JP2012171160A - Apparatus for heating powder particle and method of manufacturing powder particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an apparatus for heating a powder particle, which stably manufactures a large amount of spherical toner having excellent transferability and cleaning property.SOLUTION: The apparatus for heating the powder particle has: a cylindrical treatment chamber where the powder particle is heated; a raw material supply means 30 for supplying the powder particle into the treatment chamber from one end of the cylindrical shape; a diffusion means 400 for diffusing the powder particle from the raw material supply means to the inside of the treatment chamber; a hot air supply means 100 for supplying hot air into the treatment chamber from the same end part side as the raw material supply means; a means for regulating the flow of the powder particle supplied to the treatment chamber; a cooling means 200 for cooling the powder particle heated powder particle; and a means 300 for recovering the heated powder particle from the other end of the cylindrical shape. A powder particle diffusion means has a rotary body, and the hot air supply means supplies the hot air from the outer peripheral side of the diffusion means to make the hot air spirally flow, and the powder particle is supplied through the diffusion means to spirally flow and to be discharged.

Description

  The present invention relates to a heat treatment apparatus for powder particles and a method for producing powder particles, and relates to a powder for toner used in an image forming method such as an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or a toner jet recording method. It relates to spheroidization of body particles.

  In image forming methods such as electrophotography, electrostatic photography, and electrostatic printing, toner for developing an electrostatic charge image is used.

  In general, the toner production method uses as a raw material a binder resin for fixing to a transfer material, various colorants for producing a color as a toner, and a charge control agent for imparting electric charges to particles. Accordingly, for example, other additives such as a release agent and a fluidity-imparting agent are added. After mixing them, melt kneading and cooling and solidifying, the kneaded product is coarsely pulverized, and the resulting coarsely pulverized product is finely pulverized to obtain toner particles. There is a method for obtaining toner particles having a desired particle diameter using various classifiers as needed. Alternatively, a method of obtaining toner particles by suspending a toner composition dissolved in a solvent in water and then distilling off the solvent. A method of obtaining toner particles by adding another material such as a colorant to an emulsion obtained by emulsion polymerization and aggregating and associating the emulsion. Also, by dissolving or dispersing vinyl monomer, colorant, wax, etc. uniformly, granulating it in an aqueous medium and completing the suspension polymerization reaction, the toner particles are filtered, washed and dried. Various methods such as a method for obtaining toner particles can be employed.

  Furthermore, the obtained toner particles are added with a fluidizing agent, a lubricant, an abrasive or the like as necessary, and are dry-mixed to obtain a toner for image formation. In the case of a toner used in the two-component development method, various magnetic carriers and the above toner are mixed and then used for image formation.

  However, in recent years, with higher image quality and higher definition of copying machines, printers, etc., the performance required of toner as a developer has become more severe, the particle size of the toner has become smaller, There is a growing demand for sharp particles that do not contain coarse particles and have few ultrafine particles.

  In addition to the widespread use of color machines, as transfer materials, there are various materials such as plain paper and overhead projector films that have been used in the past, as well as thick paper such as glossy paper, cards, and small-size paper such as postcards. As a countermeasure, the transfer system using an intermediate transfer body on the main body side is increasingly used.

  Usually, in the transfer system using an intermediate transfer member, a visualized toner image is transferred from the image carrier to the intermediate transfer member, and then transferred from the intermediate transfer member to the transfer material. For toner, improvement in transfer efficiency is required.

  Further, there is a demand for speeding up of color copiers, and as a negative effect of improving the transferability of toner, removal (cleaning) of transfer residual toner remaining slightly on the electrostatic latent image carrier (photosensitive drum, belt, etc.) Care about is also necessary.

  As for the main body side, there is a method (cleanerless) in which residual toner is collected and reused without using a removing member (cleaning blade, roller, brush, etc.) Alternatively, the cleaning property is secured by increasing the contact pressure of the removal member to the photosensitive drum or the like.

  However, there is a limit to cleaner-less support in terms of faster copying machines and higher image quality. Further, when the contact pressure of the removing member is increased, the life of the member is shortened due to scratches and scrapes on the photosensitive drum and the like, which causes a problem in terms of low running cost.

  Through various studies so far, the transferability can be improved by making the toner spherical. Further, the cleaning property can be improved by changing the shape of the toner. That is, when the transferability and the cleaning property are determined by the shape of the toner, there is a point of improvement in the opposite directionality.

  Known methods for spheroidizing toner include, for example, polymerizing toner such as suspension polymerization and emulsion polymerization, and spheroidizing a pulverized toner. However, in the case of having an existing pulverization toner plant, a new toner plant is required to produce the polymerized toner. Furthermore, problems such as fixability and developability other than transferability may occur due to restrictions on material selection due to the polymerization method and the inclusion state of the additive material in the manufacturing process.

  In addition, in the case of the method of spheroidizing by mechanical impact treatment, it is easy to add a processing device to an existing line, but it is difficult to improve the spheroidization of the toner itself, which causes a problem in terms of productivity. May occur.

  Under such circumstances, an apparatus and a method for spheroidizing toner with hot air have been proposed (Patent Documents 1 and 2). The apparatus of Patent Document 1 suppresses fusion caused by heating of particles by installing a dispersion target for the purpose of dispersing the toner in the vicinity of the outlet of the toner supply unit. In order to prevent coalescence of the particles after heating, the device of Patent Document 2 performs treatment by placing the toner placed on the swirl flow on the hot air swirl flow provided on the outer periphery, thereby processing the particles after heating. Is preventing.

  However, for scaling up to improve toner productivity, it is important to give uniform energy to each toner particle, and depending on the dispersion state of the toner itself in the apparatus, there is a problem with the spheroidizing process. May occur. Further, since it is premised on instantaneous processing at a high temperature, the processed toner has a high ratio of high circularity, which is problematic in terms of cleaning.

  As described above, various proposals have been made as to the method of spheroidizing the toner. In particular, the method and apparatus using hot air for the purpose of spheroidizing the toner produced by the pulverization method are versatile depending on the purpose. There is room for improvement.

The coarse particles, fine particles, and ultrafine particles in the powder particles (toner particles) described in the present specification are as follows.
Coarse particles: Particle group fine particles of about twice or more of the toner weight average diameter (D4): Particle group ultrafine particles of about ½ times or less of the toner weight average diameter (D4): measured by a flow type particle image analyzer 2 μm or less particles

JP 2004-276016 A Japanese Patent Publication No. 3-52858

  An object of the present invention is to provide a powder particle heat treatment apparatus and a powder particle manufacturing method capable of solving the above-described problems and obtaining a toner with higher definition and higher image quality.

  An object of the present invention is to provide a powder particle heat treatment apparatus and a powder particle manufacturing method capable of performing processing in accordance with performance required for toner.

  An object of the present invention is to provide a powder particle heat treatment apparatus and a powder particle manufacturing method capable of stably producing a large amount of a spherical toner having both transferability and cleanability.

  An object of the present invention is to provide a powder particle heat treatment apparatus and a powder particle manufacturing method that do not require a significant layout change in an existing manufacturing plant.

The present invention is an apparatus for heat-treating powder particles containing at least a binder resin and a colorant,
The heat treatment apparatus
(1) a cylindrical processing chamber in which heat treatment of powder particles is performed;
(2) Raw material supply means for supplying powder particles from one end of the cylindrical shape into the processing chamber;
(3) diffusion means for diffusing the powder particles supplied from the raw material supply means into the processing chamber;
(4) hot air supply means for supplying hot air into the processing chamber from the same end side as the raw material supply means;
(5) means for regulating the flow of the supplied powder particles provided in the processing chamber;
(6) a cooling means for cooling the heat-treated powder particles,
(7) means for recovering the heat-treated powder particles from the other end side of the cylindrical shape;
Having at least
The raw material supply means is provided on the central axis of a cylindrical processing chamber, the powder particle diffusion means has at least a rotating body, and the hot air supply means is hot air from the outer peripheral side of the diffusion means. Is supplied to the processing chamber so as to flow spirally,
The present invention relates to a heat treatment apparatus for powder particles, wherein the powder particles are supplied and discharged through the diffusion means so as to flow spirally in a processing chamber.

