JP2011237816A - Method for producing toner fine particle and mechanical pulverizing machine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing toner fine particles, for improving abrasion resistance of a pulverizing surface of a pulverizing machine and stably obtaining a desired grain size distribution for a long period of time.SOLUTION: The method for producing toner fine particles having a weight average particle diameter of from 3 to 11 μm includes steps of melting and kneading a mixture containing a binder resin and a colorant, cooling the obtained kneaded material, followed by coarsely pulverizing, and pulverizing a powder raw material comprising the coarsely pulverized material by a pulverizing means. In the method, the pulverizing means is a mechanical pulverizing machine including at least a rotor 314 as a rotating body and a stator 310 arranged as keeping a given gap from a rotor surface, and functions by keeping the gap. The rotor and/or the stator has a surface hardness A (Vickers hardness) in the range of HV1300<A≤HV1800, which is achieved by coating the surface of the rotor and/or the stator with a chromium alloy plating containing chromium carbide, and then subjecting to a mechanical surface treatment.

Description

  The present invention relates to a toner fine particle manufacturing method and a manufacturing apparatus used in an image forming method such as an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or a toner jet recording method.

  In an image forming method such as electrophotography, a toner for developing an electrostatic image is used. The toner production method is roughly classified into a pulverization method and a polymerization method, and a simple and popular production method includes a pulverization method. As a general manufacturing method thereof, a binder resin for fixing to a transfer material, a colorant for giving a color as a toner is used, and a charge control agent for imparting electric charges to particles as necessary, Add and mix magnetic materials for imparting transportability to the toner itself, additives such as release agents, fluidity imparting agents, etc., melt knead, cool and solidify, and then refine the kneaded material by pulverizing means If necessary, the toner is classified into a desired particle size distribution, or further added with a fluidizing agent or the like to provide 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.

  Various pulverizers are used as the pulverizing means, and a jet airflow pulverizer using a jet airflow as shown in FIG. 1, particularly a collision airflow pulverizer is often used. A collision type airflow crusher conveys powder raw material with a high-pressure gas such as a jet stream, injects it from the outlet of the acceleration tube, and collides with the collision surface of the collision member provided facing the opening surface of the outlet of the acceleration tube. The powder raw material is pulverized by the impact force.

  In the collision-type airflow crusher shown in FIG. 1, a collision member 164 is provided opposite to the outlet 163 of the acceleration tube 162 connected to the high-pressure gas supply nozzle 161, and the acceleration tube 162 is halfway through the high-pressure gas supplied to the acceleration tube 162. The pulverized raw material is sucked into the accelerating tube 162 from the pulverized raw material supply port 165 communicated with the pulverized raw material, and the pulverized raw material is jetted together with the high-pressure gas to collide with the collision surface 166 of the collision member 164. It is discharged from the pulverized product discharge port 167.

  However, the above collision type airflow pulverizer requires a large amount of air (compressed air) in order to produce toner having a small particle diameter. Therefore, power consumption is extremely high, and there is room for improvement in terms of energy costs. Particularly in recent years, there has been a demand for energy saving of devices in order to cope with environmental problems.

  On the other hand, a mechanical pulverizer shown in FIG. 2 has been proposed as a pulverizer that is energetically more efficient than a jet stream pulverizer (see, for example, Patent Document 1). This mechanical pulverizer pulverizes by introducing a powder raw material into an annular space formed between a rotor rotating at high speed and a stator arranged around the rotor. According to the mechanical pulverizer, since compressed air is not required, it can be finely pulverized with much less energy than the jet airflow pulverizer, and it is less excessively pulverized, so there is less generation of fine powder and the yield is improved. It becomes possible.

  Focusing on the shape of the toner particles pulverized by these pulverizers, the toner particles pulverized by the jet airflow pulverizer have an irregular and angular shape, and the toner particles pulverized by the mechanical pulverizer have corners. It is known that the shape is round and round. This is thought to be due to the difference in the grinding process. That is, in the pulverization method using a jet stream, most of the pulverization is performed by collision of particles or collision with a collision member. However, in a mechanical pulverizer, most of the pulverization is performed by a rotor that rotates at high speed. This is because the particles collide with the wall surface of the stator. In mechanical pulverization, heat is generated by pulverization, and the shape of the pulverized toner particles is considered to be rounded due to the effect of thermal spheroidization.

