JP6768308B2 - Method for manufacturing resin fine particles and method for manufacturing toner particles - Google Patents

Description

The present invention relates to a method for producing resin fine particles and a method for producing toner particles in a suspension polymerization method.

Submicron to micrometer-order resin fine particles obtained by the suspension polymerization method are polymerized by preparing droplets of the polymerizable monomer by high-speed shearing of the polymerizable monomer composition in an aqueous medium. It is manufactured by polymerizing droplets of a sex monomer. Therefore, the obtained resin fine particles become spherical due to the influence of surface tension.
There are many industries in which resin fine particles on the order of submicron to micrometer are desired, and depending on the industry field, there are also fields in which irregular resin fine particles are desired instead of spherical ones.

For example, in the field of electrophotographic photography, printing is performed by transferring a toner image developed on a photoconductor to a transfer member such as paper. In order to continue printing a beautiful image, it is necessary to remove the residual toner remaining on the photoconductor with a cleaning member such as a blade. In order to improve this cleaning property, there is a demand for a deformed toner and a deformed auxiliary agent added to the toner surface. In this way, there are industry fields that require irregularly shaped resin fine particles.

Therefore, a method for producing irregular resin fine particles is required in the suspension polymerization method, and many methods for producing irregular resin fine particles have been proposed.
For example, by dissolving a dispersant in which a polymerizable monomer is dispersed while the conversion rate of the polymerizable monomer is between 40% and 80%, the polymerizable monomers are aggregated and deformed. A method for producing various resin fine particles has been proposed (see Patent Document 1).

Further, as a dispersant for a polymerizable monomer, a method has been proposed in which suspension polymerization is carried out in combination with inorganic fine particles, and after the polymerization reaction is completed, the inorganic fine particles on the surface of the resin fine particles are dissolved to form irregularities ( See Patent Document 2).
Further, a method has been proposed in which suspension polymerization is carried out in a state where a low crystallinity elastomer is dissolved in a polymerizable monomer, and the shape is deformed by utilizing the temperature responsiveness of the elastomer (see Patent Document 3). ..

JP-A-5-720808 Japanese Patent Application Laid-Open No. 7-114212 Japanese Unexamined Patent Publication No. 2003-277417

Since the technique disclosed in Patent Document 1 agglomerates and deforms a plurality of polymerizable monomers, the particle size distribution of the obtained resin fine particles is broad and there is a risk that coarse particles are likely to be generated. , There is still room for improvement.
The technique disclosed in Patent Document 2 may require a large amount of time to dissolve the inorganic fine particles.
In the technique disclosed in Patent Document 3, it is necessary to dissolve another kind of material such as an elastomer in the polymerizable monomer to polymerize it. Therefore, when it is desired to use the third and fourth materials together, the polymerizable monomer is used. It greatly affects the solubility in the inside and may narrow the degree of freedom of production. Further, when many materials are used in combination, the material dissolved in the polymerizable monomer may be depleted and aggregated, so that the material may become unevenly distributed resin fine particles.
As described above, many methods for producing irregularly shaped resin fine particles in the suspension polymerization method have been proposed, but there is still room for improvement in any of the production methods.
An object of the present invention is to provide a method for producing resin fine particles having a sharp particle size distribution and an irregular shape and a method for producing toner particles in a suspension polymerization method.

As a result of diligent studies by the present inventors, a method has been found in which the particle size distribution of the suspended polymerized fine particles obtained by the suspension polymerization method is sharp and the shape can be easily controlled. That is, according to the present invention.
(A) The polymerizable monomer composition containing the polymerizable monomer is dispersed in a first aqueous medium containing an acid-soluble dispersant A, and the dispersant A adheres to the surface of the polymerizable simpler. Granulation step to obtain a dispersion containing droplets of a body composition,
(B) in the dispersion, the pH adjustment of the dispersion to dissolve the dispersant A attached to the surface of the droplets, after dissolution of the dispersant A, acid-soluble different from the dispersant A dissolved thereby adhesion dispersant B to the surface of the droplet - reattachment process, and (c) polymerizing step of polymerizing the polymerizable monomer to form the fine resin particles contained in the droplets,
It is a method for producing resin fine particles having
The dispersant A is calcium phosphate or magnesium hydroxide.
When the dispersant A is calcium phosphate, the dispersant B is aluminum hydroxide, and when the dispersant A is magnesium hydroxide, the dispersant B is calcium phosphate or aluminum hydroxide.
A method for producing fine resin particles is provided.

According to the method for producing resin fine particles of the present invention, resin fine particles and toner particles having a sharp particle size distribution and irregular shape can be produced in the suspension polymerization method.

It is a figure which shows an example of the process of the suspension polymerization method of this invention. It is a conceptual diagram which shows the state of a dispersant and a droplet of a polymerizable monomer composition in a dissolution-reattachment step. It is a figure which shows an example of the deformed particle and the particle formed by coalescing.

Hereinafter, the present invention will be described in detail.
1 (a) and 1 (b) are examples of steps of a suitable suspension polymerization method used in the present invention, and the present invention is not limited thereto.

The process example shown in FIG. 1A includes the following granulation step, dissolution-reattachment step, and polymerization step.
(A) Granulation step In step S111, a dispersion in which droplets of the polymerizable monomer composition having the acid-soluble dispersant A adhered to the surface are dispersed in the first aqueous medium using a stirring means. This is the process of obtaining.
FIG. 2A is a conceptual diagram showing droplets of the polymerizable monomer composition in which the dispersant A adheres to the surface.

Examples of the stirring means used in the granulation step include the following. Paddle wing, inclined paddle wing, three swept wing, anchor wing, full zone (manufactured by Shinko Pantech), Max Blend (manufactured by Sumitomo Heavy Industries), Supermix (manufactured by Satake Chemical Machinery Co., Ltd.), Hi-F mixer (Soken) Those with a stirring blade such as (manufactured by Kagaku Co., Ltd.). Further, a manufacturing method capable of imparting a high shearing force and achieving uniform circulation is more preferable. As the high shear stirrer, a stirrer having a stirring chamber formed by a stirring rotor rotating at high speed and a screen provided so as to surround the stirring rotor is preferably used. Specifically, Ultratarax (manufactured by IKA), Polytron (manufactured by Kinematica), TK Homomixer (manufactured by Special Machinery Co., Ltd.), Clairemix (manufactured by M-Technique) and the like are used.

