JP2007148077A - Method for manufacturing toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing toner by which toner surface reforming particles having a small grain size, containing little fine powder and having a sharp grain size distribution can be efficiently and stably obtained. <P>SOLUTION: The method comprises; (1) introducing a powder raw material into a first fixed quantity feeding machine; (2) introducing a prescribed amount of the powder raw material from the first fixed quantity feeding machine into a mechanical pulverizing machine constituted of a rotor having a recessed part and a projecting part and a stator, and finely pulverizing the powder raw material accompanying the rotation of the rotor in the pulverizing zone, (3) discharging the fine powder pulverized matter subjected to pulverization from the mechanical pulverizing machine, and introducing the same into a second fixed quantity feeding machine; (4) introducing the prescribed amount of the fine powder pulverized matter from the second fixed quantity feeding machine into a batch type surface reforming device; (5) repeating fixed time classification and surface reforming treatment using mechanical impact force for the fine powder pulverized matter; thereby (6) obtaining the toner particles of the small grain size which are surface reforming-treated particles from which the fine powder below the prescribed grain size is removed. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  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.

  In an image forming method such as electrophotography, a toner for developing an electrostatic image is used. The toner production method is roughly classified into a pulverization method and a polymerization method, and a simple and popular production method includes a pulverization method.

  As a general manufacturing method of the pulverization method, a binder resin for fixing to a transfer material and a colorant for producing a color as a toner are used, and charge control for imparting electric charges to particles as necessary. Add additives such as a magnetic material for imparting transportability to the agent and toner itself, a release agent, a fluidity imparting agent, etc., mix, melt knead, cool and solidify, and then knead the kneaded material by pulverizing means The toner is finely divided and classified into a desired particle size distribution as necessary, or a fluidizing agent or the like is added to obtain a toner for image formation.

  In the case of a toner used in the two-component development method, various magnetic carriers and the above toner are mixed and then used for image formation.

  As the pulverizing means, various pulverizing apparatuses are used. In many cases, a jet airflow pulverizer using a jet airflow as shown in FIG. 11, particularly a collision airflow pulverizer is used.

  A collision type airflow crusher conveys powder raw material with a high-pressure gas such as a jet stream, injects it from the outlet of the acceleration tube, and collides with the collision surface of the collision member provided facing the opening surface of the outlet of the acceleration tube. The powder raw material is pulverized by the impact force.

  For example, in the collision-type airflow crusher shown in FIG. 11, a collision member 436 is provided facing the outlet of the acceleration tube to which the high-pressure gas supply nozzle 435 is connected, and is communicated with the middle of the acceleration tube by the high-pressure gas supplied to the acceleration tube. The powder raw material is sucked into the accelerating tube from the powder raw material supply port, and the powder raw material is jetted together with the high-pressure gas so as to collide with the collision surface of the collision member 436 and pulverized by the impact. It is discharging more.

  However, the above collision type airflow pulverizer has a configuration in which the powder raw material is jetted together with the high-pressure gas, collides with the collision surface of the collision member, and is pulverized by the impact. Requires a lot of air. Therefore, power consumption is extremely large, and there is a problem in terms of energy cost.

  Particularly in recent years, there has been a demand for energy saving of devices in order to cope with environmental problems. In addition, when trying to obtain a toner having a weight average particle diameter of 6 μm or less and pulverizing with a collision airflow pulverizer, it is possible to obtain a toner having a weight average particle diameter of 6 μm or less, but the amount of fine powder generated increases. In the subsequent classification step, the classification yield is lowered, which is not preferable in terms of toner productivity.

  On the other hand, a mechanical pulverizer shown in FIG. 3 is used as a pulverizer that is energetically more efficient than a jet airflow pulverizer (see, for example, Patent Document 1, Document 2, and Document 3).

  The mechanical pulverizer shown in FIG. 3 pulverizes by introducing a powder raw material into an annular space formed between a rotor rotating at high speed and a stator arranged around the rotor. According to the mechanical pulverizer, finer pulverization can be achieved with much lower energy consumption than a jet airflow pulverizer, and since it is less excessively pulverized, the generation of fine powder is reduced 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 airflow pulverizer have an irregular and angular shape, and the toner particles pulverized by the mechanical pulverizer have corners. It is known that the shape is round and round.

  This is thought to be due to the difference in the grinding process. That is, in the pulverization method using a jet stream, most of the pulverization is performed by collision with the collision member. However, in the mechanical pulverizer, most of the pulverization is performed on the walls of the rotor and the stator that rotate at high speed. This is because the particles collide. In mechanical pulverization, heat is generated by pulverization, and the shape of the pulverized toner particles is considered to be rounded due to the effect of thermal spheroidization.

  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 good and the voids are small. It has the advantage of being excellent and having only a small amount of external additive added.

  In addition, there are merits in quality such as excellent chargeability and transferability. That is, according to the mechanical pulverizer, it is possible to produce toner of excellent quality with energy saving and high yield.

  However, the mechanical pulverizer is configured to pulverize by introducing a powder raw material into an annular space formed between a rotor rotating at high speed and a stator arranged around the rotor. Therefore, most of the factors that determine the toner particle size are determined by the number of rotations of the rotor and the minimum distance between the rotor and the stator.

  However, the number of rotations of the rotor and the minimum distance between the rotor and the stator are naturally limited. Therefore, the mechanical pulverizer described above has a small particle diameter, particularly a toner particle having a weight average particle diameter of 6 μm or less. It was unsuitable to get.

  However, in recent years, with higher image quality and higher definition of copiers and printers, the performance required of toner as a developer has become more severe, the particle size of the toner is small, and the particle size distribution of the toner is coarse. There is a growing demand for a sharp product that does not contain a small amount of fine powder.

  In addition, in order to achieve cleaner-less and waste toner reduction, improvement in toner transferability is required, and further spheroidization to improve the surface shape of toner particles has been required. Yes.

  For example, as a method for manufacturing the toner described above, a toner that has been spheroidized by a mechanical impact force has been proposed (see, for example, Patent Document 4). In addition to the method using the mechanical impact force described above, a method for melting the surface with hot air, a method using heat, and the like are known as methods for making the toner shape spherical (see, for example, Patent Document 5). ).

  However, in the method using a mechanical impact force, excessive pulverization is likely to occur during spheroidization, and particularly in the case of toner, the toner is pulverized due to the impact associated with spheronization, resulting in an increase in fine powder. Yes, it is not preferable in terms of toner productivity and quality.

  In addition, the toner has a problem that the surface composition changes due to heat. In particular, since the presence state of the wax component added as a release agent changes, the method of melting the surface by heat may not be preferable in terms of toner quality.

  Thus, since the toner requires many different properties, the properties of the toner are often influenced by the method of producing the toner in addition to the raw materials used. Particularly in recent years, it has been required to efficiently and stably produce toner surface modified particles having a small particle size and a sharp particle size distribution with few fine powders.

JP 59-24855 A JP 59-105853 A Japanese Patent Publication No. 3-15489 Japanese Patent Laid-Open No. 9-85741 JP 2000-29241 A

  SUMMARY OF THE INVENTION An object of the present invention is a method for producing a toner that can efficiently and stably obtain toner surface-modified particles having a sharp particle size distribution with a small particle size and a small amount of fine powder, eliminating such problems. Is to provide.

  A further object of the present invention is to provide a toner production method for obtaining a long-life toner having good developability, transferability, cleaning property, and stable chargeability.

The present invention provides a coarse pulverization step in which a composition containing at least a binder resin and a colorant is melt-kneaded, the obtained kneaded product is cooled and solidified, and the cooled solidified product is coarsely pulverized to obtain a coarsely pulverized product. A finely pulverized step of finely pulverizing the coarsely pulverized product to obtain a finely pulverized product having a weight average particle size of 3 to 11 μm; In a method for producing a toner having
The fine pulverization step is performed by using a mechanical pulverizer, and the mechanical pulverizer includes at least a powder inlet for introducing into a pulverizing means to finely pulverize a coarsely pulverized product, a stator, , At least a rotor attached to the central rotation shaft, and at least a powder discharge port for discharging finely pulverized powder from the pulverizing means, the stator enclosing the rotor, The rotor is arranged so as to have a predetermined gap between the surface of the stator and the surface of the rotor to form a pulverization zone. In the pulverization zone, a coarsely pulverized product is produced as the rotor rotates. Pulverized,
The outer peripheral surface of the rotor of the mechanical pulverizer and / or the inner peripheral surface of the stator has a plurality of convex portions and concave portions formed between the convex portions and the convex portions. The repetition distance between the portion and the convex portion is 2.0 mm or more and less than 3.5 mm,
In the toner particles of 2 μm or more of the toner particles which are finely pulverized products obtained by the mechanical pulverizer, the following formula (1)
Circularity a = L0 / L (1)
[In the formula, L0 represents the circumference of a circle having the same projected area as the particle image, and L represents the particle image when image processing is performed at an image processing resolution of 512 × 512 (pixels of 0.3 μm × 0.3 μm). Indicates the perimeter. ]
The value (average circularity) obtained by dividing the total sum of circularity a determined by the total number of particles is 0.930 or more,
And the average surface roughness measured by a scanning probe microscope of the toner particles is 15.0 nm or more and less than 45.0 nm,
The surface modification step is performed using a batch type surface modification device, and the batch type surface modification device includes classification means for continuously discharging and removing fine powder having a predetermined particle size or less to the outside of the device. Surface treatment means using mechanical impact force, and guide means for partitioning the space between the classification means and the surface treatment means into a first space and a second space, and Introduced into one space and introduced into the surface treatment means using mechanical impact force through the second space while continuously discharging and removing fine powder having a predetermined particle size or less from the apparatus by the classifying means. Then, by performing surface modification treatment and circulating again to the first space, a predetermined amount of fine powder having a predetermined particle diameter or less is removed by repeating the surface modification treatment using a predetermined time classification and mechanical impact force. Obtained surface modified particles,
In the toner particles of 2 μm or more of the toner particles which are surface modified particles obtained by the batch type surface modifying apparatus, the following formula (1)
Circularity a = L0 / L (1)
[In the formula, L0 represents the circumference of a circle having the same projected area as the particle image, and L represents the particle image when image processing is performed at an image processing resolution of 512 × 512 (pixels of 0.3 μm × 0.3 μm). Indicates the perimeter. ]
The value (average circularity) obtained by dividing the total sum of circularity a obtained by the total number of particles is 0.935 or more,
In addition, the present invention relates to a toner production method, wherein the toner particles have an average surface roughness measured by a scanning probe microscope of 5.0 nm or more and less than 35.0 nm.

As a result of intensive studies to solve the above-described problems of the prior art, the present inventor,
(1) A pulverizer for finely pulverizing a powder raw material comprising a coarsely pulverized product, a powder input port for introducing into a pulverizing means in order to finely pulverize the coarsely pulverized product, a stator, At least a rotor attached to the central rotating shaft, and a powder discharge port for discharging finely pulverized powder from the pulverizing means, the stator enclosing the rotor, The rotor is arranged so that the stator surface and the rotor surface have a predetermined gap, and the mechanical grinder is configured to form a grinding zone;
(2) The outer peripheral surface of the rotor and / or the inner peripheral surface of the stator of the mechanical grinder has a plurality of convex portions and concave portions formed between the convex portions and the convex portions. By setting the repetition distance between the convex part and the convex part to 2.0 mm or more and less than 3.5 mm, in the pulverization zone of the mechanical pulverizer, with the rotation of the rotor of the mechanical pulverizer By finely pulverizing the powder raw material, a finely pulverized product having a small particle size and a sharp particle size distribution with few fine powders can be obtained.
(3) Classifying means for continuously discharging and removing the finely pulverized product (= surface-modified particles) at least a predetermined particle size or less from the apparatus, surface treatment means using mechanical impact force, and The space between the classifying means and the surface treatment means is the first space before being introduced into the classification means, and the surface-modified particles from which fine powder is classified and removed by the classification means are supplied to the surface treatment means. Introducing into a batch-type surface modification device configured to have a guide means for partitioning into a second space for introduction,
(4) The finely pulverized product (= surface modified particles) is introduced into the first space, and the fine powder having a predetermined particle size or less is continuously discharged and removed from the apparatus by the classification means, By introducing the surface treatment means using a mechanical impact force through a space, performing a surface modification treatment, and circulating again to the first space, a surface modification using a fixed time classification and a mechanical impact force is performed. By repeating quality processing,
(5) The present inventors have found that toner particles, which are surface-modified particles, from which fine particles having a small particle size and a predetermined particle size or less are removed can be obtained efficiently.

  According to the present invention, a finely pulverized product having a small particle size (= toner particles having a weight average particle size of 6 μm or less) that has been difficult with a conventional mechanical pulverizer and a sharp particle size distribution with a small amount of fine powder is obtained by a mechanical method. It can be obtained with a pulverizer.

  Further, by introducing the finely pulverized product (= surface-modified particles) into a specific surface treatment apparatus, the surface-modified particles obtained by removing fine particles having a small particle size and a predetermined particle size or less. Certain toner particles can be obtained efficiently.

  Furthermore, according to the present invention, toner surface modified particles having a small particle size and a sharp particle size distribution with few fine powders can be obtained efficiently and stably, and further, good developability and transferability. In addition, a method for producing a toner that obtains a long-life toner having a cleaning property and a stable charging property is provided.

  Hereinafter, the present invention will be described in more detail with reference to preferred embodiments.

  First, the toner production method of the present invention will be specifically described with reference to the drawings.

  FIG. 1 is a schematic diagram showing a basic process flow in the toner manufacturing method of the present invention, and FIG. 2 is a schematic diagram showing a preferable process flow in the toner manufacturing method of the present invention.

