JP5366524B2 - Toner heat treatment apparatus and toner manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To reduce increase of coarse particles due to toner coalescence in heat conglobation treatment of a toner for performing stable production. <P>SOLUTION: In a toner heat treatment device including a material supply means 8, a hot air supply means 2, and a discharge part 13 for sucking and discharging toner, the hot air supply means is arranged annularly in a position closed to or separated in the horizontal direction from the outer circumferential surface of the material supply means, and from the outlet of the material supply means, materials are supplied toward the hot air supplied from the hot air supply means. The thermal treatment device also includes a straightening means 14 regulating the flow of heat-treated toner, and the location of the straightening means is in the axial center part inside the device, below the material supply means and the hot air supply means, and above the discharge part. The thermally treated toner passes through between the device inside wall surface and the straightening means. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an apparatus for producing 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, and a method for producing toner using the device. .

  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 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, After adding and mixing magnetic materials for imparting transportability etc. to the toner itself, additives such as a release agent and fluidity imparting agent, and melt-kneading and cooling and solidifying, the kneaded material is refined by a 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 a two-component development method, various magnetic carriers and the above toner are mixed and then used for image formation.

  In recent years, with higher image quality and higher definition of copiers and printers, the performance required of toner as a developer has become more severe, the particle size of toner is small, and the particle size distribution of toner contains coarse particles. There is a growing demand for sharp products that are not broken and have few fine particles.

  In addition, as transfer materials for copying machines and printers, it has become necessary to support various materials other than ordinary paper, and since it is required to improve the transferability of toner, the surface of the toner is required. The shape has been improved and further spheroidization has been demanded.

  Furthermore, there is a demand for toner as a developer to reduce or simplify the component parts for the purpose of lowering the price of the main body or to extend the life of the component parts to reduce running costs.

  As described above, since the toner is required to have many different properties, it is necessary to devise the toner characteristics by the toner production method and surface modification in addition to the raw materials used. .

  Examples of the manufacturing method and surface modification relating to the toner described above include a method of making the toner spherical by mechanical impact force (see Patent Document 1). In addition, as a manufacturing method using heat and surface modification, toner particles are dispersed and sprayed in hot air with compressed air to achieve surface modification and spheroidization (see Patent Document 2), and toner particles such as silica are used. After adding an additive, the method of removing the additive liberated by performing heat treatment and fixing it (see Patent Document 3) and the like can be mentioned.

  However, in the method using mechanical impact force, there is a problem that the toner is excessively pulverized due to the impact at the time of spheroidization, resulting in an increase in the amount of fine powder, especially severe conditions such as high temperature and high humidity and low temperature and low humidity. In an environment, it may be unpreferable on quality.

  Further, in the method using heat, if more heat than necessary is applied to the toner, the toners coalesce to produce coarse particles, which may be undesirable from the viewpoint of toner quality.

  Furthermore, there has been proposed a spheronization treatment apparatus provided with a collision member at a distance from the lower end outlet of the raw material injection port when the thermoplastic particles are spheroidized by contact with hot air (see Patent Document 4).

  However, when a member in the apparatus receives heat and stores heat, the toner is fused to the stored member, and stable production cannot be performed, and toner productivity may not be preferable.

  Further, in order to solve the above problems, there has been proposed a spheronization processing apparatus having a configuration in which a raw material supply unit is provided at the center of the apparatus and a hot air supply unit is provided outside the raw material supply unit (see Patent Document 5).

  However, in this configuration, it is necessary to provide a plurality of raw material injection nozzles, which is unfavorable in terms of manufacturing energy because the apparatus configuration is increased in size and a larger amount of compressed gas is required for supplying the raw materials. In addition, since a straight line is injected to the annular hot air, a loss occurs in the processing portion, which is inefficient in increasing the processing amount.

  Thus, in order to efficiently and stably produce toner surface-modified particles that do not contain coarse particles and have a sharp particle size distribution with few fine powders, the surface of the toner manufacturing apparatus and method There is room for improvement.

The coarse particles and fine particles in the toner described in the present specification are as follows.
Coarse particles: Particle group approximately twice or more of toner weight average diameter (D4) Fine particles: Particle group approximately ½ times or less of toner weight average diameter (D4) Particles of 2.0 μm or less: Flow type particle image analyzer Particles of 2.0 μm or less measured with “FPIA-3000 type” (manufactured by Sysmex Corporation)
Japanese Patent Laid-Open No. 9-85741 JP 11-295929 A JP 7-271090 A JP 2004-276016 A JP 2004-189845 A

  The object of the present invention is to solve the above-mentioned problems and to improve the toner surface modified particles having a sharp particle size distribution that does not contain coarse particles and has few fine powders even when the processing amount is increased. An object of the present invention is to provide a toner heat treatment apparatus and a toner manufacturing method that can be obtained.

