JP2017058533A - Method for manufacturing toner particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing toner, capable of suppressing the occurrence of a scale deposit to an inner wall surface or the like in a polymerization vessel when manufacturing toner particles by a wet process.SOLUTION: The method for manufacturing toner by a suspension polymerization method or a dissolution suspension method includes adding an inorganic compound having poor water solubility in the polymerization step or the solvent removal step. A volume median size A of the inorganic compound having poor water solubility satisfies the formula (1); the mass B of a particle having a diameter equal to the volume median size of the inorganic compound having poor water solubility satisfies the formula (2); the polymerization step and the solvent removal step are performed in a vessel having an agitation blade; the peripheral velocity C of the agitation blade satisfies the formula (3); and the kinetic energy D of the inorganic compound particle having poor water solubility satisfies the formula (4). The formula(1) 10.0≤A(μm)≤40.0, the formula(2) 1.64×10≤B(kg)≤1.05×10, the formula(3) 1.0≤C(m/s)≤4.0 and the formula(4) 8.22×10≤D(kg m/s)≤8.41×10.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing toner particles.

  In recent years, as a method for producing toner particles, proposals for wet toners such as a suspension polymerization method using a polymerizable monomer, an emulsion polymerization aggregation method, a dissolution suspension method in which a binder resin is granulated in a solvent, etc. Is actively done.

  In the production of toner by suspension polymerization, the polymerization process is usually carried out using a polymerization vessel having a stirring means and a heating / cooling means. During the polymerization, the polymer composition is formed on the inner wall of the container, the surface of the stirring means, the surface of the baffle plate, etc. When an object adheres, it polymerizes in situ and becomes a scale adhering substance. The scale deposit remains in the polymerization vessel even after the polymerization process is completed. When this deposit is left as it is, the amount thereof increases every time the number of polymerization process batches is repeated, which deteriorates the heat transfer performance of the polymerization vessel and adversely affects the stability of the polymerization reaction.

  Furthermore, the time required for raising the polymerization temperature and for cooling after completion of the polymerization increases with the growth of the scale deposits, and the productivity is remarkably lowered. Since the jacket area ratio with respect to the container capacity decreases as the scale increases, the influence of the decrease in heat transfer performance increases as the scale increases.

Therefore, problems such as 1) a decrease in the stability of the polymerization reaction, and 2) an increase in the time required for heating and cooling are aggravated as the scale becomes larger. . Further, when the scale deposits are peeled off and fall off and mixed into the toner, which is a product, they are observed as irregular coarse particles. When the proportion of irregularly shaped coarse particles in the toner increases, the toner characteristics such as triboelectric chargeability and the development characteristics when the image is evaluated are adversely affected, resulting in fluctuations in image density, white streaks and fogging. This is not preferable because it causes a deterioration in properties.
If the scale deposit grows to a sufficient size and then peels / drops off, it may cause clogging or sticking in the piping part or valve connected to the polymerization vessel. For this reason, the frequent removal operation | work of a deposit | attachment is needed and the fall of the operation rate of a manufacturing apparatus is caused.

In the dissolution suspension method, a toner particle composition such as a binder resin, a colorant, a release agent and other additives is dispersed and dissolved in a volatile solvent such as a low-boiling organic solvent to obtain a toner particle composition. Next, the toner particle composition is granulated in an aqueous medium in the presence of a dispersing agent to form droplets, and then the volatile solvent is removed.
In the dissolution suspension method, the solvent removal step, like the polymerization step of the suspension polymerization method described above, grows the scale adhesion of the toner particle composition on the inner wall of the container, thereby deteriorating the thermal conductivity of the container, Significantly lowers productivity.

As a method for suppressing such scale adhesion, for example, in Patent Document 1, polymerization is performed in an aqueous dispersion stabilizing medium containing a dispersion stabilizer, and the polymerization conversion rate of the monomer composition is 0.2 to 0.7. Has further proposed a method of additionally adding a dispersion stabilizer to the dispersion stabilizing medium.
Patent Document 2 discloses an aqueous dispersion medium containing water or a dispersion stabilizer on the inner wall of a gas phase portion in a polymerization vessel as a method for suppressing adhesion of scales to the gas phase portion and the gas-liquid interface in the vessel. A method of spraying is proposed.

In Patent Document 3, an aqueous dispersion medium containing a dispersion stabilizer prepared separately is mixed with dispersion of an aqueous dispersion medium containing a dispersion stabilizer on the inner wall of the container and a dispersion of the polymerizable monomer composition. A method is disclosed in which scale adhesion is suppressed by simultaneously charging the prepared liquid into a container.
On the other hand, several methods for efficiently removing the generated scale deposits have been proposed. For example, a method in which a removing agent such as an organic solvent or an alkaline aqueous solution is sprayed into or filled in a polymerization vessel and heating and stirring are used together is simple and general (Patent Document 4).

JP-A-11-084722 JP-A-5-287564 Japanese Patent Laid-Open No. 2003-287928 JP 2012-93555 A

The methods of Patent Documents 1 to 3 are attached to increase the repulsion with the dispersed droplets of the polymerizable monomer by adding a dispersion stabilizer before the start of the polymerization process or at the initial stage of the polymerization as compared with the conventional method. The main focus is on suppression. However, with this method, the adhesion suppression effect is insufficient, and a satisfactory scale suppression effect cannot be obtained. According to the applicant's study, the above-described method does not provide a sufficient scale suppression effect. In particular, when continuously produced, the adhesion suppression effect lasts only a few batches.
In the method of Patent Document 4, the main point is how to dissolve or swell the scale deposit in the liquid, and it takes a certain amount of time to remove all the deposit even if it is heated.

An object of the present invention is to provide a method for producing toner particles that solves the above-described problems.
That is, the present invention provides a method for producing toner particles capable of suppressing the generation of scale deposits on the inner wall of the container and easily removing the generated scale deposits in the polymerization step or the solvent removal step. With the goal.

As a result of intensive studies on the suppression of the generation of the polymer scale in the polymerization step or the toner composition scale in the solvent removal step and the removal thereof, the inventors have found the following method.
In a method for producing toner particles containing a colorant and having the following steps i) or ii):
Adding a poorly water-soluble inorganic compound in the polymerization step or the solvent removal step;
The volume median diameter of the poorly water-soluble inorganic compound: A satisfies the following formula (1),
The mass of particles having a diameter equal to the volume median diameter of the sparingly water-soluble inorganic compound: B satisfies the following formula (2):
The polymerization step and the solvent removal step are performed in a container equipped with a stirring blade,
The peripheral speed of the stirring blade: C satisfies the following formula (3),
Kinetic energy of the poorly water-soluble inorganic compound particles: D satisfies the following formula (4):
Formula (1) 10.0 ≦ A (μm) ≦ 40.0
Formula (2) 1.64 × 10 ⁻¹² ≦ B (kg) ≦ 1.05 × 10 ⁻¹⁰
Formula (3) 1.0 <= C (m / s) <= 4.0
Formula (4) 8.22 × 10 ⁻¹³ ≦ D (kg · m ² / s ² ) ≦ 8.41 × 10 ⁻¹⁰
i) A granulating step of dispersing a toner particle composition containing a polymerizable monomer and a colorant in an aqueous medium to form particles of the polymerizable monomer composition, and the polymerizable monomer composition A polymerization step of polymerizing the polymerizable monomer present in the particles to obtain toner particles;
ii) a granulating step of dispersing a mixed solution in which a toner particle composition containing a binder resin and a colorant is dissolved or dispersed in an organic solvent in an aqueous medium to form particles of the mixed solution, and the mixing A solvent removal step of obtaining toner particles by removing an organic solvent present in the particles of the solution;

As described above, a polymer scale or a toner composition scale can be generated in the container in the polymerization step at the time of toner production by the suspension polymerization method and the solvent removal step at the time of toner production by the dissolution suspension method.
According to the present invention, it is possible to suppress the generation of such scale and to easily remove even when the scale is generated, thereby suppressing the mixing of irregularly shaped coarse particles due to the scale deposits into the product toner. it can. In addition, since the change in temperature control due to the heat conduction hindrance by the deposited polymer deposit is suppressed, stable quality toner particles can be obtained.
Furthermore, since the temperature rise in the container and the decrease in cooling efficiency due to the decrease in thermal conductivity due to the deposited polymer deposit are suppressed, productivity is improved. In addition, since the piping is not clogged due to the drop of the polymer deposit, frequent removal of the polymer deposit is essentially unnecessary, and the productivity is improved.

It is sectional drawing of the container used at the superposition | polymerization process or solvent removal process of an Example.

The present invention is suitably used for a method for producing toner particles by a suspension polymerization method using a polymerizable monomer or the like, an emulsion polymerization aggregation method, or a dissolution suspension method in which a binder resin or the like is granulated in a solvent. Can do. As an example, the case where the present invention is used in a toner production method by a suspension polymerization method will be described below.
In the suspension polymerization method, a polymerizable monomer composition containing at least a polymerizable monomer and a colorant is added to an aqueous medium, and particles of the polymerizable monomer composition are formed in the aqueous medium to perform polymerization. Is a production method for obtaining toner particles by polymerizing a polymerizable monomer contained in particles of a polymerizable monomer composition.

<Preparation process of polymerizable monomer composition>
A polymerizable monomer composition containing at least a polymerizable monomer and a colorant is prepared. The colorant may be dispersed in the polymerizable monomer in advance with a medium stirring mill or the like and then mixed with another composition, or may be dispersed after mixing all the compositions.