  For this reason, the toner particles pulverized by the mechanical pulverizer have a smaller specific surface area than the toner particles pulverized by the jet airflow pulverizer, so that the fluidity is improved. Moreover, since the space | gap at the time of filling with a container becomes small, there exists an advantage that the amount of filling is excellent, and also the addition amount of an external additive may be small. In addition, since the external additive functions effectively as a spacer, there are also merits in quality such as excellent transferability. That is, according to the mechanical pulverizer, it is possible to produce toner of excellent quality with energy saving and high yield.

  However, mechanical pulverizers such as high-speed rotary fine pulverizers wear the pulverizing surface of the pulverizer, i.e., the outer peripheral surface of the rotor and the inner peripheral surface of the stator, and the pulverizing ability decreases. There has been a problem that the quality of the pulverized product is changed or the reliability is lowered due to the mixing of the worn product.

  On the other hand, examples of the binder resin contained in the toner include styrene acrylic resins, polyester resins, and epoxy resins, and polyester resins are preferably used from the viewpoint of low-temperature fixability. However, the polyester resin is inferior in grindability at the time of toner production, and there is a problem that the rotational speed of the grinder must be increased or the processing amount must be reduced in order to obtain a desired particle size distribution.

  A magnetic toner having magnetic particles as a colorant is used as a one-component developer because of its density stability and convenience such as downsizing of the developing device. However, when the magnetic toner is pulverized by a mechanical pulverizer, the surface of the pulverized surface wears out much faster than the toner containing no magnetic substance. Along with this wear, the particle shape tends to be non-uniform, stable production becomes difficult, and the life of the rotor and stator is short, so the replacement frequency increases and the cost of the product increases.

  Therefore, in order to improve the wear resistance of the surfaces of the rotor and the stator, the base material is quenched, carburized, or nitrided. However, although this method increases the surface hardness, the cured layer is thin and processing at a high temperature may cause distortion and cracks. Abrasion was insufficient.

  In addition, a method has been proposed in which the surface of the base material of the rotor and the stator is lined with a titanium material to improve wear resistance (see, for example, Patent Document 2). Although this method has the advantage that the surface hardness is high, there is a problem that voids are easily generated between the base material surface and the surface treatment material during lining treatment, and peeling and cracking are likely to occur. However, there was a problem of high cost.

  Furthermore, although a ceramic material is spray-coated on the surface of the base material of the rotor and the stator, the coating layer is easily peeled off and the wear resistance is insufficient.

  On the other hand, a method of improving the wear resistance by coating the surfaces of the rotor and the stator with a chromium alloy containing chromium carbide has been proposed (for example, Patent Document 3). In this method, the abrasion resistance of the pulverized surface is improved and the replacement frequency of the rotor and the stator is reduced. However, when performing a long run for a long time, local peeling due to minute cracks on the plating surface is not caused. As a result, stable production over a long period of time was difficult.

Japanese Patent Publication No. 3-15489 JP-A-11-212480 JP 2003-173046 A

  An object of the present invention is to solve the above-mentioned problems, improve the abrasion resistance of the pulverizing surface of a pulverizer, and to produce a toner fine particle capable of stably obtaining a desired particle size distribution over a long period of time. To provide an apparatus.

The present invention melts and kneads a mixture containing at least a binder resin and a colorant, cools the obtained kneaded material, coarsely pulverizes the cooled material, and pulverizes the powder raw material made of the coarsely pulverized material by a pulverizing means. In the method for producing toner fine particles having a weight average particle diameter of 3 to 11 μm, which includes at least a step of:
The crushing means includes at least a rotor that is a rotating body attached to a central rotating shaft, and a stator that is arranged around the rotor while maintaining a predetermined distance from the surface of the rotor. A mechanical crusher formed by holding
The surface of the rotor and / or stator is coated with a chromium alloy plating containing at least chromium carbide, and then subjected to a mechanical surface treatment to thereby obtain a surface hardness A of the rotor and / or stator. The present invention relates to a method and an apparatus for producing toner fine particles, wherein (Vickers hardness) is HV1300 <A ≦ HV1800.

  According to the present invention, in the method / apparatus for producing toner fine particles using a mechanical pulverizer, the surface of the rotor and / or stator in the mechanical pulverizer is plated with chromium alloy containing at least chromium carbide. The rotor and / or the stator is subjected to a mechanical surface treatment after the coating, and the surface hardness A (Vickers hardness) of the rotor and / or the stator is set to HV1300 <A ≦ HV1800. Can extend the lifetime of

It is a schematic sectional drawing of the conventional collision type airflow crusher. FIG. 3 is a schematic cross-sectional view of an example mechanical pulverizer used in the toner fine particle pulverization step of the present invention. It is a schematic sectional drawing in the D-D 'surface in FIG. FIG. 3 is a perspective view of the rotor shown in FIG. 2.

