nozzle 42 at the rear end of the material supply nozzle 16, and an opening in the classifying chamber 32. The nozzle 16 is provided on the right side of the side wall 22, and the Coanda block 26 is provided so as to draw a long elliptical arc in the extending direction of the lower tangent of the raw material supply nozzle 16.
The left block 27 of the classifying chamber 32 has a knife-edge type inlet edge 19 on the right side of the classifying chamber 32, and further, on the left side of the classifying chamber 32, there are provided inlet pipes 14 and 15 opening to the classifying chamber 32. It is.

The positions of the classification edges 17, 18, the G block 23 and the inlet edge 19 are adjusted according to the type and desired particle size of the toner to be classified.

The discharge ports 11, 1 opening into the classification chamber are provided on the upper surface of the classification chamber 32 so as to correspond to the respective division areas.
2 and 13, and communication means such as a pipe is connected to the discharge ports 11, 12 and 13, and each of them may be provided with an opening / closing means such as a valve means.

The raw material supply nozzle 16 is composed of a right-angled cylinder and a pyramidal cylinder. The ratio of the inner diameter of the right-angled cylinder to the inner diameter of the narrowest part of the pyramidal cylinder is 20: 1 to 1: 1, preferably 10: 1. : 1
If the ratio is set to 2: 1 from, a good introduction speed can be obtained.

The classification operation in the multi-division classification region configured as described above is performed, for example, as follows. That is, the pressure in the classification chamber is reduced through at least one of the discharge ports 11, 12, and 13, and the air flow flowing by the reduced pressure and the high-pressure air supply nozzle 41 in the raw material supply nozzle 16 having an opening in the classification chamber are injected. Due to the ejector effect of compressed air, the powder is ejected into the classification chamber through the raw material supply nozzle 16 at a flow rate of preferably 10 to 350 m / sec, and dispersed.

The particles in the powder introduced into the classification chamber move in a curved line due to the action of the Coanda effect of the Coanda block 26 and the action of gas such as air flowing in at that time. Depending on the particle size and the magnitude of the inertial force, large particles (coarse particles) are outside the airflow, ie, the first fraction outside the classification edge 18, and intermediate particles are the second fraction between the classification edges 18 and 17. , The small particles are classified into a third fraction inside the classification edge 17, the classified large particles are discharged from the outlet 11, the intermediate classified particles are discharged from the outlet 12, and the classified small particles are discharged. Are respectively discharged from the discharge ports 13.

In the above-described classification of the powder, the classification point is determined mainly by the edge tip positions of the classification edges 17 and 18 with respect to the lower end portion of the Coanda block 26 where the powder jumps into the classification chamber 32. Further, the classification point is affected by the suction flow rate of the classification airflow, the powder ejection speed from the raw material supply nozzle 16, and the like.

The multi-divided airflow classifier described above is particularly effective in classifying toner or toner colored resin powder used in an image forming method by electrophotography.

Further, in the multi-split air classifier of the type shown in FIG. 10, a raw material supply nozzle, a raw material powder introduction nozzle, and a high pressure air supply nozzle are provided on the upper surface of the multi-split air flow classifier, and A classification edge block having
Since the position of the classification area can be changed so that the shape of the classification area can be changed, the classification accuracy can be dramatically improved as compared with the conventional airflow type classification apparatus.

The toner coarse powder generated by the classification in the classification step is returned to the pulverization step again and pulverized. The fine powder generated in the classification step may be returned to the toner raw material mixing step and reused.

Further, inorganic fine particles having an average particle diameter of 50 nm or less are externally added to the toner particles obtained as described above as an external additive. As a method of externally adding an external additive to the toner, a predetermined amount of the classified toner and various known external additives are blended, and a high-speed stirrer for applying a shearing force to powder such as a Henschel mixer or a super mixer is used. Used as an auxiliary machine,
It is preferable to stir and mix. At this time, heat is generated inside the external additive machine and aggregates are easily generated. Therefore, it is preferable to adjust the temperature by means such as cooling the periphery of the container of the external additive machine with water.

[0179]

Next, the present invention will be described more specifically with reference to examples and comparative examples of the present invention.

Example 1 Materials having the following formulation were mixed with a mixer, and then mixed with a twin-screw kneader (P) set at a temperature of 130 ° C.
CM-30, manufactured by Ikegai Iron Works Co., Ltd.). The obtained kneaded material was cooled and coarsely pulverized to 2 mm or less with a hammer mill to obtain a powder raw material (coarse pulverized material) as a powder raw material for toner production.・ Styrene-n-butyl acrylate copolymer (Tg: 58 ° C., Mw: 15000) 100 parts by mass ・ Spherical magnetic iron oxide (average particle size: 0.20 μm, BET specific surface area: 8.0 m ² / g, coercive force) : 3.7 kA / m, saturation magnetization: 82.3 Am ² / kg, residual magnetization: 4.0 Am ² / kg) 100 parts by mass-Iron azo compound (negative charge control agent) 2 parts by mass-Polypropylene wax (DSC endothermic peak) Temperature: 145 ° C) 3 parts by mass

The obtained powdery raw material was converted into a mechanical pulverizer 301 (turbo mill T250 manufactured by Turbo Kogyo KK) as shown in FIG.
-RS type was modified as follows), and the obtained finely pulverized product was classified by a multi-division airflow classifier shown in FIG.

