JP5773769B2 - Heat treatment method for powder particles and toner production method - Google Patents

Description

  The present invention relates to a toner heat treatment apparatus and a toner manufacturing method 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.

  Image forming apparatuses using electrophotographic technology have been used not only as printers and multifunction machines in offices and homes, but also in commercial printing applications such as advertisements and brochures in recent years. For this reason, the performance required for the toner as the developer is diversified, and various types of toners are required depending on the application.

  In recent years, as a transfer material for copying machines and printers, in addition to plain paper and overhead projector film (OHT), there is a need for various materials for thick paper such as glossy paper, cards, and small size paper such as postcards. It has been demanded. For this reason, the performance required for toner as transfer performance is becoming more severe.

  As one of the techniques for increasing these transfer efficiencies, studies have been made in recent years to improve a toner produced by a pulverization method (hereinafter also referred to as a pulverized toner) by sphering it with heat. However, if the toner shape is made too spherical, problems are likely to occur in the cleaning process in the electrophotographic process, and a high degree of control of the degree of spheroidization of the toner is required in order to achieve both transferability and cleaning ability.

  For example, in Patent Document 1, a slewing mechanism for dispersing powder particles as a raw material and a heating mechanism for heating the dispersed powder particles from the inside thereof are used as a method for thermal spheronization of the pulverized toner. A heat treatment apparatus is proposed. In the above apparatus configuration, the powder particles are supplied so that the dispersed air flow and heated air flow of the raw material powder particles are in the opposite swirl direction, thereby facilitating dispersion and ensuring the desired sphericity. . However, when the processing amount of the powder particles is increased or used for a long period of time, there are cases where problems such as fusion of raw materials in the apparatus occur.

  Moreover, in the above apparatus configuration, when continuously producing various types of powder particles having different compositions, physical properties, etc., the dispersion of the raw materials in the apparatus depends on the particle diameter or the specific gravity of the raw material powder particles. As a result, the desired sphericity could not be obtained, and it was easy to cause fusion in the apparatus.

  Moreover, in patent document 2, after carrying out the heat processing by applying the hot air from the outer peripheral part to the dispersion | distribution airflow of the powder particle | grains which are raw materials, the adhesion and turbulent flow of a particle | grain are suppressed by blowing the cooling air from the side wall upper part in slit shape. A proposal has been made to improve productivity (see Patent Document 2).

  However, in this apparatus configuration, a large amount of dispersed air flow of the powder particles as the raw material is required, so that the heated air flow is cooled, and more heat than necessary is required to spheroidize the powder particles. For this reason, the amount of heat that the powder particles receive in the apparatus varies, and uniform heat treatment cannot be performed, and the shape of the toner particles after processing may not be uniform. Similarly, in the case of continuously producing various types of powder particles having different compositions and physical properties, it is difficult to adjust the hot air temperature and the amount of hot air, which tends to increase the operating time and increase the energy consumption.

  In this way, although it is possible to spheroidize powder particles under a certain condition, the degree of spheroidization can be easily adjusted, and a variety of powder particles can be produced continuously and stably over a long period of time. There is no manufacturing method yet.

  Incidentally, the coarse particles of the toner particles described in the specification of the present invention indicate a particle group that is twice or more the toner particle weight average particle diameter (D4).

Japanese Patent Laid-Open No. 62-133466 JP 59-125742 A

The object of the present invention is to reduce the time for changing the conditions and stably spheroidize the powder particles over a long period of time even when continuously producing various types of powder particles having different compositions and physical properties. It is to provide a manufacturing method capable of.

An object of the present invention is to provide a production method capable of obtaining a toner satisfying both high transferability and cleanability and satisfying a high-definition and high-quality image.

The present invention, the powder particles containing a binder resin and a colorant, a heat treatment method of the powder particles heat treatment using a heat treatment apparatus,
The heat treatment apparatus
(1) a cylindrical processing chamber in which the powder particles are heat-treated;
(2) powder particle supply means for supplying the powder particles to the processing chamber;
(3) a hot air supply means for the hot air for heat treating the supplied powder particles in the processing chamber for supplying to the processing chamber,
( 4) cold air supply means for supplying cold air for cooling the heat treated powder particles to the processing chamber ;
(5) recovery means for recovering the powder particles heat-treated from the lower end side of the processing chamber;
Have
The cylindrical processing chamber is installed so that its central axis is in the vertical direction,
The powder particle supply means includes
(I) the outer peripheral portion of the processing chamber is provided plurality of lower flow side than the outlet portion of the hot air supply means,
(Ii) the direction of injection the powder particles ejected from the outlet portion of the powder particle supply means is provided with an adjustable adjustment mechanism with respect to the vertical direction and the horizontal direction of the treatment chamber,
The hot air supply means is provided so that hot air supplied to the processing chamber swirls in the processing chamber,
The recovery means so as to maintain the turning direction of the powder particles to pivot the processing chamber are arranged on the outer peripheral portion of the processing chamber,
In the vertical cross section of the processing chamber,
An injection direction of the powder particles injected from an outlet of the powder particle supply means;
Horizontal and
The angle formed by the vertical ejection angle α (°),
In the horizontal cross section of the processing chamber,
An injection direction of the powder particles injected from an outlet of the powder particle supply means;
A direction connecting the outlet of the powder particle supplying means and the central axis of the processing chamber in a horizontal direction;
When the angle formed by the horizontal injection angle β (°),
The vertical ejection angle α (°) and the horizontal ejection angle β (°) are
−45 (°) ≦ α ≦ + 45 (°)
−20 (°) ≦ β ≦ + 90 (°)
The present invention relates to a heat treatment method for powder particles , wherein the powder particles are supplied to the treatment chamber so as to satisfy the above .

Further, the present invention is that the powder particles containing a binder resin and a colorant, in the method for producing a toner having a heat treatment step of heat treatment using a heat treatment apparatus, the heat treatment step is performed by heat treatment method having the aforementioned configuration The present invention relates to a toner production method.

  According to the apparatus for producing powder particles of the present invention, even when continuously producing various types of toner particles having different compositions, physical properties, etc., the condition change time is shortened and the processing amount is affected. Thus, a toner having a desired sphericity can be obtained.

