JP2008122754A - Device for modification of toner surface and method for manufacturing toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a device for efficiently modifying surfaces of toner particles and to provide a method for manufacturing toner. <P>SOLUTION: The surface modification device is provided for modifying surfaces of power particles containing at least a binder resin and a colorant, wherein the surface modification device includes a dispersion rotor 32 for surface modification of power particles and a liner 34 as a fixed body disposed in the periphery of the dispersion rotor by keeping a given distance, and the dispersion rotor has a straightening vane 52 at the center on the upper face, generating an air flow going downward. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an apparatus for modifying a toner surface 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, and a toner manufacturing method.

  In general, toner particles can be produced by a pulverization method or a polymerization method. Toner particles produced by the pulverization method are still widely used in toners used in copying machines and printers.

  When producing toner particles by a pulverization method, a predetermined amount of binder resin, colorant, etc. are mixed, the mixture is melt-kneaded, the kneaded product is cooled, the cooled and solidified kneaded product is pulverized, and the pulverized product is classified. Thus, toner particles having a predetermined particle size distribution are obtained, and a toner is manufactured by externally adding a fluidity improver to the obtained toner particles.

  In recent years, copiers and printers are required to have high image quality, energy saving, environmental friendliness, and the like. On the other hand, the technical concept of the toner has been shifted to make the toner particles spherical in order to achieve high transfer efficiency and reduce waste toner.

  In order to achieve such a technical concept by the pulverization method, a method for spheroidizing toner particles by a mechanical pulverization method is proposed (see Patent Document 1), and a method for sphering toner particles by hot air is proposed. (See Patent Document 2).

  However, at present, sufficient spheroidization cannot be achieved by the method of spheroidizing toner particles using only mechanical pulverization.

  In addition, the method of spheroidizing toner particles with hot air makes it difficult to control the charging of the toner particles when the toner particles contain a large amount of wax, so that the melting of the wax starts and the quality is stable. Issues remain in sex.

  On the other hand, there has been proposed a surface modifying apparatus for modifying the surface of toner particles that can achieve high-performance surface treatment and fine powder removal simultaneously (see Patent Document 3).

  However, the surface modification apparatus has a tendency to cause image fogging as a result of a decrease in fine powder removal efficiency, so-called classification yield, when maintaining a high degree of spheroidization. It is rare.

Japanese Patent Laid-Open No. 9-85741 JP 2000-29241 A JP 2002-233787 A

  An object of the present invention is to solve the above-mentioned problems and provide an apparatus and a method for producing a toner for efficiently modifying the surface of toner particles.

  Furthermore, an object of the present invention is to provide a toner production method in which toner particles can be made highly spherical and the yield of toner particles is high.

  Another object of the present invention is to provide a toner manufacturing method for efficiently manufacturing a toner that is less likely to cause fog in an image.

The present invention is a surface modification device for performing surface modification of powder particles containing at least a binder resin and a colorant,
The surface modification apparatus has at least a dispersion rotor for performing surface modification treatment of powder particles, and a liner which is a fixed body arranged at a constant interval on the outer periphery of the dispersion rotor,
The dispersion rotor relates to a toner surface reforming device having a baffle plate that generates an airflow from the upper side to the lower side at the center of the upper surface thereof.

Furthermore, the present invention relates to a toner production method for obtaining toner particles or toner by performing a surface modification step for modifying the surface of powder particles containing at least a binder resin and a colorant.
The surface modification step is performed by simultaneously performing a surface modification step for modifying the surface of the powder particles and a classification step for performing classification for removing the fine powder contained in the powder particles. Having a step of obtaining
The step is performed using a batch type surface modification device,
Cylindrical body casing,
A charging unit for charging the powder particles into the main casing;
A classification unit having a rotary classification rotor for continuously removing fine powder from the powder particles put into the main body casing to the outside of the apparatus;
A fine powder discharger for discharging the fine powder removed by the classification rotor to the outside of the main body casing,
A surface modification unit having a dispersion rotor that rotates in the same direction as the rotation direction of the classification rotor, wherein the powder particles are subjected to a surface modification treatment using a mechanical impact force;
A guide portion having a cylindrical partition member for forming a first space and a second space in the main body casing;
Having at least a discharge part for discharging powder particles subjected to surface modification treatment by the dispersion rotor to the outside of the main body casing;
The charging portion is formed on the side surface of the main body casing, and the fine powder discharging portion is formed on the upper surface of the main body casing,
The first space provided between the inner wall of the main body casing and the outer wall of the guide means having a cylindrical partition member is a space for guiding the powder particles to the classification rotor,
The second space is a space for processing the powder particles with a dispersion rotor,
In the surface reforming apparatus, the powder particles introduced into the main body casing from the charging unit are introduced into the first space, and the fine powder is removed by the classification rotor and continuously discharged out of the apparatus. The powder particles from which the particles are removed are moved to the second space and processed by the dispersion rotor to perform surface modification treatment of the powder particles. The powder particles are again separated into the first space and the second space. The present invention relates to a method for producing a toner, characterized in that the classification and the surface modification treatment are repeated by circulation to obtain a toner particle or toner having fine particles removed and surface-modified.

  According to the present invention, excessive pulverization associated with the surface modification of toner particles is prevented, the influence of heat is small, sharp particle size distribution with little fine powder, and highly spherical toner particles are more efficient. It can be obtained well, and the surface shape of the toner particles can be arbitrarily controlled.

  In addition, according to the present invention, a long-life toner having good developability, transferability, cleanability, and stable chargeability can be obtained.

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

  As a result of intensive studies to solve the above-mentioned problems of the prior art, the inventor of the present invention is a batch-type surface reforming apparatus that classifies toner particle raw materials and spheroidizes toner particles. In addition, by installing a baffle plate that generates an air flow from the upper side to the lower side, toner particles are prevented from being crushed, are not affected by heat, have a sharp particle size distribution with little fine powder, and have high sphericity. Has been found to be obtained efficiently, and the surface shape of the toner particles can be efficiently controlled.

  Furthermore, it has been found that toner particles having good developability, transferability, cleaning properties, and stable chargeability can be obtained by performing the surface modification treatment of the toner particles using the surface modification device of the present invention. Thus, the present invention has been achieved.

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

  First, the surface modification apparatus used in the production method of the present invention will be described.

  FIG. 1 is a schematic cross-sectional view showing a preferred example of a surface modifying apparatus used in the present invention.

  The surface modification apparatus of the present invention is a batch for simultaneously performing a surface modification step for performing surface modification of powder particles and a classification step for performing classification for removing fine powder contained in the powder particles. It consists of a device of the type.

  The surface reforming apparatus of the present invention includes a cylindrical main body casing 30, a charging unit for charging the powder particles into the main body casing, and fine powders continuously from the powder particles charged into the main body casing 30. At least a classification part having a rotary classification rotor 35 to be removed.

  Furthermore, the surface modification apparatus of the present invention performs a surface modification treatment on the powder particles using a mechanical impact force, and a fine powder discharge portion 44 for discharging the fine powder removed by the classification rotor 35 to the outside of the main body casing 30. And at least a surface modification portion having a dispersion rotor 32 that rotates in the same direction as the rotation direction of the classification rotor 35.

  Furthermore, the surface modification apparatus of the present invention includes a guide ring 36 that is a guide portion having a cylindrical partition member for forming a first space 47 and a second space 48 in the main body casing 30, the dispersion It has at least a product discharge section for discharging powder particles subjected to the surface modification treatment by the rotor 32 to the outside of the main casing.

  Further, in the surface reforming apparatus of the present invention, the input portion is formed on the side surface of the main body casing 30, and the fine powder discharge portion 44 is formed on the upper surface of the main body casing 30.

  Further, in the surface modification apparatus of the present invention, the first space 47 provided between the inner wall of the main body casing 30 and the outer wall of the guide ring 36 guides the powder particles to the classification rotor 35. Space. The second space 48 is a space for processing the powder particles with the dispersion rotor 33.

  The surface modification apparatus of the present invention introduces the powder particles charged into the main body casing 30 from the charging section into the first space 47 in the surface modification apparatus. The fine particles are removed by the classification rotor 35 and continuously discharged out of the apparatus, and the powder particles from which the fine particles have been removed are moved to the second space 48. The surface treatment of the powder particles is performed by the dispersion rotor 32, and the powder particles are circulated again to the first space 47 and the second space 48 to thereby perform the surface modification treatment and the classification. Is repeated to obtain toner particles or toner from which fine powder has been removed and whose surface has been modified.

