JP6056469B2 - Method for producing toner for developing electrostatic image - Google Patents

Description

The present invention relates to a method for producing a toner for developing an electrostatic charge image that can be used for developing an image forming apparatus utilizing electrophotography such as a copying machine, a facsimile machine, and a printer.

  In an image forming apparatus such as an electrophotographic apparatus, an electrostatic recording apparatus, and an electrostatic printing apparatus, a desired image is formed by developing an electrostatic latent image formed on a photoreceptor with toner for developing an electrostatic image. An image forming method to be formed is widely implemented and applied to a copying machine, a printer, a facsimile, a multi-function machine and the like.

  For example, in an electrophotographic apparatus using electrophotography, generally, the surface of a photoconductor made of a photoconductive material is uniformly charged by various means, and then an electrostatic latent image is formed on the photoconductor. . Next, the electrostatic latent image is developed using toner, the toner image is transferred onto a recording material such as paper, and then fixed by heating or the like to obtain a copy.

In recent years, there has been a strong demand for an electrophotographic apparatus that can cope with high image quality and high-speed printing, and accordingly, there are various demands on toner.
Various analytical instruments have been developed to evaluate these toners, and many proposals have been made that define their characteristics. A powder fluidity analyzer is known as an analyzer for toner evaluation, and one of them is commercially available under the trade name of a powder rheometer. Several proposals have been made that measure the toner using a powder rheometer and define the measured toner characteristics.

  For example, Patent Document 1 specifies a total energy difference in the presence or absence of ventilation at a tip speed of a rotary blade of 100 mm / sec and an entrance angle of the rotary blade of −5 ° using a powder rheometer in a developer supply type development method. A developing method using a developer in the range is disclosed, and it is also disclosed that the occurrence of fog is suppressed and toner is not ejected from the developing device. Patent Document 2 discloses a non-magnetic one-component developing toner used in a vertical developing device, and a powder rheometer is used to enter a toner powder layer to which a load of 5 N is applied while rotating a screw blade. Toner having a specific range when the total energy calculated from the torque and load generated at the time of blade rotation is 100 mm / s and having a transportability index within the specific range is disclosed, thereby suppressing uneven image density. It is also disclosed that a high-quality image with uniform image quality can be obtained.

  Patent Document 3 discloses a non-magnetic toner having toner particles and inorganic fine powder, the viscosity at 100 ° C. by a flow tester is in a specific range, and the peripheral speed of the propeller blade measured by a powder rheometer is 100 mm / sec. The sum of the rotational torque and the vertical load obtained when entering the toner layer is within a specific range, and when entering the toner layer at 100 mm / sec and when entering the toner layer at 10 mm / sec. A toner in which the ratio of the sum of the rotational torque and the vertical load is in a specific range is disclosed, and it is also disclosed that long-term durability is excellent while achieving low-temperature fixability. In Patent Document 4, in a developing device including a toner image forming unit and a developer replenishing unit, the replenishing developer includes a replenishing toner containing toner particles and a weakly attached external additive. When measured under conditions of aeration fluidity energy when measured with a powder rheometer under conditions of aeration flow rate of 80 ml / min, tip speed of rotor blade of 100 mm / sec, and approach angle of rotor blade of 5 °, and aeration flow rate of 0 ml / min. The ratio AR is in a specific range, and even when the process speed during image formation is high, the increase in low-charged toner hardly occurs, and even when high-fluidity replenishing toner is used, fog occurs. It is also disclosed that there is no.

  However, in the toner of the above-mentioned patent document, the toner is stressed due to long-term printing, and is caused by toner leakage that is compressed and leaked at the seal portion or toner deterioration when the developer is filled with toner and left in a high-density state. The design for print quality, such as jetting after standing at high temperature, was insufficient.

JP 2007-86532 A JP 2007-248913 JP 2008-102395 A JP 2009-109726 A

  An object of the present invention is to provide a toner that is excellent in printing durability and that suppresses occurrence of toner leakage and toner ejection after being left at a high temperature.

  The inventor of the present invention uses a compression index CI (EAC / BFE) calculated from a ratio between a value of basic fluidity energy (BFE) obtained using a powder fluidity analyzer and a value of total energy after compression (EAC). It was found that the above problem can be solved by setting the value of) within a specific range.

  That is, according to the present invention, in a toner for electrostatic charge development containing a colored resin particle containing a binder resin and a colorant, and an external additive, it is obtained by a stability test using a powder fluidity analyzer. The value of the compression index CI (EAC / BFE), which is the ratio of the value of total energy after compression (EAC) obtained by the compression test using the powder fluidity analyzer to the value of basic fluidity energy (BFE) 1.5 to 3.2, the first electrostatic image developing toner is provided.

  In the present invention, as the external additive, inorganic fine particles A having a number average primary particle size of 36 to 100 nm, inorganic fine particles B having a number average primary particle size of 15 to 35 nm, and number average primary particle sizes of 6 to It is preferable to contain 14 nm inorganic fine particles C.

  In the present invention, it is more preferable that the external additive further contains inorganic fine particles D having a number average primary particle size of 0.3 to 2.0 μm.

  Further, according to the present invention, in the electrostatic charge developing toner containing a binder resin and a colorant, and an external additive, as an external additive with respect to 100 parts by mass of the colored resin particles, 0.1 to 2.5 parts by mass of inorganic fine particles A having a number average primary particle size of 36 to 100 nm, 0.1 to 2.0 parts by mass of inorganic fine particles B having a number average primary particle size of 15 to 35 nm, 0.05 to 2.0 parts by mass of inorganic fine particles C having a number average primary particle size of 6 to 14 nm, and 0.05 to 2 inorganic fine particles D having a number average primary particle size of 0.3 to 2.0 μm. 0.0 parts by mass and obtained by a compression test using the powder flowability analyzer with respect to the basic fluidity energy (BFE) value obtained by a stability test using the powder flowability analyzer. Total energy after compression (EAC) The value of the compression index is the ratio of the values CI (EAC / BFE) is a second electrostatic image developing toner is provided which is a 1.5 to 3.2.

  In the present invention (first and second electrostatic image developing toners), the value of the basic fluidity energy (BFE) is determined by the blade included in the powder fluidity analyzer in the stability test, This is the sum of the rotational torque and vertical load generated when the blade enters the powder layer of the electrostatic charge image developing toner at a tip speed of 100 mm / second and after the compression. In the compression test, the total energy (EAC) value is calculated by using a blade provided in the powder fluidity analyzer in a compressed powder layer of the electrostatic charge image developing toner after being pressurized at 10 kPa at a tip speed of 100 mm / It is the sum total of the rotational torque and vertical load generated by the intrusion in seconds and the blade moving in the compressed powder layer.

  According to the electrostatic charge image developing toner of the present invention as described above, by setting the compression index CI within a specific range, the printing durability is excellent, the occurrence of toner leakage, and after leaving under high temperature conditions. A toner with very little ejection of the toner is provided.

  In the first electrostatic charge image developing toner of the present invention, a powder fluidity analyzer was used in the electrostatic charge developing toner containing a colored resin particle containing a binder resin and a colorant, and an external additive. Compression index CI (EAC), which is a ratio of the value of total energy (EAC) after compression obtained by a compression test using the powder fluidity analyzer to the value of basic fluidity energy (BFE) obtained by a stability test / BFE) is 1.5 to 3.2.

  The second electrostatic charge image developing toner of the present invention is a colored resin particle containing a binder resin and a colorant, and an electrostatic charge developing toner containing an external additive, with respect to 100 parts by weight of the colored resin particles. As an external additive, 0.1 to 2.5 parts by mass of inorganic fine particles A having a number average primary particle size of 36 to 100 nm, and 0.1 to 2.5 parts of inorganic fine particles B having a number average primary particle size of 15 to 35 nm. 0.05 to 2.0 parts by mass of inorganic fine particles C having 2.0 parts by mass, number average primary particle size of 6 to 14 nm, and inorganic fine particles D having number average primary particle sizes of 0.3 to 2.0 μm Is used for the value of the basic fluidity energy (BFE) determined by a stability test using a powder fluidity analyzer. Total energy after compression required by the compression test The value of the Guy compression index is the ratio of the value of (EAC) CI (EAC / BFE), characterized in that it is 1.5 to 3.2.

According to the first and second inventions of the present invention, “a colored resin particle containing a binder resin and a colorant, and a toner for electrostatic charge development containing an external additive, which is stable using a powder fluidity analyzer. Compression index CI (EAC / EAC), which is the ratio of the value of total energy after compression (EAC) determined by the compression test using the powder fluidity analyzer to the value of basic fluidity energy (BFE) determined by the property test BFE) is in the range of 1.5 to 3.2 ". That is, the second invention of the present invention corresponds to the invention that further defines the composition of the external additive in the first invention.
The first invention of the present invention will be described below. The description of the composition of the external additive also serves as the description of the second invention.

Hereinafter, the toner for developing an electrostatic charge image of the present invention (hereinafter sometimes simply referred to as “toner”) will be described.
The toner of the present invention contains colored resin particles containing a binder resin and a colorant, and an external additive.
Hereinafter, the manufacturing method of the colored resin particles used in the present invention, the colored resin particles obtained by the manufacturing method, the manufacturing method of the toner of the present invention using the colored resin particles, and the toner of the present invention will be described in order.

1. Production method of colored resin particles Generally, the production method of colored resin particles is roughly classified into dry methods such as a pulverization method, and wet methods such as an emulsion polymerization aggregation method, a suspension polymerization method, and a dissolution suspension method. The wet method is preferable because it is easy to obtain a toner excellent in printing characteristics such as the property. Among wet methods, a polymerization method such as an emulsion polymerization aggregation method and a suspension polymerization method is preferable because a toner having a relatively small particle size distribution on the order of microns is preferable. A suspension polymerization method is more preferable among polymerization methods. preferable.

  In the emulsion polymerization aggregation method, an emulsified polymerizable monomer is polymerized to obtain a resin fine particle emulsion, which is aggregated with a colorant dispersion or the like to produce colored resin particles. The dissolution suspension method produces droplets of a solution in which toner components such as a binder resin and a colorant are dissolved or dispersed in an organic solvent in an aqueous medium, and the organic solvent is removed to produce colored resin particles. Each of which is a known method.

