JP2013029790A - Toner production method and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner production method which is capable of depositing inorganic particles and/or a charge control agent on surfaces of base particles in one step and of making toner particles spherical, and to provide the toner.SOLUTION: The toner production method for producing toner where inorganic particles and/or a charge control agent are deposited on surfaces of base particles, includes a step of mixing the base particles and the inorganic particles and/or the charge control agent by using a mixing device 100 including a shaft-like member 101 having a plurality of agitating members 102 provided on a surface thereof, a casing 103 capable of covering the plurality of agitating members 102 with prescribed gaps among them, and a driving member 112 rotationally driving the shaft-like member 101 with a center axis A of the shaft-like member 101 as a rotation axis. The casing 103 is, in a state of covering the plurality of agitating members 101, circular to have a fixed distance between a cross section vertical to the center axis A of the shaft-like member 101, of an inner peripheral surface thereof and the center axis A of the shaft-like member 101, and power consumption per unit mass is 0.20 kWh/kg or more.

Description

  The present invention relates to a toner manufacturing method and a toner.

  In recent years, since copiers and printers are required to have high image quality and energy saving, it is necessary for the toner to reduce the adhesion of base particles containing a binder resin and a colorant. At this time, if the adhesion of the base particles is reduced, the toner has good developability, transferability, and stable chargeability, so that high image quality and energy saving can be achieved.

  As a method for reducing the adhesion force of the base particles, a method of attaching inorganic particles and / or a charge control agent to the surface of the base particles is known.

  Patent Document 1 includes a rotating shaft provided with a plurality of stirring members on the outer peripheral portion, and a casing having an inner peripheral portion located with a minute gap with respect to the stirring member, and moves as the rotating shaft rotates. The processing apparatus which stir-processes the processed material in a casing with the stirring member to perform is disclosed. At this time, when viewed from the direction orthogonal to the axial direction of the rotating shaft, the end positions of the plurality of stirring members in the direction parallel to the axial direction of the rotating shaft are more than the end positions of the other adjacent stirring members. It is located inside the other stirring member.

  Patent Document 2 discloses a method for producing an electrophotographic toner in which a charge control agent is fixed to the surface of a toner base by a fluid stirring type mixing device.

  On the other hand, as a method for reducing the adhesion force of the base particles, a method of making the base particles spherical is known.

  Patent Document 3 discloses a spherical toner manufacturing apparatus having means for obtaining a spherical toner having a small particle diameter by installing a plurality of rotating devices having rotating blades in a tube after a pulverizing section and passing the rotating blades. Has been.

  Patent Document 4 discloses a method for producing an electrophotographic toner in which toner particles are heat-treated using a heat treatment apparatus, and then the toner particles dispersed in hot air are cooled in a cooling container provided on the downstream side of the heat treatment space. Has been.

  However, it is desired to make the inorganic particles and / or the charge control agent adhere to the surface of the base particles and to make them spherical in one step.

  In view of the above-described problems of the prior art, the present invention provides a method for producing a toner capable of adhering inorganic particles and / or a charge control agent to the surface of a base particle and making it spherical in one step, and the toner. It is an object of the present invention to provide a toner manufactured using the manufacturing method.

  The method for producing a toner of the present invention is a method for producing a toner in which inorganic particles and / or a charge control agent are adhered to the surface of base particles containing a binder resin and a colorant. A shaft-shaped member provided on the casing, a casing capable of covering the plurality of stirring members at a predetermined interval, and the shaft-shaped member is driven to rotate about the central axis of the shaft-shaped member as a rotation axis. A step of mixing the base particles and the inorganic particles and / or the charge control agent using a mixing device having a drive member, and the casing covers the plurality of stirring members; The cross section perpendicular to the central axis of the shaft-shaped member is a circular shape with a constant distance between the central axis of the shaft-shaped member, and the base particles and the inorganic particles and / or the charge control agent are Unit mass consumed when mixing The amount of power or is equal to or is 0.20kWh / kg or more.

  The toner of the present invention is manufactured using the toner manufacturing method of the present invention.

  According to the present invention, in one step, the inorganic particles and / or the charge control agent are attached to the surface of the base particles and the toner can be spheroidized, and the toner is manufactured using the toner manufacturing method. Toner can be provided.

It is the schematic which shows an example of the mixing apparatus used by this invention. It is the schematic which shows the stirring member of FIG. It is the schematic which shows the modification of the stirring member of FIG.

  Next, the form for implementing this invention is demonstrated with drawing.

  FIG. 1 shows an example of a mixing apparatus used in the present invention. The mixing apparatus 100 includes a shaft-shaped member 101, a plurality of stirring members 102 provided on the surface of the shaft-shaped member 101, and a casing 103 that can cover the plurality of stirring members 102. At this time, the distance between the casing 103 and the central axis A of the shaft-like member 101 is constant in a state where the casing 103 covers the plurality of stirring members 102. Further, a jacket 104 through which a heat medium flows is provided on the outer peripheral surface of the casing 103. For this reason, in a state where the plurality of stirring members 102 are covered with the casing 103, the particles are put into the casing 103, and then the shaft-shaped member 101 is rotated about the central axis A as the rotation axis, thereby efficiently particles. And the temperature of the atmosphere in the casing 103 can be adjusted. Moreover, since the center axis | shaft A is substantially perpendicular | vertical with respect to the vertical direction, the shaft-shaped member 101 can mix a particle uniformly.