It is the perspective view which showed an example of the heat processing apparatus by this invention. It is a schematic sectional drawing in the A-A 'plane in FIG. It is a turning member for turning hot air spirally used for the heat treatment apparatus of the present invention. It is a schematic sectional drawing of the powder supply means division | segmentation used for the heat processing apparatus of this invention. It is a schematic sectional drawing for demonstrating the raw material introduction direction used for the heat processing apparatus of this invention. It is a schematic sectional drawing for demonstrating the raw material introduction direction used for the heat processing apparatus of this invention. It is a schematic sectional drawing of the heat processing apparatus used for the comparative example 1 of this invention. It is a schematic sectional drawing of the hot air and raw material supply part of the heat processing apparatus used for the comparative example 2 of this invention.

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

  First, the outline of the heat processing apparatus used for this invention is demonstrated using FIG.1, FIG.2, FIG.3 and FIG.

  FIG. 1 is a schematic sectional view showing an example of a heat treatment apparatus according to the present invention. FIG. 2 is a schematic cross-sectional view taken along the plane A-A ′ in FIG. 1. Furthermore, FIG. 3 is a turning member for turning hot air spirally used in the heat treatment apparatus of the present invention. FIG. 4 is a schematic cross-sectional view of the powder particle supply means division used in the heat treatment apparatus of the present invention.

  As shown in FIGS. 1 and 2, the heat treatment apparatus of the present invention has a cylindrical processing chamber 1 in which heat treatment of powder particles, which are raw materials of toner particles, is performed.

  In the heat treatment apparatus of the present invention, the shape of the processing chamber may be a cylindrical shape, but the diameter T (mm) of the processing chamber is preferably 350 mm ≦ T ≦ 900 mm. If the diameter of the processing chamber is within the above range, the heat-treated toner particles can be produced efficiently. When the diameter T (mm) of the processing chamber is T <350 mm, the dust concentration of the powder particles in the processing chamber increases, and the processing amount of the powder particles may not be increased. On the other hand, if 900 mm <T, it is necessary to increase the size of ancillary equipment of a heat treatment device such as a blower, a heater, or a cold air generator, which may be undesirable in terms of toner production energy.

  Further, the inside of the processing chamber is preferably cooled by a cooling jacket in order to prevent fusion of the powder particles. It is desirable to introduce cooling water (preferably an antifreeze such as ethylene glycol) into the cooling jacket, and the surface temperature of the cooling jacket is preferably 40 ° C. or lower.

  Hot air for heat-treating the powder particles that are the raw material of the toner in the heat treatment apparatus of the present invention is supplied from the hot air supply means 3. The hot air supplied into the processing chamber preferably has a temperature N (° C.) at the outlet of the hot air supply means 3 of 100 ° C. ≦ N ≦ 300 ° C. If the temperature at the outlet of the hot air supply means is within the above range, it is possible to obtain toner particles that are uniformly spheroidized while preventing fusion and coalescence of the powder particles due to excessive heating.

  The hot air supply means in the heat treatment apparatus of the present invention is characterized in that the supplied hot air is provided so as to swirl within the apparatus. As its configuration, for example, a revolving member 8 shown in FIG. 3 has a plurality of blades 9 and a blade capable of controlling the swirling of hot air according to the number and angle of the blades 9 is disposed at the heat supply means outlet. A configuration is preferred.

  In addition, it is preferable that the wind speed Vh (m / s) of the hot air introduced into the processing chamber from the swirling member of the hot air supply means is 25 m / s ≦ Vh ≦ 85 m / s. If the flow velocity of the hot air is within the above range, the shearing force applied to the toner is improved, and the powder particles are heat-treated in a more dispersed state.

  When the wind velocity Vh (m / s) of the hot air introduced from the swirling member into the processing chamber becomes Vh <25 m / s, the hot air swirling in the processing chamber is weakened, so that sufficient centrifugal force is not applied to the powder particles, The dispersion of the powder particles may not be improved. On the other hand, when 85 m / s <V, the flow rate of hot air in the processing chamber becomes too fast, and sufficient heat treatment may not be performed.

  In the heat treatment apparatus of the present invention, the powder particle supply means for supplying the powder particles to the processing chamber is an apparatus downstream from the hot air supply means outlet 3a as shown in the powder supply means 2 of FIGS. A plurality of outer peripheral portions are provided.

  As shown in FIG. 4, the number of divisions of the powder supply means of the heat treatment apparatus of the present invention is preferably 4 divisions, more preferably 8 divisions. When the powder supply means is divided into eight parts, an increase in the coalesced particles of the powder particles can be suppressed even if the amount of treatment is increased during the heat treatment. As the number of divisions of the powder particle supply means increases, the powder particles introduced into the processing chamber can be heat-treated in a state where the dust concentration is reduced, and the amount of heat necessary for the heat treatment can be reduced. That is, at the same temperature, the circularity of the toner particles after the heat treatment increases as the number of divided powder particle supply means increases. Furthermore, since it is configured to be supplied from the outer peripheral portion of the apparatus into the processing chamber, the contact time is increased in the swirling of hot air in the processing chamber, and the surface treatment can be performed efficiently.

  Further, one of the features of the present invention is that the raw material introduction direction can be adjusted according to the composition and state of the raw material or the required sphericity.

  Normally, the convection time in the processing chamber and hot air swirl changes due to differences in physical properties such as the particle size and specific gravity of the powder particles that are the raw material of the toner particles, and the sphericity of the processed toner particles, the particle size distribution, etc. Affects. For this reason, it is usually necessary to control the amount of heat applied to the raw material particles by adjusting the apparatus configuration or operating conditions such as the amount of hot air and the temperature of hot air. However, when such a condition adjustment is performed during continuous production, it takes a certain amount of time for the operating conditions to stabilize. This leads to an increase in energy consumption, and the remaining raw material tends to cause fusion in the apparatus when the apparatus is stabilized. Therefore, as in the present invention, production stability and efficiency can be achieved by adjusting the powder particle introduction direction according to the raw material composition and physical properties, and making the behavior of the raw material constant in the processing chamber.