That is, the present invention is a toner heat treatment apparatus having a raw material supply means for supplying a raw material, a hot air supply means for heat-treating the supplied raw material, and a discharge section for discharging the heat-treated toner. And
Hot air supply means is provided in an annular shape so as to surround the raw material supply means at a position close to the outer peripheral surface of the raw material supply means or at a distance from the horizontal direction,
From the outlet of the raw material supply means, the raw material is supplied toward the hot air supplied from the hot air supply means,
The discharge part is present downstream of the raw material supply means and the hot air supply means,
The toner heat treatment apparatus adjusts the flow of the heat-treated toner at the axial center portion inside the apparatus, downstream of the raw material supply means and hot air supply means and upstream of the discharge section. The toner heat treatment apparatus is characterized in that the toner subjected to heat treatment by introducing a cooling medium into the rectification means passes between the inner wall surface of the heat treatment apparatus and the rectification means. About.
The present invention is also a toner heat treatment apparatus having a raw material supply means for supplying a raw material, a hot air supply means for heat-treating the supplied raw material, and a discharge portion for discharging the heat-treated toner. There,
Hot air supply means is provided in an annular shape so as to surround the raw material supply means at a position close to the outer peripheral surface of the raw material supply means or at a distance from the horizontal direction,
From the outlet of the raw material supply means, the raw material is supplied toward the hot air supplied from the hot air supply means,
The discharge part is present downstream of the raw material supply means and the hot air supply means,
The toner heat treatment apparatus adjusts the flow of the heat-treated toner at the axial center portion inside the apparatus, downstream of the raw material supply means and hot air supply means and upstream of the discharge section. The heat-treated toner having the rectifying means passes between the inner wall surface of the heat treatment apparatus and the rectifying means,
In the horizontal cross section of the toner heat treatment apparatus at the position where the rectification means is provided, the relationship between the outer diameter A of the rectification means and the inner diameter B of the heat treatment apparatus is:
0.5 × B ≦ A ≦ 0.95 × B
The present invention relates to a heat treatment apparatus for toner.
Furthermore, the present invention is a toner heat treatment apparatus having a raw material supply means for supplying a raw material, a hot air supply means for heat-treating the supplied raw material, and a discharge portion for discharging the heat-treated toner. There,
Hot air supply means is provided in an annular shape so as to surround the raw material supply means at a position close to the outer peripheral surface of the raw material supply means or at a distance from the horizontal direction,
From the outlet of the raw material supply means, the raw material is supplied toward the hot air supplied from the hot air supply means,
The raw material supply means has a first nozzle and a second nozzle that expand in a tapered shape from the upstream to the downstream in the raw material supply direction at the outlet, and the second nozzle is the first nozzle. The raw material disposed and supplied inside the nozzle passes through a space formed by the inside of the first nozzle and the outside of the second nozzle,
The discharge part is present downstream of the raw material supply means and the hot air supply means,
The toner heat treatment apparatus adjusts the flow of the heat-treated toner at the axial center portion inside the apparatus, downstream of the raw material supply means and hot air supply means and upstream of the discharge section. The heat-treated toner having the rectifying means passes through between the inner wall surface of the heat treatment apparatus and the rectifying means.

Further, the present invention undergoes a more Netsusho Polytechnic of toner particles to a method for manufacturing a toner to obtain a toner,
The toner has a weight average particle diameter of 4 μm or more and 12 μm or less,
In the heat treatment step, a method for producing a toner, wherein the heat treatment apparatus of the toner having the above structure is used.

  According to the present invention, it is possible to provide a heat treatment apparatus capable of stably producing while suppressing coalescence of heat-treated toner particles, suppressing generation of coarse particles, and preventing fusion.

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

  First, the outline of the heat processing apparatus used for this invention is demonstrated using figures. FIG. 1 is a cross-sectional perspective view showing an example of the heat treatment apparatus of the present invention.

  The toner supplied to the raw material supply means (8) is accelerated by the compressed gas supplied by the compressed gas supply means (not shown), and the first nozzle (provided at the outlet portion of the raw material supply means (8)) 9) and the second nozzle (10) are passed through the space and injected in a ring shape toward the radially outer side in the apparatus. Furthermore, a tubular member 1 (6) and a tubular member 2 (7) are provided inside the raw material supply means (8), and compressed gas is also supplied into each of them. The compressed gas that has passed through the tubular member 1 (6) passes through a space formed by the first nozzle (9) and the second nozzle (10). The tubular member 2 (7) penetrates the second nozzle (10), and the compressed gas is injected from the outlet of the tubular member 2 (7) toward the inner surface of the second nozzle (10) inside the second nozzle (10). Is done.

  In this apparatus, the hot air supply means (2) is provided in an annular shape outside the raw material supply means (8), and the heat-treated toner is cooled and the temperature inside the apparatus is further increased on the outer and downstream sides. Thus, cold air supply means 1 (3), 2 (4) and 3 (5) for preventing toner coalescence and fusing are provided.

  The hot air supply means (2) is provided in an annular shape at a position close to or spaced from the outer peripheral surface of the raw material supply means (8) in the horizontal direction. This is because the outlet portions of the first and second nozzles are heated by the supplied hot air to prevent the toner particles ejected from the outlet portions from melting and adhering.

  In this apparatus, it is preferable that the cold air supplied from the cold air supply means 1 (3), 2 (4), 3 (5) is divided and introduced into a plurality of parts in the horizontal cross section of the apparatus. In this embodiment, the system is introduced into four parts. This is to facilitate uniform control of the wind flow in the apparatus, and the amount of cold air in the four-way introduction path can be controlled independently.

  Furthermore, a rectifying means (14) is provided in the apparatus main body, and a cooling medium (cold air) can be supplied to the inside. The supplied cold air is configured to escape to the downstream side of the apparatus. This is to prevent the rectifying means (14) itself from accumulating heat by the heat supplied from the hot air supply means (2) and preventing the heat-treated toner from adhering and fusing. Further, cooling water may be supplied instead of cold air. In this case, it is possible to cope with this by making the rectifying means (14) into a jacket.

  It is desirable that the rectifying means (14) is disposed at the center of the shaft inside the apparatus and is provided at a position spaced apart from the raw material supply means (8) in the vertical direction. A preferred position is in the vicinity of the cold air supply means 3 (5).

  This is to prevent the toner particles ejected from the raw material supply means (8) from colliding with the rectifying means (14) and being fused in the state heated by the hot air.

In addition, the outer diameter A of the rectifying means (14) is more preferably in the following relationship with the inner diameter B of the apparatus.
0.5 × B ≦ A ≦ 0.95 × B Formula 1

  In the apparatus of the present invention, it is more preferable that the downstream end of the first nozzle (9) provided at the outlet of the raw material supply means (8) is positioned below or the same as the downstream end of the hot air supply means (2).

  This is because the toner sprayed into the apparatus generates a turbulent flow at the outlets of the first nozzle (9) and the second nozzle (10), and flows up to the upper part of the apparatus, and is supplied from the hot air supply means (2). This is because it may be melted by the generated heat and fused to the upper part of the apparatus.