<Granulation process>
The polymerizable monomer composition is put into an aqueous medium containing an inorganic dispersion stabilizer, granulated by dispersing, and the polymerizable monomer composition is formed by forming particles of the polymerizable monomer composition in the aqueous medium. A body composition dispersion is obtained. The granulation step can be performed, for example, in a vertical stirring tank provided with a stirrer having a high shearing force. As a stirrer having a high shearing force, a high shear mixer (manufactured by IKA Japan), T.W. K. Homo mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) K. Commercially available products such as Filmix (made by Special Machine Industry Co., Ltd.) and Claremix (made by M Technique Co., Ltd.) can be used.

  Examples of the inorganic dispersion stabilizer include, for example, carbonates such as barium carbonate, calcium carbonate, and magnesium carbonate; metal phosphates such as aluminum phosphate, magnesium phosphate, calcium phosphate, barium phosphate, and zinc phosphate; barium sulfate, sulfuric acid Examples thereof include sulfates such as calcium; metal hydroxides of calcium hydroxide, aluminum hydroxide, magnesium hydroxide, and ferric hydroxide; These can be used alone or in combination of two or more. These exhibit functions as a dispersion stabilizer by being present as fine particles in an aqueous medium.

<Polymerization process>
By polymerizing the polymerizable monomer in the dispersion of the polymerizable monomer composition obtained by the granulation step, a polymer fine particle dispersion is obtained. In the polymerization step in the present invention, a general polymerization vessel having a stirring means and adjustable in temperature can be used.
The polymerization temperature is 40 ° C. or higher, generally 50 to 90 ° C. The polymerization temperature may be constant throughout, but may be raised in the latter half of the polymerization step for the purpose of obtaining a desired molecular weight distribution. Any stirring means may be used as the stirring means used in the polymerization vessel as long as the dispersed polymerizable monomer composition is floated without stagnation and the temperature in the tank can be kept uniform. As a stirring means, a stirring blade is suitable. For example, a general stirring blade such as a paddle blade, an inclined paddle blade, a three-blade retracted blade, a propeller blade, a disk turbine blade, a helical ribbon blade, an anchor blade, a full zone (shinko pan). Tech Co., Ltd.), Twin Star (Shinko Pantech Co., Ltd.), Max Blend (Sumitomo Heavy Industries, Ltd.), Super Mix (Satake Chemical Machinery Co., Ltd.), Hi-F Mixer ( Sokenken Chemical Co., Ltd.).

  When the inner diameter of the polymerization vessel is Y and the maximum blade diameter of the stirring blade is X, the ratio between the inner diameter of the polymerization vessel: Y and the maximum blade diameter of the stirring blade: X: X / Y is 0.30 or more and 0.70 The following is preferred. If it is 0.30 or more, it is difficult to generate a retention part inside the container. If it is 0.70 or less, it is easy to install a baffle plate inside the container.

As a result of intensive studies, the inventors have added a hardly water-soluble inorganic compound during the polymerization of the dispersion of the polymerizable monomer composition obtained by the granulation step, thereby stirring the wall surface of the polymerization vessel and stirring. It was found that it is very effective in suppressing adhesion to the wing.
That is,
Volume median diameter of poorly water-soluble inorganic compound: A satisfies the following formula (1),
The mass of particles having a diameter equal to the volume median diameter of the poorly water-soluble inorganic compound: B satisfies the following formula (2),
The peripheral speed of the stirring blade: C satisfies the following formula (3),
It is important that the kinetic energy D of the poorly water-soluble inorganic compound particles satisfies the following formula (4).
Formula (1) 10.0 ≦ A (μm) ≦ 40.0
Formula (2) 1.64 × 10 ⁻¹² ≦ B (kg) ≦ 1.05 × 10 ⁻¹⁰
Formula (3) 1.0 <= C (m / s) <= 4.0
Formula (4) 8.22 × 10 ⁻¹³ ≦ D (kg · m ² / s ² ) ≦ 8.41 × 10 ⁻¹⁰

The mass of particles having a diameter equal to the volume median diameter of the sparingly water-soluble inorganic compound: B means the mass of a spherical equivalent when the sparingly water-soluble inorganic compound has a volume median diameter: A. To do. That is, it is expressed by B = 4/3 × π × (A / 2) ³ × (mass per unit volume).
The peripheral speed of the stirring blade: C means the peripheral speed at the maximum diameter portion of the stirring blade.
Kinetic energy: D of the poorly water-soluble inorganic compound particles is a value obtained by multiplying the mass: B of particles having a diameter equal to the volume median diameter of the poorly water-soluble inorganic compound by the circumferential speed of the stirring blade: the square of C. , and the expressed by ^{D = B × C 2/2} .

  When the polymerization is carried out under the conditions of the formulas (1) to (4), the kinetic energy generated in the poorly water-soluble inorganic compound particles during stirring removes the adhesion that grows on the inner wall of the container and the stirring blade surface during the polymerization Polymerize. For this reason, adhesion does not grow on the inner wall of the container after the completion of polymerization, and the improvement in productivity and the stability of quality are dramatically improved.

  In this invention, it is preferable to implement on the conditions whose peripheral speed C of this stirring blade is 1.0 m / s or more and 4.0 m / s or less. If the peripheral speed of the stirring blade is less than 1.0 m / s, the generation rate of adhesion exceeds the speed at which the adhesion is removed, so that adhesion cannot be sufficiently suppressed. Furthermore, since a staying part is generated in the polymerizable monomer composition dispersion inside the container, the effect of removing the adhesion by the hardly water-soluble inorganic compound particles is remarkably reduced. In addition, since the shearing force by the stirring blade is insufficient in the staying portion inside the container, coarse particles are generated by coalescence of the particles of the polymerizable monomer composition, and the productivity is greatly reduced during wind classification. I will let you.

  On the other hand, when it exceeds 4.0 m / s, the vortex generated at the gas-liquid interface of the polymerizable monomer composition dispersion inside the container increases, and accordingly the gas-liquid contact open area also increases. The evaporation of the polymerizable monomer composition dispersion becomes very intense. Next, the evaporated polymerizable monomer component is cooled at the inner wall of the gas layer portion of the container, liquefied again, mixed into the container, and becomes coarse particles, which greatly reduces productivity during air classification. Also, since a large amount of latent heat is taken away from the inside of the polymerization system when the dispersion of the polymerizable monomer composition is evaporated, it is not preferable because energy efficiency is also lowered.

In the present invention, the volume median diameter of the hardly water-soluble inorganic compound: A is 10.0 μm or more and 40.0 μm or less, and the mass of the particles having a diameter equal to the volume median diameter of the hardly water-soluble inorganic compound: B is 1.64 × 10 ⁻¹² kg or more and 1.05 × 10 ⁻¹⁰ kg or less.
Volume median diameter of poorly water-soluble inorganic compound: When A is less than 10.0 μm 1.64 × 10 ⁻¹² , the kinetic energy of the poorly water-soluble inorganic compound particles is insufficient to remove adhesion. There is not preferable.
When the mass of the particles having a diameter equal to the volume median diameter of the poorly water-soluble inorganic compound: B is less than 1.64 × 10 ⁻¹² kg, similarly, the kinetic energy of the poorly water-soluble inorganic compound particles is It is insufficient and undesirable for removing the adhesion.

  Furthermore, when the volume median diameter of the poorly water-soluble inorganic compound: A is less than 10.0 μm, it is difficult to add a fine particle of 2 μm or less of the polymerizable monomer composition generated at the end of granulation. It is stabilized by the electrostatic repulsive force of the water-soluble compound and exists without coalescence until the end of the polymerization. For this reason, the proportion of fine particles in the toner particle dispersion increases. An increase in fine particles is undesirable because it adversely affects electrophotographic characteristics such as development streaks.

When the A exceeds 40.0 μm, it is estimated that the gravity with respect to the poorly water-soluble inorganic compound becomes larger than the kinetic energy of the 1.05 × 10 ⁻¹⁰ hardly water-soluble inorganic compound particles, and the vessel is stirred during stirring. A poorly water-soluble inorganic compound tends to accumulate on the bottom, and the deposits cannot be removed sufficiently. The same applies to the case where the mass B of the particles having a diameter equal to the volume median diameter of the slightly water-soluble inorganic compound exceeds 1.05 × 10 ⁻¹⁰ kg.

In the present invention, the kinetic energy: D of the poorly water-soluble inorganic compound particles is 8.22 × 10 ⁻¹³ kg · m ² / s ² or more and 8.41 × 10 ⁻¹⁰ kg · m ² / s ² or less. .
When the kinetic energy D of the poorly water-soluble inorganic compound particles: D is less than 8.22 × 10 ⁻¹³ kg · m ² / s ² , the poorly water-soluble inorganic compound particles can sufficiently remove the adhesion. Can not.
Kinetic energy of poorly water-soluble inorganic compound particles: When D exceeds 8.41 × 10 ⁻¹⁰ kg · m ² / s ² , as described above, poorly water-soluble inorganic compound particles of the formula (2) The mass B exceeds 1.05 × 10 ⁻¹⁰ kg, or the stirring blade C of the formula (3) exceeds 4.0 m / s. For this reason, it is not preferable for the same reason as described above.

  In the present invention, the timing of adding the poorly water-soluble inorganic compound in the polymerization step is preferably such that the polymerization conversion rate of the polymerizable monomer composition is 30% or less. If the polymerization conversion rate is 30% or less, the adhesion firmly adheres to the inner wall surface of the container, and the removal effect by the hardly water-soluble inorganic compound does not become insufficient. When the polymerization conversion rate is 30% or less and is slightly attached to the inner wall surface of the container, by adding a hardly water-soluble inorganic compound, a sufficient effect can be obtained for adhesion removal.