Moreover, the powder particle supply means of the heat treatment apparatus of the present invention includes an adjustment mechanism that can inject the powder particles from the powder particle supply means outlet in either the vertical direction or the horizontal direction of the main body. . Specifically, the powder particle introduction (injection) direction is, as shown in FIGS. 5 and 6, the injection direction and the horizontal direction of the powder particles injected from the powder particle supply means outlet in the vertical section of the apparatus. Vertical ejection angle α (°),
And a horizontal injection angle formed by the injection direction of the powder particles injected from the outlet of the powder particle supply means in the horizontal section of the apparatus and the direction connecting the outlet portion of the powder particle supply means and the center of the apparatus β (°) is −45 (°) ≦ α ≦ + 45 (°)
−20 (°) ≦ β ≦ + 90 (°)
In order to control the degree of spheroidization and particle size distribution of the surface-modified particles after the treatment, it is preferable to make the adjustment within the range satisfying the above. Note that α in FIG. 6 indicates a case of “+”, and becomes “−” when the powder particle injection direction is upward. In addition, β in FIG. 5 indicates a case of “+”, and becomes “−” when the powder particle injection direction opposes the hot air swirling direction.

  When α (°) is larger than 45 (°), the powder particles are in a direction away from the hot air swirl region, and a large amount of energy is required to obtain a desired sphericity, which is not preferable. When it is smaller than −45 (°), the powder particles suddenly enter the hot air swirl region, and coarse particles are likely to be generated due to the influence of coalescence between the particles.

  On the other hand, when the horizontal injection angle β (°) is smaller than −20 (°), the swirling flow in the apparatus is disturbed, and the dispersion of the powder particles becomes insufficient, and similarly, the unity between particles is likely to occur.

  In the heat treatment apparatus of the present invention, the cold air supply means for cooling the heat-treated powder particles is disposed downstream of the powder particle supply means outlet as shown in the cold air supply means 4 of FIGS. It is characterized by that.

  By arranging the cold air supply means downstream of the powder particle supply means, the introduced cold air does not excessively cool the heat treatment zone in the processing chamber, and the heat treatment necessary for making the powder particles spherical. Prevent excessive temperature.

  The temperature R (° C.) supplied from the cold air supply means 4 is preferably −20 ° C. ≦ R ≦ 30 ° C. If the temperature of the cold air is within the above range, the powder particles can be efficiently cooled, and the powder particles can be fused or coalesced without hindering the uniform spheroidization of the powder particles. Can be prevented.

  A plurality of cold air supply means 4 of the heat treatment apparatus of the present invention are provided on the outer periphery of the processing chamber, and the cold air supplied from the cold air supply means is in the same direction as the swirling direction of the hot air along the inner peripheral surface of the processing chamber. It is preferable that it is provided so that it may be supplied to.

  By taking the above configuration, the cold air supplied from the cold air supply means is supplied from the outer periphery of the apparatus to the peripheral surface of the processing chamber in a horizontal and tangential direction, and the powder particles rotating around the peripheral surface of the processing chamber are more uniformly and Cooling can be efficiently performed, and adhesion of powder particles to the processing chamber wall surface is suppressed.

  In addition, since the swirl direction of the cool air supplied from the cool air supply means is the same direction as the swirl direction of the hot air, no turbulent flow occurs in the processing chamber, so when the processing amount increases and the dust concentration in the apparatus increases. In addition, coalescence of the powder particles can be prevented.

  In addition, by adopting a configuration in which a plurality of cold air supply means are provided and the cold air is divided and introduced, it is easy to uniformly control the flow of air in the apparatus, and the swirl flow is further strengthened, and centrifugal force is applied to the powder particles. Even in long-term use, the dispersibility of the powder particles in the apparatus is improved, and problems such as coalescence of the powder particles are less likely to occur.

  Moreover, it is preferable that the air volume and temperature of the introduced cold air can be controlled independently. For example, as shown in FIG. 1, it is preferable that the cold air supply means is provided in three stages so as not to be in the same circumferential direction.

  In this case, as shown in FIG. 1, the first stage cool air (4-1) is a cool air for efficiently feeding the toner introduced into the processing chamber into the heat treatment zone, and the second stage (4-2) is a powder. In order to cool the body particles, the function can be separated from the cold air. Further, the third stage cool air (4-3) is used to cool the toner collecting means, and the functions of the respective cool air can be separated. In addition, when cold air introduction is two-stage, two combinations among the above three cold air functions may be arbitrarily selected.

  Further, the recovery means for recovering the heat-treated powder particles from the lower end side of the processing chamber, as shown in the recovery means 6 of FIGS. 1 and 2, maintains the swirling direction of the swirled powder particles. It is provided in the outer peripheral part of a chamber.

  As a result, the swirling flow in the apparatus can be maintained, the centrifugal force applied to the powder particles is maintained, the flow of the raw material particles in the apparatus is stabilized, and adhesion and fusion to the apparatus members are reduced. The In the heat treatment apparatus of the present invention, the powder particle recovery means may be in the direction of maintaining the swirling flow at the lowermost end in the apparatus, and there may be a plurality of powder particle recovery means. In addition, a blower (not shown) is provided at the tip of the collecting means, and is configured to be sucked and conveyed by the blower.

  In the heat treatment apparatus of the present invention, the relationship between the total amount QIN of the flow rate of compressed air, hot air, and cold air supplied into the device and the air amount QOUT sucked by the blower is adjusted to satisfy the relationship of QIN ≦ QOUT. Is preferred. If QIN ≦ QOUT, the pressure in the apparatus becomes negative, so that the toner particles in the processing chamber are easily discharged out of the apparatus, and the toner particles can be prevented from receiving excessive heat. As a result, an increase in united powder particles and fusion within the apparatus can be prevented, and a toner can be manufactured stably even in long-term use.

  Further, in the heat treatment apparatus of the present invention, in order to regulate the flow of the powder particles, a columnar member having a circular cross section like the regulating means 5 in FIG. 2 protrudes from the lower end portion to the upper end portion of the processing chamber. Thus, it is preferable to arrange on the central axis of the processing chamber. In FIG. 2, the conical member 7 is provided on the upper portion of the regulating means 5, but is not particularly involved in the present invention.