  Note that “substantially vertical (or substantially parallel)” means that a deviation of about 5 ° from vertical (or parallel) is allowed as an error.

  As shown in FIG. 2, the stirring member 102 is disposed with a clearance C [mm] with respect to the inner wall of the casing 103, and a shaft-like member 101 having a plurality of stirring members 102 provided on the surface is provided. By rotating, the particles in the casing 103 can be mixed.

When the outer diameter of the shaft-like member 101 is D ₁ [mm] and the inner diameter of the casing 103 is D ₂ [mm], the formula D ₂ / D ₁ ≦ 2.0
2.5 ≦ D ₁ ^1/2 /C≦10.0
It is preferable to satisfy.

When D ₂ / D ₁ exceeds 2, the stirring force by the stirring member 102 may not be strongly applied to the particles. D ₂ / D ₁ is usually 1.2 or more. If D ₂ / D ₁ is less than 1.2, the particles may not be mixed efficiently.

When D ₁ ^1/2 / C is less than 2.5 or exceeds 10.0, the compression force, grinding force, and shear force in the clearance portion between the stirring member 102 and the inner wall of the casing 103 are efficiently used. It may become impossible to apply to particles well.

  The shaft-like member 101 is supported by the bearing member 105 only on the left side in FIG. 1 and is connected to a driving member 112 such as a motor. The inlet 106 for introducing the particles to be mixed is installed at the upper part in FIG. 1 at the end of the casing 103 on the side where the driving member 112 is installed, and the outlet 107 for discharging the mixed particles is 1, the end of the casing 103 on the side where the drive member 112 is not installed is installed in the lower part in FIG.

  The casing 103 has a bottomed cylindrical shape that opens on the left side and closes on the right side in FIG. 1, and is supported by the guide rod 108 and the boss 109 to cover the plurality of stirring members 102 (see FIG. 1). ) And a non-actuated position (not shown) that does not cover the plurality of agitating members 102, it can move in a direction substantially parallel to the central axis A of the shaft-like member 101.

  An exhaust pipe 110 is installed in the casing 103 in order to release pressure caused by air expansion due to temperature rise in the casing 103 and to release seal air from a shaft seal portion (not shown) of the shaft-shaped member 101. Has been. Further, a filter 111 is installed in the exhaust pipe 110 in order to suppress dust scattering.

  The stirring member 102 includes three return stirring members 102a (1), 102a (2), 102a (3), and three return stirring members 102a ′ (1), 102a ′ (2), 102a ′ (3 ) 3 feeding stirring members 102b (1), 102b (2), 102b (3) and 3 feeding stirring members (not shown). At this time, the return stirring member and the feeding stirring member are each installed in a direction substantially parallel to the central axis A of the shaft-like member 101. The return stirring member has a plate shape substantially parallel to the central axis A of the shaft-like member 101, and is installed point-symmetrically so that a symmetric point exists on the central axis A. Further, the feeding stirring member has a plate shape having a predetermined inclination with respect to the central axis A of the shaft-like member 101, and is installed point-symmetrically so that a symmetric point exists on the central axis A.

  The sending stirring member 102b sends the particles to the right in FIG. 1, and the returning stirring member returns the particles to the left in FIG. Thereby, the flow of particles can be activated in the casing 103. For example, the particles are prevented from aggregating and fusing at the clearance between the stirring member 102 and the inner wall of the casing 103. it can. Further, the moving path of the particles in the casing 103 becomes complicated and long, and as a result, the stirring force by the stirring member 102 can be strongly applied to the particles.

  In the rotation direction B of the shaft-shaped member 101, the adjacent stirring members 102 are arranged so as to overlap in a direction parallel to the central axis A of the shaft-shaped member 101. For example, when an arc L is drawn in the rotation direction B of the shaft-like member 101 from the end of the return stirring member 102a (1), L is a feed stirring member 102b (adjacent to the return stirring member 102a (1). 1) Crosses with the stirring member for feeding. As a result, the particles move from the end of the stirring member 102 to the inside of the adjacent stirring member 102, and as a result, the stirring force by the stirring member 102 can be strongly applied to the particles.

  The shape of the stirring member 102 is not limited to a plate shape, and examples include a stirrup shape, a groove shape, a paddle shape, and a fin shape.

  Note that three or more return stirring members and feeding stirring members may be installed in a direction substantially parallel to the central axis A of the shaft-like member 101. If one or two returning stirring members and feeding stirring members are provided in a direction substantially parallel to the central axis A of the shaft-like member 101, the particles may not be stirred uniformly.

  Moreover, you may install the stirring member for a feed, and the stirring member for a return at the edge part in the side in which the insertion port 106 and the discharge port 107 of the shaft-shaped member 101 are formed, respectively. Thereby, the movement of the particles to both ends of the shaft-shaped member 101 can be suppressed, and as a result, the particles to which the stirring force by the stirring member 102 is not sufficiently applied can be suppressed from being discharged from the discharge port 107.