In this embodiment, the shape of the crushing surface of the rotor and the stator of the mechanical crusher is of the type shown in FIG. 4A. That is, the angle of β1 of the stator is 45 °, and β2 is 1
0 °, the height H of the protrusions of the stator was 2.0 mm, and the length L1 of the flat surface at the bottom of the recesses of the stator was 1.4 mm. Further, the surfaces of these rotors and stators are coated with a chromium alloy plating containing chromium carbide (plating thickness 150 mm).
μm, surface hardness HV1050), and the minimum gap between the rotor and the stator was set to 1.5 mm. Then, the temperature of the air introduced into the mechanical crusher is -15 ° C, and the peripheral speed of the tip of the rotor is 10
The powder material was finely pulverized while setting the supply of pulverization at 5 m / s and the supply amount of pulverization at 45 kg / h, and the jacket cooling water was passed through. The weight average diameter of the obtained pulverized product was 6.7 μm. Was.

When the powder material was finely pulverized for 2 hours under the above-mentioned pulverization conditions, the temperature T1 of the spiral chamber in the pulverizer was-
10 ° C., the rear room temperature T2 was 41 ° C., and ΔT of T1 and T2 was 51 ° C. Further, Tg-T1 is 68 ° C., Tg-T
2 could be finely pulverized stably at 17 ° C. The obtained finely pulverized product has a weight average particle size of 6.7 μm, particles having a particle size of 4.0 μm or less being 32.8% by number, and a particle size of 10.1%.
It had a sharp particle size distribution containing 3.0% by volume of particles of μm or more.

When the inside of the pulverizer was inspected after being pulverized for 2 hours in the manner described above, no fusion of the toner was observed inside the pulverizer.

Next, the obtained finely pulverized product was introduced into a multi-segment airflow type classifier having the structure shown in FIG. 10 and strictly classified.
Particles having a weight average particle diameter of 6.6 μm, particles having a particle diameter of 4.0 μm or less are 21.0% by number, and particles having a particle diameter of 10.1 μm or more are 1.
A classified product containing 5% by volume was obtained. At this time, the ratio of the mass of the classified product to the mass of the finely pulverized product, that is, the classification yield was 88% by mass.

Table 1 summarizes the conditions and results for the above pulverization classification.

To 100 parts by mass of the classified product, 1.2 parts by mass of dry silica hydrophobized with hexamethyldisilazane and silicone oil was added, and the mixture was externally added and mixed with a Henschel mixer. I got

[Embodiment 2] In this embodiment, the crushing surfaces of the rotor and the stator of the mechanical crusher are of the type shown in FIG. The powder raw material was finely pulverized for 2 hours in the same manner as in Example 1 except that the pulverization supply amount was set to 108 m / s and the pulverization supply amount was set to 43 kg / h.
° C, rear room temperature T2 is 43 ° C, and ΔT of T1 and T2 is 53 ° C.
° C. In addition, Tg-T1 was 68 ° C and Tg-T2 was 15 ° C. The obtained finely pulverized product has a weight average particle size of 6.8 μm and particles having a particle size of 4.0 μm or less are 35.
8% by volume, 3.3% by volume of particles having a particle size of 10.1 μm or more
It had a sharp particle size distribution.

When the inside of the pulverizer was inspected after being pulverized for 2 hours in the manner described above, no fusion of the toner was found inside the pulverizer.

Next, the obtained finely pulverized product was introduced into a multi-segment airflow classifier having the structure shown in FIG. 10 and strictly classified.
22.3% by number of particles having a weight average particle diameter of 6.6 μm and a particle diameter of 4.0 μm or less, and 1.23 particles of a particle diameter of 10.1 μm or more.
A classified product containing 6% by volume was obtained. At this time, the ratio of the mass of the classified product to the mass of the finely pulverized product, that is, the classification yield was 89% by mass.

Table 1 summarizes the conditions and results for the above pulverization classification.

This classified product was externally added and mixed in the same manner as in Example 1 to obtain Toner 2 for evaluation.

[Embodiment 3] In this embodiment, the crushing surfaces of the rotor and the stator of the mechanical crusher are of the type shown in FIG. 5, the tip peripheral speed of the rotor is 110 m / s, and the crushing supply is performed. When the powder raw material was finely pulverized for 2 hours in the same manner as in Example 1 except that the amount was 41 kg / h, the spiral room temperature T1 in the pulverizer was -15 ° C, and the rear room temperature T2 was 4 ° C.
At 5 ° C., ΔT of T1 and T2 was 55 ° C. Also, Tg
-T1 was 68 ° C and Tg-T2 was 13 ° C. The obtained finely pulverized product has a weight average particle size of 6.7 μm, 39.6% by number of particles having a particle size of 4.0 μm or less, and a particle size of 10.1%.
It had a sharp particle size distribution containing 3.6% by volume of particles of μm or more.

When the inside of the pulverizer was inspected after being pulverized for 2 hours in the manner described above, no fusion of the toner was found inside the pulverizer.

Next, the obtained finely pulverized product was introduced into a multi-segment airflow classifier having the structure shown in FIG. 10 and strictly classified.
Particles having a weight average particle diameter of 6.6 μm, particles having a particle diameter of 4.0 μm or less are 21.1% by number, and particles having a particle diameter of 10.1 μm or more are 1.
A classified product containing 7% by volume was obtained. At this time, the ratio of the mass of the classified product to the mass of the finely pulverized product, that is, the classification yield was 88% by mass.

Table 1 summarizes the conditions and results for the above pulverization classification.

This classified product was externally added and mixed in the same manner as in Example 1 to obtain Toner 3 for evaluation.

