JP4280991B2 - Method for finely pulverizing charge control agent for toner, and method for producing toner for developing electrostatic image using the method - Google Patents

Description

  The present invention relates to a method for finely pulverizing a charge control agent used in an electrostatic image developing toner and a method for producing an electrostatic image developing toner using the method.

  In order to control charging of the electrostatic image developing toner, a charge control agent such as an organometallic complex, an organic compound having a salt structure, or a resin having a polar group is usually used. The charge control agent exerts the charge control function of the toner by being contained in the toner, but in order to exhibit the function more effectively, it is necessary to be uniformly dispersed in the toner particles. It is important that the dispersed particle size is smaller.

  Further, it is considered that the charge control agent is more effective when present on the surface of the toner particle than when present in the toner particle. After the toner base particles are produced, the charge control agent is applied to the particle surface. A method of fixing is proposed. Also in this method, it is important that the charge control agent having a smaller particle diameter is uniformly dispersed on the surface of the toner particles in order to impart appropriate charge to the toner and maintain it for a long period of time.

  Conventionally, various studies have been made as a method for making the charge control agent fine particles and fixing the charge control agent uniformly on the toner surface. For example, Japanese Patent Laid-Open No. 5-127423 discloses an example in which a charge control agent is wet pulverized in advance using a sand mill in the presence of an organic solvent, dried, and then fixed to the surface of toner base particles together with inorganic fine particles. Has been. Further, although there is a description of the BET specific surface area of the finely dispersed charge control agent fine particles, the measurement method can be used as an index of the particle size of the primary particles, but the presence or absence of aggregation cannot be determined. In order to uniformly adhere to the toner surface, the most important issue is how to prevent the dispersion state of the charge control agent, that is, aggregation.

  However, there is no description regarding the degree of aggregation of the charge control agent fine particles in this publication. In the technique disclosed in the publication, the finely pulverized charge control agent aggregates before being fixed to the surface of the toner base particles. In other words, it is difficult to uniformly fix the toner with a smaller particle size because it is already aggregated during drying even if it is finer, and the charging characteristics of the toner produced by this method are sufficiently satisfactory. It was not a thing.

JP-A-5-127423 (paragraphs 63 and 64, Example 1)

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a fine pulverization method for producing fine particles of a charge control agent having a smaller particle diameter. Another object of the present invention is to provide a charge control agent fine pulverization method for producing charge control agent fine particles having the property of being uniformly dispersed on the toner particle surface without being re-aggregated after fine pulverization. There is to do. Furthermore, another object of the present invention is to provide a method for producing a toner for developing an electrostatic image using the fine pulverization method.

As a result of intensive studies, the present inventors have found a method for finely pulverizing a charge control agent for toner that can solve the above problems, and have completed the present invention. That is, the present invention is a method for finely pulverizing a charge control agent for toner, which is finely pulverized by a mechanical pulverizer in the presence of inorganic fine particles having a BET specific surface area of 20 to ²⁰⁰ m ² / g. The present invention provides a method for finely pulverizing a charge control agent for toner.

  Further, the present invention provides the colored dispersion by emulsifying a colored dispersion obtained by dissolving or dispersing a binder resin containing a carboxyl group and a colorant in an organic solvent in an aqueous medium in the presence of a basic compound. An emulsifying step for forming the fine particles (A), an evaporation step for forming the colored resin fine particles (B) by evaporating and removing the organic solvent in the fine particles (A), and the colored resin fine particles (B) from an aqueous medium. A separation and drying step of separating and drying, and a surface treatment step of fixing the charge control agent fine particles containing the inorganic fine particles obtained by the above method to the surfaces of the colored resin fine particles (B) are sequentially performed. The present invention provides a method for producing a toner for developing an electrostatic image.

The inorganic fine particles having a BET specific surface area of 20 to ²⁰⁰ m ² / g used in the present invention are materials excellent in fluidity. Therefore, when the charge control agent is finely pulverized in the presence of the inorganic fine particles, the inorganic fine particles adhere to or adhere to the charge control agent particles, and the fluidity of the charge control agent particles is improved. As a result, the charge control agent particles are easily pulverized. Further, since the inorganic fine particles adhere to or adhere to the finely pulverized charge control agent fine particles, the fluidity of the charge control agent fine particles is improved, and the charge control agent fine particles are uniformly fixed to the surface of the base toner particles. Can do. Further, the pulverized charge control agent fine particles can be prevented from re-aggregating, and can be fixed to the surface of the base toner particles while maintaining a fine particle size state.

  According to the method for finely pulverizing the charge control agent for toner of the present invention, the charge control agent fine particles having a smaller particle diameter and having the property of being uniformly dispersed on the surface of the base toner particles without being re-aggregated even after fine pulverization. Can be manufactured.

  In the present invention, a known charge control agent can be used. For example, as the positive charge control agent, nigrosine dyes, modified nigrosine dyes, triphenylmethane dyes, quaternary ammonium salts, resins containing quaternary ammonium groups and / or amino groups, etc. can be used, and negative charge control agents As trimethylethane dye, metal salt or complex of salicylic acid, metal salt or complex of benzyl acid, copper phthalocyanine, perylene, quinacridone, metal salt or complex of azo compound, calixarene type phenolic condensate, cyclic polysaccharide, Resins containing a carboxyl group and / or a sulfonyl group can be used.

  Suitable positively chargeable charge control agents that can be used in the present invention include, for example, “NIGROSINE BASE EX”, “OIL BLACK BS”, “BONTRON N-01”, “BONTRON N-07” (orientated as the nigrosine dye). Chemical Co., Ltd.), as modified nigrosine dyes, include “BONTRON N-04”, “BONTRON N-21” (oriental chemical Co., Ltd.), “CHUO-3” (Chuo Synthetic Chemical Co., Ltd.), etc. Is mentioned. Examples of triphenylmethane include “OIL BLUE” (Orient Chemical Co., Ltd.), “COPY BLUE PR” (Clariant Co., Ltd.), and the like. The quaternary ammonium salts include "TP-415" (Hodogaya Chemical Co., Ltd.), "FCA201PS" (Fujikura Kasei Co., Ltd.), "PX-04", "COPY CHARGE PSY" (Clariant Japan Co., Ltd.) ) And the like. Moreover, as a negative charge control agent, "E-81", "E-88", "E-84" (above Orient Chemical Co., Ltd.), "TN-105" (Hodogaya Chemical Co., Ltd.), "LR" -147 "(Nippon Carlit Co., Ltd.) and the like.

The inorganic fine particles having a BET specific surface area of 20 to ²⁰⁰ m ² / g used in the present invention are not particularly limited as long as the BET specific surface area is in the above range. For example, silicon dioxide, titanium oxide, aluminum oxide, oxidized Surface treatment of inorganic fine powders such as cerium, zinc oxide, tin oxide, zirconium oxide, silicon carbide, boron carbide, titanium nitride, zirconium nitride, and magnesium fluoride, and hydrophobizing agents such as silicone oil and silane coupling agents Used.

  Among these, silicon dioxide (silica) whose surface is hydrophobized with various polyorganosiloxanes, hexamethylene disilazane, silane coupling agents, and the like can be particularly preferably used. As such a thing, there exists what is marketed by the following brand names, for example.

AEROSIL R972, R974, R202, R805, R812, RX200, RY200, R809, RX50, RA200HS, RA200H [Nippon Aerosil Co., Ltd.]
WACKER HDK H2000, H1018, H2050EP, HDK H3050EP, HVK2150 [Wacker Chemicals East Asia Co., Ltd.]
Nipsil SS-10, SS-15, SS-20, SS-50, SS-60, SS-100, SS-50B, SS-50F, SS-10F, SS-40, SS-70, SS-72F, [ Nippon Silica Industry Co., Ltd.]
CABOSIL TG820F, TS-530, TS-720 [Cabot Specialty Chemicals, Inc.]

The BET specific surface area, more preferably those wherein 30 to 150 m ² / g, it is particularly preferable in 40 to 100 m ² / g.

  The polarity of the inorganic compound with respect to the charge control agent to be used is preferably the same polarity. In order to control the charge control function of the charge control agent, an inorganic compound having a reverse polarity or a conductive inorganic compound may be used. Furthermore, the inorganic fine particles used in the present invention preferably have a higher hardness and a higher specific gravity than the charge control agent used. If only the charge control agent is used, even if a shearing force or a compressive force is applied, it is soft and thus agglomeration is likely to occur, and uniform fine dispersion becomes difficult.

  The mechanical pulverizer that can be used in the present invention is preferably a pulverizer that uses media such as glass beads, stainless beads, and ceramic beads. Specific examples include a ball mill, a motor mill, a sand mill, and an SC mill. A high pressure homogenizer can also be used. Examples of the stirring mixer include a Henschel mixer and a Q-type mixer.

  In the present invention, the charge control agent is finely pulverized by the pulverizer in the presence of the inorganic fine particles. In this case, the inorganic fine particles and the charge control agent are preferably mixed in advance. In this case, the mixing ratio (mass ratio) is preferably inorganic fine particles / charge control agent = 10/90 to 80/20. Moreover, it is more preferable that it is 20 / 80-70 / 30, and it is especially preferable that it is 20 / 80-50 / 50.

  When the inorganic fine particles and the charge control agent are mixed in advance, various mixers such as a Henschel mixer and a Nauter mixer can be used.