  As the poorly water-soluble inorganic compound added during the polymerization, a poorly water-soluble metal phosphate, a poorly water-soluble metal hydroxide, and a carbonate are preferably used. Examples of the hardly water-soluble metal phosphate include aluminum phosphate, magnesium phosphate, calcium phosphate, barium phosphate, zinc phosphate and the like. Examples of the hardly water-soluble metal hydroxide include calcium hydroxide, aluminum hydroxide, magnesium hydroxide, and ferric hydroxide. Examples of the carbonate include barium carbonate, calcium carbonate, and magnesium carbonate.

  The slightly water-soluble inorganic compound added during the polymerization may be dissolved and removed by acid or alkali treatment after the polymerization step, or may be separated and removed by a commercially available wet classifier. When mixing into the product is taken into consideration, it is preferable to dissolve and remove by acid or alkali treatment in the washing step described later.

<Distillation process>
If necessary, in order to remove volatile impurities such as unreacted polymerizable monomers and by-products, a part of the aqueous medium may be distilled off after the polymerization. The distillation step can be performed under normal pressure or reduced pressure.

<Washing step, solid-liquid separation step and drying step>
In order to remove the dispersion stabilizer adhering to the surface of the polymer particles, the polymer particle dispersion can be treated with an acid or an alkali. Thereafter, the polymer particles are separated from the liquid phase by a general solid-liquid separation method. However, in order to completely remove the acid or alkali and the dispersion stabilizer component dissolved therein, water is added again to remove the polymer particles. Wash. This washing process is repeated several times, and after sufficient washing, solid-liquid separation is performed again to obtain toner particles. The obtained toner particles are dried by a known drying means if necessary.

<Classification process>
The toner particles obtained in this way have a sufficiently sharp particle size as compared with conventional pulverized toners, but if a sharper particle size is required, classification can be performed by an air classifier or the like. Particles deviating from the particle size distribution can be separated and removed.
Next, an example in which the present invention is used in a toner production method by a dissolution suspension method will be described. The dissolution suspension method is a toner particle production method including a granulation step and a solvent removal step. In the granulation step, a mixed solution in which a toner particle composition containing a binder resin and a colorant is dissolved or dispersed in an organic solvent is dispersed in an aqueous medium to form particles of the mixed solution. In the solvent removal step, the organic solvent present in the particles of the mixed solution is removed.

<Toner particle composition preparation process>
As a method for preparing a toner particle mixture in which a toner particle composition such as a resin and a colorant is dissolved or dispersed in an organic solvent, a resin, a colorant and the like are gradually added to the organic solvent while stirring. It may be dissolved or dispersed. However, when using a pigment as a colorant or adding a release agent or charge control agent that is difficult to dissolve in an organic solvent, the particles should be made smaller prior to addition to the organic solvent. It is preferable. For dispersion, a known disperser such as a bead mill or a disk mill can be used.

<Granulation process>
The toner particle composition obtained in the above-described step is dispersed in an aqueous medium containing at least a surfactant or an inorganic dispersion stabilizer to prepare a dispersion of the toner particle composition. When a modified resin having an isocyanate group is added to the end of the toner particle composition, an active hydrogen group-containing compound can be added to react with the active hydrogen group-containing compound and the active hydrogen group-containing compound in an aqueous medium. A modified resin having various sites is reacted. A dispersion of the toner particle composition may be formed while producing the binder resin. The apparatus used in the granulation step can be performed in a vertical stirring tank provided with a stirrer having a high shearing force, for example, as in the suspension polymerization method described above. As a stirrer having a high shearing force, a high shear mixer (manufactured by IKA Japan), T.W. K. Homo mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) K. Commercially available products such as Filmix (made by Special Machine Industry Co., Ltd.) and Claremix (made by M Technique Co., Ltd.) can be used.

As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, fatty acid amide derivative, polyhydric alcohol Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine. It is.
Examples of the inorganic dispersion stabilizer used for the production of toner particles by the dissolution suspension method include those similar to the suspension polymerization method, and can be used alone or in combination of two or more.

<Demelting process>
In order to remove the organic solvent from the resulting dispersion of the toner particle composition, it is possible to employ a method in which the temperature of the entire system is gradually raised while stirring to completely evaporate and remove the organic solvent in the droplets. it can. Alternatively, the organic solvent may be removed by evaporation under reduced pressure while stirring the dispersion of the toner particle composition.

<Aging process>
When a modified resin having an isocyanate group at the end is added, an aging step may be performed in order to advance the elongation / crosslinking reaction of the isocyanate. The aging time is usually 10 minutes to 40 hours, preferably 2 to 24 hours. The reaction temperature is usually 0 to 65 ° C, preferably 35 to 50 ° C.
A container having the same shape as the polymerization step described above can be used as the container in the present invention used in the desorption step and the aging step.

(Washing process, solid-liquid separation process, drying process and classification process)
About said process, what is necessary is just to perform operation similar to the method in the suspension polymerization method mentioned above.
When the present invention is applied in the production of toner by the dissolution suspension method, a slightly water-soluble inorganic compound is added before the solvent removal step or immediately after the start of the solvent removal step. It was found that it is very effective in suppressing adhesion to the wall and the stirring blade.
The physical properties and stirring conditions of the poorly water-soluble inorganic compound are the same as those in the suspension polymerization method described above.

<Polymerizable monomer>
As the polymerizable monomer suitably used in the toner of the present invention, a vinyl polymerizable monomer capable of radical polymerization is used. As the vinyl polymerizable monomer, a monofunctional or polyfunctional monomer can be used. Examples of the monofunctional polymerizable monomer include the following.

Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- Styrene derivatives such as n-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene; methyl acrylate , Ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, -Acrylic monomers such as nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl Methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate Ethyl methacrylate, dibutyl phosphate Methacrylic polymerizable monomers such as til methacrylate; Methylene aliphatic monocarboxylic acid esters, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether, vinyl ethyl ether Vinyl ethers such as vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  The following are mentioned as a polyfunctional polymerizable monomer. Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2 '-Bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylol methane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene Glycol dimethacrylate, 1,3-buty Glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2′-bis (4- (methacryloxydiethoxy) phenyl) propane, 2,2′-bis (4- (methacryloxypolyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether.

  In the present invention, the above monofunctional polymerizable monomers are used alone or in combination of two or more, or the above monofunctional polymerizable monomers and polyfunctional polymerizable monomers are used in combination. . Among the above-described monomers, styrene or a styrene derivative is preferably used alone or in combination, or in combination with other monomers from the viewpoint of toner development characteristics and durability.

<Colorant>
Examples of the colorant preferably used in the present invention include the following organic pigments or dyes and inorganic pigments.
As an organic pigment or organic dye as a cyan colorant, a copper phthalocyanine compound and a derivative thereof, an anthraquinone compound, or a basic dye lake compound can be used.

Specific examples include the following. C. 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. Pigment Blue 66.
Examples of the organic pigment or organic dye as the magenta colorant include the following. Condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds.

  Specific examples include the following. C. 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 150, 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. Pigment Red 254. As the organic pigment or organic dye as the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used.

  Specific examples include the following. C. 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. Pigment Yellow 194. As the black colorant, carbon black and those which are toned in black using the yellow / magenta / cyan colorant are used.

These colorants can be used alone or mixed and further used in the form of a solid solution. The colorant used in the toner of the present invention is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner.
The colorant is preferably used by adding 1 part by mass or more and 20 parts by mass or less to 100 parts by mass of the binder resin.

  In selecting a colorant, it is necessary to pay attention to the polymerization inhibitory property and water phase transferability of the colorant. In particular, since dyes and carbon black often have polymerization inhibiting properties, care must be taken when using them. Preferably, these should be subjected to surface modification, for example, a hydrophobic treatment with a substance that does not inhibit polymerization. Examples of the surface treatment of the dye include a method of polymerizing a polymerizable monomer in the presence of these dyes in advance, and the obtained colored polymer is added to a raw material for toner such as a polymerizable monomer composition. . In addition to carbon black, the carbon black may be grafted with a substance that reacts with the surface functional groups of the carbon black, such as polyorganosiloxane.

<Release agent>
As the release agent used in the present invention, a wax in a solid state at room temperature may be used in terms of toner blocking resistance, multi-sheet durability, low-temperature fixability, and offset resistance.
Examples of the wax include the following. Paramethylene waxes, polyolefin waxes, microcrystalline waxes, polymethylene waxes such as Fischer-Tropsch waxes, amide waxes, higher fatty acids, long chain alcohols, ester waxes and their graft compounds, and their block compounds. These are preferably removed from the low molecular weight component and have a sharp maximum endothermic peak in the endothermic curve obtained by a differential scanning calorimeter. In order to improve the translucency of the image fixed on the OHP, a linear ester wax is particularly preferably used. It is preferable that 1-40 mass parts is contained with respect to 100 mass parts of polymerizable monomers, and, as for a linear ester wax, it is more preferable that 4-30 mass parts is contained.

  In the present invention, a second release agent having a melting point lower than 80 ° C. can be used in combination in order to increase the plasticity of the toner particles and improve the fixability in the low temperature region. As the second release agent, a linear alkyl alcohol having 15 to 100 carbon atoms, a linear fatty acid, a linear acid amide, a linear ester, or a montan derivative wax is preferably used. It is more preferable that impurities such as liquid fatty acid have been previously removed from these waxes.

<Charge control agent>
The toner produced according to the present invention may contain a charge control agent. Known charge control agents can be used. For example, the following are examples of toners that are controlled to be negatively charged. Organic metal compounds and chelate compounds are effective, and monoazo dye metal compounds, acetylacetone metal compounds, aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, phenol derivatives such as bisphenol Kind. Furthermore, the following are mentioned. Urea derivatives, metal-containing salicylic acid compounds, quaternary ammonium salts, calixarene, silicon compounds, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-acrylic-sulfonic acid copolymers, non-metallic carboxylic acids Compounds.

