JP2009276512A - Method for manufacturing toner for development of electrostatic charge image - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new method for manufacturing a toner excellent in image stability, blocking property, and fixability. <P>SOLUTION: The method for manufacturing a toner includes: a step for aggregating a mixture containing a resin particle dispersion liquid, a coloring particle dispersion liquid, and a release agent particle dispersion liquid to form flocculated particles; and a step for heating and fusing the aggregated particles. The release agent particle dispersion liquid in which release agent particles are dispersed is acquired by a manufacturing method including a dispersion step for acquiring an O/W emulsion by dispersing the release agent on a dispersion device having shear force while heating a release agent mixture containing at least a release agent, a surfactant, and an aquatic medium to a temperature higher than the melting point of the release agent, and a cooling step for cooling the acquired O/W emulsion to the temperature lower than the melting point of the release agent. The 50% particle size on a volumetric basis of the release agent particle in the release agent particle dispersion liquid is 0.05 μm-0.40 μm, and the content of the release agent particle of 0.80 μm or more is one volumetric percent or less. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for efficiently producing a toner for developing an electrostatic charge image that is suitably used for image formation by electrophotography.

  A method of visualizing image information through an electrostatic charge image, such as electrophotography, is currently widely used in various fields. In electrophotography, an electrostatic charge image is formed on a photoreceptor through a charging process, an exposure process, etc., and the electrostatic charge image is developed using a developer containing toner, followed by a transfer process, a fixing process, and the like. The charge image is visualized. In the toner, it is desirable that the particle shape and the surface structure are intentionally controlled from the viewpoint of developability, transferability, cleaning property, and the like.

  In recent years, an emulsion polymerization aggregation method has been proposed as a method for intentionally controlling the particle shape and surface structure of a toner. The emulsion polymerization agglomeration method corresponds to the toner particle size by preparing a resin particle dispersion by emulsion polymerization, creating a colorant particle dispersion in which a colorant is dispersed in a solvent, and mixing them. It is a method comprising an aggregating step for forming aggregated particles and a fusion step for fusing the aggregated particles by heating. According to this emulsion polymerization aggregation method, the toner shape can be arbitrarily controlled from an indeterminate shape to a spherical shape by selecting the heating temperature condition. Further, it is possible to easily add the release agent into the toner by adding a release agent particle dispersion such as wax in the mixing step (Patent Documents 1 and 2).

However, when a release agent is internally added in the emulsion polymerization aggregation method, if the particle size of the release agent is too small, the effect of improving the fixing property is reduced. The powder properties tend to deteriorate. If it is larger, there is a problem that the release agent particles are not included in the aggregated particles in the aggregation process, or the release agent particles fall off in the fusion process. A method of adding a dispersion liquid having a thickness of 0.0 μm has been proposed. (Patent Document 3).
However, when trying to disperse a substance such as a release agent in water, the final particle size when using a conventional high-speed stirring type disperser such as a sand gland mill or rotor stator is several microns. It was difficult to atomize the release agent.

In addition, in the method for producing toner particles by the suspension polymerization method, a release agent is sufficiently small and has a uniform particle size in the polymerizable monomer using a high-speed stirring type emulsifying disperser having high shearing force. A method of fine dispersion has been proposed (Patent Document 4).
However, it is difficult to disperse the release agent in water by this method because of the dispersion of the release agent in the polymerizable monomer and the dispersion by heating below the melting point of the release agent.

On the other hand, in order to improve color developability, OHP permeability, fixability, etc. in color toners, the release agent particle dispersion is emulsified using an emulsification disperser classified as a high-pressure discharge type, thereby releasing the release agent particles. A method has been proposed in which the dispersion diameter is controlled to 0.05 μm or more and 0.4 μm or less, and coarse particles of 0.8 μm or more are controlled to 5% or less (Patent Document 5).
JP-A-63-282749 JP-A-6-250439 JP-A-5-11501 JP 2006-221023 A Japanese Patent Laid-Open No. 11-2922

In recent years, the demand for low-temperature fixing has increased, and the release agent used has also shifted to a low melting point release agent. However, the liquid specific gravity of the release agent generally tends to decrease as the melting point decreases. It has been known.
However, when dispersing a release agent having a low liquid specific gravity, the method proposed in Japanese Patent Application Laid-Open No. 11-2922 has few coarse particles, and it may be difficult to finely disperse the release agent uniformly.
Further, the presence of a few coarse particles of the release agent not only adversely affects the particle size distribution of the toner particles, but also causes deterioration in image characteristics, and is easy to reaggregate. Storage stability deteriorates.

  An object of the present invention is to provide a method for producing an electrostatic charge image developing toner (hereinafter also simply referred to as a toner) that solves the above-described problems. That is, an object of the present invention is to uniformly disperse a low-melting-point release agent having a low liquid specific gravity in water, and a 50% particle size based on volume distribution of the obtained release agent particles is 0.05 μm to 0.40 μm. To provide a new toner production method in which a release agent particle dispersion liquid in which coarse particles are further reduced is prepared, and the release agent is finely and uniformly contained in the toner particles. . Furthermore, an object of the present invention is to provide a new method for producing a toner excellent in image stability, blocking property and fixing property.

  As a result of intensive studies to solve the above problems, the present inventors have found that, according to the following method, the above-mentioned coarse particles are small, and the low melting point release agent is obtained by uniformly finely dispersing the release agent. Has been found to be uniformly encapsulated in the toner particles. That is, the gist of the present invention is as follows.

<1> A liquid mixture including a resin particle dispersion in which resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a release agent particle dispersion in which release agent particles are dispersed is prepared. A step comprising agglomerating at least resin particles, colorant particles, and release agent particles contained in the prepared mixed liquid to form aggregated particles, and heating and aggregating the aggregated particles. A method for producing a toner for developing a charge image, wherein a release agent particle dispersion in which release agent particles are dispersed is a release agent mixed solution containing at least a release agent, a surfactant, and an aqueous medium. The dispersion step of dispersing the release agent in a dispersing device having shearing force while heating to above the melting point of the release agent to obtain an O / W emulsion, and the obtained O / W emulsion to the release agent It was obtained by a manufacturing method including a cooling step for cooling to below the melting point. The dispersing device has at least a stirring blade that rotates and a screen that rotates around the stirring blade in a direction opposite to the stirring blade, a container in which the stirring device is installed, and a release agent mixture for the container Is a dispersion apparatus having at least a circulation means for circulating introduction and discharge repeatedly, and the dispersion step uses a stirring means of the dispersion apparatus to cause the release agent mixture liquid to have a velocity gradient of 110000 sec ⁻¹ or more and 200000 sec ⁻¹ or less. And a step of dispersing the release agent by circulating the release shearing mixture using the circulation means of the dispersing device, and dispersing the release agent particles in the release agent particle dispersion liquid. One release agent particle having a volume distribution standard 50% particle size measured by a diffraction / scattering particle size distribution analyzer of 0.05 μm or more and 0.40 μm or less and 0.80 μm or more Method for producing a toner, wherein the% or less.

<2> The method for producing a toner according to <1>, wherein in the cooling step, the O / W emulsion is cooled to a temperature lower than the melting point of the release agent at a cooling rate of 5 ° C./min or more.

<3> In the above cooling step, the O / W emulsion is 20
The toner according to <1> or <2>, wherein the toner is subjected to rotational shear stirring at a speed gradient of 000 sec ⁻¹ or less, and the O / W emulsion is circulated and cooled using a circulation unit of a dispersion device. Production method.

<4> In the cooling step, using a cooling device having at least a stirring means having a stirring blade and a container provided with the stirring means, cooling to below the melting point of the release agent while stirring with the stirring blade. <1> or <2>, wherein the toner production method is characterized.

<5> The toner production method according to any one of <1> to <4>, wherein the release agent has a melting point of 40 ° C. or higher and 120 ° C. or lower.

<6> The method for producing a toner according to any one of <1> to <5>, wherein the liquid density at the melting point of the release agent is 0.70 g / cm ³ or more and 0.95 g / cm ³ or less. .

<7> The method for producing a toner according to any one of <1> to <6>, wherein the release agent is a higher aliphatic alcohol.

  According to the present invention, a release agent can be easily finely dispersed in water, and in particular, a release agent having a low liquid specific gravity can be uniformly finely dispersed with few coarse particles. Therefore, according to the present invention, it is possible to provide a toner in which a desired release agent is finely and uniformly encapsulated and excellent in image stability, blocking property and fixing property.

The toner production method of the present invention includes a resin particle dispersion in which resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a release agent particle dispersion in which release agent particles are dispersed. A step of preparing a mixed liquid, a step of aggregating at least the resin particles, the colorant particles, and the release agent particles contained in the prepared mixed liquid to form aggregate particles, and heating the aggregate particles. A method for producing an electrostatic charge image developing toner comprising a fusing step,
The release agent particle dispersion in which the release agent particles are dispersed is obtained by heating a release agent mixed solution containing at least a release agent, a surfactant, and an aqueous medium to a temperature equal to or higher than the melting point of the release agent. However, a dispersion step of dispersing the release agent in a dispersing device having a shearing force to obtain an O / W (also referred to as oil-in-water) emulsion, and the obtained O / W emulsion with the melting point of the release agent Obtained by a production method including a cooling step of cooling to less than
The dispersing device includes at least a stirring blade that rotates and a screen that rotates around the stirring blade in a direction opposite to the stirring blade, a container in which the stirring device is installed, and the separation with respect to the container. A dispersing device having at least a circulating means for circulating the mold mixture liquid repeatedly by introducing and discharging;
In the dispersion step, the release agent mixed solution is rotationally sheared and stirred at a speed gradient of 110000 sec ⁻¹ or more and 200000 sec ⁻¹ or less using the stirring means of the dispersion apparatus, and the circulation means of the dispersion apparatus is used to Circulating the release agent mixture to disperse the release agent,
The 50% particle size of the volume distribution standard of the release agent particles in the release agent particle dispersion measured with a laser diffraction / scattering particle size distribution measuring device is 0.05 μm or more and 0.40 μm or less, and The release agent particles of 0.80 μm or more are 1% by volume or less.