  In addition, when pulverizing with a fine pulverizer using a medium, it is preferable to finely pulverize with a wet method. Of these, water is preferred. When dispersion is difficult using water as a medium, it is preferable to add an organic solvent or both. In addition, it is necessary to pay attention to the solubility of the charge control agent, and it is preferable to select a solvent having as low a solubility as possible. The solvent to be selected is preferably selected while paying attention to solubility as appropriate according to the type of charge control agent. Examples of organic solvents that can be used include hydrocarbons such as pentane, hexane, heptane, benzene, toluene, xylene, cyclohexane, and petroleum ether; methylene chloride, chloroform, dichloroethane, dichloroethylene, trichloroethane, trichloroethylene, and carbon tetrachloride. Halogenated hydrocarbons; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate and butyl acetate are used. These solvents can be used in combination of two or more. Among these, a water-soluble organic solvent is preferable, and isopropyl alcohol, methanol, ethanol, and acetone are more preferable.

  When a solvent such as water or an organic solvent is added and pulverized, the addition amount is preferably 10/90 to 40/60, and the ratio (mass) of the total mass of the inorganic fine particles and the charge control agent to the solvent. Moreover, it is more preferable that it is 20 / 80-30 / 70.

In a particularly preferred embodiment of the pulverization method, inorganic fine particles having a BET specific surface area of 20 to ²⁰⁰ m ² / g and a charge control agent are mixed at the above ratio, and water or an organic solvent or both are added at the above ratio, Is then finely pulverized by a mechanical pulverizer (first pulverization step), and then water or an organic solvent is removed to separate a mixture of inorganic fine particles and charge control agent fine particles (separation step) and dried. (Drying step) In this method, inorganic fine particles are further added to the dried mixture, and the mixture is finely pulverized with a stirring mixer such as a Henschel mixer (second pulverizing step). In this case, in the first pulverization step, the mass ratio of the inorganic fine particles to the charge control agent is preferably 10/90 to 50/50, and the total mass of the inorganic fine particles and the charge control agent to the mass ratio of the solvent is 10 / 90 to 30/70 is preferable. In the second pulverization step, the inorganic fine particles are added so that the final ratio between the inorganic fine particles and the charge control agent falls within the above preferable range.

  As a method of separating the mixture of inorganic fine particles and charge control agent fine particles by removing water or organic solvent, most of the solvent is distilled off under reduced pressure, or the solvent and solid content are separated by a centrifugal separator or the like. -It may be removed. Next, the solvent is removed with a freeze dryer or a mixed vacuum dryer which is a known and commonly used dryer.

  Thereafter, it is preferable to finely pulverize a mixture of inorganic fine particles and charge control agent fine particles, which are further re-agglomerated in the drying step after the addition of inorganic fine particles, in the second pulverization step to return to the original finely dispersed state. The amount of the inorganic compound added at this time is preferably 10 to 30% with respect to the total amount of the mixture of inorganic fine particles and charge control agent fine particles. In the present invention, since it is a mixture of inorganic fine particles and charge control agent fine particles in advance, the reaggregation in the drying step can be easily pulverized. The charge control agent alone not only makes the fine dispersion in the wet state insufficient, but also makes it difficult to finely disperse the aggregate after drying, and the effect of the production method of the present invention is great.

Under the above pulverization conditions, the charge control agent fine powder is produced in the present invention. As a final particle size distribution, the peak top volume particle size is in the range of 0.5 to 2 μm, and particles or aggregates larger than 10 μm. It is preferable to appropriately set the conditions so that the volume particle size of is 3% or less, preferably 1% or less. Moreover, it is preferable that a BET specific surface area is 15-50 m < ² > / g. As the particle size distribution of the fine powder of the charge control agent obtained by the production method of the present invention, the volume particle size of the peak top is measured with LS-910 manufactured by Horiba. A volume particle size larger than 10 μm is measured with a multisizer TAII type (aperture tube diameter: 100 μm) manufactured by Coulter.

  The toner base particles (hereinafter referred to as base toner) using the charge control agent fine powder manufactured by the above method can be manufactured by the following method. Examples of the binder resin for the base toner include vinyl copolymer resins such as polystyrene resin, styrene acrylic resin, or styrene butadiene resin, and polyester resin, epoxy resin, butyral resin, xylene resin, and coumarone indene resin. Among these, a vinyl copolymer resin and a polyester resin are preferable, and a polyester resin can be particularly preferably used because of a good balance of fixability, offset resistance, transparency, and the like.

  The polyester resin is synthesized by dehydration condensation of a polybasic acid and a polyhydric alcohol. Examples of the polybasic acid include aromatic carboxylic acids such as terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, and naphthalenedicarboxylic acid; maleic anhydride, fumaric acid, succinic acid, alkenyl succinic anhydride Aliphatic carboxylic acids such as acid and adipic acid; and alicyclic carboxylic acids such as cyclohexanedicarboxylic acid. These polybasic acids can be used alone or in combination of two or more. Of these polybasic acids, aromatic carboxylic acids are preferably used.

  Examples of the polyhydric alcohol include aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, and pentaerythritol; cyclohexanediol and cyclohexanedi Examples include alicyclic diols such as methanol and hydrogenated bisphenol A; aromatic diols such as ethylene oxide adduct of bisphenol A and propylene oxide adduct of bisphenol A. These polyhydric alcohols can be used alone or in combination of two or more. Among these polyhydric alcohols, aromatic diols and alicyclic diols are preferable, and aromatic diols are more preferable.

  In addition, monocarboxylic acid and / or monoalcohol is further added to the polyester resin obtained by polycondensation of polycarboxylic acid and polyhydric alcohol to esterify the hydroxyl group and / or carboxyl group at the polymerization terminal. The acid value of the polyester resin can be adjusted. Examples of the monocarboxylic acid used for such purpose include acetic acid, acetic anhydride, benzoic acid, trichloroacetic acid, trifluoroacetic acid, and propionic anhydride. Examples of the monoalcohol include methanol, ethanol, propanol, octanol, 2-ethylhexanol, trifluoroethanol, trichloroethanol, hexafluoroisopropanol, and phenol.

  The polyester resin can be produced by subjecting the polyhydric alcohol and polyhydric carboxylic acid to a condensation reaction according to a conventional method. For example, the above polyhydric alcohol and polyvalent carboxylic acid are mixed in a reaction vessel equipped with a thermometer, a stirrer, and a flow-down condenser, and heated at 150 to 250 ° C. in the presence of an inert gas such as nitrogen, By removing the by-product low molecular weight compound continuously from the reaction system, when the predetermined physical property value is reached, the reaction is stopped, and cooling is performed, whereby the desired reactant can be obtained.

  Such a polyester resin can be synthesized by adding a catalyst. Examples of the esterification catalyst used include organic metals such as dibutyltin dilaurate and dibutyltin oxide, and metal alkoxides such as tetrabutyl titanate. Further, when the carboxylic acid component to be used is a lower alkyl ester, a transesterification catalyst can be used. Examples of the transesterification catalyst include metal acetates such as zinc acetate, lead acetate, and magnesium acetate; metal oxides such as zinc oxide and antimony oxide; metal alkoxides such as tetrabutyl titanate, and the like. About the addition amount of a catalyst, it is preferable to set it as the range of 0.01-1 mass% with respect to the total amount of a raw material.

  In such a polycondensation reaction, in order to produce a branched or cross-linked polyester resin, in particular, a polybasic acid having three or more carboxyl groups in one molecule or an anhydride thereof, and / or one molecule What is necessary is just to use the polyhydric alcohol which has a 3 or more hydroxyl group in as an essential synthetic | combination raw material.

  The polyester resin has a glass transition temperature (Tg) of preferably 50 ° C. or higher, and particularly preferably has a Tg of 55 ° C. or higher. When the Tg is 50 ° C. or less, the toner tends to cause a blocking phenomenon (thermal aggregation) when the toner is stored, transported, or exposed to a high temperature inside the developing device of the machine.

  Moreover, as a softening point of a polyester resin, the thing of the range of 90 to 180 degreeC among these is preferable, More preferably, it is the range of 95 to 160 degreeC. When the softening point is less than 90 ° C., the toner tends to cause an agglomeration phenomenon, which tends to cause troubles during storage and printing, and when it exceeds 180 ° C., the fixability often deteriorates.

  Furthermore, as a full color toner, particularly when color reproducibility and transparency at the time of color superposition are required, the softening point of the resin is preferably in the range of 90 ° C. to 140 ° C., more preferably 95 It is the range of ° C to 135 ° C.

The softening point of the resin is defined by a T1 / 2 temperature measured using a flow tester CFT-500 manufactured by Shimadzu Corporation, which is a constant load extrusion type capillary rheometer. The measurement conditions with a flow tester were: piston cross-sectional area 1 cm ² , cylinder pressure 0.98 MPa, die length 1 mm, die hole diameter 1 mm, measurement start temperature 50 ° C., temperature rise rate 6 ° C / min, sample mass 1. It carried out on the conditions of 5g.