  In addition, it is more desirable that the positions of the downstream end of the first nozzle (9) and the downstream end of the second nozzle (10) are the same in the vertical direction, or the second nozzle (10) is located on the downstream side. .

  This is because when the first nozzle (9) is positioned on the upstream side, the toner conveyed by the compressed gas passes through the space formed by the first nozzle (9) and the second nozzle (10). This is because the state of being annularly injected toward the hot air is small and sufficient heat treatment may not be performed.

  The toner ejected into the apparatus is spherocized by being sprayed and heat-treated toward the hot air supplied from the hot air supply means (2).

  Further, for the case of using the apparatus of the present invention as a thermal spheronizing apparatus, the outer peripheral part of the raw material supply means (8), the outer peripheral part of the apparatus, the inner peripheral part of the hot air supply means, the recovery, for the purpose of preventing toner fusion. A cooling jacket is provided on the outer periphery of the means. It is desirable to introduce cooling water (preferably an antifreeze such as ethylene glycol) into the cooling jacket.

  Moreover, the raw material supply means (8) and the first nozzle (9) are integrally formed and can be cooled to increase the cooling efficiency. In the path from the raw material supply means (8) upstream to the first nozzle (9), the diameter of the portion connected to the first nozzle (9) is designed to be smaller than the diameter of the upstream end of the raw material supply means (8). Yes. A so-called tapered shape is more preferable. This is because the flow rate of the supplied toner is accelerated once at the entrance of the first nozzle (9), so that it is possible to further assist the dispersion of the toner.

  The hot air supplied into the apparatus preferably has a temperature C (° C.) at the outlet of the hot air supply means (2) of 100 ≦ C ≦ 450.

  When the temperature is lower than 100 ° C., the toner spheroidization process may vary, which is not preferable in terms of toner transferability. On the other hand, when the temperature exceeds 450 ° C., it is not preferable because the toner may be coalesced due to excessive progress of the melted state, resulting in toner coarsening and fusing.

  The heat-treated toner is cooled by the cold air supply means 1 (3). At this time, cold air may be introduced from the cold air supply means 2 (4) provided on the side surface of the main body of the apparatus for the purpose of controlling the temperature in the apparatus and controlling the surface state of the toner. The outlet of the cold air supply means 2 (4) can be slit, louvered, perforated plate, mesh, etc. The direction of introduction is selected according to the purpose: horizontal to the center or along the wall of the device. Is possible.

  At this time, the temperature E (° C.) in the cold air supply means 1 (3) and the cold air supply means 2 (4) is preferably −20 ≦ E ≦ 20. When the temperature of the cold air is less than −20 ° C., the temperature in the apparatus is too low, and the spheroidization due to heat, which is the original purpose, is not sufficiently performed, and the toner transfer performance may not be improved. Yes, not preferred. Moreover, when it exceeds 20 degreeC, control of the hot air zone in an apparatus is inadequate and cooling efficiency falls, coalescence of particle | grains progresses and powder particle coarsening may arise, and is unpreferable.

  The apparatus of the present invention includes a cooling and conveying means (cold air supply means 3) (5) for assisting the cooled toner to be transferred to the collecting means (13) which is a discharge section and for cooling the collecting means. Is provided.

  A blower (not shown) is provided on the downstream side of the collecting means (13), and is sucked and conveyed by the blower.

  In this apparatus, it is preferable that the relationship between the total amount QIN of the flow rates of the compressed gas, hot air, and cold air supplied into the apparatus and the air amount QOUT sucked by the blower is adjusted so as to satisfy the relationship of QIN ≦ QOUT.

  This is because, when QIN> QOUT, the pressure in the apparatus becomes positive, and the injected toner tends to stay in the apparatus, excessively receiving heat and increasing the number of particles that are combined and the increase in fusion within the apparatus. Because it leads to.

  Next, the raw material supply means and each nozzle provided in the spheroidizing apparatus will be described with reference to the drawings. FIG. 2 is a partial cross-sectional perspective view showing an example of the raw material supply means (8) and the nozzles (9, 10) according to the present invention.

  As shown in the figure, the raw material supply means (8) is cylindrical and has a structure having a first nozzle (9) at the outlet. The path from the upstream side of the raw material supply means (8) to the first nozzle (9) has a shape narrowed in a tapered shape from upstream to downstream. Furthermore, the raw material supply means (8) is entirely jacketed and also has a cooling mechanism.

  A second nozzle (10) is provided inside the first nozzle (9).

  The raw material supply means (8) is provided with a tubular member 1 (6) at the shaft center, and the lower end of the tubular member 1 (6) is provided above the upper end of the second nozzle (10). The compressed gas is introduced into the tubular member 1 (6), and the compressed gas is injected toward the outer surface of the second nozzle (10). The toner that has passed through the space formed by the first nozzle (9) and the second nozzle (10) is accelerated by the jetted compressed gas, and is further dispersed and jetted into the apparatus.

  Further, a tubular member 2 (7) is provided inside the tubular member 1 (6), and the tubular member 2 (7) is connected to the second nozzle (10). The tubular member 2 (7) passes through the second nozzle (10) and reaches the inner surface. At the downstream end, the injection means (11, 12) for injecting compressed gas toward the inner surface of the second nozzle (10) is provided. It is equipped. The toner ejected from the space formed by the first nozzle (9) and the second nozzle (10) may generate a flow that winds up toward the inner surface of the second nozzle (10) at the outlet. Since the toner on the winding flow may adhere to the inner surface of the second nozzle (10) and cause fusion, the compressed gas is jetted toward the inner surface of the second nozzle (10). In addition, the toner riding on the above-described updraft flow cannot be applied to the supplied hot air, and thus is in an unprocessed state. Therefore, in order not to produce unprocessed toner, the compressed gas is applied to the inner surface of the second nozzle (10). To maintain the diffusion state of the toner. A spinning nozzle (11) or a spray nozzle (12) (both manufactured by Spraying System Japan Co., Ltd.) is used as the spraying means.