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

  2 shows an example of a pulverization system incorporating a mechanical pulverizer used in the present invention, FIG. 3 shows a schematic cross-sectional view taken along the line DD ′ in FIG. 2, and FIG. The perspective view of the rotor which rotates at high speed is shown.

  Although FIG. 2 shows a schematic cross-sectional view of a horizontal general mechanical pulverizer, it may be a vertical type. Rotation in which a large number of grooves are provided on the surface of the casing 313, a jacket 316 that can pass cooling water in the casing 313, and a surface that rotates in the casing 313 and that is attached to the central rotating shaft 312 and that rotates at high speed. The stator 310, the stator 310 having a large number of grooves on the surface thereof arranged at regular intervals on the outer periphery of the rotor 314, the raw material inlet 311 for introducing the raw material to be processed, and the post-treatment And a raw material outlet 302 for discharging the powder.

  In the mechanical pulverizer configured as described above, when a predetermined amount of the powder raw material is charged into the raw material inlet 311 of the mechanical pulverizer shown in FIG. It is introduced indoors. The impact generated between the rotor 314 provided with a large number of grooves on the surface rotating at high speed in the pulverization chamber and the stator 310 provided with a large number of grooves on the surface, and the many generated behind this Are pulverized instantaneously by the ultrahigh-speed vortex flow and the high-frequency pressure vibration generated thereby. Thereafter, the material passes through the material discharge port 302 and is discharged. The air carrying the particles (air) passes through the pulverization chamber and is discharged out of the apparatus system through the raw material discharge port 302, the pipe 219, the collecting cyclone 229, the bag filter 222, and the suction blower 224. The In the present invention, since the powder raw material is pulverized in this manner, a desired pulverization treatment can be easily performed without increasing the fine powder and coarse powder.

  Examples of such mechanical crushers include Inomizer (manufactured by Hosokawa Micron), Cryptrine (manufactured by Kawasaki Heavy Industries), Super Rotor (manufactured by Nisshin Engineering), Turbo Mill (manufactured by Turbo Industry), Tornado Mill (manufactured by Nikkiso Co., Ltd.) ) And the like. These can be used as they are or after being appropriately modified.

  In the toner production method by the pulverization method, an intermediate pulverization step may be inserted between the coarse pulverization step to make the particle size about 2 mm and the fine pulverization step to make the desired particle size. An intermediate pulverization process or a fine pulverization process may be used. Further, the pulverization process of the present invention may be pulverized by connecting two or more stages in series or in parallel. However, the effect of the present invention can be maximized in a process of directly reducing the particle size from the coarsely pulverized toner in one pass.

The present invention melts and kneads a mixture containing at least a binder resin and a colorant, cools the obtained kneaded material, coarsely pulverizes the cooled material, and pulverizes the powder raw material made of the coarsely pulverized material by a pulverizing means. In the method for producing toner fine particles having a weight average particle diameter of 3 to 11 μm, which includes at least a step of:
The crushing means includes at least a rotor that is a rotating body attached to a central rotating shaft, and a stator that is arranged around the rotor while maintaining a predetermined distance from the surface of the rotor. A mechanical crusher formed by holding
The surface of the rotor and / or stator is coated with a chromium alloy plating containing at least chromium carbide, and then subjected to a mechanical surface treatment to thereby obtain a surface hardness A of the rotor and / or stator. (Vickers hardness) is HV1300 <A ≦ HV1800.

  In many cases, carbon steel such as S45C or chromium molybdenum steel such as SCM material is used as a base material of a rotor or a stator in a mechanical pulverizer. By applying a mechanical surface treatment after coating these base metal surfaces with a chromium alloy, the surface hardness and wear resistance of the pulverized surface are increased, and a long-life rotor and stator can be obtained. Long run is possible.

  In the present invention, the coating of the chromium alloy containing chromium carbide on the base material surface is processed by plating, and the surface can be finished uniformly and smoothly, and the friction coefficient can be reduced 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 rotor or stator.

  However, in the surface treatment by plating, micro cracks may occur on the treated surface. Due to the micro cracks, the hard powder material such as magnetic toner is pulverized, especially while continuing the pulverization to reduce the particle size from the coarsely pulverized toner in one pass. Although the degree is small, the possibility of abrasion of the grinding surface or local delamination cannot be completely ruled out.