Further, the present invention provides a method for producing powder particles having a weight average particle diameter (D4) of 3 to 11 μm, comprising at least a step of heat-treating the powder particles containing at least a binder resin and a colorant.
The heat treatment step
(1) a cylindrical processing chamber in which heat treatment of powder particles is performed;
(2) a raw material supply step of supplying powder particles from one end of the cylindrical shape into the processing chamber;
(3) a diffusion step of diffusing the powder particles supplied from the raw material supply step into the processing chamber;
(4) a hot air supply step for supplying hot air into the processing chamber from the same end side as the raw material supply step;
(5) a step for regulating the flow of the supplied powder particles provided in the processing chamber;
(6) cooling the heat-treated powder particles;
(7) recovering the heat-treated powder particles from the other end side of the cylindrical shape;
Having at least
The raw material supply step is provided on the central axis of a cylindrical processing chamber, the powder particle diffusion step uses at least a rotating body, and the hot air supply step generates hot air from the outer peripheral side of the diffusion step. It is supplied into the processing chamber so as to flow spirally,
The present invention relates to a method for producing powder particles, wherein the powder particles are supplied and discharged so as to flow spirally in a processing chamber through the diffusion step.

  According to the present invention, even when the toner is spheroidized by the heat treatment method, it is possible to maintain a uniform processing state and achieve both transferability and cleaning property regardless of the amount of processing.

It is a flowchart which shows an example at the time of introducing the heat processing apparatus of this invention. It is the schematic which shows an example of a hot air supply means. It is explanatory drawing which shows an example of a cold wind supply means. It is explanatory drawing which shows an example of a cold wind supply means. It is a figure which shows the example at the time of providing four introduction parts in a cold wind supply means. It is sectional drawing which showed an example of the heat processing apparatus by this invention. It is explanatory drawing of the powder particle diffusion means in the heat processing apparatus. It is the schematic of the heat processing apparatus of a comparative example.

  For the purpose of controlling the sphericity of the toner, which is a resin powder particle, as a result of research on a toner manufacturing apparatus using heat treatment, in order to increase the productivity of the toner manufacturing apparatus, It is important to suppress the coalescence phenomenon such as sticking or fusion that occurs. Furthermore, it was determined that it is important for the toner manufacturing apparatus to uniformly disperse the toner itself before the treatment and to control the temperature distribution in the apparatus.

  Many proposals have been made in the past regarding the uniform dispersion of toner. One method is to uniformly disperse toner in the apparatus using a rotating body (Japanese Patent Laid-Open No. 2009-20386). However, when considering application to the main body, as described above, particularly for toner for high-speed color copiers, there is a large difference between the circularity for improving transferability and the toner shape for maintaining cleaning properties. The present invention has been reached by further research on the above.

  That is, the present invention enables heat treatment that achieves a toner average circularity that improves transferability and does not increase the ratio of high-circularity products that deteriorate the cleaning performance.

  Specifically, the toner has a weight average particle diameter of 3 to 11 μm, but in order to ensure good transferability, the average circularity of the heat-treated toner or toner particles is 0.960 or more. Is preferred. Furthermore, it is preferably 0.965 or more. Further, when considering the use of a cleaning member such as a blade to deal with the main body that removes residual toner from the photosensitive member, it is preferable to lower the particle content with a circularity of 0.990 or more. More preferably, the increase in the particle content of 0.990 or more is slow as the average circularity increases.

  Next, the configuration of a preferable apparatus for achieving the object in the present invention will be described in detail below.

  First, the flow when this apparatus is introduced will be described. FIG. 1 is a flow chart showing one example when a toner production apparatus according to the present invention is introduced.

  The raw material stocker (1) is filled with powder particles (toner particles) or toner prepared by various production methods according to the purpose of the treatment, and the toner particle heat treatment device (3) is supplied by a quantitative feeder (2). To be introduced into the powder introduction tube. At this time, the airflow is introduced from the airflow supply device (9) into the powder introduction tube to the toner manufacturing apparatus (3). The toner particles or toner accelerated by the air flow is supplied to the powder diffusion rotating body from the outlet of the powder introduction tube, and is dispersed while receiving centrifugal force into the apparatus by the rotating body.

  Alternatively, a powder introduction tube is formed in the vertical direction on the upper part of the rotating body, and toner particles or toner is directly supplied from the metering feeder to the powder introduction tube, and from a powder supply means (30 in FIG. 3) described later. The powder is supplied to the powder diffusing means (400 in FIG. 4), and dispersed by the rotating body while receiving centrifugal force in the apparatus.

At this time, dehumidified compressed air or N ₂ gas can be used as the air flow. The temperature of the introduced airflow is not more than the toner Tg, preferably Tg minus 10 ° C. or less, more preferably Tg minus 20 ° C. or less. If the temperature of the airflow itself used for the airflow is higher than the Tg of the toner, fusion may occur in the powder introduction tube, the outlet, the inside of the apparatus, and the like, which may cause a problem in the stability of the apparatus.

  At this time, the rotating body rotates in the same direction as the hot air at a rotational peripheral speed of 2.5 m / s to 25.0 m / s, preferably at a rotational peripheral speed of 4.1 m / s to 20.0 m / s. Yes.

  When the rotational peripheral speed is less than 2.5 m / s, even if the dispersion of the particles is sufficient, the toner particles or toner ejected from the rotating body may not be placed on the swirling of the hot air described below, and uniform processing In some cases, there is no effect in terms of preventing coalescence and suppressing the high circularity ratio.

  When the rotational peripheral speed is more than 25.0 m / s, the toner particles or toner ejected from the rotating body is not placed on the hot air rotation described below even if the dispersion of the particles is sufficient, or the rotating body The swirl that is caused by itself disturbs the swirl of the hot air, thereby creating a turbulent flow, which may not be effective in terms of uniform processing, prevention of coalescence, and suppression of the high circularity ratio.

  An example of the hot air supply means (100) for introducing the hot air supplied from the hot air supply machine (10) into the apparatus is shown in FIG.

  The hot air supply means (100) is annularly provided at a distance from the outer periphery of the raw material supply means. This is a measure for preventing the toner from fusing to the rotating body when the powder diffusion rotating body is directly heated by the hot air and heated.

  The hot air supply means (100) is provided with an air flow adjusting unit (100A) for supplying hot air so that the hot air is inclined and swirled into the processing chamber, and is configured by a plurality of plate-like louvers.

  The angle of the louver was arbitrarily adjustable depending on the object to be processed. Specifically, the angle between the louver and the angle formed by the louver and the vertical direction is preferably in the range of 20 degrees to 70 degrees. A more preferable range is 30 degrees or more and 60 degrees or less.

  When the angle is less than 20 degrees, swirling of hot air in the processing chamber is weakened, and generation of coalesced particles may not be suppressed when the processing amount is increased. Furthermore, the frequency of occurrence of high circularity products may increase.

  Further, when the angle exceeds 70 degrees, the swirl of hot air in the processing chamber is strengthened, but the temperature near the upper part of the apparatus, that is, the diffusion rotating member may rise, and fusion may occur.

  The hot air introduced from the hot air supply means (100) is 100 ° C. or higher and 450 ° C. or lower. However, when the purpose is to achieve both transferability and cleanability as in the present invention, the temperature is preferably 140 ° C. or higher and 250 ° C. or lower.