<Releasing agent used in the present invention>
The release agent used in the present invention is not particularly limited. For example, polyolefins such as polyethylene, silicones having a melting point (softening point) by heating, oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide Fatty acid amides such as stearyl stearate, behenyl behenate wax, carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil and other plant waxes, beeswax animal waxes, montan wax, ozokerite, Minerals such as ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, ester wax, petroleum-based wax, higher fatty acids such as stearic acid and behenic acid, stearyl alcohol,
Examples thereof include higher aliphatic alcohols such as behenyl alcohol, and modified products such as these graft compounds and derivatives such as block compounds.
Of these, higher aliphatic alcohols are more preferred from the viewpoint of low-temperature fixability as the release agent used in the present invention.

  The melting point of the release agent used in the present invention is preferably from room temperature to 150 ° C. from the viewpoint of toner blocking resistance, multi-sheet durability, low-temperature fixability, and offset resistance, and is from 40 ° C. to 120 ° C. Those are more preferred.

The release agent used in the present invention preferably has a liquid density at the melting point of the release agent of 0.70 g / cm ³ or more and 0.95 g / cm ³ or less from the viewpoint of low-temperature fixability, and 0.70 g. It is more preferable that it is not less than / cm ^{3 and not} more than 0.85 g / cm ³ .
The melting point indicates a main endothermic peak temperature in a DSC curve measured according to ASTM D3418-82. Specifically, the measurement temperature range is 30 to 200 ° C., the temperature increase rate is 10 ° C./min, and the temperature is increased to 30 to 20 by the second temperature increase process in a normal temperature and humidity environment.
The DSC curve is obtained in the range of 0 ° C., and is the value of the main endothermic peak temperature in the obtained DSC curve.
The release agent is preferably used in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the resin constituting the toner.

The 50% particle size on the basis of volume distribution measured by a laser diffraction / scattering particle size distribution measuring device of the release agent particles in the release agent particle dispersion obtained using the release agent is 0.05 μm. The amount of the release agent is 0.40 μm or less and 0.80 μm or more in an amount of 1% by volume or less. Preferably, the 50% particle size based on volume distribution is 0.07 μm or more and 0.30 μm or less, and the release agent of 0.80 μm or more is 0.1% by volume or less.
When the amount of the release agent of 0.80 μm or more exceeds 1% by volume, the coarse particles serve as nuclei and are liable to re-aggregate, so that the storage stability of the release agent particle dispersion is lowered, which is not preferable. Further, when the 50% particle size based on the volume distribution exceeds 0.40 μm, the release agent is easily exposed on the toner surface, which is not preferable from the viewpoint of blocking and the like.
The presence state of the 50% particle size based on the volume distribution and the release agent of 0.80 μm or more can be adjusted to the above range by controlling the velocity gradient using the stirring means of the dispersing device. is there.

<Surfactant used in the present invention>
In the present invention, a surfactant can be used to finely disperse the release agent in water. Specifically, anionic surfactants such as sulfate ester type, sulfonate type, phosphate ester type and soap type; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol type, alkylphenol Nonionic surfactants such as ethylene oxide adducts and polyhydric alcohols can be used. The said surfactant may be used individually by 1 type, and may use 2 or more types together. The concentration of the surfactant in the aqueous medium is preferably about 0.1 to 5% by mass.

<Method for Preparing Release Agent Particle Dispersion in the Present Invention>
In the present invention, the release agent particle dispersion in which the release agent particles are dispersed is such that the release agent mixed solution containing at least the release agent, the surfactant, and the aqueous medium exceeds the melting point of the release agent. Dispersing step of dispersing release agent in a dispersing device having shearing force while heating to obtain O / W emulsion, and cooling step of cooling the obtained O / W emulsion to below the melting point of the releasing agent It was obtained by the manufacturing method containing.
In addition, the said aqueous medium means the medium which has water as the main component. Specific examples of the aqueous medium include water itself, water added with a pH adjusting agent, and water added with an organic solvent.

<Dispersing step of release agent particle dispersion>
In the dispersion step, a release agent mixture containing at least a release agent, a surfactant, and an aqueous medium is heated to a temperature equal to or higher than the melting point of the release agent to bring the release agent into a liquid state, A two-phase system of oil phase is formed. At this time, an endotherm due to melting of the mold release agent occurs. Therefore, in order to completely melt the mold release agent, it is preferable to heat at a temperature of the melting point of 5 ° C. or higher. Furthermore, after that, by using a dispersing device having a shearing force, a fine O / W emulsion is formed, whereby dispersion in an aqueous medium becomes possible.

<Dispersing device for release agent particle dispersion>
The dispersing device for the release agent particle dispersion preferably used in the present invention will be described below, but is not limited thereto.
FIG. 1 shows a schematic view of a dispersing device for a release agent particle dispersion liquid equipped with a mixing vessel 11 with a jacket, stirring means (rotating shear stirring apparatus with jacket 12) and circulating means (circulation pump 13).
Further, FIG. 2 shows a detailed view of the shearing stirring part of the jacketed rotary shearing stirring device 12.
The mixture of the release agent, water, and surfactant heated in the jacketed mixing vessel 11 passes through the circulation pump 13 to the shear stirring portion (FIG. 2) of the jacketed rotary shear stirring device 12. Subjected to shear. Here, in the shear stirring portion, the stirring blade (rotor) 21 in FIG. 2 rotates, and the screen 22 disposed outside the rotor 21 rotates in the direction opposite to the rotor 21, In the clearance 31, which is a minute gap between the screens 22, sheared and dissolved release agent is dispersed as minute droplets, that is, forms a fine O / W emulsion.

Since the screen 22 rotates in the direction opposite to the rotation direction of the rotor 21, the relative rotational speed of both can be increased, and the shearing force applied to the release agent particle dispersion can be increased. Thereby, since a mold release agent can form a fine droplet more than before, it can form a fine O / W emulsion.
In the above rotary shear stirring device, the sum of the peripheral speed of the rotating rotor and the peripheral speed of the screen is expressed as x.
If the clearance between the rotor and the screen is y mm, the velocity gradient can be expressed by x / y × 1000 sec ⁻¹ .
In the present invention, the release agent mixed solution is rotationally sheared and stirred at a speed gradient of 110000 sec ⁻¹ or more and 200000 sec ⁻¹ or less using the rotating shear stirrer.
In particular, the velocity gradient, the outer diameter of the rotor, preferably 150000Sec ^-1 or more 200000Sec ^-1 or less in 10cm below the range of 1 cm, the outer diameter of the rotor, 110000Sec ^-1 or more in 50cm below the range of 10cm It is preferably 150,000 sec ⁻¹ or less. If the velocity gradient is too small, mixing and fine dispersion of the two liquids of the release agent and water are insufficient, and coarse aggregated particles are likely to be generated.
Here, the unit of the peripheral speed is m / sec, which is a value represented by the following equation.
(Formula) peripheral speed (m / sec) = rotor outer diameter (cm) / 100 × rotor rotational speed (rpm) /
60 × π.

Further, the release agent mixed solution is rotationally sheared and stirred at a specific speed gradient as described above, and circulation is repeated using a circulation means (circulation pump 13) to disperse the release agent. By repeating the circulation between the jacketed mixing vessel 11 and the jacketed shear stirring device 12, the up and down flow is promoted in the vessel, and even in a release agent having a small liquid specific gravity, the release agent is uniformly and efficiently. Can be dispersed.
The rotary shear stirring device is not particularly limited as long as the specific velocity gradient can be achieved. For example, Claremix W-Motion (manufactured by M Technique) can be preferably used.

<Cooling step of release agent particle dispersion>
In the present invention, the cooling step of the release agent particle dispersion is a step of cooling the O / W emulsion obtained in the dispersion step to below the melting point of the release agent.
The apparatus used for the cooling step may be cooled using the dispersing apparatus, or may be cooled with stirring after being transferred to a cooling apparatus different from the dispersing apparatus. Moreover, it may cool continuously while extracting the O / W emulsion, or may be cooled in a batch manner.

In the cooling step of the release agent particle dispersion, the cooling rate during cooling is less than the melting point of the release agent at a cooling rate of 5 ° C./min or more, more preferably 8 ° C./min or more for the O / W emulsion. More preferably, it is preferable to cool to a temperature lower than 10 ° C. lower than the melting point of the release agent, more preferably to a temperature lower than 30 ° C. lower than the melting point of the release agent. When cooled at a cooling rate of less than 5 ° C./min, the release agent may be cooled in a non-uniform dispersion state. This causes the generation of coarse particles, the release agent particles tend to reaggregate, and the coarse particles tend to increase with time. Therefore, toner particles produced using a release agent particle dispersion that has changed over time are likely to cause deterioration in particle size distribution, image stability, and blocking. Moreover, it is preferable that the upper limit of a cooling rate is an economically useful range.
Furthermore, it is desirable that excessive shearing force is not applied to the release agent particles during cooling. This may cause deformation of the release agent particles due to excessive shearing to the release agent particles and increase in the specific surface area, and the release agent particles are likely to re-aggregate, and coarse particles may increase with time.
However, if the minimum required flow state is not secured in the O / W emulsion, the fine droplets of the release agent formed in the dispersion process coalesce, causing liquid-liquid two-phase separation, and releasing agent particle dispersion It tends to be difficult to obtain a liquid. Therefore, until it cools below the melting point of the release agent, O /
It is preferable to ensure a fluid state necessary for stabilizing the W emulsion.

When cooling using the above dispersing device, the speed of the rotary shearing stirrer is sufficient to ensure the flow state necessary to stabilize the O / W emulsion without applying excessive shearing force to the release agent particles. The gradient is preferably 20000 sec ⁻¹ or less (more preferably 10000 sec ⁻¹ or less) and is cooled to below the melting point of the release agent. Furthermore, in the cooling step, it is more preferable to appropriately apply a speed gradient of the rotary shear stirring device corresponding to the circulation state of the stirring means, and the circulation state is appropriate and the necessary flow state is ensured. The rotary shear stirring device may be stopped.