  As a result, the toner flow rate at the end of the powder particle collecting means side can be increased, the powder particle discharge performance can be improved, and adhesion and fusion in the collecting unit and coalescence of the powder particles can be prevented. Can do.

  In the heat treatment apparatus of the present invention, the ratio V (% by volume) of the regulating means 5 for regulating the flow of the powder particles in the processing chamber is preferably 5% by volume ≦ V ≦ 60% by volume. By being within the above range, it is considered that the flow rate of the powder particles in the processing chamber can be controlled, and the dispersibility and dischargeability of the powder particles are improved. When the ratio V (volume%) of the regulating means 5 for regulating the flow of the powder particles in the processing chamber is V <5% by volume, the toner swirl in the processing chamber is weakened. The centrifugal force is not applied and the dispersion of the powder particles may not be improved. On the other hand, if 60% by volume <V, the flow rate of the powder particles in the processing chamber becomes too fast, and sufficient heat treatment may not be performed.

  The columnar member is preferably provided with a cooling jacket in order to prevent fusion of the powder particles. Further, it is desirable to introduce cooling water (preferably an antifreeze such as ethylene glycol) into the cooling jacket, and the surface temperature of the cooling jacket is preferably 40 ° C. or lower.

  Next, a procedure for producing toner using the toner particle production apparatus of the present invention will be described.

  First, in the raw material mixing step, at least a resin and a colorant are weighed and mixed as a toner raw material, and mixed. As an example of a mixing apparatus, Henschel mixer (Mitsui Mining Co., Ltd.); Super mixer (Kawata Co., Ltd.); Ribocorn (Okawara Seisakusho Co., Ltd.); There are mixers (manufactured by Taiheiyo Kiko Co., Ltd.);

  Further, the mixed toner material is melt-kneaded in a melt-kneading step to melt the resins and disperse the colorant and the like therein. As an example of a kneading apparatus, a TEM type extruder (manufactured by Toshiba Machine Co., Ltd.); a TEX twin-screw kneader (manufactured by Nippon Steel Works); a PCM kneader (manufactured by Ikekai Iron Works Co., Ltd.); However, a continuous kneader such as a single-screw or twin-screw extruder is preferable to a batch kneader because of the advantage of being capable of continuous production.

  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 with a crusher, a hammer mill, a feather mill, etc., and further finely pulverized with a kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), a super rotor (manufactured by Nisshin Engineering Co., Ltd.) to obtain toner fine particles. .

  The obtained toner fine particles are classified into powder particles having a desired particle diameter in the classification step. Examples of the classifier include turboplex, faculty, TSP separator, TTSP separator (manufactured by Hosokawa Micron), elbow jet (manufactured by Nippon Steel Mining).

  Subsequently, the obtained powder particles are subjected to a spheronization treatment in the heat treatment step using the heat treatment apparatus of the present invention to obtain toner particles.

  In the method for producing a toner of the present invention, it is preferable to add inorganic fine particles or the like to the obtained powder particles as necessary before the heat treatment step. As a method of adding the inorganic fine powder to the powder particles, a predetermined amount of the powder particle particles and various known inorganic fine powders are blended, and the Henschel mixer, Mechano Hybrid (Mitsui Mining Co., Ltd.), Super Mixer, Nobilta (Hosokawa Micron Co., Ltd.) The mixture is stirred and mixed using a high-speed stirrer that applies shear force to the powder.

  In the toner manufacturing method of the present invention, before the heat treatment step, the inorganic fine powder is added to the powder particles so that fluidity is imparted to the powder particles, and the powder particles introduced into the processing chamber are It becomes possible to disperse more uniformly and contact with hot air, and surface-modified particles having excellent uniformity can be obtained.

  In the toner manufacturing method of the present invention, when coarse particles exist in the toner particles after the heat treatment, a step of removing the coarse particles by classification may be included as necessary. Examples of the classifier for removing coarse particles include a turboplex, a TSP separator, a TTSP separator (manufactured by Hosokawa Micron), and an elbow jet (manufactured by Nippon Steel Mining).

  Furthermore, after the surface modification, for example, Ultrasonic (manufactured by Koei Sangyo Co., Ltd.); Resona sieve, Gyroshifter (Tokuju Kogakusha Co., Ltd.); A sieving machine such as Hivolter (Toyo Hitec Co., Ltd.) may be used.

  The heat treatment step of the present invention may be after the fine pulverization or after classification.

  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, 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 acid anhydride and cinnamic acid 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.

  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.

  In the present invention, inorganic fine powders such as a fluidizing agent, a transfer aid, and a charge stabilizer can be mixed with powder particles or 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.

  The above fluidizing agents may be used alone or in combination of two or more.

  The fluidizing agent may be used in an amount of 0.1 to 8.0 parts by mass, preferably 0.1 to 4.0 parts by mass with respect to 100 parts by mass of powder particles or toner particles. . If the addition amount is less than 0.1 parts by mass, it is not preferable because the fluidity cannot be imparted to the powder particles or toner particles. When the amount exceeds 4.0 parts by mass, mixing of the powder particles or toner particles and the inorganic fine powder becomes difficult, which is not preferable in terms of material dispersibility.

  A method for measuring various physical properties of the powder particles and toner particles and a method for measuring various physical properties measured in the following examples will be described below.

<Measurement method of weight average particle diameter (D4)>
The weight average particle diameter (D4) of the powder particles and toner particles is calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.

  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.

  On the “Change Standard Measurement Method (SOM)” 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 By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush 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, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the 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%. . 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) is calculated. The “average diameter” on the “analysis / volume statistics (arithmetic average)” screen when the graph / volume% is set in the dedicated software is the weight average particle diameter (D4).

<Calculation method of fine powder amount>
The number-based fine powder amount (number%) of the powder particles and toner particles is calculated by analyzing the data after measuring the Multisizer 3 described above.

  For example, the number% of particles of 4.0 μm or less in the toner is calculated by the following procedure. First, the graph / number% is set with the dedicated software, and the measurement result chart is displayed in number%. Then, 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. The numerical value of the “<4 μm” display portion when the “analysis / number statistics (arithmetic mean)” screen is displayed 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 powder particles and toner particles is calculated by analyzing the data after measuring the above-mentioned Multisizer 3.