  Next, the features of the surface modification apparatus of the present invention will be described with reference to FIGS.

  2 to 5, (A) is a schematic cross-sectional view showing the characteristics of the surface modification device of the present invention, (B) is a perspective view of a guide ring 36 suitably used in the present invention, (C) is a horizontal projection for demonstrating the baffle plate installed in the center part of the upper surface of the dispersion | distribution rotor 32. FIG.

  A feature of the surface modification apparatus of the present invention is that, as shown in FIG. 2 (C), a rectifying plate 52 that generates an airflow from the upper side to the lower side is provided at the center of the upper surface of the dispersion rotor 32.

  As a result of diligent investigations in the batch type surface modification device, the surface shape of the toner particles can be efficiently controlled and toner particles having a high sphericity can be obtained in high yield. Attention was paid to the dispersion state of the toner particles.

  The degree of spheroidization of the toner particles is maintained at a constant interval around the rotational peripheral speed of the dispersion rotor 32 in the surface modification device, the dispersion hammers 33 installed at the upper end of the dispersion rotor 32, and the dispersion rotor 32. And the minimum distance from the fixedly arranged liner 34.

  Further, in addition to the above, it is considered that the dispersion state of the powder particles in the surface modifying apparatus has a great influence. That is, it is important to introduce the toner particles into the surface modification zone 49 in a state where the dispersion state of the powder particles in the apparatus is improved and the dispersibility is further improved.

  Further, as shown in FIG. 2C, by installing the rectifying plate 52 at the center of the upper surface of the distributed rotor 32, the rectifying plate 52 also rotates with the rotation of the distributed rotor 32, so that the upper (= classifying rotor 35). ) From below (= distributed rotor 32) is generated.

  The powder particles from which fine powder has been removed by the classification rotor 35 are forcibly introduced into the surface modification zone 49 in a state of being dispersed by the impact of the air flow and the rectifying plate 52 rotating at high speed. By surface modification with the dispersion rotor 32 and the liner 34, toner particles having a high degree of spheroidization can be obtained.

  The rectifying plate 52 installed at the center of the upper surface of the dispersion rotor 32 can be a known rectifying plate. Those having 54 are preferred.

  In a more preferred embodiment, the side edge of the rectifying blade 54 has a predetermined gap with the inner surface of the guide ring 36.

  In this case, all the powder particles are forcibly introduced into the surface modification zone 49 in an dispersed state by the air flow generated from the upper side to the lower side as the rectifying blades 54 rotate. Thereby, the surface modification of the powder particles can be achieved more effectively, and the object of the present invention can be achieved more suitably.

  Furthermore, as shown in FIG. 3 (B), the surface modification device of the present invention is characterized in that a plurality of louvers 51 in which the upper portion of the guide ring 36 is pointed in the tangential direction of the inner circumferential direction of the guide ring 36. It is made up of. Furthermore, as shown in FIG. 3C, a rectifying plate 52 is provided at the center of the upper surface of the dispersion rotor 32.

  As a result of the study by the present inventor, as shown in FIG. 3B, the upper portion of the guide ring 36 is configured to have a plurality of louvers 51 whose tips are directed in the tangential direction of the inner circumferential direction of the guide ring 36. It is preferable. With this configuration, the dispersibility of the powder particles is promoted when the powder particles pass through the louver 51.

  Since the powder particles introduced into the first space 47 are introduced into the classification rotor 35 in a state of being dispersed by the louver 51, the dust density density around the classification rotor 35 is made uniform, and the stationary classification is performed. Therefore, toner particles having a high degree of spheroidization can be obtained with good yield.

  Further, as a result of investigation by the present inventor, as shown in FIG. 3B, when the upper portion of the guide ring 36 has a plurality of louvers 51, the overall height of the guide ring 36 is L0, and the louver When the height of the 51 portion is L1, L1 / L0 is preferably set to 0.10 or more and 0.50 or less.

  As a result of investigation by the present inventor, when it is smaller than 0.10, a sufficient dispersion effect cannot be obtained, and when it is larger than 0.50, there is a possibility that powder that cannot reach the classification rotor 35 from the first space 47 may be generated. This is not preferable because suitable classification and circulation treatment cannot be performed.

  In a more preferred embodiment, the upper end portion of the guide ring 36 is in close contact with the inner surface of the top plate 43. In this case, all the powder particles that reach the classification rotor 35 reach the louver 51, so that the uniform dispersion of the powder particles inside the apparatus is more effectively achieved, and the object of the present invention is more preferably achieved. Is possible.

  Further, as shown in FIG. 3C, toner particles having a high degree of sphericity can be obtained by having a baffle plate 52 at the center of the upper surface of the dispersion rotor 32.

  Further, the surface modification device of the present invention is characterized in that the upper portion of the guide ring 36 includes a plurality of louvers 51 as shown in FIG. Further, the guide ring 36 has a conical shape whose inner diameter is continuously reduced toward the central portion of the dispersion rotor 32, and further has a current plate 52 as shown in FIG.

  As a result of the study by the present inventor, as shown in FIG. 4B, the inner diameter of the guide ring 36 is preferably a conical shape whose inner diameter is continuously reduced toward the central portion of the dispersion rotor 32. . With this configuration, the swirl flow generated on the inner peripheral surface of the guide ring 36 becomes stronger as it goes downward.

  The powder particles from which fine powder has been removed by the classifying rotor 35 are generated on the inner peripheral surface of the guide ring 36 and dispersed by a swirl flow that becomes stronger as it goes downward, and in addition, the air flow generated by the current plate 52 By being forcedly introduced into the surface modification zone 49 in a dispersed state by impact with the rectifying plate 52 rotating at high speed, toner particles having a high sphericity can be obtained.

  As shown in FIG. 4B, when the inner diameter of the guide ring 36 is a conical shape whose inner diameter is continuously reduced toward the central portion of the dispersion rotor 32, the uppermost stage of the guide ring 36 is used. Where D is the inner diameter of the lowermost step part where the inner diameter is continuously reduced toward the center of the dispersion rotor 32 and d is D / D of 0.30 or more and 0.90 or less. Is preferred.

  As a result of the study by the present inventor, the reason is not clear, but when it is smaller than 0.30, the powder particles cannot be quantitatively introduced from the guide ring 36 into the surface modification zone 49. If it is larger than 0.90, the strength of the swirling flow generated on the inner peripheral surface of the guide ring 36 may not change greatly between the upper and lower sides, and it is not preferable because a suitable fine dispersion cannot be achieved.

  Furthermore, as shown in FIG. 5 (B), the surface modification apparatus of the present invention is characterized in that the upper portion of the guide ring 36 is composed of a plurality of louvers 51, and the guide ring 36 is located at the center of the dispersion rotor 32. That is, it has a conical shape whose inner diameter is continuously reduced toward the part. Further, a rectifying plate 52 is provided at the center of the upper surface of the dispersion rotor 32, and further, a crushing means 53, which is a perforated plate having a large number of gaps, arranged at regular intervals on the outer periphery of the rectifying plate 52, is provided. In addition, a rectifying plate 52 is provided as shown in FIG.

  As a result of investigation by the present inventor, it is preferable to install a crushing means that is a perforated plate having a large number of gaps at a constant interval on the outer periphery of the rectifying plate 52 as shown in FIG. With this configuration, the powder particles are introduced into the surface modification zone 49 in a more finely dispersed state.

  Since the powder particles from which fine powder has been removed by the classification rotor 35 are introduced into the dispersion rotor 32 in a state of being dispersed by the crushing means, the dust density density around the dispersion rotor 32 is made uniform, and the steady state Surface treatment is possible. In addition, a toner having a high sphericity degree is forcibly introduced into the surface modification zone 49 in a further dispersed state by the impact of the airflow generated by the current plate 52 and the current plate 52 rotating at high speed. Particles can be obtained.

  Further, as a result of investigation by the present inventor, as shown in FIG. 5 (B), it is preferable that the crushing means maintain a constant interval on the outer periphery of the rectifying plate 52, and more It is preferable to include a screen 53 having a plurality of holes.