(B) Dissolution-Reattachment Step In step S121, the dispersant A adhering to the surface of the droplet is dissolved, and after the dissolution, an acid-soluble dispersant B different from the dispersant A or the dispersant A is added to the droplet. Adhere to the surface.
FIG. 2B shows a state in which the dispersant A adhering to the surface of the droplet is partially dissolved.
FIG. 2C shows a droplet whose surface is unstable and deformed.
FIG. 2D shows a state in which the dispersant A is reattached to the surface of the deformed droplet.

First, a medium for dissolving the acid-soluble dispersant A adhering to the surface of the droplets in the dispersion is added, and the acid-soluble dispersant A is dissolved by mixing by a stirring means. As a means for dissolving the dispersant A, a strong acid or a weak acid such as hydrochloric acid, sulfuric acid, nitric acid, or acetic acid is added, and the pH value of the first aqueous medium is adjusted to be equal to or lower than the pH value at which the dispersant A starts to dissolve. There is a way to do it.
Next, the dispersant A or the dispersant B is added to the dispersion liquid and stirred to redeposit the dispersant A or the dispersant B on the surface of the droplet.

(C) Polymerization Step S131 is a step of producing resin fine particles by polymerizing the polymerizable monomer that has undergone the reattachment step while stirring.

Examples of the stirring means used in the (b) dissolution-reattachment step and (c) polymerization step include the following. Paddle wing, inclined paddle wing, three swept wing, anchor wing, full zone (manufactured by Shinko Pantech), Max Blend (manufactured by Sumitomo Heavy Industries), Supermix (manufactured by Satake Chemical Machinery Co., Ltd.), Hi-F mixer (Soken) Those with a stirring blade such as (manufactured by Kagaku Co., Ltd.).

As a result of diligent studies by the present inventors, the dispersant A on the surface of the droplet is dissolved, and the dispersant A or the acid-soluble dispersant B other than the dispersant A is reattached to the surface of the droplet to form a variant. It has been found that it is possible to produce resin fine particles having an excellent particle size distribution.
The reason for this is not clear, but I think it is as follows.

First, in the granulation step, droplets of the polymerizable monomer composition in which the acid-soluble dispersant A adheres to the entire surface are generated. The droplets have a spherical shape due to surface tension.
Next, in the dissolution-reattachment step, the dispersant A on the surface of the suspension droplet starts to be dissolved by adding and mixing a medium for dissolving the dispersant A adhering to the surface of the suspension droplet. To do. When the dispersant A dissolves, the area of contact between the water and the droplets increases. As a result, the interface of the droplet to which the acid-soluble dispersant A is not attached becomes unstable, so that it is difficult to maintain the spherical shape and the shape changes to a deformed shape.

However, if this state continues, the droplets will coalesce, and irregularly shaped resin fine particles having a coarse particle size distribution and a broad particle size distribution will be formed.
Therefore, in the present invention, by reattaching the dispersant A or the acid-soluble dispersant B other than the dispersant A to the surface of the droplets, the droplets do not coalesce with each other and the particle size distribution is sharp. We believe that there are droplets in a deformed state.

Further, (b) the dissolution-reattachment step is a mixing step of mixing the dispersion liquid with the second aqueous medium containing the dispersant A or the acid-soluble dispersant B other than the dispersant A.
It is preferable that the solubility of the dispersant A in the second aqueous medium is higher than the solubility of the dispersant A in the first aqueous medium.
The reason for this is thought to be as follows.

In the mixing step (step S122), the dispersion liquid is mixed with the second aqueous medium containing the acid-soluble dispersant A or the dispersant B other than the dispersant A, and (b) in the dissolution-reattachment step. This is a process in which dissolution and reattachment are performed at once.
At the beginning of the mixing step, the dispersant A on the surface of the droplet dissolves on the surface of the droplet, and the droplet is deformed.
After that, since the dispersant A or the dispersant B adheres to the surface of the deformed droplets, it is considered that the coalescence of the droplets can be prevented from proceeding and the deformed droplets can be obtained.
The case where the dispersant A dissolved at the initial stage of the mixing step reattaches to the surface of the deformed droplets is, for example, when the dispersion liquid is gradually added to the second dispersion medium, the dispersion liquid is added. This is a case where the solubility of the dispersant A in the mixed solution gradually decreases as the amount increases. In such a case, the dispersant A once dissolved precipitates as the amount of the dispersion liquid added increases, and reattaches to the surface of the droplet.

Further, in the method for producing resin fine particles of the present invention, as a means for adjusting the solubility of the acid-soluble dispersant A or dispersant B,
In the dissolution-reattachment step, the pH of the dispersion is preferably
In the mixing step, the pH of the mixed solution obtained by mixing the dispersion liquid and the second aqueous medium.
Is preferable.
The use of a special solvent in the production of resin fine particles may narrow the latitude (degree of freedom) of material selectivity in terms of production. Therefore, the method of changing the pH as in the present invention is the easiest and is preferable from the viewpoint of productivity.

[Dispersant A]
Examples of the acid-soluble dispersant A whose solubility can be adjusted by pH include the following materials.
For example, calcium phosphate, magnesium phosphate, calcium carbonate, magnesium carbonate, magnesium hydroxide and the like.
These materials are acid-soluble inorganic fine particles composed of metal ions and organic ions. Therefore, by lowering the pH value in the aqueous medium, the concentration of organic ions is lowered and the solubility is increased. Specifically, taking calcium phosphate as an example, the solubility of calcium phosphate is determined by the concentration of calcium ions and the concentration of phosphate ions. Phosphate ion has a triacid dissociation state of phosphate ion, phosphate monohydrogen ion, and phosphate dihydrogen ion in an aqueous medium, and the concentration of phosphate ion decreases as the pH value decreases, and phosphate monohydrogen ion. And the concentration of dihydrogen phosphate ions increase. Therefore, calcium phosphate can be improved in solubility by reducing the concentration of phosphate ions, that is, lowering the pH value.

[Dispersant B]
In addition, the types of the dispersant B are listed below.
Calcium phosphate, magnesium phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, calcium metasilicate, aluminum hydroxide, calcium sulfate, barium sulfate, bentonite, silica, alumina and the like.
However, as the dispersant B used in the production method of the present invention, a material having a lower solubility in an acid than the acid-soluble dispersant A or a material insoluble in an acid is preferable. Therefore, the preferred dispersant B among the above-mentioned materials differs depending on the type of acid-soluble dispersant A.