In FIG. 1, the method for producing the toner of the present invention is as follows.
After melt-kneading a mixture containing at least a binder resin and a colorant, and cooling the obtained kneaded product, the cooled product is roughly pulverized by a pulverizing means,
(1) The powder raw material made of the coarsely pulverized product is introduced into the first fixed amount feeder,
(2) A powder feed port for feeding a predetermined amount of powder raw material from the first metering feeder into the pulverizing means to pulverize at least the coarsely pulverized product, a stator, and at least center rotation At least a rotor attached to the shaft and a powder discharge port for discharging finely pulverized powder from the pulverizing means, the stator enclosing the rotor, The outer peripheral surface and / or the inner peripheral surface of the stator has a plurality of convex portions and concave portions formed between the convex portions and the convex portions, and the repetition distance between the convex portions and the convex portions. The mechanical pulverization is configured such that the rotor is arranged so as to form a pulverization zone so that the surface of the stator and the surface of the rotor have a predetermined gap. Introduced into a machine, and in the grinding zone, the powder raw material is finely pulverized as the rotor rotates,
(3) The finely pulverized finely pulverized product is discharged from the powder discharge port of the mechanical pulverizer and introduced into the second quantitative supply device,
(4) Classifying means for continuously discharging and removing a predetermined amount of finely pulverized material (= surface-modified particles) from the second fixed quantity feeder to the outside of the apparatus, and mechanical impact A surface treatment means using force, a first space before introduction of the space between the classification means and the surface treatment means into the classification means, and toner particles from which fine powder has been removed by classification. Introducing into a batch-type surface reformer configured to have a guide means for partitioning into a second space for introduction into the surface treatment means,
(5) The finely pulverized product (= surface-modified particles) is introduced into the first space, and the fine powder having a predetermined particle size or less is continuously discharged and removed from the apparatus by the classifying means. By introducing the surface treatment means using a mechanical impact force through a space, performing a surface modification treatment, and circulating again to the first space, a surface modification using a fixed time classification and a mechanical impact force is performed. By repeating quality processing,
(6) Toner particles which are surface-modified particles from which fine powder having a small particle size and a predetermined particle size or less are removed are obtained.

Further, in FIG. 2, the method for producing the toner of the present invention is as follows.
After melt-kneading a mixture containing at least a binder resin and a colorant, and cooling the obtained kneaded product, the cooled product is roughly pulverized by a pulverizing means,
(1) The powder raw material made of the coarsely pulverized product is introduced into the first fixed amount feeder,
(2) A powder feed port for feeding a predetermined amount of powder raw material from the first metering feeder into the pulverizing means to pulverize at least the coarsely pulverized product, a stator, and at least center rotation At least a rotor attached to the shaft, and a powder discharge port for discharging finely pulverized powder from the pulverizing means, the stator enclosing the rotor, The rotor is arranged so that there is a predetermined gap between the surface and the surface of the rotor and is introduced into a mechanical crusher configured to form a crushing zone, in which the rotation of the rotor Along with the powder raw material,
(3) The toner particles pulverized in the medium are discharged from the powder discharge port of the mechanical pulverizer and introduced into the second metering feeder.
(4) A powder feed port for feeding a predetermined amount of powder raw material from the second constant quantity feeder into the pulverizing means to pulverize at least the powder raw material, a stator, and at least center rotation At least a rotor attached to the shaft and a powder discharge port for discharging finely pulverized powder from the pulverizing means, the stator enclosing the rotor, The outer peripheral surface and / or the inner peripheral surface of the stator has a plurality of convex portions and concave portions formed between the convex portions and the convex portions, and the repetition distance between the convex portions and the convex portions. The mechanical pulverization is configured such that the rotor is arranged so as to form a pulverization zone so that the surface of the stator and the surface of the rotor have a predetermined gap. Introduced into a machine, and in the grinding zone, the powder raw material is finely pulverized as the rotor rotates,
(5) discharging the finely pulverized finely pulverized product from the powder discharge port of the mechanical pulverizer and introducing it into the third quantitative supply machine;
(6) Classifying means for continuously discharging and removing a predetermined amount of finely pulverized material (= surface-modified particles) from the third fixed quantity feeder to the outside of the apparatus, and mechanical impact A surface treatment means using force, and a space between the classification means and the surface treatment means, the first space before being introduced into the classification means, and the surface modification to which fine powder has been removed by the classification means Introducing into a batch-type surface modification device configured to have a guide means for partitioning the particle into a second space for introducing the particle into the surface treatment means,
(7) The finely pulverized product (= surface-modified particles) is introduced into the first space, and the fine particles having a predetermined particle diameter or less are continuously discharged and removed from the apparatus by the classifying means. By introducing the surface treatment means using a mechanical impact force through a space, performing a surface modification treatment, and circulating again to the first space, a surface modification using a fixed time classification and a mechanical impact force is performed. By repeating quality processing,
(8) Toner particles which are surface-modified particles from which fine powder having a small particle size and a predetermined particle size or less are removed are obtained.

  Next, the pulverizing means and the surface modifying means used in the present invention will be described in more detail using schematic diagrams.

[Crushing means]
First, an outline of a pulverization method using a mechanical pulverizer used in the pulverizing means of the present invention will be described with reference to FIGS.

  FIG. 3 shows an example of a pulverization system incorporating a mechanical pulverizer used in the present invention, FIG. 4 shows a perspective view of a rotor that rotates at a high speed in FIG. 3, and FIG. The enlarged view of a tooth | gear part is shown.

  In FIG. 3, a plurality of grooves are provided on the surface of the casing 313, a jacket 316 that is capable of passing cooling water inside the casing 313, and a surface that rotates inside the casing 313 and is attached to the central rotating shaft 312 and that rotates at high speed. The rotor 314, the stator 310 provided with a number of grooves on the outer surface of the rotor 314, which is arranged at a constant interval, and the raw material inlet for introducing the raw material to be treated. 311 and a raw material discharge port 302 for discharging the processed powder.

  In FIG. 3, a schematic sectional view of a horizontal type general mechanical crusher is shown, but a vertical type may also be used.

  In the mechanical pulverizer configured as described above, when a predetermined amount of powder raw material is charged from the quantitative feeder 315 shown in FIG. 3 into the raw material inlet 311 of the mechanical pulverizer, the raw material is pulverized. An impact generated between a rotor 314 having a large number of grooves provided on the surface thereof introduced into the chamber and rotating at a high speed in the crushing treatment chamber, and a stator 310 having a large number of grooves on the surface; It is pulverized instantaneously by a large number of ultrahigh-speed vortex flows behind this and high-frequency pressure vibrations generated thereby.

  Thereafter, the material passes through the material discharge port 302 and is discharged. The air carrying the particles (air) passes through the pulverization chamber and is discharged out of the apparatus system through the raw material discharge port 302, the pipe 219, the collecting cyclone 229, the bag filter 222, and the suction filter 224. The

  In the present invention, since the powder raw material is pulverized in this manner, a desired pulverization treatment can be easily performed without increasing the fine powder and coarse powder.

  Examples of such a mechanical pulverizer include an inomizer (manufactured by Hosokawa Micron), a kryptron (manufactured by Kawasaki Heavy Industries), a super rotor (manufactured by Nisshin Engineering), a turbo mill (manufactured by Turbo Kogyo Co., Ltd.), and the like. These can be used as they are or after being appropriately modified.

  The present invention melts and kneads a mixture containing at least a binder resin and a colorant, cools the obtained kneaded product, coarsely pulverizes the cooled product, and pulverizes the powder raw material composed of the coarsely pulverized product by a pulverizing means. Then, in the toner manufacturing method including a step of surface modification of the obtained finely pulverized product by the surface modification unit, the pulverization unit includes at least a rotor that is a rotating body attached to a central rotation shaft, and the rotation A mechanical system comprising a stator surface and a stator arranged around the rotor with a constant interval, and an annular space formed by maintaining the interval being in an airtight state The outer peripheral surface of the rotor and / or the inner peripheral surface of the stator includes a plurality of convex portions and concave portions formed between the convex portions and the convex portions. 2. The repetition distance L between the portion and the convex portion is 2.0 mm or more. A method for producing a toner and less than mm.

  The mechanical crusher used in the present invention is characterized in that, as shown in FIG. 5, the outer peripheral surface of the rotor and / or the inner peripheral surface of the stator includes a plurality of convex portions, the convex portions, and the convex portions. And a repetition distance L between the convex portions and the convex portions is 2.0 mm or more and less than 3.5 mm.

  As a result of intensive studies to solve the problems of the prior art, the present inventor has made the repetition distance L between the convex portion and convex portion of the rotor and / or stator to be 2.0 mm or more and less than 3.5 mm. It was found that toner particles having a smaller particle size, specifically, a weight average particle size of 6 μm or less, which was difficult with a conventional mechanical pulverizer, can be obtained with a mechanical pulverizer.

  Furthermore, it has been found that toner particles with higher circularity can be obtained by setting the repetition distance L between the convex portions of the rotor and / or stator to 2.0 mm or more and less than 3.5 mm.

  As the above reason, the repetition distance L between the convex part and the convex part of the rotor and / or the stator is set to 2.0 mm or more and less than 3.5 mm. Compared with the case of 5 mm or more, the number of teeth on the rotor and / or stator surface increases.

  Therefore, the impact force on the powder raw material can be increased, and compared with the case where the repetition distance L between the convex portion and the convex portion is 3.5 mm or more, it was difficult with the conventional mechanical pulverizer, It is considered that toner particles having a smaller particle diameter, specifically, a weight average particle diameter of 6 μm or less can be obtained by a mechanical pulverizer.

  Furthermore, by setting the repetition distance L between the convex part and convex part of the rotor and / or stator to 2.0 mm or more and less than 3.5 mm, a large number of ultrahigh-speed eddy currents are generated between the rotor and the stator. Therefore, it is considered that toner particles having higher circularity can be obtained as compared with the case where the repetition distance L between the convex portions is 3.5 mm or more.

  That is, compared with the case where the repetition distance L between the convex portion and the convex portion is 3.5 mm or more, the repetition distance L between the convex portion and the convex portion of the rotor and / or stator used in the present invention is 2.0 mm. If it is less than 3.5 mm, it is possible to obtain toner particles having a small particle diameter of 6 μm or less, which is difficult with a conventional mechanical pulverizer, and to obtain toner particles having a higher degree of circularity. it can.

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

  As a measuring device, a multisizer type II or type IIe (manufactured by Coulter Co.) of a Coulter counter is used, and an interface (manufactured by Nikkiki) that outputs number distribution and volume distribution is connected to a general personal computer. A 1% NaCl aqueous solution is prepared using special grade or first grade sodium chloride.

  As a measuring method, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and measured using a Coulter counter Multisizer II type with a 100 μm aperture. The volume and number of toners are measured to calculate a volume distribution and a number distribution, and a weight-based weight average diameter obtained from the volume distribution is obtained.

  In the present invention, among the toner particles pulverized by the mechanical pulverizer, the average circularity of particles having an equivalent circle diameter of 2 μm or more is 0.930 or more, preferably 0.930 or more and less than 0.945. It is characterized by that.

  As a result of the study by the present inventors, when the average circularity is less than 0.930, an attempt is made to obtain surface-modified particles having a high circularity in the next surface modification step, to a surface modification device described later. This is not satisfactory from the standpoint of toner productivity because the toner is liable to be subject to thermal deterioration and in-machine fusion. In addition, when the average circularity is 0.945 or more, the toner surface may be affected by heat during pulverization, which is liable to cause in-machine fusion, which is problematic in terms of toner production and development / transfer performance. May be.

The average circularity in the present invention is used as a simple method for quantitatively expressing the shape of the particles. In the present invention, the average circularity is measured using a flow type particle image analyzer FPIA-2100 manufactured by Sysmex Corporation. , Particles having a circle equivalent diameter of 0.6 to 400 μm are measured, and the circularity of the measured particles is obtained by the following equation (1). Further, in the particles having a circle equivalent diameter of 2 μm to 400 μm, The value obtained by dividing the total by the total number of particles is defined as the average circularity.
Circularity a = L ₀ / L (1)
[In the formula, L ₀ represents the perimeter of a circle having the same projection area as the particle image, and L represents the particle projection when image processing is performed at an image processing resolution of 512 × 512 (pixels of 0.3 μm × 0.3 μm). Indicates the perimeter of the image. ]

  The circularity used in the present invention is an index of the degree of unevenness of the toner particles and the toner, and indicates 1.00 when the toner particles and the toner are perfectly spherical, and the circularity becomes smaller as the surface shape becomes more complicated. Become.

  In addition, "FPIA-2100" which is a measuring apparatus used in the present invention calculates the circularity of each particle, and then calculates the average circularity by calculating the circularity of each particle. A calculation method is used in which the average circularity is calculated using the center value and the frequency of the division points by dividing the class into 61 divided into 1.0.

  However, the error of the average circularity calculated by the calculation formula using the average circularity value calculated by this calculation method and the total circularity of each particle is very small and can be substantially ignored. In the present invention, for the reason of handling data such as shortening the calculation time and simplifying the calculation operation formula, the concept of the calculation formula using the sum of the circularity of each particle is used and partly changed. Such a calculation method may be used.

  Furthermore, the measurement device used in the present invention, “FPIA-2100”, improves the magnification of the processed particle image as compared with “FPIA1000”, which has been conventionally used for calculating the toner particles and the shape of the toner. Further, by improving the processing resolution of the captured image (256 × 256 → 512 × 512), the accuracy of toner particle and toner shape measurement has been improved, thereby achieving more reliable capture of fine particles. It is.

  Therefore, when it is necessary to measure the shape and particle size distribution more accurately as in the present invention, the FPIA 2100 that can obtain information on the shape and particle size distribution more accurately is more useful.

  As a specific measuring method, 10 ml of ion-exchanged water from which impure solids have been removed in advance is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant therein, followed by further measurement. Add 0.02 g of sample and disperse uniformly.