  In the present invention, in order to cope with such a situation, in order to obtain a long-life rotor or stator, by using shot peening as a mechanical surface treatment on the pulverized surface after plating, Micro cracks were eliminated, and 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 pressure A of the rotor and the stator can 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.

  The Vickers hardness A of the surface of the rotor and / or stator is preferably HV1300 <A ≦ HV1800.

  When the Vickers hardness A on the surface of the rotor and / or stator is in the range of HV1300 <A ≦ HV1800, the amount of wear on the pulverized surface can be reduced, and the replacement frequency of the rotor and stator is reduced. In addition, the device can be run for a long time.

  When the Vickers hardness A on the surface of the rotor and / or the stator is HV1300 or less, when performing a long run over a long period of time, wear of the pulverized surface proceeds and a desired particle size cannot be obtained. Therefore, it is necessary to replace the rotor and the stator.

  After the surface of the rotor and / or stator is coated with a chromium alloy plating containing at least chromium carbide as described above, the rotor and / or stator is subjected to a mechanical surface treatment. When the surface hardness A (Vickers hardness) is pulverized by a mechanical pulverizer having a rotor and / or stator where HV1300 <A ≦ HV1800, the wear on the pulverized surface of the rotor and / or stator is extremely reduced. The life can be increased by reducing the number. Moreover, since the surface is hard even when pulverizing to a desired particle size, the rotator can be pulverized at a low peripheral speed, so that the pulverization load is reduced and the pulverization capacity can be improved accordingly.

  In addition, since it can be pulverized to a desired particle size at a low peripheral speed, the generation amount of fine powder and ultrafine powder due to excessive pulverization is small, and the particle size distribution of the pulverized product obtained by pulverization becomes very sharp and the desired particle size distribution Toner particles are obtained in a very high yield.

  Furthermore, since it can be pulverized to a desired particle size at a low peripheral speed, the amount of heat generated during pulverization is reduced, and the occurrence of fusion and coarse particles in the pulverizer and thermal denaturation of toner fine particles are suppressed, resulting in mechanically roundedness Toner particles having a shape can be produced without variation in shape distribution.

  Such an improvement in pulverization ability is more noticeable as the powder raw material to be pulverized is harder, and is particularly remarkable in a magnetic toner containing 40 to 200 parts by mass of a magnetic material with respect to 100 parts by mass of the binder resin. .

  As described above, the surface of the rotor and / or stator is coated with a chromium alloy plating containing at least chromium carbide, and then subjected to a mechanical treatment, whereby the rotor and / or the stator is fixed. When the powder raw material is pulverized by a mechanical pulverizer having a rotor and / or a stator whose surface hardness A (Vickers hardness) is HV1300 <A ≦ HV1800, a high pulverization treatment that has not been obtained conventionally With the capability, a desired particle size distribution can be obtained over a long period of time.

  Next, a procedure for producing toner fine particles by the production method and production apparatus of the present invention will be described.

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

  Further, the toner raw materials blended and mixed as described above are melt-kneaded to melt the resins and disperse the colorant and the like therein. In the melt-kneading step, for example, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. In recent years, single-screw or twin-screw extruders have become mainstream due to the advantage of being capable of continuous production. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type twin screw extruder manufactured by Toshiba Machine Co., Ltd. In general, a twin-screw extruder manufactured by Kay Sea Kay, a co-kneader manufactured by Buss, or the like is used. Furthermore, the colored resin composition obtained by melt-kneading the toner raw material is rolled by a two-roll roll after melt-kneading, and then cooled through a cooling step of cooling by water cooling or the like.

  The cooled product of the colored resin composition obtained above is then pulverized to a desired particle size in a pulverization step. In the pulverization step, first, coarse pulverization is performed by a crusher, a hammer mill, a feather mill or the like. Furthermore, it is finely pulverized by a mechanical pulverizer such as an inomizer (manufactured by Hosokawa Micron), kryptron (manufactured by Kawasaki Heavy Industries), super rotor (manufactured by Nissin Engineering), turbo mill (manufactured by Turbo Industry). In the pulverization step, the toner is pulverized to a predetermined toner particle size step by step.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  When the toner fine particles of the present invention are used as a magnetic toner, the magnetic material contained in the magnetic toner is not particularly limited as long as it is a commonly used magnetic material. For example, iron oxide such as magnetite, maghemite, ferrite, and others Iron oxide containing metal oxides of: 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, alloys with metals such as V, and mixtures thereof.