  The base toner can contain a release agent. In this case, the release agent is selected from the group of hydrocarbon waxes such as polypropylene wax, polyethylene wax, and Fischer-Tropsch wax, and natural ester waxes such as synthetic ester wax, carnauba wax, and rice wax. The mold release agent used is used. Of these, natural ester waxes such as carnauba wax and rice wax, and synthetic ester waxes obtained from polyhydric alcohols and long-chain monocarboxylic acids are preferably used. As the synthetic ester wax, for example, WEP-5 (manufactured by NOF Corporation) is preferably used. If the content of the release agent is less than 1% by mass, the releasability is likely to be insufficient, and if it exceeds 40% by mass, the wax is likely to be exposed on the toner particle surface, and the chargeability and storage stability are reduced. Since it becomes easy, the inside of the range of 1-40 mass% is preferable.

  Furthermore, a charge control agent may be contained in the base toner particles. The charge control agent contained in the base toner particles is not particularly limited, but is preferably the same compound as the charge control agent to be fixed to the surface of the base toner particles after the base toner particles are produced.

  The amount of the charge control agent contained in the base toner particles is preferably 0.01 to 10% by mass. It is especially preferable that it is 0.1-6 mass%. The dispersion diameter of the charge control agent in the base toner particles is preferably in the range of 0.5 to 0.01 μm. A range of 0.2 to 0.01 is more preferable. If it is larger than 0.5 μm, the dispersion of the charge control agent in the particles tends to be non-uniform and adversely affects the charging characteristics, which is not preferable. On the other hand, if it is smaller than 0.01 μm, the function as a charge control agent becomes insufficient, which is not preferable.

  There are no particular restrictions on the colorant used in the production of the base toner, and known and commonly used ones are used. For example, as the black colorant, carbon black such as furnace black, channel black, acetylene black, thermal black, lamp black, etc. classified according to the production method, or C.I. I. Pigment Black 11 and other iron oxide pigments, C.I. I. Pigment Black 12 and other iron-titanium complex oxide pigments and blue colorants include phthalocyanine C.I. I. Pigment Blue 1, 2, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 15, 16, 17: 1, 27, 28, 29, 56, 60, 63, and the like. The blue colorant is preferably C.I. I. Pigment Blue 15: 3, 15, 16, 60, and most preferably C.I. I. Pigment Blue 15: 3,60.

  Examples of yellow colorants include C.I. I. Pigment Yellow 1, 3, 4, 5, 6, 12, 13, 14, 15, 16, 17, 18, 24, 55, 65, 73, 74, 81, 83, 87, 93, 94, 95, 97, 98, 100, 101, 104, 108, 109, 110, 113, 116, 117, 120, 123, 128, 129, 133, 138, 139, 147, 151, 153, 154, 155, 156, 168, 169, 170, 171, 172, 173, 180, 185 and the like. Preferably, C.I. I. Pigment Yellow 17, 74, 93, 97, 110, 155, and 180, and more preferably C.I. I. Pigment Yellow 74, 93, 97, 180, and C.I. I. Pigment Yellow 93, 97, 180 is preferable.

  Further, examples of red colorants include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 15, 17, 18, 22, 23, 31, 37, 38, 41, 42, 48: 1 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 54, 57: 1, 58: 4, 60: 1 63: 1, 63: 2, 64: 1, 65, 66, 67, 68, 81, 83, 88, 90, 90: 1, 112, 114, 115, 122, 123, 133, 144, 146, 147, 149,150,151,166,168,170,171,172,174,175,176,177,178,179,185,187,188,189,190,193,194,202,208,209,214, 216, 220, 221, 224, 2 42,243,243: 1,245,246,247 etc. are mentioned. Preferably, C.I. I. Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 53: 1, 57: 1, 122 and 209, most preferably C.I. I. Pigment Red 57: 1, 122 and 209.

  The content of these colorants is preferably 1 to 20% by mass with respect to the whole base toner. Especially, it is more preferable that it is 2-15 mass%, and it is especially preferable that it is 2-10 mass%. These colorants can be used alone or in combination of two or more.

  The method for producing the base toner particles is not particularly limited. For example, using a Henschel mixer, raw materials including a binder resin and a colorant are mixed, the mixture is kneaded with a melt kneader, and then the kneaded product is pulverized and classified to obtain a base toner having a predetermined particle size. A conventional pulverization method can be used. The shape of the base toner produced by such a method is indefinite. However, the spherical base toner manufactured by the following manufacturing method is surface-treated by the charge control agent fine particles manufactured by the manufacturing method of the present invention, rather than the amorphous base toner obtained by such a pulverization method. This is preferable because a uniform treatment can be performed.

  When the toner is manufactured using the charge control agent fine particles manufactured by the manufacturing method of the present invention, a preferable base toner manufacturing method is to dissolve or disperse a binder resin containing a carboxyl group and a colorant in an organic solvent. The colored dispersion is emulsified in an aqueous medium in the presence of a basic compound to form fine particles (A) of the colored dispersion, and the organic solvent in the fine particles (A) is evaporated and removed. In this way, the toner is manufactured through an evaporation step for forming the colored resin fine particles (B), and a separation drying step for separating the colored resin fine particles (B) from the aqueous medium and drying them. In this case, in addition to the binder resin and the colorant, if necessary, a release agent, a charge control agent, or the like may be added to perform the dispersion step. In addition, each raw material may be separately subjected to dispersion treatment.

  Further, among the above production methods, after the emulsification step, the fine particles (A) are combined, or the colored resin fine particles (B) are associated to form an aggregate of the fine particles, and then the aqueous medium is used. It is preferable to adopt a method of producing a base toner by separating. By such a production method, a spherical base toner having no emulsification loss, a sharp particle size distribution, and a surface covered with a curved surface can be obtained easily, in a short time, and in a high yield. Therefore, the charge control agent fine particles can be uniformly fixed to the particle surface, which is preferable.

  In addition, the manufacturing method by "unification" is a method of manufacturing the colored resin fine particles (B) by performing aggregation and coalescence of the fine particles (A) containing the organic solvent produced by emulsification dispersion in one step and then removing the solvent after that. The unionized particles before solvent removal are called “union”. Further, the colored resin fine particles (B) are produced by removing the organic solvent in the fine particles (A) produced by emulsification and dispersion, and then aggregated to produce aggregates, and then the aggregates by heating. A method for fusing the colored resin fine particles (B) together is referred to as a “association” production method, and an aggregate of the colored resin fine particles (B) is referred to as an “aggregate”. As a manufacturing method of the base toner, a manufacturing method by “unification” is particularly preferable.

Hereinafter, the manufacturing method by unity and meeting will be described. The manufacturing method of the base toner by unity and association is as follows:
First step: A colored dispersion is produced by dissolving or dispersing a binder resin having a carboxyl group and a colorant in an organic solvent, and then emulsifying the colored dispersion in an aqueous medium using a basic compound. A step of forming fine particles (A) of the colored dispersion in the aqueous medium,
Second step: The step of producing the colored resin fine particles (B) by unifying the fine particles (A) to produce the union and removing the organic solvent contained in the unification, or the fine particles (A ) The organic solvent is removed, and then the fine particles are associated to produce the aggregates to produce the colored resin fine particles (B). Third step: The colored resin fine particles (B) are separated from the aqueous medium and dried. A process for producing a base toner,
It consists of three steps.

  In the first step, a colored dispersion liquid containing a binder resin, a colorant, and an organic solvent is prepared by charging and dissolving or dispersing the binder resin and the colorant in the organic solvent. In this case, if necessary, a release agent, a charge control agent, or other additives can be used together with a binder resin or the like.

  Examples of the organic solvent for dissolving or dispersing the binder resin and the coloring agent or release agent added as necessary include hydrocarbons such as pentane, hexane, heptane, benzene, toluene, xylene, cyclohexane, and petroleum ether. Halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, dichloroethylene, trichloroethane, trichloroethylene, carbon tetrachloride; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate, etc. Used. These solvents can be used in combination of two or more, but from the viewpoint of solvent recovery, it is preferable to use the same type of solvent alone. The organic solvent is preferably one that dissolves or disperses the binder resin, has a relatively low toxicity, and has a low boiling point that can be easily removed in a subsequent step. As such a solvent, methyl ethyl ketone is most preferable.

  Next, the mixture containing the binder resin and the organic solvent is emulsified in an aqueous medium. In this case, the colored dispersion prepared by the above method is mixed with an aqueous medium and emulsified in the presence of a basic neutralizing agent. In this step, a method of gradually adding an aqueous medium (water or a liquid medium containing water as a main component) to a mixture composed of a binder resin, a colorant, and the like and an organic solvent is preferable. In that case, by gradually adding water to the organic continuous phase of the mixture, a water-in-oil discontinuous phase is generated, and by adding additional water, the oil-in-water discontinuous phase is added. To form a suspension / emulsion in which the mixture is suspended as particles (droplets) in an aqueous medium (hereinafter, this method is referred to as phase inversion emulsification).

  In phase inversion emulsification, water is added so that the ratio of water to the total amount of the organic solvent and added water is 30 to 70%. More preferably, it is 35 to 65%, and particularly preferably 40 to 60%. The aqueous medium used is preferably water, more preferably deionized water.