  As a means for dispersion, an ultrasonic disperser “Tetora 150 type” (manufactured by Nikka Ki Bios Co., Ltd.) is used, and dispersion treatment is performed for 2 minutes to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of this dispersion may not be 40 degreeC or more.

  In order to suppress variation in circularity, the installation environment of the apparatus is controlled at 23 ° C. ± 0.5 ° C. so that the temperature inside the flow type particle image analyzer FPIA-2100 is 26 to 27 ° C. Preferably, autofocus is performed using 2 μm latex particles every 2 hours.

  To measure the circularity of the toner particles, the flow type particle image measuring device is used, and the concentration of the dispersion is readjusted so that the toner particle concentration at the time of measurement is 3000 to 10,000 particles / μl. Measure more than one. After the measurement, the average circularity of the toner particles is obtained for particles having an equivalent circle diameter of 2 μm or more and 400 μm or less using this data.

  In the present invention, the average surface roughness of the toner particles pulverized by the mechanical pulverizer is 15.0 nm or more and less than 45.0 nm.

  As a result of investigation by the present inventors, when the average surface roughness of the toner particles is 45.0 nm or more, an attempt is made to obtain surface modified particles having a smoother surface roughness in the next surface modification step. Therefore, the burden on the surface reforming apparatus is increased, and the toner is likely to undergo thermal alteration and in-machine fusion, so that it is not satisfactory from the viewpoint of toner productivity.

  In addition, when the average surface roughness of the toner particles is less than 15.0 nm, the toner surface may be affected by heat during pulverization, which is liable to cause in-machine fusion, and in terms of toner production and development / transfer performance. It can be a problem.

In the present invention, the average surface roughness of the toner particles that are finely pulverized is measured using a scanning probe microscope. Below, the example of a measuring method is shown.
Probe station: SPI3800N (manufactured by Seiko Instruments Inc.)
Measuring unit: SPA400
Measurement mode: DFM (resonance mode) shape image Cantilever: SI-DF40P
Resolution: Number of X data 256
Number of Y data 128
In the present invention, the area of 1 μm square of the toner particles and the toner surface is measured. The area to be measured is a 1 μm square area at the center of the toner particles and the toner surface measured with a scanning probe microscope. As the toner particles and toner to be measured, toner particles and toner equal to the weight average particle diameter (D ₄ ) measured by the Coulter counter method are randomly selected, and the toner particles and toner are measured. The measured data is subjected to secondary correction. Five or more different toner particles and toners are measured, and the average value of the obtained data is calculated to obtain the average surface roughness of the toner particles and toner.

  The average surface roughness is a three-dimensional extension of the centerline average roughness Ra defined in JIS B0601 so that it can be applied to the measurement surface. The absolute value of the deviation from the reference plane to the specified plane is averaged and expressed by the following formula.

Ｆ（Ｘ，Ｙ）：全測定データの示す面
Ｓ₀ ：指定面が理想的にフラットであると仮定したときの面積
Ｚ₀ ：指定面内のＺデータの平均値

F (X, Y): surface S ₀ indicated by all measurement data: area Z ₀ when the designated surface is assumed to be ideally flat: average value of Z data in the designated surface

  In the present invention, the designated surface means a measurement area of 1 μm square.

  The average circularity and average surface roughness of the finely pulverized product can be adjusted according to the pulverization conditions of the toner particles. Hereinafter, the pulverization conditions of the toner particles for obtaining the above-described average circularity and average surface roughness will be described.

  In the present invention, the minimum distance between the rotor and the stator in the mechanical pulverizer is preferably 0.5 to 10.0 mm, and more preferably 0.5 to 5.0 mm.

  By setting the distance between the rotor and the stator to 0.5 to 10.0 mm, more preferably 0.5 to 5.0 mm, insufficient pulverization and excessive pulverization of the toner can be suppressed, and the pulverized raw material can be efficiently obtained. The desired average circularity and average surface roughness can be obtained.

  If the distance between the rotor and the stator is larger than 10.0 mm, a short pass is caused without being pulverized, which is not satisfactory from the viewpoint of toner productivity. Also, if the distance between the rotor and the stator is smaller than 0.5 mm, the load on the device itself will increase, and at the same time, it will be excessively pulverized during pulverization, which will easily cause thermal deterioration of the toner and in-machine fusion. This is not satisfactory from the viewpoint of toner productivity.

  Further, as a more preferable form of pulverization of the toner, it is preferable to blow air of + 30 ° C. or less into the pulverizer, the temperature of the air is more preferably +30 to −50 ° C., and +20 to −40 ° C. It is particularly preferred.

  By the cold air generating means, the room temperature T1 in the spiral chamber 212 communicating with the powder inlet in the mechanical pulverizer is set to + 20 ° C. or less, more preferably +20 to −40 ° C., further preferably +10 to −30 ° C. It is preferable in terms of toner production and development performance.

  By setting the room temperature T1 of the swirl chamber in the mechanical 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. Reduce variation in toner particle shape distribution and reduce fog. When the room temperature T1 of the spiral chamber in the pulverizer exceeds + 20 ° C., the toner is likely to be thermally altered or fused in the machine during pulverization, which may cause problems in toner production and development / transfer performance.

  The refrigerant used in the cold air generating means 321 is preferably an alternative chlorofluorocarbon from the viewpoint of environmental problems of the entire earth.

  The finely pulverized product generated in the mechanical pulverizer is discharged from the powder discharge port 302 to the outside through the rear chamber 320 of the mechanical pulverizer. At that time, the room temperature T2 of the rear chamber 320 of the mechanical pulverizer is preferably 55 ° C. or lower, more preferably 30 ° C. or higher and 55 ° C. or lower in terms of toner production and development / transfer performance.

  By setting the room temperature T2 of the rear chamber 320 of the mechanical pulverizer to 30 ° C. or higher and 55 ° C. or lower, insufficient pulverization or excessive pulverization of the toner can be suppressed, and the pulverized raw material can be efficiently pulverized. Degree and average surface roughness can be obtained.

  In addition, variation in the shape distribution of toner particles is suppressed, and occurrence of fog is reduced. When the temperature T2 of the mechanical pulverizer is lower than 30 ° C., there is a possibility that a short pass is caused without being pulverized, which is not satisfactory from the viewpoint of toner productivity.

  On the other hand, when the temperature is higher than 55 ° C., the toner may be excessively pulverized at the time of pulverization, and the toner is likely to undergo thermal alteration and in-machine fusion, which may cause problems in toner production and development / transfer performance.

  As an in-machine cooling means of the mechanical pulverizer body, the mechanical pulverizer preferably has a structure having a jacket structure 316, and it is preferable to pass cooling water (preferably an antifreeze such as ethylene glycol).

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

  In the toner manufacturing method of the present invention, as shown in FIG. 2, toner particles having a weight average diameter of 5 to 12 μm are obtained before the pulverization step for obtaining toner particles having a weight average particle diameter of 6 μm or less. A middle grinding step may be included.

  As a result of the study by the present inventor, it is preferable that the intermediate pulverization step is performed using a mechanical pulverizer. This is because the average circularity of particles having an equivalent circle diameter of 2 μm or more of the finely pulverized product obtained in the subsequent fine pulverization step can be easily controlled in the range of 0.930 or more and less than 0.945.

  In addition, in the mechanical pulverizer in the middle pulverization, it is preferable that the repetition distance L between the convex portion and the convex portion of the rotor and / or the stator is 2.0 mm or more and less than 5.0 mm. When the distance L between the convex portions and the convex portions is 5.0 mm or more, the weight average diameter of the obtained intermediate pulverization becomes too large. Therefore, toner particles having a weight average particle diameter of 6 μm or less are added in the next pulverization step. It becomes difficult to obtain and is not preferable.

  Next, an outline of a surface modification method using a batch type surface modification apparatus used in the toner production method of the present invention will be described with reference to FIGS.

[Surface modification means]
FIG. 6 is a schematic view of a batch-type surface reforming apparatus used in the present invention, and FIG. 7 is an example of a top view of the surface modifying means that rotates at a high speed in FIG.

  In the batch type surface reforming apparatus shown in FIG. 6, a main body casing 30, a top plate 43 installed at the top of the main body casing so as to be opened and closed, a fine powder discharge casing 44 which is a fine powder discharge section, cooling water or antifreeze liquid It is comprised from the cooling jacket 31 which can permeate | transmit water.

  Further, a rotating body on a disk that rotates at a high speed and has a plurality of rectangular disks or cylindrical pins 33 on the upper surface, which is mounted on the central rotating shaft in the main body casing 30 as surface modification means. The dispersion rotor 32, and the liner 34, which is a fixed body that is arranged on the outer periphery of the dispersion rotor 32 while maintaining a constant interval and has a large number of grooves on the surface (there is no groove on the liner surface) It does not matter.)

  Further, the surface-modified raw material is classified to a predetermined particle size, and the fine powder classified by the classification rotor 35, which is a means for discharging the fine powder out of the main body casing 30, is discharged out of the apparatus. And a fine powder discharge port 45.

  Furthermore, a cold air inlet 46 for introducing cold air, a raw material inlet 37 and a raw material supply port 39 for introducing surface modified particles, and opening and closing so that the surface modification time can be freely adjusted. It comprises a raw material supply valve 38, a product discharge valve 41, a product discharge port 40 for discharging the surface-modified powder, and a product extraction port 42 installed as possible.

  Further, the space between the classification rotor 35 as the classification means and the dispersion rotor 32-liner 34 as the surface modification means is divided into the first space 47 before being introduced into the classification rotor 35 and the classification rotor 35. It is composed of a cylindrical guide ring 36 which is a guide means for partitioning the particles, from which fine powder has been classified and removed, into a second space 48 for introducing the particles into the surface treatment means.

  A gap between the plurality of rectangular disks or cylindrical pins 33 installed on the dispersion rotor 32 and the liner 34 is the surface modification zone 49, and the classification rotor 35 and the peripheral portion of the rotor are the classification zone 50. is there.

  The classifying rotor may be installed in the vertical direction as shown in FIG. 6 or in the horizontal direction. Further, the number of classifying rotors may be single as shown in FIG. 6 or plural.

  Moreover, it is preferable that the rotation direction of a dispersion | distribution rotor and a classification rotor is the same direction. If the rotation directions of the dispersion rotor and the classification rotor are reversed, the load on the classification rotor increases, and normal operation cannot be performed, which is not satisfactory from the viewpoint of toner productivity.

  In the batch-type surface reforming apparatus configured as described above, with the product discharge valve 39 closed, the raw material supply valve 38 is opened, and the surface modified particles are charged from the raw material charging port 37. After a certain period of time, the raw material supply valve 38 is closed.

  The surface modified particles introduced into the apparatus from the raw material supply port 39 are first sucked by a blower (not shown) and classified by the classification rotor 35. At that time, the classified fine powder having a predetermined particle size or less is continuously discharged and removed through the fine powder discharge casing 44 and the fine powder discharge port 45 to the outside of the apparatus.

  Surface-modified particles having a predetermined particle diameter or more are swirled along the inner periphery (second space 48) of the guide ring 36 by centrifugal force, and are circulated by the circulating flow generated by the dispersion rotor 32 to the surface modification zone 49. Led.

  The surface-modified particles guided to the surface modification zone 49 are subjected to a mechanical impact force between the liner 34 and the square disk or cylindrical pin 33 installed on the dispersion rotor 32. The surface is modified.

  The surface-modified surface-modified particles are guided to the classification zone 50 while swirling along the outer periphery (first space 47) of the guide ring 36 along the cold air and the blower suction flow passing through the machine, By the classification rotor 35, the fine powder is again discharged to the outside of the machine through the fine powder discharge casing 44 and the fine powder discharge port 45, and the coarse powder is returned to the surface modification zone 49 again through the circulation flow, and repeatedly surface modified. Affected.

  After a certain period of time, the product discharge valve 41 is opened, and the surface modified particles are recovered from the product extraction port 42.

  It is preferable in terms of toner productivity that the fine powder generated by the batch-type surface reforming apparatus is collected by a collecting device such as a cyclone or a bag and returned to the toner raw material mixing step and reused.

  The feature of the toner production method of the present invention is that the outer peripheral surface of the rotor and / or the inner peripheral surface of the stator shown in FIG. 5 are formed between a plurality of convex portions and the convex portions. The powder raw material is pulverized by a mechanical pulverizer having a repetition distance L of 2.0 mm or more and less than 3.5 mm. The surface modified particles having a small particle size, high circularity, and smooth surface roughness are obtained by introducing the surface modified particles into the batch type surface modifying apparatus shown in FIG. Is obtained with good yield.

  That is, as a result of examination by the present inventors, the outer peripheral surface of the rotor and / or the inner peripheral surface of the stator shown in FIG. 5 are formed between a plurality of convex portions and the convex portions. The surface used for the surface modification step by finely pulverizing the powder raw material with a mechanical pulverizer having a concave portion and a repeating distance L between the convex portion and the convex portion of 2.0 mm or more and less than 3.5 mm The reforming apparatus is a batch type surface modifying apparatus as shown in FIG. 6 and has a built-in classification rotor for classifying the surface modified particles into a predetermined particle diameter. When the surface modification is further performed, the batch type surface modifying apparatus is used. Even when the surface of toner that is prone to over-pulverization is modified by setting and controlling the relationship between the components in the quality device and the operating conditions in the surface modification zone, Prevents the increase in fine powder and sharply classifies the toner particle size distribution. .

  Further, the surface state of the toner can be arbitrarily controlled, and a long-life toner having good developability, transferability, cleaning property, and stable chargeability can be obtained.

  As the above reason, the surface state of the surface modified particles depends on the motion state of the surface modified particles in the surface modifying apparatus. That is, in order to control the surface state of the surface modified particles, it is important to control the motion state of the surface modified particles in the surface modifying apparatus.