Examples of controlling the toner to be positively charged include the following. Modified products with nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate; onium salts such as phosphonium salts and lake pigments thereof, tri Phenylmethane dyes and their lake pigments (Laketungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, or ferrocyanide), higher fatty acid Metal salt. These can be used alone or in combination of two or more. Among these, charge control agents such as quaternary ammonium salts are particularly preferably used.
0.01-20 mass parts is preferable with respect to 100 mass parts of polymerizable monomers, and, as for the usage-amount of these charge control agents, 0.5-10 mass parts is more preferable.

<Polymerization initiator>
Examples of the polymerization initiator that can be used in the present invention include azo polymerization initiators. Examples of the azo polymerization initiator include the following. 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis -4-methoxy-2,4-dimethylvaleronitrile, azobismethylbutyronitrile.

  An organic peroxide initiator can also be used. The following are mentioned as an organic peroxide type | system | group initiator. Benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, tert-butyl-peroxypivalate.

  A redox initiator in which an oxidizing substance and a reducing substance are combined can also be used. Examples of the oxidizing substance include hydrogen peroxide, inorganic peroxides such as persulfates (sodium salts, potassium salts, ammonium salts, etc.), and oxidizing metal salts such as tetravalent cerium salts. Reducing substances include reducing metal salts (divalent iron salts, monovalent copper salts, trivalent chromium salts), ammonia, lower amines (amines having 1 to 6 carbon atoms such as methylamine and ethylamine), hydroxyl Amino compounds such as amines, sodium thiosulfate, sodium hydrosulfite, sodium hydrogen sulfite, sodium sulfite, reducing sulfur compounds such as sodium formaldehyde sulfoxylate, lower alcohols (1-6 carbon atoms), ascorbic acid or salts thereof, And lower aldehyde (C1-6). The initiator is selected with reference to the 10-hour half-life temperature, and is used alone or in combination. Although the addition amount of this polymerization initiator changes with the target degree of polymerization, generally 0.5-20 mass parts is added with respect to 100 mass parts of polymerizable monomers.

<Crosslinking agent>
Various cross-linking agents can also be used in the present invention. The following are mentioned as a crosslinking agent. Divinylbenzene, 4,4′-divinylbiphenyl, hexanediol diacrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycidyl (meth) acrylate, trimethylolpropane tri (meth) acrylate.

<Binder resin>
The binder resin used in the suspension polymerization method and dissolution suspension method of the present invention is not particularly limited and may be appropriately selected from known ones. For example, styrenes such as styrene and chlorostyrene; ethylene , Propylene, butylene, isoprene, and other monoolefins; vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, and other vinyl esters; methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate , Α-methylene aliphatic monocarboxylic esters such as phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl butyl ether; Ketone, bi Hexyl ketone, vinyl ketones such as vinyl isopropenyl ketone, and the like homopolymers or copolymers of such.

  Examples of the polymer of styrene or a substituted product thereof include polystyrene, poly p-chlorostyrene, and polyvinyl toluene. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.

  Particularly representative binder resins include, for example, polystyrene resins, polyester resins, styrene-alkyl acrylate copolymers, styrene-alkyl methacrylate copolymers, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, styrene. -Maleic anhydride copolymer, polyethylene resin, polypropylene resin and the like. These may be used individually by 1 type and may use 2 or more types together.

<Organic solvent>
The organic solvent used in the dissolution suspension method of the present invention is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal of the solvent later. Examples of such organic solvents include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, Ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. When the resin to be dissolved or dispersed in an organic solvent is a resin having a polyester skeleton, it is better to use an ester solvent such as methyl acetate, ethyl acetate, or butyl acetate or a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone. Highly preferable. Of these, methyl acetate, ethyl acetate, and methyl ethyl ketone, which have high solvent removability, are particularly preferable.

<Modified resin added to organic solvent>
The modified resin (hereinafter sometimes referred to as “prepolymer”) used in the dissolution suspension method of the present invention is not particularly limited as long as it has at least a site capable of reacting with an active hydrogen group-containing compound. And can be appropriately selected from known resins and the like. For example, a polyol resin, a polyacrylic resin, a polyester resin, an epoxy resin, a derivative resin thereof, and the like can be given.

These may be used individually by 1 type and may use 2 or more types together. Among these, a polyester resin is particularly preferable in terms of high fluidity and transparency during melting.
The site capable of reacting with the active hydrogen group-containing compound in the prepolymer is not particularly limited and may be appropriately selected from known substituents. For example, an isocyanate group, an epoxy group, a carboxylic acid, an acid A chloride group, and the like.
These may be contained singly or in combination of two or more. Among these, an isocyanate group is particularly preferable.

<Active hydrogen group-containing compound>
The active hydrogen group-containing compound used in the dissolution suspension method of the present invention is an extender, a crosslinking agent, etc. when a modified resin capable of reacting with the active hydrogen group-containing compound undergoes an extension reaction, a crosslinking reaction, etc. in an aqueous medium. Works.
The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected according to the purpose. For example, when the polymer capable of reacting with an active hydrogen group-containing compound is the above-mentioned isocyanate group-containing polyester prepolymer, it can be increased in molecular weight by an isocyanate group-containing polyester prepolymer and a reaction such as an extension reaction or a crosslinking reaction. Amines are preferred.

The active hydrogen group is not particularly limited and may be appropriately selected depending on the intended purpose, for example, hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), amino group (-NH _2), carboxyl group (-COOH) , A mercapto group (—SH), and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, alcoholic hydroxyl groups are particularly preferable.

<External additive>
In the production method of the present invention, an external additive can be used for the purpose of imparting various properties to the toner. The external additive preferably has a particle size of 1/10 or less of the weight average particle size of the toner particles from the viewpoint of durability when added to the toner. Examples of the external additive include the following. Metal oxides such as aluminum oxide, titanium oxide, strontium titanate, cerium oxide, magnesium oxide, chromium oxide, tin oxide, zinc oxide; nitrides such as silicon nitride; carbides such as carbide silicon carbide; calcium sulfate, barium sulfate, Inorganic metal salts such as calcium carbonate; fatty acid metal salts such as zinc stearate and calcium stearate; carbon black, silica.
These external additives are used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of toner particles. The external additives may be used singly or in combination of two or more, but those subjected to hydrophobic treatment are more preferable.

<Magnetic material>
The production method of the present invention can also be applied to a production method of a magnetic toner containing a magnetic material, and the magnetic material contained in the toner can also serve as a colorant. In the present invention, the magnetic material contained in the magnetic toner includes iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel; and these metals and aluminum, cobalt, copper, lead, magnesium, tin, Alloys of metals such as zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium and mixtures thereof.

These magnetic materials have a volume average particle diameter (Dv) of 0.5 μm or less, preferably about 0.1 to 0.5 μm.
The volume average particle diameter (Dv) of the magnetic body is a circle of the same area as the projected area of 100 magnetic bodies in the field of view at a magnification of 10,000 to 40,000 times using a transmission electron microscope (TEM). The equivalent diameter is obtained, and the volume average particle diameter is calculated based on the equivalent diameter.

The content of the magnetic substance in the toner is 20 to 200 parts by weight, particularly preferably 40 to 150 parts by weight, based on 100 parts by weight of the polymerizable monomer. .
In addition, it is preferable that the magnetic material has a saturation magnetization (σs) of 50 to ²⁰⁰ Am ² / kg and a residual magnetization (σr) of ^{2 to} 20 Am ² / kg when 800 kA / m is applied. The magnetic properties of the magnetic material are measured using an oscillating magnetometer VSM P-1-10 (manufactured by Toei Industry Co., Ltd.) at a room temperature of 25 ° C. and an external magnetic field of 79.6 kA / m.

<Hydrophobicizing agent>
In order to improve the dispersibility of these magnetic materials in the toner particles, it is also preferable to subject the surface of the magnetic material to a hydrophobic treatment. Coupling agents such as a silane coupling agent and a titanium coupling agent are used for the hydrophobic treatment. Of these, silane coupling agents are preferably used. The following are mentioned as a silane coupling agent. Vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxy Silane, hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane.

As described above, the toner produced according to the present invention can be used as either a one-component developer or a two-component developer.
In the case of a magnetic toner containing a magnetic material in the toner as a one-component developer, a method of transporting or charging the magnetic toner using a magnet built in the developing sleeve is used. When non-magnetic toner containing no magnetic material is used, there is a method in which a blade and a fur brush are used to forcibly frictionally charge with a developing sleeve and the toner is deposited on the sleeve to be conveyed.

  When the toner obtained by the production method of the present invention is used as a two-component developer, a carrier is used with the toner as a developer. Although it does not specifically limit as a carrier used for this invention, It is comprised by the single or composite ferrite state which mainly consists of iron, copper, zinc, nickel, cobalt, manganese, and a chromium atom.

  The carrier shape is also important from the viewpoint that saturation magnetization and electric resistance can be controlled over a wide range, and it is preferable to select, for example, spherical, flat, or indeterminate, and also to control the fine structure of the carrier surface state, for example, surface irregularity. In general, a method is used in which a carrier core particle is generated in advance by firing and granulating the above metal compound, and then a resin is coated. In order to reduce the load on the toner of the carrier, the metal compound and the resin are kneaded and then pulverized and classified to obtain a low-density dispersed carrier, or the kneaded product of the metal compound and the polymerizable monomer directly in the aqueous medium A method for obtaining a polymer carrier dispersed in a spherical shape by suspension polymerization therein can also be used.

The particle size of the carrier is measured based on the volume of the carrier using a laser diffraction particle size distribution measuring apparatus (Hellos <HELOS>) manufactured by SYNPATEC and equipped with a dry disperser (Rodos <RODOS>). Measured as 50% average particle size.
The average particle size of these carriers is 10 to 100 μm, more preferably 20 to 50 μm.

