JP2016224371A - Manufacturing method of magnetic toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a magnetic toner that can suppress a reduction in image density caused by a reduction in charge amount of toner even in a high-humidity environment, and can suppress the occurrence of fogging caused by failure in forming a toner layer due to excessive charge of toner even in a low-humidity environment.SOLUTION: A manufacturing method of a magnetic toner comprising a plurality of toner particles is provided. The manufacturing method includes a step of obtaining the toner particles by adding a second magnetic powder to a primary ground product containing a first magnetic powder and a binder resin and secondarily grinding a resulting product. The first magnetic powder is the same as or different from the second magnetic powder.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a magnetic toner (in particular, a magnetic toner for developing an electrostatic latent image).

  Magnetic toners used in image forming apparatuses tend to require a certain level of magnetic retention. This is for the purpose of transporting the magnetic toner to the developing area of the developing sleeve and forming a thin layer with the magnetic toner on the developing sleeve. The strength of magnetism is determined, for example, by the amount of magnetic powder added to the magnetic toner particles contained in the magnetic toner. If the amount of magnetic powder added is increased, the fixability of the magnetic toner to the recording medium may be reduced. Moreover, since magnetic powder has electrical conductivity, the amount of magnetic powder added tends to affect the charge amount of the magnetic toner. For this reason, the amount of magnetic powder added to the magnetic toner particles tends to be limited. Therefore, it is desired to improve the quality of images formed using magnetic toner while keeping the amount of magnetic powder added constant.

  For example, in the method for producing a magnetic toner described in Patent Document 1, magnetic particles are added (external addition treatment) to the magnetic toner composition. In this manufacturing method, the magnetic toner composition contains magnetic powder and a resin.

Japanese Patent Laid-Open No. 03-249760

  However, since the magnetic toner produced by the method described in Patent Document 1 is externally treated with magnetic powder, the magnetic powder is easily detached from the toner particles due to stress (friction) in the developing device. For this reason, it is difficult to stabilize the charge amount of the magnetic toner.

  The present invention has been made in view of the above problems, and can suppress a decrease in image density due to a decrease in charge amount of a toner even in a high humidity environment (particularly in a high temperature and high humidity environment). Provided is a method for producing a magnetic toner capable of suppressing the occurrence of fog due to poor toner layer formation due to toner overcharging even under low temperatures (particularly in low temperature and low humidity environments).

  The method for producing a magnetic toner according to the present invention is a method for producing a magnetic toner containing a plurality of toner particles. A step of obtaining the toner particles by adding the second magnetic powder to the primary pulverized product containing the first magnetic powder and the binder resin and performing secondary pulverization is included. The first magnetic powder is the same as or different from the second magnetic powder.

  According to the present invention, it is possible to suppress a decrease in image density due to a decrease in charge amount of toner even in a high humidity environment (particularly in a high temperature and high humidity environment). Furthermore, even in a low humidity environment (particularly in a low temperature and low humidity environment), it is possible to suppress the occurrence of fog due to poor toner layer formation due to toner overcharging.

  Embodiments of the present invention will be described below. However, the present invention is not limited to the following embodiments. The present invention can be implemented with appropriate modifications within the scope of the object of the present invention. In addition, about the location where description overlaps, although description may be abbreviate | omitted suitably, the summary of invention is not limited.

  Hereinafter, a compound and its derivatives may be generically named by adding “system” after the compound name. In addition, when “polymer” is added after the compound name to indicate the polymer name, it means that the repeating unit of the polymer is derived from the compound or a derivative thereof.

  Hereinafter, the average value means a number average value unless otherwise specified. In addition, an evaluation value (a value indicating a shape or physical property) regarding a powder (for example, toner, toner particles, toner base particles, first magnetic powder, or second magnetic powder, which will be described later) is not specified at all. Means the number average value. The number average value is a value obtained by dividing the sum of the values measured for a considerable number of measurement objects by the measured number. Furthermore, the particle diameter of the powder is the equivalent-circle diameter of primary particles measured using an electron microscope unless otherwise specified. The equivalent circle diameter is the diameter of a circle having the same area as the projected area of the particles.

  The present embodiment relates to a method of manufacturing a magnetic toner (hereinafter sometimes referred to as “toner”). The production method of the present embodiment includes a step of obtaining toner particles by adding the second magnetic powder to the primary pulverized product containing the first magnetic powder and the binder resin and performing secondary pulverization.

  Of the magnetic powder contained in the toner particles, the magnetic powder present on the surface portion of the toner particles tends to affect the charge amount of the toner. Therefore, in order to control the charge amount of the toner, for example, it is considered effective to control the amount and type of the magnetic powder present on the surface portion of the toner particles. In the manufacturing method of the present embodiment, the second magnetic powder is added to the primary pulverized product having the first magnetic powder, and the secondary pulverization is performed. Thereby, it is considered that the first magnetic powder can be contained in the central part of the toner particles, and the second magnetic powder can be contained in the surface part of the toner particles. This makes it easy to control the charge amount of the toner even when the amount of magnetic powder added to the toner particles is kept constant.

  For example, the toner is easily overcharged in a low humidity environment (particularly in a low temperature and low humidity environment). On the other hand, in a high humidity environment (particularly in a high temperature and high humidity environment), the charge amount of the toner tends to decrease. Therefore, by using the manufacturing method of the present embodiment, the amount and type of magnetic powder present on the surface portion of the toner particle is controlled to control the conductivity of the surface portion of the toner particle (for example, the charge can be easily removed). Can be considered). As a result, toner overcharge tends to be suppressed even in a low humidity environment. As a result, it is considered that occurrence of fog caused by toner layer formation failure on the developing sleeve caused by overcharging of the toner can be suppressed. At the same time, it is considered that the conductivity of the central part of the toner particles can be controlled (for example, it is difficult to remove the charge) by controlling the amount and type of the magnetic powder present in the central part of the toner particles. As a result, the toner charge amount tends to be maintained even in a high humidity environment. As a result, it is considered that a decrease in image density due to a decrease in the charge amount of the toner can be suppressed.

  Moreover, in the manufacturing method of this embodiment, as already stated, the second magnetic powder is added to the primary pulverized product and the secondary pulverization is performed. Thereby, a shear force is applied to the primary pulverized product and the second magnetic powder. As a result, the second magnetic powder is buried in the primary pulverized product and is easily fixed. This makes it difficult for the second magnetic powder to be detached from the primary pulverized product, and the charge amount of the toner is easily stabilized.

  The toner manufactured by the method of this embodiment includes a plurality of toner particles. Hereinafter, the toner particles will be described.

<1. Toner particles>
The toner particles contain a first magnetic powder, a second magnetic powder, and a binder resin. The toner particles may contain a colorant, a charge control agent, and / or a release agent as necessary. Further, an external additive may be attached to the surface of the toner particles as necessary. Hereinafter, the toner particles before attaching the external additive may be referred to as toner mother particles. Hereinafter, the first magnetic powder, the second magnetic powder, and the binder resin contained in the toner base particles will be described. The colorant, charge control agent, and release agent that may be contained in the toner base particles will be described. Further, the external additive will be described.

<1-1. First and second magnetic powder>
The first magnetic powder and the second magnetic powder are not particularly limited as long as they can be used for toner. Examples of the first magnetic powder and the second magnetic powder include a ferromagnetic metal, an alloy of a plurality of types of ferromagnetic metals, a magnetic powder mainly composed of a ferromagnetic metal, and a magnetic powder obtained by doping cobalt oxide or nickel into iron oxide. An alloy that does not contain a ferromagnetic metal element but becomes ferromagnetic by heat treatment, or chromium dioxide. Examples of ferromagnetic metals include iron, cobalt, or nickel. Iron may be used in the form of iron oxide (eg, magnetite or ferrite). One kind of these magnetic powders may be used alone or in combination of two or more kinds for the first magnetic powder. In addition, one kind of these magnetic powders may be used alone or in combination of two or more kinds for the second magnetic powder. Magnetite is preferable as the first magnetic powder and the second magnetic powder because the charge amount of the toner particles can be easily adjusted.

  The first magnetic powder may be the same as the second magnetic powder. In the manufacturing method of the present embodiment, the second magnetic powder is added to the primary pulverized product having the first magnetic powder, and the secondary pulverization is performed. Thus, even if the first magnetic powder and the second magnetic powder are of the same type, the amount of the first magnetic powder present in the central part of the toner particles is reduced to the second magnetic powder present in the surface part of the toner particles. It becomes easy to set the amount different from the amount. As a result, it becomes easy to change the conductivity of the central portion of the toner particles and the conductivity of the surface portion. As a result, it is easy to suppress overcharging of the toner even in a low humidity environment, and it is easy to maintain the charge amount of the toner even in a high humidity environment.