  In the vertical cross section at the axial center of the raw material supply means (8), the respective ridgelines of the first nozzle (9) and the second nozzle (10) have angles α and β spreading from upstream to downstream in the raw material supply direction. The relationship is more preferably α ≦ β. This is necessary for maintaining or accelerating the flow rate of the ejected toner, and it is possible to maintain a good diffusion state of the ejected toner by having such a relationship. In addition, α and β are preferably 20 ≦ α ≦ 120 (°) and 40 ≦ β ≦ 140 (°), respectively.

  Furthermore, it is more preferable that the second nozzle (10) has a shape (return portion (10A)) that continuously or intermittently expands in the radial direction at the downstream end (FIG. 2). With this configuration, the toner can pass at an earlier stage with respect to the supplied hot air, the cooling after the heat treatment can be sufficiently performed, and the increase of the coalesced particles can be further suppressed.

  When the angles α and β are both small beyond the range, the ejected toner may not be sufficiently diffused and heat treatment may not be sufficiently performed. On the other hand, when the angle is larger than the range, the ejected toner may be attached to the upper part of the apparatus and fused on the air stream that is rolled up by the turbulent flow. In order to prevent this, fusion or the like can be prevented by lowering the raw material supply means downward. In that case, since the distance from the hot air supply means (2) is increased, heat treatment is also performed here. There is a possibility of not being able to fully.

  A mechanism for making toner spherical using the apparatus having the above-described configuration will be described with reference to FIGS.

  The toner particles ejected from the raw material supply means (8) are diffused by the negative pressure inside the apparatus and attracted by the hot air supplied in an annular form from the outside, and pass through the heat treatment zone. Spheroidized and cooled with cold air. However, since the apparatus is configured to perform suction conveyance by a blower (not shown), hot air and cold air are attracted to the center of the apparatus shaft by suction of the blower. Therefore, the heat treatment zone gathers at the center of the apparatus as shown in FIG. In this portion, when the supplied toner particles are heat-treated, the dispersion of the toner particles is not good, so the coalescence of the toner particles increases and coarse particles are generated.

  Therefore, in this apparatus, by providing the rectifying means (14) in the central part of the apparatus, the air flow and the toner flow in the apparatus are directed toward the inner wall side (outside) even if suction is performed by the blower, and the heat treatment zone is located in the central part The toner particles supplied from the raw material supply means (8) are heat-treated without being collected in the flow to suppress the increase of coarse particles (FIG. 4).

  The relationship between the outer diameter A of the rectifying means (14) and the inner diameter A of the device is preferably the relationship of Equation 1. When the outer diameter B is less than 0.5 times the inner diameter A, the influence of the pulling of the blower increases and the dispersion tends to decrease, and the coarse particles tend to increase slightly. When the outer diameter B exceeds 0.95 times the inner diameter A, the clearance between the outer wall of the apparatus and the rectifying means (14) becomes narrower, and the temperature of the path narrowed by the supplied heat tends to increase. This also shows a tendency for coarse particles to gradually increase.

  Next, a procedure for producing the toner of the present invention will be described. The toner of the present invention melts and kneads a binder resin, a colorant, a wax, and an arbitrary material, cools and pulverizes the material, and spheroidizes and classifies the pulverized product as necessary. If necessary, it can be produced by mixing the fluidizing agent.

  Specific examples are shown below.

  First, in the raw material mixing step, as a toner internal additive, at least a resin, a colorant, and a wax are weighed and mixed 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 the colorant and the like are dispersed therein. In the melt-kneading step, for example, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. In recent years, single-screw or twin-screw extruders have become 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. A twin screw extruder manufactured by Kay Sea Kay, a co-kneader manufactured by Buss, etc. are generally 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.

  In general, the cooled 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 with a crusher, a hammer mill, a feather mill, etc., and further, pulverization is performed with a kryptron system manufactured by Kawasaki Heavy Industries, Ltd., a super rotor manufactured by Nissin Engineering Co., Ltd.

  After that, if necessary, classification is performed using a classifier such as an inertia class elbow jet (manufactured by Nippon Steel Mining Co., Ltd.) or a centrifugal classifier turboplex (manufactured by Hosokawa Micron Co., Ltd.) to obtain a classified product. .

  Furthermore, as a method of externally adding the external additive, a predetermined amount of classified toner and various known external additives are blended, and a high-speed stirrer that gives a shearing force to the powder such as a Henschel mixer or a super mixer is removed. A method of stirring and mixing can be used as an accessory.

  In addition, the surface modification process using the surface modification apparatus of the present invention may be after the above classification or after the external addition treatment.

  The raw material quantitative supply step for quantitatively supplying the pulverized product, classified product or external additive to the surface reforming apparatus is a quantitative supply machine FS type (manufactured by Ganken Powtex), Finetron FT (manufactured by Hosokawa Micron), etc. The pulverized product, classified product, or externally supplied product supplied from the feeder is conveyed by compressed air.

  As a method for producing a toner having a weight average diameter (D4) of 4 μm or more and 12 μm or less according to the present invention, a general production apparatus is used to finely pulverize or classify the toner particles or toner added externally. As long as the desired circularity and particle diameter can be obtained by the treatment with the above, there is no particular limitation. When processing toner particles or toner having a weight average diameter (D4) of less than 4 μm, it may be difficult to balance the processing amount and the operating conditions of the apparatus. The same applies to processing of toner particles or toner having a weight average diameter (D4) exceeding 12 μm.

  Next, the toner constituent materials used in the toner manufacturing method of the present invention will be described.

  As the binder resin used in the present invention, known resins can be used. For example, homopolymers of styrene derivatives such as polystyrene and polyvinyltoluene; styrene-propylene copolymers, styrene-vinyltoluene copolymers, styrene -Vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate Copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-octyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer , Styrene-vinyl methyl ether Polymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer Styrene copolymer such as coalesced; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene Examples thereof include resins, phenol resins, aliphatic or alicyclic hydrocarbon resins, and aromatic petroleum resins, and these resins may be used alone or in combination.

  Among these, the polymer preferably used as the binder resin of the present invention is a resin having a styrene copolymer and a polyester unit.