  In the present invention, the surface modification device used in the surface modification step is a batch-type surface modification device as shown in FIG. 6, and the relationship between each device configuration in the batch-type surface modification device, the surface By setting and controlling the operating conditions in the reforming zone to an appropriate state, it is possible to prevent an increase in fine powder during surface reforming, and to control the motion state of the surface reforming particles in the surface reforming device. The surface state of the modified particles can be arbitrarily controlled.

  In addition, by incorporating a classifying rotor that classifies surface-modified surface-modified particles into a predetermined particle size, by controlling the blower air volume and the rotational peripheral speed of the classifying rotor to an appropriate state, a fine powder below a predetermined particle Since the body is continuously discharged out of the apparatus and the coarse powder can be surface-modified again, surface-modified particles having a sharp particle size distribution from which fine powders of a predetermined particle size or less are removed can be obtained with higher yield. Can do.

  The weight average particle diameter of the toner particles which are the surface modified particles of the present invention is 4.0 to 8.0 μm. The toner of the present invention has a very small weight average particle diameter in order to achieve excellent dot reproducibility, but if it is smaller than 4.0 μm, high transferability cannot be achieved, and cleaning properties also deteriorate. . When the size is larger than 8.0 μm, excellent dot reproducibility cannot be obtained.

  In the present invention, among the surface modified particles surface-modified by the batch type surface modifying apparatus, the average circularity of particles having an equivalent circle diameter of 2 μm or more is 0.935 or more, and The average surface roughness of the surface-modified particles surface-modified by the batch-type surface modifying apparatus is 5.0 nm or more and less than 35.0 nm.

  As a result of investigation by the present inventors, the average circularity is 0.935 or more, preferably 0.940 or more, more preferably 0.945 or more, and further, the average surface roughness is 5.0 nm or more and less than 35.0 nm, It was found that the transfer efficiency is improved and the dot reproducibility is improved without impairing the developability by preferably 5.0 nm or more and less than 30.0 nm, more preferably 5.0 nm or more and less than 25.0 nm. . Moreover, it turned out that the effect of the fluidity | liquidity provision by an external additive becomes large.

  When the average circularity is less than 0.935 and the average surface roughness is 35.0 or more, the fluidity imparting effect by the external additive is reduced, so that the toner fluidity is lowered and the toner charge is reduced. Variations in the amount tend to cause a decrease in transfer efficiency and dot reproducibility. In addition, when the average surface roughness is less than 5.0, the toner surface may be affected by heat during the surface modification, and the toner is likely to be thermally deteriorated and fused in the machine. In addition, there may be a problem in development / transfer performance.

  Further, in the present invention, the transmittance (%) of the toner particles, which are the surface modified particles obtained by the batch type surface modifying apparatus, in a 45 volume% methanol aqueous solution is in the range of 20% or more and less than 70%. It is characterized by being in

  As a result of the study by the present inventors, the transmittance (%) of the toner particles, which are the surface modified particles obtained by the batch type surface modifying device, in a 45 volume% methanol aqueous solution is 20% or more and less than 70%. It is preferable to be in the range.

  Since the toner of the present invention contains a wax in the toner, at least the wax is present on the surface of the toner particles. When the wax on the toner surface is small, the releasing effect at the time of fixing hardly appears, and the low temperature fixing effect desired from the viewpoint of energy saving decreases.

  In addition, when there is a lot of wax on the toner surface, the charge imparting member is contaminated with wax, and, for example, the resistance is increased by fusing on the developing sleeve, and the effectiveness of the actual development bias for development is reduced. In some cases, the image density decreases and the development durability deteriorates.

  As described above, when the wax is contained in the toner, it is important to control the amount of wax on the toner surface.

  As a result of the study by the present inventors, when the transmittance (%) of the toner particles as surface modified particles in a 45 volume% methanol aqueous solution is smaller than 20%, a binder resin and a hydrophilic colorant, for example, on the toner surface, for example, Dyes and C.I. Since B and the like are biased, it is considered that the difference in charging environment is large.

  This makes it impossible to obtain a sufficient contrast of the photosensitive drum, so that the image density fluctuation is likely to be large and the gradation is poor. Therefore, in a full-color image, color reproducibility is very poor. .

  Conversely, when the transmittance (%) in a 45% by volume methanol aqueous solution is greater than 70%, there are many release agents such as organic pigments and wax on the toner surface, so that insulating substances gather together. However, it is considered that the charging ability of the toner is broadened because the charging ability is quite different.

  This is because there is little transfer of charge between toners during continuous copying, so the difference in charge level opens, and eventually fogging and toner scattering occur.

  That is, by making the transmittance (%) of toner particles as surface modified particles in a 45 volume% methanol aqueous solution in a range of 20% or more and less than 70%, various materials can be present on the toner surface in a balanced manner. Thus, a long-life toner having good developability, transferability, cleaning property, and stable chargeability can be obtained.

  The amount of wax on the toner surface can be measured easily and with high accuracy by measuring the transmittance (%) in a 45% by volume aqueous solution of methanol.

  In this measurement method, toner particles are forcibly dispersed once in a methanol / water mixture solvent to easily reveal the characteristics of the surface wax amount of each toner particle, and then the transmittance after a certain time is measured. The amount of wax on the toner surface can be accurately grasped.

  In this invention, the transmittance | permeability in 45 volume% methanol aqueous solution was measured in the following procedures.

(1) Preparation of toner dispersion An aqueous solution having a volume mixing ratio of methanol: water of 45:55 is prepared. 10 ml of this aqueous solution is placed in a 30 ml sample bottle (Nippon Denka Glass: SV-30), and 20 mg of toner is impregnated on the liquid surface to cover the bottle.

  Then, it is made to shake at 2.5S-1 for 5 seconds with a Yayoi type shaker (model: YS-LD). At this time, the angle of shaking is such that the shaking column moves 15 degrees forward and 20 degrees backward, assuming that the vertical (vertical) of the shaker is 0 degree.

  The sample bottle is fixed to a fixing holder (with the sample bottle lid fixed on the extension at the center of the column) attached to the tip of the column. After removing the sample bottle, the dispersion after 30 seconds is used as a dispersion for measurement.

(2) Transmittance measurement The dispersion obtained in (1) was placed in a 1 cm square quartz cell, and the transmittance at a wavelength of 600 nm of the dispersion after 10 minutes using a spectrophotometer MPS2000 (manufactured by Shimadzu Corporation) ( %).
Transmittance (%) = I / I0 × 100 I: incident light flux, I0: transmitted light flux

  The average circularity, average surface roughness, and transmittance in a 45 volume% methanol aqueous solution of the surface modified particles can be adjusted according to the surface modification conditions of the surface modified particles. Hereinafter, the surface modification conditions of the surface modified particles for obtaining the above-described average circularity, average surface roughness, and transmittance in a 45 volume% methanol aqueous solution will be described.

  In the toner production method of the present invention, the surface modification time in the batch type surface modification apparatus is 5 seconds or more and 180 seconds or less, more preferably 15 seconds or more and 150 seconds or less, and further preferably 15 seconds or more and 120 seconds. It is preferable that it is below second.

  When the surface modification time is less than 5 seconds, since the surface modification time is too short, surface modified particles having a desired circularity and average surface roughness cannot be obtained, which is not preferable in terms of toner quality.

  In addition, when the surface modification time exceeds 180 seconds, the surface modification time is too long, so it causes surface deterioration due to heat generated during surface modification, occurrence of in-machine fusion, and reduction in processing capacity. This is not satisfactory from the viewpoint of toner productivity.

  Further, in the toner production method of the present invention, the cold air temperature T1 introduced into the batch type surface reforming apparatus is preferably 5 ° C. or less, more preferably 0 ° C. or less, and further preferably −5 ° C. or less. .

  By setting the cold air temperature T1 introduced into the batch type surface reforming apparatus to 5 ° C. or less, preferably 0 ° C. or less, more preferably −5 ° C. or less, surface alteration due to heat generated during surface modification, Fusion can be prevented.

  If the cold air temperature T1 introduced into the batch-type surface reforming apparatus exceeds 5 ° C. or more, surface modification due to heat generated during the surface modification or in-machine fusion is likely to occur. It is not satisfactory enough.

  In addition, as a refrigerant used in the cold air generator introduced into the batch type surface reforming apparatus, an alternative chlorofluorocarbon is preferable from the viewpoint of environmental problems of the entire earth.

  The cold air introduced into the batch type surface reforming apparatus is preferably dehumidified from the viewpoint of preventing condensation in the apparatus from the viewpoint of toner productivity. A well-known thing can be used as a dehumidifier. The supply air dew point temperature is preferably −15 ° C. or lower, and more preferably −20 ° C. or lower.

  Further, in the toner production method of the present invention, the batch type surface reforming apparatus is provided with a jacket for cooling inside the apparatus, and a refrigerant (preferably cooling water, more preferably ethylene glycol or the like) is provided in the jacket. The surface-modified particles are preferably subjected to a surface modification treatment while passing through an antifreeze solution.

  In-machine cooling by the jacket can prevent surface alteration and in-machine fusion due to heat during surface modification.

  The temperature of the refrigerant passed through the jacket of the batch type surface reformer is preferably 5 ° C. or less, more preferably 0 ° C. or less, and further preferably −5 ° C. or less.

  By changing the temperature of the refrigerant passed through the jacket in the batch type surface reforming apparatus to 5 ° C. or less, more preferably 0 ° C. or less, and further preferably −5 ° C. or less, surface alteration due to heat generated during the surface modification In addition, in-machine fusion can be prevented.

  If the temperature of the refrigerant introduced into the cooling jacket exceeds 5 ° C., surface deterioration due to heat generated during surface modification and in-machine fusion are likely to occur. Absent.

  Furthermore, in the method for producing the toner of the present invention, the temperature T2 in the fine powder outlet located behind the classification rotor in the batch type surface reforming apparatus is 60 ° C. or less, more preferably 55 ° C. or less, and further preferably 50 ° C. The following is preferable.

  The temperature T2 in the fine powder outlet located behind the classification rotor in the batch type surface reforming apparatus is 60 ° C. or less, more preferably 55 ° C. or less, and even more preferably 50 ° C. or less. It can prevent surface deterioration due to heat and in-machine fusion.

  If the temperature T2 in the fine powder outlet located behind the classifying rotor in the batch type surface reforming apparatus exceeds 60 ° C, it is assumed that the temperature above the surface reforming zone has an effect. However, it is not satisfactory from the viewpoint of toner productivity because it easily causes surface deterioration due to heat generated during surface modification and in-machine fusion.

  Furthermore, in the toner production method of the present invention, the minimum distance between the square disk or cylindrical pin on the dispersion rotor in the batch surface modification device and the liner is 0.5 mm to 15.0 mm. It is preferable that the thickness is 2.0 mm to 10.0 mm.

  The rotational peripheral speed of the dispersion rotor is preferably 30 m / sec to 175 m / sec, and more preferably 40 m / sec to 160 m / sec.

  As a result of the study by the present inventors, when the minimum distance between the dispersion rotor and the liner in the batch type surface reforming apparatus is less than 0.5 mm, the load on the apparatus itself is increased, and at the same time during the surface modification. Since it is excessively pulverized and easily undergoes surface alteration and in-machine fusion due to heat, it is not satisfactory from the viewpoint of toner productivity.

  Further, if the minimum distance between the dispersion rotor and the liner exceeds 15.0 mm, the processing capability must be reduced to obtain surface-modified particles having a desired average circularity and average surface roughness. This is also not satisfactory in terms of toner productivity.

  Further, if the rotational peripheral speed of the dispersion rotor in the batch type surface reforming apparatus is less than 30 m / sec, the processing capacity must be reduced in order to obtain a predetermined circularity and average surface roughness. It is not satisfactory in nature.

  Further, if the rotational speed of the dispersion rotor exceeds 175 m / sec, the load on the apparatus itself increases, and at the same time, the surface-modified particles are excessively pulverized during the surface modification, and at the same time, the surface is altered by heat. This is also not satisfactory from the standpoint of toner productivity.

  As a result of the study by the present inventors, by controlling the surface modification conditions of the batch surface modification device within the above range, an increase in fine powder during the surface modification is prevented, and the influence of heat during the surface modification. The surface state of the surface-modified particles (= circularity, average surface roughness, and transmittance (%) in a 45% by volume methanol aqueous solution) can be controlled as desired, and good developability, transferability, and cleaning And a long-life toner having a stable chargeability can be obtained.

  That is, according to the toner production method of the present invention, the average circularity of the surface-modified particles obtained in the surface modification step is 0.935 or more, the average surface roughness is 5.0 to 35.0 nm, and methanol 45 The transmittance (%) in the volume% aqueous solution can be in the range of 20% or more and less than 70%.

  As described above, this is because the surface reforming time from the closing of the raw material supply valve to the product discharge valve of the surface reformer, the cold air temperature T1, the fine powder outlet temperature T2, the rectangular disk or cylindrical shape on the dispersion rotor By controlling the minimum distance between the pin and the liner, the rotational peripheral speed of the dispersion rotor, etc. to an appropriate state, the surface state of the toner (= circularity, average surface roughness, and transmittance in a 45 volume% methanol aqueous solution (%) ) Can be controlled arbitrarily.

  Next, a procedure for producing a toner in the toner production method of the present invention will be described.

  First, in the raw material mixing step, as a toner internal additive, at least a resin and a colorant are weighed and mixed in a predetermined amount and mixed. Examples of the mixing apparatus include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, and a Nauter mixer.

  Further, the toner raw materials blended and mixed as described above are melt-kneaded to melt the resins and disperse the colorant and the like 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 mainstream due to the advantage of being capable of continuous production. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type twin screw extruder manufactured by Toshiba Machine Co., Ltd. In general, a twin-screw extruder manufactured by Kay Sea Kay, a co-kneader manufactured by Buss, or the like is used.