  Alternatively, the first magnetic powder may be different from the second magnetic powder. The first magnetic powder is preferably different from the second magnetic powder. By using a different kind of magnetic powder than the second magnetic powder present on the surface portion of the toner particle as the first magnetic powder present on the central portion of the toner particle, the conductivity and surface portion of the central portion of the toner particle It becomes easy to change the conductivity. As a result, it becomes easier to control the charge amount of the toner. As a result, it is easy to suppress overcharging of the toner even in a low humidity environment, and it is easy to maintain the charge amount of the toner even in a high humidity environment.

  The first magnetic powder is different from the second magnetic powder in, for example, one or more of shape, aspect ratio, volume resistivity, material, remanent magnetization, saturation magnetization, BET specific surface area, and bulk density. May be.

(shape)
The shape of the first magnetic powder is preferably different from the shape of the second magnetic powder. Examples of the shape of the first magnetic powder and the second magnetic powder include a needle shape, a spherical shape, and a polyhedral shape. An example of the polyhedron shape is an octahedron shape, and specifically, an octahedron shape that is a convex polyhedron surrounded by eight triangles. Another example of the polyhedron shape is a hexahedron shape, and specifically, a hexahedron shape that is a convex polyhedron surrounded by six squares. When the shape is a polyhedron, the polyhedron may have a shape in which each vertex and each side of the polyhedron are curved and a portion that can be regarded as a straight line exists in the outer periphery of the projected image of the polyhedron.

  More preferably, the first magnetic powder is acicular and the second magnetic powder is spherical or polyhedral. Alternatively, it is more preferable that the first magnetic powder is spherical or polyhedral, and the second magnetic powder is needle-shaped.

  Since acicular magnetic powder easily releases electric charge, toner particles including such magnetic powder are difficult to overcharge. On the other hand, since spherical or polyhedral magnetic powder easily retains electric charge, toner particles including such magnetic powder are less likely to have a reduced charge amount. Therefore, when one of the first magnetic powder and the second magnetic powder is needle-shaped and the other is spherical or polyhedral, it becomes easy to improve the balance of the charge amount of the toner particles.

  Among these, it is more preferable that the first magnetic powder is needle-shaped and the second magnetic powder is spherical or polyhedral.

  Hereinafter, an example of a method for producing the first magnetic powder and the second magnetic powder will be described. In addition, the manufacturing method of a 1st magnetic powder and a 2nd magnetic powder can be suitably changed and implemented as needed. Further, unnecessary operations may be omitted as appropriate.

First, ferrous sulfate and sodium hydroxide aqueous solution are mixed to obtain a mixed solution. The temperature of the mixed solution is raised to obtain an aqueous ferrous salt solution containing iron hydroxide (Fe (OH) ₂ ). The pH of the obtained ferrous salt aqueous solution is adjusted. By passing air through the ferrous salt aqueous solution after pH adjustment for a predetermined time, an oxidation reaction of iron hydroxide is performed. Thereby, magnetic powder (magnetite) is obtained. The obtained magnetic powder is washed with water, filtered, and then dried. By pulverizing the dried magnetic powder, a magnetic powder (magnetite) having a desired shape can be obtained.

  In the above manufacturing method, for example, the shape of the first magnetic powder and the second magnetic powder is changed by changing the pH of the ferrous salt aqueous solution and the time of the oxidation reaction (time for aeration of air). For example, by adjusting the pH of the ferrous salt aqueous solution to 12.5 and performing an oxidation reaction for 220 minutes, octahedral magnetic powder can be obtained. For example, by adjusting the pH of the aqueous ferrous salt solution to 6.8 and performing an oxidation reaction for 180 minutes, and subsequently adjusting the pH of the aqueous ferrous salt solution to 12.0 and performing the oxidation reaction for 60 minutes, A spherical magnetic powder is obtained. For example, by adjusting the pH of the ferrous salt aqueous solution to 6.8 and performing an oxidation reaction for 120 minutes, and subsequently adjusting the pH of the ferrous salt aqueous solution to 3.8 and performing the oxidation reaction for 60 minutes, Acicular magnetic powder is obtained.

  The shapes of the obtained first magnetic powder and second magnetic powder are observed at a magnification of 50000 with a scanning electron microscope (“JSM-7500F” manufactured by JEOL Ltd.), for example.

(aspect ratio)
The aspect ratio (number average major axis diameter / number average minor axis diameter) of the first magnetic powder is preferably different from the aspect ratio of the second magnetic powder. More preferably, the aspect ratio of the first magnetic powder is 3.0 or more, and the aspect ratio of the second magnetic powder is less than 3.0. Alternatively, the aspect ratio of the first magnetic powder is less than 3.0, and the aspect ratio of the second magnetic powder is more preferably 3.0 or more.

  The aspect ratio of the acicular magnetic powder is, for example, 3.0 or more. The aspect ratio of the spherical or polyhedral magnetic powder is, for example, less than 3.0.

  Since magnetic powder having an aspect ratio of 3.0 or more easily releases electric charge, toner particles including such magnetic powder are difficult to be overcharged. On the other hand, since toner particles including magnetic powder having an aspect ratio of less than 3.0 easily retain charge, toner particles including such magnetic powder are less likely to have a reduced charge amount. Therefore, one of the first magnetic powder and the second magnetic powder is a magnetic powder having an aspect ratio of 3.0 or more, and the other is a magnetic powder having an aspect ratio of less than 3.0. It becomes easy to improve the balance of the charge amount of the particles.

  Especially, it is more preferable that the first magnetic powder is a magnetic powder having an aspect ratio of 3.0 or more, and the second magnetic powder is a magnetic powder having an aspect ratio of less than 3.0.

  The aspect ratio of the first magnetic powder and the second magnetic powder is measured, for example, as follows. 100 samples (first magnetic powder or first sample) selected at random using a scanning electron microscope (“JSM-7500F” manufactured by JEOL Ltd.) at a predetermined magnification (for example, 50,000 times). An image of the two magnetic powder) is obtained. Subsequently, the obtained image is analyzed using image analysis software, and the major axis diameter and the minor axis diameter are measured for each of the 100 samples. Subsequently, the sum of all measured major axis diameters and the sum of all measured minor axis diameters are each divided by the number of measured samples (100). Thereby, the number average major axis diameter and the number average minor axis diameter of the sample are obtained. Moreover, the aspect ratio (number average major axis diameter / number average minor axis diameter) of the first magnetic powder and the second magnetic powder is determined by dividing the number average major axis diameter by the number average minor axis diameter.

(Volume resistivity)
The volume resistivity of the first magnetic powder is preferably different from the volume resistivity value of the second magnetic powder. More preferably, the volume resistivity of the first magnetic powder is 1 × 10 ³ Ω · cm or more, and the volume resistivity of the second magnetic powder is less than 1 × 10 ³ Ω · cm. Alternatively, the volume resistivity of the first magnetic powder is less than 1 × 10 ³ Ω · cm, and the volume resistivity of the second magnetic powder is more preferably 1 × 10 ³ Ω · cm or more.

  Hereinafter, an example of a method for producing magnetic powder having different volume specific resistance values will be described. Magnetic powder particles from the group consisting of aluminum (Al), magnesium (Mg), manganese (Mn), zinc (Zn), nickel (Ni), copper (Cu), titanium (Ti), and silicon (Si) Coat with a compound containing one or more selected metals. By adjusting the type and amount of metal contained in the compound for coating the magnetic powder, the volume resistivity value of the magnetic powder is adjusted.

  For example, when the metal contained in the compound for coating the magnetic powder is aluminum, the magnetic powder is produced as follows. Specifically, the magnetic powder slurry is heated. A sodium hydroxide solution is added to the heated magnetic powder slurry. Thereby, the pH of the slurry is adjusted to the basic side (for example, to 8.5). After adjusting the pH, an aqueous aluminum sulfate solution is added to the slurry. Simultaneously with the addition of the aqueous aluminum sulfate solution, the aqueous sodium hydroxide solution is also added to the slurry to maintain the pH of the aqueous solution containing the slurry. Next, the obtained liquid is aged. Next, dilute sulfuric acid is added to the aged liquid to adjust the pH of the liquid to neutral (for example, 7.0). The liquid is then filtered, washed with water and dried. Thereby, the magnetic powder (magnetic powder surface-treated with aluminum) whose volume specific resistance value was adjusted is obtained.