In the cooling step, it is also a preferable aspect to cool to below the melting point of the release agent by using a stirring device having a stirring blade and a cooling device having at least a container provided with the stirring device.
In the case of cooling with stirring after transferring to a cooling device different from the above dispersing device, it is necessary to stabilize the O / W emulsion in order to easily obtain a uniform and stable release agent particle dispersion. In order to ensure the flow state necessary for the stabilization, it is more preferable to provide an appropriate peripheral edge speed corresponding to the cooling device. If the stirring is stopped, the fine droplets of the release agent formed in the dispersion step coalesce, causing liquid-liquid two-phase separation, and it may be difficult to easily obtain the release agent particle dispersion. is there.
Moreover, also about the case where it cools continuously, extracting O / W emulsion, it is preferable to ensure a fluid state required in order to stabilize O / W emulsion.

<Method for Producing Toner of the Present Invention>
Next, a method for producing the toner of the present invention will be described.
The toner production method of the present invention includes a resin particle dispersion in which resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a release agent particle dispersion in which release agent particles are dispersed. A step of preparing a mixed solution, a step of aggregating at least the resin particles, the colorant particles, and the release agent particles contained in the prepared mixed solution to form aggregate particles, and heating the aggregate particles for fusion Including the step of:
In the toner manufacturing method of the present invention, it is possible to further add a charge control particle dispersion liquid in which charge control particles are dispersed in the step of preparing the mixed liquid.

The resin used in the resin particle dispersion is not particularly limited as long as it is a resin suitable for a toner having the following characteristics.
As the resin, a resin having a hydroxyl group, a carboxyl group, a sulfate ester group, or the like at a molecular end, a side chain, or the like is preferable. Examples of such resins include styrenes such as styrene, parachlorostyrene, and α-methylstyrene, methyl acrylate, ethyl acrylate, n-propyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, Vinyl group monomers such as ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, acrylonitrile and methacrylonitrile, vinyl ether monomers such as vinyl methyl ether and vinyl isobutyl ether, vinyl methyl ketone, vinyl It is obtained by combining a vinyl ketone monomer such as ethyl ketone and vinyl isopropenyl ketone and a polyolefin monomer such as ethylene, propylene and butadiene, or a combination of two or more thereof. Copolymers or mixtures thereof. In addition, epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, etc., non-vinyl condensation resins, or a mixture of these with the above vinyl resins or vinyl monomers in the presence of these resins The graft polymer obtained when superposing | polymerizing can be mentioned. These resins may be used alone or in combination of two or more.

Moreover, it does not specifically limit as a preparation method of the resin particle dispersion liquid in which the resin particle was disperse | distributed, A well-known method can be used.
For example, the monomer constituting the resin is dispersed in an aqueous medium in the presence of a surfactant, a water-soluble polymerization initiator such as potassium persulfate is added, and emulsion polymerization is performed to obtain resin particles. It is possible to prepare a dispersed resin particle dispersion. The mass ratio of the monomer constituting the resin to the aqueous medium is preferably 0.1 or more and 1.0 or less.
In addition, the glass transition temperature (Tg) of resin mentioned later is a physical-property value measured based on JISK7121, and means the midpoint glass transition temperature described in this specification.

Preferred examples of the colorant used in the present invention include the following organic pigments or dyes.
As the cyan organic pigment or organic dye, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. Specifically, C.I. I. Pigment blue 1, C.I. I. Pigment blue 7, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. And CI Pigment Blue 66.

Examples of magenta organic pigments or organic dyes include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds, and the like. Specifically, C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment violet 19, C.I. I. Pigment red 23, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 166, C.I. I. Pigment red 169, C.I. I. Pigment red 177, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. And CI Pigment Red 254.

  As the yellow organic pigment or organic dye, compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, allylamide compounds, and the like are used. Specifically, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 176, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 181, C.I. I. Pigment yellow 191, C.I. I. And CI Pigment Yellow 194.

  As the black colorant, carbon black, or a color toned to black using the yellow, magenta and cyan colorants can be used.

These colorants can be used alone or in combination, and further in a solid solution state.
These colorants are selected from the viewpoints of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in toner.
The colorant is used by adding 1 to 20 parts by mass with respect to 100 parts by mass of the resin.
Moreover, it does not specifically limit as a preparation method of the coloring agent particle dispersion liquid in which coloring agent particles were disperse | distributed, A well-known method can be used.
For example, it is possible to prepare a colorant particle dispersion in which the colorant particles are dispersed by dispersing the colorant in an aqueous medium using a disperser such as a homogenizer in the presence of a surfactant.

The charge control agent for obtaining a charge control particle dispersion in which the charge control particles are dispersed is, for example, a complex such as a quaternary ammonium salt compound, a nigrosine compound, aluminum, iron, chromium, zinc, or zirconium. Compounds and the like. The charge control agent is preferably made of a material that is difficult to dissolve in water from the viewpoint of controlling ionic strength that affects the stability at the time of aggregation or fusion and recycling of wastewater.
The charge control agent is preferably used in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin from the viewpoint of further improving the chargeability.
The method for preparing the charge control particle dispersion in which the charge control particles are dispersed is not particularly limited, and a known method can be used.
For example, it is possible to prepare a charge control particle dispersion in which the charge control particles are dispersed by dispersing the charge control agent in an aqueous medium using a disperser such as a homogenizer in the presence of a surfactant.

The method for producing the toner of the present invention will be described in more detail, but is not limited to the following method.
<Aggregation process>
The aggregation step includes a resin particle dispersion in which resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, a release agent particle dispersion in which release agent particles are dispersed, and charging as necessary. A mixture liquid containing a charge control particle dispersion liquid in which control particles are dispersed is prepared, and resin particles, colorant particles, release agent particles, and charge control particles contained in the prepared liquid mixture are aggregated to form aggregate particles. It is a process of forming. The agglomerated particles can be formed in the mixed solution by, for example, adding and mixing a pH adjusting agent, a flocculant, and a stabilizer in the mixed solution, and appropriately adding temperature, mechanical power, and the like.
Examples of the pH adjuster include alkalis such as ammonia and sodium hydroxide; acids such as nitric acid and citric acid. Examples of the flocculant include monovalent metal salts such as sodium and potassium; divalent metal salts such as calcium and magnesium; trivalent metal salts such as iron and aluminum; and alcohols such as methanol, ethanol and propanol. can give. Examples of the stabilizer mainly include a surfactant itself or an aqueous medium containing the surfactant.
The addition / mixing of the aggregating agent and the like is preferably performed at a temperature not higher than the glass transition temperature (Tg) of the resin fine particles contained in the mixed solution. When addition and mixing are performed under this temperature condition, aggregation proceeds in a stable state. The aggregating agent and the like can be mixed using a known mixing device, homogenizer, mixer or the like.
The aggregation state of the aggregate particles formed here is confirmed with an optical microscope. After confirming the formation of aggregate particles, the average particle size is measured by particle size distribution analysis by the Coulter method described later. At this time, the weight average particle diameter (D4) is not particularly limited, but it is usually preferable to control the weight average particle diameter (D4) to be approximately the same as the weight average particle diameter (D4) of the toner to be obtained. Control can be easily performed, for example, by appropriately setting and changing the temperature and the stirring and mixing conditions. In the above aggregation step, aggregate particles having an average particle diameter substantially the same as the weight average particle diameter (D4) of the toner are formed, and an aggregate particle dispersion liquid in which the aggregate particles are dispersed is prepared.

<Fusion process>
The fusion step is a step of heating and aggregating the aggregate particles.
Before entering the fusing step, the pH adjusting agent, surfactant and the like can be appropriately added to prevent fusion between the aggregate particles.
The heating temperature may be between the glass transition temperature (Tg) of the resin contained in the aggregate particles and the decomposition temperature of the resin.
As the fusion time, a short time is sufficient if the heating temperature is high, and a long time is necessary if the heating temperature is low. That is, the fusion time depends on the temperature of heating and cannot be defined unconditionally, but is generally 30 minutes to 10 hours.
In the present invention, it is preferable to obtain toner particles by washing, filtering, drying, etc., toner particles obtained after completion of the fusing step under suitable conditions. Further, a shearing force is applied to the surface of the obtained toner particles by applying inorganic particles such as silica, alumina, titania, calcium carbonate, and resin particles such as vinyl resin, polyester resin, and silicone resin in a dry state. It may be added. These inorganic particles and resin particles function as external additives such as fluidity aids and cleaning aids.

Below, the physical property measuring method in this invention is demonstrated.
<Measurement of Weight Average Molecular Weight (Mw) Measured by Gel Permeation Chromatography (GPC) of Resin or Resin Particles in Tetrahydrofuran (THF)>
The molecular weight distribution and weight average molecular weight (Mw) measured by GPC of the THF soluble content of the resin or resin particles are determined as follows.
The column is stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 ml / min, and about 100 μl of THF sample solution is injected and measured. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, a standard polystyrene sample having a molecular weight of about 1 × 10 ² to 1 × 10 ⁷ manufactured by Tosoh Corporation or Showa Denko is used. Is appropriate. An RI (refractive index) detector is used as the detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, a combination of shodex GPC KF-801, 802, 803, 804, 805, 806, 807, 800P manufactured by Showa Denko, Examples include combinations of TSKgel G1000H (HXL), G2000H (HXL), G3000H (HXL), G4000H (HXL), G5000H (HXL), G6000H (HXL), G7000H (HXL), and TSKguardcolumn.
The sample is prepared as follows.
The resin or resin particles are placed in tetrahydrofuran (THF), allowed to stand for several hours, then shaken well, mixed well with THF (until the sample is no longer integrated), and allowed to stand for an additional 12 hours or longer. At this time, the standing time in THF is set to be 24 hours or more. Thereafter, a sample processing filter (pore size 0.45 to 0.5 μm, for example, Mysori Disc H-25-5: manufactured by Tosoh Corporation, Excro Disc 25CR: manufactured by Gelman Science Japan Co., Ltd., etc. can be used) is passed. This is used as a GPC sample. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

<Measurement of particle size distribution of fine particles such as release agent particles>
The particle size distribution of fine particles such as release agent particles is measured by a laser diffraction / scattering particle size distribution analyzer (LA-
950: manufactured by HORIBA, Ltd.) and measurement is performed according to the operation manual of the apparatus.
Specifically, the measurement sample was prepared and the volume distribution was measured at the sample introduction part of the measurement apparatus so that the transmittance was within the measurement range (70 to 95%). In the present invention, the 50% particle size based on volume distribution is used as the particle size of the release agent particles and the like. The 50% particle size based on the volume distribution is a particle size (median diameter) corresponding to a cumulative 50% based on the volume distribution.
Further, the existence ratio (volume%) of the release agent particles of 0.80 μm or more is obtained by a method of reading the cumulative frequency% value of 0.80 μm or more with respect to the calculation result of the volume distribution standard.