  As a result of the study by the present inventor, the diameter of a large number of apertures existing on the screen 53 is preferably 1.0 to 10.0 mm. If it is smaller than 1.0 mm, powder particles cannot be quantitatively introduced into the surface modification zone 49, and if it is larger than 10.0 mm, a sufficient dispersion effect may not be obtained, which is not preferable. .

  By operating the batch-type surface modification device having the above-described device configuration in an appropriate state, the surface shape of the toner particles can be controlled efficiently, and good developability, transferability, cleaning property, and stable chargeability can be obtained. A long-life toner having the above can be obtained.

  Furthermore, a feature of the surface modification apparatus of the present invention is that a part of the members constituting the surface modification apparatus is coated with a chromium alloy plating containing at least chromium carbide.

  As the base material of the member constituting the surface reforming apparatus, carbon steel such as S45C or chromium molybdenum steel such as SCM material is often used. By coating these base metal surfaces with a chromium alloy and then applying a mechanical surface treatment, the surface hardness and wear resistance of the treated surface is increased, and a long-life member can be obtained, enabling long-term operation. Become.

  In the present invention, the coating on the base material surface of the chromium alloy containing chromium carbide can be processed by plating to finish the surface uniformly and smoothly and reduce the friction coefficient to improve the wear resistance. After the plating process, a polishing process such as buffing or a blasting process such as shot blasting may be performed to adjust the surface roughness of the member.

  However, in the surface treatment by plating, micro cracks may occur on the treated surface. Due to this micro-cracking, the surface of hard powder particles such as magnetic toner continues to be modified to a lesser degree than the conventional anti-wear treatment, but wear or local delamination occurs. The possibility of doing this cannot be completely denied.

  In the present invention, in order to cope with such a situation and to obtain a long-life member, by using shot peening as a mechanical surface treatment on the treated surface after the plating treatment, micro cracks on the treated surface are eliminated. The surface hardness and abrasion resistance of the pulverized surface were further improved.

  Here, shot peening is a processing method in which particles such as steel are sprayed onto the surface of a mold by, for example, compressed air or centrifugal force, and can eliminate surface treatment microcracks applied to the mold. . In the present invention, it is preferably performed by injection of ceramic particles.

  In addition, it is known that the microcracks generated on the surface have a high injection pressure (shot pressure) and show a tendency to decrease due to plastic deformation as the time increases.

  In order to further improve the surface hardness and wear resistance, it is preferable to harden the plating layer before shot peening to improve the adhesion.

  In the present invention, the surface hardness A of the member could be improved to HV1800 by changing the shot pressure and time by the above method and eliminating the microcracks on the treated surface after plating.

  A part of the member constituting the surface modification device is treated with a chromium alloy plating containing at least chromium carbide, so that the surface hardness A (Vickers hardness) of the member is HV700 <A ≦ HV1800. Is preferred.

  When the Vickers hardness A of the surface of the member is in the range of HV700 <A ≦ HV1800, the amount of wear of the member can be reduced, the replacement frequency can be reduced, and the apparatus can be run for a long time. .

  Further, if the Vickers hardness A of the surface of the member is HV700 or less, when continuous operation is performed for a long time, the member is worn out and must be replaced, so that it is sufficiently satisfied from the viewpoint of toner productivity. It is not possible.

  Next, a batch type surface reforming apparatus suitably used in the toner production method of the present invention will be described.

  FIG. 7 is a partial flowchart for explaining the toner production method of the present invention.

  The batch type surface reforming apparatus shown in FIG. 7 includes a cylindrical main body casing 30, a top plate 43 installed so as to be openable and closable at the upper part of the main body casing; a fine powder discharge section 44 having a fine powder discharge casing and a fine powder discharge pipe. A cooling jacket 31 through which cooling water or antifreeze can be passed.

  Further, the batch type surface modifying apparatus shown in FIG. 7 has a plurality of dispersing hammers 33 which are square disks on the upper surface, which are attached to the central rotating shaft in the main body casing 30 as surface modifying means. is doing. In addition, a distributed rotor 32 that is a disk-shaped rotating body that rotates at a high speed in a predetermined direction; a large number of grooves are provided on the surface facing the distributed rotor 32 that is fixedly arranged around the distributed rotor 32 at a constant interval. The liner 34 is provided.

  Further, the batch type surface modification apparatus shown in FIG. 7 is provided with a classification rotor 35 for continuously removing fine powder having a predetermined particle size or less in the powder particles; cold air introduction for introducing cold air into the main body casing 30. The inlet 46 has an input pipe having a raw material input port 37 and a raw material supply port 39 formed on the side surface of the main casing 30 for introducing powder particles (raw material).

  Further, the batch-type surface modification apparatus shown in FIG. 7 includes a product discharge pipe having a product discharge port 40 and a product extraction port 42 for discharging the toner particles after the surface modification treatment to the outside of the main body casing 30; An openable and closable raw material supply valve 38 installed between the raw material inlet 37 and the raw material supply port 39; and a product outlet 40 and a product outlet 42 so that the time can be adjusted freely. A product discharge valve 41 is provided.

  Further, the batch type surface modification apparatus shown in FIG. 7 has a guide ring 36 as a cylindrical guide means having an axis perpendicular to the top plate 43 in the main body casing 30. As described above, the guide ring 36 is installed such that the upper end portion of the guide ring is in close contact with the inner surface of the top plate and the classification rotor 36 is covered with the cylinder.

  Further, the lower end of the guide ring 36 is provided at a predetermined distance from the dispersion hammer 33 which is a disk portion of the dispersion rotor 32 or a square disk. By this guide ring 36, the space between the classification rotor 35 and the dispersion rotor 32-liner 34 in the apparatus is divided into a first space 47 outside the guide ring and a second space 48 inside the guide ring. .

  Here, the first space 47 is a space for introducing the powder particles into the classification rotor 35, and the second space is a space for introducing the powder particles into the dispersion rotor.

  A gap between the dispersion hammer 33, which is a square disk 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. .

  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 powder particles introduced into the apparatus from the raw material supply port 39 are first sucked by the blower 364 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 out of the apparatus through the fine powder discharge casing 44 and the fine powder discharge port 45.

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

  The powder particles guided to the surface modification zone 49 are subjected to a mechanical impact force between the dispersion hammer 33, which is a square disk installed on the dispersion rotor 32, and the liner 34. Quality.

  The surface-modified powder 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 blower suction flow passing through the machine. Here, fine powder is again discharged from the machine through the fine powder discharge casing 44 and the fine powder discharge port 45 by the classifying rotor 35, and the coarse powder is returned to the surface modification zone 49 again in the circulating flow, and repeatedly on the surface. Reform action.

  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.

  Next, the surface modification conditions of a batch type surface modification apparatus suitably used in the toner production method of the present invention 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 less than 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. It 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 known dehumidifying device can be used. The supply air dew point temperature is preferably −15 ° C. or lower, and more preferably −20 ° C. or lower.

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

  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 toner production method of the present invention, it is preferable that the minimum distance between the dispersion hammer on the dispersion rotor and the liner in the batch type surface modification device is 0.5 mm to 15.0 mm. Furthermore, it is preferable to set it as 1.0 mm thru | or 5.0 mm.

  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 increases. At the same time, it is not sufficiently satisfactory from the viewpoint of toner productivity because it is excessively pulverized during surface modification and is liable to cause surface alteration and in-machine fusion due to heat.

  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.

  Furthermore, in the toner production method of the present invention, 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 investigation by the present inventor, when the rotational peripheral speed of the dispersion rotor in the batch type surface reforming apparatus is less than 30 m / sec, the processing capability must be reduced in order to obtain a predetermined circularity. Productivity is not fully satisfactory.

  Further, if the rotational peripheral 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. At the same time, surface deterioration and in-machine fusion due to heat are likely to occur, and this is also not satisfactory from the viewpoint 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 (= circularity) of the surface modified particles can be controlled to a desired value.

  Furthermore, a long-life toner having good developability, transferability, cleaning property, and stable chargeability can be obtained.

  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 crushing 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) Medium pulverization and fine pulverization by a mechanical pulverizer such as Kogyo Co., Ltd.