For example, when the acid-soluble dispersant A is calcium phosphate, aluminum hydroxide, calcium sulfate, barium sulfate, bentonite, silica, or alumina, which are more soluble in acid than calcium phosphate, are preferable as the dispersant B.
When the dispersant A is magnesium hydroxide, calcium phosphate, magnesium phosphate, aluminum hydroxide, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, calcium metasilicate, calcium sulfate, and sulfuric acid Barium, bentonite, silica, or alumina are preferred as the dispersant B.
As described above, a material having lower solubility in acid than acid-soluble dispersant A or insoluble in acid is preferable as dispersant B, so that the type of dispersant B preferred varies depending on the type of dispersant A. ..

When calcium phosphate is used as the dispersant A, the value obtained by subtracting the pH value of the second aqueous medium from the pH value of the dispersion solution when mixed in the mixing step is 0.5 or more with respect to the pH of calcium phosphate. It is preferable because the solubility changes.

When calcium phosphate is used as the dispersant A and the value obtained by subtracting the pH value of the second aqueous medium from the pH value of the dispersion liquid when mixed in the mixing step is 0.5 or more.
The pH value of the dispersion liquid when mixed in the mixing step is preferably 4.5 or more and 6.0 or less from the viewpoint of the particle size distribution of the resin fine particles, and the pH value of the second aqueous medium at that time is 5. It is preferable that the value is less than .0 because the deformed resin fine particles can be efficiently obtained.

Further, from the viewpoint of excellent particle size distribution and shape control in the present invention, the following production conditions are preferable.
In the method for producing resin fine particles of the present invention, the ratio of the mass of the second aqueous medium to the mass of the first aqueous medium during the mixing step (mass of the second aqueous medium / mass of the first aqueous medium) is determined. It is preferably 0.10 or more and 0.70 or less. When the mass ratio is less than 0.10, since the amount of the second aqueous medium is small, the effect of dissolving the dispersant A adhering to the droplet surface is weakened, and the degree of deformation is reduced. Further, when the mass ratio exceeds 0.70, the solubilization of the dispersant A adhering to the droplet surface is promoted, so that the resin fine particles may aggregate and become coarse.

The amount of the acid-soluble dispersant A contained in the first aqueous medium is 1.0 part by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. Is preferable.
The amount of the dispersant A, the amount of the dispersant B, or the total amount of the dispersant A and the dispersant B contained in the second aqueous medium is 0 with respect to 100 parts by mass of the polymerizable monomer. It is preferable to use it in an amount of 1 part by mass or more and 10.0 parts by mass or less.

Further, in the method for producing resin fine particles of the present invention, it is preferable that the peripheral speed of the tip of the stirring member in the mixing step is 0.1 m / sec or more and 40.0 m / sec or less. If it is less than 0.1 m / sec, the first aqueous medium and the second aqueous medium are difficult to mix. Therefore, since the dispersant A adhering to the surface of the droplets exists in a solubilized state for a long time, the resin fine particles may aggregate. Further, when the value exceeds 40.0 m / sec, the dispersant A adhering to the surface of the droplet is immediately solubilized, and the dispersant stably exists in the second aqueous medium that supplements the solubilized portion. Since A or a dispersant B other than the dispersant A adheres immediately, the deforming effect may be weakened.
The following suitable materials used in the present invention will be described.

[Polymerizable monomer]
As the polymerizable monomer used in the present invention, a vinyl-based polymerizable monomer capable of radical polymerization may be used in addition to styrene. As the vinyl-based polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. Examples of the monofunctional polymerizable monomer include styrene; α-methylstyrene, β-methylstyrene, ο-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p. Styrene derivatives such as −phenylstyrene; 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 Acrylic-based polymerizable properties such as -ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, and 2-benzoyloxyethyl acrylate. Monomer; 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, Methacrylic polymerizable monomers such as n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, and dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl acetate, vinyl propionate, vinyl butyrate, benzoate Vinyl esters such as vinyl acid acid and vinyl formate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

Examples of the polyfunctional polymerizable monomer include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and tripropylene glycol. Diacrylate, polypropylene glycol diacrylate, 2,2'-bis (4- (acryloxy diethoxy) phenyl) propane, trimethylpropan triacrylate, tetramethylolmethanetetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis ( 4- (methacryloxy diethoxy) phenyl) propane, 2,2'-bis (4- (methacryloxy polyethoxy) phenyl) propane, trimethyl propanetrimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalin, divinyl ether, etc. Can be mentioned.
In the present invention, the above-mentioned monofunctional polymerizable monomer is used alone or in combination of two or more, or the above-mentioned monofunctional polymerizable monomer and the polyfunctional polymerizable monomer are used in combination. To do.

[Polymerization initiator]
As the polymerization initiator used in the suspension polymerization method, an oil-soluble initiator is generally used. For example, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis Azo compounds such as -4-methoxy-2,4-dimethylvaleronitrile; acetylcyclohexylsulfonyl peroxide, diisopropyl peroxy carbonate, decanonyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide, acetyl peroxide, tert-Butylperoxy-2-ethylhexanoate, benzoyl peroxide, tert-butylperoxyisobutyrate, cyclohexanone peroxide, methylethylketone peroxide, dicumyl peroxide, tert-butylhydroperoxide, di-tert- Peroxide-based initiators such as butyl peroxide, tert-butyl peroxypivalate, and cumene hydroperoxide can be mentioned.

A water-soluble initiator may be used in combination as the polymerization initiator, if necessary, ammonium persulfate, potassium persulfate, 2,2'-azobis (N, N'-dimethyleneisobutyroamidine) hydrochloride, 2, Examples thereof include 2'-azobis (2-aminodinopropane) hydrochloride, azobis (isobutylamidine) hydrochloride, sodium 2,2'-azobisisobutyronitrile sulfonate, ferrous sulfate or hydrogen peroxide.
The timing of adding these polymerization initiators may be any of a granulation step and a polymerization step. Further, it may be added in a plurality of times and divided in any step. Further, two or more kinds of the above-mentioned polymerization initiators may be used in combination.