<Measurement of Number Average Particle Size (D1) and Weight Average Particle Size (D4) of Toner Particles>
The number average particle diameter (D1) and the weight average particle diameter (D4) of the toner particles are measured by particle size distribution analysis by the Coulter method. A Coulter Counter TA-II or Coulter Multisizer II (manufactured by Coulter, Inc.) is used as a measuring device, and measurement is performed according to the operation manual of the device. About 1% sodium chloride aqueous solution is prepared using 1st grade sodium chloride as electrolyte solution. For example, ISOTON-II (manufactured by Coulter Scientific Japan) can be used. Specifically, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant in 100 to 150 ml of an electrolytic aqueous solution, and 2 to 20 mg of a measurement sample (toner particles) is further added. Add. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes. The volume and number distribution of the toner particles are calculated by measuring the volume and number of toner particles having a diameter of 2.00 μm or more with the above-described measuring apparatus equipped with a 100 μm aperture as the aperture of the obtained dispersion treatment liquid. Then, the number average particle diameter (D1) obtained from the number distribution of the toner particles and the weight average particle diameter (D4) of the toner particles based on the weight obtained from the volume distribution of the toner particles (the median value of each channel is determined for each channel). As a representative value).
The channels include: 2.00 to 2.52 μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm; 4.00 to 5.04 μm; 5.04 to 6.35 μm; 6.35 to 8 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 20.20 μm; 20.20 to 25.40 μm; 25.40 to 32.00 μm Use 13 channels from 32.00 to 40.30 μm.

<Measurement of liquid density of release agent>
Place the precisely weighed release agent in the volumetric flask and heat to the melting point. When the release agent becomes liquid, the volume of the volumetric flask is read, and the liquid density of the release agent is obtained using the following formula.
(Formula) Liquid density of release agent [g / cm ³ ]
= Mass of release agent [g] / Capacity of release agent in liquid [cm ³ ]

<Measurement of melting point of release agent>
The melting point of the release agent indicates a main endothermic peak temperature in a DSC curve measured according to ASTM D3418-82. Specifically, the melting point of the release agent is DSC822 (manufactured by METTLER TOLEDO), the measurement temperature range is 30 to 200 ° C., the heating rate is 10 ° C./min, and the second time in a normal temperature and humidity environment. The DSC curve in the temperature range of 30 to 200 ° C. is obtained by the temperature raising process, and is the main endothermic peak temperature in the obtained DSC curve.

<Measurement of glass transition temperature of resin particles>
The glass transition temperature (Tg) of the resin particles is a physical property value measured in accordance with JIS K7121, and means the midpoint glass transition temperature described in the standard.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. In addition, the number of parts in the following composition is part by mass unless otherwise specified.

The types and characteristics of the release agent used in the following examples are as follows.
Mold release agent A: higher aliphatic alcohol wax (manufactured by Nippon Seiwa Co., Ltd .: Paracol, melting point 73 ° C., liquid density 0.77 g / cm ³ )
Release agent B: ester wax (behenyl behenate, melting point 75 ° C., liquid density 0.80 g / c
m ³ )
Release agent C: Paraffin wax (manufactured by Nippon Seiwa Co., Ltd .: HNP-51, melting point 78 ° C., liquid density 0.77 g / cm ³ )
Mold release agent D: Carnauba wax (melting point 82 ° C., liquid density 0.80 g / cm ³ )

<Example 1>
[Preparation of Toner Particles 1]
(Preparation of release agent particle dispersion 1)
-Release agent A 100 parts by mass-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 10 parts by mass-Ion-exchanged water 880 parts by mass (dispersing step)
After the above was put into the jacketed mixing vessel 11 shown in FIG. 1, it was heated to 90 ° C. and circulated at a shear stirring site where the rotor outer diameter was 3 cm and the clearance was 0.3 mm, the rotor rotation speed was 19000 rpm, the screen The mixture was stirred under the conditions of a rotational speed of 19000 rpm and a speed gradient of 199000 sec ⁻¹ and dispersed for 60 minutes.
(Cooling process)
After the dispersion treatment for 60 minutes, the release agent particle dispersion liquid 1 was continuously cooled to 40 ° C. under the conditions of a rotor rotation speed of 1000 rpm, a screen rotation speed of 0 rpm, a speed gradient of 5200 sec ⁻¹ , and a cooling speed of 10 ° C./min. Got.
The release agent particle dispersion 1 was measured using a laser diffraction / scattering particle size distribution analyzer (LA-950: manufactured by HORIBA, Ltd.), and a 50% particle size (median diameter) based on the volume distribution of the release agent particles. Was 0.15 μm, and release agent particles (coarse particles) of 0.80 μm or more were less than 0.01% by volume.
The release agent particle dispersion 1 immediately after the preparation and the release agent particle dispersion 1 after 2 months from the preparation were filtered through a 400 mesh wire mesh, and then the wire mesh was observed. No coarse particles were observed. It was. The results are shown in Table 1.

(Preparation of resin particle dispersion 1)
-Styrene 82.6 parts by mass-n-butyl acrylate 9.2 parts by mass-Acrylic acid 1.3 parts by mass-Hexanediol acrylate 0.4 parts by mass-n-lauryl mercaptan 3.2 parts by mass (Wako Pure Chemical Industries, Ltd.) Made)
The oil phase obtained by mixing and dissolving the above and the water phase obtained by dissolving 1.5 parts by mass of Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.) in 120 parts by mass of ion-exchanged water are mixed and dispersed in the flask, and further for 10 minutes. After slowly mixing, 5 parts by mass of ion-exchanged water in which 0.15 parts by mass of potassium persulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved was added thereto. After sufficiently purging with nitrogen, the inside of the flask was stirred and heated in an oil bath until the content reached 70 ° C., and emulsion polymerization was continued for 6 hours. Thereafter, the reaction solution was cooled to room temperature to prepare a resin particle dispersion 1. The particle size distribution in the resin particle dispersion 1 was measured using a laser diffraction / scattering type particle size distribution measuring device (LA-950: manufactured by Horiba, Ltd.). (Median diameter) is 0.2 μm, and coarse particles exceeding 1 μm were not observed.

(Preparation of Colorant Particle Dispersion 1)
Cyan pigment 100 parts by mass (Daiichi Seika Co., Ltd .: Pigment Blue 15: 3)
-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 15 parts by mass-Ion-exchanged water 885 parts by mass The above were mixed and dispersed for about 1 hour using a homogenizer (manufactured by IKA: Ultra Turrax). When the particle size distribution in this colorant particle dispersion 1 was measured using a laser diffraction / scattering type particle size distribution measuring device (LA-950: manufactured by Horiba, Ltd.), it was 50% of the volume distribution standard of the colorant particles contained. The particle diameter (median diameter) was 0.2 μm, and no coarse particles exceeding 1 μm were observed.

(Preparation of charge control particle dispersion 1)
20 parts by mass of a metal compound of dialkyl salicylic acid (charge control agent, manufactured by Orient Chemical Industries, Ltd .: Bontron E-84)
-Anionic surfactant 2 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
-Ion exchange water 78 mass parts The above was mixed, and it disperse | distributed using the homogenizer (the product made by IKA: Ultra Turrax). The particle size distribution in the charge control particle dispersion 1 was measured using a laser diffraction / scattering particle size distribution measuring device (LA-950: manufactured by Horiba, Ltd.). The diameter (median diameter) was 0.2 μm, and coarse particles exceeding 1 μm were not observed.

(Mixed liquid preparation process)
-Resin particle dispersion 1 360 parts by weight-Colorant particle dispersion 1 50 parts by weight-Release agent particle dispersion 1 70 parts by weight The dispersion immediately after preparation was equipped with a stirrer, a condenser, and a thermometer. The mixture was put into a 1 liter separable flask and stirred. The mixture was adjusted to pH = 5.2 using 1N potassium hydroxide.
(Aggregation process)
To this mixed solution, 150 parts by mass of a 10% sodium chloride aqueous solution was added dropwise as a flocculant, and the flask was heated to 57 ° C. while stirring in the heating oil bath. At this temperature, 3 parts by mass of resin particle dispersion 2 described later and 10 parts by mass of charge control agent particle dispersion 1 were added. After maintaining at 50 ° C. for 1 hour, observation with an optical microscope confirmed the formation of aggregate particles. Subsequently, when the weight average particle diameter (D4) was measured by Coulter Multisizer II (manufactured by Coulter, Inc.), it was 4.9 μm.
(Fusion process)
Thereafter, 3 parts by mass of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) was further added to the above mixed solution, and then the stainless steel flask was sealed and 105 ° C. while stirring was continued using a magnetic seal. And heated for 3 hours. Then, after cooling, the reaction product was filtered, washed thoroughly with ion exchange water, and then dried to obtain toner particles 1.

[Evaluation of Toner Particles 1]
The obtained toner particles 1 were measured by Coulter Counter TA-II (manufactured by Coulter Co.). As a result, D4 was 5.2 μm and D4 / D1 was 1.15. Further, when the cross section of the toner particle 1 was observed with a transmission electron microscope, the degree of dispersion of the release agent was good. Further, when the surface state of the toner particles 1 was observed with a scanning electron microscope, the exposure of the wax-like material on the surface of the toner particles 1 was slight, and no free particles were observed.

[Confirmation of stability of release agent particle dispersion 1]
In addition, using the release agent particle dispersion 1 that has passed 2 months after the preparation, the mixture liquid preparation step, the aggregation step, and the fusion step were performed in the same manner as described above to produce toner particles. Toner particles having the same characteristics as when the particle dispersion 1 was used were obtained.

[Production and Evaluation of Toner 1]
About 100 parts by mass of toner particles 1 obtained, 1.8 parts by mass of hydrophobized silica fine powder having a specific surface area measured by the BET method of 200 m ² / g was added to Henschel mixer (Mitsui Mining Co., Ltd.). ) And dry-mixed to obtain cyan toner 1.