  Furthermore, a horizontal stirring member may be installed instead of the return stirring member 102a and the feeding stirring member 102b.

  FIG. 3 shows a modification of the stirring member 102. The stirring member 102 ′ may be formed with a groove-like portion 102 a ′ so as to face the inner wall of the casing 103. 3A and 3B are a side view and a top view, respectively. In the stirring member 102 ′, a region facing the inner wall of the casing 103 is divided into three regions by two groove-like portions 102 a ′. As described above, when the region facing the inner wall of the casing 103 is divided, even if the stirring member 102 ′ is enlarged, the action of stirring the particles is reduced, or the particles are separated between the stirring member 102 ′ and the inner wall of the casing 103. It can suppress that the frictional heat accompanying the applied shear force concentrates locally.

  The ratio of the surface area of the region where the groove-like portion 102a ′ is formed to the surface area of the region facing the inner wall of the casing 103 of the stirring member 102 ′ is usually 15 to 50%, and preferably 20 to 40%.

  As the shape of the casing 103, a distance between the rotation axis of the shaft-shaped member 101 and a cross section perpendicular to the rotation axis of the shaft-shaped member 101 on the inner peripheral surface covers the plurality of stirring members 102. As long as is a substantially constant circular shape, it is not limited to a cylindrical shape, and examples thereof include a spherical shape and a conical shape.

  The peripheral speed of the stirring member 102 when rotating the shaft-like member 101 is usually 10 to 150 m / s, and preferably 10 to 120 m / s.

  Moreover, the diameter of the circular orbit of the stirring member 102 at the time of rotating the shaft-shaped member 101 is 0.09-1.00 m normally, and 0.12-0.75 m is preferable.

  When the base particles containing the binder resin and the colorant are mixed with the inorganic particles and / or the charge control agent using the mixing device 100, the collision force between the stirring member 102 and the base particles, the stirring member 102 and the inorganic particles and / or the charge is charged. In addition to the impact force of the control agent, the impact force of the base particles and inorganic particles and / or the charge control agent, and the compressive force, grinding force and shear force at the clearance between the stirring member 102 and the inner wall of the casing 103 Thus, inorganic particles and / or a charge control agent can be attached to the surface of the base particles.

  At this time, the amount of electric power per unit mass consumed when mixing the base particles with the inorganic particles and / or the charge control agent is 0.20 kWh / kg or more, preferably 0.30 kWh / kg or more. More preferably, it is 50 kWh / kg or more. When the power amount per unit mass consumed when mixing the base particles and the inorganic particles and / or the charge control agent is less than 0.20 kWh / kg, the surface of the base particles cannot be sufficiently tanned, and the toner Cannot be spheroidized. That is, the collision force between the stirring member 102 and the base particles, the collision force between the stirring member 102 and the inorganic particles and / or the charge control agent, the collision force between the base particles and the inorganic particles and / or the charge control agent, the stirring member 102 and the casing 103 In addition to the compressive force, grinding force, and shear force in the clearance between the inner wall and the inner wall, the left and right convection mixing becomes insufficient, and the toner cannot be made spherical. In addition, the electric energy per unit mass consumed when mixing the base particles and the inorganic particles and / or the charge control agent is usually 1.50 kWh / kg or less, preferably 1.20 kWh / kg or less. When the amount of electric power per unit mass consumed when mixing the base particles with the inorganic particles and / or the charge control agent exceeds 1.50 kWh / kg, the inorganic particles and / or the charge control agent is embedded in the base particles. Sometimes.

  The amount of electric power per unit mass consumed when the base particles and the inorganic particles and / or the charge control agent are mixed is the driving per 1 kg of the total mass of the base particles, the inorganic particles and / or the charge control agent to be mixed. It means the power consumption of the member 112. The amount of power consumed by the driving member 112 here is the amount of power consumed when the base particles and inorganic particles and / or charge control agent are mixed, and other than not using the base particles, inorganic particles and / or charge control agent. Is the difference in the amount of power consumed under the same conditions as when the base particles and the inorganic particles and / or the charge control agent are mixed.

  At this time, the temperature rise of the atmosphere in the casing 103 can be suppressed by flowing a cooling medium through the jacket 104.

  The temperature of the atmosphere in the casing 103 is preferably 50 ° C. lower than the glass transition point of the base particles to 15 ° C. lower than the glass transition point of the base particles. When the temperature of the atmosphere in the casing 103 is lower than a temperature lower by 50 ° C. than the glass transition point of the base particles, it may be difficult to attach the inorganic particles and / or the charge control agent to the surfaces of the base particles. On the other hand, when the temperature of the atmosphere in the casing 103 exceeds 15 ° C. lower than the glass transition point of the base particles, the stirring force by the stirring member 102 is applied to the base particles, so that the base particles are melted or separated. The mold may be exposed.

  In addition, after spheroidizing the base particles using the apparatus disclosed in Patent Document 3, the surface of the base particles is inorganicized using the apparatus disclosed in Patent Document 1 or the method disclosed in Patent Document 2. When particles and / or a charge control agent are attached, fine powder increases and the particle size distribution changes. As a result, the adhesion force of the base particles is increased, and it adheres to the surface of the carrier or the surface of the photoconductor, or selective development occurs remarkably.