  The colored resin particles of the present invention can be produced by employing a wet method or a dry method. Among the wet methods, a preferred suspension polymerization method is adopted, and the following process is performed.

(A) Suspension polymerization method (A-1) Preparation step of polymerizable monomer composition First, other additions such as a polymerizable monomer, a colorant, and a charge control agent added as necessary The product is mixed to prepare a polymerizable monomer composition. For mixing at the time of preparing the polymerizable monomer composition, for example, a media type disperser is used.

  In the present invention, the polymerizable monomer means a monomer having a polymerizable functional group, and the polymerizable monomer is polymerized to become a binder resin. It is preferable to use a monovinyl monomer as the main component of the polymerizable monomer. Examples of the monovinyl monomer include styrene; styrene derivatives such as vinyl toluene and α-methylstyrene; acrylic acid and methacrylic acid; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid 2 Acrylic esters such as ethylhexyl and dimethylaminoethyl acrylate; methacrylic esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and dimethylaminoethyl methacrylate; acrylonitrile And nitrile compounds such as methacrylonitrile; amide compounds such as acrylamide and methacrylamide; and olefins such as ethylene, propylene, and butylene. These monovinyl monomers can be used alone or in combination of two or more. Of these, styrene, styrene derivatives, and acrylic esters or methacrylic esters are preferably used as monovinyl monomers.

In order to improve hot offset and storage stability, it is preferable to use any crosslinkable polymerizable monomer together with the monovinyl monomer. A crosslinkable polymerizable monomer means a monomer having two or more polymerizable functional groups. Examples of the crosslinkable polymerizable monomer include aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene, and derivatives thereof; alcohols having two or more hydroxyl groups such as ethylene glycol dimethacrylate and diethylene glycol dimethacrylate; Ester compounds in which two or more carboxylic acids having a carbon-carbon double bond are ester-bonded; other divinyl compounds such as N, N-divinylaniline and divinyl ether; compounds having three or more vinyl groups; Can be mentioned. These crosslinkable polymerizable monomers can be used alone or in combination of two or more.
In the present invention, the crosslinkable polymerizable monomer is usually used at a ratio of 0.1 to 5 parts by mass, preferably 0.3 to 2 parts by mass with respect to 100 parts by mass of the monovinyl monomer. desirable.

  Furthermore, it is preferable to use a macromonomer as a part of the polymerizable monomer because the balance between the storage stability of the obtained toner and the fixing property at low temperature is improved. The macromonomer has a polymerizable carbon-carbon unsaturated double bond at the end of the molecular chain, and is a reactive oligomer or polymer having a number average molecular weight of usually 1,000 to 30,000. The macromonomer is preferably one that gives a polymer having a higher Tg than the glass transition temperature of the polymer obtained by polymerizing the monovinyl monomer (hereinafter sometimes referred to as “Tg”). The macromonomer is preferably used in an amount of 0.03 to 5 parts by mass, more preferably 0.05 to 1 part by mass, with respect to 100 parts by mass of the monovinyl monomer.

In the present invention, a colorant is used. However, when producing a color toner, black, cyan, yellow, and magenta colorants can be used.
As the black colorant, carbon black, titanium black, magnetic powder such as iron zinc oxide and nickel iron oxide can be used.

  As the cyan colorant, for example, a copper phthalocyanine compound, a derivative thereof, and an anthraquinone compound can be used. Specifically, C.I. I. Pigment blue 2, 3, 6, 15, 15: 1, 15: 2, 15: 3, 15: 4, 16, 17: 1, 60, and the like.

  Examples of the yellow colorant include monoazo pigments, azo pigments such as disazo pigments, and compounds such as condensed polycyclic pigments. I. Pigment yellow 3, 12, 13, 14, 15, 17, 62, 65, 73, 74, 83, 93, 97, 120, 138, 155, 180, 181, 185, 186, and 213.

  Examples of the magenta colorant include compounds such as monoazo pigments, azo pigments such as disazo pigments, and condensed polycyclic pigments. I. Pigment Red 31, 48, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 149, 150, 163, 170, 184, 185, 187, 202, 206, 207, 209, 237, 238, 251, 254, 255, 269 and C.I. I. Pigment violet 19 and the like.

  In the present invention, each colorant can be used alone or in combination of two or more. The amount of the colorant is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the monovinyl monomer.

  From the viewpoint of improving the releasability of the toner from the fixing roll during fixing, it is preferable to add a release agent to the polymerizable monomer composition. Any releasing agent can be used without particular limitation as long as it is generally used as a releasing agent for toner.

The release agent preferably contains at least one of ester wax and hydrocarbon wax. By using these waxes as a release agent, the balance between low-temperature fixability and storage stability can be made suitable.
The ester wax suitably used as a release agent in the present invention is more preferably a polyfunctional ester wax, such as pentaerythritol ester such as pentaerythritol tetrapalinate, pentaerythritol tetrabehenate, pentaerythritol tetrastearate, etc. Compound: hexaglycerin tetrabehenate tetrapalinate, hexaglycerin octabehenate, pentaglycerin heptabehenate, tetraglycerin hexabehenate, triglycerin pentabehenate, diglycerin tetrabehenate, glycerin tribe Glycerin ester compounds such as henate; Dipentaerythritol ester compounds such as dipentaerythritol hexamyristate and dipentaerythritol hexapalmitate; Are, among others glycerin ester compounds are preferred, hexaglycerol ester is more preferable.

Examples of the hydrocarbon wax suitably used as a release agent in the present invention include polyethylene wax, polypropylene wax, Fischer-Tropsch wax, paraffin wax, microstarin wax, petroleum-based wax, etc., among which Fischer-Tropsch wax, petroleum-based wax Waxes are preferred and petroleum waxes are more preferred.
The number average molecular weight of the hydrocarbon wax is preferably 300 to 800, more preferably 400 to 600. Moreover, the penetration of the hydrocarbon wax measured by JIS K2235 5.4 is preferably 1 to 10, and more preferably 2 to 7.

In addition to the mold release agent, for example, natural wax such as jojoba; mineral wax such as ozokerite;
The release agent is preferably used in combination of one or more waxes as described above.
The release agent is preferably used in an amount of 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the monovinyl monomer.

As other additives, a positively or negatively chargeable charge control agent can be used to improve the chargeability of the toner.
The charge control agent is not particularly limited as long as it is generally used as a charge control agent for toner, but among charge control agents, the compatibility with the polymerizable monomer is high, and stable chargeability. (Charge stability) can be imparted to the toner particles, and therefore a positively or negatively chargeable charge control resin is preferred. Further, from the viewpoint of obtaining a positively chargeable toner, a positively chargeable charge control resin is preferred. More preferably used. The toner of the present invention is preferably a positively chargeable toner.
Examples of positively chargeable charge control agents include nigrosine dyes, quaternary ammonium salts, triaminotriphenylmethane compounds and imidazole compounds, polyamine resins as charge control resins that are preferably used, and quaternary ammonium group-containing copolymers. , And quaternary ammonium base-containing copolymers.
Negatively chargeable charge control agents include azo dyes containing metals such as Cr, Co, Al, and Fe, salicylic acid metal compounds and alkylsalicylic acid metal compounds, and sulfonic acid group containing charge control resins that are preferably used Examples thereof include a copolymer, a sulfonate group-containing copolymer, a carboxylic acid group-containing copolymer, and a carboxylic acid group-containing copolymer.
In the present invention, the charge control agent is usually used in a proportion of 0.01 to 10 parts by mass, preferably 0.03 to 8 parts by mass, with respect to 100 parts by mass of the monovinyl monomer. If the addition amount of the charge control agent is less than 0.01 parts by mass, fog may occur. On the other hand, when the addition amount of the charge control agent exceeds 10 parts by mass, printing stains may occur.

As other additives, it is preferable to use a molecular weight modifier when polymerizing a polymerizable monomer that is polymerized to become a binder resin.
The molecular weight modifier is not particularly limited as long as it is generally used as a molecular weight modifier for toner. For example, t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, and 2,2, Mercaptans such as 4,6,6-pentamethylheptane-4-thiol; tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, N, N′-dimethyl-N, N′-diphenylthiuram disulfide, N, And thiuram disulfides such as N′-dioctadecyl-N, N′-diisopropylthiuram disulfide; These molecular weight modifiers may be used alone or in combination of two or more.
In this invention, it is desirable to use a molecular weight modifier in the ratio of 0.01-10 mass parts normally with respect to 100 mass parts of monovinyl monomers, Preferably it is 0.1-5 mass parts.

(A-2) Suspension step for obtaining a suspension (droplet formation step)
In the present invention, a polymerizable monomer composition containing at least a polymerizable monomer and a colorant is dispersed in an aqueous medium containing a dispersion stabilizer, and after adding a polymerization initiator, a polymerizable monomer Form body composition droplets. The method for forming droplets is not particularly limited. For example, an (in-line type) emulsifying disperser (trade name “Milder” manufactured by Ebara Manufacturing Co., Ltd.), a high-speed emulsifying disperser (trade name “T. K. Homomixer MARK Type II ") or the like capable of strong stirring.

  As a polymerization initiator, persulfates such as potassium persulfate and ammonium persulfate: 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-methyl-N- (2- Hydroxyethyl) propionamide), 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2′-azobisisobutyronitrile Azo compounds such as: di-t-butyl peroxide, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxydiethyl acetate, t-hexylperoxy-2-ethylbutanoate Diisopropyl peroxydicarbonate, di-t-butylperoxyisophthalate, and t-butylperoxyiso Organic peroxides such as Chireto like. These can be used alone or in combination of two or more. Among these, it is preferable to use an organic peroxide because residual polymerizable monomers can be reduced and printing durability is excellent.

  Among organic peroxides, peroxyesters are preferable because non-aromatic peroxyesters, that is, peroxyesters having no aromatic ring, are preferable because initiator efficiency is good and the amount of remaining polymerizable monomers can be reduced. More preferred.