  The following are mentioned as a polymerizable monomer used for a styrene-type copolymer. For example, 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, Styrene and its derivatives such as 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene; unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; and styrene and derivatives thereof such as butadiene and isoprene. Saturated polyenes; vinyl chloride, vinylidene chloride, vinyl bromide, fluorine 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, Alkenyl succinic acid half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester unsaturated dibasic acid half ester; dimethylmaleic acid, dimethyl fumaric acid unsaturated dibasic acid ester; acrylic acid, meta Α, β-unsaturated acids such as rillic acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride, the α, β-unsaturated acid and lower fatty acids And monomers having a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof.

  Further, 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.

  In the present invention, a resin having a polyester unit is particularly preferably used.

  The “polyester unit” means a part derived from polyester. Specifically, as a component constituting the polyester unit, a divalent or higher alcohol monomer component and a divalent or higher carboxylic acid, a divalent or higher valent acid, and the like. Examples include acid monomer components such as carboxylic acid anhydrides and divalent or higher carboxylic acid esters.

  For the toner used in the present invention, a resin having a polycondensation portion using a component constituting these polyester units as a part of a raw material can be used.

  For example, as a dihydric or higher alcohol monomer component, specifically, as a dihydric alcohol monomer component, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene ( 3.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -poly Alkylene oxide adducts of bisphenol A such as oxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, Ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1, -Propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol , Polypropylene glycol, polytetramethylene glycol, bisphenol A, hydrogenated bisphenol A, and the like.

  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.

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

  Examples of the black colorant include carbon black; a magnetic material; a black colorant prepared 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 present invention, for the purpose of improving the performance of the toner, external additives such as a fluidizing agent, a transfer aid, and a charge stabilizer can be mixed with the toner particles using a mixer such as a Henschel mixer. .

  As the fluidizing agent, any fluidizing agent can be used as long as it can increase the fluidity before and after the addition. For example, fluorine resin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; fine powder silica such as titanium oxide fine powder, alumina fine powder, wet process silica, and dry process silica; and silane compounds and organic It is possible to use treated silica that has been surface treated with a silicon compound, a titanium coupling agent, or silicone oil.

  In the case of titanium oxide fine powder, fine particles of titanium oxide obtained by low-temperature oxidation (thermal decomposition, hydrolysis) of sulfuric acid method, chlorine method, volatile titanium compounds such as titanium alkoxide, titanium halide and titanium acetylacetonate are used. As the crystal system, any of anatase type, rutile type, mixed crystal type thereof, and amorphous type can be used.

  And if it is alumina fine powder, buyer method, improved buyer method, ethylene chlorohydrin method, underwater spark discharge method, organoaluminum hydrolysis method, aluminum alum pyrolysis method, ammonium aluminum carbonate pyrolysis method, aluminum chloride flame Alumina fine powder obtained by a decomposition method is used. As the crystal system, α, β, γ, δ, ξ, η, θ, κ, χ, ρ type, mixed crystal type, amorphous type, α, δ, γ, θ, mixed crystal can be used. A mold or an amorphous material is preferably used.

  More preferably, the surface of the fine powder is subjected to a hydrophobic treatment with a coupling agent or silicone oil.

  The method of hydrophobizing the surface of the fine powder is a method of chemically or physically treating with an organosilicon compound that reacts or physically adsorbs with the fine powder.

  A preferable method for the hydrophobic treatment is a method in which silica fine particles produced by vapor phase oxidation of a silicon halogen compound are treated with an organosilicon compound. Examples of the organosilicon compound used in such a method include the following. Hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloro Ethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyl Disiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane Siloxane and dimethylpolysiloxane containing 2 to 12 siloxane units per molecule and containing hydroxyl groups bonded to one Si at each terminal unit. These are used alone or in a mixture of two or more.

The fluidizing agent preferably has 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 from the viewpoint of fluidity imparting property. The fluidizing agent is used in an amount of 0.1 to 8.0 parts by weight, preferably 0.1 to 4.0 parts by weight, based on 100 parts by weight of the toner.

  In the present invention, in order to further improve the dot reproducibility, it is preferable to use it as a two-component developer by mixing with a magnetic carrier because a stable image can be obtained over a long period of time.

  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.

  A method for measuring various physical properties of the toner will be described below.

<Measurement of particle size distribution>
The particle size distribution can be measured by various methods. In the present invention, the particle size distribution was performed 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 disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios) with 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.

<Measurement of average circularity of toner particles>
The average circularity of the 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 the calibration operation.

  As a specific measurement method, an appropriate amount of a surfactant, preferably an alkyl benzene sulfonate, is added to 20 ml of ion-exchanged water, and then 0.02 g of a measurement sample is added, and an oscillation frequency of 50 kHz and an electric output of 150 W is added. Dispersion treatment was carried out for 2 minutes using a desktop type ultrasonic cleaner / disperser (for example, “VS-150” (manufactured by VervoCrea Co., Ltd.)) to obtain a dispersion for measurement. It cools suitably so that it 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 determined.

  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.

<Measurement of specific surface area BET of toner>
The BET specific surface area is measured using a specific surface area measuring device Tristar 3000 (manufactured by Shimadzu Corporation).

  The specific surface area of the toner is calculated by adsorbing nitrogen gas on the sample surface according to the BET method and using the BET multipoint method. Prior to the measurement of the specific surface area, about 2 g of the sample is precisely weighed in a sample tube and evacuated at room temperature for 24 hours. After evacuation, the mass of the entire sample cell is measured, and the exact mass of the sample is calculated from the difference from the empty sample cell.

  An empty sample cell is set in the balance port and analysis port of the BET measuring device. Next, a Dewar bottle containing liquid nitrogen is set at a predetermined position, and P0 is measured by a saturated vapor pressure (P0) measurement command. After the P0 measurement is completed, the prepared sample cell is set in the analysis port, the sample mass and P0 are input, and the measurement is started by the BET measurement command. After that, the BET specific surface area is automatically calculated.