Specifically, examples of the magnetic material 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 ), niobium 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) 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 iron tetroxide or γ-iron sesquioxide.

  Further, these magnetic materials are preferably contained in an amount of 60 to 200 parts by mass, and more preferably 80 to 150 parts by mass with respect to 100 parts by mass of the binder resin.

  As described above, in the toner fine particles of the present invention, a magnetic material may be used as a colorant, but a nonmagnetic colorant or the like can also be used as another 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 colorant used in the present invention, as a black colorant, carbon black, a magnetic material, and a yellow / magenta / cyan colorant shown below are used, and a black colorant 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 measurement method used in the present invention is shown below.

-Measurement of Vickers hardness The Vickers hardness in this invention can be measured, for example using Shimadzu Corporation dynamic microhardness meter DVH-200, and it is preferable to measure on the conditions which hold | maintain the load 0.4903N for 30 seconds.

Measurement of particle size distribution The particle size distribution can be measured by various methods. In the present invention, the weight average particle size and the particle size distribution of the toner fine particles were obtained by using a Coulter Multisizer (manufactured by Beckman Coulter). As the electrolytic solution, a 1% NaCl aqueous solution is prepared using primary sodium chloride. For example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, 0.1 to 5 ml of a surfactant, preferably alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion process for about 1 to 3 minutes with an ultrasonic disperser, and the volume and number of toner fine particles of 2.00 μm or more are measured using the 100 μm aperture as the aperture by the measuring device. The volume distribution and the number distribution are calculated, and the weight average particle diameter (the median value of each channel is used as a representative value for each channel) is obtained.

  As channels, 2.00 to 2.52 μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm; 4.00 to 5.04 μm; 5.04 to 6.35 μm; 6.35 to 8. 00 μm; 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 20.20 μm; 20.20 to 25.40 μm; 25.40 to 32.00 μm; 13 channels of 32.00-40.30 μm are used.

-Molecular weight distribution by GPC measurement of binder resin The molecular weight of the chromatogram by gel permeation chromatography (GPC) is measured under the following conditions.

The column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a solvent was passed through the column at this temperature at a flow rate of 1 ml / min, and the sample concentration was adjusted to 0.05 to 0.6% by mass. About 50 to 200 μl of THF sample solution is injected and measured. 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 (retention time). Examples of standard polystyrene samples for preparing a calibration curve include those manufactured by Tosoh Corporation or Pressure Chemical Co. The molecular weights manufactured are 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, used as a 4.48 × 10 ^6, 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, it is preferable to combine a plurality of commercially available polystyrene gel columns in order to accurately measure a molecular weight region of 10 ^{3 to} 2 × 10 ⁶ . For example, the combination of shodex GPC KF-801, 802, 803, 804, 805, 806, and 807 manufactured by Showa Denko KK, and the combination of μ-styragel 500, 10 ³ , 10 ⁴ , and 10 ⁵ manufactured by Waters it can.

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

(Powder raw material production example)
Hybrid resin: 100 parts by mass [styrene, 2-ethylhexyl acrylate, α-methylstyrene, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) Hybrid resin comprising -2,2-bis (4-hydroxyphenyl) propane, succinic acid, trimellitic anhydride, fumaric acid: weight average molecular weight (Mw) 81300, number average molecular weight (Mn) 3000, peak molecular weight (Mp) 15400]
-Paraffin wax: 5 parts by mass-Charge control agent (1,4-di-t-butylsalicylate aluminum compound): 1 part by mass-Spherical magnetic iron oxide: 90 parts by mass After mixing the materials of the above formulation with a mixer, It knead | mixed with the biaxial kneader (PCM-87 type | mold, Co., Ltd. product made from Ikegai) which set temperature to 130 degreeC. The obtained kneaded product was cooled and coarsely pulverized to 2 mm or less with a hammer mill to obtain a powder raw material (coarse pulverized product) E which is a powder raw material for toner production.

  Further, the obtained powder raw material E was finely pulverized by a mechanical pulverizer (Turbo Mill T250-RS type manufactured by Turbo Kogyo Co., Ltd.).

  The mechanical pulverizer used in this example coated the hard chromium carbide alloy plating on the surfaces of the rotor and the stator, and after quenching, changed the surface hardness by changing the conditions of the shot peening process. It was.