  When the two-component developer is prepared, the mixing ratio of the carrier and the toner in the present invention is usually good when the toner concentration in the developer is 2% by mass to 15% by mass, preferably 4% by mass to 13% by mass. Results are obtained. If the toner concentration is less than 2% by mass, the image density is low and impractical, and if it exceeds 15% by mass, fog and in-machine scattering tend to increase, and image deterioration and developer consumption increase easily occur.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but these do not limit the present invention in any way.
The measurement method used in the present invention will be described below.

<Measuring method of weight average particle diameter (D4) and number average particle diameter (D1)>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method provided with a 100 μm aperture tube is used. The attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used for setting measurement conditions and analyzing measurement data. Note that the measurement is performed with 25,000 effective measurement channels.

As the electrolytic aqueous solution used for the measurement, a special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used. .
Prior to measurement and analysis, the dedicated software was set as follows.
On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter ( The value obtained by using the product) is set. By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.
In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

The specific measurement method is as follows.
1) About 200 mL of the electrolytic solution is placed in a glass 250 mL round-bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
2) About 30 mL of the electrolytic solution is put into a glass 100 mL flat bottom beaker. As a dispersant, “Contaminone N” (a nonionic surfactant, an anionic surfactant, a 10% by weight aqueous solution of a neutral detergent for washing a pH 7 precision measuring instrument comprising an organic builder, Wako Pure Chemical Industries, Ltd. About 0.3 mL of a diluted solution obtained by diluting (made in ()) with ion-exchanged water about 3 times by mass.

3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared. About 3.3 liters of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 mL of Contaminone N is added to the water tank.
4) The beaker of 2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.

5) In a state where the electrolytic aqueous solution in the beaker of 4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
6) Into the round bottom beaker of 1) installed in the sample stand, the electrolyte solution of 5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. The measurement is performed until the number of measured particles reaches 50,000.

7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated.
The “average diameter” on the “analysis / volume statistics (arithmetic average)” screen when the graph / volume% is set in the dedicated software is the weight average particle diameter (D4). The “average diameter” on the “analysis / number statistical value (arithmetic average)” screen when the graph / number% is set in the dedicated software is the number average particle diameter (D1).

<Method for measuring volume median diameter of sparingly water-soluble inorganic substance>
The volume median diameter (D50) of the poorly water-soluble inorganic compound used in the present invention is measured according to JIS Z8825-2 (2001), and is specifically as follows.
As a measuring device, a laser diffraction / scattering particle size distribution measuring device “LA-920” (manufactured by Horiba, Ltd.) is used. The dedicated software attached to LA-920 is used for setting measurement conditions and analyzing measurement data. As the measurement solvent, ion-exchanged water from which impure solids are removed in advance is used.

The measurement procedure is as follows.
(1) A batch type cell holder is attached to LA-920.
(2) A predetermined amount of ion-exchanged water is put into a batch type cell, and the batch type cell is set in a batch type cell holder.
(3) The inside of the batch cell is stirred using a dedicated stirrer chip.
(4) The solvent refractive index of ion-exchanged water is set to 1.333. The refractive index of the poorly water-soluble inorganic compound is set according to the sample.
(5) In the “display condition setting” screen, the particle diameter reference is set as the volume reference.
(6) After performing warm-up operation for 1 hour or more, optical axis adjustment, optical axis fine adjustment, and blank measurement are performed.
(7) A slightly water-soluble metal compound is added little by little, and the transmittance of the tungsten lamp is adjusted to 90% to 95%. Then, the particle size distribution is measured. The volume median diameter (D50) is calculated based on the obtained volume-based particle size distribution data.

<Measurement of polymerization conversion rate of polymerizable monomer>
In the production of the toner or the binder resin, the polymerization conversion rate of the polymerizable monomer was calculated by quantifying the residual styrene monomer. That is, the polymerization conversion rate is 0% when the total amount of the added styrene monomer is detected in the following measurement, and the polymerization conversion rate is 100% when the styrene monomer is no longer detected in the toner as the polymerization reaction proceeds. It was. The quantification of residual styrene monomer is measured by gas chromatography (GC) as follows.

  About 500 mg of toner or binder resin is precisely weighed and placed in a sample bottle. About 10 g of acetone precisely weighed was added to the lid, mixed well, and mixed well. A desktop ultrasonic cleaner (trade name “B2510J-MTH”, manufactured by Branson) with an oscillation frequency of 42 kHz and an electrical output of 125 W was used. Irradiate with ultrasonic waves for 30 minutes. Thereafter, filtration is performed using a solvent-resistant membrane filter “Maysho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm, and 2 μL of the filtrate is analyzed by gas chromatography. And the residual amount of a residual styrene monomer is computed with the analytical curve created beforehand using styrene.

The measurement apparatus and measurement conditions are as follows.
GC: HP 6890GC
Column: HP INNOWax (200 μm × 0.40 μm × 25 m)
Carrier gas: He (constant pressure mode: 20 psi)
Oven: (1) Hold at 50 ° C. for 10 minutes, (2) Temperature rise to 200 ° C. at 10 ° C./minute, (3) Hold at 200 ° C. for 5 minutes Inlet: 200 ° C., pulsed splitless mode (20 → 40 psi, until 0.5 min)
Split ratio: 5.0: 1.0
Detector: 250 ° C. (FID)

<Calculation method of scale increase rate>
In the polymerization step or the solvent removal step / ripening step, an increase in time required to raise the temperature in the container accompanying the growth of the scale deposit is calculated. After cleaning the inside of the container, the time required for temperature increase / decrease during the first batch polymerization process or solvent removal process / aging process is t1, and the nth batch polymerization process or solvent removal process / aging process in the same container The time required for the temperature increase / decrease in time is defined as tn.
The scale increase rate is calculated by the following formula.
Scale increase rate (%) = (tn−t1) / t1 × 100
The larger the increase, the worse the adhesion, which is not preferable because it causes a decrease in productivity and a bad quality. In particular, if the increase exceeds 30%, the productivity is greatly affected, which is not preferable. Furthermore, it is not preferable because it causes a large fluctuation in molecular weight.

<Toner matrix productivity>
When the weight average particle diameter (D4) measured by the Coulter counter is measured, particles having a particle size of 12.0 μm or more are cut during wind classification because of low charging performance. That is, the larger the ratio of particles of 12.0 μm or more, the lower the productivity.

(Preparation of sparingly water-soluble inorganic compound 1)
As a poorly water-soluble inorganic compound, commercially available calcium phosphate powder (produced by Taihei Chemical Industry: βTCP100: specific gravity 3140 kg / m ³ ) is classified by a wind classifier (elbow jet classifier: manufactured by Nittetsu Mining Co., Ltd.). A slightly water-soluble inorganic compound 1 was obtained. Subsequently, when the volume median diameter: A of the poorly water-soluble inorganic compound 1 was measured by LA920, it was 10.0 μm. At this time, the refractive index of calcium phosphate was set to 1.62 and measured.
Next, from the volume median diameter and the specific gravity of calcium phosphate, the mass B of the slightly water-soluble inorganic compound particles: B was 1.64 × 10 ⁻¹² kg.

(Preparation of sparingly water-soluble inorganic compound 2)
Except for the poorly water-soluble inorganic compound 1 and the classification conditions, the same operation was performed to obtain a poorly water-soluble inorganic compound 2. Subsequently, when the volume median diameter: A of the poorly water-soluble inorganic compound 2 was measured by LA920, it was 40.0 μm.
Further, from the volume median diameter and the specific gravity of calcium phosphate, the mass B of the poorly water-soluble inorganic compound 2 particles was 1.05 × 10 ⁻¹⁰ kg.

(Preparation of sparingly water-soluble inorganic compound 3)
The slightly water-soluble inorganic compound 1 was subjected to a dry pulverization treatment with a wind mill: turbo mill (manufactured by Turbo Kogyo). Subsequently, classification was performed by a wind classifier (Elbow Jet Classifier: manufactured by Nippon Steel Mining Co., Ltd.) to obtain a slightly water-soluble inorganic compound 3. Subsequently, when the volume median diameter: A of the slightly water-soluble inorganic compound 3 was measured by LA920, it was 1.0 μm.
Further, from the volume median diameter and the specific gravity of calcium phosphate, the mass B of the poorly water-soluble inorganic compound 3 particles was 1.6 × 10 ⁻¹⁵ kg.

(Preparation of sparingly water-soluble inorganic compound 4)
Except for the poorly water-soluble inorganic compound 1 and the classification conditions, the same operation was performed to obtain a poorly water-soluble inorganic compound 4. Subsequently, when the volume median diameter: A of the slightly water-soluble inorganic compound 4 was measured by LA920, it was 50.0 μm.
Further, from the volume median diameter and the specific gravity of calcium phosphate, the mass B of the poorly water-soluble inorganic compound 4 particles was 2.0 × 10 ⁻¹⁰ kg.

<Example 1>
(Manufacture of toner particles 1)
Toner particles 1 were produced by the following procedure. The material was adjusted at the following ratio so that the total amount of the aqueous medium and the polymerizable monomer composition was 5000 kg.

(Preparation of aqueous medium)
To 240 parts by mass of ion-exchanged water, 5.3 parts by mass of Na ₃ PO ₄ : 2.1 parts by mass of 10% hydrochloric acid was added, and 2,000 s ⁻ was used using a high shear mixer (manufactured by IKA Japan Co., Ltd.). While stirring at ¹ (per second), warm water was introduced into the jacket 6 and heated to 60 ° C. To this, an aqueous solution in which 3.1 parts by mass of CaCl ₂ was dissolved in 30 parts by mass of ion-exchanged water was added, and stirring and temperature control were continued for 60 minutes to prepare a calcium phosphate aqueous medium. At this time, when the weight average particle diameter of the produced calcium phosphate aqueous medium was measured by LA920, it was 0.18 μm.