  The volume specific resistance values of the first magnetic powder and the second magnetic powder are measured, for example, as follows. A 5 g sample (first magnetic powder or second magnetic powder) is put in a measurement cell of an electric resistance meter (“R6561” manufactured by Advantest Corporation), and a load of 1 kg is applied to the sample. Subsequently, the electrode of the electric resistance meter is connected to the sample. Subsequently, a DC voltage of 10 V is applied to the electrode, and the electrical resistance of the sample is measured. The measurement is performed in an environment of a temperature of 20 ° C. and a humidity of 50% RH. Then, based on the measured value of electric resistance and the size of the sample at the time of measuring electric resistance, the volume specific resistance value of the sample is obtained. The volume specific resistance value is represented by the expression “volume specific resistance value = electric resistance value × current path cross-sectional area / current path length”.

  Here, the first magnetic powder and the second magnetic powder are subjected to surface treatment from the viewpoint of improving the dispersibility of the first magnetic powder in the binder resin and the durability of the first magnetic powder and the second magnetic powder. It may be done. When surface-treating the first magnetic powder and the second magnetic powder, examples of the surface treatment agent include a cationic surfactant, an anionic surfactant, an amphoteric surfactant, a silane coupling agent, a titanium coupling agent, and an aluminum cup. Examples thereof include a ring agent, a phenol resin, an epoxy resin, a cyanate resin, and a urethane resin. You may use a surface treating agent individually by 1 type or in combination of 2 or more types.

  When surface-treating the first magnetic powder and the second magnetic powder, the amount of the surface treatment agent used is 0.1 parts by mass or more and 100 parts by mass with respect to 100 parts by mass of the first magnetic powder or 100 parts by mass of the second magnetic powder. It is preferably no greater than 0.5 parts by mass, more preferably no greater than 0.5 parts by mass and no greater than 20 parts by mass, and particularly preferably no less than 1.0 parts by mass and no greater than 10 parts by mass.

  The number average particle diameters of the first magnetic powder and the second magnetic powder are each preferably 0.1 μm or more and 1.0 μm or less, and more preferably 0.1 μm or more and 0.5 μm or less. When the first magnetic powder having a particle diameter in such a range is used, it is easy to uniformly disperse the first magnetic powder in the binder resin. Moreover, when using the 2nd magnetic powder which has a particle diameter in such a range, it is easy to embed the 2nd magnetic powder in the 1st ground material. The number average particle diameter of the first magnetic powder and the second magnetic powder is measured using, for example, an image obtained by further enlarging the image taken at a magnification of 10,000 times with a transmission electron microscope four times.

  The total addition amount of the first magnetic powder and the second magnetic powder is preferably 30 parts by mass or more and 60 parts by mass or less, and 35 parts by mass or more and 45 parts by mass or less with respect to 100 parts by mass of the toner base particles. Is more preferable. If the total amount of the first magnetic powder and the second magnetic powder is too small, fog due to poor formation of the toner layer on the developing sleeve tends to occur in the formed image. On the other hand, if the total addition amount of the first magnetic powder and the second magnetic powder is excessive, the image density of the formed image tends to be lowered.

  The content of the second magnetic powder is preferably less than 30 parts by mass with respect to 30 parts by mass of the first magnetic powder, more preferably 1 part by mass to 25 parts by mass, and more preferably 5 parts by mass to 15 parts by mass. It is particularly preferred that the amount is not more than parts. When the content of the second magnetic powder is less than the content of the first magnetic powder, the formed toner particles are difficult to break. Further, when the content of the second magnetic powder is within such a range, it is difficult to improve the balance of the charge amount of the toner particles.

  The toner particles may further contain another magnetic powder other than the first magnetic powder and the second magnetic powder. When the toner particles contain another magnetic powder, the other magnetic powder is appropriately selected from known magnetic powders.

<1-2. Binder resin>
The binder resin is not particularly limited as long as it is a binder resin used for toner. As the binder resin, a thermoplastic resin is preferable from the viewpoint of improving the fixing property of the toner. Examples of the thermoplastic resin include acrylic acid resin, styrene acrylic acid resin, polyester resin, polyamide resin, urethane resin, or vinyl alcohol resin. Among these resins, a styrene acrylic resin or a polyester resin is preferable from the viewpoints of dispersibility in toner particles, toner chargeability, and toner fixability to a recording medium. Hereinafter, the styrene acrylic acid resin and the polyester resin will be described.

  The styrene acrylic acid resin is a copolymer of a styrene monomer and an acrylic acid monomer. Examples of the styrene monomer include styrene, α-methylstyrene, vinyltoluene, α-chlorostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, or p-ethylstyrene. Examples of acrylic monomers include acrylic acid alkyl esters or methacrylic acid alkyl esters. Examples of alkyl acrylate esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, or 2-ethylhexyl acrylate. . Examples of alkyl methacrylates include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, or 2-ethylhexyl methacrylate. .

  The polyester resin can be obtained by, for example, condensation polymerization or co-condensation polymerization of alcohol and carboxylic acid.

  Examples of the alcohol used when synthesizing the polyester resin include dihydric alcohols and trihydric or higher alcohols.

  Examples of the dihydric alcohol include diols or bisphenols. Examples of diols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1, Examples include 5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, or polytetramethylene glycol. Examples of bisphenols include bisphenol A, hydrogenated bisphenol A, polyoxyethylene bisphenol A ether, or polyoxypropylene bisphenol A ether.

  Examples of trihydric or higher alcohols include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, diglycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, or 1,3,5-trihydroxy Mention may be made of methylbenzene.

  Examples of the carboxylic acid used when synthesizing the polyester resin include a divalent carboxylic acid or a trivalent or higher carboxylic acid.

  Examples of divalent carboxylic acids include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, succinic acid. Examples include acids, alkyl succinic acids, or alkenyl succinic acids. Examples of alkyl succinic acids include n-butyl succinic acid, isobutyl succinic acid, n-octyl succinic acid, n-dodecyl succinic acid, or isododecyl succinic acid. Examples of alkenyl succinic acids include n-butenyl succinic acid, isobutenyl succinic acid, n-octenyl succinic acid, n-dodecenyl succinic acid, or isododecenyl succinic acid.

  Examples of trivalent or higher carboxylic acids include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalene tricarboxylic acid, 1,2,4-naphthalene tricarboxylic acid, 4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, or empole trimer acid.

  Alcohol and carboxylic acid may be used individually by 1 type, respectively, and may be used in combination of 2 or more type. Furthermore, the carboxylic acid may be derivatized into an ester-forming derivative. Examples of ester-forming derivatives include acid halides, acid anhydrides, or lower alkyl esters. Here, “lower alkyl” means an alkyl group having 1 to 6 carbon atoms.

  The acid value of the polyester resin is preferably 5 mgKOH / g or more and 30 mgKOH / g or less. The hydroxyl value of the polyester resin is preferably 15 mgKOH / g or more and 80 mgKOH / g or less.

  The acid value and hydroxyl value of the polyester resin are adjusted, for example, by changing the amount of alcohol used and the amount of carboxylic acid used when preparing the polyester resin. When the molecular weight of the polyester resin is increased, the acid value and hydroxyl value of the polyester resin tend to decrease. The acid value and hydroxyl value of the polyester resin are measured, for example, according to a method based on JIS (Japanese Industrial Standard) K0070-1992.

  When a thermoplastic resin is used as the binder resin, one type of thermoplastic resin may be used alone, or two or more types may be used in combination. Moreover, you may add a crosslinking agent or a thermosetting resin to a thermoplastic resin. When a crosslinked structure is partially introduced into the binder resin, it is easy to improve the storage stability of the toner, the toner shape retention, and the durability of the toner while ensuring the toner fixability.

  Thermosetting resins that can be used with thermoplastic resins include bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, novolac type epoxy resins, polyalkylene ether type epoxy resins, cycloaliphatic type epoxy resins, or cyanate type resins. Is preferred. One kind of thermosetting resin may be used alone, or two or more kinds may be used in combination.

  The glass transition point (Tg) of the binder resin is preferably 30 ° C. or higher and 60 ° C. or lower. The glass transition point of the binder resin is measured, for example, according to the following method.

(Glass transition point measurement method)
The endothermic curve of the binder resin is measured using a differential scanning calorimeter (DSC) (for example, “DSC-6220” manufactured by Seiko Instruments Inc.). 10 mg of binder resin (measurement sample) is placed in an aluminum pan. Use an empty aluminum pan as a reference. The endothermic curve of the binder resin is measured under the conditions of a measurement temperature range of 25 ° C. to 200 ° C. and a temperature increase rate of 10 ° C./min. The glass transition point of the binder resin is determined from the obtained endothermic curve (specifically, the change point of the specific heat of the binder resin).