  In the pulverization step, the toner is pulverized to a predetermined toner particle size step by step. Thereafter, according to convenience, 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 Henschel mixer, super mixer, mechano hybrid, nobilta, cyclomix, etc. 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.

  In the present invention, the particle size distribution was measured using a Coulter counter multisizer.

  As a measuring device, a Coulter counter multisizer type II or type IIe (manufactured by Coulter, Inc.) is used. An interface (manufactured by Nikka Ki) that outputs number distribution and volume distribution is connected to a general personal computer, and a 1% NaCl aqueous solution is prepared using special grade or first grade sodium chloride as the electrolyte.

  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 aqueous electrolytic 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 when measuring the particle size of a medium pulverized product with a multisizer type II of the Coulter counter, a 400 μm aperture is used. The particle size of the finely pulverized product is measured using a 100 μm aperture.

  Thereafter, the volume and the number of toners are measured to calculate the volume distribution and the number distribution, and the weight-based weight average particle diameter obtained from the volume distribution is obtained.

The average circularity in the present invention is used as a simple method for quantitatively expressing the shape of particles. In the present invention, the average circularity is measured using a flow type particle image analyzer FPIA-2100 manufactured by Sysmex Corporation. . Particles in the range of equivalent circle diameters of 0.6 to 400 μm are measured, and the degree of circularity of the measured particles is obtained by the following formula (1). The value obtained by dividing 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. is there. In the present invention, the concept of the calculation formula using the total sum of the circularity of each particle is used for reasons of handling data such as shortening the calculation time and simplification of the calculation formula. Various calculation methods may be used.

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

  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 measurement dispersion. 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.

  The toner produced by the production method of the present invention has toner particles containing at least a binder resin and a colorant, and an external additive added to and mixed with the toner particles as necessary.

  The raw material for the toner particles will be described. The toner particles contain at least a binder resin and a colorant, and further contain components such as a wax and a charge control agent as necessary.

  As the binder resin used in the present invention, a resin conventionally known as a binder resin for toner can be used. For example, vinyl resin, phenol resin, natural resin modified phenolic resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene Examples thereof include resins, polyvinyl butyral, terpene resins, coumaroindene resins, and petroleum resins. Of these, vinyl resins and polyester resins are preferred in terms of chargeability and fixability.

Examples of vinyl resins include styrene; o-methylstyrene, m-methylstyrene, p-methylenestyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene. 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, styrene derivatives such as pn-dodecylstyrene;
Ethylenically unsaturated monoolefins such as ethylene, propylene, butylene, isobutylene; unsaturated polyenes such as butadiene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride;
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate;
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylamino methacrylate Α-methylene aliphatic monocarboxylic esters such as ethyl and diethylaminoethyl methacrylate;
Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, acrylic acid Acrylic esters such as phenyl;
Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone;
N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide;
Esters of α, β-unsaturated acids, diesters of dibasic acids; acrylic acids such as acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, cinnamic acid, vinyl acetic acid, isocrotonic acid, angelic acid and the like -Or β-alkyl derivatives;
Polymers using vinyl monomers such as unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, alkenyl succinic acid, itaconic acid, mesaconic acid, dimethylmaleic acid and dimethylfumaric acid, and monoester derivatives or anhydrides thereof Is mentioned.

  In the vinyl resin, the vinyl monomers as described above are used alone or in combination of two or more. Among these, a combination of monomers that is a styrene copolymer or a styrene-acrylic copolymer is preferable.

  In addition, the binder resin used in the present invention may be a polymer or copolymer cross-linked with a cross-linkable monomer as exemplified below if necessary.

  As the crosslinkable monomer, a monomer having at least two crosslinkable unsaturated bonds can be used. As such a crosslinkable monomer, various monomers as shown below are known and can be suitably used for the toner used in the present invention.

Monofunctional monomers among the crosslinkable monomers include divinylbenzene and divinylnaphthalene as aromatic divinyl compounds;
Examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, and 1,6-hexanediol. Diacrylate, neopentylglycol diacrylate, and those obtained by replacing acrylate of the above compound with methacrylate;
Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, and dipropylene glycol. And diacrylate and the above compounds in which acrylate is replaced by methacrylate;
Examples of diacrylate compounds linked by a chain containing an aromatic group and an ether bond include polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2, 2-bis (4-hydroxyphenyl) propane diacrylate and those in which the acrylate of the above compound is replaced with methacrylate;
As the polyester-type diacrylates, trade name MANDA (Nippon Kayaku) can be mentioned.

As polyfunctional crosslinkable monomers, pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and those obtained by replacing acrylate of the above compounds with methacrylate;
Examples include triallyl cyanurate and triallyl trimellitate.

  As the binder resin, the following polyester resins are also preferable. It is preferable that 45 to 55 mol% of the polyester resin is an alcohol component and 55 to 45 mol% is an acid component in all components.

  Examples of alcohol components include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, and 1,6- Xanthdiol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, bisphenol derivatives represented by the following formula (B);

（式中、Ｒはエチレン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 or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10.)

  Diols represented by the following formula (C);

  Or polyhydric alcohols, such as glycerin, sorbit, sorbitan, are mentioned.

As the acid component, a carboxylic acid is preferable. Divalent carboxylic acids include benzene dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride, or anhydrides thereof;
Examples thereof include alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid and itaconic acid or anhydrides thereof. Examples of the trivalent or higher carboxylic acid include trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, and anhydrides thereof.

  A particularly preferable alcohol component of the polyester resin is a bisphenol derivative represented by the formula (B). Examples of the acid component include phthalic acid, terephthalic acid, isophthalic acid or its anhydride, succinic acid, n-dodecenyl succinic acid or its anhydride, dicarboxylic acids such as fumaric acid, maleic acid, maleic anhydride; trimellitic acid or its anhydrous Tricarboxylic acids of the product. This is because the heat roller fixing toner using a polyester resin obtained from these acid components and alcohol components as a binder resin has good fixability and excellent offset resistance.

When the toner is a magnetic toner, the magnetic material contained in the magnetic toner is not particularly limited as long as it is normally used. Iron oxides including, for example, iron oxides such as magnetite, maghemite, ferrite, and other metal oxides;
Metals such as Fe, Co, Ni, or these metals and Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W, Examples include alloys with metals such as V, and mixtures thereof.

Specifically, examples of the magnetic substance include triiron tetroxide (Fe ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), iron yttrium oxide (Y ₃ Fe ₅ O ₁₂ ), and iron cadmium oxide (CdFe ₂ O ₄ ), iron gadolinium oxide (Gd ₃ Fe ₅ O ₁₂ ), copper iron oxide (CuFe ₂ O ₄ ), lead iron oxide (PbFe ₁₂ O ₁₉ ), nickel iron oxide (NiFe ₂ O ₄ ), neodymium iron oxide (NdFe ₂ O ₃ ), iron barium oxide (BaFe ₁₂ O ₁₉ ), magnesium iron oxide (MgFe ₂ O ₄ ), iron lanthanum oxide (LaFeO ₃ ), iron powder (Fe), cobalt powder (Co), nickel powder ( Ni). The magnetic materials described above are used alone or in combination of two or more. A particularly suitable magnetic material is a fine powder of triiron tetroxide or γ-iron sesquioxide.

These magnetic materials have a number average particle size of 0.05 to 2 μm, magnetic properties of 795.8 kA / m applied, coercive force of 1.6 to 12.0 kA / m, saturation magnetization of 50 to ²⁰⁰ Am ² / kg (preferably Is preferably 50 to 100 Am ² / kg) and a residual magnetization of ^{2 to 20} Am ² / kg, particularly for use in an electrophotographic image forming method. In addition, these magnetic materials are preferably contained in an amount of 60 to 200 parts by mass, more preferably 80 to 150 parts by mass with respect to 100 parts by mass of the binder resin.

  A non-magnetic colorant can also be used as the colorant. Such non-magnetic colorants include any suitable pigment or dye. Examples of the pigment include carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, bengara, phthalocyanine blue, and indanthrene blue. These are added in an amount of 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the binder resin. Similarly, a dye is used, and an addition amount of 0.1 to 20 parts by mass, preferably 0.3 to 10 parts by mass is good with respect to 100 parts by mass of the binder resin.

  As the nonmagnetic black colorant, carbon black, which is toned to black using the yellow / magenta / cyan colorant shown below, is used.