(Preparation of polymerizable monomer composition)
The following materials were dissolved with a propeller type stirring device at 100 s ⁻¹ to prepare a solution.
Styrene 60.0 parts by mass n-butyl acrylate 25.0 parts by mass Polyester resin 5.0 parts by mass (terephthalic acid: isophthalic acid: propylene oxide modified bisphenol A (2 mol adduct): ethylene oxide modified bisphenol A ( 2 mol adduct) = 30: 30: 30: 10 (mass ratio) polycondensate, acid value 11 mgKOH / g, Tg (glass transition temperature) = 74 ° C., Mw (weight average molecular weight) = 11,000, Mn (Number average molecular weight) = 4,000)
・ Low molecular weight polystyrene resin 15.0 parts by mass (Mw = 3,000, Mn = 1,050, Tg = 55 ° C.)

Next, the following materials were added to the solution.
Cyan coloring agent (CI Pigment Blue 15: 3) 7.0 parts by mass Negative charge control agent (Bontron E-88, manufactured by Orient Chemical) 1.5 parts by mass Hydrocarbon wax having a melting point of 77 ° C ( HNP-51, manufactured by Nippon Seiro at Co., Ltd.) 10.0 parts by mass the above mixture TK homomixer after heated to a temperature 60 ° C. the manufactured (Tokushu Kika Kogyo (Co.)), 4,000s ^{- The} mixture was stirred at ¹ , dissolved and dispersed.
In this, 10.0 parts by mass of perbutyl PV (10-hour half-life temperature 54.6 ° C. (manufactured by NOF Corporation)) as a polymerization initiator was dissolved to prepare a polymerizable monomer composition.

(Granulation process)
The polymerizable monomer composition is charged into the aqueous medium, and stirred at 2,000 s ^-1 for 30 minutes using a high shear mixer (manufactured by IKA Japan) at a temperature of 60 ° C. A dispersion of the monomer composition was obtained.

(Polymerization process)
After completion of the granulation process, the dispersion of the polymerizable monomer composition was transferred to the container 1 in FIG.
FIG. 1 is a cross-sectional view of a container used in the polymerization process or solvent removal process of the examples.

  As shown in FIG. 1, the container 1 includes a stirring blade 2, a baffle plate 3, a stirring motor 4, a temperature adjusting jacket 6, a polymerization container thermometer 7, a jacket thermometer 8, a discharge valve 9, and a shower nozzle 10. Is provided. The stirring motor 4 rotates the stirring blade 2. Warm water or the like is allowed to flow inside the jacket 6 to adjust the temperature of the container 1. 5 indicates a gas-liquid interface, X indicates the maximum diameter of the stirring blade 2, and Y indicates the inner diameter of the container 1.

After the dispersion was received, the peripheral speed of the stirring blade: C was set to 1.0 m / s, stirring was started, and 3.0 parts of a slightly water-soluble inorganic compound 1 was further added.
Further, simultaneously with the addition of the hardly water-soluble inorganic compound 1, the dispersion of the polymerizable monomer composition was sampled, and the conversion rate was measured. Next, the dispersion of the polymerizable monomer composition was heated to 70 ° C., and then reacted at 70 ° C. for 5 hours. Subsequently, the temperature inside the jacket 6 was set to 95 ° C., the temperature inside the container 1 was raised to 85 ° C., and the reaction was further performed at 80 ° C. for 5 hours to produce toner particles 1.

At this time, the time required to raise the temperature from 70 ° C. to 85 ° C. was 40 minutes. Moreover, flame-soluble inorganic compound particles kinetic energy: D is the mass of the hardly water-soluble inorganic compound particles: B and the peripheral speed of the stirring blade: formula consisting of ^{C (D = B × C 2} /2) According to the above, it was 8.22 × 10 ⁻¹³ (kg · m ² / s ² ).
After completion of the polymerization reaction, the slurry containing the toner particles 1 was cooled to 35 ° C. and transferred to a distillation step. Distillation, acid washing, filtration, washing, drying, followed by air classification gave a toner base. Table 1 shows the weight average particle size (D4) at the end of the polymerization and the particle ratio of 12.0 μm or more.

After the slurry was transferred, the inner wall of the container was washed with RO (Reverse Osmosis) water to wash away the slurry. Thereafter, when the inner wall of the container 1 was visually observed, no scale deposits remained on the inner wall of the container 1, the glass lining portion of the inner wall of the container was clearly exposed, and the poorly water-soluble inorganic compound 1 was added. As a result, it seems that no adhesion was generated.
After repeating the above steps 10 batches using the container 1, when the inside of the container 1 was visually confirmed, no scale deposit was observed on the inner wall of the container 1, and the scale deposit grew. It was confirmed that they did not. Moreover, the scale increase rate was calculated | required from the time spent for the temperature increase from 70 to 85 degreeC of 1st batch and 10th batch. Table 1 shows the result list.

<Example 2>
In the polymerization step, toner particles 2 were obtained in the same manner as in Example 1 except that the poorly water-soluble inorganic compound 2 was used in place of the poorly water-soluble inorganic compound 1.
After repeating the above process 10 batches using this container 1, when the inside of the container 1 was confirmed visually, adhesion to the inner wall of the container was not produced | generated like Example 1, at all. Table 1 shows the result list.

<Example 3>
In the polymerization step, toner particles 3 were obtained in the same manner as in Example 1 except that the peripheral speed of the stirring blade: C was set to 4.0 m / s.
After repeating the above process 10 batches using this container 1, when the inside of the container 1 was confirmed visually, adhesion to the inner wall of the container was not produced | generated like Example 1, at all. Table 1 shows the result list.

<Example 4>
In the polymerization step, instead of the poorly water-soluble inorganic compound 1, the poorly water-soluble inorganic compound 2 was used, and in the polymerization step, the peripheral speed of the stirring blade: C was set to 4.0 m / s. Then, toner particles 4 were obtained in the same manner as in Example 1.
After repeating the above process 10 batches using this container 1, when the inside of the container 1 was confirmed visually, adhesion to the inner wall of the container was not produced | generated like Example 1, at all. Table 1 shows the result list.

<Example 5>
In the polymerization step, the hardly water-soluble inorganic compound 1 was added to the dispersion of the polymerizable monomer composition 60 minutes after the start of stirring. At the same time, the dispersion of the polymerizable monomer composition was sampled and the conversion rate was measured. Except for the above, toner particles 5 were obtained in the same manner as in Example 1.
After repeating the above process 10 batches using this container 1, when the inside of the container 1 was confirmed visually, adhesion slightly produced | generated to the container inner wall partially. Table 1 shows the result list.

<Example 6>
In the polymerization step, the hardly water-soluble inorganic compound 1 was added to the dispersion of the polymerizable monomer composition 90 minutes after the start of stirring. At the same time, the dispersion of the polymerizable monomer composition was sampled and the conversion rate was measured. Except for the above, toner particles 6 were obtained in the same manner as in Example 1.
After repeating the above process 10 batches using this container 1, when the inside of the container 1 was confirmed visually, the adhesion | attachment slightly produced | generated to the whole inner wall of the container. Table 1 shows the result list.

<Example 7>
(Manufacture of toner particles 7)
The material was adjusted at the following ratio so that the total amount of the aqueous medium and the toner particle composition was 5000 kg.

(Production of resin fine particle dispersion)
The following materials were mixed in a reaction vessel equipped with a stirrer and a thermometer and stirred at 400 rpm for 15 minutes to obtain a white emulsion.
683 parts of water,
Sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries) 11 parts,
83 parts of styrene,
83 parts of methacrylic acid,
110 parts of butyl acrylate,
1 part ammonium persulfate.
The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours to be a vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A fine particle dispersion was obtained. The weight average particle diameter of the resin fine particle dispersion measured by LA-920 was 105 nm. A part of the resin fine particle dispersion was dried to isolate the resin component. The resin content had a Tg of 59 ° C. and a weight average molecular weight of 150,000.

(Manufacture of low molecular weight polyester)
The following materials were put into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and reacted at 230 ° C. for 5 hours under normal pressure.
229 parts by mass of bisphenol A ethylene oxide 2 mol adduct,
529 parts by mass of bisphenol A propion oxide 3 mol adduct,
208 parts by weight of terephthalic acid,
46 parts by mass of isophthalic acid and 2 parts by mass of dibutyltin oxide.
Next, the reaction solution was reacted for 5 hours under a reduced pressure of 10 to 15 mmHg, and then 44 parts by mass of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure. Molecular polyester was synthesized. The obtained low molecular weight polyester has a THF (tetrahydrofuran) soluble content weight average molecular weight (Mw) of 5,200, a glass transition temperature (Tg) of 45 ° C., an acid value of 20 mgKOH / g, and a hydroxyl value of 50 mgKOH / g. Met.

(Prepolymer production)
Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 795 parts of bisphenol A ethylene oxide 2-mole adduct, 200 parts of isophthalic acid, 65 parts of terephthalic acid, and 2 parts of dibutyltin oxide were added, and atmospheric nitrogen Under an air stream, the condensation reaction was performed at 210 ° C. for 8 hours.
Next, the reaction was continued for 5 hours while dehydrating under reduced pressure of 10 to 15 mmHg, then cooled to 80 ° C., and reacted with 170 parts of isophorone diisocyanate in 1,500 parts of ethyl acetate for 2 hours to obtain a prepolymer solution. It was. The weight average molecular weight of the prepolymer in the obtained prepolymer solution was 90,000. Moreover, the prepolymer pure content in this prepolymer solution was 50%.