  For example, the volume percentage of particles of 10.0 μm or more in the powder particles and toner particles is calculated by the following procedure. First, graph / volume% is set with dedicated software, and the measurement result chart is displayed as volume%. Then, 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. When the “analysis / volume statistic (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.

<Measuring method of average circularity>
The average circularity of the powder particles and the toner particles is measured by a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration operation.

  A specific measurement method is as follows. First, about 20 ml of ion-exchanged water from which impure solids are removed in advance is put in a glass container. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.2 ml of a diluted solution obtained by diluting the solution with ion exchange water about 3 times by mass. Further, about 0.02 g of a measurement sample is added, and dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC. As the ultrasonic disperser, a desktop ultrasonic cleaner disperser (“VS-150” (manufactured by Vervo Creer)) having an oscillation frequency of 50 kHz and an electric output of 150 W is used. Exchange water is added, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.

  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, and 3000 toner particles are measured in the HPF measurement mode and in the total count mode. Then, the binarization threshold at the time of particle analysis is set to 85%, the analysis particle diameter is limited to the circle equivalent diameter of 1.985 μm or more and less than 39.69 μm, and the average circularity of the toner particles is obtained.

  In the measurement, automatic focus adjustment is performed using standard latex particles ("DISE Scientific AND RESPARTIC AND TEST PARTILES Latex Microsphere Suspensions 5200A" diluted with ion-exchanged water) before starting the measurement. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.

  In the examples of the present application, a flow-type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, was used. Measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that the analysis particle size was limited to a circle equivalent diameter of 1.985 μm or more and less than 39.69 μm.

<Calculation method of the proportion of particles having a circularity of 0.990 or more>
In the present invention, the proportion of particles having a circularity of 0.990 or more is used as an index indicating the distribution of circularity, and is represented by frequency (%). Specifically, in the average circularity of the powder particles and toner particles measured by FPIA-3000, the frequency (%) value in the frequency table range 1.00 and the frequency 0.990-> 1.000 ( %) Value was used.

  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.

(Production example 1 of powder particles)
Resin having a polyester unit: 100 parts by mass (weight average molecular weight (Mw): 87000, average molecular weight (Mn): 3300, peak molecular weight: (Mp) 9200)
Paraffin wax: 6 parts by mass (maximum endothermic peak temperature 78 ° C.)
3,5-di-t-butylsalicylic acid aluminum compound: 1.5 parts by mass Carbon black: 7.5 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.) The mixture was kneaded with a biaxial kneader PCM-30 type (manufactured by Ikekai Tekko Co., Ltd.) set at a temperature of 120 ° C. The obtained kneaded product is cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a toner crushed material. The obtained toner crushed material is pulverized with a mechanical pulverizer T-250 (manufactured by Turbo Kogyo Co., Ltd.). Thus, toner fine particles were obtained. Subsequently, the obtained toner fine particles were classified by a faculty (manufactured by Hosokawa Micron).

  The obtained powder particles have a weight average particle diameter (D4) of 6.5 μm, 28.5% by number of toner particles having a particle diameter of 4.0 μm or less, and powder particles having a particle diameter of 10.0 μm or more. Was 3.0 vol% and the true specific gravity was 1.15 g / cc. Furthermore, as a result of measuring the circularity with FPIA3000, the average circularity was 0.950, and the frequency of particles having a circularity of 0.990 or more was 1.5 (%). Hereinafter, this is referred to as powder particle A.

Furthermore, the following materials were put into a Henschel mixer (FM-75 type, manufactured by Nippon Coke Co., Ltd.), and the peripheral speed of the rotary blade was 50.0 m / sec. Powder-treated particles A-1 having silica and titanium oxide adhered to the surface were obtained.
Toner particles A: 100 parts by mass Silica: 3.0 parts by mass (Silica fine particles prepared by the sol-gel method were surface-treated with 1.5% by mass of hexamethyldisilazane treatment and then adjusted to a desired particle size distribution by classification. )
Titanium oxide: 0.5 part by mass (surface-treated metatitanic acid having anatase crystallinity)

(Production example 2 of powder particles)
Powder-treated particles A-2 were obtained in the same manner as in Production Example 1 of powder particles except that the addition amount of silica was changed to 1.0 part by mass and the addition amount of titanium oxide was changed to 0.2 part by mass.

(Production example 3 of powder particles)
Resin having a polyester unit: 100 parts by mass (weight average molecular weight (Mw): 82400, average molecular weight (Mn): 3300, peak molecular weight: (Mp) 8450)
Hydrocarbon wax: 6 parts by mass (maximum endothermic peak temperature 102 ° C.)
3,5-di-t-butylsalicylic acid aluminum compound: 1.0 part by mass Magnetic iron oxide (average particle size 0.20 μm): 70 parts by mass The material of the above prescription is made into a Henschel mixer FM-75 type (manufactured by Nippon Coke) ), And then kneaded in a biaxial kneader PCM-30 type (manufactured by Ikekai Tekko Co., Ltd.) with the temperature set at 140 ° C. The obtained kneaded product is cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a toner crushed material. The obtained toner crushed material is pulverized with a mechanical pulverizer T-250 (manufactured by Turbo Kogyo Co., Ltd.). Thus, toner fine particles were obtained. Subsequently, the obtained toner fine particles were classified by a faculty (manufactured by Hosokawa Micron).

  The obtained powder particles have a weight average particle diameter (D4) of 6.8 μm, 23.4% by number of powder particles having a particle diameter of 4.0 μm or less, and toner particles having a particle diameter of 10.0 μm or more. Was 2.5 vol% and the true specific gravity was 1.65 g / cc. Further, as a result of measuring the circularity with FPIA3000, the average circularity was 0.945, and the frequency of particles having a circularity of 0.990 or more was 1.0 (%). Hereinafter, this is referred to as powder particle B.