  Further, after spheronizing the base particles using the method disclosed in Patent Document 4, the surface of the base particles is inorganicized using the apparatus disclosed in Patent Document 1 or the method disclosed in Patent Document 2. When the particles and / or the charge control agent are attached, the release agent oozes out to the surface of the base particle, and the surface state of the base particle changes. As a result, the adhesion force of the base particles is increased, and it adheres to the surface of the carrier and the surface of the photoconductor, or the development efficiency and the transfer efficiency are reduced. Further, the dispersion state of the component having a low glass transition point and the component having a high glass transition point in the binder resin changes, which affects the fixing characteristics.

  On the other hand, after the inorganic particles and / or the charge control agent are attached to the surface of the base particles using the apparatus disclosed in Patent Document 1 or the method disclosed in Patent Document 2, the method is disclosed in Patent Document 3. When the base particles are spheroidized using a device disclosed in JP-A No. 2004-86105 or the method disclosed in Patent Document 4, inorganic particles and / or charge control agents are detached or buried.

  The binder resin is not particularly limited, but is a homopolymer of styrene such as polystyrene, poly (p-chlorostyrene), polyvinyltoluene and the like; a styrene-p-chlorostyrene copolymer, a styrene-vinyltoluene copolymer. Polymer, styrene-vinyl naphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene Styrene such as vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer Copolymer; polyvinyl chloride Phenol resin; natural modified phenolic resin; natural resin modified maleic resin; acrylic resin; methacrylic resin; polyvinyl acetate; silicone resin; polyester; polyurethane; Coumarone indene resin; petroleum-based resin and the like may be mentioned, and two or more may be used in combination. Among these, a styrene copolymer or polyester is preferable.

  As the colorant, a yellow pigment, a magenta pigment, a cyan pigment, or the like can be used.

  Although it does not specifically limit as a yellow pigment, A condensed azo compound, an isoindolinone compound, an anthraquinone compound, an azo metal complex, a methine compound, an allylamide compound etc. are mentioned, You may use 2 or more types together.

  Examples of commercially available yellow pigments include C.I. I. Pigment Yellow 3, 12, 13, 14, 15, 17, 62, 65, 73, 74, 83, 90, 93, 95, 96, 97, 109, 110, 111, 120, 128, 129, 138, 147, 155, 168, 180, 181; Nephthol Yellow S, Hansa Yellow G, C.I. I. Examples thereof include bat yellow.

  Examples of magenta pigments include, but are not limited to, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds, and the like. Two or more kinds may be used in combination.

  Commercially available magenta pigments include C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48, 48: 2, 48: 3, 48: 4, 57, 57: 1, 58, 60, 63, 64, 68, 81, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 149, 163, 166, 169, 170, 177, 184, 185, 187, 202, 206, 207, 209, 220, 251, 254; C.I. I. Pigment violet 19 and the like.

  Although it does not specifically limit as a cyan-type pigment, A copper phthalocyanine compound, its derivative (s), an anthraquinone compound, a basic dye lake compound, etc. are mentioned, You may use 2 or more types together.

  Examples of commercially available cyan pigments include C.I. I. Pigment Blue 1, 2, 3, 6, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 16, 17, 60, 62, 66; phthalocyanine blue, C.I. I. Bat Blue, C.I. I. Acid blue and the like.

  The addition amount of the colorant is usually 2 to 20% by mass and preferably 4 to 15% by mass with respect to the binder resin. When the content of the colorant is less than 2% by mass with respect to the binder resin, the coloring power may be reduced. When the content exceeds 20% by mass, the coloring power is increased more than necessary, and a light color, etc. It may be difficult to reproduce.

  The base particle may further contain a release agent.

  Although it does not specifically limit as a mold release agent, The wax which has a carbonyl group, polyolefin wax, a long chain hydrocarbon, etc. are mentioned, You may use 2 or more types together. Among these, a wax having a carbonyl group is preferable.

  Examples of the wax having a carbonyl group include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, and 1,18-octadecanediol diester. Polyalkanoic acid esters such as stearate; polyalkanol esters such as tristearyl trimellitic acid and distearyl maleate; polyalkanoic acid amides such as dibehenyl amide; polyalkylamides such as trimellitic acid tristearyl amide; distearyl ketone And dialkyl ketones. Of these, polyalkanoic acid esters are preferred.

  Examples of the polyolefin wax include polyethylene wax and polypropylene wax.

  Examples of the long chain hydrocarbon include paraffin wax and sazol wax.

  The melting point of the release agent is usually 40 to 160 ° C, preferably 50 to 120 ° C, and more preferably 60 to 90 ° C. When the melting point of the release agent is less than 40 ° C., the heat-resistant storage stability of the toner may be lowered, and when it exceeds 160 ° C., the low-temperature fixability of the toner may be lowered.

  The content of the release agent in the base particles is usually 3 to 15% by mass with respect to the binder resin.