(Image stability evaluation)
The obtained cyan toner 1 was evaluated for image stability. As the image forming apparatus, a modified machine in which a fixing oil application mechanism of a laser beam printer (manufactured by Canon Inc .: LBP-2160) is omitted is used. The cyan toner 1 is put into the process cartridge of this printer, the plain paper for copying machine (75 g / m ² ) is used as a transfer material, and the printing area ratio is 4 in the monochrome mode.
After printing out 10,000 character images at a printout speed of 28 (A4 size) / min, image fogging and image fogging due to poor charging were evaluated. As a result, the image density on the 10,000th sheet and the image fog suppression were the same as in the initial stage of printing, and were good.

(Blocking evaluation)
The cyan toner 1 was allowed to stand for 24 hours in a thermostatic chamber adjusted to 50 ° C., and the degree of blocking was evaluated. As a result, no blocking occurred.

(Fixability evaluation)
An unfixed image was formed on plain paper for copying machines (75 g / m ² ) using the LBP-2160 modified machine used in the image stability evaluation. For the unfixed image formed on the plain paper (recording material), the fixing test of the laser beam printer (Canon: LBP-2510) is used to modify the process speed and fixing temperature so that the process speed and fixing temperature can be controlled. went. In the fixing test, the process speed was set to 100 mm / second under normal temperature and normal humidity, and the state of offset when the unfixed image was fixed in the range of 120 ° C. to 220 ° C. was visually evaluated. As a result, sufficient fixability was exhibited at 120 ° C., and no offset occurred up to 210 ° C., indicating good fixability. Table 2 shows the results of these evaluations.

<Example 2>
[Preparation of Toner Particles 2]
(Preparation of release agent particle dispersion 2)
In the preparation of the release agent particle dispersion 1, the conditions in the dispersion process were changed to a rotor rotation speed of 18000 rpm, a screen rotation speed of 18000 rpm, a speed gradient of 188500 sec ⁻¹ , a treatment time of 10 minutes, and the cooling process conditions were changed to a rotor rotation speed of 0 rpm. A release agent particle dispersion 2 was obtained in the same manner as in the preparation of the release agent particle dispersion 1, except that the screen rotation speed was 0 rpm, the speed gradient was 0 sec ⁻¹ , and the cooling rate was 20 ° C./min. The release agent particle dispersion 2 was measured in the same manner as in Example 1. As a result, the 50% particle size (median diameter) of the release agent particles based on the volume distribution was 0.29 μm. Coarse particles of 80 μm or more were less than 0.01% by volume.
About the release agent particle dispersion 2 immediately after the preparation and the release agent particle dispersion 2 which has passed 2 months after the preparation, after filtering through a 400 mesh wire mesh, the wire mesh was observed, and no coarse particles were observed. It was. The results are shown in Table 1.

  Toner particles 2 were prepared in the same manner as in Example 1 except that the release agent particle dispersion 1 was changed to the release agent particle dispersion 2 in the mixed solution preparation step of [Production of toner particles 1].

[Evaluation of Toner Particles 2]
The obtained toner particles 2 were measured in the same manner as in Example 1. As a result, D4 was 5.5 μm, D4 /
D1 was 1.16. Further, when the cross section of the toner particles 2 was observed with a transmission electron microscope, the degree of dispersion of the release agent was good. Further, when the surface state of the toner particles 2 was observed with a scanning electron microscope, the exposure of the wax-like material on the surface of the toner particles 2 was slight, and no free particles were observed.

[Confirmation of stability of release agent particle dispersion 2]
In addition, using the release agent particle dispersion 2 that has passed 2 months after preparation, the mixture liquid preparation step, the aggregation step, and the fusion step were performed in the same manner as in Example 1 to produce toner particles. Toner particles having characteristics similar to those obtained when the mold agent particle dispersion 2 was used were obtained.

[Production and Evaluation of Toner 2]
With respect to the obtained toner particles 2, a toner was prepared in the same manner as in Example 1, and the same image stability evaluation and blocking property evaluation as in Example 1 were performed. As a result, the same results as in Example 1 were obtained. . Further, as a result of evaluating the fixing property in the same manner as in Example 1, the fixing property was sufficient at 120 ° C., no offset was generated up to 210 ° C., and good fixing property was shown.
The results are shown in Table 2.

<Example 3>
[Preparation of Toner Particle 3]
(Preparation of release agent particle dispersion 3)
In the preparation of the release agent particle dispersion 2, the release agent A is changed to the release agent B, and the conditions in the dispersion step are changed to a rotor rotation speed of 15000 rpm, a screen rotation speed of 15000 rpm, and a speed gradient of 157100 sec ⁻¹ and cooling. In the process, the O / W emulsion is transferred from the dispersing device to a vessel equipped with a propeller type stirring blade having a diameter of 0.06 m and a cooling jacket, and cooled at a rotation speed of the propeller type stirrer at 300 rpm and a cooling rate of 8 ° C./min. Except for the above, release agent particle dispersion 3 was obtained in the same manner as in the preparation of release agent particle dispersion 2. The release agent particle dispersion 3 was measured by the same method as in Example 1. As a result, the 50% particle size (median diameter) of the release agent particles based on the volume distribution was 0.27 μm. Coarse particles of 80 μm or more were less than 0.01% by volume.
About the release agent particle dispersion 3 immediately after the preparation and the release agent particle dispersion 3 which has passed 2 months after the preparation, after filtering through a 400 mesh wire mesh, the wire mesh was observed and no coarse particles were observed. It was. The results are shown in Table 1.

Toner particles 3 were prepared in the same manner as in Example 1 except that the release agent particle dispersion 1 was changed to the release agent particle dispersion 3 in the mixed solution preparation step of [Production of toner particles 1].

[Evaluation of Toner Particle 3]
The obtained toner particles 3 were measured in the same manner as in Example 1. As a result, D4 was 5.1 μm, D4 /
D1 was 1.17. Further, when the cross section of the toner particles 3 was observed with a transmission electron microscope, the degree of dispersion of the release agent was good. Further, when the surface state of the toner particles 3 was observed with a scanning electron microscope, the exposure of the wax-like material on the surface of the toner particles 3 was slight, and no free particles were observed.

[Confirmation of stability of release agent particle dispersion 3]
In addition, using the release agent particle dispersion 3 that has passed two months after the preparation, toner mixture was produced by performing the mixed solution preparation step, the aggregation step, and the fusion step in the same manner as in Example 1. Toner particles having the same characteristics as those obtained when the mold agent particle dispersion 3 was used were obtained.

[Production and Evaluation of Toner 3]
With respect to the obtained toner particles 3, a toner was prepared in the same manner as in Example 1, and the same image stability evaluation and blocking property evaluation as in Example 1 were performed. As a result, the same results as in Example 1 were obtained. . Further, as a result of performing the fixing property evaluation in the same manner as in Example 1, sufficient fixing property was shown at 130 ° C., no offset was generated up to 220 ° C., and good fixing property was shown. The results are shown in Table 2.

<Example 4>
[Preparation of Toner Particles 4]
(Preparation of release agent particle dispersion 4)
In the preparation of the release agent particle dispersion 2, the release agent A is changed to the release agent C, and the conditions in the dispersion process are changed to a rotor rotation speed of 13000 rpm, a screen rotation speed of 13000 rpm, a speed gradient of 136100 sec ⁻¹ and cooling. In the process, a release agent was prepared in the same manner as in the preparation of the release agent particle dispersion 2 except that cooling was performed at a rotor rotation speed of 1000 rpm, a screen rotation speed of 0 rpm, a speed gradient of 5200 sec ⁻¹ , and a cooling speed of 15 ° C./min. A particle dispersion 4 was obtained. The release agent particle dispersion 4 was measured in the same manner as in Example 1. As a result, the 50% particle size (median diameter) of the release agent particles based on the volume distribution was 0.25 μm. Coarse particles of 80 μm or more were less than 0.01% by volume.
About the release agent particle dispersion 4 immediately after the preparation and the release agent particle dispersion 4 which has been adjusted for 2 months, after filtering through a 400 mesh wire net, when the wire mesh is observed, no coarse particles are observed. It was. The results are shown in Table 1.

(Preparation of resin particle dispersion 2)
68 parts by mass of polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane, 16 parts by mass of isophthalic acid, 16 parts by mass of terephthalic acid, 0.03 of dibutyltin oxide
A mass part was charged in a flask, and the reaction was continued at 230 ° C. for 24 hours under a nitrogen atmosphere to obtain a polyester resin A.
-Polyester resin A 200 parts by mass-Tetrahydrofuran (manufactured by Wako Pure Chemical Industries) 400 parts by mass-Anionic emulsifier 10 parts by mass (Neogen RK, Daiichi Kogyo Seiyaku Co., Ltd.)
After mixing the above components, 250 parts by mass of ion-exchanged water was added, followed by dispersion for 60 minutes at 28 kHz in an ultrasonic cleaning machine (Honda Electronics, W-113), and then a high-pressure impact disperser Ultimateizer (Sugino Machine) Dispersion was performed at 200 MPa using HJP30006.
After completion of the dispersion, tetrahydrofuran is removed by an evaporator, so that the 50% particle size (median diameter) of the resin particles based on volume distribution is 0.25 μm, the glass transition temperature is 60 ° C., and the weight average molecular weight (Mw) is 12, Resin particle dispersion 2 having a molecular weight of 000 was prepared.

  In the mixed liquid preparation step of [Production of toner particles 1], except that the resin particle dispersion 1 is changed to the resin particle dispersion 2 and the release agent particle dispersion 1 is changed to the release agent particle dispersion 4. In the same manner as in Example 1, toner particles 4 were prepared.

[Evaluation of Toner Particles 4]
The obtained toner particles 4 were measured in the same manner as in Example 1. As a result, D4 was 5.8 μm, D4 /
D1 was 1.15. Further, when the cross section of the toner particles 4 was observed with a transmission electron microscope, the degree of dispersion of the release agent was good. Further, when the surface state of the toner particles 4 was observed with a scanning electron microscope, the exposure of the wax-like material on the surface of the toner particles 4 was slight, and no free particles were observed.

[Confirmation of stability of release agent particle dispersion 4]
Further, using the release agent particle dispersion 4 that has passed 2 months after the preparation, the mixture liquid preparation step, the aggregation step, and the fusion step were performed in the same manner as in Example 1 to produce toner particles. Toner particles having characteristics similar to those obtained when the mold agent particle dispersion 4 was used were obtained.