  As described above, the polymerization initiator may be added before the droplet formation after the polymerizable monomer composition is dispersed in the aqueous medium. However, the polymerization initiator is not dispersed in the aqueous medium. It may be added to the monomer composition.

  The addition amount of the polymerization initiator used for the polymerization of the polymerizable monomer composition is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 100 parts by mass of the monovinyl monomer. It is -15 mass parts, Most preferably, it is 1-10 mass parts.

  In the present invention, the aqueous medium refers to a medium containing water as a main component.

  In the present invention, the aqueous medium preferably contains a dispersion stabilizer. Examples of the dispersion stabilizer include sulfates such as barium sulfate and calcium sulfate; carbonates such as barium carbonate, calcium carbonate and magnesium carbonate; phosphates such as calcium phosphate; metals such as aluminum oxide and titanium oxide. Oxides; metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and ferric hydroxide; inorganic compounds such as; water-soluble polymers such as polyvinyl alcohol, methylcellulose, and gelatin; anionic surfactants; Organic compounds such as nonionic surfactants; amphoteric surfactants; The said dispersion stabilizer can be used 1 type or in combination of 2 or more types.

  Among the above dispersion stabilizers, inorganic compounds, particularly colloids of poorly water-soluble metal hydroxides are preferred. By using a colloid of an inorganic compound, particularly a poorly water-soluble metal hydroxide, the particle size distribution of the colored resin particles can be narrowed, and the residual amount of the dispersion stabilizer after washing can be reduced. The toner can reproduce the image clearly and has excellent environmental stability.

(A-3) Polymerization step As in (A-2) above, droplet formation is performed, the resulting aqueous dispersion medium is heated to initiate polymerization, and an aqueous dispersion of colored resin particles is formed.
The polymerization temperature of the polymerizable monomer composition is preferably 50 ° C. or higher, more preferably 60 to 95 ° C. The polymerization reaction time is preferably 1 to 20 hours, more preferably 2 to 15 hours.

  The colored resin particles may be used as a polymerized toner by adding an external additive as it is, but the so-called core-shell type obtained by using the colored resin particles as a core layer and forming a shell layer different from the core layer on the outside thereof. It is preferable to use colored resin particles (also referred to as “capsule type”). The core-shell type colored resin particles balance the reduction of the fixing temperature and the prevention of aggregation during storage by coating the core layer made of a material having a low softening point with a material having a higher softening point. be able to.

  There is no restriction | limiting in particular as a method of manufacturing a core shell type colored resin particle using the said colored resin particle mentioned above, It can manufacture by a conventionally well-known method. An in situ polymerization method and a phase separation method are preferable from the viewpoint of production efficiency.

A method for producing core-shell type colored resin particles by in situ polymerization will be described below.
Addition of a polymerizable monomer (polymerizable monomer for shell) and a polymerization initiator to form a shell layer into an aqueous medium in which colored resin particles are dispersed, and then polymerize to form a core-shell type color. Resin particles can be obtained.

  As the polymerizable monomer for the shell, the same monomers as the aforementioned polymerizable monomers can be used. Among them, it is preferable to use monomers such as styrene, acrylonitrile, and methyl methacrylate, which can obtain a polymer having a Tg exceeding 80 ° C., alone or in combination of two or more.

  As a polymerization initiator used for polymerization of the polymerizable monomer for shell, persulfate metal salts such as potassium persulfate and ammonium persulfate; 2,2′-azobis (2-methyl-N- (2-hydroxyethyl) Water-soluble such as azo initiators such as) propionamide) and 2,2′-azobis- (2-methyl-N- (1,1-bis (hydroxymethyl) 2-hydroxyethyl) propionamide); A polymerization initiator can be mentioned. These can be used alone or in combination of two or more. The amount of the polymerization initiator is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer for shell.

  The polymerization temperature of the shell layer is preferably 50 ° C. or higher, more preferably 60 to 95 ° C. The polymerization reaction time is preferably 1 to 20 hours, more preferably 2 to 15 hours.

(A-4) Washing, filtration, dehydration, and drying steps The aqueous dispersion of colored resin particles obtained by polymerization is washed, dehydrated, and filtered to remove the dispersion stabilizer according to a conventional method after completion of the polymerization. The drying operation is preferably repeated several times as necessary.

  As the above washing method, when an inorganic compound is used as the dispersion stabilizer, the dispersion stabilizer can be dissolved in water and removed by adding an acid or alkali to the aqueous dispersion of colored resin particles. preferable. When a colloid of a poorly water-soluble inorganic hydroxide is used as the dispersion stabilizer, it is preferable to adjust the pH of the colored resin particle aqueous dispersion to 6.5 or less by adding an acid. As the acid to be added, inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid, and organic acids such as formic acid and acetic acid can be used. Particularly, since the removal efficiency is large and the burden on the manufacturing equipment is small, Sulfuric acid is preferred.

  Various known methods and the like can be used as the method of dehydration and filtration, and there is no particular limitation. Examples thereof include a centrifugal filtration method, a vacuum filtration method, and a pressure filtration method. Also, the drying method is not particularly limited, and various methods can be used.

(B) Pulverization method When the pulverization method is used to produce colored resin particles, the following process is performed.
First, a binder resin, a colorant, and other additives such as a charge control agent added as necessary are mixed in a mixer, such as a ball mill, a V-type mixer, a Henschel mixer (trade name), a high-speed dissolver, Mix using an internal mixer, Fallberg, etc. Next, the mixture obtained as described above is kneaded while being heated using a pressure kneader, a twin-screw extrusion kneader, a roller or the like. The obtained kneaded material is coarsely pulverized using a pulverizer such as a hammer mill, a cutter mill, or a roller mill. Furthermore, after finely pulverizing using a pulverizer such as a jet mill or a high-speed rotary pulverizer, it is classified into a desired particle size by a classifier such as an air classifier or an airflow classifier, and colored resin particles obtained by a pulverization method. Get.

  In addition, as other additives such as a binder resin and a colorant used in the pulverization method, and a charge control agent added as necessary, those mentioned in the above (A) suspension polymerization method can be used. . Further, the colored resin particles obtained by the pulverization method can be made into core-shell type colored resin particles by a method such as an in situ polymerization method in the same manner as the colored resin particles obtained by the suspension polymerization method (A) described above.

  As the binder resin, other resins that have been widely used for toners can be used. Specific examples of the binder resin used in the pulverization method include polystyrene, styrene-butyl acrylate copolymer, polyester resin, and epoxy resin.

2. Colored resin particles Colored resin particles are obtained by a production method such as the above-described (A) suspension polymerization method or (B) pulverization method.
Hereinafter, the colored resin particles constituting the toner will be described. The colored resin particles described below include both core-shell type and non-core type.

  The volume average particle diameter (Dv) of the colored resin particles is preferably 4 to 12 μm, and more preferably 5 to 10 μm. When Dv is less than 4 μm, the fluidity of the toner is lowered, the transferability may be deteriorated, and the image density may be lowered. When Dv exceeds 12 μm, the resolution of the image may decrease.

  The colored resin particles have a ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of preferably 1.0 to 1.3, more preferably 1. 0-1.2. If Dv / Dn exceeds 1.3, transferability, image density, and resolution may decrease. The volume average particle diameter and the number average particle diameter of the colored resin particles can be measured using, for example, a particle size analyzer (trade name “Multisizer” manufactured by Beckman Coulter).

From the viewpoint of image reproducibility, the average circularity of the colored resin particles of the present invention is preferably 0.96 to 1.00, more preferably 0.97 to 1.00, and 0.98 to More preferably, it is 1.00.
When the average circularity of the colored resin particles is less than 0.96, the fine line reproducibility of printing may be deteriorated.

  In the present invention, the circularity is defined as a value obtained by dividing the circumference of a circle having the same projected area as the particle image by the circumference of the projected image of the particle. The average circularity in the present invention is used as a simple method for quantitatively expressing the shape of the particles, and is an index indicating the degree of unevenness of the colored resin particles. The average circularity is determined by the colored resin particles. 1 is shown in the case of a perfect sphere, and the value becomes smaller as the surface shape of the colored resin particles becomes more complicated.

3. Toner Production Method In the present invention, the colored resin particles are mixed and stirred together with an external additive and subjected to an external addition treatment, whereby the external additive is adhered to the surface of the colored resin particles to develop a one-component toner (development). Agent). The one-component toner may be further mixed and stirred together with carrier particles to form a two-component developer.

In the present invention, it is preferable to contain inorganic fine particles A having a number average primary particle size of 36 to 100 nm as an external additive.
When the number average primary particle size of the inorganic fine particles A is less than 36 nm, the spacer effect is lowered and print performance such as fogging may be adversely affected. On the other hand, when the number average primary particle diameter of the inorganic fine particles A exceeds 100 nm, the inorganic fine particles A are easily released from the surface of the toner particles, the function as an external additive is lowered, and the printing performance is adversely affected. May affect.
The number average primary particle size of the inorganic fine particles A is more preferably 40 to 80 nm, and further preferably 45 to 70 nm. In addition, the inorganic fine particles A may be hydrophobized.

The content of the inorganic fine particles A is preferably 0.1 to 2.5 parts by mass, more preferably 0.3 to 2.0 parts by mass with respect to 100 parts by mass of the colored resin particles. More preferably, it is 5-1.5 mass parts.
When the content of the inorganic fine particles A is less than 0.1 part by mass, the function as the external additive cannot be sufficiently exhibited, and the printing performance may be adversely affected. On the other hand, when the content of the inorganic fine particles A exceeds 2.5 parts by mass, the inorganic fine particles A are easily released from the surface of the toner particles, the function as an external additive is lowered, and the printing performance is adversely affected. May affect.
Although depending on the type and amount of other external additives and other external addition conditions, the toner compression index CI decreases as the content of inorganic fine particles A decreases, as shown in the examples described later. On the other hand, the fluidity of the toner tends to increase. On the other hand, as the content of the inorganic fine particles A increases, the compression index CI of the toner increases and the durability tends to improve.