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

  As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacdrine compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254 are particularly preferred.

  As the cyan colorant, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, and 66 can be particularly preferably used.

  The toner in the present invention may further contain a wax. As the wax used in the present invention, various waxes conventionally known as mold release agents can be used, and there are the following. For example, hydrocarbon waxes include aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymers, polyolefin wax, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax.

Examples of the wax having a functional group include oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; or block copolymers thereof; plant waxes such as candelilla wax, carnauba wax, wood wax, jojoba wax;
Animal waxes such as beeswax, lanolin and whale wax; mineral waxes such as ozokerite, ceresin and petrolactam; waxes based on aliphatic esters such as montanate wax and castor wax: deacidified carnauba wax The thing which partly or entirely deoxidized aliphatic ester is mentioned.

In addition, saturated straight chain fatty acids such as palmitic acid, stearic acid, montanic acid, or long chain alkyl carboxylic acids having a further long chain alkyl group; unsaturated fatty acids such as brassic acid, eleostearic acid, valinalic acid;
Stearyl alcohol, eicosyl alcohol, behenyl alcohol, cannavir alcohol, seryl alcohol, melyl alcohol, or saturated alcohols such as alkyl alcohols having a long chain alkyl group; polyhydric alcohols such as sorbitol;
Aliphatic amides such as linoleic acid amide, oleic acid amide, lauric acid amide; saturated aliphatic bisamides such as methylene bis stearic acid amide, ethylene bis capric acid amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide;
Unsaturated fatty acid amides such as ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide; Aromatic bisamides such as N, N'-distearylisophthalamide; aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate (commonly referred to as metal soap);
A partially esterified product of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol; a methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

  Wax grafted with a vinyl monomer can also be used in the toner of the present invention. As such a wax, there is a wax obtained by grafting an aliphatic hydrocarbon wax with a vinyl monomer such as styrene or acrylic acid.

Preferred waxes include polyolefins obtained by radical polymerization of olefins under high pressure; polyolefins obtained by purifying low molecular weight by-products obtained during polymerization of high molecular weight polyolefins; polymerized using catalysts such as Ziegler catalysts and metallocene catalysts under low pressures Polyolefins;
Polyolefins polymerized using radiation, electromagnetic waves or light; paraffin wax, microcrystalline wax, Fischer-Tropsch wax; synthetic hydrocarbon wax synthesized by the Gintor method, Hydrocol method, Age method;
Synthetic waxes having a single carbon compound as a monomer; hydrocarbon waxes having a functional group such as a hydroxyl group, a carboxyl group or an ester group; a mixture of a hydrocarbon wax and a hydrocarbon wax having a functional group; Examples thereof include waxes graft-modified with vinyl monomers such as styrene, maleic esters, acrylates, methacrylates, and maleic anhydrides.

  In addition, these waxes have a sharp molecular weight distribution using a press perspiration method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method or a melt liquid crystal deposition method, a low molecular weight solid fatty acid, a low A molecular weight solid alcohol, a low molecular weight solid compound, and other impurities are preferably used.

  In order to further stabilize the chargeability of the toner, a charge control agent can be used as necessary. The charge control agent is preferably used in an amount of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight per 100 parts by weight of the binder resin, in order to control the chargeability of the toner.

  As the charge control agent, various conventionally known charge control agents can be used, and examples thereof include the following. As a negative charge control agent for controlling the toner to be negative charge, for example, an organometallic complex or a chelate compound is effective. Examples thereof include monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acid metal complexes, and aromatic dicarboxylic acid metal complexes. Other examples include aromatic hydroxycarboxylic acids, aromatic mono and polycarboxylic acids and metal salts thereof, anhydrides or esters thereof, or phenol derivatives of bisphenol. Preferable examples include metal complexes of Cr, Co, and Fe, which are monoazo dyes synthesized from phenol or naphthol, which is a monoazo metal compound having an alkyl group, halogen, nitro group, carbamoyl group or the like as a substituent. A metal compound of an aromatic carboxylic acid is also preferably used, and examples thereof include benzene, naphthalene, anthracene, phenanthrene carboxylic acid, hydroxycarboxylic acid, and dicarboxylic acid metal compounds having an alkyl group, a halogen, and a nitro group.

  Among these, an azo metal complex represented by the following formula (1) is preferable.

〔式中、Ｍは配位中心金属を表し、Ｓｃ，Ｔｉ，Ｖ，Ｃｒ，Ｃｏ，Ｎｉ，Ｍｎ又はＦｅが挙げられる。Ａｒはアリール基であり、フェニル基、ナフチル基の如きアリール基であり、置換基を有してもよい。この場合の置換基としては、ニトロ基、ハロゲン基、カルボキシル基、アニリド基及び炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基がある。Ｘ，Ｘ’，Ｙ及びＹ’は−Ｏ−，−ＣＯ−，−ＮＨ−，−ＮＲ−（Ｒは炭素数１〜４のアルキル基）である。Ｃ＋はカウンターイオンを示し、水素、ナトリウム、カリウム、アンモニウム、脂肪族アンモニウム或いはそれらの混合イオンを示す。〕

[In the formula, M represents a coordination center metal, and examples thereof include Sc, Ti, V, Cr, Co, Ni, Mn, and Fe. Ar is an aryl group, which is an aryl group such as a phenyl group or a naphthyl group, and may have a substituent. In this case, examples of the substituent include a nitro group, a halogen group, a carboxyl group, an anilide group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. X, X ′, Y and Y ′ are —O—, —CO—, —NH—, —NR— (R is an alkyl group having 1 to 4 carbon atoms). C + represents a counter ion, and represents hydrogen, sodium, potassium, ammonium, aliphatic ammonium, or a mixed ion thereof. ]

  In the above formula (1), Fe or Cr is particularly preferable as the central metal, halogen, alkyl group, or anilide group is preferable as the substituent, and hydrogen, alkali metal, ammonium, or aliphatic ammonium is preferable as the counter ion. A mixture of complex salts having different counter ions is also preferably used.

  A basic organometallic complex represented by the following formula (2) is also preferable as a charge control agent imparting negative chargeability.

Examples of the positive charge control agent that controls the toner to be positively charged include nigrosine, nigrosine derivatives, triphenylmethane compounds, and organic quaternary ammonium salts. For example, modified products with nigrosine and fatty acid metal salts, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and phosphonium salts which are analogs thereof Onium salts and their lake pigments,
Triphenylmethane dyes and their lake pigments (including phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide), higher fatty acids The metal salt is mentioned. These can be used alone or in combination of two or more.

  Among these, triphenylmethane compounds and quaternary ammonium salts whose counter ions are not halogen are preferably used.

  Moreover, following formula (3)

〔式中、Ｒ₁はＨ又はＣＨ₃を示し、Ｒ₂及びＲ₃は置換又は未置換のアルキル基（好ましくは、Ｃ１〜Ｃ４）を示す。〕
で表されるモノマーの単重合体；前述したスチレン、アクリル酸エステル、メタクリル酸エステルの如き重合性モノマーとの共重合体を正荷電性制御剤として用いることができる。この場合、この単重合体及び共重合体は荷電制御剤としての機能と、結着樹脂としての機能を有する。

[Wherein, R ₁ represents H or CH ₃ , and R ₂ and R ₃ represent a substituted or unsubstituted alkyl group (preferably C1 to C4). ]
A copolymer with a polymerizable monomer such as styrene, acrylic acid ester or methacrylic acid ester described above can be used as a positive charge control agent. In this case, the homopolymer and the copolymer have a function as a charge control agent and a function as a binder resin.

  In particular, a compound represented by the following formula (4) is preferable as the toner positive charge control agent of the present invention.