<Measurement of toner endothermic peak number and maximum endothermic peak maximum temperature>
Temperature curve: Temperature increase I (30 ° C. to 200 ° C., temperature increase rate 10 ° C./min)
Temperature drop I (200 ° C to 30 ° C, temperature drop rate 10 ° C / min)
Temperature rise II (30 ° C to 200 ° C, temperature rise rate 10 ° C / min)

  The maximum endothermic peak of the toner is measured according to ASTM D3418-82 using a differential scanning calorimeter (DSC measuring device) DSC2920 (manufactured by TA Instruments Japan).

  The measurement sample is precisely weighed in an amount of 3 to 7 mg, preferably 4 to 5 mg. Put it in an aluminum pan, use an empty aluminum pan as a reference, and measure at a temperature rise rate of 10 ° C / min at room temperature and humidity (23 ° C / 50% RH) between 30 and 200 ° C. Do.

  The number of endothermic peaks is the number of peak tops in the process of temperature increase II.

  For the maximum endothermic peak temperature, the temperature at the top of the peak with the highest endotherm among the peaks in the process of temperature increase II is measured.

<Measurement of molecular weight (main peak) by GPC (toner)>
The molecular weight of the chromatogram by gel permeation chromatograph (GPC) is measured under the following conditions.

The column was stabilized in a 40 ° C. heat chamber, and tetrahydrofuran (THF) as a solvent was allowed to flow through the column at this temperature at a flow rate of 1 ml / min. Is measured by injecting 100 μm. An RI (refractive index) detector is used as the detector. As the 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, μ-styragel 500, 103, 104, 105 manufactured by Waters And combinations of shodex KA-801, 802, 803, 804, 805, 806, and 807 manufactured by Showa Denko KK are preferable.

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 , It is appropriate to use 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples of the present invention, but the present invention is not limited to these examples.

(Manufacture of toner particles)
Resin having a polyester unit (weight average molecular weight (Mw) 82000, number average molecular weight (Mn) 3400, peak molecular weight (Mp) 8200) 100 parts by mass paraffin wax (maximum endothermic peak temperature 78 ° C.) 5 parts by mass 3 , 5-Di-t-butylsalicylic acid aluminum compound 1.0 part by mass I. Pigment Blue 15: 3 5 parts by mass After mixing the materials of the above formulation with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.), a twin-screw kneader (PCM-30 type, Kneaded by Ikekai Tekko Co., Ltd. The obtained kneaded material was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized material. The obtained coarsely pulverized toner was pulverized by a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.) to obtain toner fine particles.

  Further, the obtained toner fine particles were subjected to 6.2 μm ≦ D4 ≦ 6.8 μm, 20% by number ≦ toner particle size of 4.0 μm or less ≦ 35% by number, 1.0% by a multi-division classifier utilizing the Coanda effect. Classification was performed by adjusting the apparatus conditions so that the toner particles had a volume% ≧ particle diameter of 10.0 μm or more.

  The obtained toner particles have a weight average particle size (D4) of 6.2 μm, 26.7% by number of toner particles having a particle size of 4.0 μm or less, and 0.2 volume of toner particles having a particle size of 10.0 μm or more. %Met. Furthermore, as a result of measuring the circularity with FPIA3000, the average circularity was 0.935.

<Example 1>
The toner particles were heat-treated using the apparatus shown in FIG. The operating conditions at this time are hot air temperature = 250 ° C., hot air flow rate = 6.0 m ³ / min, cold air 1 = 3.0 m ³ / min, cold air 2 = 1.0 m ³ / min, cold air 3 = 3.0 m ³ / min, the cold air temperature = 5 ° C., floors air volume = 23.0m ³ / min, an injection flow rate = 2.4 m ³ / min, the tubular member 1 in the flow rate of 0.4 m ³ / min, the tubular member 2 in the flow rate = 0. It was 2 m ³ / min. The operation time was 1 hour.

  In the present embodiment, the raw material supply means and the first nozzle are integrally formed and formed into a jacket.

  The ridge line angle α of the first nozzle is 40 ° and the ridge line angle β of the second nozzle is 60 °, and a return portion is provided at the lower end of the second nozzle. The outermost diameter of the lower end of the first nozzle is Φ77, the outermost diameter of the lower end of the second nozzle is Φ71, and the vertical distance (H1) between the lower end of the first nozzle and the lower end of the second nozzle is 5 mm. Furthermore, the distance (H2) between the lower end of the first nozzle and the lower end of the hot air supply means is 10 mm below. A spinning nozzle is used as the spraying means.

  The outermost diameter of the tubular member 1 was Φ15 mm, the outermost diameter of the tubular member 2 was Φ8 mm, and the lower end position of the tubular member 1 was 5 mm above the rear end of the second nozzle.

  The hot air supply means and the supply portion of the cold air 1 have an inner diameter (B) of 450 mm. The hot air supply means outlet has an inner diameter of 200 mm and an outer diameter of 300 mm, and the cold air supply means 1 is arranged with an inner diameter of 350 mm and an outer diameter of 450 mm.

  The outer diameter (A) of the rectifying means was Φ350 mm.

  First, heat treatment was performed at a feed rate of 15 kg / hr.

  As for the particle size distribution of the spheroidized toner particles obtained at this time, the weight average particle size is 6.4 μm, the particle size is 4.0 μm or less is 25.8% by number, and 10.0 μm or more is 4.1 volume. %Met.

  When the average circularity of the obtained toner particles and the particle content of 2 μm or less were measured, the average circularity was 0.982.

  Next, heat treatment was performed at a feed rate of 40 kg / hr without changing operating conditions.

  The particle size distribution of the spheroidized toner particles obtained at this time has a weight average particle size of 6.6 μm, a particle size of 4.0 μm or less is 23.9% by number, and 10.0 μm or more is 6.2 volumes. %Met.

  When the average circularity of the obtained toner particles and the particle content of 2 μm or less were measured, the average circularity was 0.978.

  In the obtained particle size distribution, the following criteria were evaluated by paying attention to a numerical value of 10.0 μm or more.