  Furthermore, the colored resin composition obtained by melt-kneading the toner raw material is rolled by a two-roll roll after melt-kneading, and then cooled through a cooling step of cooling by water cooling or the like.

  The cooled product of the colored resin composition obtained above is then pulverized to a desired particle size in a pulverization step. In the pulverization process, first, coarse crushing is performed with a crusher, a hammer mill, a feather mill, etc., and further, an inomizer (manufactured by Hosokawa Micron), a kryptron (manufactured by Kawasaki Heavy Industries), a super rotor (manufactured by Nisshin Engineering), a turbo mill (turbo) Finely pulverized with a mechanical pulverizer such as Kogyo Kogyo).

  In the pulverization step, the toner is pulverized to a predetermined toner particle size step by step. Thereafter, surface modification = spheronization treatment is performed in the surface modification step to obtain surface modified particles. Note that a classification step may be provided before and after the surface modification step according to convenience.

  In addition, it is preferable in terms of toner productivity that the toner fine powder generated by the classification in the surface modification step is returned to the toner raw material blending step and reused.

  Furthermore, in the method for producing a toner of the present invention, inorganic fine particles having an average particle diameter of 50 nm or less are externally added as external additives to the toner particles that are surface-modified particles obtained as described above.

  As a method of externally adding an external additive to toner particles, a predetermined amount of surface-modified toner particles and various known external additives are blended, and a Henschel mixer, a super mixer, a Q-type mixer (mechano hybrid), or the like is used. It is preferable to stir and mix using a high-speed stirrer that gives a shearing force to the powder as an external additive.

  At this time, since heat is generated inside the external adder and it becomes easy to generate aggregates, it is preferable in terms of toner productivity to adjust the temperature by means such as cooling the periphery of the container of the external adder with water.

  Next, raw materials for toner particles containing at least a binder resin and a colorant used in the present invention will be described.

  The toner of the present invention is a toner used in a full-color image forming method, and is characterized in that the binder resin is a resin having at least a polyester unit.

  The “polyester unit” used in the present invention means a part derived from polyester. Specifically, as a component constituting the polyester unit, a divalent or higher valent alcohol monomer component and a divalent or higher carboxylic acid, It means an acid monomer component such as a divalent or higher carboxylic acid anhydride and a divalent or higher carboxylic acid ester.

  The toner of the present invention is characterized in that a component having these polyester units is used as a part of a raw material and a resin having a condensation-polymerized portion is used.

  The binder resin used in the present invention is a polyester resin, a hybrid resin having a polyester unit and a vinyl polymer unit, a mixture of a hybrid resin and a vinyl polymer, or a mixture of a hybrid resin and a polyester resin. Or a resin selected from a polyester resin, a hybrid resin, and a vinyl polymer, or a mixture of a polyester resin and a vinyl polymer.

  The hybrid resin is formed by a transesterification reaction between a polyester unit component and a vinyl polymer unit obtained by polymerizing a monomer component having a carboxylic acid ester group such as (meth) acrylic acid ester. A graft copolymer (or block copolymer) in which the coalescence is a trunk polymer and the polyester unit is a branch polymer is formed.

As a dihydric or higher alcohol monomer component which is a polyester unit component, specifically, as a dihydric alcohol monomer component, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, poly Oxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0 ) -Polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane and other alkylene oxides of bisphenol A Adduct, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-pro Lenglycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, Examples include dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, and hydrogenated bisphenol A.

  Examples of the trivalent or higher alcohol monomer component include sorbit, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol. 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. Is mentioned.

  Examples of the divalent carboxylic acid monomer component include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof; alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; And succinic acid substituted with an alkyl group or alkenyl group having 6 to 18 carbon atoms or an anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid, or anhydrides thereof.

  Examples of the trivalent or higher carboxylic acid monomer component include trimellitic acid, pyromellitic acid, polyvalent carboxylic acid such as benzophenone tetracarboxylic acid and its anhydride, and the like.

  Examples of other monomers include polyhydric alcohols such as oxyalkylene ethers of novolak type phenol resins.

  Among them, in particular, a carboxylic acid component comprising a bisphenol derivative represented by the following general formula (I) as a dihydric alcohol monomer component and a divalent or higher carboxylic acid or an acid anhydride thereof, or a lower alkyl ester thereof. (For example, fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) are used as acid monomer components, and resins obtained by condensation polymerization with these polyester unit components have good charging characteristics. Since it has, it is preferable.

（式中、Ｒはエチレン基又はプロピレン基を示し、ｘ及びｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値は２〜１０である。）

(In the formula, R represents an ethylene group or a propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10.)

  The binder resin contained in the toner of the present invention may be a resin having at least a polyester unit. Preferably, the polyester unit component contained in the total binder resin is 30% of the total binder resin. It is preferable for it to be at least mass% in order to exhibit the effects of the present invention. More preferably, it is 40 mass% or more, Most preferably, it is 50 mass% or more.

  When the polyester unit component contained in the total binder resin is 30% by mass or more based on the total binder resin, the dispersibility of the colorant in the toner particles is improved, and the toner color mixing property and transparency in the fixed image are improved. It is possible to obtain a toner having excellent color reproducibility such as a high covering power on the transfer material. In particular, it is more effective when the pigment content such as the colorant master batch is large.

  The following are mentioned as a vinyl-type monomer for producing | generating the vinyl-type polymer unit or vinyl-type polymer used for hybrid resin. Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert- Butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-chloro styrene, 3, Styrene and derivatives thereof such as 4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene; styrene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated such as butadiene and isoprene Polyenes; vinyl chloride, vinyl chloride, vinyl bromide, fluoride Vinyl halides such as vinyl; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-methacrylate Α-methylene aliphatic monocarboxylic acid esters such as octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate Propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-acrylate Acrylic esters such as lorethyl and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole; N-vinyl compounds such as N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

  In addition, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, etc. Unsaturated dibasic acid anhydride; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, Unsaturated dibasic acid half esters such as alkenyl succinic acid methyl half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester; dimethyl maleic acid, unsaturated dibasic acid ester such as dimethyl fumaric acid; acrylic acid, Α, β-unsaturated acids such as phosphoric acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic anhydride and cinnamic anhydride, the α, β-unsaturated acids and lower fatty acids And monomers having a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof.

  Furthermore, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1) -Methylhexyl) Monomers having a hydroxy group such as styrene.

  The vinyl polymer or vinyl polymer unit used in the hybrid resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups, but the crosslinking agent used in this case is Examples of aromatic divinyl compounds include divinylbenzene and divinylnaphthalene; examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, and 1,4-butanediol di Examples include acrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate, and the above compounds in which acrylate is replaced by methacrylate; linked by an alkyl chain containing an ether bond. Diacrylate compound Examples include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and acrylates of the above compounds as methacrylates. Examples of diacrylate compounds linked by a chain containing an aromatic group and an ether bond include, for example, polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, poly Examples include oxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing acrylates of the above compounds with methacrylate.

  Polyfunctional cross-linking agents include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate; triallylcia Examples include nurate and triallyl trimellitate.

  The hybrid resin used in the present invention preferably contains a monomer component capable of reacting with both resin components in the vinyl polymer or unit and / or the polyester resin or unit. Among the monomers constituting the polyester resin or unit, those capable of reacting with the vinyl polymer or unit include, for example, unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid and itaconic acid, or anhydrides thereof. It is done. Among the monomers constituting the vinyl polymer or unit, those capable of reacting with the polyester resin or unit include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  As a method for obtaining a reaction product of a vinyl polymer and a polyester resin, either a polymer or a resin containing a monomer component capable of reacting with each of the vinyl polymer and the polyester resin listed above is present. A method obtained by polymerizing one or both of the polymers or resins is preferred.

  Examples of the polymerization initiator used in producing the vinyl polymer or vinyl polymer unit of the present invention include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4- Methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (-2,4-dimethylvaleronitrile), 2,2′-azobis (-2methylbutyronitrile), dimethyl-2,2′- Azobisisobutyrate, 1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2- Phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2′-azobis (2-methyl-propane), methyl ethyl ketone peroxide, acetyla Ketone peroxides such as ton peroxide, cyclohexanone peroxide, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethyl Butyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α, α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide Decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl Ruperoxy dicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetyl Cyclohexylsulfonyl peroxide, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxylaurate T-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxyisophthalate, t-butyl peroxyallyl carbonate, t-amyl peroxy 2-ethylhexanoate, -t- butyl peroxy hexahydro terephthalate, di -t- butyl peroxy azelate and the like.

  As a manufacturing method which can prepare the hybrid resin used by this invention, the manufacturing method shown to the following (1)-(6) can be mentioned, for example.

  (1) A method in which a vinyl polymer and a polyester resin are blended after production. The blend is produced by dissolving and swelling in an organic solvent (for example, xylene) and then distilling off the organic solvent. The hybrid resin component is synthesized by separately producing a vinyl polymer and a polyester resin, dissolving and swelling in a small amount of an organic solvent, adding an esterification catalyst and alcohol, and performing a transesterification reaction by heating. A hybrid resin having a polyester unit and a vinyl polymer unit can be obtained.

  (2) A method of producing a hybrid resin component having a polyester unit and a vinyl polymer unit by producing and reacting a polyester resin in the presence of the vinyl polymer after production. The hybrid resin component is produced by a reaction between a vinyl polymer (a vinyl monomer can be added if necessary) and a polyester monomer (alcohol, carboxylic acid) and / or polyester resin. Also in this case, an organic solvent can be appropriately used.

  (3) A method for producing a hybrid resin component having a polyester unit and a vinyl polymer unit by producing and reacting a vinyl polymer in the presence of the polyester resin after production. The hybrid resin component is produced by a reaction between a polyester resin (a polyester monomer can be added if necessary) and a vinyl monomer and / or a vinyl polymer.

  (4) After the vinyl polymer and the polyester resin are produced, the hybrid resin component is produced by adding a vinyl monomer and / or a polyester monomer (alcohol, carboxylic acid) in the presence of these polymer units. Also in this case, an organic solvent can be appropriately used.

  (5) After producing a hybrid resin component having a polyester unit and a vinyl polymer unit, by adding a vinyl monomer and / or a polyester monomer (alcohol, carboxylic acid) and performing an addition polymerization and / or a condensation polymerization reaction. A vinyl polymer and / or polyester resin, or further a hybrid resin component is produced. In this case, as the hybrid resin component having the polyester unit and the vinyl polymer unit, those produced by the production methods (2) to (4) can be used, and if necessary, by a known production method. What was manufactured can also be used. Furthermore, an organic solvent can be used as appropriate.

  (6) By mixing a vinyl monomer and a polyester monomer (alcohol, carboxylic acid, etc.) and continuously performing addition polymerization and condensation polymerization reaction, a vinyl polymer, a polyester resin, a polyester unit and a vinyl polymer unit are obtained. A hybrid resin component is produced. Furthermore, an organic solvent can be used as appropriate.

  In the production methods (1) to (6) above, the vinyl copolymer unit and / or the polyester unit can use a plurality of polymer units having different molecular weights and cross-linking degrees.

  In the present invention, the vinyl polymer or vinyl polymer unit means a vinyl homopolymer, a vinyl copolymer, a vinyl monopolymer unit, or a vinyl copolymer unit.

  Further, the molecular weight distribution measured by gel permeation chromatography (GPC) of the resin having the polyester unit of the present invention has a main peak in the region of molecular weight 3,500 to 15,000, preferably molecular weight. It has in the area | region of 4,000 thru | or 13,000, and it is preferable that Mw / Mn is 3.0 or more, and it is more preferable that it is 5.0 or more. When the main peak is in a region having a molecular weight of less than 3,500, the high temperature offset resistance of the toner decreases. On the other hand, when the main peak is in a region having a molecular weight of more than 15000, sufficient low-temperature fixability of the toner and OHP permeability are deteriorated. Moreover, when Mw / Mn is less than 3.0, good offset resistance is reduced.

  The glass transition temperature (Tg) of the resin having the polyester unit of the present invention is preferably 40 to 90 ° C., and the softening temperature (Tm) is 80 to 150 ° C., storage stability, low temperature fixability, high temperature offset resistance, It is preferable for achieving both dispersibility of the colorant.

  The acid value of the resin is preferably less than 50 mgKOH / g from the viewpoint of improving the development durability stability and the dispersibility of the colorant.

  As the colorant used in the toner of the present invention, known dyes and / or pigments are used. Although the pigment alone may be used, it is more preferable from the viewpoint of the image quality of the full-color image that the combination of the dye and the pigment improves the sharpness.

  Examples of the coloring pigment for magenta toner include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perlin compounds. Specifically, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 202, 206, 207.209, 238, C.I. I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.

  Examples of the magenta toner dye include C.I. I solvent red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; I. Disper thread 9; I. Solvent violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. B. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; I. Basic dyes such as basic violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28 may be mentioned.

  Examples of the color pigment for cyan toner include C.I. I. Pigment blue 2, 3, 15: 3, 15: 4, 16, 17; I. Bat Blue 6; C.I. I. Acid Blue 45, and a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on a phthalocyanine skeleton having a structure represented by the following formula.

〔式中、ｎは１〜５の整数を示す。〕

[In formula, n shows the integer of 1-5. ]

  Examples of the color pigment for yellow include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; I. Bat yellow 1, 3, 20, etc. are mentioned.

  Examples of the coloring dye for yellow include C.I. I. Solvent Yellow 162 and the like, and it is also preferable to use a pigment and a dye together.

  As the black colorant used in the present invention, carbon black, iron oxide, and those which are toned in black using the yellow / magenta / cyan colorant shown above can be used.

  In the toner of the present invention, it is preferable to use a toner obtained by mixing a colorant in advance with the binder resin of the present invention to form a master batch. Then, the colorant can be favorably dispersed in the toner by melt-kneading the colorant master batch and other raw materials (binder resin, wax, etc.).