Embodiment 4 In this embodiment, the crushing surfaces of the rotor and the stator of the mechanical crusher are of the type shown in FIG. 6, the peripheral speed of the rotor tip is 105 m / s, and the crushing supply is performed. The powder raw material was finely pulverized for 2 hours in the same manner as in Example 1 except that the amount was set to 44 kg / h. As a result, the spiral room temperature T1 in the pulverizer was −15 ° C., and the rear room temperature T2 was 4 ° C.
At 3 ° C., ΔT of T1 and T2 was 53 ° C. Also, Tg
-T1 was 68 ° C and Tg-T2 was 15 ° C. The obtained finely pulverized product has a weight average particle size of 6.7 μm, 33.5% by number of particles having a particle size of 4.0 μm or less, and a particle size of 10.1%.
It had a sharp particle size distribution containing 3.1% by volume of particles of μm or more.

After the inside of the pulverizer was inspected after the pulverization was performed for 2 hours in the above manner, no fusion of the toner was found inside the pulverizer.

Next, the obtained finely pulverized product was introduced into a multi-split airflow classifier having the structure shown in FIG. 10 and strictly classified.
Particles having a weight average particle diameter of 6.5 μm, particles having a particle diameter of 4.0 μm or less are 22.8% by number, and particles having a particle diameter of 10.1 μm or more are 2.
A classified product containing 0% by volume was obtained. At this time, the ratio of the mass of the classified product to the mass of the finely pulverized product, that is, the classification yield was 90% by mass.

Table 1 summarizes the conditions and results for the above pulverization classification.

This classified product was externally added and mixed in the same manner as in Example 1 to obtain a toner 4 for evaluation.

Embodiment 5 In this embodiment, the crushing surfaces of the rotor and the stator of the mechanical crusher are of the type shown in FIG. 8, and the temperature of the cold air introduced into the mechanical crusher is -5. ° C
, The flow of the jacket cooling water was stopped, the peripheral speed of the rotor tip was set at 93 m / s, and the amount of pulverized feed was set at 56 kg / h. After pulverization over time, the temperature T1 of the swirl chamber in the pulverizer is 0 ° C, the temperature T2 of the rear chamber is 40 ° C, and Δ of T1 and T2.
T was 40 ° C. Tg-T1 is 58 ° C.
-T2 was 18C. The obtained finely pulverized product has a weight average particle size of 9.1 μm, 33.4% by number of particles having a particle size of 4.0 μm or less, and 32.3% of particles having a particle size of 10.1 μm or more.
It had a sharp particle size distribution containing 9% by volume.

When the inside of the pulverizer was inspected after being pulverized for 2 hours in the manner described above, no fusion of the toner was observed inside the pulverizer.

Next, the obtained finely pulverized product was introduced into a multi-segment airflow classifier having the structure shown in FIG. 10 and strictly classified.
Particles having a weight average particle diameter of 9.0 μm, particles having a particle diameter of 4.0 μm or less are 6.3% by number, and particles having a particle diameter of 10.1 μm or more are 29.
A classified product containing 7% by volume was obtained. At this time, the ratio of the mass of the classified product to the mass of the finely pulverized product, that is, the classification yield was 84% by mass.

Table 1 summarizes the conditions and results for the above pulverization classification.

To 100 parts by mass of the classified product, 0.8 parts by mass of dry silica hydrophobized with hexamethyldisilazane and silicone oil was added, and the mixture was externally added and mixed with a Henschel mixer. I got

[Embodiment 6] In this embodiment, the temperature of the cold air introduced into the mechanical pulverizer is set at -17 ° C, the peripheral speed of the rotor tip is 133 m / s, and the pulverization supply rate is 35 kg / h. Except for the setting, the powder raw material was finely pulverized for 2 hours in the same manner as in Example 1. As a result, the spiral room temperature T1 in the pulverizer was −12 ° C., the rear room temperature T2 was 46 ° C., and T1 and T2
ΔT was 58 ° C. In addition, Tg-T1 is 70 ° C.
Tg-T2 was 12 ° C. The obtained finely pulverized product has a weight average particle size of 5.7 μm, and contains 42.7% by number of particles having a particle size of 4.0 μm or less and 1.3% by volume of particles having a particle size of 10.1 μm or more. The particle size distribution.

When the inside of the pulverizer was inspected after being pulverized for 2 hours in the manner described above, no fusion of the toner was found inside the pulverizer.

Next, the obtained finely pulverized product was introduced into a multi-segment airflow classifier having the structure shown in FIG. 10 and strictly classified.
31.4% by number of particles having a weight average particle diameter of 5.8 μm and a particle diameter of 4.0 μm or less, and 0.1% of particles having a particle diameter of 10.1 μm or more.
A classified product containing 3% by volume was obtained. At this time, the ratio of the mass of the classified product to the mass of the finely pulverized product, that is, the classification yield was 88% by mass.

Table 1 summarizes the conditions and results for the above pulverization classification.

To 100 parts by mass of the classified product, 1.5 parts by mass of dry silica hydrophobized with hexamethyldisilazane and silicone oil was added, and the mixture was externally added and mixed with a Henschel mixer. I got

[Embodiment 7] In this embodiment, first, the plating thickness was set to 20 μm, and the minimum gap between the rotor and the stator was set to 1.
The powder material was finely pulverized over 2 hours in the same manner as in Example 1 except that the tip speed was 8 mm and the peripheral speed of the rotor was 144 m / s.
10 ° C., the rear room temperature T2 was 40 ° C., and ΔT of T1 and T2 was 50 ° C. Further, Tg-T1 is 68 ° C., Tg-T
2 was 18 ° C. The obtained finely pulverized product A has a weight average particle size of 6.7 μm, and particles having a particle size of 4.0 μm or less
It had a sharp particle size distribution containing 3.2% by volume of 6.1% by number and particles having a particle size of 10.1 μm or more.