  The binder resin used in such a method is a carboxyl group-containing binder resin, and is a binder resin that becomes self-water dispersible by neutralizing the carboxyl group (hereinafter referred to as self-water dispersible resin). The acid value of the self-water dispersible binder resin is preferably from 3 to 30, and more preferably from 3 to 20. The resin having self-water dispersibility becomes an anionic type by neutralizing a carboxyl group with a basic compound. As a result, the hydrophilicity of the resin is increased, and the resin can be stably dispersed in the aqueous medium without using a dispersion stabilizer or a surfactant. The basic compound for neutralization is not particularly limited, and for example, inorganic bases such as sodium hydroxide, potassium hydroxide, and ammonia, and organic bases such as diethylamine, triethylamine, and isopropylamine are used. Of these, inorganic bases such as ammonia, sodium hydroxide, and potassium hydroxide are preferred.

  As a method of neutralizing the carboxyl group of the binder resin with a base, for example, (1) a method of producing a mixture containing a binder resin having a carboxyl group, an organic pigment, a wax and an organic solvent, and then neutralizing with a base, Alternatively, (2) a method in which a basic neutralizing agent is mixed in advance in an aqueous medium and the acidic group of the binder resin contained in the mixture is neutralized when phase inversion emulsification is performed.

  The basic compound is used in an amount of 0.5 to 3 equivalents based on the total amount of carboxyl groups in the binder resin. More preferably, it is more than 1 equivalent and 2 equivalents or less. Thus, by adding in excess of the amount required to neutralize the carboxyl group of the binder resin, it is possible to prevent the generation of irregularly shaped particles, improve the sphericity of the base toner, The particle size distribution can be sharpened.

  The 50% volume average particle size of the fine particles (A) of the colored dispersion produced in the first step is more than 1 μm and not more than 6 μm, more preferably more than 1 μm and 4 μm. When the thickness is 1 μm or less, when an organic pigment or a release agent is used, it is not preferable because it is not sufficiently encapsulated by the binder resin, which adversely affects charging characteristics and development characteristics. Further, if the particle size is large, the particle size of the obtained base toner is limited, so it is necessary to make the particle size smaller than the target particle size, but if it is larger than 6 μm, coarse particles are likely to be generated. Therefore, it is not preferable. The particle size distribution of the fine particles (A) produced in the first step has a volume particle size ratio of 10 μm or more of 2% or less, more preferably 1% or less, and a volume particle size ratio of 5 μm or more is 10%. Below, more preferably 6% or less.

  In the second step, the fine particles (A) obtained in the first step are coalesced or associated to form a unitary or aggregate of the fine particles (A) to form base toner particles having a desired particle size. . The manufacturing method by the union method and the manufacturing method by the association method will be explained in order.

  In the coalescence method, the dispersion of fine particles (A) obtained in the first step is diluted with water to adjust the amount of solvent. Thereafter, a dispersion stabilizer is added and coalescence is advanced by dropping an aqueous electrolyte solution in the presence of the dispersion stabilizer to obtain an aggregate having a predetermined particle diameter.

  The fine particles (A) obtained in the first step are stably dispersed in the aqueous medium by the action of the electric double layer by the carboxylate. In the second step, the particles are destabilized by adding an electrolyte that breaks or reduces the electric double layer to the aqueous medium in which the fine particles (A) are dispersed. Examples of the electrolyte include acidic substances such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, and oxalic acid. In addition, organic and inorganic water-soluble salts such as sodium sulfate, ammonium sulfate, potassium sulfate, magnesium sulfate, sodium phosphate, sodium dihydrogen phosphate, sodium chloride, potassium chloride, ammonium chloride, calcium chloride, sodium acetate, etc. It can be used effectively as an electrolyte. These electrolytes may be used alone or in combination of two or more substances. Among them, monovalent cation sulfates such as sodium sulfate and ammonium sulfate are preferable for promoting uniform coalescence.

  By the way, only by adding an electrolyte or the like, the dispersion stability of the fine particles (A) in the system is unstable, so the coalescence becomes non-uniform and coarse particles and aggregates are generated. In order to prevent the aggregates of the fine particles (A) generated by the electrolyte or acidic substance from repeating reunion to form aggregates having a particle size larger than the target particle size, before adding the electrolyte, etc. It is necessary to add an inorganic dispersion stabilizer such as hydroxyapatite or an ionic or nonionic surfactant as a dispersion stabilizer. The dispersion stabilizer to be used is required to have a property capable of maintaining dispersion stability even in the presence of an electrolyte added later. Examples of the dispersion stabilizer having such characteristics include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester. , Polyoxyethylene sorbitan fatty acid esters and the like, or various nonionic emulsifiers such as pluronics, alkyl sulfate ester type anionic emulsifiers, and quaternary ammonium salt type cationic dispersion stabilizers. Among these, even if an anion type or nonionic type dispersion stabilizer is added in a small amount, the dispersion stability of the system is effective, which is preferable. The cloud point of the nonionic surfactant is preferably 40 ° C. or higher. The surfactants described above may be used alone or in combination of two or more. By adding an electrolyte in the presence of a dispersion stabilizer (emulsifier), it becomes possible to prevent non-uniform coalescence, resulting in a sharp particle size distribution and a corresponding increase in yield. Is done.

  In the case of producing a unity, it is preferable to further dilute the dispersion of fine particles (A) obtained by phase inversion emulsification in the first step with water. Thereafter, a dispersion stabilizer and an electrolyte are sequentially added to perform coalescence. Alternatively, it is preferable to adjust the amount of the solvent in the dispersion by adding an aqueous solution of a dispersion stabilizer and / or an electrolyte to obtain particles having a predetermined particle diameter. The amount of the solvent contained in the system before adding the electrolyte is preferably in the range of 15 to 45% by mass. Moreover, the inside of the range of 20-40 mass% is more preferable, and the inside of the range of 25-40 mass% is especially preferable. When the amount of the solvent is less than 15% by mass, the electrolytic mass required for coalescence is increased, which is not preferable. On the other hand, if the amount of the solvent is more than 45% by mass, the generation of aggregates due to non-uniform coalescence increases, and the amount of dispersion stabilizer added increases, which is not preferable.

  Further, the shape of the toner particles after coalescence can be controlled by adjusting the amount of the solvent. When the amount of the solvent is in the range of 25 to 45% by mass, the degree of swelling of the fine particles by the solvent is large, so that spherical to substantially spherical particles can be easily obtained by coalescence. On the other hand, when the amount of the solvent is in the range of 15 to 25% by mass, the degree of swelling of the fine particles by the solvent is small, so that irregularly to substantially spherical toner particles can be easily obtained.

  The amount of the dispersion stabilizer to be used is preferably in the range of 0.5 to 3.0% by mass with respect to the solid content of the fine particles, for example. The range of 0.5 to 2.5% by mass is more preferable, and the range of 0.8 to 2.5% by mass is particularly preferable. If it is less than 0.5% by mass, the desired effect of preventing the generation of coarse particles cannot be obtained. On the other hand, if the amount is more than 3.0% by mass, coalescence does not proceed sufficiently even if the amount of the electrolyte is increased, and particles having a predetermined particle diameter cannot be obtained. As a result, fine particles remain and yield. Is not preferable.

  The amount of the electrolyte is preferably in the range of 0.5 to 15% by mass with respect to the solid content of the fine particles (A). It is more preferably within a range of 1 to 12% by mass, and particularly preferably within a range of 1 to 10% by mass. When the amount of the electrolyte is less than 0.5% by mass, the coalescence does not proceed sufficiently, which is not preferable. On the other hand, when the amount of the electrolyte is more than 15% by mass, the coalescence becomes non-uniform, which is not preferable because aggregates and coarse particles are generated and the yield is lowered.

  The temporary temperature is preferably in the range of 10 to 50 ° C. More preferably, it exists in the range of 20-40 degreeC, and it is especially preferable that it is 20-35 degreeC. When the temperature is lower than 10 ° C., it is difficult to perform coalescence, which is not preferable. On the other hand, when the temperature is higher than 50 ° C., the coalescence speed is increased, and aggregates and coarse particles are easily generated, which is not preferable. In the production method of the present invention, it is possible to produce aggregates by coalescence under low temperature conditions such as 20 to 40 ° C.

  The unitary shape obtained in the second step can be changed from an indeterminate shape whose surface is covered with a curved surface to a spherical shape depending on the degree of unity. The average circularity can also be obtained by taking a SEM (scanning electron microscope) photograph of the finally obtained toner particles, measuring and calculating it, etc., but the flow formula manufactured by Toa Medical Electronics Co., Ltd. It can be easily measured by using a particle image analyzer FPIP-1000.

  As for the shape of the mother toner particles, the powder fluidity and the transfer efficiency are improved by adopting a substantially spherical shape or a spherical shape whose surface having an average circularity of 0.97 or more is covered with a curved surface. When used as a toner, the above range is preferable. At the same time, uniform surface treatment is possible, which is preferable.

  In the flow type particle image analyzer FPIP-1000, the average circularity is measured by the following method.

  First, a sample is prepared by suspending base toner particles in water containing a small amount of a surfactant. Next, this sample is allowed to flow down into a transparent and flat cell provided in the flow type particle image analyzer FPIP-1000. A light source that emits pulsed light is installed on one side of the cell, and an imaging camera is provided on the opposite side of the cell so as to face the light source. The base toner particles in the sample flowing down in the cell of the FPIP-1000 are captured as a still image by a camera facing the light source while holding the cell when irradiated with pulsed light.