  The softening point (Tm) of the binder resin is preferably 60 ° C. or higher and 150 ° C. or lower. Two or more kinds of resins having different softening points may be used in combination so that the softening point of the binder resin is within such a range. The softening point of the binder resin is measured, for example, according to the following method.

(Softening point measurement method)
The binder resin (sample) is set in a Koka flow tester (for example, “CFT-500D” manufactured by Shimadzu Corporation). A sample of 1 cm ³ is melted and discharged under the conditions of a die pore diameter of 1 mm, a plunger load of 20 kg / cm ² , and a heating rate of 6 ° C./min. Thereby, an S-shaped curve relating to temperature (° C.) / Stroke (mm) is obtained. The softening point of the sample is read from the obtained S-shaped curve. Specifically, with respect to the resulting S-shaped curve, the maximum value of the stroke and S _1, the stroke value of the low-temperature side of the base line and S _2. The temperature at which the stroke value is (S ₁ + S ₂ ) / 2 is taken as the softening point of the sample. Thereby, the softening point of the binder resin (sample) is obtained.

  The mass average molecular weight (Mw) of the binder resin is preferably 5000 or more and 100,000 or less. When the weight average molecular weight of the binder resin is within such a range, the low-temperature fixability of the toner is easily improved.

  The molecular weight distribution (Mw / Mn) of the binder resin is preferably 10 or more and 50 or less. The molecular weight distribution (Mw / Mn) of the binder resin is the ratio between the mass average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin. When the molecular weight distribution of the binder resin is within such a range, it is easy to improve the low-temperature fixability of the toner.

  The mass average molecular weight and the number average molecular weight of the binder resin are measured using, for example, gel permeation chromatography (GPC). Hereinafter, an example of a method for measuring the mass average molecular weight and the number average molecular weight using GPC will be described.

(Measurement method of molecular weight using GPC)
A measurement sample (binder resin) is put into tetrahydrofuran (THF) so as to have a concentration of 3.0 mg / mL, and left to stand for 1 hour to be dissolved in THF. The obtained THF solution is filtered through a pretreatment filter (“Chromatodisc 25N”, Kurashiki Boseki Co., Ltd., non-aqueous, membrane pore size 0.45 μm) to obtain a solution of a measurement sample. The measurement of GPC is performed with the following apparatus and conditions. First, the column is stabilized in a 40 ° C. heat chamber. Subsequently, THF is allowed to flow through the column at 40 ° C. at a flow rate of 1 mL / min, and a solution of a measurement sample of 50 μL or more and 200 μL or less is introduced into the column. Then, the molecular weight distribution of the measurement sample introduced into the column is measured.

GPC measurement condition apparatus: HLC-8220 (manufactured by Tosoh Corporation)
Eluent: THF (tetrahydrofuran)
Column: TSKgel GMHXL (manufactured by Tosoh Corporation)
Number of columns: 2 Detector: RI
Eluent flow rate: 1 mL / min Sample solution concentration: 3.0 mg / mL
Column temperature: 40 ° C
Sample solution volume: 100 μL
Calibration curve: Calibration curve prepared using standard polystyrene

<1-3. Colorant>
The toner color tends to become black due to the first magnetic powder and the second magnetic powder. Therefore, when the toner is a black toner, it is not necessary to use a colorant. Carbon black may be used as a black colorant for color reinforcement. Examples of carbon black include acetylene black and aniline black. The content of the black colorant is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin.

<1-4. Charge Control Agent>
The charge control agent is used for the purpose of improving the charge level of the toner and the charge rising characteristics of the toner. Further, it is used for the purpose of obtaining a toner having excellent durability. The charge rising characteristic is an index as to whether or not charging to a predetermined charge level is possible in a short time.

  When developing with positively charged toner, it is preferable to use a positively chargeable charge control agent. On the other hand, when developing using a negatively charged toner, it is preferable to use a negatively chargeable charge control agent. However, if a sufficient charge amount is secured in the toner, the charge control agent may not be used.

  Examples of positively chargeable charge control agents include azine compounds, direct dyes made from azine compounds, nigrosine compounds, acid dyes made from nigrosine compounds, metal salts of naphthenic acid or higher fatty acids, alkoxylated amines, alkylamides, or 4 A class ammonium salt is mentioned.

  Examples of azine compounds include pyridazine, pyrimidine, pyrazine, 1,2-oxazine, 1,3-oxazine, 1,4-oxazine, 1,2-thiazine, 1,3-thiazine, 1,4-thiazine, 1 , 2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, 1,2,4-oxadiazine, 1,3,4-oxadiazine, 1,2,6-oxadiazine, 1,3 , 4-thiadiazine, 1,3,5-thiadiazine, 1,2,3,4-tetrazine, 1,2,4,5-tetrazine, 1,2,3,5-tetrazine, 1,2,4,6 -Oxatriazine, 1,3,4,5-oxatriazine, phthalazine, quinazoline or quinoxaline.

  Examples of direct dyes composed of azine compounds include azine fast red FC, azine fast red 12BK, azine violet BO, azine brown 3G, azine light brown GR, azine dark green BH / C, azine deep black EW, or Azin Deep Black 3RL is mentioned. Examples of nigrosine compounds include nigrosine, nigrosine salts, or nigrosine derivatives.

  Examples of acidic dyes composed of a nigrosine compound include nigrosine BK, nigrosine NB, or nigrosine Z. Examples of quaternary ammonium salts include benzyldecylhexylmethylammonium chloride or decyltrimethylammonium chloride.

  Further, a resin having a quaternary ammonium salt, a carboxylate, or a carboxyl group can also be used as a positively chargeable charge control agent. A nigrosine compound is particularly preferred in order to obtain good toner charge rise characteristics. One charge control agent may be used alone, or two or more charge control agents may be used in combination.

<1-5. Release agent>
The release agent is used, for example, for the purpose of improving the toner fixing property and offset resistance. In order to improve the fixing property and offset resistance of the toner, the content of the release agent is preferably 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin. More preferably, it is 20 parts by mass or less.

  Examples of release agents include aliphatic hydrocarbon waxes, oxides of aliphatic hydrocarbon waxes, plant-derived waxes, animal-derived waxes, mineral-derived waxes, waxes based on fatty acid esters, or fatty acid esters. And a wax in which a part or all of the above is deoxidized. Examples of aliphatic hydrocarbon waxes include ester wax, polyethylene wax (eg, low molecular weight polyethylene), polypropylene wax (eg, low molecular weight polypropylene), polyolefin copolymer, polyolefin wax, microcrystalline wax, paraffin wax, or fisher Tropsch wax is mentioned. Examples of the oxide of the aliphatic hydrocarbon wax include an oxidized polyethylene wax or a block copolymer of oxidized polyethylene. Examples of plant-derived waxes include candelilla wax, carnauba wax, wood wax, jojoba wax, or rice wax. Examples of animal-derived waxes include beeswax, lanolin, or whale wax. Examples of mineral-derived waxes include ozokerite, ceresin, or petrolatum. Examples of the wax mainly composed of a fatty acid ester include montanic acid ester wax and caster wax. Deoxidized carnauba wax is an example of a wax in which a part or all of the fatty acid ester has been deoxidized.

  A mold release agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  The melting point of the release agent is preferably 50 ° C. or higher and 150 ° C. or lower. When the melting point of the release agent is within such a range, the low-temperature fixability of the toner containing the release agent is improved, and the occurrence of offset at a high temperature of the toner tends to be suppressed. The melting point of the release agent is measured using, for example, a differential scanning calorimeter (DSC) (for example, “DSC-6220” manufactured by Seiko Instruments Inc.).

<1-6. External additive>
Examples of the external additive include silica or metal oxide (more specifically, alumina, titanium oxide, magnesium oxide, zinc oxide, strontium titanate, or barium titanate). An external additive may be used individually by 1 type, and may be used in combination of 2 or more type. The number average particle size of the external additive is preferably 1 nm or more and 1 μm or less, and more preferably 1 nm or more and 50 nm or less. The amount of the external additive used is preferably 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the toner base particles.

<2. Toner Production Method>
Hereinafter, an example of a toner manufacturing method will be described. The toner manufacturing method includes a secondary pulverization step. The toner production method may further include a kneading step and a primary pulverization step. In addition, the toner manufacturing method may include an external addition step and other known steps as necessary. Hereinafter, the kneading step, the primary pulverization step, the secondary pulverization step, and the external addition step will be described.

<2-1. Kneading process>
In the kneading step, the first magnetic powder and the binder resin are melted and kneaded to obtain a kneaded product. Specifically, the mixture is obtained by mixing the binder resin and the first magnetic powder using a mixer (for example, FM mixer or Nauter mixer (registered trademark)). If necessary, a colorant, a charge control agent, and / or a release agent may be further added to the mixture. Subsequently, the obtained mixture is melted and kneaded using a twin-screw extruder (for example, “PCM-30” manufactured by Ikegai Co., Ltd.). The kneading temperature is preferably 80 ° C. or higher and 150 ° C. or lower. Thereby, a kneaded material is obtained.