When the inside of the pulverizer was inspected after being pulverized for 2 hours in the manner described above, no fusion of the toner was found inside the pulverizer.

Next, the obtained finely pulverized product A was introduced into a multi-segment airflow classifier having the structure shown in FIG. 10 and strictly classified, whereby the weight average particle size was 6.6 μm and the particle size was 4.0 μm. Classified product A containing 19.7% by number of the following particles and 2.2% by volume of particles having a particle size of 10.1 μm or more was obtained. At this time, the ratio of the mass of the classified product A to the mass of the finely pulverized product A, that is, the classification yield was 89% by mass.

This classified product A was externally added and mixed in the same manner as in Example 1 to obtain a toner 7A for evaluation.

Next, the plating applied to the rotor and the stator was completely removed, and the coating was performed again by plating to have a plating thickness of 300 μm. Then, the powder raw material was pulverized for 2 hours in the same manner as in Example 1 except that the minimum gap between the rotor and the stator was set to 1.4 mm, and the peripheral speed of the tip of the rotor was set to 94 m / s. As a result, the internal temperature T1 of the swirl inside the pulverizer was −10 ° C., and the internal temperature T2 was 4 ° C.
At 5 ° C., ΔT of T1 and T2 was 55 ° C. Also, Tg
-T1 was 68 ° C and Tg-T2 was 13 ° C. The obtained finely pulverized product B has a weight average particle size of 6.6 μm, and particles having a particle size of 4.0 μm or less are 41.4% by number and a particle size of 10.1%.
It had a sharp particle size distribution containing 2.8% by volume of particles of μm or more.

When the inside of the pulverizer was inspected after being pulverized for 2 hours in the manner described above, no fusion of the toner was found inside the pulverizer.

Next, the obtained finely pulverized product B was introduced into a multi-segment airflow classifier having the structure shown in FIG. 10 and strictly classified to obtain a weight average particle size of 6.6 μm and a particle size of 4.0 μm. A classified product B containing 20.3% by number of the following particles and 2.0% by volume of particles having a particle size of 10.1 μm or more was obtained. At this time, the ratio of the mass of the classified product B to the mass of the finely pulverized product B, that is, the classification yield was 89% by mass.

This classified product B was externally added and mixed in the same manner as in Example 1 to obtain a toner for evaluation 7B.

Table 1 summarizes the conditions and results of the pulverization classification of this example.

According to the present example, it was confirmed that the change amount of the minimum gap in the re-plating was 0.4 mm, and the pulverization processing ability equivalent to that of the initial plating could be exhibited.

[Embodiment 8] In this embodiment, the crushing surfaces of the rotor and the stator of the mechanical crusher were of the type shown in FIG. 4A, and the surfaces thereof were coated with chromium plating. Hardness HV850), plating thickness 15
0 μm, and the minimum gap between the rotor and the stator was set to 1.5 mm. Then, the powder raw material was finely pulverized for 2 hours in the same manner as in Example 1 except that the peripheral speed of the tip of the rotor was set to 118 m / s and the pulverization supply amount was set to 36 kg / h.
The spiral room temperature T1 in the crusher is −10 ° C., and the rear room temperature T
2 was 43 ° C., and ΔT of T1 and T2 was 53 ° C. In addition, Tg-T1 was 68 ° C and Tg-T2 was 15 ° C. The obtained finely pulverized product has a weight average particle diameter of 6.7 μm, and contains 38.8% by number of particles having a particle diameter of 4.0 μm or less and 3.7% by volume of particles having a particle diameter of 10.1 μm or more. The particle size distribution.

After the inside of the pulverizer was inspected after the pulverization was performed for 2 hours in the manner described above, no fusion of the toner was observed inside the pulverizer.

Next, the obtained finely pulverized product was introduced into a multi-segment airflow type classifier having the structure shown in FIG. 10 and strictly classified.
Particles having a weight average particle size of 6.7 μm, particles having a particle size of 4.0 μm or less are 18.5% by number, and particles having a particle size of 10.1 μm or more are 2.
A classified product containing 1% by volume was obtained. At this time, the ratio of the mass of the classified product to the mass of the finely pulverized product, that is, the classification yield was 82% by mass.

Table 1 summarizes the conditions and results for the above pulverization classification.

This classified product was externally added and mixed in the same manner as in Example 1 to obtain Toner 8 for evaluation.

[Embodiment 9] In this embodiment, the crushing surfaces of the rotor and the stator of the mechanical crusher were of the type shown in FIG. 4A, and the surfaces thereof were coated with nickel plating. Hardness HV500), plating thickness 1
The minimum gap between the rotor and the stator was set to 50 μm and 1.5 mm. Then, the powder material was finely ground for 2 hours in the same manner as in Example 1 except that the peripheral speed of the tip of the rotor was set to 126 m / s and the supply amount of grinding was set to 33 kg / h. The room temperature T1 was −10 ° C., the rear room temperature T2 was 44 ° C., and ΔT of T1 and T2 was 54 ° C.
In addition, Tg-T1 was 68 ° C and Tg-T2 was 14 ° C. The obtained finely pulverized product has a weight average particle size of 6.7 μm, and contains 40.2% by number of particles having a particle size of 4.0 μm or less and 4.1% by volume of particles having a particle size of 10.1 μm or more. The particle size distribution.