  Based on the image of the mother toner particles thus imaged, the contour is extracted by the image analysis device, and the projection area and perimeter (perimeter of the mother toner particle projection image) are calculated. Further, from the calculated projected area, the circumference of a circle having the same area (the circumference of the circle having the same area as the base toner particle projected area) is calculated. The average circularity is obtained by dividing the circumference of the circle having the same area as the base toner particle projection area calculated in this way by the circumference of the base toner particle projection image.

The conditions when measuring with the above apparatus are as follows.
(1) Preparation of base toner particle suspension 0.1 g of a surfactant (ELCLEAR (manufactured by Chugai Photo Chemical Co., Ltd.)) is added to 20 g of water, and 0.04 g of a base toner as a sample is further added. Then, the base toner particles are suspended in water with an ultrasonic disperser.
(2) Measurement conditions Measurement temperature: 25 ° C
Measuring humidity: 60%
Measurement base toner particle number: 5000 ± 2000

  After coalescing the fine particles (A), the solvent is removed. The method for removing the solvent is not limited at all, and it is carried out under normal pressure or reduced pressure. In order to remove the solvent quickly under a low temperature condition, it is preferably carried out under reduced pressure.

  Next, the meeting method will be explained. In the association method, first, the organic solvent contained in the fine particles (A) obtained in the first step is removed. In the solvent removal step, it is not necessary to completely remove the organic solvent, and it is preferable to remove 60 to 98% of the used organic solvent. Moreover, it is more preferable to remove 70 to 95%, and it is particularly preferable to remove 80 to 95%. By leaving a part of the organic solvent, the operation of the agglomeration / fusion process of fine particles performed in the next process becomes easy, and particles having a desired particle shape can be produced. For example, there are spherical aggregates in which the fusion has progressed to such an extent that the aggregated resin particles do not retain their shape, or irregular aggregates that do not substantially collapse the aggregated microparticles.

  In addition, if the amount of the organic solvent remaining in the fine particles (A) is large, coarse particles are likely to be generated at the time of agglomeration and fusion, and if the amount of the residual organic solvent is small, the fusion operation takes time or fusion. This is not preferable because the temperature must be increased and coarse particles are likely to be generated. The remaining organic solvent is completely removed after the association.

  In the association method, the dispersion of fine particles (A) obtained in the first step is diluted with water to adjust the solid content. Thereafter, the aqueous solution of the electrolyte is dropped to advance the association, thereby obtaining an aggregate having a predetermined particle size. In that case, it is preferable to carry out the association by adding a dispersion stabilizer. As solid content before dropping aqueous solution of electrolyte, the range of 10-30 mass% is preferable. If the amount is less than 10% by mass, the yield of the kettle is greatly reduced, which is not preferable. On the other hand, if it is more than 30% by mass, it is difficult to produce aggregates having a uniform size. The electrolyte and dispersion stabilizer used can be the same as those used for coalescence. The aggregated particles are fused by heating the entire aqueous medium in which the aggregates are dispersed above the glass transition point of the binder resin. The fusion is performed at 60 to 100 ° C, more preferably at 70 to 90 ° C.

  In the third step, the unity or aggregate obtained in the second step is separated from the aqueous medium and dried. Separation from the aqueous medium can be performed by a known and commonly used means such as a centrifugal separator, a filter press, a belt filter or the like. Subsequently, the base toner particles can be obtained by drying the particles. Toner particles produced using an emulsifier or a dispersion stabilizer are preferably washed more thoroughly.

  As a drying method, any known and commonly used method can be adopted. For example, a method in which the base toner particles are dried at normal or reduced pressure at a temperature at which the base toner particles are not thermally fused or aggregated, a freeze-dried method, etc. Can be mentioned. Another example is a method of simultaneously separating and drying the base toner particles from the aqueous medium using a spray dryer or the like. In particular, a method in which powder is stirred and dried under reduced pressure while heating at a temperature at which the base toner particles are not thermally fused or agglomerated, or a flash jet dryer (Seishin) that is instantaneously dried using a heated and dried air stream. A method using a company corporation) is efficient and preferable.

  The particle size distribution of the base toner is preferably 50% volume particle size / 50% number particle size of 1.25 or less, more preferably, as measured by a multisizer TAII type (aperture tube diameter: 100 μm) manufactured by Coulter. 1.20 or less. It is preferable that it is 1.25 or less because good images can be easily obtained. Moreover, GSD is preferably 1.30 or less, and more preferably 1.25 or less. The GSD is a value obtained from the square root of (16% volume particle size / 84% volume particle size) as measured by a multisizer TAII type manufactured by Coulter. The smaller the GSD value, the sharper the particle size distribution and the better the image.

  The base toner preferably has a volume average particle size in the range of 1 to 13 μm from the viewpoint of image quality to be obtained, and about 3 to 10 μm is easily matched with the current machine. More preferred. For a color toner, a range in which the volume average particle diameter is 3 to 8 μm is preferable. When the volume average particle size is reduced, not only the resolution and gradation are improved, but also the effect that the thickness of the toner layer for forming the printed image is reduced and the toner consumption per page is reduced is preferable.

  When the fine particles of the charge control agent containing inorganic fine particles are fixed on the surface of the base toner produced by the above method, various mixing and stirring devices and various surface modifying devices can be used. As the mixing and stirring device, known and commonly used devices can be used, and examples thereof include a Henschel mixer and a Q-type mixer. Examples of the surface modification device include a hybridization system (manufactured by Nara Machinery Co., Ltd.), a mechanofusion system (manufactured by Hosokawa Micron Corporation), and the like. The method of processing with a mixing and stirring device is preferable from the viewpoint of productivity and efficiency. Further, if the charge control agent fine particles are not aggregated and are finely dispersed, the surface can be sufficiently fixed to the toner surface even by a surface treatment using a mixing and stirring device.

  The charge control agent fine particles containing inorganic fine particles are preferably added in the range of 0.01 to 1% by mass with respect to the whole toner. More preferably, it is 0.02-0.5 mass%, and it is especially preferable that it is 0.05-0.3 mass%. If it is less than 0.01% by mass, the effect of addition cannot be obtained, which is not preferable. If it is more than 1% by mass, free charge control agent fine particles that cannot be fixed are easily generated, which is not preferable.

  The toner having the charge control agent fine particles containing inorganic fine particles fixed on the surface may be further externally added with the same or different inorganic fine particles or organic fine particles, if necessary.

  By mixing a carrier with the toner particles, an electrostatic charge image developer can be obtained. Iron powder, magnetite, ferrite, etc. used in the usual two-component development system can be used as the carrier core agent (magnetic carrier) used in the electrostatic image developer, but the true specific gravity is low, the resistance is high, and the environment Ferrite or magnetite that is excellent in stability and easy to be spherical and has good fluidity is preferably used. The shape of the core agent can be used without any problem, such as a spherical shape or an indefinite shape. The average particle size is generally 10 to 200 μm, but 30 to 110 μm is preferable for printing a high resolution image.

  Examples of the coating resin for coating these core agents include polyethylene, polypropylene, polystyrene, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether polyvinyl ketone, vinyl chloride / vinyl acetate. Copolymers, styrene / acrylic copolymers, straight silicone resins composed of organosiloxane bonds or modified products thereof, fluorine resins, (meth) acrylic resins, polyesters, polyurethanes, polycarbonates, phenol resins, amino resins, melamine resins, benzoguanamine resins Urea resin, amide resin, epoxy resin and the like can be used.

  Among these, silicon resin and (meth) acrylic resin are particularly excellent in charging stability and coating strength, and can be used more suitably. Further, the charging characteristics of a developer composed of toner particles and a carrier can be adjusted by adjusting the coating amount of a coating agent such as silicon, adding a charge control agent, or adding a conductive material typified by carbon. That is, the resin-coated carrier used in the present invention is a resin-coated magnetic carrier coated with one or more resins selected from silicon resin and (meth) acrylic resin using ferrite or magnetite as a core agent. It is preferable to adjust the charging characteristics by adding a charge control agent, carbon or the like during coating.

  In addition, the toner manufactured by the above-described manufacturing method may be a normal non-magnetic one-component developing type printing apparatus, a two-component developing type printing apparatus, a magnetic one-component developing type printing apparatus, or the like, and a toner jet type printer. Etc. can also be suitably used.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In Examples and Comparative Examples, unless otherwise indicated, “part” means “mass part” and “water” means deionized water.

(Method of finely dispersing charge control agent by dry method)
(Example 1)
Using a batch-type high-speed planetary mill Higie (BX254E type) manufactured by Kurimoto Seiko Co., Ltd., N-01 (Nigrosine dye: manufactured by Orient Chemical Industries) as a charge control agent was finely dispersed under the following conditions.
The above-mentioned mill pot of 170 ml is filled with 51 ml of zirconia beads having a diameter of 2 mm, and N-01 / HDK H05TA (silica manufactured by Wacker Chemicals, Inc .: BET specific surface area 50 m ² / g) = 50/50 Inorganic compound and charge control agent Was charged into a 17 ml container. Thereafter, dispersion was performed for 3 minutes under a gravity of 150 G, and fine dispersion was performed.