  The charge control agent is not particularly limited, but nigrosine dye, triphenylmethane dye, chromium-containing metal complex dye, molybdate chelate pigment, rhodamine dye, alkoxy amine, quaternary ammonium salt (fluorine-modified quaternary ammonium salt) Salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorosurfactants, metal salts of salicylic acid and its derivatives, copper phthalocyanine, perylene, quinacridone, azo pigments, sulfonic acid groups, carboxyl Group, a polymer compound having a functional group such as a quaternary ammonium base, and the like, and two or more of them may be used in combination.

  Commercially available charge control agents include Nigrosine dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal Complex E-84, phenol-based condensate E-89 (above, Orient Chemical Industry Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Industry Co., Ltd.), 4 Copy charge PSY VP2038 of quaternary ammonium salt, copy blue PR of triphenylmethane derivative, copy charge NEG VP2036 of quaternary ammonium salt, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR- which is a boron complex 147 (made by Nippon Carlit Co., Ltd.).

  The addition amount of the charge control agent is usually 0.1 to 10% by mass and preferably 1 to 5% by mass with respect to the binder resin.

  The base particles may contain a charge control agent.

  The material constituting the inorganic particles is not particularly limited, but silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, Examples include wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

  The average primary particle size of the inorganic particles is usually 10 nm to 1 μm, preferably 30 nm to 500 nm.

  The added amount of the inorganic particles is usually 0.1 to 10% by mass and preferably 0.5 to 8% by mass with respect to the base particles.

  The base particles preferably have a glass transition point of 40 to 65 ° C. When the glass transition point of the base particles is less than 40 ° C., the storage stability of the toner may be lowered, and when it exceeds 65 ° C., the low-temperature fixability of the toner may be lowered.

  In addition, the glass transition point of the base particle can be measured using TA-60WS and DSC-60 (manufactured by Shimadzu Corporation).

  The base particles preferably have a volume average particle size of 3 to 9 μm. If the volume average particle size of the base particles is less than 3 μm, toner fusion may easily occur, and if it exceeds 9 μm, it may be difficult to form a high-quality image.

  The volume average particle size of the base particles can be measured using Coulter Counter Multisizer II (manufactured by Coulter).

  Although it does not specifically limit as a manufacturing method of a base particle, A grinding method, a polymerization method, etc. are mentioned.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to an Example. Hereinafter, a part means a mass part.

[Preparation of parent particles 1]
100 parts of polyester having a 1/2 outflow start temperature of 126 ° C., 3 parts of fluorine-containing quaternary ammonium salt and copper phthalocyanine C.I. I. 3 parts of Pigment Blue 15: 3 (manufactured by Dainichi Seika Co., Ltd.) were mixed using a blender, melt-kneaded using two rolls heated to 100 to 110 ° C., and allowed to cool naturally. Next, after coarsely pulverizing using a cutter mill, it was finely pulverized using a fine pulverizer using a jet stream. Furthermore, it classify | categorized using the wind classifier and the base particle 1 was obtained. Base particle 1 had a glass transition point of 60 ° C., a volume average particle size of 7.4 μm, and an average circularity of 0.935.

[Preparation of parent particles 2]
An acid monomer composed of 98 mol% dimethyl sebacate and 2 mol% dimethylsodium 5-sulfoisophthalate and an alcohol monomer composed of ethylene glycol were put into a heat-dried three-necked flask at a molar ratio of 1: 1. Next, after adding 0.3% by mass of dibutyltin oxide based on the total amount of the acid monomer and alcohol monomer, the air in the container was replaced with nitrogen and refluxed at 180 ° C. for 5 hours. Furthermore, after raising the temperature to 230 ° C. under reduced pressure and stirring for 2 hours, the mixture was cooled to air when it became a viscous state, the reaction was stopped, and a crystalline polyester was obtained. The crystalline polyester had a weight average molecular weight (polystyrene equivalent) of 9700 and a melting point of 72 ° C.

  90 parts of crystalline polyester, 1.8 parts of cationic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.) and 210 parts of ion-exchanged water were heated to 100 ° C. Next, after being dispersed using a homogenizer Ultra Turrax T50 (manufactured by IKA), it was dispersed for 1 hour using a pressure discharge type gorin homogenizer, and a crystal having a volume average particle size of 200 nm and a solid content of 20% by mass. A neutral polyester dispersion was obtained.

  In a 5 L flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a rectifying column, an acid monomer composed of 30 mol% terephthalic acid and 70 mol% fumaric acid, 20 mol% of bisphenol A ethylene oxide 2 mol adduct and bisphenol A After adding an alcohol monomer consisting of 80 mol% of propylene oxide adduct in a molar ratio of 1: 1, the temperature was raised to 190 ° C. over 1 hour. Next, 1.2% by mass of dibutyltin oxide was added to the total amount of acid monomer and alcohol monomer. Further, the temperature was raised to 240 ° C. over 6 hours while distilling off generated water, and then maintained for 3 hours to obtain amorphous polyester. The amorphous polyester had an acid value of 12.0 mg / KOH, a weight average molecular weight (polystyrene conversion) of 9700, and a glass transition point of 61 ° C.