[Production and Evaluation of Toner 4]
With respect to the obtained toner particles 4, a toner was prepared in the same manner as in Example 1, and the same image stability evaluation and blocking evaluation as in Example 1 were performed. As a result, the same results as in Example 1 were obtained. . Further, as a result of performing the fixing property evaluation in the same manner as in Example 1, sufficient fixing property was shown at 130 ° C., no offset was generated up to 220 ° C., and good fixing property was shown. The results are shown in Table 2.

<Example 5>
[Preparation of Toner Particles 5]
(Preparation of release agent particle dispersion 5)
In the preparation of the release agent particle dispersion 2, the release agent A is changed to the release agent D, and the conditions in the dispersion process are the rotor rotation speed 17000 rpm, the screen rotation speed 16000 rpm, the speed gradient 172800 sec ⁻¹ , and the cooling process conditions. Release agent particle dispersion liquid in the same manner as in the preparation of the release agent particle dispersion liquid 2 except that the rotor rotation speed is 2000 rpm, the screen rotation speed is 1000 rpm, the speed gradient is 15700 sec ⁻¹ , and the cooling speed is 5 ° C./min. 5 was obtained. The release agent particle dispersion 5 was measured in the same manner as in Example 1. As a result, the 50% particle size (median diameter) of the release agent particles based on the volume distribution was 0.35 μm. Coarse particles of 80 μm or more were 0.2% by volume.
About the release agent particle dispersion 5 immediately after the preparation and the release agent particle dispersion 5 which has been adjusted for 2 months, after filtration through a 400 mesh wire mesh, the wire mesh is observed, particularly coarse particles are observed. There wasn't. The results are shown in Table 1.

  Toner particles 5 were prepared in the same manner as in Example 1 except that the release agent particle dispersion 1 was changed to the release agent particle dispersion 5 in the mixed solution preparation step of [Production of toner particles 1].

[Evaluation of Toner Particles 5]
The obtained toner particles 5 were measured in the same manner as in Example 1. As a result, D4 was 5.2 μm, D4 /
D1 was 1.24. Further, when the cross section of the toner particles 5 was observed with a transmission electron microscope, the degree of dispersion of the release agent was good. Further, when the surface state of the toner particles 5 was observed with a scanning electron microscope, exposure of pigments and wax-like materials to the surface of the toner particles 5 was observed, but no free particles were observed.

[Confirmation of stability of release agent particle dispersion 5]
In addition, using the release agent particle dispersion 5 that has passed two months after the preparation, toner mixture was manufactured by performing the mixed solution preparation step, the aggregation step, and the fusion step in the same manner as in Example 1. Toner particles having the same characteristics as those obtained when the mold agent particle dispersion 5 was used were obtained.

[Production and Evaluation of Toner 5]
For the obtained toner particles 5, a toner was prepared in the same manner as in Example 1, and image stability evaluation and blocking property evaluation were performed in the same manner as in Example 1. As a result, a slight decrease in image density was observed at the 10,000th sheet. The results were good as in Example 1 except that image fogging was observed. Further, as a result of evaluating the fixability in the same manner as in Example 1, sufficient fixability was shown at 140 ° C., no offset occurred up to 210 ° C., and good fixability was shown.

<Example 6>
[Preparation of Toner Particle 6]
(Preparation of release agent particle dispersion 6)
Except for changing the conditions in the dispersion step of the preparation of the release agent particle dispersion 2 to a rotor rotation speed of 11000 rpm, a screen rotation speed of 10000 rpm, a speed gradient of 110000 sec ⁻¹ and a cooling process condition of 10 ° C./min. In the same manner as in the preparation of the release agent particle dispersion 2, the release agent particle dispersion 6 was obtained. The release agent particle dispersion 6 was measured by the same method as in Example 1. As a result, the 50% particle size (median diameter) of the release agent particles based on the volume distribution was 0.39 μm. Coarse particles of 80 μm or more were 0.7% by volume.
About the release agent particle dispersion 6 immediately after the preparation and the release agent particle dispersion 6 which has been adjusted for 2 months, after filtering through a 400 mesh wire mesh, the wire mesh was observed, and no coarse particles were observed. It was. The results are shown in Table 1.

  Toner particles 6 were prepared in the same manner as in Example 1 except that the release agent particle dispersion 1 was changed to the release agent particle dispersion 6 in the mixed solution preparation step of [Production of toner particles 1].

[Evaluation of Toner Particles 6]
The obtained toner particles 6 were measured in the same manner as in Example 1. As a result, D4 was 5.4 μm, D4 /
D1 was 1.27. Further, when the cross section of the toner particle 6 was observed with a transmission electron microscope, the degree of dispersion of the release agent was good. Further, when the surface state of the toner particles 6 was observed with a scanning electron microscope, exposure of pigments and wax-like materials to the surface of the toner particles 6 was observed, but no free particles were observed.

[Confirmation of stability of release agent particle dispersion 6]
In addition, using the release agent particle dispersion 6 after 2 months from the preparation, the mixture liquid preparation step, the aggregation step, and the fusion step were performed in the same manner as in Example 1 to produce toner particles. Toner particles having characteristics similar to those obtained when the mold agent particle dispersion 6 was used were obtained.

[Production and Evaluation of Toner 6]
For the obtained toner particles 6, a toner was prepared in the same manner as in Example 1, and image stability evaluation and blocking property evaluation were performed in the same manner as in Example 1. As a result, a slight decrease in image density was observed at the 10,000th sheet. The results were good as in Example 1 except that image fogging was observed. Further, as a result of evaluating the fixability in the same manner as in Example 1, it showed sufficient fixability at 120 ° C., and no offset occurred up to 180 ° C., indicating good fixability.

<Example 7>
[Production of Toner Particles 7 and 8]
(Preparation of release agent particle dispersion 7)
The release agent particle dispersion 2 was prepared in the same manner as the release agent particle dispersion 2 except that the condition in the cooling step for the preparation of the release agent particle dispersion 2 was changed to a cooling rate of 3 ° C./min. 7 was obtained. When the release agent particle dispersion 7 was measured by the same method as in Example 1, the 50% particle size (median diameter) of the release agent particles based on the volume distribution was 0.36 μm, and 0 Coarse particles of 80 μm or more were 0.6% by volume.
The release agent particle dispersion 7 immediately after the preparation, the release agent particle dispersion 7 after one month has passed after the adjustment, and the release agent particle dispersion 7 after two months have passed after the adjustment, after filtering through a 400 mesh wire mesh, When the above was observed, no coarse particles were observed especially for the samples immediately after preparation and for 1 month after adjustment, but for the samples for 2 months after adjustment, coarse particles were confirmed. The results are shown in Table 1.

  Toner particles 7 were prepared in the same manner as in Example 1 except that the release agent particle dispersion 1 was changed to the release agent particle dispersion 7 in the mixed solution preparation step of [Production of toner particles 1]. Further, in the mixed liquid preparation step of [Production of Toner Particles 1], the same procedure as in Example 1 was performed except that the release agent particle dispersion 1 was changed to the release agent particle dispersion 7 that had passed 2 months after the preparation. Toner particles 8 were prepared.

[Evaluation of Toner Particles 7]
The obtained toner particles 7 were measured in the same manner as in Example 1. As a result, D4 was 5.5 μm, D4 /
D1 was 1.24. Further, when the cross section of the toner particles 7 was observed with a transmission electron microscope, the degree of dispersion of the release agent was good. Further, when the surface state of the toner particles 7 was observed with a scanning electron microscope, exposure of the pigment and wax-like material to the surface of the toner particles 7 was observed, but no free particles were observed.

[Confirmation of stability of release agent particle dispersion 7]
In addition, using the release agent particle dispersion liquid 7 months after the preparation, a mixed liquid preparation step, an aggregation step, and a fusion step were performed in the same manner as in Example 1 to produce toner particles. Toner particles having characteristics similar to those obtained when the mold agent particle dispersion 7 was used were obtained.

[Evaluation of Toner Particles 8]
On the other hand, the obtained toner particles 8 were measured in the same manner as in Example 1. As a result, D4 was 6.5 μm and D4 / D1 was 1.41. Further, when the cross section of the toner particles 8 was observed with a transmission electron microscope, a part of the release agent was exposed on the surface. Further, when the surface state of the toner particles 8 was observed with a scanning electron microscope, the exposure of the wax-like material on the surface of the toner particles 8 was confirmed, and a free wax-like substance was observed.

[Production of Toners 7 and 8 and Evaluation thereof]
For the obtained toner particles 7 and 8, a toner was prepared in the same manner as in Example 1, and image stability evaluation and blocking evaluation were performed in the same manner as in Example 1. As a result, the toner 7 was as good as Example 1 except that a slight decrease in image density and image fogging were observed on the 10,000th sheet. A slight decrease in image density and image fogging were observed on the first sheet, and when force was applied, it was easily dispersed, but blocking occurred. The toner 7 was evaluated for fixability in the same manner as in Example 1. As a result, sufficient fixability was exhibited at 120 ° C., no offset was generated up to 180 ° C., and good fixability was exhibited.

<Example 8>
[Production of Toner Particles 9 and 10]
(Preparation of release agent particle dispersion 8)
The preparation of the release agent particle dispersion 2 was the same as the preparation of the release agent particle dispersion 2 except that the conditions in the cooling step were changed to a rotor rotation speed of 2000 rpm, a screen rotation speed of 2000 rpm, and a speed gradient of 20900 sec ^−1. Thus, a release agent particle dispersion 8 was obtained. The release agent particle dispersion 8 was measured by the same method as in Example 1. As a result, the 50% particle size (median diameter) of the release agent particles based on the volume distribution was 0.31 μm. Coarse particles of 80 μm or more were 0.3% by volume.
The release agent particle dispersion 8 immediately after the preparation, the release agent particle dispersion 8 that has passed for 1 month after the adjustment, and the release agent particle dispersion 8 that has passed 2 months after the adjustment are filtered through a 400 mesh wire mesh, and then the wire mesh. When the above was observed, no coarse particles were observed especially for the samples immediately after preparation and for 1 month after adjustment, but for the samples for 2 months after adjustment, coarse particles were confirmed. The results are shown in Table 1.