(Method of finely dispersing charge control agent by wet method)
(Example 2)
5 mm diameter stainless steel beads are charged in an amount that is half the ball mill volume, 72 parts of N-01 (nigrosine dye: manufactured by Orient Chemical Industries), H05TA (silica: BET specific surface area manufactured by Wacker Chemicals) 8 parts of 50 m ² / g) and 320 parts of water were charged and mixed and dispersed over a period of 24 hours. The obtained dispersion was subjected to solid-liquid separation with a centrifuge, and the supernatant was separated by decantation, and then the wet cake was dried with a freeze dryer for 24 hours. The obtained dried product was stirred and mixed with a Henschel mixer to obtain fine particles comprising a mixture of an inorganic compound and a charge control agent.

(Example 3)
5 mm diameter stainless steel beads are charged in an amount that is half the ball mill volume, 72 parts of N-01 (nigrosine dye: manufactured by Orient Chemical Industries), H05TA (silica: BET specific surface area manufactured by Wacker Chemicals) 8 parts of 50 m ² / g) and 320 parts of water were charged and mixed and dispersed over a period of 24 hours. The obtained dispersion was subjected to solid-liquid separation with a centrifuge, and the supernatant was separated by decantation, and then the wet cake was dried with a freeze dryer for 24 hours. Next, 2.5 parts of H05TA is added to 20 parts of the dried product composed of the mixture of the inorganic compound and the charge control agent, and the mixture is stirred and mixed with a Henschel mixer to obtain fine particles composed of the mixture of the inorganic compound and the charge control agent. Obtained.

(Example 4)
5 mm diameter stainless steel beads were charged in an amount that would be 1/2 of the ball mill volume, 72 parts of TP-415 (Hodogaya Chemical Co., Ltd.), H05TA (Silica manufactured by Wacker Chemicals Co., Ltd .: BET specific surface area of 50 m ² / 8) g) and 320 parts of water were charged and mixed and dispersed over 24 hours. The obtained dispersion was subjected to solid-liquid separation with a centrifuge, and the supernatant was separated by decantation, and then the wet cake was dried with a freeze dryer for 24 hours. Next, 4.0 parts of H05TA is added to 20 parts of the dried product composed of the mixture of the obtained inorganic compound and the charge control agent, and the mixture is stirred and mixed with a Henschel mixer to obtain fine particles composed of the mixture of the inorganic compound and the charge control agent. Obtained.

(Example 5)
5 mm diameter stainless steel beads are charged in an amount that is half the ball mill volume, 24 parts of TP-415 (Hodogaya Chemical Co., Ltd.), N-01 (Nigrosine dye: Orient Chemical Industries Co., Ltd.) 48 parts, 8 parts of H05TA (silica manufactured by Wacker Chemicals Co., Ltd .: BET specific surface area of 50 m ² / g) and 320 parts of water were charged and mixed and dispersed over 24 hours. The obtained dispersion was subjected to solid-liquid separation with a centrifuge, and the supernatant was separated by decantation, and then the wet cake was dried with a freeze dryer for 24 hours. Next, 2.5 parts of H05TA is added to 20 parts of the dried product composed of the mixture of the inorganic compound and the charge control agent, and the mixture is stirred and mixed with a Henschel mixer to obtain fine particles composed of the mixture of the inorganic compound and the charge control agent. Obtained.

(Example 6)
72 parts of E-84 (manufactured by Orient Chemical Co., Ltd.), 8 parts of H05TD (silica manufactured by Wacker Chemicals Co., Ltd .: BET specific surface area of 50 m ² / g), and 320 parts of a solvent having a water / acetone ratio of 80/20 were charged. After blur dispersion, the dispersion was carried out with an Eiger motor mill (Migrated by Eiger, USA: M-250) filled with zirconia beads having a diameter of 1.5 mm. The obtained dispersion was subjected to solid-liquid separation with a centrifuge, and the supernatant was separated by decantation, and then the wet cake was dried with a freeze dryer for 24 hours. Next, 2.5 parts of H05TD is added to 20 parts of the dried product composed of the mixture of the inorganic compound and the charge control agent, and the mixture is stirred and mixed with a Henschel mixer to obtain fine particles composed of the mixture of the inorganic compound and the charge control agent. Obtained.

(Comparative Example 1)
5mm diameter stainless steel beads are charged in an amount that is half the ball mill volume, 80 parts of N-01 (Nigrosine dye: manufactured by Orient Chemical Industry Co., Ltd.) and 320 parts of water are mixed and mixed over a period of 24 hours. Dispersion was performed. The obtained dispersion was subjected to solid-liquid separation with a centrifuge, and the supernatant was separated by decantation, and then the wet cake was dried with a freeze dryer for 24 hours. The obtained dried product was stirred and mixed with a Henschel mixer to obtain fine particles consisting only of a charge control agent.

(Comparative Example 2)
Eiger motor mill (US Eiger USA) filled with 1.5 mm zirconia beads after 80 parts of E-84 (Oriental Chemical Industries) and 320 parts of solvent having a water / acetone ratio of 80/20 were charged and dispersed. (Made by M-250). The obtained dispersion was subjected to solid-liquid separation with a centrifuge, and the supernatant was separated by decantation, and then the wet cake was dried with a freeze dryer for 24 hours. Subsequently, the obtained dried product was stirred and mixed with a Henschel mixer to obtain fine particles of a charge control agent.

  Examples 7 to 11 and Comparative Examples 3 to 6 were produced in the same manner as in Example 3, except that only the charge control agent and inorganic fine particles shown in Table 1 were changed. Table 1 shows the composition of each example and comparative example.

H-05TA ワッカーケミカルズ社製 シリカ
H-13TA ワッカーケミカルズ社製 シリカ
H-05TD ワッカーケミカルズ社製 シリカ
H-13TD ワッカーケミカルズ社製 シリカ
EC-300 チタン工業（株）社製 導電性チタン
EC-210 チタン工業（株）社製 導電性チタン
SW-360 チタン工業（株）社製 チタン酸ストロンチウム
SW-320 チタン工業（株）社製 チタン酸ストロンチウム

Silica manufactured by H-05TA Wacker Chemicals
Silica manufactured by H-13TA Wacker Chemicals
H-05TD Silica manufactured by Wacker Chemicals
H-13TD Silica manufactured by Wacker Chemicals
EC-300 Conductive titanium manufactured by Titanium Industry Co., Ltd.
EC-210 Titanium Industry Co., Ltd. conductive titanium
SW-360 Strontium titanate manufactured by Titanium Industry Co., Ltd.
SW-320 Titanium Industry Co., Ltd. Strontium Titanate

  Table 2 shows the evaluation results of the fine particles obtained in Examples and Comparative Examples.

  The volume particle diameter of the peak was measured using LS-910 manufactured by Horiba, Ltd., and the particle diameter having the highest volume frequency of the measurement value was taken as the measurement value. Moreover, the volume% of 10 micrometers or more made the value calculated | required by the measurement by the multisizer TAII type | mold (Aperture tube diameter: 100 micrometers) by a Coulter company made into the measured value. Each measurement sample was performed after the obtained fine particles were added to water to which an emulsifier was added and dispersed by ultrasonic waves for 1 to 30 minutes. Moreover, the BET specific surface area was measured using the flow type specific surface area measuring apparatus (Shimadzu FLOW SORB-II 2300) made by Shimadzu Corporation. In addition, the aggregated state is obtained by adding the obtained fine particles to water to which an emulsifier is added or a mixed solution of water / organic solvent, and performing dispersion for 1 to 30 minutes by ultrasonic waves, and then a 200 × optical microscope. When the aggregate is almost not seen, ◎ when the aggregate of 5 μm or less is slightly observed, Δ when the aggregate of 5 to 10 μm is slightly observed, Δ when the aggregate of 20 μm or more is seen What was made was set as x.

(Example of base toner production)
(Example of polyester resin synthesis)
Trimellitic anhydride (TMA) as the polyvalent carboxylic acid, terephthalic acid (TPA), isophthalic acid (IPA) as the divalent carboxylic acid, and polyoxypropylene (2.4) -2,2-bis (4 as the aromatic diol -Hydroxyphenyl) propane (BPA-PO), polyoxyethylene (2.4) -2,2-bis (4-hydroxyphenyl) propane (BPA-EO), ethylene glycol (EG) as an aliphatic diol, 1 is used at a molar composition ratio shown in FIG. 1, and tetrabutyl titanate as a polymerization catalyst is charged into a separable fresco at 0.3% by mass with respect to the total monomer amount. In a mounting electric heating mantle heater, after reacting at 220 ° C. for 15 hours under a normal pressure nitrogen stream, the pressure was reduced in order. The reaction was continued at mHg. The reaction was followed by a softening point according to ASTM E28-517. When the softening point reached a predetermined temperature, the vacuum was stopped and the reaction was terminated. Table 3 shows the composition and physical property values (characteristic values) of the synthesized resin.