〔式中、Ｒ₁，Ｒ₂，Ｒ₃，Ｒ₄，Ｒ₅及びＲ₆は、各々互いに同一でも異なっていてもよく、水素原子、置換もしくは未置換のアルキル基又は、置換もしくは未置換のアリール基を表す。Ｒ₇，Ｒ₈及びＲ₉は、各々互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、アルキル基、アルコキシ基を表す。Ａ^-は、硫酸イオン、硝酸イオン、ホウ酸イオン、リン酸イオン、水酸イオン、有機硫酸イオン、有機スルホン酸イオン、有機リン酸イオン、カルボン酸イオン、有機ホウ酸イオン、テトラフルオロボレートの如き陰イオンを示す。〕

[Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may be the same or different from each other, and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted group. Represents an aryl group. R ₇ , R ₈ and R ₉ may be the same as or different from each other, and each represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. A ⁻ is a sulfate ion, nitrate ion, borate ion, phosphate ion, hydroxide ion, organic sulfate ion, organic sulfonate ion, organic phosphate ion, carboxylate ion, organic borate ion, tetrafluoroborate, etc. Indicates an anion. ]

  As a method for adding the charge control agent to the toner, there are a method of adding the charge control agent inside the toner particles and a method of adding the toner to the toner particles. The amount of these charge control agents used is determined by the toner production method including the type of binder resin, the presence or absence of other additives, and the dispersion method, and is not uniquely limited. Preferably, it is used in the range of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the binder resin.

  As described above, the toner of the present invention generally contains, in addition to toner particles, external additives for adjusting the fluidity and chargeability of the toner as necessary. As such an external additive, a fluidity improver may be added to the toner. The fluidity improver can be added to the toner particles to increase the fluidity before and after the addition. For example, fluororesin powder such as vinylidene fluoride fine powder; fine powder silica such as wet process silica and dry process silica; fine powder titanium oxide; fine powder alumina; surface of them with silane compound, titanium coupling agent, silicone oil There are treated fine powders that have been treated.

  The hydrophobizing method is applied by chemically treating with an organosilicon compound that reacts or physically adsorbs with fine powder.

Examples of organosilicon compounds include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethridimethylchlorosilane,
α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane,
Diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and 2-12 siloxane units per molecule with terminal units There are dimethylpolysiloxanes each containing a hydroxyl group bonded to one Si. Furthermore, silicone oils such as dimethyl silicone oil can be mentioned. These are used in one kind or a mixture of two or more kinds.

  As the external additive particles of 0.1 to 5.0 μm used in the present invention, inorganic fine particles, organic fine particles, and mixtures and composites thereof can be used. Specifically, metal oxides such as strontium titanate, cerium oxide, aluminum oxide, and magnesium oxide, fluorine resin powder, resin fine particles, and the like can be given. Particularly in terms of charging characteristics, strontium titanate and cerium oxide are preferable.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples of the present invention.

<Example 1>
Binder resin: 100 parts by mass (styrene-butyl acrylate-butyl maleate half ester copolymer)
(Tg 62 ° C., molecular weight: Mp13000, Mw 600000, abundance ratio of components having a molecular weight of 1000 to 30000: 60%)
Magnetic iron oxide 90 parts by mass (average particle diameter 0.22 [mu] m, the characteristics in 795.8 kA / m magnetic field ^{Hc5.1kA / m, σs85.1Am 2 /kg,σr5.1Am 2} / kg)
Monoazo metal complex (negative charge control agent, E-88 manufactured by Orient): 2 parts by mass Low molecular weight ethylene-propylene copolymer: 3 parts by mass After thoroughly mixing the materials of the above formulation with a Henschel mixer, the temperature It knead | mixed with the biaxial kneader set to 130 degreeC. The obtained kneaded product was cooled and coarsely pulverized to 2 mm or less with a hammer mill to obtain a coarsely pulverized product.

  The obtained coarsely pulverized product was finely pulverized using a mechanical pulverizer (Turbo Mill T250-RS type manufactured by Turbo Kogyo Co., Ltd.).

  Thereafter, the finely pulverized product was subjected to coarse powder classification using an air classifier Turboplex (100-ATP type: manufactured by Hosokawa Micron Corporation), and the obtained toner particles are shown in FIGS. 1 and 7. Surface modification was performed using a surface modification apparatus.

  In this example, the obtained toner particles were put into a batch type surface modification treatment apparatus shown in FIG. 2A, and the fine particle classification and surface modification of the toner particles were performed simultaneously.

  At this time, in this embodiment, the guide ring 36 shown in FIG. 2 (B) is used, the dispersion rotor 32 is shown in FIG. 2 (C), and the current plate 52 is installed at the center of the upper surface of the dispersion rotor 32. Using.

  The operating conditions of the surface reformer were such that the rotational peripheral speed of the dispersion rotor 32 was 120 m / sec, the distance between the dispersion hammer 32 and the liner 34 was 3.0 mm, and the surface treatment time was 30 seconds. The feed amount was 20 kg / hr.

In addition, in order to keep the particle size distribution of the surface-modified toner particles within a desired range, the rotational peripheral speed of the classification rotor 35 is fine within the range of 80 ± 8 m / sec, and the suction air volume of the blower 364 is within the range of 7 ± 1 m ³ / min. It was adjusted.

  As a result of operating for 30 minutes in this state, the rear temperature T2 of the classification rotor 35 was stable at 35 ° C. The classification yield was 62% (the classification yield was determined from ((total amount of classified product obtained) ÷ (total amount of finely pulverized product charged)) × 100).

  In addition, as a result of measuring the average circularity of the obtained toner particles as the surface modified particles, the average circularity is 0.950, and the ratio of particles having an equivalent circle diameter of 0.6 μm to 2 μm as the amount of ultrafine powder. Was 3.0% by number.

  1.0 part by mass of dry silica having a primary particle size of 12 nm hydrophobized with hexamethyldisilazane and silicone oil was added to 100 parts by mass of the toner particles which are the surface modified particles thus obtained, and the mixture was removed by a Henschel mixer. The toner for evaluation was added and mixed.

  Using this toner, it was mounted on a Canon LBP-930 remodeling machine (modified to a printing speed of 1.5 times equivalent to 235 mm / sec), and an image output test was conducted. Evaluated.

(Evaluation-1: Transferability evaluation)
The evaluation toner is put in a developing device and left in a high temperature and high humidity chamber (32.5 ° C., 85%) overnight (12 hours). After measuring the mass of the developing device, the developing device was installed, and the developing sleeve was rotated from 3 minutes.

At this time, the cleaner unit and the waste toner collecting unit in the main body are once removed in advance and the mass is measured. Using a test chart with a printing ratio of 6%, 500 images were printed and the transfer rate was evaluated. The results are shown in Table 2.
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)
330 g of the toner for evaluation is put in a developing device and left in a low temperature and low humidity chamber (15 ° C., 50%) overnight (for 12 hours or more). 200 images are printed using the density evaluation chart. Before and after this, the fog in the solid white image was measured. The evaluation criteria are as follows. The results are shown in Table 2.
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%)

<Example 2>
The coarsely pulverized product obtained in Example 1 was pulverized, classified and surface-modified in the same manner as in Example 1.

  In this example, the obtained toner particles were put into a batch-type surface modification treatment apparatus shown in FIG. 3A, and the fine particle classification and surface modification of the toner particles were performed simultaneously.

  At this time, in this embodiment, the guide ring 36 having the louver 51 installed on the upper portion shown in FIG. 3B is used, and the dispersion rotor 32 is connected to the rectifying plate 52 shown in FIG. What was installed in the center part was used. In addition, L1 / L0 in the guide ring 36 was set to 0.30.

  As a result of measuring the average circularity of the obtained toner particles as the surface-modified particles, the average circularity is 0.950, and the ratio of particles having an equivalent circle diameter of 0.6 μm to 2 μm, which is the amount of ultrafine powder, is 1. 8% by number. The classification yield was 67%.

  This is considered to be due to the effect of installing the louver 51 on the upper portion of the guide ring 36, and also because L1 / L0 was adjusted to an appropriate range.

  The obtained surface-modified toner particles were externally added and mixed with a Henschel mixer in the same manner as in Example 1 to obtain a toner for evaluation, and image output was evaluated. The results are shown in Table 2.

<Example 3>
Toner particles were produced using the same method as in Example 2, except that L1 / L0 in the guide ring 36 (FIG. 3B) used in Example 2 was set to 0.13.

  The obtained surface-modified toner particles were externally added and mixed with a Henschel mixer in the same manner as in Example 1 to obtain a toner for evaluation, and image output was evaluated. The results are shown in Table 2.

<Example 4>
Toner particles were produced using the same method as in Example 2, except that L1 / L0 in the guide ring 36 (FIG. 3B) used in Example 2 was set to 0.46.