Furthermore, the following materials were put into a Henschel mixer (FM-75 type, manufactured by Nippon Coke Co., Ltd.), the peripheral speed of the rotary blade was 50.0 m / sec, and the mixing was performed for 5 minutes. Powder-treated particles B-1 having silica and titanium oxide adhered to the surface were obtained.
Toner particles A: 100 parts by mass Silica: 3.0 parts by mass (Silica fine particles prepared by the sol-gel method were surface-treated with 1.5% by mass of hexamethyldisilazane treatment and then adjusted to a desired particle size distribution by classification. )
Titanium oxide: 0.5 part by mass (surface-treated metatitanic acid having anatase crystallinity)

(Production example 4 of powder particles)
Powder-treated particles B-2 were obtained in the same manner as in Powder Particle Production Example 3 except that the silica addition amount was changed to 1.0 part by mass and the titanium oxide addition amount was changed to 0.2 part by mass.

[Example 1]
Using the heat treatment apparatus shown in FIG. 1, using the swiveling member of FIG. 3, the powder particle supply means is divided into eight parts of FIG. 5, the vertical angle α = 10 ° in the powder particle introduction direction, and the horizontal angle β = 90 °. Then, the powder particles were heat-treated. The inner diameter of the heat treatment apparatus main body was Φ450 mm, the outer diameter of the center pole was Φ330 mm, and the height from the top plate to the bottom surface of the apparatus was 1350 mm.

  Furthermore, the cool air is supplied in three stages as shown in FIG. 1, the first and second cool air are supplied in four tangential directions, and the third cool air is supplied in three tangential directions. did.

  The above apparatus configuration is referred to as apparatus configuration 1.

  In the apparatus configuration 1 described above, the powder-treated particles A-1 are used, the supply amount is 150 kg / hr, the operating conditions are adjusted so as to obtain toner particles having an average circularity of 0.970, and heat treatment is performed. 1 was obtained.

The operating conditions at this time were a hot air temperature of 175 ° C., a hot air flow rate of 27.0 m ³ / min, a cold air temperature of −5 ° C., and a flow rate of injection air supplied from the high pressure air supply nozzle was 1.75 m ³ / min. .

Moreover, the cold air of the 1st step | paragraph divided into 6.0 m < ³ > / min into 4 parts, and supplied the cold air of 1.5 m < ³ > / min in the process chamber, respectively. Further, the cold air at the second stage was divided into 2.0 m ³ / min into four, and 0.5 m ³ / min of cold air was supplied into the processing chamber. Furthermore, the cold air of the 3rd stage supplied 4.2 m < ³ > / min by 3 divisions, and supplied the cold air of 1.4 m < ³ > / min to the process chamber, respectively.

  The above operating condition is set as operating condition R-1.

  The toner particles a-1 obtained at this time have a weight average particle diameter (D4) of 6.8 μm, 25.3% by number of particles having a particle diameter of 4.0 μm or less, and 3.3% of particles having a particle diameter of 10.0 μm or more. The toner particles were 8% by volume, and there were very few coarse particles.

  Furthermore, as a result of measuring the frequency of particles having a circularity of 0.990 or more with an FPIA 3000, the value was 29.0 (%), and toner particles having excellent uniformity were obtained.

  Next, heat treatment was performed using the powder-treated particles B-1 while maintaining the operating conditions R-1. The obtained toner had an average circularity of 0.963 and could not be sufficiently heat-treated. The weight average particle size (D4) at that time was 6.8 μm, particles having a particle size of 4.0 μm or less were 26.4% by number, and particles having a particle size of 10.0 μm or more were 1.2% by volume.

  Next, similarly, the powder-treated particles B-1 are used, the supply amount is similarly set to 150 kg / hr, and only the hot air temperature is adjusted under the operating condition R-1 so that toner particles having an average circularity of 0.970 can be obtained. Then, heat treatment was performed. At this time, the hot air temperature required 185 ° C.

  Subsequently, similarly, the powder treated particles B-1 are used, the supply amount is 150 kg / hr, the powder particle introduction direction is changed to α = −15 ° and β = 45 °, and the toner has an average circularity of 0.970. The operating conditions were adjusted to obtain particles and heat treatment was performed to obtain toner particles b-1.

  The operating conditions at this time were the same as the operating conditions R-1 except for the introduction direction of the powder particles. Let this operating condition be Q-1.

  The obtained toner particles b-1 have a weight average particle diameter (D4) of 6.6 μm, 27.2% by number of particles having a particle diameter of 4.0 μm or less, and 4.2% by weight of particles having a particle diameter of 10.0 μm or more. It was 3% by volume.

  Further, when the difference Δs (volume%) in the amount of coarse powder between the toner particles a-1 and the toner particles b-1 is taken, it becomes 0.5 volume%. The result was stable regardless of the change.

  Also, when the powder particles A-1 were operated for 1 hour under the operating condition R-1 and the powder particles B-1 were operated for 1 hour under the operating condition Q-1, the fusion situation in the apparatus was confirmed. Kimono was not recognized at all.

  The resulting toner particles a-1 and b-1 and their operating conditions were evaluated for the following items. The results are shown in Table 1.

<Evaluation for the frequency of particles having a circularity of 0.990 or more>
The toner particles a-1 and toner particles b-1 were evaluated according to the following criteria, using the frequency s (%) of particles having a circularity of 0.990 or more as an index of toner particle shape uniformity.
A: s <30.0
B: 30.0 ≦ s <35.0
C: 35.0 ≦ s <40.0
D: 40.0 ≦ s <45.0
E: 45.0 ≦ s

<Evaluation for the amount of coarse powder>
The difference Δm (volume%) between the ratio of the powder particles before heat treatment and the particles of 10.0 μm or more in the toner particles after heat treatment was used as an index of coarse particle increase / decrease in the heat treatment, and judged according to the following criteria.
A: Δm <5.0
B: 5.0 ≦ Δm <10.0
C: 10.0 ≦ Δm <15.0
D: 15.0 ≦ Δm <20.0
E: 20.0 ≦ Δm

<Evaluation of the amount of change in the amount of coarse powder when the specific gravity of the powder particles as the raw material is changed>
The difference Δp (volume%) between the amounts of the coarse particles of the toner particles a-1 and the toner particles b-1 was taken as an index of stable productivity when changing the powder particles as a raw material, and the following criteria were used.
A: 2.0 <Δp
B: 2.0 ≦ Δp <4.0
C: 4.0 ≦ Δp <6.0
D: 6.0 ≦ Δp <8.0
E: 8.0 ≦ Δp