＞６０万；分子量６０万以上の成分の面積比率
＜１万 ；分子量１万以下の成分の面積比率
ＴＭＡ；無水トリメリット酸
ＴＰＡ；テレフタル酸
ＩＰＡ；イソフタル酸
ＢＰＡ−ＰＯ；ポリオキシプロピレン（２．４）−２，２−ビス（４−ヒドロキシフェニル）プロパン
ＢＰＡ−ＥＯ；ポリオキシエチレン（２．４）−２，２−ビス（４−ヒドロキシフェニル）プロパン
ＥＧ；エチレングリコール
ＦＴ値；フローテスター値

>600,000; area ratio of components having a molecular weight of 600,000 or more <10,000; area ratio of components having a molecular weight of 10,000 or less TMA; trimellitic anhydride TPA; terephthalic acid IPA; isophthalic acid BPA-PO; 4) -2,2-bis (4-hydroxyphenyl) propane BPA-EO; polyoxyethylene (2.4) -2,2-bis (4-hydroxyphenyl) propane EG; ethylene glycol FT value; flow tester value

As described above, the softening point of the resin in the present invention is defined by the T1 / 2 temperature measured using a flow tester CFT-500 manufactured by Shimadzu Corporation, which is a constant load extrusion type capillary rheometer. The measurement conditions with a flow tester were: piston cross-sectional area 1 cm ² , cylinder pressure 0.98 MPa, die length 1 mm, die hole diameter 1 mm, measurement start temperature 50 ° C., temperature rise rate 6 ° C / min, sample mass 1. It carried out on the conditions of 5g. The glass transition temperature “Tg” (° C.) is an onset value measured at a rate of temperature increase of 10 ° C. per minute by the second run method using a differential scanning calorimeter (DSC-50) manufactured by Shimadzu Corporation. .

(Example of preparation of mold release agent dispersion)
Carnauba wax "Carnauba wax No. 1" (imported by Yoko Kato) 30 parts and 50 parts of polyester resin (R1 in Table 3) were kneaded with a pressure kneader, and the kneaded product and 185 parts of methyl ethyl ketone were charged into a ball mill. After stirring for a time, it was taken out and the solid content was adjusted to 35% by mass to obtain a fine dispersion of a release agent.

(Example of preparation of colorant master chip)
The coloring pigment and resin R1 were kneaded at a mass ratio of 40/60 according to the formulation shown in Table 4 to produce a colorant master chip P1. The color pigment and the resin were kneaded using a pressure kneader.

表４に示した着色剤は以下の通りである。
黒色顔料：チタン工業社製黒色顔料「ETB-100」

The colorants shown in Table 4 are as follows.
Black pigment: Black pigment “ETB-100” manufactured by Titanium Industry Co., Ltd.

  After melt-kneading the colored pigment and the resin (R1 in Table 3) with a heated two roll with the formulation of Table 5, methyl ethyl ketone was added to the obtained kneaded product so that the solid content was 30 to 35% by mass. In addition, a colorant master solution was prepared by wet dispersion using an Eiger motor mill (Eiger, USA: M-1000). The solid content was adjusted to 30% by mass with methyl ethyl ketone.

（帯電制御剤分散液の調製例）
表６の組成にて帯電制御剤とメチルエチルケトンを３０／７０の質量比率で配合し、モーターミル（米国アイガー社製）で分散を行い、固形分含有量を３０質量％に調整し、帯電制御剤分散液を得た。

(Preparation example of charge control agent dispersion)
A charge control agent and methyl ethyl ketone are blended at a mass ratio of 30/70 with the composition shown in Table 6 and dispersed by a motor mill (manufactured by Eiger, USA), and the solid content is adjusted to 30% by mass. A dispersion was obtained.

・Ｎ−０４；ボントロンＮ−０４（オリエント化学工業社製、ニグロシン染料）

N-04; Bontron N-04 (manufactured by Orient Chemical Industries, Nigrosine dye)

(Preparation example of mill base MB1)
47.6 parts of the release agent dispersion (R1 content: 11.7 parts), 24 parts of the colorant master chip P1 (content of R1: 12 parts), dilution resin (additional resin), methyl ethyl ketone The mixture was added and mixed for 3 hours with a desper in a temperature range of 30 to 40 ° C. to dissolve and disperse. The obtained mixture was adjusted to a solid content of 60% to make a mill base. The mass ratio of each raw material at this time was R1 / R2 / colorant / wax = 49.8 / 33.2 / 12/5.

(Preparation example of Millbase MB2)
47.6 parts of the release agent dispersion (R2 content: 11.7 parts), 20 parts of colorant master chip P2 (content of R2: 3 parts), dilution resin (additional resin), methyl ethyl ketone The mixture was added and mixed for 3 hours with a desper in a temperature range of 30 to 40 ° C. to dissolve and disperse. The obtained mixture was adjusted to a solid content of 60% to make a mill base. The mass ratio of each raw material at this time was R1 / R2 / colorant / wax = 55.2 / 36.8 / 3/5.

  Table 7 shows the properties of the blend resin used in the production of the mill base. The resin blend was obtained by blending resin particles having passed through 200 meshes at the above mass ratio and measuring each physical property value.

＞６０万；分子量６０万以上の成分の面積比率
＜１万 ；分子量１万以下の成分の面積比率

>600,000; area ratio of components having a molecular weight of 600,000 or more <10,000; area ratio of components having a molecular weight of 10,000 or less

The molecular weight of the THF-soluble component obtained by filtering a solution obtained by putting the resin obtained in each synthesis example in tetrahydrofuran (THF) and allowing it to stand for 12 hours was measured. For analysis, gel permeation chromatography (GPC) method was used, and molecular weight was calculated from a calibration curve prepared with standard polystyrene.
GPC device: HLC-8120GPC manufactured by Tosoh Corporation
Column: Tosoh Co., Ltd. TSK Guardcolumn SuperH-H TSK-GEL SuperHM-M 3 linked
Concentration: 0.5% by mass
Flow rate: 1.0 ml / min

Further, the tetrahydrofuran insoluble content of the binder resin was determined by the following method.
A value obtained by accurately weighing 1 g of resin is defined as (X). This resin is dissolved in 40 ml of tetrahydrofuran, and then filtered using a funnel (diameter 40 mm) in which 2 g of radiolite (# 700, Showa Chemical Co., Ltd.) is uniformly packed on Kiriyama filter paper (No. 3). The filtrate is put on an aluminum petri dish, dried at 140 ° C. for 1 hour, and the mass (Y) of the resin contained in the filtrate is measured. The tetrahydrofuran insoluble matter is calculated according to the following formula.
Tetrahydrofuran insoluble matter (%) = {1- (Y) / (X)} × 100

  The acid value was measured according to JIS K6901, and Tg was measured according to JIS K7121.

(Preparation Example 1 of base toner)
A cylindrical 2 L separable flask having a Max blend blade as a stirring blade was charged with 480 parts of mill base MB1, 40 parts of nigrosine dispersion E1, and 25.5 parts of methyl ethyl ketone, and the solid content was adjusted to 55%. Next, 38.4 parts of 1N aqueous ammonia (equivalent ratio with respect to the total amount of carboxyl groups of the resins R1 and R2 is 1.2) was added and sufficiently stirred at 210 rpm with a three-one motor, and then 133 parts of deionized water was added. In addition, stirring was further performed to adjust the temperature to 23 ° C. Subsequently, 133 parts of deionized water was added dropwise under the same conditions to prepare a fine particle dispersion by phase inversion emulsification. The peripheral speed of the stirring blade at this time was 0.71 m / s. Next, 259 parts of deionized water was added (the amount of deionized water in such an amount that the total amount of 1N ammonia water and water was 563 parts) to adjust the amount of solvent.

The equivalent ratio of the basic compound (ammonia water) to the total amount of carboxyl groups of the resins R1 and R2 in the base toner preparation example 1 was obtained by the following calculation.
(1) Total amount of carboxyl groups contained in resins R1 and R2 (A)
7.7 (resin acid value) × 288 (mill base solid content) × 0.89 (resin ratio in the solid content) /56100=0.0320 mol
(2) Amount of hydroxyl group in 38.4 parts of 1N aqueous ammonia (B)
1 × 38.4 / 1000 = 0.0384 mol
(3) Equivalent (B) / (A) of basic compound (ammonia water)
0.0474 / 0.0352 = 1.2

  (Joint operation) Next, 2.8 parts of Emar 0 (manufactured by Kao Corporation), which is an anionic emulsifier, was diluted with 30 parts of water and added. Thereafter, the temperature is adjusted to 25 ° C. and the rotation speed is adjusted to 158 rpm, and an aqueous solution of 5.2% ammonium sulfate is dropped until the particle size grows to 5.5 μm. Thereafter, the particle size is adjusted to 7 μm under the same conditions. Stirring was continued until growth and the coalescence operation was completed. Thereafter, solid-liquid separation was performed using a centrifuge and the additive was washed by rinsing three times, followed by drying with a mixed vacuum dryer to obtain a base toner. The volume average particle diameter of Dv50 was 7.2 μm, Dv / Dn was 1.10, and the number% of 5 μm or less was 11.0%. Further, the toner was a spherical base toner having an average circularity of 0.981 and a surface covered with a curved surface. The obtained base toner was embedded in a resin, then cut with a microtome and observed with TEM. As a result, it was confirmed that the nigrosine particles were dispersed to 0.5 μm or less.

(Preparation Example 2 of base toner)
A cylindrical 2 L separable flask having a Max blend blade as a stirring blade was charged with 500 parts of mill base MB1 and 45.5 parts of methyl ethyl ketone, and the solid content was adjusted to 55%. Next, 49.4 parts of 1N ammonia water (equivalent ratio with respect to the total amount of carboxyl groups of resins R1 and R2 is 1.2) was added and sufficiently stirred at 210 rpm with a three-one motor, and then 133 parts of deionized water was added. In addition, stirring was further performed to adjust the temperature to 23 ° C. Subsequently, 133 parts of deionized water was added dropwise under the same conditions to prepare a fine particle dispersion by phase inversion emulsification. The peripheral speed of the stirring blade at this time was 0.71 m / s. Next, 248 parts of deionized water was added (amount of deionized water such that the total amount of 1N ammonia water and water was 563 parts) to adjust the amount of solvent.