<2-2. Primary grinding process>
In the primary pulverization step, the obtained kneaded product is primarily pulverized to obtain a primary pulverized product. Specifically, the obtained kneaded material is cooled using a drum flaker. The cooled kneaded material is first ground using a hammer mill. A sieve (for example, an opening of 5 mm) may be set on the hammer mill. Thereby, a primary pulverized product is obtained. The volume median diameter (D ₅₀ ) of the obtained primary pulverized product is preferably 100 μm or more and 1 mm or less.

<2-3. Secondary grinding process>
In the secondary pulverization step, toner base particles (toner particles before external addition) are obtained by adding the second magnetic powder to the primary pulverized product containing the first magnetic powder and the binder resin and performing secondary pulverization. Get. Specifically, the obtained primary pulverized product is subjected to secondary pulverization using a mechanical pulverizer (for example, “Turbomill T250” manufactured by Freund Turbo Inc.). The secondary pulverization conditions are preferably set so that at least a part of the second magnetic powder is buried in the primary pulverized product. More preferably, the second magnetic powder is set so as to be completely buried in the primary pulverized product. For example, the secondary pulverization is preferably performed at a rotational speed of 5000 rpm to 15000 rpm. By performing secondary pulverization under such conditions, the second magnetic powder is easily embedded in the primary pulverized product. As a result, toner mother particles in which the second magnetic powder is difficult to be detached from the primary pulverized product tend to be obtained. Subsequently, the obtained secondary pulverized product is classified using a classifier (for example, an air classifier). Thereby, toner mother particles are obtained. The obtained toner base particles have a volume median diameter (D ₅₀ ) of preferably less than 10.0 μm, and more preferably 5.0 μm or more and 9.0 μm or less.

<2-4. External process>
In the external addition step, an external additive is attached to the surface of the toner base particles. As an example of the method of attaching the external additive, using a mixer (for example, FM mixer or Nauter mixer (registered trademark)) under the condition that the external additive is not buried in the surface of the toner base particles, Examples thereof include a method of mixing toner base particles and an external additive. By attaching an external additive to the surface of the toner base particles, a toner containing toner particles can be obtained.

  The toner manufacturing method can be arbitrarily changed according to the required configuration or characteristics of the toner. Further, processes other than the secondary pulverization process and unnecessary operations may be omitted. In order to produce the toner efficiently, it is preferable to form a large number of toner particles simultaneously.

  As described above, according to the toner manufacturing method of the present embodiment, it is possible to suppress a decrease in image density due to a decrease in the charge amount of the toner even in a high humidity environment. Further, even under a low humidity environment, it is possible to suppress the occurrence of fog due to toner layer formation failure due to overcharging of the toner.

  Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the scope of the examples.

<1. Measuring method>
First, a method for measuring aspect ratio, number average major axis diameter, number average minor axis diameter, number average particle diameter, volume resistivity, volume median diameter, and particle size distribution will be described.

(Aspect ratio, number average major axis diameter, and number average minor axis diameter)
The aspect ratio of the first magnetic powder was measured as follows. Using a scanning electron microscope (“JSM-7500F” manufactured by JEOL Ltd.), the first magnetic powder was photographed at a magnification of 50000 times to obtain images of 100 randomly selected first magnetic powders. Subsequently, the obtained image was analyzed using image analysis software, and the major axis diameter and the minor axis diameter were measured for each of the 100 first magnetic powders. Subsequently, the sum of all measured major axis diameters and the sum of all measured minor axis diameters were each divided by the number of measured first magnetic powders (100). Thereby, the number average major axis diameter and the number average minor axis diameter of the first magnetic powder were obtained. Further, the aspect ratio (number average major axis diameter / number average minor axis diameter) of the first magnetic powder was determined by dividing the number average major axis diameter by the number average minor axis diameter. The number average major axis diameter, number average minor axis diameter, and aspect ratio of the second magnetic powder are also measured in the same manner as the number average major axis diameter, number average minor axis diameter, and aspect ratio of the first magnetic powder. did.

(Number average particle diameter)
The number average particle size of the first magnetic powder was measured as follows. Using a scanning electron microscope (“JSM-7500F” manufactured by JEOL Ltd.), the first magnetic powder was photographed at a magnification of 50000 times to obtain images of 100 randomly selected first magnetic powders. Subsequently, the obtained image was analyzed using image analysis software, and the equivalent circle diameter was measured for each of the 100 first magnetic powders. Subsequently, the sum of all measured equivalent circle diameters was divided by the number of measured first magnetic powders (100). Thereby, the number average particle diameter of the first magnetic powder was obtained. The number average particle size of the second magnetic powder was also measured in the same manner as the method for measuring the number average particle size of the first magnetic powder.

(Volume resistivity)
The volume resistivity value of the first magnetic powder was measured as follows. 5 g of the first magnetic powder was put in a measurement cell of an electric resistance meter (“R6561” manufactured by Advantest Co., Ltd.), and a load of 1 kg was applied to the first magnetic powder in the measurement cell. Subsequently, an electrode of an electric resistance meter was connected to the first magnetic powder in the measurement cell, and a DC voltage of 10 V was applied to the electrode to measure the electric resistance of the first magnetic powder. And the volume specific resistance value of the 1st magnetic powder was calculated | required based on the value of the measured electrical resistance, and the dimension of the 1st magnetic powder at the time of an electrical resistance measurement. The volume resistivity value of the second magnetic powder was also measured in the same manner as the method for measuring the volume resistivity value of the first magnetic powder. The volume resistivity value was measured in an environment at a temperature of 20 ° C. and a humidity of 50% RH.

(Measurement of volume median diameter and particle size distribution)
The volume median diameter (D ₅₀ ) and particle size distribution of the toner base particles were measured using a precision particle size distribution measuring device (“Coulter Counter Multisizer 3” manufactured by Beckman Coulter Inc.). The volume median diameter (D ₅₀ ) is a median diameter calculated on a volume basis using a Coulter counter method.

<2. Production of magnetic powder>
Spherical magnetic powder and acicular magnetic powder were produced as follows. In addition, magnetic powder having a volume resistivity of 4 × 10 ³ Ω · cm and magnetic powder having a volume resistivity of 2 × 10 ² Ω · cm were produced.

(Spherical magnetic powder)
1.8 L of ferrous sulfate containing iron ions (Fe ²⁺ ) at a concentration of 1.8 mol / L was mixed with 2.8 L of a 1.346N aqueous sodium hydroxide solution. The temperature of the mixed solution was raised to 90 ° C. to obtain a ferrous salt aqueous solution containing iron hydroxide (Fe (OH) ₂ ). The obtained aqueous solution was aerated with air at a rate of 15 L / min for 180 minutes under the conditions of an aqueous solution temperature of 90 ° C. and pH 6.8. As a result, an oxidation reaction of iron hydroxide was performed to obtain a ferrous salt aqueous solution containing magnetite particles. When the pH of the ferrous salt aqueous solution containing the magnetite particles began to drop to 6.0, 4 L of 4N sodium hydroxide aqueous solution was added to the ferrous salt aqueous solution. Thereby, the pH of the ferrous salt aqueous solution was adjusted to 12.0. Under the conditions of a ferrous salt aqueous solution at a temperature of 90 ° C. and a pH of 12.0, air was bubbled through the ferrous salt aqueous solution at a rate of 15 L / min for 60 minutes. Thereby, magnetic powder (magnetite) was obtained. The obtained magnetic powder was washed with water, filtered, and dried. A spherical magnetic powder (magnetite) was obtained by pulverizing the dried magnetic powder. The aspect ratio of the obtained spherical magnetic powder was 1.1, and the number average particle diameter was 0.4 μm.