  When the temperature is lower than 140 ° C., sufficient heat history cannot be received in the processing apparatus, and toner particles or toner that can be discharged without shape control may increase dramatically.

  When the temperature exceeds 250 ° C., depending on the amount of treatment and the residence time in the apparatus, the occurrence frequency of high circularity products may increase.

  An example of the cold air supply means (200) for introducing the cold air supplied from the air flow supply device (11) into the apparatus is shown in FIGS.

  Powder that has been adjusted to receive arbitrary thermal energy by supplying cold air from the upper part of the apparatus and / or the side of the apparatus from the cooling means (11), and then heat-treated from the other end side of the cylindrical shape The particles are sucked and transported to the collecting device (4) through the means (12) for collecting the particles.

  As shown in FIG. 3, when the cold air supply means (200-1) is provided on the outer periphery of the hot air supply means (100), an air flow adjusting unit for supplying the cold air to be inclined and swirled into the processing chamber ( 200A), and is composed of a plurality of plate-like louvers.

  The angle of the louver was arbitrarily adjustable depending on the object to be processed. Specifically, the angle of the louver is preferably in a range where the angle between the vertical direction and the louver is 20 degrees or more and 70 degrees or less. A more preferable range is 30 degrees or more and 60 degrees or less.

  When the angle is less than 20 degrees, the swirl of the cold air in the processing chamber is weakened, and the generation of coalesced particles may not be suppressed when the processing amount is increased. Furthermore, the frequency of occurrence of high circularity products may increase.

  In addition, when the angle exceeds 70 degrees, the swirl of the cold air in the processing chamber is strengthened, but the turbulent flow is generated between the hot air in the upper part of the apparatus and the swirl flow generated by the rotating body, and is fused to the apparatus top plate. May occur or it may become impossible to control a high circularity product.

  Further, when KA is the louver angle provided in the hot air supply means and KB is the louver angle provided in the cold air supply means, the outward turning force is stronger when KA ≦ KB, and the supplied toner or Toner particles can be processed in a wide range.

  Further, when the cold air supply means (200-2) and / or (200-3) is provided on the side of the apparatus as shown in FIG. 4, the introduction part into the toner manufacturing apparatus has a slit shape or a louver shape. Design with a mesh shape or the like is possible. The cold air is along the wall surface of the apparatus so as to be in the same direction as the swirling direction of the hot air.

  Furthermore, as shown in FIG. 5, the cold air supply means may be provided with four gas introduction portions on the same peripheral surface.

  The gas introduced from the air flow feeder (11) is dehumidified, and the temperature is preferably −30 ° C. or higher and 60 ° C. or lower, more preferably −20 ° C. or higher and 20 ° C. or lower. If the temperature itself is too high or too low, excessive energy may be required for the heat treatment, and further, the treatment itself may be non-uniform.

  One or more recovery means (300 in FIG. 6) are provided at the lower part of the apparatus, and one or more recovery means are provided so as to be drawn in the same direction with respect to the spiral flow of toner or toner particles.

  In the recovery device (4), the target powder is recovered to the product stocker (5) via a pipe and / or a damper, a double damper, a rotary valve and the like provided in the lower portion of the recovery device (4). The powder that has not been collected by the collection device is collected by a filter cloth or the like provided in the bag (6) and collected in the bug stocker (7). The collected bug powder can be reused.

  Next, a heat treatment apparatus for powder particles (toner particles) will be described.

  FIG. 6 is a sectional view showing an example of a heat treatment apparatus according to the present invention. The outer periphery of the apparatus is designed with a maximum diameter of 500 mm and a height from the bottom surface of the lower apparatus to the top plate (powder introduction pipe outlet) of approximately 1200 mm.

  In addition, the range of the apparatus structure and operating conditions described below is based on the case where the apparatus scale is used.

  A cooling jacket (60) is provided on the outer periphery of the apparatus, and a 5 ° C. refrigerant flows at 2.0 l / min or more. The diffusing rotator installed from the bottom of the center of the apparatus under the toner supply unit outlet has a cooling jacket (60-1) covering the shaft for connecting the rotator and the rotator driving unit. Also in the cooling jacket, a 5 ° C. refrigerant flows at 2.0 l / min or more. The diffusion rotating body will be described later.

The apparatus top plate (toner supply surface) is provided with a supply section for supplying toner onto the central axis of the processing chamber, and a hot air provided with a restricting means for swirling the hot air into the apparatus at a position close to the outer periphery of the supply section. It has a supply section. From the hot air supply means, hot air of 100 ° C. or more and 450 ° C. or less is supplied into the apparatus at 5 m ³ / min or more and 20 m ³ / min or less.

Cooling air for cooling is provided in four directions from a side surface approximately 150 mm below the apparatus top plate, and is introduced from the cold air supply means (200-2) so as to be in the same direction as the swirling direction of hot air. It is preferable that the cold air supply means (200-2) introduction position is a position below 50 mm and 300 mm or less below the top plate. From the cold air supply means (200-2), a total amount of cold air of −20 ° C. or more and 50 ° C. or less is supplied into the apparatus at 2 m ³ / min or more and 10 m ³ / min or less.

Furthermore, the cooling air is introduced from the cold air supply means (200-3) provided in four directions from the lower side surface of the apparatus top plate by about 700 mm so as to be in the same direction as the hot air swirling direction. The cold air supply means (200-3) introduction position is preferably a position below 400 mm and below 1000 mm below the top plate. Further, from the cold air supply means (200-3), the cold air of −30 ° C. or more and 20 ° C. or less is supplied into the apparatus at a total amount of 2 m ³ / min or more and 10 m ³ / min or less.

  When the apparatus is operated under the above-described configuration and conditions, the toner or toner particles supplied from the toner supply unit to the diffusion rotator are dispersed while receiving a turning force uniformly in the outer circumferential direction of the apparatus by the rotational force of the rotator. The dispersed toner or toner particles are placed on the swirl flow of hot air swirled and introduced into the apparatus from the hot sphere supply means provided on the outer periphery of the supply unit, and are carried downward in a spiral manner in the apparatus. At this time, the temperature distribution in the apparatus is controlled so that the supplied toner has an arbitrary circularity and a high circularity ratio by the cold air introduced from the lower side of the top plate.

When the average circularity after the treatment is 0.970 or more and the ratio of high circularity (circularity 0.990 or more) is reduced, the temperature of the hot air needs to be 200 ° C. or less and the amount of introduced air must be 10 m ³ / min or more. is there. At this time, the cold air may have the same temperature and the same air volume for both the introducing means (200-2) and (200-3), but the higher the top side cold air temperature and the lower the discharge side cold air temperature, the higher It is easy to adjust the circularity (roundness 0.990 or more) ratio.

  In addition, when both the general average circularity and high circularity ratio after processing are to be increased, the hot air temperature is increased, the air volume is decreased, the cold air temperature is decreased, and the air volume is increased. It can be adjusted.

  The toner or toner particles that have undergone the above-described processing are discharged out of the system in the same direction as the flow in the apparatus from the collecting means provided on the lower side surface of the apparatus.

  Next, the powder particle diffusing means equipped in the toner manufacturing apparatus will be described.

  FIG. 7 is a sectional view showing an example of the powder particle diffusing means when the rotating member is held from the lower part of the apparatus to the outlet of the powder introduction pipe according to the present invention.