(Preparation of pigment dispersion)
In a beaker, 20 parts of a prepolymer solution, 155 parts of low molecular weight polyester, and 80 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 110 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes.
The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 1.2 parts of isophorone diamine was added to the dispersion, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain a pigment dispersion.
To 70 parts of the resin fine particle dispersion, 405.1 parts of the pigment dispersion was added and stirred to obtain a toner particle composition.

(Granulation process)
The toner composition is placed in 529.5 parts of ion-exchanged water and 0.5 part of sodium dodecylbenzenesulfonate, and dispersed with a TK homomixer at 12,000 rpm for 30 minutes to obtain a toner particle dispersed slurry. It was.

(Solvent removal / aging)
After completion of the granulation step, the toner particle composition dispersion was transferred to the container 1 of FIG. After receiving the dispersion, the stirring blade peripheral speed: C was set to 1.0 m / s and stirring was started. Further, 3.0 parts of the poorly water-soluble inorganic compound 1 was added, and then the solvent was removed for 5 hours. It was. Subsequently, the temperature inside the jacket was set to 70 ° C., the temperature inside the container 1 was raised to 55 ° C., and aging was further performed at 55 ° C. for 5 hours to produce toner particles 7.

At this time, the time required to raise the temperature from 40 ° C. to 55 ° C. was 30 minutes. The kinetic energy: D of the poorly water-soluble inorganic compound particles is 8.2 × 10 ⁻²⁰ according to the calculation formula consisting of the mass of the poorly water-soluble inorganic compound particles: B and the peripheral speed of the stirring blade: C. (Kg · m ² / s ² ).
After completion of the solvent removal / ripening process, the slurry containing the toner particles 7 was transferred to the next process. Filtration, washing, drying and then air classification gave a toner base. Table 1 shows the weight average particle size (D4) at the end of solvent removal / ripening and the particle ratio of 12.0 μm or more.

After the slurry is transferred, the inner wall of the container is washed with RO water, the slurry is washed away, and the inner wall of the container 1 is visually observed. As a result, no scale deposit remains on the inner wall of the container 1, and the glass lining portion of the inner wall of the container However, it was exposed cleanly. It seems that no adhesion was generated at all by adding the hardly water-soluble inorganic compound 1.
After repeating the above steps 10 batches using the container 1, when the inside of the container 1 was visually confirmed, no scale deposit was observed on the inner wall of the container 1, and the scale deposit grew. It was confirmed that they did not. Moreover, the scale increase rate was calculated | required from the time spent for the temperature increase from 40 degreeC of 1st batch and 10th batch to 55 degreeC. Table 1 shows the result list.

<Example 8>
In the solvent removal / ripening step, toner particles 8 were obtained in the same manner as in Example 7, except that the poorly water-soluble inorganic compound 2 was used in place of the poorly water-soluble inorganic compound 1.
After repeating the above process 10 batches using this container 1, when the inside of the container 1 was confirmed visually, adhesion to the inner wall of the container was not produced | generated at all like Example 7. FIG. Table 1 shows the result list.

<Example 9>
In the solvent removal / ripening step, toner particles 9 were obtained in the same manner as in Example 7, except that the stirring blade was stirred at 4.0 m / s.
After repeating the above process 10 batches using this container 1, when the inside of the container 1 was confirmed visually, adhesion to the inner wall of the container was not produced | generated at all like Example 7. FIG. Table 1 shows the result list.

<Example 10>
In the solvent removal / ripening step, the same procedure as in Example 7 was performed except that the hardly water-soluble inorganic compound 2 was used instead of the slightly water-soluble inorganic compound 1 and the stirring blade was stirred at 4.0 m / s. Thus, toner particles 10 were obtained.
After repeating the above process 10 batches using this container 1, when the inside of the container 1 was confirmed visually, adhesion to the inner wall of the container was not produced | generated at all like Example 7. FIG. Table 1 shows the result list.

<Comparative Example 1>
In the polymerization step, instead of the sparingly water-soluble inorganic compound 1, the sparingly water-soluble inorganic compound 3 is used, and after 90 minutes from the start of stirring, the sparingly water-soluble inorganic compound 3 is dispersed in the polymerizable monomer composition dispersion liquid. Added to. At the same time, the dispersion of the polymerizable monomer composition was sampled and the conversion rate was measured. Further, in the polymerization step, toner particles 11 were obtained in the same manner as in Example 1 except that the stirring blade peripheral speed: C was stirred at 0.05 m / s. When the stirring state during the polymerization was confirmed, it was observed that a stagnant portion was present at a part of the gas-liquid interface.

  After repeating this process 10 batches using this container 1, when the inside of the container 1 was confirmed visually, the whole inner wall of the container was completely covered with adhesion. This is probably because the peripheral speed of the stirring blade was too low, and the kinetic energy of the poorly water-soluble inorganic compound was insufficient. Table 1 shows the result list.

<Comparative example 2>
In the polymerization step, toner particles 12 were obtained in the same manner as in Comparative Example 1 except that the poorly water-soluble inorganic compound 4 was used in place of the poorly water-soluble inorganic compound 3. When the stirring state during the polymerization was confirmed, it was observed that a stagnant portion was present at a part of the gas-liquid interface.
After repeating this process 10 batches using this container 1, when the inside of the container 1 was confirmed visually, the whole inner wall of the container was completely covered with adhesion. This is probably because the peripheral speed of the stirring blade was too low, and the kinetic energy of the poorly water-soluble inorganic compound was insufficient. Table 1 shows the result list.

<Comparative Example 3>
In the polymerization step, toner particles 13 were obtained in the same manner as in Comparative Example 1 except that the stirring blade peripheral speed: C was stirred at 5.0 m / s. As a result of confirming the stirring state during the polymerization, it seems that the peripheral speed is excessive, and a large vortex is generated at the gas-liquid interface, and the dispersion of the polymerizable monomer composition is vigorously vaporized. It was liquefied in the gas layer at the upper part of the tank and recirculated in a large amount inside the container.
After repeating this process 10 batches using this container 1, when the inside of the container 1 was confirmed visually, the whole inner wall of the container was completely covered with adhesion. Since the weight average particle diameter of the poorly water-soluble inorganic compound was small, it is considered that the kinetic energy of the poorly water-soluble inorganic compound was insufficient and adhesion could not be removed. Table 1 shows the result list.

<Comparative example 4>
Comparative Example 1 except that in the polymerization step, the poorly water-soluble inorganic compound 4 was used in place of the poorly water-soluble inorganic compound 3, and the peripheral speed of the stirring blade: C was stirred at 5.0 m / s. Toner particles 14 were obtained by the same method as described above. As a result of confirming the stirring state during the polymerization, it seems that the peripheral speed is excessive, and a large vortex is generated at the gas-liquid interface, and the dispersion of the polymerizable monomer composition is vigorously vaporized. It was liquefied in the gas layer at the upper part of the tank and recirculated in a large amount inside the container.
After repeating the above process 10 batches using this container 1, when the inside of the container 1 was visually confirmed, the bottom of the container was slightly adhered, but the side trunk was completely covered by the adhesion. It was broken. Since the weight average particle size of the poorly water-soluble inorganic compound was large, the sedimentation rate of the poorly water-soluble inorganic compound seems to have been large relative to the kinetic energy of the poorly water-soluble inorganic compound. It seems that the inorganic compound was retained. Table 1 shows the result list.

<Comparative Example 5>
Example except that in the solvent removal / ripening step, the poorly water-soluble inorganic compound 3 was used in place of the poorly water-soluble inorganic compound 1, and the peripheral speed of the stirring blade: C was stirred at 0.05 m / s In the same manner as in Example 7, toner particles 15 were obtained. When the stirring state during the polymerization was confirmed, it was observed that a stagnant portion was present at a part of the gas-liquid interface.
After repeating this process 10 batches using this container 1, when the inside of the container 1 was confirmed visually, the whole inner wall of the container was completely covered with adhesion. This is probably because the peripheral speed of the stirring blade was too low, and the kinetic energy of the poorly water-soluble inorganic compound was insufficient. Further, the inside of the container near the staying portion was in a particularly bad state. Table 1 shows the result list.

<Comparative Example 6>
Toner particles 16 were obtained in the same manner as in Comparative Example 5 except that, in the solvent removal / ripening step, the poorly water-soluble inorganic compound 4 was used instead of the poorly water-soluble inorganic compound 3. When the stirring state during the polymerization was confirmed, it was observed that a stagnant portion was present at a part of the gas-liquid interface.
After repeating this process 10 batches using this container 1, when the inside of the container 1 was confirmed visually, the whole inner wall of the container was completely covered with adhesion. This is probably because the peripheral speed of the stirring blade was too low, and the kinetic energy of the poorly water-soluble inorganic compound was insufficient. Further, the inside of the container near the staying portion was in a particularly bad state. Table 1 shows the result list.

<Comparative Example 7>
Toner particles 17 were obtained in the same manner as in Comparative Example 5 except that the stirring blade peripheral speed: C was stirred at 5.0 m / s in the solvent removal / ripening step. As a result of confirming the stirring state during the polymerization, it seems that the peripheral speed is excessive, and a large vortex is generated at the gas-liquid interface, and the dispersion of the polymerizable monomer composition is vigorously vaporized. It was liquefied in the gas layer at the upper part of the tank and recirculated in a large amount inside the container.
After repeating this process 10 batches using this container 1, when the inside of the container 1 was confirmed visually, the whole inner wall of the container was completely covered with adhesion. Since the weight average particle diameter of the poorly water-soluble inorganic compound was small, it is considered that the kinetic energy of the poorly water-soluble inorganic compound was insufficient and adhesion could not be removed. Table 1 shows the result list.