While the amorphous polyester in the molten state is transferred to Cavitron CD1010 (Eurotech Co., Ltd.) at 100 g / min, 0.37% by mass of dilute aqueous ammonia is heated to 120 ° C. with a heat exchanger, while Cavitron CD1010 (Eurotech Co., Ltd.) was transferred at 0.1 L / min. Furthermore, Cavitron CD1010 (manufactured by Eurotech) was operated at a rotor rotation speed of 60 Hz and a pressure of 5 kg / cm ² , and an amorphous polyester having a volume average particle size of 0.16 μm and a solid content of 30% by mass. A dispersion was obtained.

  Copper phthalocyanine C.I. I. Pigment Blue 15: 3 (manufactured by Dainichi Seika Co., Ltd.) 45 parts, cationic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts and ion-exchanged water 200 parts were mixed, and then the homogenizer Ultra Turrax T50 ( And a colorant dispersion having a volume average particle size of 168 nm and a solid content of 22% by mass was obtained.

  45 parts of paraffin wax HNP9 (manufactured by Nippon Seiki Co., Ltd.) having a melting point of 75 ° C., 5 parts of cationic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 200 parts of ion-exchanged water are mixed and heated to 95 ° C. did. Next, after being dispersed using a homogenizer Ultra Turrax T50 (manufactured by IKA), it was dispersed using a pressure discharge type gorin homogenizer, and a release agent having a volume average particle size of 200 nm and a solid content of 20% by mass. A dispersion was obtained.

  In a round stainless steel flask, 256.7 parts of an amorphous polyester dispersion, 33.3 parts of a crystalline polyester dispersion, 27.3 parts of a colorant dispersion, and 35 parts of a release agent dispersion are placed. It was dispersed using an ultra turrax T50 (manufactured by IKA). Next, 0.20 part of polyaluminum chloride was added and dispersed using a homogenizer Ultra Turrax T50 (manufactured by IKA), and then the temperature was raised to 48 ° C. and held for 60 minutes. Furthermore, after adding 70 parts of amorphous polyester dispersion liquid, pH was set to 9.0 using 0.5 mol / L sodium hydroxide aqueous solution. Next, the stainless steel flask was sealed, heated to 96 ° C., held for 5 hours, cooled, and filtered. Further, the residue was washed with ion exchange water, and then solid-liquid separated by Nutsche suction filtration. Next, the residue was added to 1 L of ion-exchanged water at 40 ° C., and the operation of filtration was repeated after stirring for 15 minutes at 300 rpm using an ultra turrax T50 (manufactured by IKA), a homogenizer. When the pH of the filtrate was 7.5 and the electric conductivity was 7.0 μS / cm, solid-liquid separation was performed by Nutsche suction filtration. Furthermore, it vacuum-dried for 12 hours, and the base particle 2 was obtained. Base particles 2 had a glass transition point of 56 ° C., a volume average particle size of 5.9 μm, and an average circularity of 0.940.

[Glass transition point of base particles]
The glass transition point of the base particles was measured under the following measurement conditions using TA-60WS and DSC-60 (manufactured by Shimadzu Corporation).

Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50 mL / min)
(Temperature rise condition 1)
Starting temperature: 20 ° C
Rate of temperature increase: 10 ° C / min End temperature: 150 ° C
Holding time: None (Cooling condition 1)
Temperature drop: 10 ° C / min End temperature: 20 ° C
Holding time: None (Temperature rise condition 2)
Rate of temperature increase: 10 ° C / min End temperature: 150 ° C
The measurement results were analyzed using data analysis software TA-60, version 1.52 (manufactured by Shimadzu Corporation). Specifically, using the peak analysis function of the analysis software, specify a range of ± 5 ° C around the point showing the maximum peak on the lowest temperature side of the DrDSC curve, which is the DSC differential curve of the second temperature increase. The peak temperature was determined. Next, the maximum endothermic temperature of the DSC curve was determined using the peak analysis function of the analysis software in the range of the peak temperature + 5 ° C. and −5 ° C. in the DSC curve.

[Volume average particle size of base particles]
The volume average particle diameter of the base particles was measured using Coulter Counter Multisizer II (manufactured by Coulter). Specifically, first, 0.1 to 5 ml of polyoxyethylene alkyl ether was added to 100 to 150 ml of about 1% by mass aqueous sodium chloride solution ISOTON-II (manufactured by Coulter). Next, 2 to 20 mg of base particles were added and then dispersed for about 1 to 3 minutes using an ultrasonic disperser. Further, the volume average particle diameter of the base particles was measured using a 100 μm square aperture. As a channel, it is 2.00 micrometers or more and less than 2.52 micrometers; 2.52 micrometers or more and less than 3.17 micrometers; 3.17 micrometers or more and less than 4.00 micrometers; 4.00 micrometers or more and less than 5.04 micrometers; 5.04 micrometers or more and less than 6.35 micrometers; .35 μm or more and less than 8.00 μm; 8.00 μm or more and less than 10.08 μm; 10.08 μm or more and less than 12.70 μm; 12.70 μm or more and less than 16.00 μm; 16.00 μm or more and less than 20.20 μm; Less than 40 μm; 25.40 μm or more and less than 32.00 μm; 3 channels having a particle diameter of 2.00 μm or more and less than 40.30 μm were used as measurement objects.