  The diffusion means (400) used in this apparatus had a diameter of 160 mm. The diffusion means (400) is held by a cylindrical shaft (402) (Φ10 mm), a shaft guide (403) (Φ20 mm), and a jacket (60-1) (Φ50 mm) extending from the rotational drive power motor (401). On a disk, it is comprised from the rotary disk which distribute | arranged the braid | blade of thickness 0.1mm or more and 3mm or less on the outer periphery to the space | interval of the braid | blade adjacent to 0.5 mm or more and 50mm or less.

  Further, the jacket (60-1) on the outer periphery of the shaft guide can be used as a means for regulating the flow of the powder particles. When this specification is also used, it is preferable to make the outer diameter of the jacket (60-1) equal to the outer diameter of the rotator for diffusion.

  The diameter of the powder introduction port provided at the upper part of the rotating disk is substantially equal to the diameter of the powder introducing pipe outlet, and the outer periphery of the rotating disk is substantially equal to the outer periphery of the air flow E supply zone (111). A conical introduction member (404) is placed on the disk for the purpose of urging the introduced powder outward.

  The toner particles or toner supplied from the powder inlet is urged to the outer periphery by the introduction member (404) and is rotated by the rotation drive motor (401) to rotate at a peripheral speed of 2.0 m / s to 25.0 m / s. It is supplied to the inside of the apparatus through the gap between the plate blades provided in the means (400). At this time, when the peripheral speed of the rotating body is less than 2.0 m / s, the supplied toner particles or toner may not be placed on the swirling flow of hot air supplied to the outer periphery. Further, when the peripheral speed exceeds 25.0 m / s, the fluid behavior in the apparatus may become unstable due to the swirling flow from the rotating means.

  Further, in the present invention, a member used for the inner surface of the powder fluid acceleration means and / or the diffusing means and the introducing means is formed with a chromium alloy plating containing at least chromium carbide after forming a number of uneven surfaces on at least the surface. A coating may be applied. In some cases, the coating prevents the inner surface of the powder fluid accelerating means from adhering to the diffusing member and the introducing member, thereby further exerting the effect of making it difficult to form the aggregate in the apparatus.

  Further, a diffusion member having at least a plurality of holes at the outlet of the powder fluid acceleration means of the present apparatus can be additionally used. The diffusion member may exert an effect of loosening the agglomerates before the powder is supplied to the rotating body that is the introduction means or the diffusion means.

  Next, a preferable toner configuration for achieving the object in the present invention will be described in detail below.

  Examples of the binder resin used in the present invention include vinyl resins, polyester resins, and epoxy resins. Of these, vinyl resins and polyester resins are more preferable in terms of chargeability and fixability. In particular, when a polyester resin is used, the effect of introducing this apparatus is great.

  In the present invention, vinyl monomer monopolymer or copolymer, polyester, polyurethane, epoxy resin, polyvinyl butyral, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic Petroleum resin or the like can be mixed with the above-described binder resin as necessary.

  When two or more kinds of resins are mixed and used as a binder resin, it is preferable that those having different molecular weights are mixed in an appropriate ratio as a more preferable form.

  The glass transition temperature of the binder resin is preferably 45 to 80 ° C., more preferably 55 to 70 ° C., the number average molecular weight (Mn) is 2,500 to 50,000, and the weight average molecular weight (Mw) is 10,000. It is preferable to be 1,000,000.

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

  In the polyester resin, 45 to 55 mol% of all components is an alcohol component, and 55 to 45 mol% is an acid component.

  The acid value of the polyester resin is preferably 90 mgKOH / g or less, more preferably 50 mgKOH / g or less, and the OH value is preferably 50 mgKOH / g or less, more preferably 30 mgKOH / g or less. This is because as the number of terminal groups of the molecular chain increases, the dependency of the toner on the environment increases in the environment.

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

  When the toner of the present invention is used as a magnetic toner, the magnetic material contained in the magnetic toner includes iron oxides such as magnetite, maghemite and ferrite, and iron oxides including other metal oxides; Fe, Co, Ni, etc. Metals or alloys of these metals with metals such as Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W, V , And mixtures thereof.

Specifically, examples of magnetic materials include triiron tetroxide (Fe ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), iron oxide zinc (ZnFe ₂ O ₄ ), and iron yttrium oxide (Y ₃ Fe). ₅ O ₁₂ ), 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 ), barium iron oxide (BaFe ₁₂ O ₁₉ ), magnesium iron oxide (MgFe ₂ O ₄ ), manganese iron oxide (MnFe ₂ O ₄ ), iron lanthanum oxide (LaFeO ₃ ), iron powder (Fe), cobalt powder (Co), nickel powder (Ni) and the like. 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 may be used in an amount of 20 to 150 parts by mass, preferably 50 to 130 parts by mass, and more preferably 60 to 120 parts by mass with respect to 100 parts by mass of the binder resin.

  The following are mentioned as a nonmagnetic coloring agent used by this invention.

  Examples of the black colorant include carbon black; those adjusted to black using a yellow colorant, a magenta colorant, and a cyan colorant.

  Examples of the color pigment for magenta toner include the following. Examples include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 150, 163, 166, 169, 177, 184, 185, 202, 206, 207, 209, 220, 221, 238, 254, 269; I. Pigment violet 19, C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35 are mentioned.

  The colorant may be used alone as a pigment, but it is preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together.

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

  Examples of the color pigment for cyan toner include the following. C. I. Pigment Blue 1, 2, 3, 7, 15: 2, 15: 3, 15: 4, 16, 17, 60, 62, 66; I. Bat Blue 6, C.I. I. Acid Blue 45, a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyls are substituted on the phthalocyanine skeleton.

  Examples of the color pigment for yellow include the following. Condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal compounds, methine compounds, allylamide compounds. Specifically, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 155, 168, 174, 180, 181, 185, 191; I. Bat yellow 1, 3, and 20 are mentioned. In addition, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I. I. Dyes such as Basic Green 6 and Solvent Yellow 162 can also be used.

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

  When a colorant is mixed with the binder resin to make a master batch, even if a large amount of colorant is used, the dispersibility of the colorant is not deteriorated, and the dispersibility of the colorant in the toner particles is improved. Excellent color reproducibility such as color mixing and transparency. Further, a toner having a large covering power on the transfer material can be obtained. Further, since the dispersibility of the colorant is improved, it is possible to obtain an image having excellent durability stability of toner chargeability and maintaining high image quality.

  The amount of the colorant used is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and most preferably 3 to 15 parts by mass with respect to 100 parts by mass of the binder resin. is there.

  In the toner of the present invention, a charge control agent can be used as necessary in order to further stabilize the chargeability. The charge control agent is preferably used in an amount of 0.5 to 10 parts by mass per 100 parts by mass of the binder resin. When the amount is less than 0.5 parts by mass, sufficient charging characteristics may not be obtained, which is not preferable. When the amount exceeds 10 parts by mass, compatibility with other materials is deteriorated or charging is performed under low humidity. It may be excessive, which is not preferable.

  Examples of the charge control agent 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 include monoazo 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.

  Examples of the positive charge control agent for controlling the toner to be positively charged include modified products such as nigrosine and fatty acid metal salts, tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate and the like. As onium salts such as quaternary ammonium salts and their analogs such as phosphonium salts and their chelating pigments, triphenylmethane dyes and their lake pigments (as rake agents are phosphotungstic acid, phosphomolybdic acid, phosphotungsten) Molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanic acid, ferrocyanic compound, etc.), diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide and dibutyltin as metal salts of higher fatty acids , Dioctyl tin borate include diorgano tin borate such as dicyclohexyl tin borate.

  In the present invention, if necessary, one or more release agents may be contained in the toner particles. Examples of the release agent include the following.

  Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, paraffin wax, and the like, or oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof; And waxes mainly composed of fatty acid esters such as wax, sazol wax and montanic acid ester wax; and those obtained by partially or fully deoxidizing fatty acid esters such as deoxidized carnauba wax. Further, saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and valinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, and seryl alcohol Saturated alcohols such as melyl alcohol; long-chain alkyl alcohols; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylene bis stearic acid amide, ethylene biscaprin Saturated fatty acid bisamides such as acid amide, ethylene bislauric acid amide, hexamethylene bis stearic acid amide; ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N′-dioleyl Unsaturated fatty acid amides such as dipinamide, N, N-dioleyl sebacic acid amide; aromatic bisamides such as m-xylenebisstearic acid amide, N, N-distearylisophthalic acid amide; calcium stearate, laur Grafted with fatty acid metal salts such as calcium phosphate, zinc stearate, magnesium stearate (generally called metal soap), and aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid. Examples of waxes include partially esterified products of fatty acids such as behenic acid monoglyceride and polyhydric alcohols, and methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable oils and the like.

  The amount of the release agent is 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, per 100 parts by mass of the binder resin.

  The melting point of the releasing agent defined by the maximum endothermic peak temperature at the time of temperature rise measured by a differential scanning calorimeter (DSC) is preferably 65 to 130 ° C. More preferably, it is 80 to 125 ° C. If the melting point is less than 65 ° C., the viscosity of the toner decreases and toner adhesion to the photoreceptor is likely to occur. If the melting point exceeds 130 ° C., the low-temperature fixability may deteriorate, which is not preferable. .

  In the toner of the present invention, a fine powder that can be increased by adding the toner particles externally before and after the addition may be used as a fluidity improver. For example, fluorine resin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; wet production silica, fine powder silica such as dry production silica, fine powder titanium oxide, fine powder alumina, etc., silane coupling agent, titanium It is particularly preferable that the surface treatment is performed with a coupling agent and silicone oil, and the surface is hydrophobized, and the surface is hydrophobized as measured by a methanol titration test so as to show a value in the range of 30 to 80.

A fluidizing agent having a specific surface area by nitrogen adsorption measured by the BET method of 30 m ² / g or more, preferably 50 m ² / g or more gives good results.

  In addition to the polishing effect, the toner of the present invention may contain inorganic fine powders other than those described above as chargeability and fluidity imparting and cleaning aids. By adding the inorganic fine powder externally to the toner particles, the effect can be increased more than before and after the addition. Examples of the inorganic fine powder used in the present invention include titanates and / or silicates such as magnesium, zinc, cobalt, manganese, strontium, cerium, calcium, and barium.

  The inorganic fine particles in the present invention are used in an amount of 0.1 to 10 parts by weight, preferably 0.2 to 8 parts by weight, based on 100 parts by weight of the toner.

  The toner of the present invention can be used as a magnetic one component, a non-magnetic one component, or a two-component mixed with a carrier, but in order to achieve the effect of the present invention, it can be mixed with a magnetic carrier and used as a two-component. It is preferably used as a system developer.

  Examples of the magnetic carrier include iron powder whose surface is oxidized, non-oxidized iron powder, metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, rare earth, and the like Magnetic material-dispersed resin carriers (so-called resin carriers) containing magnetic materials such as alloy particles, oxide particles, and ferrite, and magnetic materials and binder resins that hold the magnetic materials in a dispersed state Can be used.

  When the toner of the present invention is mixed with a magnetic carrier and used as a two-component developer, the carrier mixing ratio at that time is 2% by mass to 15% by mass, preferably 4% as the toner concentration in the developer. When the content is from 13% by weight to 13% by weight, good results are usually obtained. If the toner concentration is less than 2% by mass, the image density tends to decrease, and if it exceeds 15% by mass, fogging or in-machine scattering tends to occur.

  Next, a method for measuring various physical property data measured in the following examples will be described below.

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

<Measuring method of weight average particle diameter (D4) and number average particle diameter (D1)>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are measured by a fine particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, Beckman 2) Effective measurement channel number 25,000 using “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) and attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” for measurement condition setting and measurement data analysis Measurement was performed on the channel, and the measurement data was analyzed and calculated.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, dedicated software was set up as follows.

  In the “Standard Measurement Method (SOM) Change Screen” of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked.

  In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

  The specific measurement method is as follows.

  (1) About 200 ml of the electrolytic aqueous solution is put in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rotations / second. Then, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.

  (2) About 30 ml of the electrolytic aqueous solution is put in a glass 100 ml flat bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder pH 7 precision measurement is used as a dispersant therein. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing a vessel (made by Wako Pure Chemical Industries, Ltd.) 3 times with ion-exchanged water is added.

  (3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and placed in a water tank of an ultrasonic dispersion device “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W. A fixed amount of ion-exchanged water is added, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.

  (4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.

  (5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.

  (6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . The measurement is performed until the number of measured particles reaches 50,000.

  (7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. When the graph / volume% is set with the dedicated software, the “average diameter” on the analysis / volume statistics (arithmetic average) screen is the weight average particle size (D4), and the graph / number% is set with the dedicated software. The “average diameter” on the analysis / number statistic (arithmetic average) screen is the number average particle diameter (D1).

<Calculation method of fine powder amount>
The number-based fine powder amount (number%) in the toner is calculated as follows. For example, the number% of particles having a particle size of 4.0 μm or less in the toner is measured by the above-mentioned Multisizer 3, and (1) graph / number% is set with dedicated software, and the measurement result chart is displayed in number%. (2) Check “<” in the particle size setting portion on the format / particle size / particle size statistics screen, and enter “4” in the particle size input section below. Then, (3) when the analysis / count statistics (arithmetic mean) screen is displayed, the numerical value of the “<4 μm” display portion is the number% of particles of 4.0 μm or less in the toner.

<Calculation method of coarse powder amount>
The volume-based coarse powder amount (volume%) in the toner is calculated as follows. For example, the volume% of particles of 10.0 μm or more in the toner is measured by the above-mentioned Multisizer 3, and (1) graph / volume% is set with dedicated software, and the measurement result chart is displayed as volume%. (2) Check “>” in the particle size setting portion on the format / particle size / particle size statistics screen, and enter “10” in the particle size input section below. (3) When the analysis / volume statistics (arithmetic average) screen is displayed, the numerical value of the “> 10 μm” display portion is the volume% of particles of 10.0 μm or more in the toner.

(2) Measurement of Average Circularity of Toner Particles The average circularity of toner particles was measured with a flow type particle image analyzer “FPIA-3000 type” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during calibration work.

  As a specific measurement method, 0.05 ml of a surfactant, preferably alkylbenzene sulfonate, is added to 20 ml of ion-exchanged water, and then 0.02 g of a measurement sample is added, and the oscillation frequency is 50 kHz, electrical output. Dispersion treatment was carried out for 2 minutes using a 150 W tabletop type ultrasonic cleaner / disperser (for example, “VS-150” (manufactured by VervoCrea Co., Ltd.)) to obtain a dispersion for measurement. It cools suitably so that temperature may become 10 to 40 degreeC.

  The flow type particle image analyzer equipped with a standard objective lens (10 ×) was used for the measurement, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion prepared in accordance with the above procedure is introduced into the flow type particle image analyzer, 3000 toner particles are measured in the total count mode in the HPF measurement mode, and the binarization threshold at the time of particle analysis is 85%. The analysis particle diameter was limited to a circle equivalent diameter of 2.00 μm or more and 200.00 μm or less, and the average circularity of the toner particles was obtained.

  In the measurement, automatic focus adjustment is performed using standard latex particles (for example, Duke Scientific 5200A diluted with ion-exchanged water) before the measurement is started. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.

  In this embodiment, a flow type particle image analyzer which has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, has an analysis particle diameter of 2.00 μm in equivalent circle diameter. The measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that it was limited to 200.00 μm or less.