  Toner particles 9 were prepared in the same manner as in Example 1 except that the release agent particle dispersion 1 was changed to the release agent particle dispersion 8 in the mixed liquid preparation step of [Production of toner particles 1]. Further, in the mixed liquid preparation step of [Production of Toner Particles 1], the same procedure as in Example 1 was performed, except that the release agent particle dispersion 1 was changed to the release agent particle dispersion 8 that had passed 2 months after adjustment. Toner particles 10 were prepared.

[Evaluation of Toner Particles 9]
The obtained toner particles 9 were measured in the same manner as in Example 1. As a result, D4 was 5.3 μm, D4 /
D1 was 1.21. Further, when the cross section of the toner particles 9 was observed with a transmission electron microscope, the degree of dispersion of the release agent was good. Further, when the surface state of the toner particles 9 was observed with a scanning electron microscope, exposure of pigments and wax-like materials to the surface of the toner particles 9 was observed, but no free particles were observed.

[Confirmation of stability of release agent particle dispersion 8]
In addition, using the release agent particle dispersion 8 that has passed one month after the adjustment, the mixed liquid preparation step, the aggregation step, and the fusion step were performed in the same manner as in Example 1 to produce toner particles. Toner particles having characteristics similar to those obtained when the mold agent particle dispersion 8 was used were obtained.

[Evaluation of Toner Particles 10]
On the other hand, the obtained toner particles 10 were measured in the same manner as in Example 1. As a result, D4 was 6.6 μm and D4 / D1 was 1.45. Further, when the cross section of the toner particles 10 was observed with a transmission electron microscope, a part of the release agent was exposed on the surface. Further, when the surface state of the toner particles 10 was observed with a scanning electron microscope, the exposure of the wax-like material on the surface of the toner particles 10 was confirmed, and the free wax-like substance was observed.

[Production and Evaluation of Toners 9 and 10]
For the obtained toner particles 9 and 10, a toner was prepared in the same manner as in Example 1, and image stability evaluation and blocking evaluation were performed in the same manner as in Example 1. As a result, the toner 9 was as good as in Example 1 except that a slight decrease in image density and image fogging were observed on the 10,000th sheet. A slight decrease in image density and image fogging were observed on the first sheet, and when force was applied, it was easily dispersed, but blocking occurred. The toner 9 was evaluated for fixability in the same manner as in Example 1. As a result, sufficient fixability was exhibited at 120 ° C., no offset occurred up to 190 ° C., and good fixability was exhibited.

<Example 9>
[Production of Toner Particles 11 and 12]
(Preparation of release agent particle dispersion 9)
The preparation of the release agent particle dispersion 2 is the same as the preparation of the release agent particle dispersion 2 except that the conditions in the cooling step are changed to a rotor rotation speed of 3000 rpm, a screen rotation speed of 3000 rpm, and a speed gradient of 31400 sec- ^1. Thus, a release agent particle dispersion 9 was obtained. The release agent particle dispersion 9 was measured by the same method as in Example 1. As a result, the 50% particle size (median diameter) of the release agent particles based on the volume distribution was 0.38 μm. Coarse particles of 80 μm or more were 0.6% by volume.
About the release agent particle dispersion 9 immediately after the preparation, and the release agent particle dispersion 9 after one month has passed after the adjustment, after filtering through a 400 mesh wire mesh, the wire mesh was observed. Coarse particles were not observed, but coarse particles were confirmed for the sample for 1 month after adjustment. The results are shown in Table 1.

  Toner particles 11 were prepared in the same manner as in Example 1 except that the release agent particle dispersion 1 was changed to the release agent particle dispersion 9 in the mixed liquid preparation step of [Production of toner particles 1]. Further, in the mixed liquid preparation step of [Production of Toner Particles 1], the same procedure as in Example 1 was performed, except that the release agent particle dispersion 1 was changed to the release agent particle dispersion 9 that had passed one month after adjustment. Toner particles 12 were prepared.

[Evaluation of Toner Particles 11]
The obtained toner particles 11 were measured in the same manner as in Example 1. As a result, D4 was 5.2 μm and D4 / D1 was 1.25. Further, when the cross section of the toner particles 11 was observed with a transmission electron microscope, the dispersibility of the release agent was good. Further, when the surface state of the toner particles 11 was observed with a scanning electron microscope, exposure of the pigment and wax-like material to the surface of the toner particles 11 was observed, but no free particles were observed.

[Evaluation of Toner Particles 12]
On the other hand, when the obtained toner particles 12 were measured in the same manner as in Example 1, D4 was 6.4 μm and D4 / D1 was 1.46. Further, when the cross section of the toner particles 12 was observed with a transmission electron microscope, a part of the release agent was exposed on the surface. Furthermore, when the surface state of the toner particles 12 was observed with a scanning electron microscope, the exposure of the wax-like material on the surface of the toner particles 12 was confirmed, and the free wax-like substance was observed.

[Production and Evaluation of Toners 11 and 12]
For the obtained toner particles 11 and 12, a toner was prepared in the same manner as in Example 1, and image stability evaluation and blocking evaluation were performed in the same manner as in Example 1. As a result, the toner 11 was as good as in Example 1 except that a slight decrease in image density and image fogging were observed on the 10,000th sheet. A slight decrease in image density and image fogging were observed on the first sheet, and when force was applied, it was easily dispersed, but blocking occurred. The toner 11 was evaluated for fixability in the same manner as in Example 1. As a result, sufficient fixability was exhibited at 120 ° C., no offset was generated up to 180 ° C., and good fixability was exhibited.

<Comparative Example 1>
[Production of toner particles]
(Preparation of release agent particle dispersion 10)
-Release agent A 100 parts by mass-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 10 parts by mass-Ion-exchanged water 880 parts by mass The above is a high-pressure homogenizer (SMT: Gorin homogenizer LAB2000). When heated to 90 ° C. and subjected to a dispersion treatment corresponding to 20 passes, two-layer separation was confirmed. The dispersion treatment liquid was cooled to 40 ° C. or lower at a cooling rate of 15 ° C./min to obtain a release agent particle dispersion liquid 10. When the release agent particle dispersion 10 was measured by the same method as in Example 1, the 50% particle size (median diameter) of the release agent particles based on the volume distribution was 8.9 μm.
The release agent particle dispersion 10 immediately after the preparation was filtered through a 400 mesh wire mesh and then observed on the wire mesh, whereby coarse particles were confirmed. The results are shown in Table 1.

  Preparation of toner particles was attempted in the same manner as in Example 1 except that the release agent particle dispersion 1 was changed to the release agent particle dispersion 10 in the mixed solution preparation step of [Production of toner particles 1]. However, coarse particles of 10 μm or more were generated during the formation of aggregated particles.

<Comparative Example 2>
[Preparation of Toner Particles 13]
(Preparation of release agent particle dispersion 11)
-Release agent A 100 parts by mass-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 10 parts by mass-Ion-exchanged water 880 parts by mass The above was used with a homogenizer (IKA: Ultra Turrax T50). As a result, some coarse particles were confirmed. Subsequently, the mixture was heated to 90 ° C. with a high-pressure homogenizer (manufactured by SMT: Gorin homogenizer LAB2000), dispersed for 20 passes, cooled to 40 ° C. or less at a cooling rate of 15 ° C./min, and release agent particles. Dispersion 11 was obtained. The release agent particle dispersion 11 was measured by the same method as in Example 1. As a result, the 50% particle size (median diameter) of the release agent particles based on the volume distribution was 0.32 μm. Coarse particles of 80 μm or more were 3.2% by volume.
The release agent particle dispersion 11 immediately after the preparation was filtered through a 400 mesh wire mesh and then observed on the wire mesh, whereby coarse particles were confirmed. The results are shown in Table 1.

  Toner particles 13 were prepared in the same manner as in Example 1 except that the release agent particle dispersion 1 was changed to the release agent particle dispersion 11 in the mixed liquid preparation step of [Production of toner particles 1].

[Evaluation of Toner Particles 13]
The obtained toner particles 13 were measured in the same manner as in Example 1. As a result, D4 was 5.2 μm and D4 / D1 was 1.31. Further, when the cross section of the toner particles 13 was observed with a transmission electron microscope, the degree of dispersion of the release agent was good. Further, when the surface state of the toner particles 13 was observed with a scanning electron microscope, the wax-like substance exposed to the surface of the toner particles 13 was slightly observed, but a free wax-like substance was observed.

[Production and Evaluation of Toner 13]
With respect to the obtained toner particles 13, a toner was prepared in the same manner as in Example 1, and image stability evaluation and blocking property evaluation were performed in the same manner as in Example 1. As a result, no blocking occurred. A slight decrease in image density and image fogging were observed with the eyes. The toner 13 was evaluated for fixability in the same manner as in Example 1. As a result, sufficient fixability was exhibited at 120 ° C., but offset occurred at 170 ° C.

<Comparative Example 3>
[Production of Toner Particles 14]
(Preparation of release agent particle dispersion 12)
-Release agent A 100 parts by mass-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 10 parts by mass-Ion-exchanged water 880 parts by mass CLEAMIX (M Technique Co., Ltd., CLM-0. 8S, clearance 0.
3 mm), and heated to 90 ° C. without circulation, stirred under the conditions of a rotor rotation speed of 17100 rpm and a speed gradient of 134300 sec ⁻¹ , dispersed for 10 minutes, and then rotor rotation speed 0 rpm, screen rotation speed 0 rpm, The release agent particle dispersion liquid 12 was obtained by cooling to 40 ° C. or lower under a cooling condition of a speed gradient of 0 sec ⁻¹ and a cooling rate of 20 ° C./min. In this release agent particle dispersion 12, some coarse particles were observed. The obtained release agent particle dispersion 12 was measured by the same method as in Example 1. As a result, the 50% particle size (median diameter) of the release agent particles based on the volume distribution was 2.1 μm.
The release agent particle dispersion 12 immediately after the preparation was filtered through a 400 mesh wire mesh, and then observed on the wire mesh, whereby coarse particles were confirmed. The results are shown in Table 1.

  Toner particles 14 were prepared in the same manner as in Example 1 except that the release agent particle dispersion 1 was changed to the release agent particle dispersion 12 in the mixed liquid preparation step of [Production of toner particles 1].