[Average circularity of base particles]
The average circularity of the base particles was measured using a flow particle image analyzer FPIA-2100 (manufactured by Sysmex Corporation). Specifically, first, fine dust was removed through a filter, and water with an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm was 20/10 ⁻³ cm ³ or less. After adding several drops of nonionic surfactant Contaminone N (manufactured by Wako Pure Chemical Industries, Ltd.) to 10 ml of the obtained water, 5 mg of base particles are added, and an ultrasonic disperser UH-50 (manufactured by STM) is used. , 20 kHz, 50 W / 10 cm ³ , for 5 minutes. Next, after adjusting the number of particles having an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm to 4000 to 8000/10 ⁻³ cm ³ , the average circularity was measured.

[Example 1]
Using a mixing apparatus 100 (see FIG. 1), 150 g of base particles 1 and 4.5 g of silica particles RX50 (manufactured by Nippon Aerosil Co., Ltd.) having an average primary particle size of 40 nm were mixed to obtain a toner. The toner had an average circularity of 0.953.

At this time, the clearance C was 1.0 mm, the outer diameter D ₁ of the shaft-like member 101 was 91 mm, and the inner diameter D _{2 of the} casing 103 was 130 mm. Further, while adjusting the peripheral speed of the stirring member 102 in the range of 10 to 150 m / s, the amount of electric power per unit mass consumed when mixing the base particles and the silica particles is 0.25 kWh / kg. Mixed. Furthermore, it cooled so that the temperature of the atmosphere in the casing 103 might be set to 22 degreeC.

[Example 2]
Except for mixing so that the amount of electric power per unit mass consumed when mixing the base particles and silica particles is 0.35 kWh / kg, and the temperature of the atmosphere in the casing 103 is 24 ° C., the same as in Example 1. Thus, a toner was obtained. The toner had an average circularity of 0.957.

[Example 3]
Except for mixing so that the amount of electric power per unit mass consumed when mixing the base particles and silica particles is 0.60 kWh / kg, and the temperature of the atmosphere in the casing 103 is 26 ° C., the same as in Example 1. Thus, a toner was obtained. The toner had an average circularity of 0.960.

[Example 4]
Except for mixing so that the amount of electric power per unit mass consumed when mixing the base particles and silica particles is 1.00 kWh / kg, and the temperature of the atmosphere in the casing 103 is 30 ° C., the same as in Example 1. Thus, a toner was obtained. The toner had an average circularity of 0.963.

[Example 5]
Except for mixing so that the amount of electric power per unit mass consumed when mixing the base particles and silica particles is 1.40 kWh / kg, and the temperature of the atmosphere in the casing 103 is 32 ° C., the same as in Example 1. Thus, a toner was obtained. The toner had an average circularity of 0.966.

[Example 6]
A toner was obtained in the same manner as in Example 1 except that the base particle 2 was used instead of the base particle 1 and mixing was performed so that the temperature of the atmosphere in the casing 103 was 24 ° C. The toner had an average circularity of 0.955.

[Example 7]
A toner was obtained in the same manner as in Example 1 except that the clearance C was changed to 3.5 mm. The toner had an average circularity of 0.951.

[Example 8]
A toner was obtained in the same manner as in Example 1 except that the clearance C was changed to 1.2 mm and the outer diameter of the shaft-like member 101 was changed to 65 mm. The toner had an average circularity of 0.952.

[Example 9]
A toner was obtained in the same manner as in Example 1 except that salicylic acid metal complex particles E-84 (manufactured by Orient Chemical Co., Ltd.) having an average primary particle size of 50 nm were used in place of the silica particles. The toner had an average circularity of 0.953.

[Comparative Example 1]
Except for mixing so that the amount of electric power per unit mass consumed when mixing the base particles and silica particles is 0.10 kWh / kg, and the temperature of the atmosphere in the casing 103 is 20 ° C., the same as Example 1 Thus, a toner was obtained. The toner had an average circularity of 0.935.

  Table 1 shows toner production conditions.

［耐久試験］
トナー４質量％と、シリコーン樹脂により被覆されている平均粒径が５０μｍの銅−亜鉛フェライト粒子９６質量％からなる現像剤及びｉｍａｇｉｏ Ｎｅｏ ４５０（リコー社製）を用いて、Ａ４サイズの用紙に４５枚／分で印字密度が５％で１万枚連続印字した。

[An endurance test]
Using a developer composed of 4% by mass of toner and 96% by mass of copper-zinc ferrite particles coated with a silicone resin and having an average particle diameter of 50 μm, and imagio Neo 450 (manufactured by Ricoh), 45 A4 size paper is used. 10,000 sheets were continuously printed at a printing density of 5% per sheet / min.

  The following evaluation was carried out during the durability test.

[Image density]
After outputting a solid image, the image density was measured using a 938 spectrodensitometer (X-RITE). When the image density is 1.40 or more, ◎, when it is 1.30 or more and less than 1.40, ◯, when it is 1.20 or more and less than 1.30, when it is less than 1.20 Was determined as x.

[Cover]
The blank image is stopped during development, the developer on the developed photoreceptor is tape transferred, and the difference from the image density of the untransferred tape is measured using a 938 spectrocytometer (manufactured by X-RITE). Measured and evaluated for fog. When this difference is less than 0.005, ◎, when 0.005 or more and less than 0.010, ◯, when 0.010 or more and less than 0.030, Δ, or more than 0.030 Was determined as x.