In the present invention, it is preferable to contain inorganic fine particles B having a number average primary particle size of 15 to 35 nm as an external additive.
When the number average primary particle size of the inorganic fine particles B is less than 15 nm, the inorganic fine particles B are easily embedded from the surface to the inside of the colored resin particles, and sufficient fluidity can be imparted to the toner particles. The printing performance may be adversely affected. On the other hand, when the number average primary particle size of the inorganic fine particles B exceeds 35 nm, the proportion (coverage) of the inorganic fine particles B with respect to the surface of the toner particles decreases, so that the toner particles have sufficient fluidity. May not be granted.
The number average primary particle size of the inorganic fine particles B is more preferably 17 to 30 nm, and further preferably 20 to 25 nm. In addition, the inorganic fine particles B may be hydrophobized.

The content of the inorganic fine particles B is preferably 0.1 to 2.0 parts by mass, more preferably 0.2 to 1.5 parts by mass with respect to 100 parts by mass of the colored resin particles. More preferably, it is 3 to 1.0 parts by mass.
When the content of the inorganic fine particles B is less than 0.1 parts by mass, the function as an external additive cannot be sufficiently exerted, and the fluidity is lowered or the storage stability and durability are lowered. There is. On the other hand, when the content of the inorganic fine particles B exceeds 2.0 parts by mass, the inorganic fine particles B are easily released from the surface of the toner particles, and the chargeability in a high-temperature and high-humidity environment is lowered and fogging occurs. There is a case.
Although depending on the type and amount of other external additives and other external addition conditions, the toner compression index CI decreases as the content of the inorganic fine particles B decreases, as shown in the examples described later. On the other hand, the fluidity of the toner tends to increase. On the other hand, as the content of the inorganic fine particles B increases, the toner compression index CI increases and the durability tends to improve.

In the present invention, it is preferable to contain inorganic fine particles C having a number average primary particle size of 6 to 14 nm as an external additive.
When the number average primary particle size of the inorganic fine particles C is less than 6 nm, the inorganic fine particles C are easily embedded from the surface to the inside of the colored resin particles, and sufficient fluidity can be imparted to the toner particles. The printing performance may be adversely affected. On the other hand, when the number average primary particle size of the inorganic fine particles C exceeds 14 nm, the ratio (coverage) of the inorganic fine particles C to the surface of the toner particles is reduced, so that the toner particles have sufficient fluidity. May not be granted.
The number average primary particle size of the inorganic fine particles C is more preferably 6.5 to 12 nm, and further preferably 7 to 10 nm. In addition, the inorganic fine particles C may be hydrophobized.

The content of the inorganic fine particles C is preferably 0.05 to 2.0 parts by mass, more preferably 0.1 to 1.5 parts by mass with respect to 100 parts by mass of the colored resin particles. More preferably, it is 2 to 1.0 part by mass.
When the content of the inorganic fine particles C is less than 0.05 parts by mass, the function as the external additive cannot be sufficiently exhibited, and the fluidity may be lowered or the storage stability may be lowered. On the other hand, when the content of the inorganic fine particles C exceeds 2.0 parts by mass, the inorganic fine particles C are easily released from the surface of the toner particles, and the chargeability in a high-temperature and high-humidity environment is reduced and fogging occurs. There is a case.
Although depending on the type and addition amount of other external additives and other external addition conditions, the toner compression index CI decreases as the content of inorganic fine particles C increases, as shown in the examples described later. On the other hand, the fluidity of the toner tends to increase. On the other hand, the smaller the content of the inorganic fine particles C, the higher the compression index CI of the toner tends to increase the durability.

  The toner of the present invention preferably contains any one of inorganic fine particles A to C, more preferably any two, and even more preferably all three. The toner of the present invention is prepared so as to have a compression index CI in a specific range by appropriately including the inorganic fine particles A to C and appropriately adjusting the particle size and addition amount of the inorganic fine particles A to C.

  Examples of the inorganic fine particles A to C include silica, titanium oxide, aluminum oxide, zinc oxide, tin oxide, calcium carbonate, calcium phosphate, and cerium oxide. The inorganic fine particles A to C may be different from each other, but are preferably made of the same material. Each of the inorganic fine particles A to C preferably contains silica and / or titanium oxide, and more preferably consists of silica.

As the inorganic fine particles A, various commercially available silica fine particles can be used. For example, VPNA50H manufactured by Nippon Aerosil Co., Ltd. (: trade name, number average primary particle size: 40 nm); H05TA manufactured by Clariant, Inc. (: trade name, Number average primary particle size: 50 nm);
As the inorganic fine particles B, various commercially available silica fine particles can be used. For example, NA50Y manufactured by Nippon Aerosil Co., Ltd. (: trade name, number average primary particle size: 35 nm); MSP-012 manufactured by Teika Co. (: commercial product) Name, number average primary particle size: 16 nm); TG-7120 manufactured by Cabot Corporation (: trade name, number average primary particle size: 20 nm), and the like.
As the inorganic fine particles C, various commercially available silica fine particles can be used. For example, HDK2150 (: trade name, number average primary particle size: 12 nm) manufactured by Clariant, R504 (: trade name, manufactured by Nippon Aerosil Co., Ltd.) Number average primary particle size: 12 nm), RA200HS (: trade name, number average primary particle size: 12 nm); MSP-013 manufactured by Teika (: product name, number average primary particle size: 12 nm); TG manufactured by Cabot -820F (trade name, number average primary particle size: 7 nm), and the like.

As an external additive, in addition to the inorganic fine particles A to C, it is more preferable to contain inorganic fine particles D having a number average primary particle size of 0.3 to 2.0 μm.
When the number average primary particle size of the inorganic fine particles D is within the above range, filming on the photosensitive member is difficult to occur, and stable charging with time is imparted to the toner particles, and continuous printing of a large number of sheets can be performed. Thus, it is possible to obtain a toner that hardly deteriorates in image quality due to fog or the like, and that hardly deteriorates in image quality even in a high-temperature and high-humidity environment (HH environment).
The number average primary particle size of the inorganic fine particles D is more preferably 0.4 to 1.5 μm, and further preferably 0.5 to 1.0 μm.

  In addition, the number average primary particle diameter of the external additive particles used in the present invention can be measured, for example, as follows. First, the particle diameter of each particle of the external additive is measured with a transmission electron microscope (TEM) or the like. Thus, the particle diameter of 200 or more external additive particles is measured, and the average value is defined as the number average primary particle diameter of the particles.

The content of the inorganic fine particles D is preferably 0.05 to 2.0 parts by mass, more preferably 0.07 to 1.5 parts by mass with respect to 100 parts by mass of the colored resin particles. More preferably, it is 1-1.2 parts by mass.
When the content of the inorganic fine particles D is less than 0.05 parts by mass, the function as an external additive cannot be fully exhibited, and the chargeability in a high-temperature and high-humidity environment is lowered and fogging occurs. There is. On the other hand, when the content of the inorganic fine particles D exceeds 2.0 parts by mass, the inorganic fine particles D are likely to be liberated from the surface of the toner particles, and the fluidity may be lowered.
Although depending on the type and amount of other external additives and other external additive conditions, the toner compression index CI decreases as the content of the inorganic fine particles D decreases, as shown in the examples described later. On the other hand, the fluidity of the toner tends to increase. On the other hand, as the content of the inorganic fine particles D increases, the compression index CI of the toner increases and the durability tends to improve.

As the inorganic fine particles D, the same materials as the inorganic fine particles A to C described above may be used, but it is preferable to use fatty acid zinc particles.
Fatty site of fatty acid zinc particles (R-COO ^-) and the corresponding fatty acids (R-COOH), out of a carboxyl group (-COOH) 1 piece carboxylic acid having (R-COOH), those having a chain structure Including all. In the present invention, the fatty acid moiety is preferably derived from a higher fatty acid having a large number of carbon atoms in the alkyl group (R-).

Examples of higher fatty acids include lauric acid (CH ₃ (CH ₂ ) ₁₀ COOH), tridecanoic acid (CH ₃ (CH ₂ ) ₁₁ COOH), myristic acid (CH ₃ (CH ₂ ) ₁₂ COOH), pentadecanoic acid (CH ₃ ). (CH ₂ ) ₁₃ COOH), palmitic acid (CH ₃ (CH ₂ ) ₁₄ COOH), heptadecanoic acid (CH ₃ (CH ₂ ) ₁₅ COOH), stearic acid (CH ₃ (CH ₂ ) ₁₆ COOH), arachidic acid ( CH ₃ (CH ₂ ) ₁₈ COOH), behenic acid (CH ₃ (CH ₂ ) ₂₀ COOH), lignoceric acid (CH ₃ (CH ₂ ) ₂₂ COOH) and the like. The number of carbon atoms in the alkyl group of the fatty acid is preferably 12-24, more preferably 14-22, and still more preferably 16-20. Although the fatty acid which comprises these fatty acid zinc particles can be used individually or in combination of 2 or more types, respectively, it is preferable to use independently from the point of obtaining a uniform characteristic.

  The stirrer that performs the external addition treatment is not particularly limited as long as the stirrer can attach the external additive to the surface of the colored resin particles. For example, Henschel mixer (trade name, manufactured by Mitsui Mining Co., Ltd.), FM mixer (: Trade name, manufactured by Nippon Coke Industries Co., Ltd.), super mixer (: product name, manufactured by Kawada Seisakusho Co., Ltd.), Q mixer (: product name, manufactured by Nihon Coke Industries Co., Ltd.), mechano-fusion system (: trade name, Hosokawa Micron Corporation) And a mechano mill (trade name, manufactured by Okada Seiko Co., Ltd.) and the like, and a stirrer capable of mixing and stirring can be used for external addition treatment.