(Evaluation criteria 1)
The increase rate of the toner particles of 10.0 μm or more when increasing the processing amount (= volume% at 40 kg / hr−volume% at 15 kg / hr) is A: 0 (volume%) or more to 3.0 ( Less than volume%) B: 3.0 (volume%) or more to less than 5.0 (volume%) C: 5.0 (volume%) or more to less than 10.0 (volume%) D: 10.0 (volume%) ) Or more to less than 15.0 (volume%) E: 15.0 (volume%) or more

(Evaluation criteria 2)
No fusion in device: ○
Available: ×

  As a result of evaluation based on the evaluation criteria 1 and 2, even when the feed amount was increased, there was no occurrence of fusion, and an increase in toner particles of 10.0 μm or more could be suppressed. Further, even if the feed amount is increased, the decrease in average circularity is kept small.

  These results are summarized in Table 1.

<Example 2>
In this embodiment, the raw material supply means shown in FIG. 3 was used. The lower end portion of the raw material supply means was 10 mm downstream from the hot air supply means, and the spheroidization treatment was performed under the same control conditions as in Example 1. (None tubular members 1 and 2)

  First, heat treatment was performed at a feed rate of 15 kg / hr.

  As for the particle size distribution of the spheroidized toner particles obtained at this time, the weight average particle size is 6.4 μm, the particle size of 4.0 μm or less is 25.2% by number, and the particle size distribution of 10.0 μm or more is 5.3. % By volume.

  When the average circularity of the obtained toner particles and the particle content of 2 μm or less were measured, the average circularity was 0.976.

  Next, heat treatment was performed at a feed rate of 40 kg / hr.

  As for the particle size distribution of the spheroidized toner particles obtained at this time, the weight average particle size is 6.8 μm, the particle size of 4.0 μm or less is 23.9% by number, and the particle size distribution of 10.0 μm or more is 9.2. % By volume.

  When the average circularity of the obtained toner particles and the particle content of 2 μm or less were measured, the average circularity was 0.971.

  These results are summarized in Table 1.

<Example 3>
In this example, the spheronization treatment was performed in the same manner as in Example 1 except that the rectifying means outer diameter (A) was Φ225 mm.

  These results are summarized in Table 1.

<Example 4>
In this example, the spheronization treatment was performed in the same manner as in Example 1 except that the rectifying means outer diameter (A) was set to Φ427.5 mm.

  These results are summarized in Table 1.

<Example 5>
In this example, the spheronization treatment was performed in the same manner as in Example 1 except that the rectifying means outer diameter (A) was set to Φ220 mm.

  These results are summarized in Table 1.

<Example 6>
In this example, the spheronization treatment was performed in the same manner as in Example 1 except that the rectifying means outer diameter (A) was Φ430 mm.

  These results are summarized in Table 1.

<Comparative Example 1>
In this comparative example, the spheronization process was performed using the apparatus shown in FIG. The raw material supply means (6 in the figure) is inserted into the hot air supply means (5 in the figure), and an outside air intake is provided on the outer periphery of the hot air supply means.

Hot air temperature = 350 ° C., hot air flow rate = 10.0 m ³ / min, cold air = 10.0 m ³ / min, injection flow rate = 3.0 m ³ / min, and operation time was 1 hour.

  First, heat treatment was performed at a feed rate of 15 kg / hr.

  The particle size distribution of the spheroidized toner particles obtained at this time has a weight average particle size of 6.6 μm, a particle size of 4.0 μm or less is 24.9% by number, and a particle size of 10.0 μm or more is 8. It was 3% by volume.

  When the average circularity of the obtained toner particles and the particle content of 2 μm or less were measured, the average circularity was 0.980.

  Next, heat treatment was performed at a feed rate of 40 kg / hr.

  The particle size distribution of the spheroidized toner particles obtained at this time has a weight average particle size of 8.1 μm, a particle size of 4.0 μm or less is 22.1% by number, and a particle size of 10.0 μm or more is 21. It was 2% by volume.

  When the average circularity of the obtained toner particles and the particle content of 2 μm or less were measured, the average circularity was 0.971.

  Further, when the inside of the apparatus was observed after completion of the spheronization treatment, the toner particles were found to be fused to the diffusion plate provided under the toner particle supply nozzle. This suggests that maintenance is required in a relatively short cycle, and there is concern in terms of production stability.

  These results are summarized in Table 1.

  The reason why the toner particles of 10.0 μm or more increase is that the toner particle supply nozzle is inserted in the hot air, so that the heat is trapped at the nozzle outlet, so that the toner particles coalesce and coarse particles increase. It depends. As the number of added wax parts increases, the amount of the wax exuded by heat treatment increases, and it tends to be easily affected by coalescence. In addition, compared with the embodiment, this comparative example has a large hot air flow rate, cold air flow rate, and injection flow rate to be supplied, and a high hot air temperature, which is not preferable from the viewpoint of manufacturing energy.

<Comparative example 2>
In this comparative example, the spheronization process was performed in the same manner as in Example 1 except that the apparatus configuration of Example 2 except that the apparatus of the configuration excluding the rectifying means was used.

  These results are summarized in Table 1.

  In the configuration of this comparative example, the average circularity is lower than that in Example 2, but in order to increase the average circularity to the same level, it is necessary to increase the hot air temperature or the hot air flow rate. However, in this case, the ratio of coarse particles of 10.0 μm or more due to coalescence of toner particles further increases. If it becomes so, the fall of the classification yield in the classification process for removing a coarse particle will be caused. Also, from the viewpoint of production energy, the energy increases, which is not preferable.

<Comparative Example 3>
In this comparative example, the spheronization process was performed using the apparatus shown in FIG. Hot air supply means (5 in the figure) is provided on the outer periphery of the raw material supply means (7 in the figure), and a toner supply nozzle (9 in the figure) is provided at the tip of the raw material supply means (7 in the figure). It has been. Sixteen toner particle supply nozzles are arranged.