When the inside of the pulverizer was inspected after being pulverized for 2 hours in the manner described above, no fusion of the toner was found inside the pulverizer.

Next, the obtained finely pulverized product was introduced into a multi-segment airflow type classifier having the structure shown in FIG. 10 and strictly classified.
21.3% by number of particles having a weight average particle diameter of 6.6 μm and a particle diameter of 4.0 μm or less, and 2.13% of particles having a particle diameter of 10.1 μm or more.
A classified product containing 7% by volume was obtained. At this time, the ratio of the mass of the classified product to the mass of the finely pulverized product, that is, the classification yield was 80% by mass.

Table 1 summarizes the conditions and results for the above pulverization classification.

This classified product was externally added and mixed in the same manner as in Example 1 to obtain a toner 9 for evaluation.

Comparative Example 1 In this comparative example, the crushing surfaces of the rotor and the stator of the mechanical crusher were of the type shown in FIG. 4A, and the surfaces thereof were not subjected to any abrasion treatment (the Hardness HV250), minimum gap between rotor and stator 1.5
mm. And the peripheral speed of the rotor tip is 144m /
s, the powder raw material was finely pulverized for 2 hours in the same manner as in Example 1 except that the supply amount of the pulverization was set to 20 kg / h. The temperature T2 was 50 ° C., and ΔT of T1 and T2 was 60 ° C. Tg-T1 was 68 ° C and Tg-T2 was 8 ° C. The obtained finely pulverized product has a weight average particle size of 6.7 μm.
48.9% by number of particles having a particle size of 4.0 μm or less,
It had a particle size distribution containing 5.3% by volume of particles having a particle size of 10.1 μm or more.

When the inside of the pulverizer was inspected after being pulverized for 2 hours in the manner described above, no fusion of the toner was found inside the pulverizer.

Next, the obtained finely pulverized product was introduced into a multi-segment airflow classifier having the structure shown in FIG. 10 and strictly classified.
Particles having a weight average particle diameter of 6.7 μm, particles having a particle diameter of 4.0 μm or less are 20.8% by number, and particles having a particle diameter of 10.1 μm or more are 2.
A classified product containing 4% by volume was obtained. At this time, the ratio of the mass of the classified product to the mass of the finely pulverized product, that is, the classification yield was 78% by mass.

Table 1 summarizes the conditions and results for the above pulverization classification.

This classified product was externally added and mixed in the same manner as in Example 1 to obtain a toner 10 for evaluation.

Comparative Example 2 In this comparative example, the crushing surfaces of the rotor and the stator of the mechanical crusher were of the type shown in FIG. 7, and the surfaces thereof were coated with nickel plating. Hardness HV500), and the minimum gap between the rotor and the stator was set to 1.5 mm. Then, the powder raw material was finely pulverized for 2 hours in the same manner as in Example 1 except that the peripheral speed of the tip of the rotor was set to 132 m / s and the supply amount of pulverization was set to 28 kg / h. Room temperature T1 is -10 ° C, rear room temperature T2 is 45 ° C, T1 and T2
ΔT was 55 ° C. Tg-T1 is 68 ° C.
Tg-T2 was 13 ° C. The obtained finely pulverized product has a weight average particle size of 6.8 μm, a particle size containing 45.1% by number of particles having a particle size of 4.0 μm or less and 5.0% by volume of particles having a particle size of 10.1 μm or more. Had a distribution.

When the inside of the pulverizer was inspected after being pulverized for 2 hours in the manner described above, the toner was found to fuse inside the pulverizer, mainly near the discharge ports of the rotor and the stator. A lot of coarse particles were mixed in the water.

Next, the obtained finely pulverized product was introduced into a multi-segment airflow classifier having the structure shown in FIG. 10 and strictly classified.
21.3% by number of particles having a weight average particle diameter of 6.6 μm and a particle diameter of 4.0 μm or less, and 2.13% of particles having a particle diameter of 10.1 μm or more.
A classified product containing 8% by volume was obtained. At this time, the ratio of the mass of the classified product to the mass of the finely pulverized product, that is, the classification yield was 72% by mass.

Table 1 summarizes the conditions and results for the above pulverization classification.

The classified product was externally added and mixed in the same manner as in Example 1 to obtain a toner 11 for evaluation.

Comparative Example 3 In this comparative example, the crushing surfaces of the rotor and the stator of the mechanical crusher were of the type shown in FIG. 9 and the surfaces thereof were coated with nickel plating. Hardness HV500), and the minimum gap between the rotor and the stator was set to 1.5 mm. Then, the powder raw material was finely pulverized for 2 hours in the same manner as in Example 1 except that the peripheral speed of the tip of the rotor was set to 166 m / s and the pulverization supply amount was set to 16 kg / h. Indoor temperature T1 is -10 ° C, rear indoor temperature T2 is 61 ° C, T1 and T2
ΔT was 71 ° C. Tg-T1 is 68 ° C.
Tg-T2 was −3 ° C. The obtained finely pulverized product has a weight average particle size of 6.8 μm, and a particle size containing 53.7% by number of particles having a particle size of 4.0 μm or less and 4.8% by volume of particles having a particle size of 10.1 μm or more. Had a distribution.