  When the colorant is made into a master batch using the resin of the present invention, the dispersibility of the colorant is not deteriorated even when a large amount of the colorant is used. Excellent color reproducibility such as transparency. Further, a toner having a large covering power on the transfer material can be obtained. Further, by improving the dispersibility of the colorant, it is possible to obtain an image with excellent durability stability of toner chargeability and maintaining high image quality.

  The amount of the colorant used in the toner is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 12 parts by mass, and most preferably 2 to 10 parts by mass with respect to 100 parts by mass of the binder resin. . This is preferable in terms of color reproducibility and developability.

  The toner of the present invention is characterized by containing a wax.

  The following are mentioned as an example of the wax used for this invention. Low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight alkylene copolymer, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax, and oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax, Or block copolymers thereof; waxes based on fatty acid esters such as ester wax such as behenyl behenate and stearyl stearate, carnauba wax and montanic acid ester wax, and fatty acid esters such as deoxidized carnauba wax The thing which deoxidized part or all is mentioned. Further, saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and valinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, and seryl alcohol , Saturated alcohols such as melyl alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bis laurin Saturated fatty acid bisamides such as acid amides and hexamethylene bis stearic acid amides; ethylene bis oleic acid amides, hexamethylene bis oleic acid amides, N, N′dioleyl adipic acid amides, N, N ′ geos Unsaturated fatty acid amides such as irsevacinamide; Aromatic bisamides such as m-xylene bis stearamide, N, N ′ distearyl isophthalamide; calcium stearate, calcium laurate, zinc stearate, magnesium stearate, etc. Aliphatic metal salts (generally referred to as metal soaps); waxes grafted with aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglycerides and many others Examples include partially esterified products of monohydric alcohols; methyl ester compounds having a hydroxyl group obtained by hydrogenation of vegetable oils and the like.

  Examples of waxes that are particularly preferably used in the present invention include aliphatic hydrocarbon waxes. For example, low molecular weight polyalkylene wax obtained by radical polymerization of alkylene under high pressure or Ziegler catalyst or metallocene catalyst under low pressure, paraffin wax, Fischer-Tropsch wax synthesized from coal or natural gas, or high molecular weight alkylene polymer. Preference is given to alkylene hydrocarbons obtained by decomposition, synthetic hydrocarbon waxes obtained from the distillation residue of hydrocarbons obtained by the age method from synthesis gas containing carbon monoxide and hydrogen or by hydrogenation of these. Furthermore, what carried out the fractionation of the hydrocarbon wax by the use of the press perspiration method, the solvent method, the vacuum distillation, or the fractional crystallization method is more preferably used. The hydrocarbon as a base is synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (mostly two or more multi-component systems) [for example, the Jintol method, the Hydrocol method (the fluidized catalyst bed Hydrocarbon compounds synthesized by use); hydrocarbons with up to several hundred carbon atoms obtained by the age method (using the identified catalyst bed) from which a large amount of wax-like hydrocarbons can be obtained; alkylene such as ethylene by Ziegler catalyst Polymerized hydrocarbons; paraffin waxes are preferred because they are linear hydrocarbons with little branching, small and long saturation. In particular, a wax synthesized by a method that does not rely on polymerization of alkylene is also preferred from its molecular weight distribution.

  In the present invention, a charge control agent can be used for the toner. As the charge control agent, known ones can be used. In particular, a metal compound of an aromatic carboxylic acid that is colorless, has a high toner charging speed, and can stably maintain a constant charge amount is preferable.

  Negative charge control agents include salicylic acid metal compounds, naphthoic acid metal compounds, dicarboxylic acid metal compounds, polymer compounds having sulfonic acid or carboxylic acid in the side chain, boron compounds, urea compounds, silicon compounds, calixarenes, etc. Is available. As the positive charge control agent, a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, an imidazole compound, or the like can be used. The charge control agent may be added internally or externally to the toner particles. The addition amount of the charge control agent is preferably 0.2 to 10 parts by mass in total with respect to 100 parts by mass of the binder resin.

  An external additive is added to the toner of the present invention to improve fluidity.

  As the external additive, inorganic fine powders such as silicate fine powder, titanium oxide, and aluminum oxide are preferable. The inorganic fine powder is preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

  The external additive is usually used in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of the toner particles. The present invention is very effective in non-magnetic one-component development and non-magnetic two-component development. When the toner particles are non-magnetic color toner particles for forming a full color image, it is preferable to use titanium oxide fine particles as an external additive.

  When the toner of the present invention is used for a two-component developer, the toner is used by mixing with a magnetic carrier. As the magnetic carrier, for example, surface oxidized or unoxidized iron, nickel, copper, zinc, cobalt, manganese, chromium, rare earth metal particles, alloy particles thereof, oxide particles, ferrite and the like can be used.

  The coated carrier obtained by coating the surface of the magnetic carrier particles with a resin is particularly preferable in a developing method in which an AC bias is applied to the developing sleeve. Coating methods include a method in which a coating solution prepared by dissolving or suspending a coating material such as a resin in a solvent is adhered to the surface of the magnetic carrier particles, and a method in which the magnetic carrier particles and the coating material are mixed in a powder state. A conventionally known method can be applied.

  Examples of the coating material on the surface of the magnetic carrier particles include silicone resin, polyester resin, styrene resin, acrylic resin, polyamide, polyvinyl butyral, and aminoacrylate resin. These may be used alone or in plurality.

  The treatment amount of the coating material is preferably 0.1 to 30% by mass (preferably 0.5 to 20% by mass) with respect to the magnetic carrier particles. The average particle size of the magnetic carrier is preferably 10 to 100 μm, and more preferably 20 to 70 μm.

  When preparing the two-component developer by mixing the toner of the present invention and the magnetic carrier, good results are usually obtained when the mixing ratio is 2% by mass to 15% by mass as the toner concentration in the developer. More preferably, it is 4 mass%-13 mass%.

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

[Example 1]
・ Hybrid resin 100 parts by mass (styrene, 2-ethylhexyl acrylate, α-methylstyrene, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2)- (Hybrid resin composed of 2,2-bis (4-hydroxyphenyl) propane, succinic acid, trimellitic anhydride, fumaric acid)
-Copper phthalocyanine pigment 4 parts by mass (CI Pigment Blue 15: 3)
Paraffin wax 5 parts by mass (maximum endothermic peak 67 ° C)
Charge control agent (salicylic acid metal complex) 1 part by mass The materials having the above formulation were mixed well with a Henschel mixer and then kneaded with a twin-screw kneader set at a temperature of 130 ° C. The obtained kneaded product was cooled and coarsely pulverized to 2 mm or less with a hammer mill to obtain a powder raw material (coarse pulverized product) which is a powder raw material for toner production.

  The obtained powder raw material was pulverized and surface-modified by the process flow shown in FIG. That is, as the pulverization means, the pulverization is performed using the mechanical pulverizer 301 shown in FIG. 3 (a modified machine obtained by modifying the turbo mill T250-RS manufactured by Turbo Kogyo Co., Ltd. as follows), and the surface modification means is shown in FIG. Surface modification was performed using a surface modification apparatus.

(Crushing means)
In this embodiment, the pulverized surface shapes of the rotor 314 and the stator 310 of the mechanical pulverizer 301 are of the type shown in FIG. That is, the repetition distance L between the convex portions of the rotor 314 and the stator 310 is 3 mm, the peripheral speed of the rotor 314 is 150 m / sec, the gap between the rotor 314 and the stator 310 is 0.8 mm, and pulverization The supply amount was 10 kg / hr. At this time, the cold air temperature T1 was −15 ° C., and the temperature of the refrigerant passed through the jacket was −10 ° C.

  As a result of operating for 120 minutes in this state, the outlet temperature T2 of the mechanical pulverizer 301 was stabilized at 40 ° C. Therefore, ΔT (T2−T1) was 55 ° C.

  As a result of measuring the weight average diameter, average circularity (FPIA 2100 measurement, circle equivalent diameter of 2 μm or more and 400 μm or less) and average surface roughness of the finely pulverized product obtained, the weight average particle diameter was 5.3 μm, and the particle diameter was 4 A finely pulverized product containing 58% by number of 0.000 μm or less was obtained. The average circularity was 0.931 and the average surface roughness was 24.9 nm.

(Surface modification means)
The obtained finely pulverized product was subjected to surface modification using a batch type surface modification apparatus shown in FIG. At this time, in this embodiment, eight square disks are installed on the upper part of the dispersion rotor, the distance between the guide ring and the upper square disk of the dispersion rotor is 5 mm, and the distance between the dispersion rotor and the liner is 3 mm. The rotational peripheral speed of the rotor was 100 m / sec. The cycle time was 45 sec, the cold air temperature T1 was −20 ° C., and the temperature of the refrigerant passed through the jacket was −10 ° C.

  As a result of operating for 120 minutes in this state, the temperature T2 behind the classification rotor was stabilized at 25 ° C. Therefore, ΔT (T2−T1) was 45 ° C.

At this time, the target particle size of the obtained surface-modified particles was such that the weight average diameter was 5.8 ± 0.2 μm, and 4.00 μm or less% was 35 number% or less. In this example, the classification rotor has a peripheral speed of 80 m / sec and a blower air flow of 6 m ³ / min, so that the weight average diameter is 5.8 μm and the number of particles having a particle diameter of 4.00 μm or less is 32% by number. The surface modified particles contained could be obtained.

  Moreover, as a result of measuring the average circularity of the obtained surface modified particles, it was 0.945, the average surface roughness was 10.4 nm, and the methanol hydrophobicity was 38.3%.

Furthermore, the surface shape of the surface modified particles was observed using a field emission scanning electron microscope (FE-SEM: Hitachi S-800), the magnification was set to 10,000 times, and the surface shape was observed visually and evaluated according to the following criteria. The results are shown in Table 2.
A: circular silhouette B: somewhat oval silhouette C: curved but irregular D: square silhouette

Next, with respect to 100 parts by mass of the obtained surface modified particles, 1.8 parts by mass of hydrophobic silica having a specific surface area of 200 m ² / g by BET method was externally added to obtain a toner. 95 parts by mass of an acrylic-coated ferrite carrier was mixed with 5 parts by mass of the toner to obtain a developer.

  Using this developer, image evaluation was performed under normal temperature and humidity (23 ° C., 60% RH) using a Canon full color copier CLC1000 remodeled machine (with the oil application mechanism of the fixing unit removed). .

(Evaluation-1: Transferability evaluation)
For transferability, develop and transfer images before and after the endurance of 40,000 sheets, and measure the amount of toner before transfer on the photoconductor (per unit area) and the amount of toner on the transfer material (per unit area). Obtained by the formula. The evaluation criteria are as follows.
Transfer rate (%) = (toner amount on transfer material) / (toner amount before transfer on photoconductor) × 100
A: 90% or more B: 88% or more, less than 90% C: 86% or more, less than 88% D: 85% or less

(Evaluation-2: Fog evaluation)
For the fog, the whiteness of the white background portion was measured with a reflectometer (manufactured by Tokyo Denshoku), and the fog density (%) was calculated and evaluated from the difference between the whiteness and the whiteness of the transfer paper. The evaluation criteria are as follows.
A: Very good (less than 0.5%)
B: Good (0.5% to 1.5%)
C: Normal (1.5% to 2.5%)
D: Slightly bad (2.5% to 3.5%)
E: Bad (over 3.5%)

(Evaluation-3: Dot reproducibility evaluation)
The dot reproducibility was evaluated by evaluating the dot reproducibility for 100 dots by printing out an image of an isolated dot pattern with a small diameter (40 μm) that is easily closed by a latent image electric field and is difficult to reproduce.
A: Very good 2 or less defects in 100 B: Good 3 to 5 defects in 100 C: Practical 6 to 10 defects in 100 D: Impractical 100 defects 11 or more

  The results are shown in Table 2. As a result of the evaluation, the developer in this example showed very good transferability even in image formation after 40,000 sheets, and no fogging occurred. The dot reproducibility was also good.

Further, after the operation of the surface reforming apparatus, the wear and fusion of the rectangular disk, the liner and the classification rotor on the dispersion rotor in the apparatus were visually confirmed and judged according to the following criteria. The results are shown in Table 2.
A: Fuse and no wear on each device in the machine B: Wear and fusion are slightly observed in each device in the machine, but practical use C: Some wear and fusion are seen in each device in the machine, but practical use possible D: Each device in the machine Wear and fusion are noticeable, impractical

[Example 2]
The powder raw material obtained in Example 1 was pulverized and surface-modified by the process flow shown in FIG. That is, as the pulverization means, the pulverization is performed using the mechanical pulverizer 301 shown in FIG. 3 (a modified machine obtained by modifying the turbo mill T250-RS manufactured by Turbo Kogyo Co., Ltd. as follows), and the surface modification means is shown in FIG. Surface modification was performed using a surface modification apparatus.

(Crushing means)
In this embodiment, the pulverized surface shapes of the rotor 314 and the stator 310 of the mechanical pulverizer 301 are of the type shown in FIG. That is, the repetition distance L between the convex portions of the rotor 314 and the stator 310 is 2 mm, the peripheral speed of the rotor 314 is 150 m / sec, the gap between the rotor 314 and the stator 310 is 0.8 mm, and pulverization The supply amount was 10 kg / hr. At this time, the cold air temperature T1 was −15 ° C., and the temperature of the refrigerant passed through the jacket was −10 ° C.

  As a result of operating for 120 minutes in this state, the outlet temperature T2 of the mechanical pulverizer 301 was stabilized at 44 ° C. Therefore, ΔT (T2−T1) was 59 ° C.

  As a result of measuring the weight average diameter, average circularity (FPIA 2100 measurement, circle equivalent diameter of 2 μm or more and 400 μm or less) and average surface roughness of the finely pulverized product obtained, the weight average particle diameter was 5.1 μm, and the particle diameter was 4 A finely pulverized product containing 60% by number or less of 0.000 μm or less was obtained. The average circularity was 0.934 and the average surface roughness was 23.2 nm.