  In this embodiment, the minimum gap between the rotor and the stator is set to 0.8 mm, the temperature of the air introduced into the mechanical pulverizer is set to -15 ° C., the pulverization supply amount is set to 30 kg / hr, and the jacket cooling is performed. The powder raw material E was finely pulverized while passing water. The system was operated for 1200 hours under these conditions, and the particle size distribution was measured every 50 hours. Table 1 summarizes the operation time, particle size distribution after 1200 hours, rotor tip peripheral speed, and grinding load current at which the target weight average particle size of 5.5 μm or more and 5.9 μm or less is obtained.

The operating time was judged according to the following criteria and summarized in Table 1.
A: The target average particle diameter is obtained for 1000 hr or more.
B: A target average particle size of less than 1000 hr and 500 hr or more is obtained.
C: A target average particle size of less than 500 hr is obtained.

<Evaluation for wear (1)>
After completion of the pulverizer operation, the rotor and stator in the pulverizer were visually checked for wear and judged according to the following criteria. The results are summarized in Table 1.
A: No wear on in-machine rotor / stator B: In-machine rotor / stator wear is slight, but practical use C: In-machine rotor / stator wear is noticeable, impractical

<Evaluation for wear (2)>
The evaluation of wear was also made based on the weight average particle diameter (D4) after 1200 hours, and the determination was made according to the following criteria.
A: The important average particle diameter (D4) after 1200 hours is 5.5 μm ≦ D4 ≦ 5.9 μm.
B: The important average particle size (D4) after 1200 hours is 5.9 μm <D4 <6.4 μm.
C: The important average particle size (D4) after 1200 hours is 6.4 μm ≦ D4

[Example 1]
In this example, the conditions of the shot peening process were set to a pressure of 0.5 MPa and 30 seconds, the surface hardness of the rotor and the stator was set to HV1750, and the powder raw material E was finely pulverized under the above conditions.

  As a result, the operation time for obtaining the target weight average particle size of 5.5 μm or more and 5.9 μm or less was 1200 hr, the tip peripheral speed of the rotor was 145 m / s, and the grinding load current was 28 A. The finely pulverized product (toner fine particles) obtained after 1200 hr has a weight average particle size of 5.7 μm, 55.6% by number of particles having a particle size of 4.0 μm or less, and particles having a particle size of 10.1 μm or more. It had a particle size distribution containing 0.4% by volume.

  Further, when the inside of the pulverizer was inspected after pulverizing for 1200 hours, no wear was observed on the rotor and stator. Therefore, the surface hardness of the rotor and stator was set to HV1750 by the above method. It was judged that a long run over time was possible.

[Example 2]
The powder raw material E was finely pulverized in the same manner as in Example 1 except that the pressure of the shot peening process was 0.2 MPa, 30 seconds, and the surface hardness was HV1500.

  As a result, the operation time for obtaining a target weight average particle size of 5.5 μm or more and 5.9 μm or less was 1200 hr, the rotor tip peripheral speed was 150 m / s, and the grinding load current was 33 A. The finely pulverized product (toner fine particles) obtained after 1200 hours has a weight average particle size of 5.8 μm, 54.1% by number of particles having a particle size of 4.0 μm or less, and particles having a particle size of 10.1 μm or more. The particle size distribution was 0.5% by volume.

  Further, when the inside of the pulverizer was inspected after pulverizing for 1200 hours, no wear was observed on the rotor and stator. Therefore, the surface hardness of the rotor and stator was changed to HV1500 by the above method. It was judged that a long run over time was possible.

[Example 3]
The powder raw material E was finely pulverized in the same manner as in Example 1 except that the conditions for the shot peening were 0.5 MPa for 15 seconds and the surface hardness was HV1310.

  As a result, the operation time for obtaining the target weight average particle size of 5.5 μm or more and 5.9 μm or less was 1200 hr, the rotor tip peripheral speed was 155 m / s, and the grinding load current was 36 A. The finely pulverized product (toner fine particles) obtained after 1200 hours has a weight average particle size of 5.9 μm, 52.0% by number of particles having a particle size of 4.0 μm or less, and particles having a particle size of 10.1 μm or more. It had a particle size distribution containing 0.7% by volume.

  Further, when the inside of the pulverizer was inspected after pulverizing for 1200 hours, no wear was observed on the rotor and stator. Therefore, the surface hardness of the rotor and stator was changed to HV1310 by the above method. It was judged that a long run over time was possible.

[Example 4]
Except that the surface of the rotor and the stator was coated with hard chromium carbide alloy plating and quenched, then shot peening was performed only on the rotor under the conditions of Example 1, and the surface hardness of the rotor was changed to HV1750. Pulverized the powder raw material E in the same manner as in Example 1.