<Comparative Example 8>
Comparative Example, except that, in the solvent removal / ripening step, the poorly water-soluble inorganic compound 4 was used instead of the poorly water-soluble inorganic compound 3, and the peripheral speed of the stirring blade: C was stirred at 5.0 m / s In the same manner as in Example 5, toner particles 18 were obtained. As a result of confirming the stirring state during the polymerization, it seems that the peripheral speed is excessive, and a large vortex is generated at the gas-liquid interface, and the dispersion of the polymerizable monomer composition is vigorously vaporized. It was liquefied in the gas layer at the upper part of the tank and recirculated in a large amount inside the container.
After repeating the above process 10 batches using this container 1, when the inside of the container 1 was visually confirmed, the bottom of the container was slightly adhered, but the side trunk was completely covered by the adhesion. It was broken. Since the weight average particle size of the poorly water-soluble inorganic compound was large, the sedimentation rate of the poorly water-soluble inorganic compound seems to have been large relative to the kinetic energy of the poorly water-soluble inorganic compound. It seems that the inorganic compound was retained. Table 1 shows the result list.
<Comparative Example 9>
In the polymerization step, toner particles 19 were obtained in the same manner as in Comparative Example 1 except that the stirring blade peripheral speed: C was stirred at 1.0 m / s. When the stirring state during polymerization was confirmed, the inside of the container was uniformly stirred. After repeating this process 10 batches using this container 1, when the inside of the container 1 was confirmed visually, the whole inner wall of the container was completely covered with adhesion. Since the weight average particle diameter of the poorly water-soluble inorganic compound was small, it is considered that the kinetic energy of the poorly water-soluble inorganic compound was insufficient and adhesion could not be removed. Table 1 shows the result list.
<Comparative Example 10>
Comparative Example 1 except that in the polymerization step, the poorly water-soluble inorganic compound 4 was used instead of the poorly water-soluble inorganic compound 3, and the peripheral speed of the stirring blade: C was stirred at 1.0 m / s. Toner particles 20 were obtained by the same method as above. When the stirring state during polymerization was confirmed, the inside of the container was uniformly stirred.
After repeating the above process 10 batches using this container 1, when the inside of the container 1 was visually confirmed, the bottom of the container was slightly adhered, but the side trunk was completely covered by the adhesion. It was broken. Since the weight average particle size of the poorly water-soluble inorganic compound was larger than the peripheral speed of the stirring blade, the poorly water-soluble inorganic compound was not uniformly stirred inside the container, and the poorly water-soluble inorganic compound was formed at the bottom of the container. However, it seems that it stayed. Table 1 shows the result list.
<Comparative Example 11>
In the polymerization step, toner particles 21 were obtained in the same manner as in Comparative Example 1 except that the stirring blade peripheral speed: C was stirred at 4.0 m / s. When the stirring state during polymerization was confirmed, the inside of the container was uniformly stirred. After repeating this process 10 batches using this container 1, when the inside of the container 1 was confirmed visually, the whole inner wall of the container was completely covered with adhesion. Since the weight average particle diameter of the poorly water-soluble inorganic compound was small, it is considered that the kinetic energy of the poorly water-soluble inorganic compound was insufficient and adhesion could not be removed. Table 1 shows the result list.
<Comparative Example 12>
Comparative Example 1 except that in the polymerization step, the poorly water-soluble inorganic compound 4 was used in place of the poorly water-soluble inorganic compound 3, and the peripheral speed of the stirring blade: C was stirred at 4.0 m / s. Toner particles 22 were obtained by the same method as described above. When the stirring state during polymerization was confirmed, the inside of the container was uniformly stirred.
After repeating the above process 10 batches using this container 1, when the inside of the container 1 was visually confirmed, the bottom of the container was slightly adhered, but the side trunk was completely covered by the adhesion. It was broken. Since the weight average particle size of the poorly water-soluble inorganic compound was larger than the peripheral speed of the stirring blade, the poorly water-soluble inorganic compound was not uniformly stirred inside the container, and the poorly water-soluble inorganic compound was formed at the bottom of the container. However, it seems that it stayed. Table 1 shows the result list.
<Comparative Example 13>
In the polymerization step, the same procedure as in Comparative Example 1 was conducted except that the hardly water-soluble inorganic compound 1 was used in place of the slightly water-soluble inorganic compound 3 and the peripheral speed of the stirring blade: C was stirred at 0.05 m / s. Thus, toner particles 23 were obtained. When the stirring state during the polymerization was confirmed, it was observed that a stagnant portion was present at a part of the gas-liquid interface.
After repeating this process 10 batches using this container 1, when the inside of the container 1 was confirmed visually, the whole inner wall of the container was completely covered with adhesion. This is probably because the peripheral speed of the stirring blade was too low, and the kinetic energy of the poorly water-soluble inorganic compound was insufficient. Further, the inside of the container near the staying portion was in a particularly bad state. Table 1 shows the result list.
<Comparative example 14>
In the polymerization step, the same as Comparative Example 1 except that the slightly water-soluble inorganic compound 2 was used instead of the slightly water-soluble inorganic compound 3, and the peripheral speed of the stirring blade: C was stirred at 0.05 m / s. Thus, toner particles 24 were obtained. When the stirring state during the polymerization was confirmed, it was observed that a stagnant portion was present at a part of the gas-liquid interface.
After repeating this process 10 batches using this container 1, when the inside of the container 1 was confirmed visually, the whole inner wall of the container was completely covered with adhesion. This is probably because the peripheral speed of the stirring blade was too low, and the generation rate of adhesion exceeded the adhesion removal rate due to the poorly water-soluble inorganic compound. Further, the inside of the container near the staying portion was in a particularly bad state. Table 1 shows the result list.
<Comparative Example 15>
In the polymerization step, the same as Comparative Example 1 except that the slightly water-soluble inorganic compound 1 was used instead of the slightly water-soluble inorganic compound 3, and the peripheral speed of the stirring blade: C was stirred at 5.0 m / s. Thus, toner particles 25 were obtained. As a result of confirming the stirring state during the polymerization, it seems that the peripheral speed is excessive, and a large vortex is generated at the gas-liquid interface, and the dispersion of the polymerizable monomer composition is vigorously vaporized. It was liquefied in the gas layer at the upper part of the tank and recirculated in a large amount inside the container.
After repeating the above process 10 batches using this container 1, when the inside of the container 1 was confirmed visually, adhesion had generate | occur | produced in the container side bottom part. Since the peripheral speed of the stirring blade is too large, it seems that the poorly water-soluble inorganic compound was stirred while being unevenly distributed in the container-side body. Table 1 shows the result list.
<Comparative Example 16>
In the polymerization step, the same as Comparative Example 1 except that the poorly water-soluble inorganic compound 2 was used in place of the poorly water-soluble inorganic compound 3, and the peripheral speed of the stirring blade: C was stirred at 5.0 m / s. Thus, toner particles 25 were obtained. As a result of confirming the stirring state during the polymerization, it seems that the peripheral speed is excessive, and a large vortex is generated at the gas-liquid interface, and the dispersion of the polymerizable monomer composition is vigorously vaporized. It was liquefied in the gas layer at the upper part of the tank and recirculated in a large amount inside the container.
After repeating the above process 10 batches using this container 1, when the inside of the container 1 was confirmed visually, adhesion had generate | occur | produced in the container side bottom part. Since the peripheral speed of the stirring blade is too large, it seems that the poorly water-soluble inorganic compound was stirred while being unevenly distributed in the container-side body. Table 1 shows the result list.

1: container, 2: stirring blade, 3: baffle plate, 4: stirring motor, 5: gas-liquid interface, 6: jacket for temperature adjustment, 7: thermometer in polymerization vessel, 8: jacket thermometer, 9: discharge Valve, 10: shower nozzle, X: maximum diameter of stirring blade, Y: inner diameter of container

Claims (2)

In a method for producing toner particles containing a colorant and having the following steps i) or ii):
Adding a poorly water-soluble inorganic compound in the polymerization step or the solvent removal step,
The volume median diameter of the poorly water-soluble inorganic compound: A satisfies the following formula (1),
The mass of particles having a diameter equal to the volume median diameter of the sparingly water-soluble inorganic compound: B satisfies the following formula (2):
The polymerization step and the solvent removal step are performed in a container equipped with a stirring blade,
The peripheral speed of the stirring blade: C satisfies the following formula (3),
Kinetic energy of the poorly water-soluble inorganic compound particles: D satisfies the following formula (4):
Formula (1) 10.0 ≦ A (μm) ≦ 40.0
Formula (2) 1.64 × 10 ⁻¹² ≦ B (kg) ≦ 1.05 × 10 ⁻¹⁰
Formula (3) 1.0 <= C (m / s) <= 4.0
Formula (4) 8.22 × 10 ⁻¹³ ≦ D (kg · m ² / s ² ) ≦ 8.41 × 10 ⁻¹⁰
i) A granulating step of dispersing a toner particle composition containing a polymerizable monomer and a colorant in an aqueous medium to form particles of the polymerizable monomer composition, and the polymerizable monomer composition A polymerization step of polymerizing the polymerizable monomer present in the particles to obtain toner particles;
ii) a granulating step of dispersing a mixed solution in which a toner particle composition containing a binder resin and a colorant is dissolved or dispersed in an organic solvent in an aqueous medium to form particles of the mixed solution, and the mixing A solvent removal step of obtaining toner particles by removing an organic solvent present in the particles of the solution; The method for producing toner particles according to claim 1, wherein in the polymerization step, the hardly water-soluble inorganic compound is added when the polymerization conversion rate of the polymerizable monomer composition is 30% or less.