As shown in the examples described later, the compression index CI can also be adjusted by changing external addition processing conditions such as stirring conditions and processing time. For example, as the stirring condition is more relaxed or the stirring time is shortened, the toner compression index CI tends to decrease and the fluidity of the toner tends to increase. On the other hand, the stirring condition becomes more severe or the stirring time is lengthened. The more the toner compression index CI increases, the more the durability tends to improve. However, since the toner compression index CI is also affected by the composition of the external additive described above, the above trend does not necessarily apply to all toners.
As a suitable external addition processing condition for obtaining a desired compression index CI, for example, when a stirrer having a scale of about 1 to 50 L is used, the rotational speed of the stirring blade is 3,000 to 10,000 rpm, and the external addition processing is performed. The conditions which make time 3 minutes-1 hour are mentioned. However, this condition is not always applicable when the reaction scale is different.

4). Toner of the Present Invention The toner of the present invention is a toner defined by a compression index CI (Consolidation Index).
The compression index CI is a value obtained by measuring the total energy after compression (EAC) measured by a compression test using a powder flowability analyzer by a stability test using the powder flowability analyzer. It is the value divided by the value of the basic fluidity energy (Basic Flowability Energy: BFE) to be measured.

Basic fluidity energy (BFE) refers to the total energy in the last round of stability testing. Here, the total energy (flow energy) is a work amount calculated from the torque and vertical load acting on the blade when the blade is spirally operated in the powder, and is the energy required to flow the powder. That is. Among the total energies, the basic fluidity energy (BFE) is a physical quantity that is treated as a representative value of the powder flow energy in the dynamic test.
In the stability test, the value of the basic fluidity energy (BFE) in the present invention is determined by letting the blade provided in the powder fluidity analyzer enter the powder layer of the electrostatic charge image developing toner at a tip speed of 100 mm / second. It is preferable that the total of the rotational torque and vertical load generated by the blade moving in the powder layer.

The total energy after compression (EAC) refers to the total energy (flow energy) of the powder after being compressed by applying a certain pressure. The total energy after compression (EAC) is usually a value equal to or higher than the basic fluidity energy (BFE), and the difference between both energies increases as the powder is more easily compressed or more difficult to flow due to compression. Therefore, it is considered that the powder having a higher compression index CI (= EAC / BFE) is more likely to be compressed and less likely to flow and clog.
The value of the total energy after compression (EAC) in the present invention is the tip speed in the compression powder layer of the electrostatic charge image developing toner after pressurizing the blade provided in the powder fluidity analyzer at 10 kPa in the compression test. It is preferable that the total of the rotational torque and the vertical load generated when the blade moves through the compressed powder layer by entering at 100 mm / second.

  When the stability test and / or the compression test is performed on the toner of the present invention, known documents regarding the powder flowability analyzer can be referred to, for example, “Powder Flowability Analyzer, Powder Rheometer FT-4” It is possible to refer to publicly known documents (especially pages 6-7 and 10) such as “Academic Materials” (issued by Scientific Measurement Division, Sysmex Corporation, first edition issued on September 1, 2007). However, the stability test and the compression test in the present invention are not necessarily limited to only the contents described in the above-mentioned known documents.

  As a powder fluidity analyzer (hereinafter sometimes referred to as an analyzer), for example, a powder rheometer FT4 (trade name, manufactured by Freeman Technology) can be used.

A typical example of the stability test is as follows. First, after a predetermined amount of toner sample is added to the measurement container, the tip speed of the blade provided in the analyzer is set to a predetermined speed, and the angle of entry of the blade is set to a predetermined angle to pass through the measurement container from top to bottom. Perform conditioning. After conditioning, a toner cake layer is appropriately formed. Next, with the blade tip speed set to a predetermined speed and the blade entry angle set to a predetermined angle, the blade passes through the toner cake layer formed in the measurement container from top to bottom, and the rotational torque and vertical load are Measure the sum. The sum of the rotational torque and the vertical load is defined as basic fluidity energy (BFE).
Although the operation after conditioning may be performed a plurality of times, the value of basic fluidity energy (BFE) is obtained from the sum of the rotational torque and the vertical load measured in the last round.

  A typical example of the compression test is as follows. First, after a predetermined amount of toner sample is added to the measurement container, the measurement container is set in a pressurizing device, and the toner sample is pressurized under predetermined pressure conditions. The pressurizing device may be a device provided in the analyzer, or may be a device different from the analyzer. After pressurization, if necessary, a toner sample is added on the toner cake layer, and further pressurized. The operation of adding and pressurizing the toner sample is repeated several times if necessary to form a compressed toner cake layer. Next, the blade is passed through the compressed toner cake layer formed in the measurement container from the top to the bottom with the blade tip speed provided in the analyzer set to a predetermined speed and the blade entry angle set to a predetermined angle, and rotated. Measure the sum of torque and vertical load. The sum of the rotational torque and the vertical load is defined as total energy after compression (EAC).

The toner of the present invention is a toner having a compression index CI (= EAC / BFE) of 1.5 to 3.2.
When the compression index CI is less than 1.5, the printing durability is extremely inferior. This is considered to be due to the fact that the spacer effect or the like due to the above-mentioned external additives becomes difficult to develop or the external addition conditions are too strict. On the other hand, when the compression index CI exceeds 3.2, toner leakage and ejection are extremely likely to occur. In particular, the toner leakage is considered to be caused by an increase in the difference between the toner portion flowing in the developing unit and the toner portion not flowing as a result of poor toner fluidity. Once the toner is compacted, it is difficult to fluidize it again. In particular, toner near the seal portion of the developing device is unlikely to circulate, and thus toner leakage is likely to occur. On the other hand, toner ejection tends to occur when printing is performed after the toner has poor fluidity and is left at a high temperature. In such a case, the toner at the end portion in the developing device is particularly difficult to fluidize, and the charge amount of the toner decreases due to such poor circulation of the toner and a high temperature environment. This is thought to be due to the occurrence of eruption.
The toner of the present invention preferably has a compression index CI value of 1.8 to 3.0, more preferably 2.0 to 2.8, and preferably 2.2 to 2.7. Further preferred.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited only to these examples. Parts and% are based on mass unless otherwise specified.
The test methods performed in the examples and comparative examples are as follows.

1. Production of toner for developing electrostatic image [Example 1]
75 parts of styrene and 25 parts of n-butyl acrylate as a polymerizable monomer, 5 parts of carbon black (trade name “# 25B”, manufactured by Mitsubishi Chemical Corporation) as a black colorant, an in-line type emulsifying disperser (manufactured by Ebara Corporation) , Trade name “Ebara Milder”) to obtain a polymerizable monomer mixture.
1 part of a charge control resin (manufactured by Fujikura Kasei Co., Ltd., trade name “Acrybase FCA-161P”) as a charge control agent, and hexaglycerin octabehenate (melting point: 70 ° C.) as a release agent. 5 parts, 5 parts of paraffin wax (melting point: 68 ° C.), 0.3 part of polymethacrylate macromonomer (manufactured by Toa Gosei Chemical Co., Ltd., trade name “AA6”) as a macromonomer, as a crosslinkable polymerizable monomer 0.6 parts of divinylbenzene and 1.6 parts of t-dodecyl mercaptan as a molecular weight regulator were added, mixed and dissolved to prepare a polymerizable monomer composition.

  On the other hand, at room temperature, in an aqueous solution in which 10.2 parts of magnesium chloride (water-soluble polyvalent metal salt) is dissolved in 250 parts of ion-exchanged water, sodium hydroxide (alkali metal hydroxide) 6.2 in 50 parts of ion-exchanged water. The aqueous solution in which the part was dissolved was gradually added with stirring to prepare a magnesium hydroxide colloid (slightly water-soluble metal hydroxide colloid) dispersion.

  The polymerizable monomer composition was charged into the magnesium hydroxide colloid dispersion at room temperature and stirred. Then, 4.4 parts of t-butylperoxydiethyl acetate was added as a polymerization initiator, and then rotated at 15,000 rpm using an in-line type emulsifying disperser (trade name “Ebara Milder” manufactured by Ebara Seisakusho Co., Ltd.). Dispersion was carried out by high-speed shearing stirring for several minutes for several minutes to form droplets of the polymerizable monomer composition.

  A suspension (polymerizable monomer composition dispersion) in which droplets of the polymerizable monomer composition are dispersed is placed in a reactor equipped with a stirring blade, heated to 90 ° C., and polymerized. The reaction was started. When the polymerization conversion reached almost 100%, 2,2′-azobis (shell polymerization initiator dissolved in 1 part of methyl methacrylate and 10 parts of ion-exchanged water as shell polymerizable monomer) Add 0.3 part of 2-methyl-N- (2-hydroxyethyl) -propionamide) (manufactured by Wako Pure Chemical Industries, trade name “VA-086”, water-soluble) and continue the reaction at 90 ° C. for 4 hours. Then, the reaction was stopped by cooling with water to obtain an aqueous dispersion of colored resin particles having a core-shell structure.

  The aqueous dispersion of the colored resin particles was added dropwise with stirring sulfuric acid at room temperature, and acid washing was performed until the pH was 6.5 or less. Subsequently, filtration separation was performed, 500 parts of ion-exchanged water was added to the obtained solid content to make a slurry again, and water washing treatment (washing, filtration, dehydration) was repeated several times. Next, filtration separation is performed, and the obtained solid content is put in a container of a dryer, and dried at 45 ° C. for 48 hours. The volume average particle diameter (Dv) is 7.8 μm, and the number average particle diameter (Dn) is Colored resin particles having a size of 6.9 μm, a particle size distribution (Dv / Dn) of 1.13, and an average circularity of 0.987 were obtained.

  To 100 parts of the colored resin particles obtained as described above, 1.0 part of silica fine particles having a number average primary particle size of 50 nm (made by Clariant, trade name “H05TA”) as inorganic fine particles A as an external additive, inorganic fine particles B 0.8 parts of silica fine particles having a number average primary particle diameter of 20 nm (trade name “TG-7120” manufactured by Cabot Corporation) and silica fine particles having a number average primary particle diameter of 7 nm as inorganic fine particles C (trade name “manufactured by Cabot Corporation”) 0.2 part of TG-820F ”) and 0.1 part of zinc stearate fine particles (manufactured by Sakai Chemical Industry Co., Ltd., trade name“ SPZ-100 ”) as inorganic fine particles D having a number average primary particle size of 0.5 μm are added. Then, using a 10 L lab-scale high-speed stirring device (manufactured by Nippon Coke, trade name “FM mixer”) having a cooling jacket, the rotation speed of the stirring blade is 4,000 rpm. Subjected to an external addition treatment with mixing and stirring under the conditions of external addition treatment time 5.0 minutes to produce a toner for developing electrostatic images of Example 1. The test results are shown in Table 1.