  The obtained surface-modified toner particles were externally added and mixed with a Henschel mixer in the same manner as in Example 1 to obtain a toner for evaluation, and image output was evaluated. The results are shown in Table 2.

<Example 5>
Toner particles were produced using the same method as in Example 2, except that L1 / L0 in the guide ring 36 (FIG. 3B) used in Example 2 was set to 0.04.

  The obtained surface-modified toner particles were externally added and mixed with a Henschel mixer in the same manner as in Example 1 to obtain a toner for evaluation, and image output was evaluated. The results are shown in Table 2.

<Example 6>
The coarsely pulverized product obtained in Example 1 was pulverized, classified and surface-modified in the same manner as in Example 1.

  In this example, the obtained toner particles were put into a batch type surface modification treatment apparatus shown in FIG. 4A, and the fine particle classification and surface modification of the toner particles were performed simultaneously.

  At this time, in this embodiment, the guide ring 36 having a lower diameter reduced as shown in FIG. 4B is used, and the dispersion rotor 32 is replaced with the rectifying plate 52 shown in FIG. What was installed in was used. The d / D in the guide ring 36 was set to 0.63.

  As a result of measuring the average circularity of the obtained toner particles as the surface-modified particles, the average circularity is 0.950, and the ratio of particles having an equivalent circle diameter of 0.6 μm to 2 μm, which is the amount of ultrafine powder, is 1. 8% by number. The classification yield was 70%.

  This is considered to be due to the effect that the shape of the guide ring 36 is continuously reduced toward the central portion of the dispersion rotor 32, and the d / D of the guide ring 36 is adjusted to an appropriate range. .

  The obtained surface-modified toner particles were externally added and mixed with a Henschel mixer in the same manner as in Example 1 to obtain a toner for evaluation, and image output was evaluated. The results are shown in Table 4.

<Example 7>
Toner particles were produced using the same method as in Example 5 except that d / D in the guide ring 36 (FIG. 4B) used in Example 5 was set to 0.32.

  The obtained surface-modified toner particles were externally added and mixed with a Henschel mixer in the same manner as in Example 1 to obtain a toner for evaluation, and image output was evaluated. The results are shown in Table 4.

<Example 8>
Toner particles were produced using the same method as in Example 5, except that d / D in the guide ring 36 (FIG. 4B) used in Example 5 was set to 0.87.

  The obtained surface-modified toner particles were externally added and mixed with a Henschel mixer in the same manner as in Example 1 to obtain a toner for evaluation, and image output was evaluated. The results are shown in Table 4.

<Example 9>
Toner particles were produced using the same method as in Example 5 except that d / D in the guide ring 36 (FIG. 4B) used in Example 5 was set to 0.24.

  The obtained surface-modified toner particles were externally added and mixed with a Henschel mixer in the same manner as in Example 1 to obtain a toner for evaluation, and image output was evaluated. The results are shown in Table 4.

<Example 10>
The coarsely pulverized product obtained in Example 1 was pulverized, classified and surface-modified in the same manner as in Example 1.

  In this example, the obtained toner particles were put into a batch-type surface modification treatment apparatus shown in FIG. 5A, and toner powder fine powder classification and surface modification were performed simultaneously.

  At this time, in this embodiment, the guide ring 36 shown in FIG. 5B is used, and a screen 53 is installed as a crushing means in the lower part, and the dispersion rotor 36 is shown in FIG. 5C. What installed 52 in the center part of the upper surface of the dispersion | distribution rotor 32 was used.

  In the guide ring 36, the opening diameter of the screen 53 installed in the lower part was 3 mm.

  As a result of measuring the average circularity of the obtained toner particles as the surface modified particles, the average circularity is 0.952, and the ratio of particles having an equivalent circle diameter of 0.6 μm or more and 2 μm or less, which is the amount of ultrafine powder, is 1. 0.5% by number. The classification yield was 72%.

  This is considered to be the effect of installing the screen 53 on the outer periphery of the rectifying plate 52, and also because the aperture diameter of the screen 53 was adjusted to an appropriate size.

  The obtained surface-modified toner particles were externally added and mixed with a Henschel mixer in the same manner as in Example 1 to obtain a toner for evaluation, and image output was evaluated. The results are shown in Table 6.

  Further, after 30 minutes of operation in this example, the surface was coated with hard chromium carbide alloy plating and quenched, and then subjected to shot peening (processing conditions: pressure 0.5 MPa, time 15 seconds), and the surface hardness was set to HV1310. The dispersion hammer 33 and the liner 34 were installed in the surface modification device.

  After installing the above-described members, 1200 hours of long run operation was performed. After the operation was completed, the inside of the apparatus was checked, and it was confirmed whether or not the surface of the dispersion hammer 33 and the liner 34 was worn. As a result, no wear was found. This is presumably because the surfaces of the dispersion hammer 33 and the liner 34 were subjected to wear resistance treatment as described above.

<Example 11>
Toner particles were produced using the same method as in Example 8, except that the aperture of the screen in guide ring 36 (FIG. 5B) used in Example 8 was 1 mm.

  The obtained surface-modified toner particles were externally added and mixed with a Henschel mixer in the same manner as in Example 1 to obtain a toner for evaluation, and image output was evaluated. The results are shown in Table 6.

<Example 12>
Toner particles were produced in the same manner as in Example 8, except that the aperture of the screen in guide ring 36 (FIG. 5B) used in Example 8 was 9 mm.

  The obtained surface-modified toner particles were externally added and mixed with a Henschel mixer in the same manner as in Example 1 to obtain a toner for evaluation, and image output was evaluated. The results are shown in Table 6.

<Example 13>
Toner particles were produced using the same method as in Example 8, except that the aperture of the screen in guide ring 36 (FIG. 5B) used in Example 8 was 0.5 mm.

  The obtained surface-modified toner particles were externally added and mixed with a Henschel mixer in the same manner as in Example 1 to obtain a toner for evaluation, and image output was evaluated. The results are shown in Table 6.

<Example 14>
Unsaturated polyester resin: 100 parts by mass [polyoxypropylene (2,2) -2,2 bis (4-hydroxyphenyl) propane / polyoxyethylene (2,2) -2,2 bis (4-hydroxyphenyl) Unsaturated polyester resin comprising propane / terephthalic acid / trimellitic anhydride / fumaric acid, Mw: 17000, Mw / Mn: 4.5, Tg: 60 ° C.]
Copper phthalocyanine pigment (CI Pigment Blue 15: 3): 4 parts by mass Paraffin wax (maximum endothermic peak 73 ° C): 5 parts by mass Charge control agent (salicylic acid metal complex E-88 (manufactured by Orient)): 4 parts by mass After the above materials were mixed well using a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.), a twin-screw kneader (PCM-30 type, Ikegai Iron Works Co., Ltd.) set at a temperature of 110 ° C. Kneaded). The obtained kneaded material was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized material.

  The obtained coarsely pulverized product was pulverized, classified and surface-modified in the same manner as in Example 10 to produce toner particles.

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 and mixed 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, a Canon full-color copier CLC1000 remodeled machine (with the oil application mechanism of the fixing unit removed) was used at room temperature and normal humidity (23 ° C., 60% RH) in the same manner as in Example 1. Evaluation was made. The results are shown in Table 8.

<Reference example>
The coarsely pulverized product obtained in Example 1 was pulverized, classified and surface-modified in the same manner as in Example 1.

  In this reference example, the obtained toner particles were put into a batch-type surface modification treatment apparatus shown in FIG. 6 (A), and toner powder fine powder classification and surface modification were performed simultaneously.

  At this time, in this reference example, the guide ring 36 shown in FIG. 6B was used, and the dispersion rotor 32 shown in FIG. 6C was used.

  As a result of measuring the average circularity of the surface-modified toner particles obtained, the average circularity was 0.948, and the ratio of particles having an equivalent circle diameter of 0.6 μm or more and 2 μm or less, which is the amount of ultrafine powder, was 3. It was 8% by number. The classification yield was 62%.

  The obtained surface-modified toner particles were externally added and mixed with a Henschel mixer in the same manner as in Example 1 to obtain a toner for evaluation, and image output was evaluated. The results are shown in Table 10.