[Colorant]
Further, in the method for producing resin fine particles of the present invention, a colorant may be contained in the polymerizable monomer.
As the colorant, known colorants such as various conventionally known dyes and pigments can be used.
As the magenta colorant, a condensed azo compound, a diketopyrrolopyrrole compound, anthraquinone, a quinacridone compound, a basic dye lake compound, a naphthol compound, a benzimidazolone compound, a thioindigo compound and a perylene compound are used. Specifically, C.I. I. Pigment Red 2, 3, 5-7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221 and 254, C.I. I. Pigment Bio Red 19 is particularly preferred.

As the cyan colorant, a copper phthalocyanine compound and its derivative, an anthraquinone compound, a basic dye lake compound and the like can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 are particularly preferably used.

As the yellow colorant, as the pigment system, a compound typified by a condensed azo compound, an isoindolinone compound, an anthraquinone compound, an azo metal complex methine compound, and an allylamide compound is used. Specifically, C.I. I. Pigment Yellow 3,7,10,12-15,17,23,24,60,62,74,75,83,93-95,99,100,101,104,108-111,117,123,128, 129,138,139,147,148,150,166,168-177,179,180,181,183,185,191:1,191,192,193,199 are preferably used. Examples of the dye system include C.I. I. Solvent Yellow 33,56,79,82,93,112,162,163, C.I. I. Disperse Yellow 42, 64, 2011, 211 can be mentioned.

As the black colorant, carbon black, aniline black, acetylene black, titanium black, and those toned to black using the yellow / magenta / cyan colorants shown above can be used.
These colorants can be used alone or mixed, or in the form of a solid solution. When the colorant is added, it is preferable to add the colorant in an amount of 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.

[Other additives]
In the suspension polymerization method of the present invention, the following may be contained in the polymerizable monomer.
For example, examples of the organic compound include amorphous polyester resin, crystalline polyester resin, vinyl polymer, ester wax, carnauba wax, and hydrocarbon wax.
Examples of the inorganic fine particles include titania, silica, alumina and the like.
When these additives are added, it is preferable to add them so that the amount is 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. Further, two or more kinds of the above-mentioned organic compounds and / or inorganic compounds may be used in combination.

The method for measuring the physical properties of the resin fine particles of the present invention will be described below.
<Measurement of pH of aqueous media>
A commercially available pH meter can be used for pH measurement, and for example, "glass lining pH measurement system, glass sensor pH" (manufactured by Shinko Environmental Solutions Co., Ltd.) can be used.

<Volume-based median diameter (Dv50) of resin fine particles, number-based median diameter (Dn50)>
The volume-based median diameter (Dv50) and the number-based median diameter (Dn50) of the toner are calculated as follows. As the measuring device, a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube by the pore electrical resistance method is used. For the setting of measurement conditions and the analysis of measurement data, the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter) is used. The measurement is performed with 25,000 effective measurement channels.

As the electrolytic aqueous solution used for the measurement, one in which special grade sodium chloride is dissolved in ion-exchanged water so that the concentration becomes 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter) can be used.
Before performing measurement and analysis, the dedicated software is set as follows. On the "Change standard measurement method (SOM)" screen of the dedicated software, set the total count number in the control mode to 50,000 particles, measure once, and set the Kd value to "standard particles 10.0 μm" (Beckman Coulter). Set the value obtained using (manufactured by the company). By pressing the "threshold / noise level measurement button", the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check “Flash of aperture tube after measurement”. On the "Pulse to particle size conversion setting" screen of the dedicated software, the bin spacing is set to logarithmic particle size, the particle size bin is set to 256 particle size bins, and the particle size range is set to 2 μm or more and 60 μm or less.

The specific measurement method is as follows.
(1) 200 mL of the electrolytic aqueous solution is placed in a 250 mL round bottom beaker made of glass dedicated to Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and air bubbles in the aperture tube are removed by the "aperture flush" function of the dedicated software.
(2) Put 30 mL of the electrolytic aqueous solution in a 100 mL flat bottom beaker made of glass. Among them, as a dispersant, "Contaminone N" (a 10% by mass aqueous solution of a neutral detergent for cleaning a precision measuring instrument with a pH of 7 consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd. ) Is diluted 3 times by mass with ion-exchanged water, and 0.3 mL of the diluted solution is added.

(3) Two oscillators with an oscillation frequency of 50 kHz are built in with their phases shifted by 180 degrees, and an ultrasonic disperser "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios) with an electrical output of 120 W is prepared. Put 3.3 L of ion-exchanged water in the water tank of the ultrasonic disperser, and add 2 mL of contaminantin N to this water tank. (4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.

(5) With the electrolytic aqueous solution in the beaker of (4) being irradiated with ultrasonic waves, 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. In ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10 ° C. or higher and 40 ° C. or lower.
(6) Using a pipette, the aqueous electrolyte solution of (5) in which toner is dispersed is dropped onto the round bottom beaker of (1) installed in the sample stand, and the measured concentration is adjusted to 5%. Then, the measurement is performed until the number of measurement particles reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the device, and the weight average particle size (D4), the number average particle size (D1), the volume-based median diameter, and the number-based median diameter are calculated. The "50% diameter" on the "Analysis / Volume Statistics (Arithmetic Mean)" screen when the graph / volume% is set with the dedicated software is the weight average particle size (D4), and is the "median diameter". Is the volume-based median diameter (Dv50). Further, when the graph / number% is set in the dedicated software, the "average diameter" of the "analysis / number statistical value (arithmetic mean)" screen is the number average particle size (D1), and the "median diameter" is The number-based median diameter (Dn50).

<Measuring method of equivalent circle diameter, average circularity, etc. of resin fine particles>
The average circularity of the toner particles was measured by a flow-type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration work.
The specific measurement method is as follows. First, about 20 mL of ion-exchanged water from which impure solids and the like have been removed in advance is placed in a glass container. Among them, as a dispersant, "Contaminone N" (a 10% by mass aqueous solution of a neutral detergent for cleaning a precision measuring instrument with a pH of 7 consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd. ) Is diluted about 3 times by mass with ion-exchanged water, and about 0.2 mL of the diluted solution is added. Further, about 0.02 g of the measurement sample is added, and the dispersion treatment is performed for 2 minutes using an ultrasonic disperser to prepare a dispersion liquid for measurement. At that time, the dispersion is appropriately cooled so that the temperature of the dispersion is 10 ° C. or higher and 40 ° C. or lower. As the ultrasonic disperser, a desktop ultrasonic cleaner disperser (for example, "VS-150" (manufactured by Vervocrea)) having an oscillation frequency of 50 kHz and an electrical output of 150 W is used, and a predetermined amount is contained in the water tank. Ion-exchanged water is added, and about 2 mL of the contaminanton N is added into the water tank.