(3) Melting | fusing point measurement of wax It measures using a differential thermal analysis measuring device (DSC measuring device) and DSC-7 (made by Perkin Elmer). The measurement is performed according to ASTM D3418-82. Precisely weigh 2 to 10 mg of measurement sample into an aluminum pan, and use an empty aluminum pan as a reference. I do. In this temperature raising process, an endothermic peak of a main peak in a temperature range of 30 to 200 ° C. is obtained. The temperature of this endothermic main peak is taken as the melting point of the wax.

(4) Measurement of glass transition temperature (Tg) Measured according to ASTM D3418-82 using a differential scanning calorimeter (DSC measuring device) and DSC-7 (manufactured by Perkin Elmer).

  The sample to be measured is precisely weighed from 5 to 20 mg, preferably 10 mg. This is put into an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rise rate of 10 ° C./min and normal temperature and humidity in a measurement temperature range of 30 to 200 ° C. In this temperature raising process, an endothermic peak of a main peak in a temperature range of 40 to 100 ° C. is obtained. At this time, the point of intersection between the base line midpoint before and after the endothermic peak and the differential heat curve is defined as the glass transition temperature Tg in the present invention.

(5) Measurement of molecular weight distribution of binder resin The molecular weight of the chromatogram by GPC is measured under the following conditions.

The column is stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 ml / min. The sample is dissolved in THF, filtered through a 0.2 μm filter, and the filtrate is used as a sample. Measurement is performed by injecting 50 to 200 μl of a THF sample solution of a resin adjusted to a sample concentration of 0.05 to 0.6 mass%. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Manufactured by Toyo Soda Kogyo Co., Ltd. and having molecular weights of 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3 .9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ are used, and it is appropriate to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

As a column, in order to accurately measure a molecular weight region of 10 ^{3 to} 2 × 10 ⁶ , it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, a combination of μ-styragels 500, 10 ³ , 10 ⁴ , and 10 ⁵ manufactured by Waters and a combination of shodex KA-801, 802, 803, 804, 805, 806, and 807 manufactured by Showa Denko are preferable.

(6) Measurement of acid value of resin The “acid value” of the binder resin is determined as follows. Basic operation conforms to JIS-K0070.

  The number of mg of potassium hydroxide required to neutralize free fatty acids, resin acids, etc. contained in 1 g of the sample is called the acid value, and the test is conducted as follows.

[1] Reagent (a) Solvent ethyl ether-ethyl alcohol mixture (1 + 1 or 2 + 1) or benzene-ethyl alcohol mixture (1 + 1 or 2 + 1), these solutions were subjected to N / 10 hydroxylation using phenolphthalein as an indicator just before use. Neutralize with potassium ethyl alcohol solution.
(B) Phenolphthalein solution 1 g of phenolphthalein is dissolved in 100 ml of ethyl alcohol (95 v / v%).
(C) N / 10 potassium hydroxide-ethyl alcohol solution Dissolve 7.0 g of potassium hydroxide in as little water as possible, add ethyl alcohol (95 v / v%) to 1 liter, leave it for 2 to 3 days, and filter. The standardization is performed according to JIS K 8006 (basic matters regarding titration during the reagent content test).

  [2] Operation Correctly weigh samples 1 to 20 g, add 100 ml of solvent and a few drops of phenolphthalein solution as an indicator, and shake well until the sample is completely dissolved. In the case of a solid sample, dissolve it by heating on a water bath. After cooling, this is titrated with an N / 10 potassium hydroxide ethyl alcohol solution, and the end point of neutralization is defined as the time when the indicator is slightly red for 30 seconds.

  [3] Calculation formula The acid value is calculated by the following formula.

［Ａ：酸価
Ｂ：Ｎ／１０水酸化カリウムエチルアルコール溶液の使用量（ｍｌ）
Ｃ：Ｎ／１０水酸化カリウムエチルアルコール溶液のファクター
Ｓ：試料（ｇ） ］

[A: acid value B: amount of N / 10 potassium hydroxide ethyl alcohol solution used (ml)
C: Factor of N / 10 potassium hydroxide ethyl alcohol solution S: Sample (g)]

(7) Measurement of hydroxyl value of binder resin The “hydroxyl value” of the binder resin is determined as follows. The basic operation conforms to JIS = K0070.

  When 1 g of a sample is acetylated by a prescribed method, the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group is referred to as a hydroxyl value, and the test is performed by the following reagents, operations and calculation formulas.

[1] Reagent (a) Acetylation reagent 25 g of acetic anhydride is placed in a 100 ml volumetric flask, pyridine is added to make a total volume of 100 ml, and shaken sufficiently (in some cases, pyridine may be added). The acetylating reagent should be kept away from moisture, carbon dioxide and acid vapors and stored in a brown bottle.
(B) Phenolphthalein solution 1 g of phenolphthalein is dissolved in 100 ml of ethyl alcohol (95 v / v%).
(C) N / 2 potassium hydroxide-ethyl alcohol solution Dissolve 35 g of potassium hydroxide in as little water as possible, add ethyl alcohol (95 v / v%) to 1 liter, leave it for 2 to 3 days, and filter. The orientation is performed according to JIS K 8006.

[2] Operation 0.5 to 2.0 g of a sample is correctly weighed in a round bottom flask, and 5 ml of an acetylating reagent is correctly added thereto. A small funnel is put on the mouth of the flask, and the bottom is immersed in a glycerin bath at 95 to 100 ° C. to heat the bottom. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, a cardboard disc with a round hole in it is put on the base of the neck of the flask. After 1 hour, the flask is removed from the bath, and after cooling, 1 ml of water is added from the funnel and shaken to decompose acetic anhydride. In order to further complete the decomposition, the flask was again heated in a glycerin bath for 10 minutes, allowed to cool, and then the funnel and the wall of the flask were washed with 5 ml of ethyl alcohol, and N / 2 potassium hydroxide ethyl alcohol using a phenolphthalein solution as an indicator. Titrate with solution. A blank test is performed in parallel with the main test. In some cases, a KOH-THF solution may be used as an indicator.

  [3] Calculation formula The hydroxyl value is calculated by the following formula.

［Ａ：水酸基価
Ｂ：空試験のＮ／２水酸化カリウムエチルアルコール溶液の使用量（ｍｌ）
Ｃ：本試験のＮ／２水酸化カリウムエチルアルコール溶液の使用量（ｍｌ）
ｆ：Ｎ／２水酸化カリウムエチルアルコール溶液のファクター
Ｓ：試料（ｇ）
Ｄ：酸価 ］

[A: Hydroxyl value B: Amount used of N / 2 potassium hydroxide ethyl alcohol solution in blank test (ml)
C: Amount of use of N / 2 potassium hydroxide ethyl alcohol solution in this test (ml)
f: Factor of N / 2 potassium hydroxide ethyl alcohol solution S: Sample (g)
D: Acid value]

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.

[Example 1]
<Manufacture of toner>
Binder resin (polyester resin): 100 parts by mass (Tg 58 ° C., acid value 25 mgKOH / g, hydroxyl value 20 mgKOH / g, molecular weight: Mp5500, Mn2800, Mw50000)
・ C. I. Pigment Blue 15: 3: 5 parts by mass, 1,4-di-t-butylsalicylic acid aluminum compound: 0.5 parts by mass, Fischer-Tropsch wax: 5 parts by mass (manufactured by Nippon Seiwa Co., Ltd., trade name FT-100, melting point) 98 ° C)
After mixing the materials of the above formulation with a Henschel mixer (FM-75J type, manufactured by Mitsui Mining Co., Ltd.), a twin-screw kneader (PCM-30 type, manufactured by Ikekai Steel Co., Ltd.) set at a temperature of 130 ° C. ) At a feed amount of 10 kg / hr (kneaded material temperature at the time of discharge was about 150 ° C.). The obtained kneaded product was cooled, coarsely crushed with a hammer mill, and then finely pulverized with a mechanical pulverizer (T-250: manufactured by Turbo Kogyo Co., Ltd.) with a feed amount of 15 kg / hr, and the weight average particle diameter Was a finely pulverized toner B-1 containing 55.6% by number of particles having a particle size of 4.0 μm or less and 0.8% by volume of particles having a particle size of 10.1 μm or more.