[Example 2]
A toner for developing an electrostatic charge image of Example 2 was prepared in the same manner as in Example 1 except that the rotation speed of the stirring blade was changed from 4,000 rpm to 3,000 rpm in the external addition process of Example 1. The test was conducted.

[ Reference Example 3]
In the external addition process of Example 1, the electrostatic charge image developing toner of Reference Example 3 was prepared in the same manner as in Example 1 except that the external addition process time was changed from 5.0 minutes to 2.5 minutes. The test was conducted.

[Example 4]
In the external addition process of Example 1, the toner for developing an electrostatic charge image of Example 4 was prepared and tested in the same manner as in Example 1 except that the external addition process time was changed from 5.0 minutes to 25 minutes. It was used for.

[ Reference Example 5]
In Example 1, the toner for developing an electrostatic charge image of Reference Example 5 was produced in the same manner as in Example 1 except that the inorganic fine particles A were not added, and were subjected to the test.

[Example 6]
In Example 1, the toner for developing an electrostatic charge image of Example 6 was prepared in the same manner as in Example 1 except that the addition amount of the inorganic fine particles A was changed from 1.0 part to 0.5 part. It used for the test.

[Example 7]
In Example 1, the toner for developing an electrostatic charge image of Example 7 was prepared in the same manner as in Example 1 except that the addition amount of the inorganic fine particles A was changed from 1.0 part to 2.0 parts. It used for the test.

[ Reference Example 8]
In Example 1, the toner for developing an electrostatic charge image of Reference Example 8 was produced in the same manner as in Example 1 except that the inorganic fine particles D were not added, and were subjected to the test.

[Example 9]
In Example 1, the toner for developing an electrostatic charge image of Example 9 was prepared in the same manner as in Example 1 except that the addition amount of the inorganic fine particles D was changed from 0.1 part to 0.2 part. It used for the test.

[Example 10]
In Example 1, the toner for developing an electrostatic charge image of Example 10 was prepared in the same manner as in Example 1 except that the addition amount of the inorganic fine particles D was changed from 0.1 part to 0.8 part. It used for the test.

[Example 11]
In Example 1, the toner for developing an electrostatic charge image of Example 11 was prepared in the same manner as in Example 1 except that the addition amount of the inorganic fine particles B was changed from 0.8 part to 1.5 parts. It used for the test.

[ Reference Example 12]
In Example 1, the toner for developing an electrostatic charge image of Reference Example 12 was produced in the same manner as in Example 1 except that the inorganic fine particles B were not added, and were subjected to the test.

[Example 13]
In Example 1, the toner for developing an electrostatic charge image of Example 13 was prepared in the same manner as in Example 1 except that the addition amount of the inorganic fine particles C was changed from 0.2 part to 0.1 part. It used for the test.

[ Reference Example 14]
In Example 1, without addition of inorganic fine particles B, and, except for changing the addition amount of the inorganic fine particles C to 1.5 parts 0.2 parts, in the same manner as in Example 1, Reference Example 14 A toner for developing an electrostatic image was prepared and subjected to a test.

[ Reference Example 15]
In Example 1, the toner for developing an electrostatic charge image of Reference Example 15 was produced in the same manner as in Example 1 except that the inorganic fine particles C were not added, and subjected to the test.

[Example 16]
In Example 1, the toner for developing an electrostatic charge image of Example 16 was prepared in the same manner as in Example 1 except that the addition amount of the inorganic fine particles C was changed from 0.2 part to 2.5 parts. It used for the test.

[Comparative Example 1]
In the external addition process of Example 1, the rotational speed of the stirring blade was changed from 4,000 rpm to 2,500 rpm, and the external addition process time was changed from 5.0 minutes to 1.0 minutes. In the same manner as in Example 1, the toner for developing an electrostatic charge image of Comparative Example 1 was prepared and used for the test.

[Comparative Example 2]
In Example 1, except that the inorganic fine particles A were not added and the addition amount of the inorganic fine particles B was changed from 0.8 part to 0.5 part, A toner for developing an electrostatic image was prepared and subjected to a test.

[Comparative Example 3]
Comparative Example 3 was carried out in the same manner as in Example 1 except that the amount of inorganic fine particles A added in Example 1 was changed from 1.0 part to 3.0 parts and inorganic fine particles C were not added. A toner for developing an electrostatic image was prepared and subjected to a test.

[Comparative Example 4]
In Example 1, the addition amount of the inorganic fine particles A was changed from 1.0 part to 0.5 part, the addition amount of the inorganic fine particles B was changed from 0.8 part to 0.4 part, and The electrostatic charge image developing of Comparative Example 4 was performed in the same manner as in Example 1 except that the addition amount of the fine particles C was changed from 0.2 parts to 0.4 parts and the inorganic fine particles D were not added. A toner was prepared and subjected to testing.

[Comparative Example 5]
In Example 1, except that the inorganic fine particles C were not added and the addition amount of the inorganic fine particles D was changed from 0.1 part to 1.2 parts, the same as in Example 1 was repeated. A toner for developing an electrostatic image was prepared and subjected to a test.

2. Evaluation of toner for developing electrostatic image Example 1 to Example 2, Reference Example 3, Example 4, Reference Example 5, Example 6 to Example 7, Reference Example 8, Example 9 to Example 11, Reference Regarding the electrostatic charge image developing toners of Example 12, Example 13, Reference Examples 14 to 15, Example 16, and Comparative Examples 1 to 5, the colored resin particle characteristics, toner characteristics, and printing characteristics were examined. Details are as follows.

2-1. Colored resin particle characteristics and toner characteristics 2-1-1. Volume average particle size (Dv), number average particle size (Dn) and particle size distribution (Dv / Dn) of colored resin particles
About 0.1 g of a measurement sample (colored resin particles) was weighed and taken in a beaker, and 0.1 mL of an alkylbenzene sulfonic acid aqueous solution (trade name “Drywell”, manufactured by Fuji Film) was added as a dispersant. After adding 10-30 mL of Isoton II to the beaker and dispersing for 3 minutes with a 20 W (Watt) ultrasonic disperser, use a particle size analyzer (Beckman Coulter, trade name “Multisizer”). The volume average particle diameter (Dv) and the number average particle diameter (Dn) of the colored resin particles are measured under the conditions of aperture diameter: 100 μm, medium: Isoton II, number of measured particles: 100,000 particles, The diameter distribution (Dv / Dn) was calculated.

2-1-2. Average circularity of colored resin particles 10 mL of ion-exchanged water is put in a container in advance, 0.02 g of a surfactant (alkylbenzenesulfonic acid) is added as a dispersant, and 0.02 g of a measurement sample (colored resin particles) is further added. Then, the dispersion treatment was performed with an ultrasonic disperser at 60 W (Watt) for 3 minutes. The concentration of the colored resin particles at the time of measurement is adjusted to 3,000 to 10,000 particles / μL, and 1,000 to 10,000 colored resin particles having an equivalent circle diameter of 0.4 μm or more are flow-type particle images. Measurement was performed using an analyzer (trade name “FPIA-2100” manufactured by Simex Co., Ltd.). The average circularity was determined from the measured value.
The circularity is shown in the following calculation formula 1, and the average circularity is an average of the circularity.
Formula 1: (Circularity) = (Perimeter of circle equal to projected area of particle) / (Perimeter of projected image of particle)

2-1-3. Toner compression index CI
(1) Stability test (measurement of basic fluidity energy (BFE))
The following measurements were performed using a powder flowability analyzer (trade name “Powder Rheometer FT4” manufactured by Freeman Technology).
A 50 mm x 160 mL measuring container with a clamp and an attached container of 50 mm x 85 mL are connected by a splitter, filled with about 90 g of toner to be evaluated to exceed the capacity of the measuring container, and then equipped with a blade used for measurement. The measurement container was set in the apparatus, the blade tip speed was set to 60 mm / sec, the blade entry angle was set to 5 ° counterclockwise, and conditioning was performed by passing the measurement container from top to bottom.
After conditioning, a toner cake layer was prepared using a splitter so that only the measurement container was filled with toner in order to match the capacity of the toner to be evaluated. Next, the blade tip speed is set to 100 mm / second, the blade entry angle is set to 5 ° clockwise, and the toner cake layer prepared in the measurement container is passed from the top to the bottom, so that the sum of the rotational torque and the vertical load is calculated. It was measured.
The operation after conditioning was performed 6 times (total 7 times measurement), and the sum of the 7th rotation torque and the vertical load was defined as the basic fluidity energy (BFE).

(2) Compression test (measurement of total energy after compression (EAC))
After connecting a 50 mm x 160 mL measuring container with a clamp and a 50 mm x 85 mL attached container with a splitter, and filling about 25 g of toner to be evaluated with the aim of about 1/4 for exceeding the capacity of the measuring container The measurement container was set in an analyzer equipped with a compression piston, and the toner to be evaluated was pressurized for 30 seconds at a pressure of 10 kPa after the powder was stabilized.
About 25 g of toner was further filled on the compressed toner cake layer, and the toner to be evaluated was pressurized at a pressure of 10 kPa for 30 seconds after the powder was stabilized. This operation was further repeated twice to form a compressed toner cake layer filled with about 100 g of toner. Next, in order to match the capacity of the toner to be evaluated, a compressed toner cake layer for measurement was prepared using a splitter so that only the measurement container was filled with toner.
After replacing the compression piston with the blade, the blade tip speed is set to 100 mm / second, the blade entry angle is set to 5 ° clockwise, and the compressed toner cake layer produced in the measurement container is passed from top to bottom. Then, the total of the rotational torque and the vertical load was measured, and this measured value was defined as the total energy after compression (EAC).