  As a result, the operation time for obtaining the target weight average particle diameter of 5.5 μm or more and 5.9 μm or less was 1200 hr, the tip peripheral speed of the rotor was 150 m / s, and the grinding load current was 35 A. The finely pulverized product (toner fine particles) obtained after 1200 hours has a weight average particle diameter of 5.8 μm, 53.5% by number of particles having a particle diameter of 4.0 μm or less, and particles having a particle diameter of 10.1 μm or more. It had a particle size distribution containing 0.6% by volume.

  Further, when the inside of the pulverizer was inspected after pulverizing for 1200 hours, the rotor was not worn, and the stator was slightly worn. As a result, it was determined that a long run over a long period of time was possible even with the method of this example in which only the rotor had a surface hardness of HV1750.

[Example 5]
Except that the surface of the rotor and stator was coated with hard chromium carbide alloy plating and quenched, then shot peening was performed only on the stator under the conditions of Example 1, and the surface hardness of the stator was HV1750 Pulverized the powder raw material E in the same manner as in Example 1.

  As a result, the operation time for obtaining the target weight average particle diameter of 5.5 μm or more and 5.9 μm or less was 1200 hr, the tip peripheral speed of the rotor was 150 m / s, and the grinding load current was 35 A. The finely pulverized product (toner fine particles) obtained after 1200 hours has a weight average particle size of 5.8 μm, 53.8% by number of particles having a particle size of 4.0 μm or less, and particles having a particle size of 10.1 μm or more. It had a particle size distribution containing 0.6% by volume.

  Further, when the inside of the pulverizer was inspected after pulverizing for 1200 hours, the stator was not worn, and the rotor was slightly worn. As a result, it was determined that a long run over a long period of time was possible even with the method of the present example in which only the stator had a surface hardness of HV1750.

[Reference Example 1]
The surface of the rotor and stator of the mechanical pulverizer was coated with hard chromium carbide alloy plating and the surface hardness was set to HV1050, and then the same as in Example 1 except that quenching and shot peening were not performed. Powder raw material E was pulverized. As a result, the operation time for obtaining the target weight average particle size of 5.5 μm or more and 5.9 μm or less was 950 hr, the tip peripheral speed of the rotor was 145 m / s, and the grinding load current was 38 A. The finely pulverized product (toner fine particles) obtained after 1200 hours has a weight average particle size of 6.1 μm, particles having a particle size of 4.0 μm or less are 53.3% by number, and particles having a particle size of 10.1 μm or more are used. It had a particle size distribution containing 2.0% by volume.

  Furthermore, when the inside of the crusher was inspected after operation, slight wear was observed on the rotor and stator. Thereby, in the method of setting the surface hardness to HV1050 by the method of this reference example, it was judged that long running over a long time was inferior to Examples 1 to 5, but was possible.

[Comparative Example 1]
The powder raw material E was finely pulverized in the same manner as in Example 1 except that the rotor and stator of the mechanical pulverizer were spray-coated with ceramics on the surface and the surface hardness was HV1320. As a result, the operation time for obtaining the target weight average particle size of 5.5 μm or more and 5.9 μm or less was 500 hr, the tip peripheral speed of the rotor was 150 m / s, and the grinding load current was 35 A. The finely pulverized product (toner fine particles) obtained after 1200 hours has a weight average particle size of 6.9 μm, 52.5% by number of particles having a particle size of 4.0 μm or less, and particles having a particle size of 10.1 μm or more. It had a particle size distribution containing 7.0% by volume.

  Furthermore, when the inside of the pulverizer was inspected after operation, the rotor and the stator were found to be worn, and it was determined that a long run over a long period was impossible.

[Comparative Example 2]
Powder raw material E was finely pulverized in the same manner as in Example 1 except that no abrasion-resistant treatment was applied to the surfaces of the rotor and stator of the mechanical pulverizer (surface hardness HV250). As a result, the operation time for obtaining the target weight average particle diameter of 5.5 μm or more and 5.9 μm or less was 300 hr, the tip peripheral speed of the rotor was 155 m / s, and the grinding load current was 40 A. The finely pulverized product (toner fine particles) obtained after 1200 hours has a weight average particle size of 7.0 μm, 63.5% by number of particles having a particle size of 4.0 μm or less, and particles having a particle size of 10.1 μm or more. It had a particle size distribution containing 11.0% by volume.

  Furthermore, when the inside of the pulverizer was inspected after operation, the rotor and the stator were found to be worn, and it was determined that a long run over a long period was impossible.