  The obtained finely pulverized toner B-1 was classified by cutting a fine powder and a coarse powder at a feed rate of 4.2 kg / hr with a rotary classifier (TTSP100, manufactured by Hosokawa Micron Co., Ltd.). Toner particles A-1 having a diameter of 5.6 μm, 25.6% by number of particles having a particle size of 4.0 μm or less, and 0.2% by volume of particles having a particle size of 10.1 μm or more were obtained.

  As a result of measuring the circularity of toner particle A-1 with FPIA 3000, the average circularity was 0.937, and the particle content of 2 μm or less was 11.0%.

Next, the toner particles A-1 were processed at a feed rate of 18.0 kg / hr in the configuration of FIG. 6 in the flow of FIG. 1 which is a toner manufacturing apparatus, to obtain toner particles C-1. . At this time, the rotating member as the diffusing means was rotated at a peripheral speed of 15.0 m / s as the outer peripheral plate blade type (blade thickness 1 mm, number of sheets 60) of FIG. In addition, the toner particle conveying injection air during operation of the apparatus is 25 ° C., 1.2 m ³ / min, and the hot air is passed through a rectifying blade (angle 50 °, blade thickness 1 mm, number of sheets 36 sheets) 150 ° C., 12.0 m. ³ / min, cold air from (200-2), 0 ° C., 2.0 m ³ / min, from (200-3), 0 ° C., 4.0 m ³ / min, blower air volume from 21.0 m ³ / min It was.

  The obtained toner particles C-1 have a weight average particle diameter of 5.8 μm, particles having a particle diameter of 4.0 μm or less are 24.3% by number, and particles having a particle diameter of 10.1 μm or more are 1.6% by volume. Met. Moreover, the average circularity measured by FPIA3000 was 0.970, and the content of particles having a circularity of 0.990 or more was 26.3%.

  Next, the obtained toner particles C-1 were subjected to coarse powder cutting using an ATP100 classifier manufactured by Hosokawa Micron, and 25.0% by number of particles having a weight average diameter of 5.6 μm and a particle diameter of 4.0 μm or less. Toner particles D-1 having 0.1% by volume of particles having a particle size of 10.1 μm or more were obtained. The average circularity measured by FPIA3000 was 0.971, and the content of particles having a circularity of 0.990 or more was 26.5%.

Anatase-type titanium oxide fine powder (BET specific surface area 80 m ² / g, treated with 12% by mass of isobutyltrimethoxysilane) 1.0 part by mass with respect to 100 parts by mass of the toner particles D-1 (cyan toner particles), oil treatment After externally adding 1.0 part by mass of silica fine particles (BET specific surface area 95 m ² / g, silicone oil 15% by mass treatment) with a Henschel mixer, coarse particles are removed with a vibration sieve on which # 200 mesh is placed. did.

  Next, 10 parts by mass of toner 1 is added to 90 parts by mass of the magnetic carrier 1 obtained by the following manufacturing method, and the mixture is mixed with a V-type mixer in an environment of normal temperature and normal humidity (23 ° C., 50% RH). This was designated as start developer T-1.

<Manufacture of magnetic fine particle dispersed resin core (A)>
3.5% by mass and 2.0% by mass of silane with respect to magnetite fine particles (specific resistance 5 × 10 ⁷ (Ω · cm)) and hematite fine particles (specific resistance 3 × 10 ⁸ (Ω · cm)), respectively. A system coupling agent (3- (2-aminoethylaminopropyl) trimethoxysilane) was added, and the mixture was stirred and mixed at a high speed at 120 ° C. or higher in a container to make each fine particle lipophilic.
-Phenol 10 parts by mass-Formaldehyde solution (formaldehyde 37% by weight aqueous solution) 6 parts by weight-74 parts by weight of the above treated magnetite fine particles-10 parts by weight of the above treated hematite fine particles The above materials, 5 parts by weight of 28% by weight ammonia water and water 10 parts by mass was placed in a flask, heated and maintained at 85 ° C. over 45 minutes with stirring and mixing, and cured by polymerization reaction for 3 hours. Thereafter, the mixture was cooled to 30 ° C., water was further added, the supernatant was removed, the precipitate was washed with water, and then air-dried. Next, this was dried under reduced pressure (5 hPa or less) at a temperature of 60 ° C. to obtain a magnetic fine particle dispersed resin core (A) in which magnetic fine particles were dispersed. The obtained magnetic fine particle dispersed resin core had a number average particle size of 35 μm and a BET specific surface area of 0.07 (m ² / g).

<Manufacture of magnetic carrier>
The above-mentioned magnetic fine particle dispersed resin core (A) was put into a coater, and humidified nitrogen was introduced to adjust the moisture content to 0.3% by mass. Thereafter, 3% by mass of γ-aminopropyltrimethoxysilane diluted with a toluene solvent was applied to the core surface while continuously applying a shear stress. This is carried out while volatilizing the solvent under a dry nitrogen stream, and a mixture of 0.5% by mass of straight silicone resin whose substituents are all methyl groups and 0.015% by mass of γ-aminopropyltrimethoxysilane is magnetically treated with toluene as a solvent. A fine particle dispersed resin core was coated. This was carried out while volatilizing the solvent under a dry nitrogen stream. Further, this magnetic coat carrier was baked at 140 ° C., and the aggregated coarse particles were cut with a 100 mesh sieve, and then fine particles and coarse particles were removed with a multi-division wind classifier to adjust the particle size distribution. The magnetic carrier was then conditioned for 100 hours in a hopper maintained at 23 ° C. and 60%.

(Evaluation-1): Transfer efficiency (transfer residual density)
Using start developer T-1, endurance image evaluation under normal temperature and low humidity (23 ° C, 5% RH) environment with Canon full color copier iRC5180 (modified to be compatible with sampling, etc.) (A4 horizontal, 10% printing ratio (20,000 sheets). At the initial stage of durability and after 20,000 sheets, a solid image (adjusted so that the amount of applied toner on the image is adjusted to 0.6 mg / cm ² ) is output, and the transfer residual toner on the photosensitive drum at the time of solid image formation is transferred to transparent polyester. The tape was peeled off with an adhesive tape made, and the tape was affixed to paper. Then, the density was measured using an X-Rite color reflection densitometer (500 series) to obtain a density G. After sticking only the transparent polyester adhesive tape on the same paper, the density was measured in the same manner as the density H. The transfer efficiency was judged according to the following evaluation criteria using the difference between the density G and the density H.

(Evaluation criteria)
A: Density difference Less than 0.05 B: Density difference 0.05 or more and less than 0.08 C: Density difference 0.08 or more and less than 0.15 D: Density difference 0.15 or more and less than 0.20 E: Density difference 0. 20 or more

(Evaluation-2): Cleaning property evaluation (solid white image stain)
A full-color copying machine iRC3580 made by Canon (cleaning blade contact pressure was reduced by 30%) was used using the starting developer T-1.

  In a high-temperature and high-humidity environment (30 ° C / 80% RH), 10 half-tone images with an image printing ratio of 100% are passed through 10 sheets of A4 paper, and then 10 images with a printing ratio of 0% are passed through. Evaluation was made by visually observing 10 images with a printing ratio of 0%.