(Needle magnetic powder)
35 L of ferrous sulfate containing iron ions (Fe ²⁺ ) at a concentration of 0.86 mol / L and 15 L of 1.4N aqueous sodium hydroxide solution were mixed. The temperature of the mixed solution was raised to 40 ° C., and the pH of the mixed solution was adjusted to 6.8 to obtain a ferrous salt aqueous solution containing iron hydroxide (Fe (OH) ₂ ). The temperature of the obtained ferrous salt aqueous solution was raised to 85 ° C., and the pH of the aqueous solution was adjusted to 3.8. Under the conditions of a ferrous salt aqueous solution temperature of 85 ° C. and pH 3.8, air was passed through the ferrous salt aqueous solution at a rate of 15 L / min for 120 minutes. Thereby, the oxidation reaction of iron hydroxide was performed and the ferrous salt aqueous solution containing a magnetite particle was obtained. When the pH of the ferrous salt aqueous solution containing the magnetite particles started to drop to 6.0, a 10N aqueous sodium hydroxide solution was added to the ferrous salt aqueous solution. Thereby, the pH of the ferrous salt aqueous solution was adjusted to 3.8. After pH adjustment, the temperature of the ferrous salt aqueous solution was raised to 90 ° C. Under the conditions of a ferrous salt aqueous solution temperature of 90 ° C. and pH 3.8, air was bubbled through the ferrous salt aqueous solution at a rate of 15 L / min for 60 minutes. Thereby, magnetic powder (magnetite) was obtained. The obtained magnetic powder was washed with water, filtered, and dried. The dried magnetic powder was pulverized to obtain acicular magnetic powder (magnetite). The obtained acicular magnetic powder had an aspect ratio of 4.0, a number average major axis diameter of 0.60 μm, and a number average minor axis diameter of 0.15 μm.

(Magnetic powder with a volume resistivity of 4 × 10 ³ Ω · cm)
100 L of the slurry containing the spherical magnetic powder produced as described above at a concentration of 90 g / L was heated to 90 ° C. Sodium hydroxide solution was added to the slurry while maintaining the temperature of the slurry at 90 ° C. This adjusted the pH of the slurry to 8.5. After adjusting the pH, 3 L of a 1.9 mol / L aluminum sulfate aqueous solution was added to the slurry over 190 minutes. Simultaneously with the addition of the aqueous aluminum sulfate solution, the aqueous sodium hydroxide solution was also added to the slurry, and the pH of the aqueous solution containing the slurry was kept at 8.5 ± 0.2. Next, the obtained liquid was aged for 60 minutes. Next, dilute sulfuric acid was added to the ripened liquid to adjust the pH of the liquid to 7.0. The liquid was then filtered, washed with water and dried. Thereby, magnetic powder (magnetite surface-treated with aluminum) was obtained. The resulting magnetic powder had a volume resistivity of 4 × 10 ³ Ω · cm.

(Magnetic powder with a volume resistivity of 2 × 10 ² Ω · cm)
The volume resistivity value is the same as the method for producing magnetic powder having a volume resistivity value of 4 × 10 ³ Ω · cm except that the addition amount of the 1.9 mol / L aluminum sulfate aqueous solution is changed from 3 L to 10 L. Obtained 2 × 10 ² Ω · cm of magnetic powder (magnetite surface-treated with aluminum).

<3. Production of toner>
Next, a toner manufacturing method will be described.

(Toner 1)
Toner 1 was produced as follows. First, a kneading step was performed. Binder resin (styrene-acrylic acid resin, mass average molecular weight (Mw) 97,000, number average molecular weight (Mn) 4,400, softening point 140 ° C.) 55 parts by mass, release agent (polypropylene wax, Mitsui Chemicals, Inc.) 4 parts by mass of “High Wax NP056” manufactured by the company, 30 parts by mass of the first magnetic powder (acicular magnetic powder obtained above), and a charge control agent (“BONTRON (registered trademark) N-” manufactured by Orient Chemical Co., Ltd.) 71 ") 1 part by mass was mixed using an FM mixer (" FM-10B "manufactured by Nippon Coke Kogyo Co., Ltd.). Thereby, each raw material was dispersed in the binder resin. The obtained mixture was melted and kneaded using a twin screw extruder ("PCM-30" manufactured by Ikegai Co., Ltd.).

  The primary grinding process was performed as follows. The obtained kneaded material was cooled using a drum flaker. The cooled kneaded material was first pulverized with a hammer mill (impact type screen crusher, “Hammer Mill H” manufactured by Hosokawa Micron Corporation). A sieve (aperture 5 mm) was set on the hammer mill. Thereby, a primary pulverized product was obtained.

The secondary grinding process was performed as follows. 90 parts by mass of the obtained primary pulverized product and 10 parts by mass of the second magnetic powder (the spherical magnetic powder obtained above) were mixed using an FM mixer (“FM-10B” manufactured by Nippon Coke Industries, Ltd.). did. The mixture was secondarily pulverized using a mechanical pulverizer (“Turbomill T250” manufactured by Freund Turbo, Inc.). Secondary pulverization was performed at a rotational speed of 9000 rpm. The obtained secondary pulverized product was classified using a classifier (“Elbow Jet EJ-LABO type” manufactured by Nippon Steel Mining Co., Ltd.). As a result, toner base particles (toner particles before external addition treatment) were obtained. The toner mother particles thus obtained had a volume median diameter (D ₅₀ ) of 7.0 μm. The particle size distribution of the toner base particles was as follows. Toner base particles having a particle diameter of 10.0 μm or more were 2.0% by volume. Toner base particles having a particle size of 3.0 μm or less were 1.0% by volume.

  The external addition process was performed as follows. 98 parts by mass of toner base particles obtained, 1.0 part by mass of dry silica fine particles (“AEROSIL (registered trademark) REA200” manufactured by Nippon Aerosil Co., Ltd.) as an external additive, and titanium oxide (Taika Co., Ltd.) as an external additive 1.0 part by mass of “JR-405” manufactured by company and titanium oxide treated with aluminum was mixed at a speed of 3000 rpm for 10 minutes using an FM mixer (“FM-10B” manufactured by Nippon Coke Industries, Ltd.). As a result, the external additive was adhered to the surface of the toner base particles. As a result, toner 1 was obtained.

(Toner 2)
A toner 2 was obtained in the same manner as the production method of the toner 1 except that the following was changed. The first magnetic powder used in the kneading step was changed from 30 parts by mass of acicular magnetic powder to 30 parts by mass of spherical magnetic powder.

(Toner A)
Toner A was produced as follows. First, a kneading step was performed. Binder resin (styrene-acrylic acid resin, mass average molecular weight (Mw) 97,000, number average molecular weight (Mn) 4,400, softening point 140 ° C.) 55 parts by mass, release agent (polypropylene wax, Mitsui Chemicals, Inc.) 4 parts by mass of “High Wax NP056” manufactured by the company, 40 parts by mass of the first magnetic powder (the spherical magnetic powder obtained above), and a charge control agent (“BONTRON (registered trademark) N-71 manufactured by Orient Chemical Industries Ltd.) “) 1 part by mass was mixed using an FM mixer (“ FM-10B ”manufactured by Nippon Coke Industries, Ltd.). Thereby, each raw material was dispersed in the binder resin. The obtained mixture was melted and kneaded using a twin screw extruder ("PCM-30" manufactured by Ikegai Co., Ltd.).

  The primary grinding process was performed as follows. The obtained kneaded material was cooled using a drum flaker. The cooled kneaded material was first pulverized with a hammer mill (impact type screen crusher, “Hammer Mill H” manufactured by Hosokawa Micron Corporation). A sieve (aperture 5 mm) was set on the hammer mill. Thereby, a primary pulverized product was obtained.

  The secondary grinding process was performed as follows. 100 parts by mass of the obtained primary pulverized product was secondarily pulverized using a mechanical pulverizer (“Turbomill T250” manufactured by Freund Turbo). Secondary pulverization was performed at a rotational speed of 9000 rpm. The obtained secondary pulverized product was classified using a classifier (“Elbow Jet EJ-LABO type” manufactured by Nippon Steel Mining Co., Ltd.). As a result, toner base particles (toner particles before external addition treatment) were obtained.

  An external addition process was performed on 98 parts by mass of the obtained toner base particles in the same manner as in the toner 1 production method. As a result, the external additive was adhered to the surface of the toner base particles. As a result, toner A was obtained.

(Toner B)
A toner B was obtained in the same manner as the production method of the toner A except that the following was changed. The first magnetic powder used in the kneading step was changed from 40 parts by mass of spherical magnetic powder to 20 parts by mass of acicular magnetic powder and 20 parts by mass of spherical magnetic powder.

(Toner C)
Toner C was produced as follows. First, a kneading step was performed. Binder resin (styrene-acrylic acid resin, mass average molecular weight (Mw) 97,000, number average molecular weight (Mn) 4,400, softening point 140 ° C.) 55 parts by mass, release agent (polypropylene wax, Mitsui Chemicals, Inc.) 4 parts by mass of “High Wax NP056” manufactured by the company, 30 parts by mass of the first magnetic powder (acicular magnetic powder obtained above), and a charge control agent (“BONTRON (registered trademark) N-” manufactured by Orient Chemical Co., Ltd.) 71 ") 1 part by mass was mixed using an FM mixer (" FM-10B "manufactured by Nippon Coke Kogyo Co., Ltd.). Thereby, each raw material was dispersed in the binder resin. The obtained mixture was melted and kneaded using a twin screw extruder ("PCM-30" manufactured by Ikegai Co., Ltd.).