  212: Swirl chamber, 219: Pipe, 220: Distributor, 222: Bag filter, 224: Suction blower, 229: Collection cyclone, 301: Mechanical pulverizer, 302: Powder outlet, 310: Stator, 311: Powder inlet, 312: Rotating shaft, 313: Casing, 314: Rotor, 315: First metering feeder, 316: Jacket, 317: Cooling water supply port, 318: Cooling water outlet, 320: Rear Chambers, 321 and 329: wave shape of the stator convex portion, 322 and 330: flat surface of the bottom portion of the stator concave portion, 323 and 331: trapezoid shape of the concave portion of the stator, 324: wave shape of the concave and convex portion of the rotor, 325: fixed 306, 332: trapezoidal shape of rotor recess, 327, 333: flat surface of rotor recess bottom, 328, 334: waveform shape of rotor protrusion, 335, 37, 339: Corrugated shape of the uneven portion of the stator, 336, 338, 340: Wave shape of the uneven portion of the rotor, 337: First slope of the rotor, 338: Second slope of the rotor, 339: Stator First slope 340: second slope of the stator

An object of the present invention is to solve the above-mentioned problems, improve the abrasion resistance of the pulverizing surface of a pulverizer, and provide a toner fine particle manufacturing method and machine capable of stably obtaining a desired particle size distribution over a long period of time. It is to provide a type pulverizer .

In the present invention, a mixture containing at least a binder resin and a colorant is melt-kneaded, the obtained kneaded product is cooled, the cooled product is coarsely pulverized, and the powder raw material comprising the coarsely pulverized product is pulverized by a pulverizing means. and crushing, a method for producing a toner particle for weight average particle diameter to obtain toner particles is 3 to 11 [mu] m,
The grinding means, center and the rotor attached to the rotary shaft as the rotational member, mechanical type by maintaining a constant distance between the rotor surface at least immediately Bei a stator disposed around the rotor A crusher,
The rotor and / or the surface of the stator, after being coated with chromium alloy plating containing at least chromium carbide, and mechanical surface treatment into force by shot peening,
Toner fine particle manufacturing method and mechanical pulverizer characterized in that the surface hardness A (Vickers hardness) of the rotor and / or stator subjected to the mechanical surface treatment is HV1300 <A ≦ HV1800 About.

Claims (6)

At least a step of melt-kneading a mixture containing at least a binder resin and a colorant, cooling the obtained kneaded product, coarsely pulverizing the cooled product, and pulverizing the powder raw material made of the coarsely pulverized product by a pulverizing means. In the method for producing toner fine particles having a weight average particle diameter of 3 to 11 μm,
The crushing means includes at least a rotor that is a rotating body attached to a central rotating shaft, and a stator that is arranged around the rotor while maintaining a predetermined distance from the surface of the rotor. A mechanical crusher formed by holding
The surface of the rotor and / or stator is coated with a chromium alloy plating containing at least chromium carbide, and then subjected to a mechanical surface treatment to thereby obtain a surface hardness A of the rotor and / or stator. (Vickers hardness) HV1300 <A ≦ HV1800   2. The method for producing toner fine particles according to claim 1, wherein the binder resin used for the toner fine particles is a resin having at least a polyester unit.   3. The method for producing toner fine particles according to claim 1, wherein the colorant used for the toner fine particles contains at least a magnetic material. A mixture containing at least a binder resin and a colorant is melt-kneaded, the obtained kneaded product is cooled, the cooled product is coarsely pulverized, and the powder raw material made of the coarsely pulverized product is pulverized by a pulverizing means. In an apparatus for producing toner fine particles having a weight average particle diameter of 3 to 11 μm and having at least an apparatus to be produced,
The crushing means includes at least a rotor that is a rotating body attached to a central rotating shaft, and a stator that is arranged around the rotor while maintaining a predetermined distance from the surface of the rotor. A mechanical crusher formed by holding
The surface of the rotor and / or stator is coated with a chromium alloy plating containing at least chromium carbide, and then subjected to a mechanical surface treatment to thereby obtain a surface hardness A of the rotor and / or stator. (Vickers hardness) HV1300 <A ≦ HV1800 An apparatus for producing toner fine particles, wherein:   5. The apparatus for producing toner fine particles according to claim 4, wherein the binder resin used for the toner fine particles is a resin having at least a polyester unit. 6. The toner fine particle manufacturing apparatus according to claim 4, wherein the colorant used for the toner fine particles includes at least a magnetic material.

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