<Evaluation for fusion in the device>
An industrial videoscope “IPLEX SA II R” (Olympus Corporation) was used after processing for 1 hour using the powder-treated particles A-1 and after processing for 1 hour using the powder-treated particles B-1. The scope part of the product was inserted from an inspection port (not shown) on the side surface of the heat treatment apparatus, the fusion situation inside the apparatus was confirmed, and judged according to the following criteria.
A: No fusion material is observed at all level B: Fused material is slightly recognized, but there is no operational trouble level C: Fusion is observed, but there is no operational trouble level D: Fusion is recognized, Level E at which operation must be stopped: Level at which large fusion material is recognized and operation must be stopped

[Example 2]
In Example 1, the toner particles a-1 were changed in the same manner as in Example 1 except that the powder-treated particles A-1 were changed to the powder-treated particles A-2 and the powder particles B-1 were changed to the powder particles B-2. -2 and toner particles b-2 were produced and evaluated in the same manner. Table 1 shows operating conditions and evaluation results.

Example 3
In the apparatus configuration 1, toner particles a-3 and toner particles b-3 are manufactured in the same manner as in Example 2 except that the apparatus configuration 2 in which the restriction means 5 of the heat treatment apparatus shown in FIG. 1 is removed is used. Was evaluated. Table 1 shows operating conditions and evaluation results.

Example 4
In the apparatus configuration 2, the toner is the same as in Example 3 except that the second stage cool air supply means 4-2 of the heat treatment apparatus shown in FIG. Particle a-4 and toner particle b-4 were produced and evaluated in the same manner.

  The operating conditions at this time were the same as the operating conditions R-1 and Q-1, except that the second stage cold air was not supplied. Table 1 shows operating conditions and evaluation results.

Example 5
In the apparatus configuration 3, the same procedure as in Example 4 is used except that the third stage cold air supply means 4-3 of the heat treatment apparatus shown in FIG. Particles a-5 and toner particles b-5 were produced and evaluated in the same manner.

  The operating conditions at this time were the same as the operating conditions R-1 and Q-1, except that the second and third cold air were not supplied. Table 1 shows operating conditions and evaluation results.

Example 6
In the apparatus configuration 4, the toner particles a-6 and the toner particles b are the same as in Example 5 except that the apparatus configuration 5 in which the number of cold air divisions in the first stage of the heat treatment apparatus shown in FIG. -6 was produced and evaluated in the same manner.

The operating condition at this time is the first stage cold air of 6.0 m ³ / min. The operation conditions R-1 and Q-1 were the same except that the second and third stages of cold air were not supplied. Table 1 shows operating conditions and evaluation results.

Example 7
In the apparatus configuration 5, toner particles a-7 and toner particles are obtained in the same manner as in Example 6 except that the first-stage cold air of the heat treatment apparatus shown in FIG. b-7 was produced and evaluated in the same manner.

The operating conditions at this time are the same as operating conditions R-1 and Q-1, except that the first stage cold air is 6.0 m ³ / min and the second and third stages are not supplied. did. Table 1 shows operating conditions and evaluation results.

Example 8
In the apparatus configuration of apparatus configuration 6, the powder-treated particles A-2 were used under the same operating conditions as in Example 7 except that the raw material introduction direction was set to α = −40 ° / β = 45 °. Then, the supply amount was 150 kg / hr, and heat treatment was performed to obtain toner particles a-8.

  Next, using the powder-treated particles B-2, similarly, the supply rate was 150 kg / hr, and heat treatment was performed by adjusting only the hot air temperature so as to obtain toner particles having an average circularity of 0.970. At this time, the hot air temperature required 185 ° C.

  Subsequently, similarly, the powder treated particle B-2 is used, the supply amount is 150 kg / hr, the powder particle introduction direction is changed to α = 40 ° and β = −15 °, and the toner has an average circularity of 0.970. The operating conditions were adjusted to obtain particles and heat treatment was performed to obtain toner particles b-8. The hot air temperature at this time was 185 ° C. Table 1 shows operating conditions and evaluation results.

[ Reference Example 9]
In the apparatus configuration of the apparatus configuration 6, using the powder-treated particles A-2 under the same operating conditions as in Example 7, except that the raw material introduction direction is α = 50 ° / β = 50 °, The supply amount was 150 kg / hr, and heat treatment was performed to obtain toner particles a-9.

  Next, using the powder-treated particles B-2, similarly, the supply rate was 150 kg / hr, and heat treatment was performed by adjusting only the hot air temperature so as to obtain toner particles having an average circularity of 0.970. At this time, the hot air temperature required 185 ° C.

  Subsequently, similarly, the powder treated particles B-2 were used, the supply amount was 150 kg / hr, the powder particle introduction direction was changed to α = −50 ° and β = −25 °, and the average circularity was 0.970. The operating conditions were adjusted to obtain toner particles and heat treatment was performed to obtain toner particles b-9. The hot air temperature at this time was 185 ° C. Table 1 shows operating conditions and evaluation results.

[Comparative Example 1]
The powder particles were heat-treated with the heat treatment apparatus shown in FIG.

  Since the powder particle supply means 10 in the heat treatment apparatus of FIG. 7 includes a swirl chamber (not shown) upstream thereof, the powder particles are introduced into the heat treatment chamber 15 while swirling. The introduced powder particles are heat-treated with hot air supplied from the hot air supply means 11.

  The method of supplying cold air is blown from the first cold air supply means 12 while turning from the tangential direction, and is formed into a vertical slit shape along the axial direction of the heat treatment chamber by vertical guide vanes and a cooling restriction plate (both not shown). Blown out. Moreover, the powder particle | grains after heat processing are cooled by introduce | transducing it from the 2nd cold air supply means 12-2, turning cold air.

  In the heat treatment apparatus of this comparative example, a jacket structure is provided on the outer periphery of the apparatus, and the refrigerant is introduced from the cooling water inlet 13 and discharged from the cooling water outlet 14.

  The above apparatus configuration is referred to as apparatus configuration 7.