(3) Compression index CI
The compression index CI was calculated based on the following formula from the values of the basic fluidity energy (BFE) measured in the stability test and the total energy after compression (EAC) measured in the compression test.
Compression index CI = Total energy after compression (EAC) / Basic fluidity energy (BFE)

2-2. Printing characteristics 2-2-1. Printing durability For the printing durability test, a commercially available non-magnetic one-component developing type printer (HL-4570CDW) was used. After the toner cartridge of the developing device was filled with toner, printing paper was set. After standing for 24 hours in a normal temperature and normal humidity (N / N) environment (temperature: 23 ° C., humidity: 50%), continuous printing was performed up to 15,000 sheets at 5% printing density in the same environment. . Every 500 sheets, black solid printing (printing density 100%) is performed, and using a reflective image densitometer (manufactured by Macbeth, trade name “RD918”), the printing density at the center of the black solid image is measured at three points. The average value was defined as the print density.
Furthermore, after that, white solid printing (printing density 0%) is performed, the printer is stopped in the middle of white solid printing, and the toner in the non-image area on the photoconductor after development is treated with an adhesive tape (manufactured by Sumitomo 3M Limited, product The name “Scotch Mending Tape 810-3-18”) was peeled off and affixed to the printing paper. Next, the whiteness (B) of the printing paper to which the adhesive tape was attached was measured with a whiteness meter (trade name “ND-1”, manufactured by Nippon Denshoku Co., Ltd.), and in the same manner, an unused adhesive. Only the tape was attached to the printing paper, the whiteness (A) was measured, and the whiteness difference (B−A) was defined as the fog value (%). Smaller values indicate better fog and better. The number of continuously printed sheets that can maintain an image quality with a print density of 1.3 or more and a fog value of 3% or less was examined.
In Tables 1 and 2, “15000 <” means that even at 15,000 sheets, the image density was 1.3 or higher and the fog value was 3% or less. Indicates.
However, when the following evaluation of toner leakage was significantly deteriorated, the evaluation was stopped halfway.

2-2-2. In addition to the evaluation of “2-2-1. Printing durability”, the evaluation of toner leakage was also performed.
During printing endurance, the periphery of the developing device was checked, and whether or not toner leakage occurred was also checked. As with the printing durability evaluation, the timing of confirmation was confirmed by visually checking the side seal portion of the developing device every 500 sheets, and the presence or absence of leakage was determined according to the following evaluation criteria.
In the following evaluation criteria, the level up to level 2 is an acceptable level for toner leakage.
However, when the evaluation of the printing durability was completed midway, the toner leakage property was evaluated at that time.

Evaluation Criteria Level 0: No toner leakage from side seal even after printing 15,000 sheets.
Level 1: A small amount of toner leaked from the side seal when 10,000 to 15,000 sheets were printed.
Level 2: A small amount of toner leaked from the side seal when 5,001 to 10,000 sheets were printed.
Level 3: A small amount of toner leaked from the side seal when 1 to 5,000 sheets were printed.
Level 4: A large amount of toner leaked from the side seal when 1 to 5,000 sheets were printed.

2-2-3. Ejection after standing at high temperature A commercially available non-magnetic one-component developing type printer (HL-4570CDW) was used for the ejection test after standing at high temperature. After the toner cartridge of the developing device was filled with toner, the toner cartridge was left in a dryer at 50 ° C. for 120 hours, and the removed cartridge and printing paper were set in a printer to perform continuous printing.
Continuous printing is performed in a normal temperature and normal humidity (N / N) environment (temperature: 23 ° C, humidity: 50%), printing is performed with 5 halftone printing at a printing density of 30%, and ejected from the toner cartridge onto the printing paper. It was confirmed whether or not there was a spot of 0.3 × 0.3 mm or more on the halftone by the toner.
When spots were seen, an additional 45 sheets were printed and it was confirmed whether the spots disappeared. When no spots were found, printing was stopped, the printed developer was checked to confirm whether it was actually ejected, and ejection after standing at high temperature was determined according to the following evaluation criteria.
In the following evaluation criteria, the level up to level 2 is a level at which ejection after allowing to stand at high temperature is acceptable.

Evaluation Criteria Level 0: No spots occur on the printed matter. No squirting is seen even after checking the toner cartridge.
Level 1: No spots appear on the printed matter. When checking the toner cartridge, a small amount of jetting is seen.
Level 2: Spots appear, but disappear by the fifth printed page.
Level 3: Spots appear, but disappear by the 50th printed page.
Level 4: Spots caused by jetting do not disappear even when 50 or more sheets are printed.

Example 1 to Example 2, Reference Example 3, Example 4, Reference Example 5, Example 6 to Example 7, Reference Example 8, Example 9 to Example 11, Reference Example 12, Example 13, Reference Example Tables 1 and 2 show the measurement results and evaluation results of toners for developing electrostatic charge images of 14 to Reference Example 15, Example 16, and Comparative Examples 1 to 5 together with the composition of external additives and external addition conditions. Show.
In Table 2 below, the leakage of toners of Comparative Example 2 and Comparative Example 4 was not evaluated because the durability of the toner was too bad.

3. Toner Evaluation Hereinafter, with reference to Tables 1 and 2, the evaluation results of the toner for developing an electrostatic image will be examined.
From Table 2, the toner of Comparative Example 1 is a toner having a compression index CI of 3.27. From Table 2, the toner of Comparative Example 1 has a continuous printing number exceeding 15,000 in the printing durability test. Therefore, the toner of Comparative Example 1 shows no problem in at least printing durability.
However, the toner of Comparative Example 1 has a toner leakage evaluation of level 3, and the ejection evaluation after being left at high temperature is level 4. Therefore, it can be seen that the toner of Comparative Example 1 having a compression index CI exceeding 3.2 causes a small amount of toner leakage with a relatively small number of printed sheets, and the spots due to ejection are difficult to disappear.

From Table 2, the toner of Comparative Example 2 is a toner having a compression index CI of 1.41. From Table 2, the toner of Comparative Example 2 has a level 0 evaluation of ejection after being left at high temperature. Therefore, the toner of Comparative Example 2 does not have a problem of ejection after being left at a high temperature when the number of printed sheets is relatively small.
However, as described above, the toner of Comparative Example 2 having a compression index CI of less than 1.5 is too poor in the durability of the toner, and the number of continuous prints in the print durability test remains at 5,000. The number of continuously printed sheets is as follows: Example 1 to Example 2, Reference Example 3, Example 4, Reference Example 5, Example 6 to Example 7, Reference Example 8, Example 9 to Example 11, Reference Example 12, Among Example 13, Reference Example 14 to Reference Example 15, Example 16, and Comparative Examples 1 to 5, there are few.

From Table 2, the toner of Comparative Example 3 is a toner having a compression index CI of 3.29. From Table 2, the toner of Comparative Example 3 has a continuous printing number exceeding 15,000 in the printing durability test. Therefore, the toner of Comparative Example 3 has no problem in at least printing durability.
However, in the toner of Comparative Example 3, both the toner leakage evaluation and the ejection evaluation after being left at high temperature are level 3. Therefore, it can be seen that the toner of Comparative Example 3 having the compression index CI exceeding 3.2 causes a small amount of toner leakage with a relatively small number of printed sheets, and the spots due to the ejection remain relatively long.

From Table 2, the toner of Comparative Example 4 is a toner having a compression index CI of 1.39. From Table 2, the toner of Comparative Example 4 has a level 0 evaluation of ejection after being left at high temperature. Therefore, the toner of Comparative Example 4 does not have a problem of ejection after being left at a high temperature when the number of printed sheets is relatively small.
However, as described above, the toner of Comparative Example 4 having a compression index CI of less than 1.5 has too poor toner durability, and the number of continuous prints in the print durability test remains at 6,000.

From Table 2, the toner of Comparative Example 5 is a toner having a compression index CI of 3.29. From Table 2, the toner of Comparative Example 5 has a continuous printing number of 14,000 in the printing durability test. Therefore, the toner of Comparative Example 5 has no problem in at least printing durability.
However, in the toner of Comparative Example 5, both the toner leakage evaluation and the ejection evaluation after being left at high temperature are level 3. Therefore, it can be seen that the toner of Comparative Example 5 having the compression index CI exceeding 3.2 causes a small amount of toner leakage with a relatively small number of printed sheets, and the spots due to the ejection remain relatively long.

On the other hand, from Table 1 and Table 2, Examples 1 to 2, Reference Example 3, Example 4, Reference Example 5, Example 6 to Example 7, Reference Example 8, Example 9 to Example 11, Reference The toners of Example 12, Example 13, Reference Example 14 to Reference Example 15 and Example 16 are toners having a compression index CI in the range of 1.5 to 3.2. From Table 1 and Table 2, these toners, both ejected after the toner leakage evaluation and high-temperature storage evaluation remaining within the scope of the levels 0 to 2, and 10,000-sheet continuous printing sheets in the print durability test That's it.
Therefore, these toners having a compression index CI in the range of 1.5 to 3.2 are excellent in printing durability, and the occurrence of toner leakage and the ejection of toner after being left under high temperature conditions. It can be seen that the amount of toner is extremely small.

Hereinafter, the influence of the external additive conditions on the compression index CI and the toner characteristics will be examined.
First, Example 1 (the number of revolutions: 4,000 rpm) and Example 2 (the number of revolutions: 3,000 rpm) which are different only in the condition of the number of revolutions of the stirring blade are compared. The compression index CI of Example 1 is smaller than the compression index CI of Example 2, and the toner leakage evaluation of Example 1 is better than the toner leakage evaluation of Example 2. From these results, it is surmised that by increasing the rotation speed of the stirring blade, the compression index CI is lowered, the toner fluidity is increased, and the possibility of toner leakage can be reduced by the proper circulation of the toner.