When the inside of the pulverizer was inspected after the pulverization for 2 hours as described above, a little fusion of the toner was observed inside the pulverizer, mainly near the discharge ports of the rotor and the stator. Coarse particles were found in the mixture.

Next, the obtained finely pulverized product was introduced into a multi-split airflow classifier having the structure shown in FIG. 10 and strictly classified.
Particles having a weight average particle size of 6.6 μm, particles having a particle size of 4.0 μm or less are 19.9% by number, and particles having a particle size of 10.1 μm or more are 3.0%.
A classified product containing 0% by volume was obtained. At this time, the ratio of the mass of the classified product to the mass of the finely pulverized product, that is, the classification yield was 75% by mass.

Table 1 summarizes the conditions and results for the above pulverization classification.

This classified product was externally added and mixed in the same manner as in Example 1 to obtain a toner 12 for evaluation.

[Comparative Example 4] The powder raw material used in Example 1 was finely pulverized by means of a collision type air current pulverizer shown in FIG.

The resulting finely pulverized product had a weight average particle size of 7.0.
The particles had a particle size distribution of 62.5% by number of particles having a particle size of 4.0 μm or less and 10.4% by volume of particles having a particle size of 10.1 μm or more.

Next, the obtained finely pulverized product was introduced into a multi-segment airflow type classifier having the structure shown in FIG. 10 and strictly classified.
Particles having a weight average particle diameter of 6.7 μm, particles having a particle diameter of 4.0 μm or less are 21.7% by number, and particles having a particle diameter of 10.1 μm or more are 3.20%.
A classified product containing 5% by volume was obtained. At this time, the ratio of the mass of the classified product to the mass of the finely pulverized product, that is, the classification yield was 69% by mass.

When the inside of the pulverizer was inspected after being pulverized for 2 hours in the manner described above, no fusion of the toner was found inside the pulverizer.

This classified product was externally added and mixed in the same manner as in Example 1 to obtain a toner 13 for evaluation.

[Evaluation] Toner 1 of the above Examples and Comparative Examples
About ~ 13, a commercially available laser beam printer LB
P-950 (manufactured by Canon) was modified into the following configuration, and a printout test was performed under the following conditions. When the toner was exhausted, a cutout was made in the toner container at the top of the cartridge, and the toner was replenished therefrom to continue the printout test. An electrostatic latent image is formed by setting the primary charge to -670 V, and the gap (290
μm) and an AC bias (f = 2000 Hz; V
pp = 1600 V) and DC bias (Vdc = −50)
0V) to the developing drum. The obtained images were evaluated for the following items. For these results,
The results are summarized in Table 2.

(1) Image density The image density is high temperature and high humidity (32.5 ° C., relative humidity 80%).
Under ordinary conditions of low temperature and low humidity (15 ° C., relative humidity 10%), 250 g of ordinary paper for copying machines (75 g / m ² )
Evaluation was performed by measuring the maintenance of the image density at the end of printing out 00 sheets. The image density was measured using a “Macbeth reflection densitometer” (manufactured by Macbeth) with respect to the printout image of the white background portion where the original density was 0.00.

(2) Fog Fog was measured in advance using a reflectometer (manufactured by Tokyo Denshoku Co., Ltd.) using the whiteness (%) of transfer paper before printing.
The fog was calculated from the comparison of the solid white image after performing 10,000-sheet durability printout in a low-temperature and low-humidity environment (15 ° C., 10% RH) with the whiteness (%) of the transfer paper after printing. .

(3) Image Scattering The “den” character pattern shown in FIG.
When printed at 5 g / m ² and 135 g / m ² ), toner scattering around the character (the state shown in FIG. 12B) was evaluated visually and with a magnifying glass. A: Almost no occurrence B: Slight scattering is observed C: Slight scattering is observed but is not conspicuous visually D: Splash is observed and can be visually confirmed E: Splash is visually observed

(4) Transfer Rate In a normal temperature and normal humidity environment, the transfer rate of the toner image from the OPC photosensitive drum to the transfer paper at the initial stage and the late stage of endurance of 25,000 sheets was determined by the following method.

The transfer rate of the toner image from the OPC photosensitive drum to the transfer paper can be determined by taking a toner image (image density of about 1.3) formed on the OPC photosensitive drum with a transparent adhesive tape, and measuring the image density with Macbeth. Densitometer or color reflection densitometer (eg, Color reflection densit)
meter X-RITE 404A manufa
cut by X-Rite Co. ). Next, a toner image is formed on the OPC photosensitive drum again,
The toner image was transferred to transfer paper, and a toner image on the transfer paper corresponding to the collected toner image on the OPC photosensitive drum was collected with a transparent adhesive tape, and the image density was measured in the same manner. The transfer rate was calculated from the following equation.

[0259]

(Equation 1)

[0260]

[Table 1]

[0261]

[Table 2]

[0262]

As described above, according to the present invention,
In a method for producing a toner using a mechanical pulverizer,
Each of the rotor and the stator in the mechanical pulverizer has a plurality of protrusions, and a recess formed between the protrusions and the protrusions, and at least one of the rotor and the stator is provided. The concave portion has a flat surface at the bottom, and the surface of the rotor and / or the stator having the flat surface at the bottom is coated with a wear-resistant plating to form the rotor and / or the stator. The life is prolonged, more efficient pulverization can be performed as compared with a conventional mechanical pulverizer, and the particle size distribution of the pulverized product is sharp, so that a toner can be produced with a high throughput and a high yield.