For the measurement, the flow type particle image analyzer equipped with "LUCPLFLN" (magnification 20 times, numerical aperture 0.40) was used as the objective lens, and the particle sheath "PSE-900A" (manufactured by Sysmex Corporation) was used as the sheath liquid. It was used. The dispersion prepared according to the above procedure is introduced into the flow type particle image analyzer, and 2000 toner particles are measured in the total count mode in the HPF measurement mode. Then, the binarization threshold value at the time of particle analysis was set to 85%, the diameter of the analyzed particle was limited to 1.977 μm or more and less than 39.54 μm, and the average circularity of the toner particles was obtained.

In the measurement, automatic focus adjustment is performed using standard latex particles (for example, "RESAARCH AND TEST PARTICLES Latex Microsphere Suspensions 5100A" manufactured by Duke Scientific) diluted with ion-exchanged water before the start of the measurement. After that, it is preferable to perform focus adjustment every 2 hours from the start of measurement.
In the embodiment of the present application, a flow-type particle image analyzer that has been calibrated by Sysmex and has received a calibration certificate issued by Sysmex was used. The measurement was carried out under the measurement and analysis conditions when the calibration certificate was obtained, except that the diameter of the analysis particle was limited to 1.977 μm or more and less than 39.54 μm in equivalent circle diameter.

<Measurement method for deformation of resin fine particles>
<Confirmation of deformation>
The confirmation of the deformity was judged from the images taken by the Hitachi ultra-high resolution field emission scanning electron microscope S-4800 (Hitachi High-Technologies Corporation). It should be noted that the particles having the shape shown in FIG. 3 were judged to be deformed, and the particles having the shape in which a plurality of particles were united were not regarded as "deformed" in the present invention.
The image capturing conditions of S-4800 are as follows.

(1) Sample preparation A thinly coated conductive paste is applied to a sample table (aluminum sample table 15 mm × 6 mm), and resin fine particles are sprayed on the conductive paste. Further, air blow is performed to remove excess resin fine particles from the sample table and the sample is sufficiently dried. Set the sample table in the sample holder and adjust the sample table height to 36 mm with the sample height gauge.

(2) Setting of observation conditions for S-4800 The degree of deformation of the resin fine particles is confirmed by using the image obtained by observing the secondary electron image of S-4800.
Inject liquid nitrogen into the anti-contamination trap attached to the mirror body of S-4800 until it overflows, and leave it for 30 minutes. The "PC-SEM" of S-4800 is started to perform flushing (cleaning of the FE chip which is an electron source). Click the accelerating voltage display part of the control panel on the screen and click the [Flushing] button to open the flushing execution dialog. Confirm that the flushing intensity is 2, and execute. Confirm that the emission current due to flushing is 20 to 40 μA. Insert the sample holder into the sample chamber of the S-4800 mirror. Press [Origin] on the control panel to move the sample holder to the observation position.

Click the accelerating voltage display to open the HV setting dialog, and set the accelerating voltage to [2.0 kV] and the emission current to [10 μA]. In the [Basic] tab of the operation panel, set the signal selection to [SE], and select [Top (U)] for the SE detector to set the mode for observing with a secondary electron image. Similarly, in the [Basic] tab of the operation panel, set the probe current of the electron optics condition block to [Normal], the focus mode to [HR], and the WD to [7.0 mm]. Press the [ON] button on the acceleration voltage display of the control panel to apply the acceleration voltage.

(3) Method for confirming the degree of deformation of the resin fine particles Drag the inside of the magnification display section of the control panel to set the magnification to 1000 (1k) times. Rotate the focus knob [COARSE] on the operation panel to adjust the aperture alignment when the focus is adjusted to some extent. Click [Align] on the control panel to display the alignment dialog, and select [Beam]. Rotate the STIGMA / ALIGNMENT knobs (X, Y) on the operation panel to move the displayed beam to the center of the concentric circles. Next, select [Aperture] and turn the STIGMA / ALIGNMENT knobs (X, Y) one by one to stop the movement of the image or adjust it to the minimum movement. Close the aperture dialog and use autofocus to focus. This operation is repeated twice more to focus.
Then, the number and shape of the resin fine particles in 100 visual fields were arbitrarily observed, and the number% of the concave resin fine particles with respect to the resin fine particles in all 100 visual fields was calculated.

The present invention will be specifically described with reference to the following examples. In this embodiment, all are based on mass unless otherwise specified.

<Production example 1 of resin fine particles>
● ion-exchanged water 1000 parts by weight in the preparation reactor of the first aqueous medium, the following materials were charged, and kept for 60 minutes at 65 ° C. with N ₂ purge.
Sodium Phosphate 14.0 parts by mass 10% Hydrochloric Acid 13.9 parts by mass Using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12,000 rpm, add 20 parts by mass of ion-exchanged water to 8. An aqueous solution of calcium chloride in which 0 parts by mass of calcium chloride was dissolved was added all at once to prepare an aqueous medium containing calcium phosphate as the dispersant A. The pH value of the prepared aqueous medium was 4.5.

● ion-exchanged water 100 parts by weight in the preparation reactor of the second aqueous medium, was charged with aluminum hydroxide 4.0 parts by mass, was kept for 60 minutes at 65 ° C. with N ₂ purge. Using a TK homomixer (manufactured by Tokushu Kagaku Kogyo), while stirring at 12,000 rpm, 9.0 parts by mass of 10% hydrochloric acid was added to prepare an aqueous medium containing aluminum hydroxide as the dispersant B. did. The pH value of the prepared aqueous medium was 4.0.