In the above apparatus configuration, in order to obtain toner particles having a powder particle supply rate of 150 kg / hr and an average circularity of 0.970, a hot air temperature of 250 ° C. and a hot air flow rate of 27.0 m ³ / min. The powder particles were heat treated. The operating conditions at this time were a cold air temperature of −5 ° C. and a flow rate of injection air supplied from the high pressure air supply nozzle of 3.5 m ³ / min. Met. The first stage cold air is 6.0 m ³ / min. Was supplied into the processing chamber. The second cold air is 4.2 m ³ / min. Was supplied to the processing chamber.

  Toner particles a-10 were obtained by using toner particles A-2 for 1 hour under the above operating conditions. Thereafter, the raw material was changed to powder particles B-2, and toner particles b-10 were obtained in the same manner for 1 hour. Table 1 shows operating conditions and evaluation results.

[Comparative Example 2]
The powder particles were heat-treated with the same apparatus configuration as the apparatus configuration 7 except that the hot air supply means and the powder particle supply means of the heat treatment apparatus shown in FIG. 8 were modified as shown in FIG.

  In the heat treatment apparatus shown in FIG. 8, hot air is supplied while turning from the hot air supply means 16. The powder particles are swirled and supplied in a direction opposite to that of the hot air from the powder particle supply means 17 located outside the hot air supply means.

  The above apparatus configuration is referred to as apparatus configuration 8.

In the above apparatus configuration, in order to obtain toner particles having an average circularity of 0.970 using powder particles A-2 at a supply rate of 150 kg / hr, a hot air temperature of 270 ° C. and a hot air flow rate of 27.0 m ³ / min. The powder particles were heat treated. The operating conditions at this time were as follows: the cold air temperature was −5 ° C., and the injection air flow rate supplied from the high pressure air supply nozzle was 3.5 m ³ / min. Met. The first stage cold air is 6.0 m ³ / min. Was supplied into the processing chamber. The second cold air is 4.2 m ³ / min. Was supplied to the processing chamber.

  Toner particles a-11 were obtained by using powder particles A-2 for 1 hour under the above operating conditions. Next, the raw material was changed to powder particle B-2, and the same treatment was performed for 1 hour to obtain toner particle b-11. Table 1 shows operating conditions and evaluation results.

  1: cylindrical processing chamber in which heat treatment is performed, 2: powder particle supply means, 3: hot air supply means, 3a: hot air supply means outlet, 4: cold air supply means, 4-1: first stage cold air supply means 4-2: second-stage cold air supply means, 4-3: third-stage cold air supply means, 5: restriction means for restricting the flow of powder particles, 6: recovery means, 7: conical member , 8: swirl member, 9: blade of swivel member, 10: powder particle supply means of Comparative Example 1, 11: hot air supply means of Comparative Example 1, 12: first cold air supply means of Comparative Example 1, 12- 2: Second cold air supply means of Comparative Example 1, 13: Cooling water inlet of Comparative Example 1, 14: Cooling water outlet of Comparative Example 1, 15: Heat treatment chamber of Comparative Example 1, 16: Hot air supply of Comparative Example 2 Means 17: Powder particle supply means of Comparative Example 2 18: Powder particles

Claims (5)

The powder particles containing a binder resin and a colorant, a heat treatment method of the powder particles heat treatment using a heat treatment apparatus,
The heat treatment apparatus
(1) a cylindrical processing chamber in which the powder particles are heat-treated;
(2) powder particle supply means for supplying the powder particles to the processing chamber;
(3) a hot air supply means for the hot air for heat treating the supplied powder particles in the processing chamber for supplying to the processing chamber,
( 4) cold air supply means for supplying cold air for cooling the heat treated powder particles to the processing chamber ;
(5) recovery means for recovering the powder particles heat-treated from the lower end side of the processing chamber;
Have
The cylindrical processing chamber is installed so that its central axis is in the vertical direction,
The powder particle supply means includes
(I) the outer peripheral portion of the processing chamber is provided plurality of lower flow side than the outlet portion of the hot air supply means,
(Ii) the direction of injection the powder particles ejected from the outlet portion of the powder particle supply means is provided with an adjustable adjustment mechanism with respect to the vertical direction and the horizontal direction of the treatment chamber,
The hot air supply means is provided so that hot air supplied to the processing chamber swirls in the processing chamber,
The recovery means so as to maintain the turning direction of the powder particles to pivot the processing chamber are arranged on the outer peripheral portion of the processing chamber,
In the vertical cross section of the processing chamber,
An injection direction of the powder particles injected from an outlet of the powder particle supply means;
Horizontal and
The angle formed by the vertical ejection angle α (°),
In the horizontal cross section of the processing chamber,
An injection direction of the powder particles injected from an outlet of the powder particle supply means;
A direction connecting the outlet of the powder particle supplying means and the central axis of the processing chamber in a horizontal direction;
When the angle formed by the horizontal injection angle β (°),
The vertical ejection angle α (°) and the horizontal ejection angle β (°) are
−45 (°) ≦ α ≦ + 45 (°)
−20 (°) ≦ β ≦ + 90 (°)
The powder particles are supplied to the treatment chamber so as to satisfy the above-described conditions, and a method for heat-treating the powder particles. It said cold air supply means, a plurality is provided on the outer periphery of the processing chamber, and, in the turning direction and the direction of the hot air cool air is supplied along the inner peripheral surface of the processing chamber from said cold air supply means heat treatment method of the powder particles according to claim 1 provided so that to turn. It said cold air supply means, the heat treatment method of the downstream of the powder particle supply means, the powder particles according to 請 Motomeko 1 or 2 that has a plurality provided so as not be a same circumferential direction. The heat treatment apparatus has a regulating means for regulating the flow of the supplied powder particles in the processing chamber into the processing chamber,
The regulating means, on the central axis of the processing chamber, arranged so as to protrude toward the upper portion from the lower portion of the processing chamber, Ru pillars der cross section is circular
Heat treatment method of the powder particles according to Izu Re or one of 請 Motomeko 1-3. The powder particles containing a binder resin and a colorant, in the method for producing a toner having a heat treatment step of heat treatment using a heat treatment apparatus,
Heat treatment step, method for producing a toner according to claim Rukoto performed by heat treatment method according to Izu Re one of claims 1-4.

Images