  The primary grinding process was performed as follows. The obtained kneaded material was cooled using a drum flaker. The cooled kneaded material was first pulverized with a hammer mill (impact type screen crusher, “Hammer Mill H” manufactured by Hosokawa Micron Corporation). A sieve (aperture 5 mm) was set on the hammer mill. Thereby, a primary pulverized product was obtained.

  The secondary grinding process was performed as follows. The obtained primary pulverized product was subjected to secondary pulverization using a mechanical pulverizer (“Turbo Mill T250” manufactured by Freund Turbo Inc.). Secondary pulverization was performed at a rotational speed of 9000 rpm. The obtained secondary pulverized product was classified using a classifier (“Elbow Jet EJ-LABO type” manufactured by Nippon Steel Mining Co., Ltd.). As a result, toner base particles (toner particles before external addition treatment) were obtained.

  The external addition process was performed as follows. 88 parts by mass of the obtained toner base particles, 1.0 part by mass of dry silica fine particles (“AEROSIL (registered trademark) REA200” manufactured by Nippon Aerosil Co., Ltd.) as an external additive, titanium oxide (Taika Co., Ltd.) as an external additive "JR-405" made by aluminum, titanium oxide treated with aluminum (1.0 part by mass), and 10 parts by mass of externally added magnetic powder (needle-like magnetic powder) were mixed with an FM mixer ("FM-10B" manufactured by Nippon Coke Industries, Ltd. )) For 10 minutes at a speed of 3000 rpm. As a result, the external additive and the external magnetic powder were adhered to the surface of the toner base particles. As a result, toner C was obtained.

(Toner D)
A toner D was obtained in the same manner as the production method of the toner C except that the following was changed. The first magnetic powder used in the kneading step was changed from 30 parts by mass of acicular magnetic powder to 30 parts by mass of spherical magnetic powder. The externally added magnetic powder used in the external addition step was changed from 10 parts by mass of acicular magnetic powder to 10 parts by mass of spherical magnetic powder.

(Toner 3)
A toner 3 was obtained in the same manner as the production method of the toner 1 except that the following was changed. The binder resin used in the kneading step was changed from the styrene-acrylic acid resin to the polyester resin P1. The first magnetic powder used in the kneading step was changed from 30 parts by mass of acicular magnetic powder to 30 parts by mass of magnetic powder having a volume resistivity of 4 × 10 ³ Ω · cm obtained above. The second magnetic powder used in the secondary pulverization step was changed from 10 parts by mass of the spherical magnetic powder to 10 parts by mass of the magnetic powder having the volume resistivity value obtained above of 2 × 10 ² Ω · cm.

  Polyester resin P1 was prepared as follows. A reaction vessel was charged with 1575 g of a propylene oxide adduct of bisphenol A, 163 g of an ethylene oxide adduct of bisphenol A, 377 g of fumaric acid, and 4 g of a catalyst (dibutyltin oxide). The air in the reaction vessel was replaced with a nitrogen atmosphere. While stirring the contents of the reaction vessel, the temperature inside the reaction vessel was raised to 220 ° C. After the contents of the reaction vessel were reacted at 220 ° C. for 8 hours, the pressure inside the reaction vessel was reduced to 8.3 kPa. Subsequently, the contents of the reaction vessel were further reacted for 1 hour. Thereafter, the contents in the reaction vessel were cooled to 210 ° C. To the contents in the reaction vessel, 336 g of trimellitic anhydride was added. After completion of the reaction, the contents in the reaction vessel were taken out and cooled. Thereby, polyester resin P1 was obtained.

The volume median diameter (D ₅₀ ) of the toner base particles obtained in the secondary pulverization step was 7.0 μm. The particle size distribution of the toner base particles was as follows. Toner base particles having a particle diameter of 10.0 μm or more were 2.0% by volume. Toner base particles having a particle size of 3.0 μm or less were 1.0% by volume.

(Toner E)
A toner E was obtained in the same manner as the production method of the toner A except that the following was changed. The binder resin used in the kneading step was changed from the styrene-acrylic acid resin to the polyester resin P1 obtained above. The first magnetic powder used in the kneading step was changed from 40 parts by mass of spherical magnetic powder to 40 parts by mass of magnetic powder having a volume resistivity of 4 × 10 ³ Ω · cm obtained above.

(Toner F)
Toner F was produced as follows. First, a kneading step was performed. 55 parts by mass of binder resin (polyester resin P1 obtained above), 4 parts by mass of release agent (polypropylene wax, “High Wax NP056” manufactured by Mitsui Chemicals, Inc.), and charge control agent (manufactured by Orient Chemical Industries, Ltd.) 1 part by mass of “BONTRON (registered trademark) N-71”) was mixed using an FM mixer (“FM-10B” manufactured by Nippon Coke Industries, Ltd.). Thereby, each raw material was dispersed in the binder resin. The obtained mixture was melted and kneaded using a twin screw extruder ("PCM-30" manufactured by Ikegai Co., Ltd.).

  The primary grinding process was performed as follows. The obtained kneaded material was cooled using a drum flaker. The cooled kneaded material was first pulverized with a hammer mill (impact type screen crusher, “Hammer Mill H” manufactured by Hosokawa Micron Corporation). A sieve (aperture 5 mm) was set on the hammer mill. Thereby, a primary pulverized product was obtained.

The secondary grinding process was performed as follows. 60 parts by mass of the obtained primary pulverized product and 40 parts by mass of the second magnetic powder (the magnetic powder having the volume resistivity of 4 × 10 ³ Ω · cm obtained above) were mixed with an FM mixer (Nippon Coke Industries, Ltd.). It mixed using "FM-10B" made by a corporation. The mixture was secondarily pulverized using a mechanical pulverizer (“Turbomill T250” manufactured by Freund Turbo, Inc.). Secondary pulverization was performed at a rotational speed of 9000 rpm. The obtained secondary pulverized product was classified using a classifier (“Elbow Jet EJ-LABO type” manufactured by Nippon Steel Mining Co., Ltd.).

  The external addition process was performed as follows. 98 parts by mass of toner base particles obtained, 1.0 part by mass of dry silica fine particles (“AEROSIL (registered trademark) REA200” manufactured by Nippon Aerosil Co., Ltd.) as an external additive, and titanium oxide (Taika Co., Ltd.) as an external additive 1.0 part by mass of “JR-405” manufactured by company and titanium oxide treated with aluminum was mixed at a speed of 3000 rpm for 10 minutes using an FM mixer (“FM-10B” manufactured by Nippon Coke Industries, Ltd.). As a result, the external additive was adhered to the surface of the toner base particles. As a result, toner F was obtained.

<4. Evaluation>
Images were formed using toners 1 to 3 and A to F, and the fog density (FD) under a low temperature and low humidity environment and the image density (ID) under a high temperature and high humidity environment were evaluated. In these evaluations, evaluation images were continuously formed on paper using an evaluation machine. A monochrome printer (“FS-4020DN” manufactured by Kyocera Document Solutions Inc.) was used as an evaluation machine. The toner was put into the toner container of the evaluation machine. As an evaluation image, an image including an image part (printing rate 4%) conforming to ISO / IEC 19752 and three solid image parts (25 mm × 25 mm) was used. Color / monochrome paper (“C ² ” manufactured by Fuji Xerox Co., Ltd.) was used as the paper.

(Cover concentration under low temperature and low humidity)
In the evaluation of the fog density in a low temperature and low humidity environment, the measurement environment was set to a temperature of 10 ° C. and a humidity of 20% RH. Using an evaluation machine, images for evaluation were continuously formed on 10,000 sheets of paper. The image density of the blank portion of the paper on which the image was formed on the 10,000th sheet was measured using a Macbeth reflection densitometer (“SpectroEye (registered trademark)” sold by Sakata Inx Engineering Co., Ltd.). A value obtained by subtracting the image density of the base paper from the image density of the obtained white paper portion was defined as a fog density in a low temperature and low humidity environment. The fog density in the obtained low-temperature and low-humidity environment was evaluated based on the following evaluation criteria. Note that when a toner layer formation failure is caused on the developing sleeve, fogging tends to occur in the formed image.
[Evaluation criteria for fog density under low temperature and low humidity]
Good (◯): The fog density is less than 0.010.
Poor (x): The fog density is 0.010 or more.