Hot air temperature = 250 ° C., hot air flow rate = 12.0 m ³ / min, cold air = 5.0 m ³ / min, injection flow rate = 3.0 m ³ / min, and operation time was 1 hour.

  First, heat treatment was performed at a feed rate of 15 kg / hr.

  The particle size distribution of the spheroidized toner particles obtained at this time has a weight average particle size of 6.5 μm, a particle size of 4.0 μm or less is 25.1% by number, and a particle size of 10.0 μm or more is 6. It was 9% by volume.

  When the average circularity of the obtained toner particles and the particle content of 2 μm or less were measured, the average circularity was 0.979.

  Next, heat treatment was performed at a feed rate of 40 kg / hr.

  The particle size distribution of the spheroidized toner particles obtained at this time has a weight average particle size of 7.5 μm, a particle size of 4.0 μm or less is 23.4 number%, and a particle size of 10.0 μm or more is 17. It was 3% by volume.

  When the average circularity of the obtained toner particles and the particle content of 2 μm or less were measured, the average circularity was 0.973.

  These results are summarized in Table 1.

  The reason why the toner particles of 10.0 μm or more increase is that the toner particles supplied from the nozzle to the hot air are supplied in an insufficiently dispersed state, and thus the aggregated toner particles are coarsely treated by heat treatment. By increasing the number of particles. As the number of added wax parts increases, the amount of the wax exuded by heat treatment increases, and it tends to be easily affected by coalescence. In addition, compared with the comparative example, the comparative example has a large flow rate of hot air to be supplied and an injection flow rate, which is not preferable from the viewpoint of manufacturing energy.

  The apparatus of the present invention is used for the thermal spheronization treatment of toner.

It is sectional drawing of the heat processing apparatus of this invention. It is a partial cross section perspective view of the heat processing apparatus of this invention. It is sectional drawing of the raw material supply means of Example 2 of this invention. It is heat processing mechanism explanatory drawing in the heat processing apparatus of this invention. It is heat processing mechanism explanatory drawing in the heat processing apparatus of this invention. 2 is a heat treatment apparatus of Comparative Example 1; 6 is a heat treatment apparatus of Comparative Example 3.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Heat processing apparatus main body 2 ... Hot-air supply means 3 ... Cold-air supply means 1
4. Cool air supply means 2
5. Cool air supply means 3 (cooling and conveying means)
6 ... Tubular member 1
7. Tubular member 2
8 ... Raw material supply means 9 ... First nozzle 10 ... Second nozzle 11 ... Injection means (spinning nozzle)
12 ... Spraying means (spray nozzle)
13 ... Recovery means 14 ... Rectification means

Claims (4)

A heat treatment apparatus for toner having a raw material supply means for supplying a raw material, a hot air supply means for heat-treating the supplied raw material, and a discharge unit for discharging the heat-treated toner,
Hot air supply means is provided in an annular shape so as to surround the raw material supply means at a position close to the outer peripheral surface of the raw material supply means or at a distance from the horizontal direction,
From the outlet of the raw material supply means, the raw material is supplied toward the hot air supplied from the hot air supply means,
The discharge part is present downstream of the raw material supply means and the hot air supply means,
The toner heat treatment apparatus adjusts the flow of the heat-treated toner at the axial center portion inside the apparatus, downstream of the raw material supply means and hot air supply means and upstream of the discharge section. The toner heat treatment apparatus is characterized in that the toner subjected to heat treatment by introducing a cooling medium into the rectification means passes between the inner wall surface of the heat treatment apparatus and the rectification means. . A heat treatment apparatus for toner having a raw material supply means for supplying a raw material, a hot air supply means for heat-treating the supplied raw material, and a discharge unit for discharging the heat-treated toner,
Hot air supply means is provided in an annular shape so as to surround the raw material supply means at a position close to the outer peripheral surface of the raw material supply means or at a distance from the horizontal direction,
From the outlet of the raw material supply means, the raw material is supplied toward the hot air supplied from the hot air supply means,
The discharge part is present downstream of the raw material supply means and the hot air supply means,
The toner heat treatment apparatus adjusts the flow of the heat-treated toner at the axial center portion inside the apparatus, downstream of the raw material supply means and hot air supply means and upstream of the discharge section. The heat-treated toner having the rectifying means passes between the inner wall surface of the heat treatment apparatus and the rectifying means,
In the horizontal cross section of the toner heat treatment apparatus at the position where the rectification means is provided, the relationship between the outer diameter A of the rectification means and the inner diameter B of the heat treatment apparatus is:
0.5 × B ≦ A ≦ 0.95 × B
Heat treatment apparatus features and to belt toner that is. A heat treatment apparatus for toner having a raw material supply means for supplying a raw material, a hot air supply means for heat-treating the supplied raw material, and a discharge unit for discharging the heat-treated toner,
Hot air supply means is provided in an annular shape so as to surround the raw material supply means at a position close to the outer peripheral surface of the raw material supply means or at a distance from the horizontal direction,
From the outlet of the raw material supply means, the raw material is supplied toward the hot air supplied from the hot air supply means,
The raw material supply means has a first nozzle and a second nozzle that expand in a tapered shape from the upstream to the downstream in the raw material supply direction at the outlet, and the second nozzle is the first nozzle. The raw material disposed and supplied inside the nozzle passes through a space formed by the inside of the first nozzle and the outside of the second nozzle ,
The discharge part is present downstream of the raw material supply means and the hot air supply means,
The toner heat treatment apparatus adjusts the flow of the heat-treated toner at the axial center portion inside the apparatus, downstream of the raw material supply means and hot air supply means and upstream of the discharge section. The toner heat treatment apparatus, wherein the heat-treated toner passes between the inner wall surface of the heat treatment apparatus and the rectification means . A toner manufacturing method for obtaining toner through a heat treatment step of toner particles,
The toner has a weight average particle diameter of 4 μm or more and 12 μm or less,
In the heat treatment step, method for producing a toner, wherein the heat treatment apparatus of the toner is used according to any one of claims 1 to 3.

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