Further, according to the present invention, a toner having good developability and transferability under high-temperature and high-humidity environments and low-temperature and low-humidity environments and with less fogging and scattering can be produced.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of an example of a mechanical pulverizer used in a pulverizing step of a toner of the present invention.

FIG. 2 is a schematic cross-sectional view taken along the line DD ′ in FIG.

FIG. 3 is a perspective view of the rotor shown in FIG. 1;

FIG. 4 is a schematic cross-sectional view of the mechanical pulverizer of the present invention taken along the line DD ′.

FIG. 5 is a schematic cross-sectional view of another embodiment of the mechanical crusher of the present invention, taken along the line DD ′.

FIG. 6 is a schematic cross-sectional view along DD ′ plane in still another embodiment of the mechanical pulverizer of the present invention.

FIG. 7 is a schematic cross-sectional view along DD ′ plane in still another embodiment of the mechanical crusher of the present invention.

FIG. 8 is a schematic cross-sectional view taken along the line DD ′ in a conventional mechanical pulverizer.

FIG. 9 is a schematic cross-sectional view of the conventional mechanical crusher taken along the line DD ′.

FIG. 10 is a schematic sectional view of a multi-split airflow classifier preferably used in the toner classifying step of the present invention.

FIG. 11 is a schematic sectional view of a conventional collision-type airflow pulverizer.

FIG. 12 is a schematic diagram showing a state in which character images are scattered.

[Explanation of symbols]

 11, 12, 13 Outlet 14, 15 Inlet pipe 16 Material supply nozzle 17, 18 Classification edge 19 Inlet edge 22, 23 Side wall 24, 25 Classification edge block 26 Coanda block 27 Left block 30 Classification area 32 Classification chamber 40 Raw material Supply port 41 High pressure air supply nozzle 42 Raw material powder introduction nozzle 212 Swirl chamber 219 Pipe 220 Distributor 222 Bag filter 224 Suction filter 229 Collection cyclone 301 Mechanical pulverizer 302 Powder discharge port 310 Stator 311 Powder input port 312 Rotation Shaft 313 Casing 314 Rotor 315 First metering device 316 Jacket 317 Cooling water supply port 318 Cooling water outlet 320 Rear chamber 321 Cold air generating means 322, 329 Corrugated shape of stator protrusion 323, 330 Bottom of stator recess Flat portions 324, 331 Trapezoidal shape of stator recess 325 Stator's uneven shape 326, 332 Trapezoidal shape of rotor recess 327, 333 Flat portion at bottom of rotor recess 328, 334 Waveform of rotor protrusion 335 Waveform shape of uneven portion of stator 336 Waveform shape of uneven portion of rotor 337 First slope of rotor 338 Second slope of rotor 339 First slope of stator 340 Second slope of stator 341 Rotor grinding Blade 342 Stator grinding blade 343 Rotor protrusion 344 Rotor recess 345 Stator protrusion 346 Stator recess

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Kaori Hiratsuka 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Nobuyuki Okubo 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inside (72) Inventor Tsutomu Onuma 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Hirohide Tanigawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. F Terms (reference) 2H005 AA02 AB04 EA03 EA10 4D063 FF14 FF21 GA10 GB02 GB07 GC19 GC31 GD04 GD12 GD22 GD24 4D065 AA05 BB04 BB11 EB20 EC02 EC09 ED05 ED24 ED31 EE02 EE12 EE18 EE19

Claims (29)