● Granulation process ・ 80 parts by mass of styrene ・ 20 parts by mass of n-butyl acrylate ・ 2 parts by mass of polyester resin

The above material was kept warm at 65 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). 2.5 parts by mass of the polymerization initiator t-hexyl peroxypivalate (manufactured by Nippon Oil & Fats Co., Ltd., trade name "Perhexyl PV", molecular weight: 202, 10-hour half-life temperature: 53.2 ° C.) was dissolved therein. A polymerizable monomer composition was prepared.
The polymerizable monomer composition was charged into the in the first aqueous medium in the first reaction vessel, 65 ° C., under _{N 2} purge, T. K.. Granulation for 5 minutes at 10,000rpm at homomixer A dispersion of droplets of the polymerizable monomer composition which was granulated and had calcium phosphate adhered to the surface was obtained.

● Mixing step The second aqueous medium is prepared in the second reaction vessel, and the dispersion is added while stirring the paddle stirring blade at a peripheral speed of 20 m / sec, and the second aqueous medium and the dispersion are added. And were mixed. Since calcium phosphate (dispersant A) dissolves at pH 4.0, in this mixing step, calcium phosphate on the surface of the droplet of the polymerizable monomer composition dissolves, and then aluminum hydroxide (aluminum hydroxide) (on the surface of the droplet). Dispersant B) adhered.

● Polymerization step After the above mixing step, the temperature was raised to 65 ° C. for 6 hours and then to 90 ° C. while stirring with a paddle stirring blade, and the reaction was carried out at 90 ° C. for 6 hours.

● Filtration and washing step After the polymerization reaction was completed, the reaction vessel was cooled, 10% hydrochloric acid was added, and the pH value was set to 2, and the dispersion stabilizer was dissolved while stirring for 2 hours. The emulsion was pressure filtered and further washed with more than 2,000 parts by mass of ion-exchanged water. The obtained cake was returned to 1000 parts by mass of ion-exchanged water, 10% hydrochloric acid was added, and the cake was rewashed with stirring for 2 hours with a pH value of 1 or less. The emulsion was pressure-filtered in the same manner as described above, further washed with ion-exchanged water of 2,000 parts by mass or more, sufficiently aerated, and then dried to obtain resin fine particles 1.

<Production Examples 2 to 5 of Resin Fine Particles>
Same as Production Example 1 of Resin Fine Particles except that the material composition and amount of the first aqueous medium of Production Example 1 of the resin fine particles and the material composition and amount of the second aqueous medium were changed as shown in Table 1. 2-5 resin fine particles were obtained.
In addition, for example, when a dispersion medium containing calcium phosphate having a pH of 4.0 is used as the second dispersion medium as in Production Example 2, in the mixing step, as the addition of the dispersion liquid progresses, the mixed liquid becomes The pH value gradually increases. Therefore, once dissolved calcium phosphate was precipitated and covered the surface of the droplet.

<Production Examples of Resin Fine Particles 6-9, 13>
The material composition and amount of the first aqueous medium and the material composition and amount of the second aqueous medium of Production Example 1 of the resin fine particles are changed as shown in Table 1, and the conditions of the mixing step are further described in Table 1. Resin fine particles 6 to 9 and 13 were obtained in the same manner as in Production Example 1 of the resin fine particles except that the resin fine particles were changed as described above.

<Production example 10 of resin fine particles>
● ion-exchanged water 1000 parts by weight in the preparation reactor of the first aqueous medium, the following materials were charged, and kept for 60 minutes at 65 ° C. with N ₂ purge.
Sodium hydroxide 12.0 parts by mass 10% hydrochloric acid 5.0 parts by mass Using a TK homomixer (manufactured by Tokushu Kika Kogyo), while stirring at 12000 rpm, 6.0 parts by mass of ion-exchanged water was added to 20 parts by mass. An aqueous solution of magnesium chloride in which magnesium chloride was dissolved was added all at once to prepare an aqueous medium containing magnesium hydroxide as the dispersant A. The pH value of the prepared aqueous medium was 7.5.

● ion-exchanged water 100 parts by weight in the preparation reactor of the second aqueous medium, was charged with aluminum hydroxide 4.0 parts by mass, was kept for 60 minutes at 65 ° C. with N ₂ purge. Using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), 5 parts by mass of 10% hydrochloric acid was added while stirring at 12,000 rpm to prepare an aqueous medium containing aluminum hydroxide as the dispersant B. The pH value of the prepared aqueous medium was 5.5.

● Granulation process ・ 80 parts by mass of styrene ・ 20 parts by mass of n-butyl acrylate Keep the above material at 65 ° C in a separate container and use a TK homomixer (manufactured by Tokushu Kika Kogyo) to make it uniform at 500 rpm. Dissolved and dispersed in. 2.5 parts by mass of the polymerization initiator t-hexyl peroxypivalate (manufactured by Nippon Oil & Fats Co., Ltd., trade name "Perhexyl PV", molecular weight: 202, 10-hour half-life temperature: 53.2 ° C.) was dissolved therein. A polymerizable monomer composition was prepared.
The polymerizable monomer composition was charged into the in the first aqueous medium in the first reaction vessel, 65 ° C., under _{N 2} purge, T. K.. Granulation for 5 minutes at 10,000rpm at homomixer A dispersion of droplets of a polymerizable monomer composition having magnesium hydroxide adhered to the surface was obtained.

● Mixing Step The second aqueous medium was prepared in the second reaction vessel, and the dispersion was charged while stirring the paddle stirring blade at a peripheral speed of 45 m / sec. Since magnesium hydroxide (dispersant A) dissolves at pH 5.5, in this mixing step, magnesium hydroxide on the surface of the droplet of the polymerizable monomer composition dissolves, and then on the surface of the droplet. Aluminum hydroxide (dispersant B) adhered.

● Polymerization step After the above mixing step, the temperature was raised to 65 ° C. for 6 hours and then to 90 ° C. while stirring with a paddle stirring blade, and the reaction was carried out at 90 ° C. for 6 hours.

● Filtration and washing step After the polymerization reaction was completed, the reaction vessel was cooled, 10% hydrochloric acid was added, and the dispersion stabilizer was dissolved while stirring for 2 hours with the pH value set to 1. The emulsion was pressure filtered and further washed with more than 2,000 parts by mass of ion-exchanged water. The obtained cake was returned to 1,000 parts by mass of ion-exchanged water, 10% hydrochloric acid was added, and the cake was rewashed while stirring for 2 hours with a pH value of 1 or less. The emulsion was pressure-filtered in the same manner as described above, further washed with ion-exchanged water of 2,000 parts by mass or more, sufficiently aerated, and then dried to obtain resin fine particles 10.