(Surface modification means)
The obtained finely pulverized product was subjected to surface modification using a batch type surface modification apparatus shown in FIG. At this time, in this embodiment, eight square disks are installed on the upper part of the dispersion rotor, the distance between the guide ring and the upper square disk of the dispersion rotor is 5 mm, and the distance between the dispersion rotor and the liner is 3 mm. The rotational peripheral speed of the rotor was 100 m / sec. The cycle time was 45 sec, the cold air temperature T1 was −20 ° C., and the temperature of the refrigerant passed through the jacket was −10 ° C.

  As a result of operating for 120 minutes in this state, the temperature T2 behind the classification rotor was stabilized at 23 ° C. Therefore, ΔT (T2−T1) was 43 ° C.

At this time, the target particle size of the obtained surface-modified particles was such that the weight average diameter was 5.8 ± 0.2 μm, and 4.00 μm or less% was 35 number% or less. In this example, by setting the peripheral speed of the classification rotor to 80 m / sec and the blower air volume to 6 m ³ / min, the weight average diameter is 5.9 μm, and the number of particles having a particle diameter of 4.00 μm or less is 30% by number. The surface modified particles contained could be obtained.

  Moreover, as a result of measuring the average circularity of the obtained surface modified particles, it was 0.946, the average surface roughness was 9.1 nm, and the methanol hydrophobicity was 40.3%.

  In the same manner as in Example 1, the obtained surface modified particles were externally mixed with hydrophobic silica to obtain a toner, and further mixed with an acrylic coated ferrite carrier to obtain a developer. Using this developer, image evaluation was performed with a Canon full-color copier CLC1000 remodeled machine as in Example 1. As shown in Table 2, a good image was obtained as in Example 1. .

[Example 3]
The powder raw material obtained in Example 1 was pulverized and surface-modified by the apparatus system shown in FIG. That is, as a pulverizing means, the mechanical pulverizer 301 shown in FIG. 3 (a modified machine obtained by modifying a turbo mill T250-RS manufactured by Turbo Industry Co., Ltd. as follows) is subjected to medium pulverization. Fine pulverization is performed using a mechanical pulverizer 301 shown in FIG. 3 (a modified machine obtained by remodeling turbo mill T250-RS manufactured by Turbo Kogyo Co., Ltd. as follows), and the surface reforming apparatus shown in FIG. 6 is used as surface modification means. Surface modification.

(Crushing means)
In this example, first, the powder raw material was internally pulverized by a mechanical pulverizer 301 shown in FIG. 3 (a modified machine obtained by modifying a turbo mill T250-RS manufactured by Turbo Industry Co., Ltd. as follows). That is, the repetition distance L between the convex portions of the rotor 314 and the stator 310 is 4 mm, the peripheral speed of the rotor 314 is 130 m / sec, the gap between the rotor 314 and the stator 310 is 1.0 mm, and pulverization The supply amount was 15 kg / hr. The cold air temperature T1 was set to −15 ° C., and the temperature of the refrigerant passed through the jacket was set to −10 ° C. At this time, the weight average diameter of the obtained medium ground product was 7.0 μm.

  As a result of operating for 120 minutes in this state, the outlet temperature T2 of the mechanical pulverizer 301 was stabilized at 40 ° C. Therefore, ΔT (T2−T1) was 55 ° C.

  Next, the obtained medium pulverized product was again finely pulverized with a mechanical pulverizer 301 (a modified machine obtained by modifying a turbo mill T250-RS manufactured by Turbo Industry Co., Ltd. as follows) shown in FIG. That is, the repetition distance L between the convex portions of the rotor 314 and the stator 310 is set to 3 mm as in the first embodiment, the circumferential speed of the rotor 314 is 150 m / sec, and the gap between the rotor 314 and the stator 310 is set. The pulverization supply rate was set to 1.0 mm and 25 kg / hr. At this time, the cold air temperature T1 was −15 ° C., and the temperature of the refrigerant passed through the jacket was −10 ° C.

  As a result of operating for 120 minutes in this state, the outlet temperature T2 of the mechanical pulverizer 301 was stabilized at 35 ° C. Therefore, ΔT (T2−T1) was 50 ° C.

  As a result of measuring the weight average diameter, the average circularity, and the average surface roughness of the finely pulverized product obtained, the pulverized product contains 59% by number of weight average particle size of 5.2 μm and particle size of 4.00 μm or less. Could get. The average circularity was 0.931 and the average surface roughness was 22.8 nm.

(Surface modification means)
The obtained finely pulverized product was subjected to surface modification using a batch type surface modification apparatus shown in FIG. At this time, in this example, each operation condition of the batch type surface treatment apparatus was set to be the same as that of Example 1.

  As a result of operating for 120 minutes in this state, the temperature T2 behind the classification rotor was stabilized at 26 ° C. Therefore, ΔT (T2−T1) was 46 ° C.

  At this time, the target particle size of the obtained surface-modified particles was the same as that in Example 1. As a result, in this example, surface modified particles having a sharp particle size distribution having a weight average diameter of 5.8 μm and containing 28% by number of particles having a particle diameter of 4.00 μm or less can be obtained. It was.

  Moreover, as a result of measuring the average circularity of the obtained surface-modified particles, it was 0.942, the average surface roughness was 7.2 nm, and the methanol hydrophobicity was 52.6%.

  Next, the surface-modified particles thus obtained were externally mixed with hydrophobic silica in the same manner as in Example 1 to prepare a toner, and further, an acrylic-coated ferrite carrier was mixed to prepare a developer. Using this developer, image evaluation was performed with a Canon full color copier CLC1000 remodeled machine as in Example 1. As shown in Table 4, a good image was obtained as in Example 1. .

[Example 4]
The powder raw material obtained in Example 1 was pulverized and surface-modified by the apparatus system shown in FIG. That is, as a pulverizing means, the mechanical pulverizer 301 shown in FIG. 3 (a modified machine obtained by modifying a turbo mill T250-RS manufactured by Turbo Industry Co., Ltd. as follows) is subjected to medium pulverization. Fine pulverization is performed using a mechanical pulverizer 301 shown in FIG. 3 (a modified machine obtained by remodeling turbo mill T250-RS manufactured by Turbo Kogyo Co., Ltd. as follows), and the surface reforming apparatus shown in FIG. 6 is used as surface modification means. Surface modification.

(Crushing means)
In this example, first, the powder raw material was internally pulverized by a mechanical pulverizer 301 shown in FIG. 3 (a modified machine obtained by modifying a turbo mill T250-RS manufactured by Turbo Industry Co., Ltd. as follows). That is, the repetition distance L between the convex portions of the rotor 314 and the stator 310 is 4 mm, the peripheral speed of the rotor 314 is 150 m / sec, the gap between the rotor 314 and the stator 310 is 1.0 mm, and pulverization The supply amount was 15 kg / hr. The cold air temperature T1 was set to −15 ° C., and the temperature of the refrigerant passed through the jacket was set to −10 ° C. At this time, the weight average diameter of the obtained finely pulverized product was 6.4 μm.

  As a result of operating for 120 minutes in this state, the outlet temperature T2 of the mechanical pulverizer 301 was stabilized at 43 ° C. Therefore, ΔT (T2−T1) was 58 ° C.

  Next, the obtained medium pulverized product was again finely pulverized with a mechanical pulverizer 301 (a modified machine obtained by modifying a turbo mill T250-RS manufactured by Turbo Industry Co., Ltd. as follows) shown in FIG. That is, the repetition distance L between the convex portions of the rotor 314 and the stator 310 is set to 3 mm as in the first embodiment, the circumferential speed of the rotor 314 is 150 m / sec, and the gap between the rotor 314 and the stator 310 is set. The pulverization supply rate was set to 1.0 mm and 25 kg / hr. At this time, the cold air temperature T1 was −15 ° C., and the temperature of the refrigerant passed through the jacket was −10 ° C.

  As a result of operating for 120 minutes in this state, the outlet temperature T2 of the mechanical pulverizer 301 was stabilized at 38 ° C. Therefore, ΔT (T2−T1) was 53 ° C.

  As a result of measuring the weight average diameter, average circularity, and average surface roughness of the finely pulverized product obtained, the pulverized product contains 59% by number of weight average particle size of 5.1 μm and particle size of 4.00 μm or less. Could get. The average circularity was 0.936 and the average surface roughness was 21.9 nm.

(Surface modification means)
The obtained finely pulverized product was subjected to surface modification using a batch type surface modification apparatus shown in FIG. At this time, in this example, each operation condition of the batch type surface treatment apparatus was set to be the same as that of Example 1.

  As a result of operating for 120 minutes in this state, the temperature T2 behind the classification rotor was stabilized at 23 ° C. Therefore, ΔT (T2−T1) was 43 ° C.

  At this time, the target particle size of the obtained surface-modified particles was the same as that in Example 1. As a result, in this example, surface modified particles having a sharp particle size distribution having a weight average diameter of 5.8 μm and containing 29% by number of particles having a particle diameter of 4.00 μm or less can be obtained. It was.

  Moreover, as a result of measuring the average circularity of the obtained surface modified particles, it was 0.949, the average surface roughness was 6.5 nm, and the methanol hydrophobicity was 54.9%.

  Next, the surface-modified particles thus obtained were externally mixed with hydrophobic silica in the same manner as in Example 1 to prepare a toner, and further, an acrylic-coated ferrite carrier was mixed to prepare a developer. Using this developer, image evaluation was performed with a Canon full color copier CLC1000 remodeled machine as in Example 1. As shown in Table 4, a good image was obtained as in Example 1. .

[Example 5]
A toner was prepared in substantially the same manner as in Example 1 except that a vinyl resin was used instead of the hybrid resin, and a developer was obtained in the same manner. Tables 5 and 6 show the operating conditions and evaluation results of each device.

[Example 6]
The powder raw material obtained in Example 1 was pulverized and surface-modified by the process flow shown in FIG. That is, as the pulverization means, the pulverization is performed using the mechanical pulverizer 301 shown in FIG. 3 (a modified machine obtained by modifying the turbo mill T250-RS manufactured by Turbo Kogyo Co., Ltd. as follows), and the surface modification means is shown in FIG. Surface modification was performed using a surface modification apparatus.

(Crushing means)
In this embodiment, the pulverized surface shapes of the rotor 314 and the stator 310 of the mechanical pulverizer 301 are of the type shown in FIG. That is, the repetition distance L between the convex portions of the rotor 314 and the stator 310 is 3 mm, the peripheral speed of the rotor 314 is 150 m / sec, the gap between the rotor 314 and the stator 310 is 0.8 mm, and pulverization The supply amount was 10 kg / hr. At this time, the cold air temperature T1 was −5 ° C., and the temperature of the refrigerant passed through the jacket was 0 ° C.

  As a result of operating for 120 minutes in this state, the outlet temperature T2 of the mechanical pulverizer 301 was stabilized at 54 ° C. Therefore, ΔT (T2−T1) was 59 ° C.

  As a result of measuring the weight average diameter, average circularity (FPIA 2100 measurement, circle equivalent diameter of 2 μm or more and 400 μm or less) and average surface roughness of the finely pulverized product obtained, the weight average particle diameter was 5.1 μm, and the particle diameter was 4 A finely pulverized product containing 60% by number or less of 0.000 μm or less was obtained. The average circularity was 0.944 and the average surface roughness was 18.3 nm.

(Surface modification means)
The obtained finely pulverized product was subjected to surface modification using a batch type surface modification apparatus shown in FIG. At this time, in this embodiment, eight square disks are installed on the upper part of the dispersion rotor, the distance between the guide ring and the upper square disk of the dispersion rotor is 5 mm, and the distance between the dispersion rotor and the liner is 3 mm. The rotational peripheral speed of the rotor was 100 m / sec. The cycle time was 45 sec, the cold air temperature T1 was −20 ° C., and the temperature of the refrigerant passed through the jacket was −10 ° C.

  As a result of operating for 120 minutes in this state, the temperature T2 behind the classification rotor was stabilized at 22 ° C. Therefore, ΔT (T2−T1) was 42 ° C.

At this time, the target particle size of the obtained surface-modified particles was such that the weight average diameter was 5.8 ± 0.2 μm, and 4.00 μm or less% was 35 number% or less. In this embodiment, the classification rotor has a peripheral speed of 80 m / sec and a blower air flow of 6 m ³ / min, so that the weight average diameter is 5.8 μm and the number of particles having a particle diameter of 4.00 μm or less is 30% by number. The surface modified particles contained could be obtained.

  Moreover, as a result of measuring the average circularity of the obtained surface-modified particles, it was 0.949, the average surface roughness was 8.8 nm, and the methanol hydrophobization degree was 68.8%.

  In the same manner as in Example 1, the obtained surface modified particles were externally mixed with hydrophobic silica to obtain a toner, and further mixed with an acrylic coated ferrite carrier to obtain a developer. Using this developer, image evaluation was carried out using a full-color copying machine CLC1000 made by Canon in the same manner as in Example 1. The results are shown in Table 6.

[Reference example]
The powder raw material obtained in Example 1 was pulverized and surface-modified by the process flow shown in FIG. That is, fine pulverization was performed using a collision-type airflow pulverizer shown in FIG. 8 as pulverization means, and surface modification was performed using a surface modification apparatus shown in FIG. 6 as surface modification means.

(Crushing means)
In this reference example, the powder raw material obtained in Example 1 was compared with the collision-type airflow pulverizer (high-pressure gas pressure: 0.6 MPa, feed amount: 15 kg / hr) using the high-pressure gas shown in FIG. The airflow classifier turboplex (200-ATP type: manufactured by Hosokawa Micron Corporation, rotor rotational peripheral speed 60 m / sec) shown in Fig. 9 was pulverized using a fine pulverizer with a closed circuit as shown in Fig. 10.