(Evaluation criteria)
A: No dirt is generated (very good)
B: Dirt is generated on one or two sheets (good)
C: Dirt is generated on 3 to 5 sheets (no problem in the present invention)
D: Dirt is generated on 5 to 10 sheets. (Not acceptable in the present invention)

  From the results of Evaluations 1 and 2, when the toner manufacturing apparatus of the present case is used, the cleaning performance is not deteriorated even if the toner has high transferability. The physical properties and evaluation results of the toner particles are shown in Table 1, and the configuration and operating conditions of the toner production apparatus are shown in Tables 2 and 3.

[Examples 2 to 24]
In Example 1, evaluation toners T-2 to T-24 were obtained in the same manner except that the apparatus configuration was changed as shown in Table 2. Evaluations were made in the same manner as in Example 1, and the results shown in Table 1 were obtained. It was.

  In the preparation of the toner particles D-2 to D-24, the conditions of the rotary classifier are adjusted so that 22.5 particles having a weight average diameter of 5.4 μm to 5.6 μm and a particle diameter of 4.0 μm or less are obtained. Toner particles having a number% to 27.5% by number and particles having a particle diameter of 10.1 μm or more were 0.5% by volume or less.

  In Examples 5 and 6, the apparatus top plate was replaced with that shown in FIG.

[Examples 25 to 32]
In Example 1, toners for evaluation T-25 to T-32 were obtained in the same manner except that the apparatus operating conditions were changed as shown in Table 3. Evaluations were made in the same manner as in Example 1, and the results in Table 1 were obtained. Obtained.

[Comparative Example 1]
In Example 1, the heat treatment apparatus for toner was changed to that shown in FIG. 8 (apparatus disclosed in JP-A-2009-20386).

Processing was performed with a feed amount of 15.0 kg / hr to obtain toner particles E-1. At this time, the toner particle supply port into the apparatus has a circular shape of Φ25 mm. In addition, the toner particle conveying injection air during operation of the apparatus is 25 ° C., 1.2 m ³ / min, and the hot air is in a state where the rectifying blade is removed (801) to 260 ° C., 8.0 m ³ / min, and the cold air is ( 802) to 0 ° C., 2.0 m ³ / min, (803) to 0 ° C., 2.0 m ³ / min, (804) to 25 ° C., 5.0 m ³ / min, and blower air volume to 20. It was set to 0 m ³ / min.

  The obtained toner particles E-1 have a weight average particle size of 6.2 μm, 23.3% by number of particles having a particle size of 4.0 μm or less, and 3.6% by volume of particles having a particle size of 10.1 μm or more. Met. Further, the average circularity measured by FPIA3000 was 0.972, and the content of particles having a circularity of 0.990 or more was 35.7%.

  Next, the obtained toner particles E-1 were subjected to coarse powder cutting using an ATP100 classifier manufactured by Hosokawa Micron Corporation, and 23.8% by number of particles having a weight average diameter of 5.8 μm and a particle diameter of 4.0 μm or less, Toner particles F-1 having a particle size of 10.1 μm or more and 0.3% by volume were obtained. Further, the average circularity measured by FPIA3000 was 0.972, and the content of particles having a circularity of 0.990 or more was 35.8%.

  Using the toner particles F-1 obtained, evaluation toner T-33 was prepared and evaluated in the same manner as in Example 1. As a result, the transferability was C rank, but the cleaning performance was D rank. .

[Comparative Examples 2 to 5]
In Comparative Example 1, toner particles F-2 to F-5 were obtained in the same manner as in Comparative Example 1 except that the temperature of the hot air to be introduced was changed to 200 ° C., 230 ° C., 280 ° C., and 310 ° C. T-34 to T-37 were prepared and evaluated. The results in Table 1 were obtained.

  1 Raw material stocker, 2 Fixed amount feeder, 3 Heat treatment device (surface reformer), 4 Recovery device, 5 Product stocker, 6 Bug, 7 Bug stocker, 8 Blower, 9 Air flow feeder, 10 Air flow feeder, 11 Air flow supply Machine, 12 discharge section, 30 powder supply means, 60 cooling jacket, 100 hot air supply means, 100A air flow adjustment section, 200 cold air supply means, 200A air flow adjustment section, 200-1 cold air supply means, 200-2 cold air supply means, 200-3 Cold air supply means, 300 Recovery means, 400 Diffusion means, 401 Rotation motor, 402 Shaft, 403 Shaft guide, 800 Powder supply means, 801 Hot air supply means, 802 Cold air supply means, 803 Cold air supply means, 804 Conveyance Airflow supply means, 805 cooling jacket

Claims (5)

An apparatus for heat-treating powder particles containing at least a binder resin and a colorant,
The heat treatment apparatus
(1) a cylindrical processing chamber in which heat treatment of powder particles is performed;
(2) Raw material supply means for supplying powder particles from one end of the cylindrical shape into the processing chamber;
(3) diffusion means for diffusing the powder particles supplied from the raw material supply means into the processing chamber;
(4) hot air supply means for supplying hot air into the processing chamber from the same end side as the raw material supply means;
(5) means for regulating the flow of the supplied powder particles provided in the processing chamber;
(6) a cooling means for cooling the heat-treated powder particles,
(7) means for recovering the heat-treated powder particles from the other end side of the cylindrical shape;
Having at least
The raw material supply means is provided on the central axis of a cylindrical processing chamber, the powder particle diffusion means has at least a rotating body, and the hot air supply means is hot air from the outer peripheral side of the diffusion means. Is supplied to the processing chamber so as to flow spirally,
An apparatus for heat-treating powder particles, wherein the powder particles are supplied and discharged through the diffusion means so as to flow spirally in the processing chamber.   The hot air supply means is provided in an annular shape at a position close to or spaced from the outer periphery of the raw material supply means, and at the outlet of the hot air supply means, an air flow adjusting unit for turning hot air in the apparatus is provided. The heat treatment apparatus for powder particles according to claim 1, wherein   The means for regulating the flow of the powder particles is provided with a cylindrical shaft at the center of the apparatus, and a rotating body as the diffusing means is provided at the upper end of the shaft. The heat processing apparatus of the described powder particle.   The cooling means is provided at a position closer to the powder particle recovery means than the raw material supply means and the hot air supply means, has at least one gas introduction part from the outer periphery of the apparatus, and is introduced from the gas introduction part. The apparatus for heat treating powder particles according to any one of claims 1 to 3, further comprising an air flow adjusting unit for rotating the gas in the apparatus in the same direction as the hot air. In the method for producing powder particles having a weight average particle diameter (D4) of 3 to 11 μm, comprising at least a step of performing a heat treatment of the powder particles containing at least a binder resin and a colorant,
The heat treatment step
(1) a cylindrical processing chamber in which heat treatment of powder particles is performed;
(2) a raw material supply step of supplying powder particles from one end of the cylindrical shape into the processing chamber;
(3) a diffusion step of diffusing the powder particles supplied from the raw material supply step into the processing chamber;
(4) a hot air supply step for supplying hot air into the processing chamber from the same end side as the raw material supply step;
(5) a step for regulating the flow of the supplied powder particles provided in the processing chamber;
(6) cooling the heat-treated powder particles;
(7) recovering the heat-treated powder particles from the other end side of the cylindrical shape;
Having at least
The raw material supply step is provided on the central axis of a cylindrical processing chamber, the powder particle diffusion step uses at least a rotating body, and the hot air supply step generates hot air from the outer peripheral side of the diffusion step. It is supplied into the processing chamber so as to flow spirally,
A method for producing powder particles, wherein the powder particles are supplied and discharged so as to flow spirally in a processing chamber through the diffusion step.

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