[Evaluation of Toner Particles 14]
The obtained toner particles 14 were measured in the same manner as in Example 1. As a result, D4 was 7.6 μm and D4 / D1 was 1.42. Further, when the cross section of the toner particles 14 was observed with a transmission electron microscope, a part of the release agent was exposed on the surface. Further, when the surface state of the toner particles 14 was observed with a scanning electron microscope, exposure of the wax-like material to the surface of the toner particles 14 was observed, and a free wax-like material was observed.

[Production and Evaluation of Toner 14]
For the obtained toner particles 14, a toner was prepared in the same manner as in Example 1, and the same image stability evaluation and blocking property evaluation as in Example 1 were performed. Image fogging was observed, and blocking that did not disperse even when force was applied occurred. The toner 14 was evaluated for fixability in the same manner as in Example 1. As a result, sufficient fixability was exhibited at 130 ° C., but offset occurred at 150 ° C.

<Comparative example 4>
[Preparation of Toner Particles 15]
(Preparation of release agent particle dispersion 13)
The release agent particle dispersion 12 was prepared in the same manner as the release agent particle dispersion 12 except that the conditions in the dispersion step were changed to a rotor rotational speed of 13000 rpm and a speed gradient of 102100 sec- ^1. Agent particle dispersion 13 was obtained. The release agent particle dispersion 13 was measured by the same method as in Example 1. As a result, the 50% particle size (median diameter) of the release agent particles based on the volume distribution was 3.1 μm.
The release agent particle dispersion 13 immediately after the preparation was filtered through a 400 mesh wire mesh and then observed on the wire mesh, whereby coarse particles were confirmed. The results are shown in Table 1.

  Toner particles 15 were prepared in the same manner as in Example 1 except that the release agent particle dispersion 1 was changed to the release agent particle dispersion 13 in the mixed solution preparation step of [Production of toner particles 1].

[Evaluation of Toner Particles 15]
The obtained toner particles 15 were measured in the same manner as in Example 1. As a result, D4 was 7.8 μm and D4 / D1 was 1.48. Further, when the cross section of the toner particles 15 was observed with a transmission electron microscope, a part of the release agent was exposed on the surface. Further, when the surface state of the toner particles 15 was observed with a scanning electron microscope, exposure of the wax-like material to the surface of the toner particles 15 was observed, and a free wax-like material was observed.

[Production and Evaluation of Toner 15]
For the obtained toner particles 15, a toner was prepared in the same manner as in Example 1, and the same image stability evaluation and blocking property evaluation as in Example 1 were performed. Image fogging was observed, and blocking that did not disperse even when force was applied occurred. The toner 15 was evaluated for fixability in the same manner as in Example 1. As a result, sufficient fixability was exhibited at 130 ° C., but offset occurred at 150 ° C.

<Comparative Example 5>
[Preparation of Toner Particles 16]
(Preparation of release agent particle dispersion 14)
-Release agent A 100 parts by mass-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 10 parts by mass-Ion-exchanged water 880 parts by mass Cavitron (Eurotech, CD-1010) And heated to 81-94 ° C., stirred at a peripheral speed of 40 m / s, treated for 10 passes, cooled to 40 ° C. or less at a cooling rate of 100 ° C./min, and release agent particle dispersion Liquid 14 was obtained. When the release agent particle dispersion 14 was measured by the same method as in Example 1, the 50% particle size (median diameter) of the release agent particles based on the volume distribution was 1.8 μm.
The release agent particle dispersion 14 immediately after the preparation was filtered through a 400 mesh wire mesh and then observed on the wire mesh, whereby coarse particles were confirmed. The results are shown in Table 1.

  Toner particles 16 were prepared in the same manner as in Example 1 except that the release agent particle dispersion 1 was changed to the release agent particle dispersion 14 in the mixed liquid preparation step of [Production of toner particles 1].

[Evaluation of Toner Particles 16]
The obtained toner particles 16 were measured in the same manner as in Example 1. As a result, D4 was 7.9 μm and D4 / D1 was 1.52. Further, when the cross section of the toner particles 16 was observed with a transmission electron microscope, a part of the release agent was exposed on the surface. Further, when the surface state of the toner particles 16 was observed with a scanning electron microscope, exposure of the wax-like material to the surface of the toner particles 16 was observed, and a free wax-like material was observed.

[Production and Evaluation of Toner 16]
For the obtained toner particles 16, a toner was prepared in the same manner as in Example 1, and image stability evaluation and blocking evaluation were performed in the same manner as in Example 1. Image fogging was observed, and blocking that did not disperse even when force was applied occurred. The toner 16 was evaluated for fixability in the same manner as in Example 1. As a result, sufficient fixability was exhibited at 120 ° C., but offset occurred at 160 ° C.

<Comparative Example 6>
[Preparation of Toner Particles 17]
(Preparation of release agent particle dispersion 15)
Except for the preparation of the release agent particle dispersion 2, the conditions in the dispersion process were changed to a rotor rotation speed of 10000 rpm, a screen rotation speed of 9000 rpm, a speed gradient of 99500 sec ⁻¹ , and the cooling process conditions were changed to a cooling speed of 10 ° C./min. In the same manner as the preparation of the release agent particle dispersion 2, the release agent particle dispersion 15 was obtained. The release agent particle dispersion 15 was measured in the same manner as in Example 1. As a result, the 50% particle size (median diameter) of the release agent particles based on the volume distribution was 0.54 μm. Coarse particles of 80 μm or more were 2.2% by volume.
The release agent particle dispersion 15 immediately after the preparation was filtered through a 400 mesh wire mesh and then observed on the wire mesh, whereby coarse particles were confirmed. The results are shown in Table 1.

  Toner particles 17 were prepared in the same manner as in Example 1 except that the release agent particle dispersion 1 was changed to the release agent particle dispersion 15 in the mixed liquid preparation step of [Production of toner particles 1].

[Evaluation of Toner Particles 17]
The obtained toner particles 17 were measured in the same manner as in Example 1. As a result, D4 was 6.8 μm and D4 / D1 was 1.36. Further, when the cross section of the toner particles 17 was observed with a transmission electron microscope, the degree of dispersion of the release agent was good. Further, when the surface state of the toner particles 17 was observed with a scanning electron microscope, exposure of the wax-like material to the surface of the toner particles 17 was observed, and a free wax-like material was observed.

[Production and Evaluation of Toner 17]
With respect to the obtained toner particles 17, a toner was prepared in the same manner as in Example 1. As a result of performing image stability evaluation and blocking property evaluation in the same manner as in Example 1, blocking did not occur. A slight decrease in image density and image fogging were observed with the eyes. The toner 17 was evaluated for fixability in the same manner as in Example 1. As a result, sufficient fixability was exhibited at 120 ° C., but offset occurred at 170 ° C.

However, the meanings of the symbols in Table 2 are shown below.
(Evaluation of image stability)
A: Image density and image fog suppression were the same as in the initial stage of printing and were good.
A: A slight decrease in image density and image fogging were observed on the 10,000th sheet.
Δ: A slight decrease in image density and image fogging were observed on the 8,000th sheet.
X: Some decrease in image density and image fogging were observed on the 5,000th sheet.

(Evaluation of blocking properties)
○: Blocking does not occur Δ: Blocking occurs but disperses easily when force is applied.
X: Blocking occurs and does not disperse even when force is applied.

1 is a schematic view of a dispersing device for a release agent particle dispersion. FIG. A detailed view of the shear stirring site is shown.

Explanation of symbols

11: Mixing vessel with jacket 12: Stirring means (rotating shear stirring device with jacket)
13: Circulation means (circulation pump)
21: Stirrer blade (rotor)
22: Screen 31: Clearance 41: Nozzle

Claims (7)

A step of preparing a mixed solution including a resin particle dispersion in which resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a release agent particle dispersion in which release agent particles are dispersed. An electrostatic charge image including a step of aggregating at least resin particles, colorant particles, and release agent particles contained in the mixed liquid to form aggregate particles, and heating and aggregating the aggregate particles A method for producing a developing toner, comprising:
The release agent particle dispersion in which the release agent particles are dispersed is obtained by heating a release agent mixed solution containing at least a release agent, a surfactant, and an aqueous medium to a temperature equal to or higher than the melting point of the release agent. However, a dispersion step of dispersing the release agent in a dispersion device having shearing force to obtain an O / W emulsion, and
The obtained O / W emulsion is obtained by a production method including a cooling step of cooling to below the melting point of the release agent,
The dispersing device includes at least a stirring blade that rotates and a screen that rotates around the stirring blade in a direction opposite to the stirring blade, a container in which the stirring device is installed, and the separation with respect to the container. A dispersing device having at least a circulating means for circulating the mold mixture liquid repeatedly by introducing and discharging;
In the dispersion step, the release agent mixed solution is rotationally sheared and stirred at a speed gradient of 110000 sec ⁻¹ or more and 200000 sec ⁻¹ or less using the stirring means of the dispersion apparatus, and the circulation means of the dispersion apparatus is used to Circulating the release agent mixture to disperse the release agent,
The 50% particle size on the basis of volume distribution measured by a laser diffraction / scattering particle size distribution measuring device of the release agent particles in the release agent particle dispersion is from 0.05 μm to 0.40 μm, and A toner manufacturing method, wherein 0.80 μm or more of release agent particles is 1% by volume or less. 2. The toner production method according to claim 1, wherein, in the cooling step, the O / W emulsion is cooled to a temperature lower than the melting point of the release agent at a cooling rate of 5 ° C./min or more. In the cooling step, an O / W emulsion is made into 200 using the stirring means of the dispersing device.
3. The toner production according to claim 1, wherein the rotary shearing stirring is performed at a speed gradient of 00 sec ⁻¹ or less, and the O / W emulsion is circulated and cooled by using a circulation unit of the dispersing device. Method.   3. The cooling process according to claim 1, wherein in the cooling step, cooling is performed to below the melting point of the release agent by using a stirring device having a stirring blade and a cooling device having at least a container in which the stirring device is installed. Toner production method.   5. The toner production method according to claim 1, wherein the release agent has a melting point of 40 ° C. or more and 120 ° C. or less. 6. The toner production method according to claim 1, wherein a liquid density at a melting point of the release agent is 0.70 g / cm ³ or more and 0.95 g / cm ³ or less.   The toner production method according to claim 1, wherein the release agent is a higher aliphatic alcohol.

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