<Production Examples of Resin Fine Particles 11-12, 14>
The material composition and amount of the first aqueous medium and the material composition and amount of the second aqueous medium of Production Example 10 of the resin fine particles are changed as shown in Table 1, and the conditions of the mixing step are further described in Table 1. Resin fine particles 11 to 12 and 14 were obtained in the same manner as in Production Example 1 of the resin fine particles except that the resin fine particles were changed as described above.

<Production example 15 of resin fine particles>
● ion-exchanged water 1000 parts by weight in the preparation reactor of the first aqueous medium, the following materials were charged, and kept for 60 minutes at 65 ° C. with N ₂ purge.
Sodium phosphate 14.0 parts by mass 10% hydrochloric acid 10.9 parts by mass Using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12,000 rpm, 2.0 parts by mass of ion-exchanged water An aqueous solution of calcium chloride in which parts of calcium chloride was dissolved was added all at once to prepare an aqueous medium containing a dispersant (calcium phosphate). The pH value of the prepared aqueous medium was 5.0.

● Granulation process ・ 80 parts by mass of styrene ・ 20 parts by mass of n-butyl acrylate ・ 2 parts by mass of polyester resin

The above material was kept warm at 65 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). 2.5 parts by mass of the polymerization initiator t-hexyl peroxypivalate (manufactured by Nippon Oil & Fats Co., Ltd., trade name "Perhexyl PV", molecular weight: 202, 10-hour half-life temperature: 53.2 ° C.) was dissolved therein. A polymerizable monomer composition was prepared.
The above-mentioned polymerizable monomer composition was put into the above-mentioned first aqueous medium in the first reaction vessel, and granulated with a TK homomixer at 10000 rpm for 5 minutes under N ₂ purge at 65 ° C. , A dispersion of droplets of a polymerizable monomer composition having calcium phosphate adhered to the surface was obtained.

● Dissolution step 10% hydrochloric acid was added to the dispersion while stirring at a peripheral speed of the paddle stirring blade of 20 m / sec, and the pH value of the dispersion was adjusted to 3.5.
● Adhesion step 4.0 parts by mass of aluminum hydroxide was added to the above dispersion.

● Polymerization Step After the above adhesion step, the temperature was raised to 65 ° C. for 6 hours and then to 90 ° C. while stirring with a paddle stirring blade, and the reaction was carried out at 90 ° C. for 6 hours.

● Filtration and washing step After the polymerization reaction was completed, the reaction vessel was cooled, 10% hydrochloric acid was added, and the dispersion stabilizer was dissolved while stirring for 2 hours with a pH value of 1.2. The emulsion was pressure filtered and further washed with more than 2,000 parts by mass of ion-exchanged water. The obtained cake was returned to 1,000 parts by mass of ion-exchanged water, 10% hydrochloric acid was added, and the cake was rewashed while stirring for 2 hours with a pH value of 1 or less. The emulsion was pressure-filtered in the same manner as described above, further washed with ion-exchanged water of 2,000 parts by mass or more, sufficiently aerated, and then dried to obtain resin fine particles 15.

<Production Examples 16 to 17 of Resin Fine Particles>
Except for the material composition and amount of the first aqueous medium of Production Example 15 of the resin fine particles, the pH adjustment of the dispersion with 10% hydrochloric acid in the dissolution step, and the conditions of the adhesion step were changed as shown in Table 2. Resin fine particles 16 to 17 were obtained in the same manner as in Production Example 15 of the resin fine particles.

<Examples 1 to 13 and Comparative Examples 1 to 4>
The deformation of the obtained resin fine particles was confirmed and evaluated by SEM (scanning electron microscope). The evaluation criteria for the degree of deformation (degree of deformation) are as follows. As described above, the particles having the shape shown in FIG. 3 were judged as the deformed particles, and the particles having the shape in which the particles were united were not regarded as the deformed particles.
Rank 4 More than 80% of the particles in all 100 confirmed visual fields have irregular shapes, and the particles are not aggregated.
Rank 3 50% or more of the particles in the 100 visual fields confirmed have irregular shapes, and the particles are not aggregated.
Rank 2 20% or more of the particles in all 100 confirmed visual fields have irregular shapes, and the particles are not aggregated.
Rank 1 Less than 20% of the particles in all 100 confirmed visual fields have irregular shapes, and the particles are not aggregated.
Rank 0 Most of the particles are agglomerated.

<Toner manufacturing example 1>
● ion-exchanged water 1000 parts by weight in the preparation reactor of the first aqueous medium, 14.0 parts by mass of sodium phosphate and 10% hydrochloric acid was charged 13.9 parts by weight, at 65 ° C. with _{N 2} purge 60 Insulated for minutes. Using a TK homomixer (manufactured by Tokushu Kagaku Kogyo Co., Ltd.), while stirring at 12,000 rpm, a calcium chloride aqueous solution in which 8 parts by mass of calcium chloride was dissolved was collectively added to 20 parts by mass of ion-exchanged water and dispersed. An aqueous medium containing calcium phosphate was prepared as Agent A. The pH value of the prepared aqueous medium was 4.5.

● ion-exchanged water 100 parts by weight in the preparation reactor of the second aqueous medium, was charged with aluminum hydroxide 4.0 parts by mass, was kept for 60 minutes at 65 ° C. with N ₂ purge. Using a TK homomixer (manufactured by Tokushu Kagaku Kogyo), while stirring at 12,000 rpm, 9.0 parts by mass of 10% hydrochloric acid was added to prepare an aqueous medium containing aluminum hydroxide as the dispersant B. did. The pH value of the prepared aqueous medium was 4.0.

● Granulation process Polymerizable monomer composition, 60 parts by mass of styrene, carbon black (manufactured by Orion Engineerred Carbons, trade name "Printex35") 7 parts by mass, charge control agent (manufactured by Orient: Bontron E-89) 0 .10 parts by mass

The above material was put into an attritor (Mitsui Miike Machinery Co., Ltd.) and further dispersed using zirconia particles having a diameter of 1.7 mm at 220 rpm for 5 hours to obtain a polymerizable monomer composition.
The following materials were added to the above polymerizable monomer composition.
・ Styrene 20 parts by mass ・ n-butyl acrylate 20 parts by mass ・ Polyester resin 5 parts by mass ・ Paraffin wax (manufactured by Nippon Seiwa Co., Ltd., melting point 75.0 ° C) 5 parts by mass

The above material was kept warm at 65 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). 2.5 parts by mass of the polymerization initiator t-hexyl peroxypivalate (manufactured by Nippon Oil & Fats Co., Ltd., trade name "Perhexyl PV", molecular weight: 202, 10-hour half-life temperature: 53.2 ° C.) was dissolved therein. A polymerizable monomer composition was prepared.
The polymerizable monomer composition was charged into the in the first aqueous medium in the first reaction vessel, 65 ° C., under _{N 2} purge, T. K.. Granulation for 5 minutes at 10,000rpm at homomixer A dispersion of droplets of the polymerizable monomer composition which was granulated and had calcium phosphate adhered to the surface was obtained.