[Transferability]
A solid image of 30 mm × 30 mm is output, and the formula (toner amount before fixing on the transfer material) / (toner amount before transfer on the photosensitive drum) × 100
From this, the transfer rate [%] was determined. The case where the transfer rate was 90% or more was judged as ◎, the case where it was 85% or more and less than 90%, ◯, the case where it was 80% or more and less than 85%, and the case where it was less than 80% as x. .

[Spent rate]
The toner was removed from the developer after the durability test by a blow-off method, and the remaining carrier mass W1 [g] was measured. Next, the mass W2 [g] after putting the carrier in toluene, washing and drying was measured. And the formula (W1-W2) / W1 × 100
From the above, the spent rate was calculated. In addition, when the spent ratio is less than 0.01%, ０．０１, when 0.01% or more and less than 0.02%, ◯, when 0.02% or more and less than 0.05%, △, 0 The case where it was 0.05% or more was judged as x.

[Filming]
The presence or absence of toner filming on the developing roller or the photoreceptor after the durability test was observed. In addition, the case where there was no filming was evaluated as ◎, the case where filming on the streaks was observed as ◯, and the case where filming was present as a whole as ×.

  Table 2 shows the evaluation results of the toners of Examples 1 to 9 and Comparative Example 1.

表２より、実施例１〜９のトナーは、母体粒子の表面にシリカ粒子又はサリチル酸金属錯体粒子を付着させる際に、球形化されているため、初期及び耐久試験後のいずれにおいても、画像濃度、かぶり及び転写性が優れることがわかる。また、実施例１〜９のトナーは、耐久試験後のスペント化率及びフィルミングも優れる。

From Table 2, since the toners of Examples 1 to 9 are formed into spheroids when silica particles or salicylic acid metal complex particles are attached to the surface of the base particles, the image density is both in the initial stage and after the endurance test. It can be seen that the fogging and transferability are excellent. In addition, the toners of Examples 1 to 9 are excellent in spent ratio and filming after the durability test.

  On the other hand, since the toner of Comparative Example 1 is not spheroidized when silica particles are adhered to the surface of the base particles, the transferability is deteriorated both in the initial stage and after the endurance test. Further, the toner of Comparative Example 1 also has decreased image density, fogging, spent ratio and filming after the durability test.

DESCRIPTION OF SYMBOLS 100 Mixer 101 Shaft-shaped member 102 Stirring member 102a Return stirrer member 102b Feed stirrer member 102 'Stirrer member 102a' Groove part 103 Casing 104 Jacket 105 Bearing member 106 Input port 107 Discharge port 108 Guide rod 109 Boss 110 Exhaust pipe 111 Filter 112 Driving member A Center axis B Rotation direction C Clearance D Outer diameter of _single shaft member D ₂ Inner diameter of casing

JP 2005-270955 A JP 2009-69640 A Japanese Patent Laid-Open No. 9-85741 JP 2000-29241 A

Claims (8)

A method for producing a toner in which inorganic particles and / or a charge control agent are attached to the surface of base particles containing a binder resin and a colorant,
A shaft-like member having a plurality of stirring members provided on the surface thereof, a casing capable of covering the plurality of stirring members at a predetermined interval, and a central axis of the shaft-like member as a rotation axis, the shaft Using a mixing device having a drive member that rotationally drives the shaped member, and mixing the base particles with the inorganic particles and / or the charge control agent,
In the state where the casing covers the plurality of stirring members, a distance between a cross section perpendicular to the central axis of the shaft-shaped member on the inner peripheral surface and the central axis of the shaft-shaped member is constant. Is circular,
A method for producing a toner, wherein an amount of electric power per unit mass consumed when mixing the base particles with the inorganic particles and / or the charge control agent is 0.20 kWh / kg or more. The plurality of stirring members have a feeding stirring member and a returning stirring member,
The feeding stirring member sends the base particles and the inorganic particles and / or the charge control agent in a direction substantially parallel to the central axis of the shaft-shaped member,
The return stirring member returns the base particles, the inorganic particles, and / or the charge control agent in a direction opposite to a direction in which the base particles, the inorganic particles, and / or the charge control agent are sent. 2. The method for producing a toner according to 1. When the interval is C [mm], the outer diameter of the shaft member is D ₁ [mm], and the inner diameter of the casing is D ₂ [mm], the formula D ₂ / D ₁ ≦ 2.0
2.5 ≦ D ₁ ^1/2 /C≦10.0
3. The toner production method according to claim 1, wherein:   4. The toner manufacturing method according to claim 1, wherein the casing has a bottomed cylindrical shape. 5.   The toner manufacturing method according to claim 1, wherein a central axis of the shaft-shaped member is substantially perpendicular to a vertical direction.   The temperature of the atmosphere in the casing is not less than 50 ° C lower than the glass transition temperature of the base particles and not more than 15 ° C lower than the glass transition temperature of the base particles. The method for producing a toner according to any one of the above.   The toner manufacturing method according to claim 1, wherein the base particles further contain a release agent.   A toner manufactured using the toner manufacturing method according to claim 1.

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