Next, Example 1 (external addition treatment time: 5.0 minutes), only Reference Example 3 (external addition treatment time: 2.5 minutes), and Example 4 (external addition treatment time: different in only the external treatment time) 25 minutes). The external treatment time is longer in the order of Example 4, Example 1, and Reference Example 3. Further, the compression index CI is smaller in the order of Example 4, Example 1, and Reference Example 3. Among these toners, the reference example 3 is a little worse in the toner leakage evaluation, and the example 4 is a little inferior in durability. From these results, it is estimated that as the external addition processing time is extended, the compression index CI decreases and the toner fluidity increases, and the possibility of toner leakage can be reduced by proper circulation of the toner, but the durability is slightly inferior. The Further, from these results, it is estimated that as the external addition processing time is shortened, the compression index CI is increased and the durability is improved, but the fluidity is lowered, so that there is a possibility of toner leakage.

  As for the external addition conditions of the toner, Example 1 (rotation speed of stirring blade: 4,000 rpm, external addition treatment time: 5.0 minutes) and Comparative Example 1 (rotation speed of stirring blade: 2,500 rpm, external addition) In comparison example 1, the rotation speed of the stirring blade is too small and the external treatment time is too short. Therefore, the toner of Comparative Example 1 is considered to cause problems of toner leakage and ejection after being left at a high temperature as a result of the compression index CI becoming too high and the toner fluidity becoming poor.

Hereinafter, the influence of the composition of the external additive of the toner on the compression index CI and the toner characteristics will be examined.
First, Example 1 (addition amount: 1.0 part), Reference Example 5 (addition amount: 0 part), Example 6 (addition amount: 0.5 part), which differ only in the condition of the addition amount of the inorganic fine particles A, And Example 7 (addition amount: 2.0 parts) is compared. The addition amount of the inorganic fine particles A is smaller in the order of Reference Example 5, Example 6, Example 1, and Example 7. Further, the compression index CI is smaller in the order of Reference Example 5, Example 6, Example 1, and Example 7. Of these toners, the toner leakage evaluation and the jetting evaluation after being left at high temperature are slightly bad in Example 7, and the reference examples 5 and 6 are slightly inferior in durability. From these results, the smaller the amount of inorganic fine particles A added, the lower the compression index CI and the higher the fluidity of the toner, and the possibility of toner leakage can be reduced by the proper circulation of the toner, but the durability is somewhat inferior. Guessed. Further, from these results, it is presumed that as the amount of the inorganic fine particles A added is increased, the compression index CI is increased and the durability is improved, but the fluidity is lowered, so that there is a possibility of toner leakage and toner ejection.

Next, Example 1 (addition amount: 1.0 part), Example 11 (addition amount: 1.5 parts), and Reference Example 12 (addition amount: 0 parts) differing only in the condition of the addition amount of the inorganic fine particles B. ). The addition amount of the inorganic fine particles B is smaller in the order of Reference Example 12, Example 1, and Example 11. Further, the compression index CI is smaller in the order of Reference Example 12, Example 1, and Example 11. Of these toners, the evaluation of ejection after being left at high temperature is slightly worse in Example 11, and the reference example 12 is slightly inferior in durability. From these results, the smaller the amount of inorganic fine particles B added, the lower the compression index CI and the toner fluidity, and the possibility of toner leakage can be reduced by the proper circulation of the toner, but the durability is slightly inferior. Guessed. From these results, it is presumed that as the amount of the inorganic fine particles B added is increased, the compression index CI is increased and the durability is improved.

  In addition, about the conditions of the addition amount of inorganic fine particles A and B, Example 1 (addition amount of inorganic fine particles A: 1.0 part, addition amount of inorganic fine particles B: 0.8 part) and Comparative Example 2 (inorganic fine particles A) The amount of inorganic fine particles A and B added to Comparative Example 2 is smaller than that of Example 1 in comparison with Example 1. Therefore, the toner of Comparative Example 2 is considered to have a particularly poor printing durability as a result of the compression index CI being too low.

Subsequently, Example 1 (addition amount: 0.2 part), Example 13 (addition amount: 0.1 part), Reference Example 15 (addition amount: 0 part) differing only in the condition of the addition amount of the inorganic fine particles C. And Example 16 (added amount: 2.5 parts). The addition amount of the inorganic fine particles C is smaller in the order of Reference Example 15, Example 13, Example 1, and Example 16. Further, the compression index CI is smaller in the order of the example 16, the example 1, the example 13, and the reference example 15. Among these toners, Example 13 and Reference Example 15 are slightly bad with respect to toner leakage evaluation, and Examples 13, Reference Example 15 and Example 16 are slightly bad with respect to ejection evaluation after being left at high temperature. From these results, it is presumed that the compression index CI decreases as the amount of the inorganic fine particles C added increases. From these results, it is presumed that the smaller the amount of inorganic fine particles C added, the higher the compression index CI and the better the durability, but the lower the fluidity, so there is a risk of toner leakage.

  In addition, about the conditions of the addition amount of inorganic fine particles A and C, Example 1 (addition amount of inorganic fine particles A: 1.0 part, addition amount of inorganic fine particles C: 0.2 part) and Comparative Example 3 (inorganic fine particles A) In Comparative Example 3, the amount of inorganic fine particles A added is larger than that of Example 1, while the amount of inorganic fine particles C added is 3.0 parts. Few. Therefore, it is considered that the toner of Comparative Example 3 has problems of toner leakage and ejection after being left at a high temperature as a result of the compression index CI being excessively increased and the toner fluidity being poor.

In addition, regarding the conditions of the addition amount of the inorganic fine particles B and C, Example 1 (addition amount of the inorganic fine particles B: 0.8 part, addition amount of the inorganic fine particles C: 0.2 part) and Reference Example 14 (inorganic fine particles B) In Comparative Example 14, the amount of inorganic fine particles C added is smaller than that of Example 1, while the amount of inorganic fine particles C added is less than that of Example 1. Many. Therefore, in the toner of Reference Example 14, the compression index CI is smaller than that of Example 1, so that the fluidity of the toner is improved and the possibility of toner leakage can be reduced by appropriate circulation of the toner. Slightly inferior in durability.

Next, Example 1 (addition amount: 0.1 part), Reference Example 8 (addition amount: 0 part), Example 9 (addition amount: 0.2 part) differing only in the condition of the addition amount of the inorganic fine particles D , And Example 10 (addition amount: 0.8 part). The addition amount of the inorganic fine particles D is in the order of Reference Example 8, Example 1, Example 9, and Example 10. Further, the compression index CI is smaller in the order of Reference Example 8, Example 1, Example 9, and Example 10. Among these toners, the toner leakage evaluation and the ejection evaluation after being left at high temperature are a little worse in Example 9 and Example 10, and the reference example 8 is slightly inferior in durability. From these results, the smaller the amount of inorganic fine particles D added, the lower the compression index CI and the toner fluidity, and the possibility of toner leakage can be reduced by proper circulation of the toner, but the durability is somewhat inferior. Guessed. From these results, it is presumed that as the amount of the inorganic fine particles D added is increased, the compression index CI is increased and the durability is improved.

  In addition, about the conditions of the addition amount of inorganic fine particles C and D, Example 1 (addition amount of inorganic fine particles C: 0.2 part, addition amount of inorganic fine particles D: 0.1 part) and Comparative Example 5 (inorganic fine particle C) In Comparative Example 5, the amount of inorganic fine particles C added is smaller than that of Example 1, while the amount of inorganic fine particles D added is small. Many. Therefore, the toner of Comparative Example 5 is considered to cause problems of toner leakage and ejection after being left at a high temperature as a result of the compression index CI being excessively increased and the toner fluidity being poor.

  Further, comparing Example 1 and Comparative Example 4 in which the additive amount of the external additive is different from all four types, Comparative Example 4 has a smaller amount of inorganic fine particles A, B, and D than Example 1, while inorganic fine particles A large amount of C is added. Therefore, the toner of Comparative Example 4 is considered to have a particularly poor printing durability as a result of the compression index CI being too low.

Claims (3)

An electrostatic charge containing colored resin particles containing a binder resin and a colorant, and an external additive (excluding resin-coated inorganic fine particles coated with 5 to 50 parts by mass of a polar group-containing copolymer resin). In the method for producing a developing toner,
A step of performing external addition treatment by mixing and stirring colored resin particles produced by a wet method together with an external additive;
The conditions for the external addition treatment are conditions in which a stirring device having a capacity of 1 to 50 L is used, the rotational speed of the stirring blade is 3,000 to 10,000 rpm, and the external addition treatment time is 3 minutes to 1 hour,
As the external additive,
Inorganic fine particles A having a number average primary particle size of 36 to 100 nm,
Inorganic fine particles B having a number average primary particle size of 15 to 35 nm,
Inorganic fine particles C having a number average primary particle size of 6 to 14 nm, and
Using fatty acid zinc particles having a number average primary particle size of 0.3 to 2.0 μm, and
In the electrostatic charge developing toner, compression obtained by a compression test using the powder flowability analyzer with respect to a basic fluidity energy (BFE) value obtained by a stability test using the powder flowability analyzer. A method for producing a toner for developing an electrostatic charge image, wherein a value of a compression index CI (EAC / BFE), which is a ratio of a value of post-total energy (EAC), is 1.5 to 3.2. For 100 parts by mass of the colored resin particles ,
0.1-2.5 parts by mass of the inorganic fine particles A,
0.1 to 2.0 parts by mass of the inorganic fine particles B,
0.05 to 2.0 parts by mass of the inorganic fine particles C, and
The method of producing an electrostatic charge image developing toner according to claim 1, characterized in Rukoto using 0.05 to 2.0 parts by weight of the fatty acid zinc particles. In the stability test, the value of the basic fluidity energy (BFE) penetrates the blade of the powder fluidity analyzer into the powder layer of the electrostatic charge image developing toner at a tip speed of 100 mm / second. And the total of the rotational torque and vertical load generated by the blade moving in the powder layer,
The value of the total energy after compression (EAC) is the tip of the blade included in the powder fluidity analyzer in the compression test in the compressed powder layer of the electrostatic charge image developing toner after being pressurized at 10 kPa. 3. The electrostatic charge image according to claim 1 , wherein the electrostatic charge image is a sum of rotational torque and vertical load generated by moving the blade through the compressed powder layer at a speed of 100 mm / sec. A method for producing a developing toner.