[Claims] 1. A mixture containing at least a binder resin and a colorant is melt-kneaded, and after cooling the obtained kneaded material, the cooled material is roughly pulverized, and a powder raw material comprising the coarsely pulverized material is pulverized by a pulverizing means. A method for producing a toner having at least a step of pulverizing and classifying the obtained pulverized product by a classifying means, wherein the pulverizing means comprises at least a rotor as a rotating body attached to a central rotating shaft, and a surface of the rotor. A stator that is arranged around the rotor while maintaining a constant interval,
And a mechanical crusher configured such that an annular space formed by maintaining a gap is in an air-tight state, wherein each of the rotor and the stator has a plurality of convex portions, A concave portion formed between the convex portion and the convex portion, wherein the concave portion of at least one of the rotor and the stator has a flat surface at a bottom portion, and a rotor having a flat surface at the bottom portion and / or Alternatively, a method for producing a toner, wherein the surface of the stator is coated with plating having wear resistance. 2. The rotor and / or the stator have a surface hardness of HV400 to 1300 (Vickers hardness of 400).
The method according to claim 1, wherein the toner is a toner. 3. The method according to claim 1, wherein the plating is chrome plating. 4. The method according to claim 1, wherein said plating is a chromium alloy plating containing at least chromium carbide. 5. A first slope of the rotor, wherein a slope of the projection rising from a bottom face of the recess of the rotor on the rear side in the rotor rotation direction is a first slope of the rotor, wherein the first slope of the rotor and the first slope of the rotor. The line connecting the point (A) at the rising edge of
A slope having a tilt angle (α1) of 10 ° or more and less than 80 ° on a minus side, and a first slope of the stator in a rotor rotation direction front side of a projection rising from a bottom face of the recess of the stator is fixed. The first slope of the stator has an inclination angle (β1) of 10 ° or more and less than 80 ° on the plus side with a line connecting the center of the rotation axis and the rising point (A ′) of the first slope of the stator as a reference line.
The method for producing a toner according to any one of claims 1 to 4, comprising: 6. A second slope of the rotor, wherein a slope of the protrusion rising from a bottom face of the recess of the rotor on the front side in the rotor rotation direction is a second slope of the rotor, wherein the second slope of the rotor is the center of the rotation shaft and the second slope of the rotor. The line connecting the vertex (C) to
The method for producing a toner according to claim 1, wherein the toner has an inclination angle (α2) of less than 0 °. 7. A second slope of the stator, wherein a slope on the rear side in the rotor rotation direction of the projection rising from the bottom of the recess of the stator is a second slope of the stator, and the second slope of the stator and the second slope of the stator. 7. The method for producing a toner according to claim 1, wherein an inclination angle (β2) of less than 20 ° is provided on a minus side with respect to a line connecting a vertex (C ′) of the toner. . 8. A second slope of the rotor, the slope of the protrusion rising from the bottom of the recess of the rotor being forward of the rotor in the direction of rotor rotation, wherein the second slope of the rotor is the center of the rotation shaft and the second slope of the rotor. The line connecting the vertex (C) to
The stator has a slope angle (α2) of less than 0 °, and a slope on the rear side in the rotor rotation direction of a protrusion rising from the bottom of the recess of the stator is a stator second slope, and the stator second slope is 8. An inclination angle (β2) of less than 20 ° on the minus side with respect to a line connecting the center of the rotation axis and the vertex (C ′) of the second slope of the stator as a reference line. The method for producing a toner according to any one of the above. 9. The method according to claim 1, wherein the bottom of the recess has curved surfaces at both ends of the flat surface. 10. The rotor according to claim 1, wherein a part of the protrusion is formed by a curved surface, and the bottom of the stator is formed by a flat surface. A method for producing the toner described in the above. 11. The rotor and / or the stator may have a convex portion formed with a curved surface, and the rotor and / or the stator may be
The method according to claim 1, wherein the bottom of the concave portion is formed with a flat surface. 12. A sectional view of the stator taken on a plane perpendicular to the direction of the rotation axis, wherein a height H (mm) of the projection is 1.0 to 3.0.
2. The length L1 (mm) of the flat surface at the bottom of the concave portion is 1.0 to 3.0 mm.
12. The method for producing a toner according to any one of items 1 to 11. 13. The method according to claim 12, wherein the height H of the convex portion and the length L1 of the flat surface at the bottom of the concave portion satisfy the following relationship: 0.25H ≦ L1 ≦ 2.5H. Manufacturing method of toner. 14. When the length of the upper surface of the protrusion of the rotor and / or the stator is L2 and the length of the surface facing the upper surface of the rotor is L3, L2 and L3 satisfy the following conditions. The method according to any one of claims 1 to 13, wherein L2 <L3 is satisfied. 15. The method according to claim 1, wherein the toner is a magnetic toner containing 40 to 200 parts by mass of a magnetic substance with respect to 100 parts by mass of a binder resin. . 16. A method of removing a worn or stripped plating component, using a rotor and / or a stator coated with the plating again, and pulverizing the annular space to a certain volume. Claims 1 to 15
The method for producing a toner according to any one of the above. 17. The powder raw material is crushed by setting a minimum gap between the rotor and the stator to 0.5 to 10.0 mm. A method for producing the toner described in the above. 18. The plating layer has a thickness of 20 to 300.
The method for producing a toner according to any one of claims 1 to 17, wherein the thickness is μm. 19. The method according to claim 1, wherein a variation width of a minimum gap between the rotor and the stator is 0.5 mm or less. 20. A method according to claim 1, wherein said powdery raw material is introduced into said pulverizer together with air at + 30 ° C. or lower.
The method for producing a toner according to any one of the above. 21. The temperature of the air is +20 to -40.
The method for producing a toner according to claim 20, wherein the temperature is ° C. 22. The mechanical pulverizer according to claim 1, further comprising a swirl chamber communicating with the powder inlet, wherein the room temperature T1 of the swirl chamber is + 20 ° C. or lower. A method for producing the toner described in the above. 23. The room temperature T1 of the spiral chamber is from +10 to-.
The method for producing a toner according to claim 22, wherein the temperature is 30 ° C. 24. The pulverized product generated in the mechanical pulverizer is discharged from the powder discharge port through a rear chamber of the mechanical pulverizer to the outside of the machine, and the room temperature T2 of the rear chamber is 30 to 60 ° C. The method for producing a toner according to any one of claims 1 to 23, wherein: 25. A temperature difference Δ between the room temperature T2 and the room temperature T1.
25. The method according to claim 24, wherein T (T2-T1) is 30 to 80C. 26. A temperature difference Δ between the room temperature T2 and the room temperature T1.
25. The method according to claim 24, wherein T (T2-T1) is 35 to 70C. 27. The binder resin has a glass transition temperature Tg of 45 to 75 ° C. and a room temperature T of a spiral chamber of a mechanical pulverizer.
1 is not higher than + 20 ° C. and 40 to 80 than Tg.
The method for producing a toner according to any one of claims 22 to 26, wherein the temperature is adjusted so that the temperature is lowered by ° C. 28. The glass transition temperature Tg of the binder resin is 45 to 75 ° C., and the room temperature T2 in the rear chamber of the mechanical pulverizer.
The method for producing a toner according to any one of claims 22 to 26, wherein the temperature is adjusted so that the temperature is lower by 0 to 30 ° C than Tg. 29. The method according to claim 1, wherein the mechanical pulverizer has a jacket for cooling the inside of the machine, and pulverizes the powder material while passing cooling water through the jacket. A method for producing the toner described in the above.