(Image density under high temperature and high humidity environment: when printing 10,000 sheets)
In the evaluation of the image density in a high temperature and high humidity environment, the measurement environment was set to a temperature of 30 ° C. and a humidity of 80% RH. Using an evaluation machine, images for evaluation were continuously formed on 10,000 sheets of paper. The image density of each of the three solid image portions of the paper on which an image was formed on the 10,000th sheet was measured using a Macbeth reflection densitometer (“SpectaEye (registered trademark)” sold by Sakata Inx Engineering Co., Ltd.). The average value of the image density was obtained by dividing the sum of the three measured image densities by 3. The obtained average value was used as an evaluation value of image density when printing 10,000 sheets in a high temperature and high humidity environment. The obtained evaluation value was evaluated based on the following evaluation criteria.
[Evaluation criteria for image density under high-temperature and high-humidity environment (when printing 10,000 sheets)]
Good (◯): The image density is 1.20 or more.
Bad (x): The image density is less than 1.20.

(Image density in high temperature and high humidity environment: 50 sheets / day, when printing for 10 days)
Next, the image density when printing 50 sheets per day for 10 days in a high temperature and high humidity environment was evaluated. The measurement environment was set to a temperature of 30 ° C. and a humidity of 80% RH. Using an evaluation machine, images for evaluation were continuously formed on 50 sheets of paper per day. This operation was performed continuously for 10 days. The image density of each of the three solid image portions of the paper on which the image was formed on the 50th sheet on the 10th day was measured using a Macbeth reflection densitometer (“SpectaEye (registered trademark)” sold by Sakata Inx Engineering Co., Ltd.). . The average value of the image density was obtained by dividing the sum of the three measured image densities by 3. The obtained average value was used as an evaluation value of image density at the time of printing for 10 days at 50 sheets / day in a high temperature and high humidity environment. The obtained evaluation value was evaluated based on the following evaluation criteria. For toners A, C, and F, one of the evaluation of the fog density in a low-temperature and low-humidity environment and the evaluation of the image density (when printing 10,000 sheets) in a high-temperature and high-humidity environment is defective ( Therefore, the image density (50 sheets / day, when printing for 10 days) in a high temperature and high humidity environment was not evaluated.
[Evaluation criteria for image density under high temperature and high humidity (50 sheets / day, when printing for 10 days)]
Good (◯): The image density is 1.20 or more.
Bad (x): The image density is less than 1.20.

  For toners 1 to 3 and A to F, evaluation of fog density in a low-temperature and low-humidity environment and image density in a high-temperature and high-humidity environment (when printing 10,000 sheets and printing for 50 days / day for 10 days) The results are shown in Tables 1 and 2. In Tables 1 and 2, “StAc” represents a styrene-acrylic acid resin, “PEs” represents a polyester resin, “FD” represents a fog density, and “ID” represents an image density.

  The manufacturing method of the toners 1 and 2 includes a step of obtaining toner particles by adding the second magnetic powder to the primary pulverized product containing the first magnetic powder and the binder resin and performing secondary pulverization. . Therefore, as shown in Table 1, with toners 1 and 2, the fog density in a low-temperature and low-humidity environment, the image density in a high-temperature and high-humidity environment (when printing 10,000 sheets), and the high-temperature and high-humidity environment (50 sheets) / Day, 10 days), all the evaluations were good.

  In the manufacturing method of the toner A, spherical magnetic powder was used as the first magnetic powder, but the second magnetic powder was not added. For this reason, it is considered that the spherical magnetic powder that easily retains the charge exists at the same density in the central portion and the surface portion of the toner particles, and the toner is easily overcharged. As a result, as shown in Table 1, when an image was formed using toner A in a low-temperature and low-humidity environment, it is considered that fog due to poor formation of the toner layer on the developing sleeve occurred.

  In the production method of the toner B, acicular and spherical magnetic powders were used as the first magnetic powder, but the second magnetic powder was not added. For this reason, it is considered that the acicular magnetic powder that easily releases charges and the spherical magnetic powder that easily holds charges exist at the same density in the central portion and the surface portion of the toner particles. For this reason, it is considered that the charge amount of the toner is easily lowered. As a result, as shown in Table 1, an image formed when an image is formed using toner B in a high-temperature and high-humidity environment (when printing 10,000 sheets and when printing 50 sheets / day for 10 days). It is thought that the image density of the image was lowered.

  In the production method of the toner C, acicular magnetic powder was used as the first magnetic powder, but the second magnetic powder was not added. In addition, acicular magnetic powder was externally added. Therefore, it is considered that the externally added needle-like magnetic powder was easily detached from the toner base particles, and the detached needle-like magnetic powder was easily attached to a member such as a developing sleeve. For this reason, it is considered that the charge amount of the toner is easily lowered. As a result, as shown in Table 1, it is considered that when the image is formed in the high temperature and high humidity environment using the toner C, the image density of the formed image is lowered.

  In the manufacturing method of the toner D, spherical magnetic powder was used as the first magnetic powder, but the second magnetic powder was not added. In addition, spherical magnetic powder was externally added. Therefore, it is considered that the externally added spherical magnetic powder was detached from the toner base particles, and the externally added spherical magnetic powder was easily attached to a member such as a developing sleeve. For this reason, it is considered that the charge amount of the toner is easily lowered. As a result, as shown in Table 1, when an image was formed using toner D in a high humidity environment (50 sheets / day, when printing for 10 days), the image density of the formed image was considered to have decreased. It is done.

The production method of the toner 3 includes a first magnetic powder (a magnetic powder having a volume resistivity of 4 × 10 ³ Ω · cm) and a primary pulverized product containing a binder resin and a second magnetic powder (a volume resistivity). A magnetic particle having a value of 2 × 10 ² Ω · cm) and secondary pulverization to obtain toner particles. Therefore, in the toner particles contained in the toner 3, a large amount of magnetic powder having a high volume resistivity is present in the central portion of the toner base particle, and a large amount of magnetic powder having a low volume resistivity is present in the surface portion of the toner base particle. It is thought that it was. Therefore, as shown in Table 2, with toner 3, the fog density in a low temperature and low humidity environment, the image density in a high temperature and high humidity environment (when printing 10,000 sheets), and the high temperature and high humidity environment (50 sheets / day, Any evaluation of the image density at 10 days) was good.

In the production method of the toner E, magnetic powder having a volume resistivity of 4 × 10 ³ Ω · cm was used as the first magnetic powder, but the second magnetic powder was not added. Therefore, although the volume resistivity value is 4 × 10 ³ Ω · cm, it is considered that the toner E exists at the same density in the central part and the surface part of the toner particles, and the toner E is easily overcharged. As a result, as shown in Table 2, when an image was formed using toner E in a low-temperature and low-humidity environment, it is considered that fogging occurred due to poor formation of the toner layer on the developing sleeve.

In the manufacturing method of the toner F, the first magnetic powder was not added, and the magnetic powder having a volume resistivity of 4 × 10 ³ Ω · cm was added as the second magnetic powder. Therefore, it is considered that the magnetic powder was not present in the central portion of the toner. For this reason, it is considered that the charge amount of the toner F was easily decreased. Therefore, as shown in Table 2, when an image is formed using toner F in a high-temperature and high-humidity environment (when printing 10,000 sheets), it is considered that the image density of the formed image has decreased.

  The toner manufacturing method according to the present invention can be used for manufacturing toner used for forming an image in an image forming apparatus.

Claims (6)

A method for producing a magnetic toner comprising a plurality of toner particles,
A step of obtaining the toner particles by adding the second magnetic powder to the primary pulverized product containing the first magnetic powder and the binder resin and performing secondary pulverization;
The method for producing magnetic toner, wherein the first magnetic powder is the same as or different from the second magnetic powder. A step of obtaining a kneaded product by melting and kneading the first magnetic powder and the binder resin;
The method for producing a magnetic toner according to claim 1, further comprising: primary pulverizing the obtained kneaded product to obtain the primary pulverized product.   The method of manufacturing a magnetic toner according to claim 1, wherein the first magnetic powder is different from the second magnetic powder.   The method of manufacturing a magnetic toner according to claim 1, wherein a shape of the first magnetic powder is different from a shape of the second magnetic powder. The first magnetic powder is acicular and the second magnetic powder is spherical or polyhedral, or
5. The method for producing a magnetic toner according to claim 1, wherein the first magnetic powder is spherical or polyhedral, and the second magnetic powder is needle-shaped. 6. The aspect ratio of the first magnetic powder is 3.0 or more, and the aspect ratio of the second magnetic powder is less than 3.0, or
The method for producing a magnetic toner according to claim 1, wherein the aspect ratio of the first magnetic powder is less than 3.0, and the aspect ratio of the second magnetic powder is 3.0 or more. .