● Mixing Step The second aqueous medium was prepared in the second reaction vessel, and the dispersion was charged while stirring the paddle stirring blade at a peripheral speed of 20 m / sec. Since calcium phosphate (dispersant A) dissolves at pH 4.0, in this mixing step, calcium phosphate on the surface of the droplet of the polymerizable monomer composition dissolves, and then aluminum hydroxide (aluminum hydroxide) (on the surface of the droplet). Dispersant B) adhered.

● Polymerization step After the above mixing step, the temperature was raised to 65 ° C. for 6 hours and then to 90 ° C. while stirring with a paddle stirring blade, and the reaction was carried out at 90 ° C. for 6 hours.

● Filtration and washing step After the polymerization reaction was completed, the reaction vessel was cooled, 10% hydrochloric acid was added, and the pH value was set to 2, and the dispersion stabilizer was dissolved while stirring for 2 hours. The emulsion was pressure filtered and further washed with 2000 parts by mass or more of ion-exchanged water. The obtained cake was returned to 1000 parts by mass of ion-exchanged water, 10% hydrochloric acid was added, and the cake was rewashed with stirring for 2 hours with a pH value of 1 or less. The emulsion was pressure-filtered in the same manner as described above, further washed with ion-exchanged water of 2,000 parts by mass or more, sufficiently aerated, dried and wind-classified to obtain black colored particles.

● Toner conversion process Add 100 parts by mass of the obtained black colored particles, 1.5 parts by mass of hydrophobic silica, and 0.3 parts by mass of hydrophobic titanium oxide, and add Mitsui Henchel Mixer (manufactured by Mitsui Miike Machinery Co., Ltd.). Toner 1 having an external additive was obtained. The physical properties of the obtained toner 1 are shown in Table 5.

<Toner manufacturing examples 2 to 6>
Toners 2 to 6 were obtained in the same manner as in Toner Production Example 1 except that the type and content of each raw material and the conditions of the mixing step were changed as shown in Table 4. Table 5 shows the physical properties of the obtained toners 2 to 6.

<Examples 14 to 17 and Comparative Examples 5 to 6>
The deformation of the obtained resin fine particles was confirmed by SEM and evaluated. The evaluation results are as shown in Table 3. The evaluation criteria for the degree of deformation (degree of deformation) are as follows.
The degree of deformation was confirmed and evaluated by SEM using the toners of Toner Production Examples 1 to 5. The evaluation results are as shown in Table 4. The evaluation criteria for the degree of deformation (degree of deformation) are as follows.
Rank 4 Atypical shape with 80% or more dents for all particles in 100 confirmed visual fields Rank 3 Atypical shape with 50% or more dents for all particles in 100 confirmed visual fields Rank 2 Confirmed Anomalous shape with dents of 20% or more for all particles in 100 visual fields Rank 1 Anomalous shape with dents of less than 20% for all particles in 100 visual fields confirmed

Claims (6)

(A) The polymerizable monomer composition containing the polymerizable monomer is dispersed in a first aqueous medium containing an acid-soluble dispersant A, and the dispersant A adheres to the surface of the polymerizable simpler. Granulation step to obtain a dispersion containing droplets of a body composition,
(B) in the dispersion, the pH adjustment of the dispersion to dissolve the dispersant A attached to the surface of the droplets, after dissolution of the dispersant A, acid-soluble different from the dispersant A dissolved thereby adhesion dispersant B to the surface of the droplet - reattachment process, and (c) polymerizing step of polymerizing the polymerizable monomer to form the fine resin particles contained in the droplets,
It is a method for producing resin fine particles having
The dispersant A is calcium phosphate or magnesium hydroxide.
When the dispersant A is calcium phosphate, the dispersant B is aluminum hydroxide, and when the dispersant A is magnesium hydroxide, the dispersant B is calcium phosphate or aluminum hydroxide.
A method for producing fine resin particles . The dissolution - redeposition process comprises a mixing step of mixing with the addition of a second aqueous medium containing the dispersing agent B in the dispersion,
Solubility second aqueous medium of the dispersant A is higher than the solubility of the first aqueous medium of the dispersant A,
The method for producing fine resin particles according to claim 1. The method for producing resin fine particles according to claim 1 or 2, wherein the dispersant A is calcium phosphate. The dispersant A is calcium phosphate,
Minus the pH value of the second aqueous medium a pH value of the dispersion at the time of being mixed in the mixing step is 0.5 or more,
The method for producing fine resin particles according to claim 2. PH value of the dispersion at the time of being mixed in the mixing step, it is 4.5 to 6.0,
PH value of the second aqueous medium when it is mixed in the mixing step is less than 5.0,
The method for producing fine resin particles according to claim 4. (A) The polymerizable monomer composition containing the polymerizable monomer and the colorant was dispersed in a first aqueous medium containing the acid-soluble dispersant A, and the dispersant A adhered to the surface. Granulation step of obtaining a dispersion containing droplets of a polymerizable monomer composition,
(B) in the dispersion, the pH adjustment of the dispersion to dissolve the dispersant A attached to the surface of the droplets, after dissolution of the dispersant A, acid-soluble different from the dispersant A dissolved depositing a dispersant B to the surface of the droplet - reattachment process, and (c) polymerizing step of polymerizing the polymerizable monomer to form a toner particles contained in the droplets,
It is a method for producing toner particles having
The dispersant A is calcium phosphate or magnesium hydroxide.
When the dispersant A is calcium phosphate, the dispersant B is aluminum hydroxide, and when the dispersant A is magnesium hydroxide, the dispersant B is calcium phosphate or aluminum hydroxide.
A method for producing toner particles .