  Next, a coalescence operation was performed in the same manner as in Preparation Example 1 of the base toner to obtain a base toner. The volume average particle diameter of Dv50 was 7.3 μm, Dv / Dn was 1.10, and the number% of 5 μm or less was 10.8%. The average circularity was 0.983, and the spherical base toner was covered with a curved surface.

(Base toner preparation example 3)
A cylindrical 2 L separable flask having a Max Blend blade as a stirring blade was charged with 500 parts of Millbase MB2 and 45.5 parts of methyl ethyl ketone, and the solid content was adjusted to 55%. Next, 41.7 parts of 1N aqueous ammonia (equivalent ratio of 1.1 relative to the total amount of carboxyl groups of resins R1 and R2 is 1.1) was added and sufficiently stirred at 210 rpm with a three-one motor, and then 133 parts of deionized water was added. In addition, the mixture was further stirred to adjust the temperature to 25 ° C. Subsequently, 133 parts of deionized water was added dropwise under the same conditions to prepare a fine particle dispersion by phase inversion emulsification. The peripheral speed of the stirring blade at this time was 0.71 m / s. Next, 285 parts of deionized water was added (the amount of deionized water such that the total amount of 1N ammonia water and water was 593 parts) to adjust the amount of solvent.

  Next, a coalescence operation was performed in the same manner as in Preparation Example 1 of the base toner to obtain a base toner. The peripheral speed of the stirring blade at this time was 0.54 m / s. The volume average particle diameter of Dv50 was 7.3 μm, Dv / Dn was 1.09, and the number percentage of 5 μm or less was 9.70%. Further, the toner was a spherical base toner having an average circularity of 0.985 and a surface covered with a curved surface.

(Application 1)
To 100 parts of the base toner obtained in the base toner preparation example, 0.075 parts of fine particles composed of the inorganic compound obtained in Example 1 and the charge control agent were added, and the peripheral speed was 40 m / second by a Henschel mixer. The surface was fixed under the conditions of s and stirring time of 10 min. In the same manner, toners of Application Examples 2 to 7 were produced. Table 7 shows formulation examples.

  In the same manner as in Application Example 1, toners in Application Examples 2 to 12 were produced. Table 8 shows formulation examples.

(Reference Example 1)
0.10 parts of the charge control agent fine particles obtained in Comparative Example 2 and H05TD (silica manufactured by Wacker Chemicals Co., Ltd .: BET specific surface area 50 m ² / g) with respect to 100 parts of the base toner obtained in Preparation Example 2 of the base toner. 0.3 parts was added, and surface fixing was performed with a Henschel mixer under conditions of a peripheral speed of 40 m / s and a stirring time of 10 min.

(Reference Example 2)
0.10 parts of the charge control agent fine particles obtained in Comparative Example 2 and H05TD (silica manufactured by Wacker Chemicals Co., Ltd .: BET specific surface area 50 m ² / g) with respect to 100 parts of the base toner obtained in Preparation Example 2 of the base toner. 0.3 part of was added, and surface fixation was performed with a hybridization system (manufactured by Nara Machinery Co., Ltd.) under conditions of a peripheral speed of 60 m / s and a stirring time of 2 minutes.

(Reference Example 3)
0.10 parts of the charge control agent fine particles obtained in Comparative Example 1 and H05TA (silica manufactured by Wacker Chemicals, Inc .: BET specific surface area 50 m ² / g) with respect to 100 parts of the base toner obtained in Preparation Example 2 of the base toner. 0.3 parts was added, and surface fixing was performed with a Henschel mixer under conditions of a peripheral speed of 40 m / s and a stirring time of 10 min.

  Toners of Reference Examples 4 to 7 were produced in the same manner as Reference Example 1. Table 9 shows formulation examples.

（評価方法）
１）ＳＥＭによる固着状態の観察：
応用例、参考例で得られたトナー粒子をＳＥＭで観察してトナー表面への固着状態、及び遊離した帯電制御剤微粒子の有無を目視で評価した。粒子表面へ均一に帯電制御剤微粒子が固着し、遊離した粒子が見られないものを○、１〜２μｍの業種した帯電制御剤粒子が表面に固着しており、均一性がやや劣るが、遊離した帯電制御剤粒子が見られないものを△、遊離した帯電制御剤粒子が確認されるものを×とした。
２）帯電安定性：
シリコンコートフェライトキャリア（パウダーテック社製）と応用例、参考例で得られたトナーの比率を９７／３とした現像剤を調製し、該現像剤を６０min及び180min間攪拌した後の帯電量、及び１８０min後の帯電量の標準偏差をE-SPARTアナライザーの測定により求めた。
評価結果を表１０に示した。

(Evaluation methods)
1) Observation of fixed state by SEM:
The toner particles obtained in the application examples and the reference examples were observed with an SEM, and the adhesion state to the toner surface and the presence or absence of free charge control agent fine particles were visually evaluated. Charge control agent fine particles are uniformly adhered to the particle surface and no free particles are observed. ○, 1-2 μm type charge control agent particles are adhered to the surface, the uniformity is slightly inferior, but free The case where no charge control agent particles were observed was indicated by Δ, and the case where free charge control agent particles were observed was indicated by ×.
2) Charging stability:
A developer having a ratio of the toner obtained in the silicon-coated ferrite carrier (Powder Tech Co., Ltd.) and the application examples and reference examples to 97/3 was prepared, and the charge amount after stirring the developer for 60 min and 180 min. The standard deviation of the charge amount after 180 minutes was obtained by measurement with an E-SPART analyzer.
The evaluation results are shown in Table 10.

In Application Examples 3 to 12, the charge control agent fine particles are uniformly fixed on the particle surface, the charge amount is stable even when stirred with a carrier for a long time, and the number% of different charges is small. On the other hand, in application examples 1 and 2 in which the fixing state is slightly non-uniform, the charge amount changes with time and the standard deviation of the charge amount tends to increase. Furthermore, in Reference Examples 1 to 7 in which the surface adhering state is non-uniform and includes free charge control agent fine particles, the charge amount changes significantly with time and the standard deviation of the charge amount also increases. This tendency correlates with the adhesion state of the charge control agent on the particle surface, and further, the adhesion state correlates with the aggregation state of the charge control agent. In order to obtain uniform charge characteristics, the dispersion of the charge control agent fine particles is dispersed. It can be seen that it is important to control the state so that there are no aggregates.

Claims (6)

A first pulverization step of finely pulverizing the charge control agent for toner with a mechanical pulverizer in the presence of inorganic fine particles having a BET specific surface area of 20 to ²⁰⁰ m ² / g and water or an organic solvent; removing the water or the organic solvent; In addition to the step of separating the mixture of the inorganic fine particles and the charge control agent fine particles, the step of drying the mixture, and the dried mixture, inorganic fine particles having a BET specific surface area of 20 to ²⁰⁰ m ² / g are added, A method for finely pulverizing a charge control agent for toner, comprising sequentially performing a second pulverization step of finely pulverizing with a stirring mixer. The colored dispersion fine particles (A) are obtained by emulsifying a colored dispersion obtained by dissolving or dispersing a carboxyl group-containing binder resin and a colorant in an organic solvent in an aqueous medium in the presence of a basic compound. An emulsifying step for forming, an evaporation step for forming colored resin fine particles (B) by evaporating and removing the organic solvent in the fine particles (A), and a separation for separating the colored resin fine particles (B) from an aqueous medium and drying. A drying process and a surface treatment process for fixing the charge control agent fine particles containing the inorganic fine particles obtained by the method according to claim 1 to the surface of the colored resin fine particles (B) are sequentially performed. A method for producing a toner for developing an electrostatic image. The colored dispersion fine particles (A) are obtained by emulsifying a colored dispersion obtained by dissolving or dispersing a carboxyl group-containing binder resin and a colorant in an organic solvent in an aqueous medium in the presence of a basic compound. An emulsifying step for forming, an evaporation step for forming colored resin fine particles (B) by evaporating and removing the organic solvent in the fine particles (A), and a separation for separating the colored resin fine particles (B) from an aqueous medium and drying. drying step, the have successively row a surface treatment step of fixing the fine particles of the inorganic fine particles and a charge control agent on the surface of the colored resin fine particles (B), fine inorganic particles and a charge control agent used for the surface treatment step, BET specific surface area 20 to 200 m 2 / ^g of the toner for developing electrostatic images you characterized in that the charge control agent in the presence of the inorganic fine particles is obtained by finely pulverized by a mechanical pulverizer Manufacturing method. The method for producing a toner for developing an electrostatic charge image according to claim 3, wherein the fine pulverization is performed by a wet method. 5. The method for producing a toner for developing an electrostatic charge image according to claim 4, wherein the inorganic fine particles and the charge control agent fine particles used in the surface treatment step are dried after the wet pulverization. The said emulsification process WHEREIN: The coalescence process which combines the microparticles | fine-particles ( A ) of the said colored dispersion liquid by adding electrolyte in presence of a dispersion stabilizer and forms 3-10 micrometers coalesced particle is performed. The method for producing a toner for developing an electrostatic charge image according to any one of 2 to 5.