<Comparative example>
The finely pulverized product obtained in Example 1 is finely coarsely classified with a multi-split airflow classifier (EJ-5 type manufactured by Nippon Steel Mining Co., Ltd.) and introduced into the surface reformer shown in FIG. went.

  In FIG. 8, 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 the surface reforming apparatus, the powder particles supplied from the raw material charging chute 164 are instantaneously impacted by a plurality of rotor blades 155 disposed in a rotary rotor 162 that rotates mainly at high speed in the impact chamber 168. Receive. Furthermore, it collides with the surrounding stator 158 and disperses the powder particles in the system while loosening the aggregation of the particles, and at the same time, the particles are made spherical.

  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, the particles are repeatedly impacted by the rotor blade 155 and the stator 158, whereby the shape of the particles is made spherical.

  The particles that have been spheroidized are collected by the bag filter 362 that passes through the discharge chute 219 and communicates with the suction blower 364 by opening the discharge valve 159 by the discharge valve control device 128.

  In this comparative example, the rotational peripheral speed of the rotary rotor 162 having the rotor blade 155 was set to 100 m / sec. The amount of finely pulverized product was 150 g, and the surface treatment time was 180 seconds. This was repeated about 10 times to obtain surface modified particles.

  As a result of measuring the average circularity of the obtained surface-modified toner particles, the average circularity was 0.948, and the ratio of particles having an equivalent circle diameter of 0.6 μm to 2 μm, which is the amount of ultrafine powder, was 8. It was 3% by number.

  Next, the obtained surface-modified toner particles were externally mixed by a Henschel mixer in the same manner as in Example 1 to obtain a toner for evaluation, and image output evaluation was performed. Although a result is shown in Table 12, it became a result inferior compared with an Example.

  Further, after the operation of this comparative example, a long run operation of 1200 hours was performed in the same manner as in Example 8 in a state where no surface was subjected to the abrasion resistance treatment on the surfaces of the rotor blade 155 and the stator 158 (surface hardness HV250).

  After completion of the operation, the inside of the apparatus was confirmed, and the presence or absence of surface wear of the rotor blade 155 and the stator 158 was confirmed. As a result, wear was observed, which was inferior to that of the example.

It is a schematic sectional drawing of an example of the batch type surface modification apparatus used in the surface modification process of this invention. (A) It is a schematic sectional drawing of an example of the surface modification apparatus used suitably for this invention, (B) The perspective view of a guide ring, (C) The horizontal projection figure of a dispersion | distribution rotor. (A) Furthermore, it is a schematic sectional drawing of an example of the surface modification apparatus used suitably for this invention, (B) The perspective view of a guide ring, (C) The horizontal projection figure of a dispersion | distribution rotor. (A) Furthermore, it is a schematic sectional drawing of an example of the surface modification apparatus used suitably for this invention, (B) The perspective view of a guide ring, (C) The horizontal projection figure of a dispersion | distribution rotor. (A) Furthermore, it is a schematic sectional drawing of an example of the surface modification apparatus used suitably for this invention, (B) The perspective view of a guide ring, (C) The horizontal projection figure of a dispersion | distribution rotor. (A) It is a schematic sectional drawing of an example of the surface modification apparatus used in the surface modification process of a reference example, (B) The perspective view of a guide ring, and (C) The horizontal projection figure of a dispersion | distribution rotor. FIG. 4 is a partial flowchart for explaining a toner manufacturing method of the present invention. 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

30 Main body casing 31 Cooling jacket 32 Dispersion rotor 33 Dispersion hammer 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 flight 42 Product extraction port 43 Top plate 44 Fine powder discharge Part 45 Fine powder discharger 46 Cold air inlet 47 First space 48 Second space 49 Surface modification zone 50 Classification zone 51 Louver 52 Current plate 53 Screen 54 Current blade 151 Main body casing 155 Rotor blade 158 Stator 159 Discharge valve 163 Recycling Pipe 164 Raw material charging chute 168 Impact chamber 177 Stator jacket 315 Constant supply machine 319 Cold air generating means 320 Cold water generating means 321 Toner particle transport means 359 Cyclone 362 Bug 364 Blower 369 Rhino Ron 380 raw material hopper

Claims (9)

A surface modification device for performing surface modification of powder particles containing at least a binder resin and a colorant,
The surface modification apparatus has at least a dispersion rotor for performing surface modification treatment of powder particles, and a liner which is a fixed body arranged at a constant interval on the outer periphery of the dispersion rotor,
The toner surface reforming apparatus, wherein the dispersion rotor has a baffle plate that generates an airflow from the upper side to the lower side at the center of the upper surface thereof. The surface reforming apparatus is configured to form a cylindrical main body casing, a charging unit for charging powder particles into the main body casing, and a first space and a second space in the main body casing. Having at least guide means having a cylindrical partition member;
The upper part of the guide means is composed of a plurality of louvers whose tips are directed in the tangential direction of the inner circumferential circle of the cylindrical partition member,
The total length height of the cylindrical partition member is L0, and when the height of the dispersion louver portion is L1, L1 / L0 is 0.10 or more and 0.50 or less. Toner surface modification device.   3. The toner surface reforming apparatus according to claim 1, wherein the guide means has a conical shape whose inner diameter is continuously reduced toward the central portion of the dispersion rotor.   When the inner diameter of the uppermost step portion of the guide means is D and the inner diameter of the lowermost step portion whose inner diameter is continuously reduced toward the central portion of the dispersion rotor is d, d / D is 0.30 or more and 0.00. 4. The toner surface modifying apparatus according to claim 1, wherein the toner surface modifying apparatus is 90 or less.   The surface reforming apparatus includes a rectifying unit that is a rectifying plate having a plurality of blades in a central portion of an upper surface of a dispersion rotor, and a perforated plate having a large number of voids arranged at regular intervals on the outer periphery of the rectifying unit 5. The toner surface modifying apparatus according to claim 1, further comprising a crushing unit.   6. The toner surface modifying apparatus according to claim 1, wherein the surface modifying apparatus has a rotary classifier in the main body casing.   7. The toner surface modifying apparatus according to claim 1, wherein a part of the member constituting the surface modifying apparatus is treated with a chromium alloy plating containing at least chromium carbide.   A part of the member constituting the surface modification device is treated with a chromium alloy plating containing at least chromium carbide, so that the surface hardness A (Vickers hardness) of the member is HV700 <A ≦ HV1800. The toner surface modifying apparatus according to claim 7. In a toner production method for obtaining toner particles or toner by performing a surface modification step for modifying the surface of powder particles containing at least a binder resin and a colorant,
The surface modification step is performed by simultaneously performing a surface modification step for modifying the surface of the powder particles and a classification step for performing classification for removing the fine powder contained in the powder particles. Having a step of obtaining
The step is performed using a batch type surface modification device,
Cylindrical body casing,
A charging unit for charging the powder particles into the main casing;
A classification unit having a rotary classification rotor for continuously removing fine powder from the powder particles put into the main body casing to the outside of the apparatus;
A fine powder discharger for discharging the fine powder removed by the classification rotor to the outside of the main body casing,
A surface modification unit having a dispersion rotor that rotates in the same direction as the rotation direction of the classification rotor, wherein the powder particles are subjected to a surface modification treatment using a mechanical impact force;
A guide portion having a cylindrical partition member for forming a first space and a second space in the main body casing;
Having at least a discharge part for discharging powder particles subjected to surface modification treatment by the dispersion rotor to the outside of the main body casing;
The charging portion is formed on the side surface of the main body casing, and the fine powder discharging portion is formed on the upper surface of the main body casing,
The first space provided between the inner wall of the main body casing and the outer wall of the guide means having a cylindrical partition member is a space for guiding the powder particles to the classification rotor,
The second space is a space for processing the powder particles with a dispersion rotor,
In the surface reforming apparatus, the powder particles introduced into the main body casing from the charging unit are introduced into the first space, and the fine powder is removed by the classification rotor and continuously discharged out of the apparatus. The powder particles from which the particles are removed are moved to the second space and processed by the dispersion rotor to perform surface modification treatment of the powder particles. The powder particles are again separated into the first space and the second space. A method of producing a toner, wherein the classification and the surface modification treatment are repeated by circulation to obtain toner particles or toner having fine particles removed and surface-modified.

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