  As a result of measuring the weight average diameter, average circularity, and average surface roughness of the finely pulverized product obtained, the pulverized product contains 65% by weight of 5.1 μm in weight average particle size and 4.00 μm in particle size. Could get. The average circularity was 0.930 and the average surface roughness was 24.3 nm.

(Surface modification means)
The obtained finely pulverized product was subjected to surface modification using a batch type surface modification apparatus shown in FIG. At this time, in this example, as shown in Table 3, the operating conditions of the batch type surface treatment apparatus were the same as those in Example 1.

  As a result of operating for 120 minutes in this state, the temperature T2 behind the classification rotor was stabilized at 25 ° C. Therefore, ΔT (T2−T1) was 45 ° C.

  At this time, the target particle size of the obtained surface-modified particles was the same as that in Example 1. As a result, in this example, surface modified particles having a weight average diameter of 5.8 μm and containing 30% by number of particles having a particle diameter of 4.00 μm or less could be obtained.

  Moreover, as a result of measuring the average circularity of the obtained surface modified particles, it was 0.935, the average surface roughness was 31.2 nm, and the methanol hydrophobicity was 32.8%.

  Next, the surface-modified particles thus obtained were externally mixed with hydrophobic silica in the same manner as in Example 1 to prepare a toner, and further, an acrylic-coated ferrite carrier was mixed to prepare a developer. Using this developer, image evaluation was carried out using a full-color copying machine CLC1000 made by Canon in the same manner as in Example 1. The results are shown in Table 8.

[Comparative example]
The powder raw material obtained in Example 1 was first classified and finely pulverized using an airflow classifier and a collision airflow pulverizer (IDS-5 manufactured by Nippon Pneumatic Industry Co., Ltd.) shown in FIG. As a two-classifying means, classification was carried out with an elbow jet classifier (EJ-LABO type manufactured by Nippon Steel & Mining Co., Ltd.), and surface modification was carried out using a surface modifying apparatus shown in FIG.

(Crushing means)
In this comparative example, the compressed air pressure used in the collision-type airflow pulverizer was 0.60 MPa. Moreover, the target particle size of the finely pulverized product obtained was set to a weight average diameter of 5.1 ± 0.2 μm as in the example, and the raw material supply rate was set to 5 kg / hr in order to obtain the target particle size.

  At this time, as shown in Table 4, the finely pulverized product obtained by pulverization by the collision-type airflow pulverizer has a weight average diameter of 5.3 μm and 75% by number of particles having a particle diameter of 4.00 μm or less. It had a particle size distribution. Compared with the Examples, the value of fine powder was large and the particle size distribution was broad.

  Moreover, as a result of measuring the average circularity and average surface roughness of the finely pulverized product, the average circularity was 0.905 and the average surface roughness was 37.9 nm.

(Classification means)
Next, the finely pulverized product obtained by pulverization with the above-described collision-type air pulverizer was second-classified with an elbow jet classifier (EJ-LABO type manufactured by Nippon Steel Mining Co., Ltd.). At this time, the target particle size of the obtained intermediate powder product was set to a weight average of 5.8 ± 0.2 μm, 4.00 μm or less, and 35 number% or less. As a result, an intermediate powder product having a particle size distribution having a weight average diameter of 5.9 μm and containing 30% by number of particles having a particle size of 4.00 μm or less was obtained.

(Surface modification means)
Next, the obtained intermediate powder product was introduced into the surface modification apparatus shown in FIG. 12 to perform surface modification.

  In FIG. 12, 151 is a main body casing, 158 is a stator, 177 is a stator jacket, 163 is a recycling pipe, 159 is a discharge valve, 219 is a discharge chute, and 164 is a raw material charging chute.

  In this apparatus, the powder particles and other fine solid particles supplied from the raw material charging chute 164 are instantaneously generated by a plurality of rotor blades 155 disposed in a rotating rotor 162 that rotates mainly at high speed in the impact chamber 168. In addition, the fine particles collide with the surrounding stator 158 and are dispersed in the system while loosening the agglomeration of the powder particles or other fine solid particles. Is attached by electrostatic force, van der Waals force or the like, or in the case of powder particles only, the particles are rounded or spheroidized. This state advances as the particles fly and collide. That is, the particles are processed by passing through a recycle pipe 163 a plurality of times along with the flow of the air flow generated by the rotation of the rotor blade 155. Further, when the particles are repeatedly hit from the rotor blade 155 and the stator 158, other fine solid particles are uniformly dispersed and fixed on the surface of the powder particles or in the vicinity thereof, or the powder particles only The shape of the particles becomes spherical.

  The particles that have been fixed are collected by the bag filter 222 or the like that passes through the discharge chute 219 and communicates with the suction blower 224 by opening the discharge valve 159 by the discharge valve control device 128.

  In this comparative example, a rotating rotor 162 having a rotor blade 155 with a longest diameter of 242 mm was used, and the rotating peripheral speed of the rotating rotor 162 was 90 m / sec. The amount of finely pulverized product was 300 g, and the cycle time was 180 seconds. This was repeated about 10 times to obtain surface modified particles.

  When the particle size distribution of the obtained surface modified particles was measured, in this comparative example, the weight average diameter was 5.7 μm, and 38% by number of particles having a particle diameter of 4.00 μm or less were contained. The number% of particles having a particle size of 4.00 μm or less was increased as compared with the particle size of the surface-modified particles before quality improvement. The increase in fine powder having a particle size of 4.00 μm or less is presumed to be because the toner was excessively pulverized.

  Moreover, as a result of measuring the average circularity of the obtained surface modified particles, it was 0.920, the average surface roughness was 33.6 nm, and the methanol hydrophobicity was 68.7%.

  Next, the surface-modified particles thus obtained were externally mixed with hydrophobic silica in the same manner as in Example 1 to prepare a toner, and further, an acrylic-coated ferrite carrier was mixed to prepare a developer. Using this developer, image evaluation was carried out using a full-color copying machine CLC1000 made by Canon in the same manner as in Example 1. The results are shown in Table 8, which is inferior to the examples. Further, when the inside of the surface treatment apparatus was inspected after the operation of the surface treatment apparatus was completed, the rotor blade was fused.

3 is a flowchart for explaining a toner manufacturing method of the present invention. 6 is another flowchart for explaining the toner production method of the present invention. 1 is a schematic cross-sectional view of an example of a mechanical pulverizer used in a toner pulverization step of the present invention. FIG. 4 is a perspective view of the rotor shown in FIG. 3. It is an enlarged view of the rotor shown in FIG. It is a schematic sectional drawing of the surface modification apparatus of an example used in the surface modification process of this invention. It is the schematic which shows an example of the surface modification means in the surface modification apparatus shown in FIG. It is a schematic sectional drawing of an example impingement airflow type crusher used in the reference example of this invention. It is a schematic sectional drawing of an example classification apparatus used in the reference example of this invention. It is a flowchart for demonstrating the reference example of this invention. It is a schematic sectional drawing of the apparatus of an example used in the classification and crushing process of a comparative example. It is a schematic sectional drawing of the surface modification apparatus of an example used in the surface modification process of a comparative example.

Explanation of symbols

11, 12, 13 Discharge port 14, 15 Inlet pipe 16 Raw 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 30 Main body casing 31 Cooling Jacket 32 Dispersion rotor 33 Square disk 34 Liner 35 Classification rotor 36 Guide ring 37 Raw material inlet 38 Raw material supply valve 39 Raw material supply port 40 Product discharge port 41 Product discharge valve 42 Product extraction port 43 Top plate 44 Fine powder discharge casing 45 Fine powder discharge Outlet 46 Cold air inlet 47 First space 48 Second space 49 Surface modification zone 50 Classification zone 62 Classification chamber 70 Raw material supply port 71 High-pressure air supply nozzle 72 Raw material powder introduction nozzle 121 Main body casing 122 Classification chamber 123 Guide chamber 124 Classification rotor 125 Raw material inlet 126 Air inlet 128 Frequency converter 129 Fine powder discharge pipe 130 Fine powder recovery means 131 Suction fan 132 Hopper 133 Rotor valve 135 Dispersion louver 151 Main body casing 155 Rotor blade 158 Stator 159 Discharge valve 163 Recycle pipe 164 Raw material input chute 168 Impact chamber 177 Stator jacket 178 Discharge valve control device 212 Swirl chamber 219 Pipe 220 Distributor 222 Bag filter 224 Suction blower 229 Collection cyclone 301 Mechanical crusher 302 Powder discharge port 310 Stator 311 Powder input port 312 Rotating shaft 313 Casing 314 Rotor 315 First metering feeder 316 Jacket 317 Cooling water supply port 318 Cooling water discharge port 320 Rear chamber 431 Pulverizer 432 Classifier 433 Feeder 434 Transport pipe 435 Nozzle 436 Collision plate 437 Grinding chamber 438 Collector 439 Main body hopper 440 Center core 441 Separate core 442 Discharge pipe 443 Secondary air supply port 521 Acceleration pipe 522 Acceleration pipe throat 523 High pressure gas supply nozzle 524 To be crushed Material supply port 525 Material supply cylinder 526 High pressure gas supply port 527 High pressure gas chamber 528 High pressure gas introduction tube 529 Acceleration tube outlet 530 Collision member 532 Grinding chamber wall 533 Grinding material discharge port 534 Grinding chamber 535 Grinding chamber 536 Collision member 537 Collision Surface 538 Crushing chamber inner wall 539 Pulverized product discharge port 621 Main casing 622 Classification chamber 623 Guide chamber 624 Classification rotor 625 Material input port 626 Air input port 628 Discharge valve control device 629 Fine powder discharge pipe 630 Fine powder recovery means 631 Suction fan 6 2 hopper 633 rotor Lee valve 635 distributed louver

Claims (5)

A coarse pulverization step for obtaining a coarse pulverized product by melt-kneading a composition containing at least a binder resin and a colorant, cooling and solidifying the obtained kneaded product, and coarsely pulverizing the cooled solidified product, and the obtained coarse pulverized product Of a toner having a finely pulverized step of obtaining a finely pulverized product having a weight average particle diameter of 3 to 11 μm and a surface modifying step of obtaining a surface-modified treated particle by subjecting the obtained finely pulverized product to surface modification treatment In the method
The fine pulverization step is performed by using a mechanical pulverizer, and the mechanical pulverizer includes at least a powder inlet for introducing into a pulverizing means to finely pulverize a coarsely pulverized product, a stator, , At least a rotor attached to the central rotation shaft, and at least a powder discharge port for discharging finely pulverized powder from the pulverizing means, the stator enclosing the rotor, The rotor is arranged so as to have a predetermined gap between the surface of the stator and the surface of the rotor to form a pulverization zone. In the pulverization zone, a coarsely pulverized product is produced as the rotor rotates. Pulverized,
The outer peripheral surface of the rotor of the mechanical pulverizer and / or the inner peripheral surface of the stator has a plurality of convex portions and concave portions formed between the convex portions and the convex portions. The repetition distance between the portion and the convex portion is 2.0 mm or more and less than 3.5 mm,
In the toner particles of 2 μm or more of the toner particles which are finely pulverized products obtained by the mechanical pulverizer, the following formula (1)
Circularity a = L0 / L (1)
[In the formula, L0 represents the circumference of a circle having the same projected area as the particle image, and L represents the particle image when image processing is performed at an image processing resolution of 512 × 512 (pixels of 0.3 μm × 0.3 μm). Indicates the perimeter. ]
The value (average circularity) obtained by dividing the total sum of circularity a determined by the total number of particles is 0.930 or more,
And the average surface roughness measured by a scanning probe microscope of the toner particles is 15.0 nm or more and less than 45.0 nm,
The surface modification step is performed using a batch type surface modification device, and the batch type surface modification device includes classification means for continuously discharging and removing fine powder having a predetermined particle size or less to the outside of the device. Surface treatment means using mechanical impact force, and guide means for partitioning the space between the classification means and the surface treatment means into a first space and a second space, and Introduced into one space and introduced into the surface treatment means using mechanical impact force through the second space while continuously discharging and removing fine powder having a predetermined particle size or less from the apparatus by the classifying means. Then, by performing surface modification treatment and circulating again to the first space, a predetermined amount of fine powder having a predetermined particle diameter or less is removed by repeating the surface modification treatment using a predetermined time classification and mechanical impact force. Obtained surface modified particles,
In the toner particles of 2 μm or more of the toner particles which are surface modified particles obtained by the batch type surface modifying apparatus, the following formula (1)
Circularity a = L0 / L (1)
[In the formula, L0 represents the circumference of a circle having the same projected area as the particle image, and L represents the particle image when image processing is performed at an image processing resolution of 512 × 512 (pixels of 0.3 μm × 0.3 μm). Indicates the perimeter. ]
The value (average circularity) obtained by dividing the total sum of circularity a obtained by the total number of particles is 0.935 or more,
The toner has a mean surface roughness measured by a scanning probe microscope of 5.0 nm or more and less than 35.0 nm.   Before the fine pulverization step, there is an intermediate pulverization step, the intermediate pulverization step is performed using at least a mechanical pulverizer, and the obtained coarsely pulverized product has a weight average particle diameter of 5 to 12 μm. The method for producing a toner according to claim 1.   3. The toner manufacturing method according to claim 1, wherein the binder resin used for the toner particles is a resin having at least a polyester unit.   The transmittance (%) of toner particles, which are surface modified particles obtained by the batch type surface modifying apparatus, in a 45 volume% methanol aqueous solution is in the range of 20% or more and less than 70%. The toner production method according to claim 1.   The method for producing a toner according to any one of claims 1 to 4, wherein a chamber temperature of a rear chamber of the mechanical pulverizer in the intermediate pulverization and fine pulverization steps is 55 ° C or less.

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