JP2018200400A - Method for manufacturing toner particle and stirring device - Google Patents

Abstract

To provide a method for manufacturing toner particles by a suspension polymerization method and a dissolution suspension method, the method for manufacturing toner particles reducing the generation of fine particles and reducing foaming.SOLUTION: In a method for manufacturing toner particles including a step of stirring fluid dispersion by using a stirring device, the stirring device includes a rotation shaft that is suspended inside a container, and a plurality of paddle blades that are provided on upper and lower multiple stages of the rotation shaft; in a maximum diameter blade having the maximum diameter from among the paddle blades, wherein a maximum diameter portion is present above the center in the height direction of the maximum diameter blade; when the maximum diameter is D1, the blade height is H1, the maximum diameter between the lowest part and a position at a height of H1×0.2 above the lowest part is D2, the maximum blade diameter of a lower stage blade provided below the maximum diameter blade is D3, the distance from the lowest part of an inner surface of the container to the liquid surface of the fluid dispersion in a stationary state is H2, and the distance from the lowest part to the highest part of the maximum diameter blade is H3, the formulas (1) to (3) are satisfied. (1) 1.1×D2≤D1; (2) 1.1×D3≤D1≤1.5×D3; (3) 0.6×H2≤H3≤H2.SELECTED DRAWING: Figure 1B

Description

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

  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, and a dissolution suspension method in which a binder resin is granulated in a solvent, etc. Is actively done.

For example, in the suspension polymerization method, a colorant is prepared by uniformly dissolving or dispersing a polymerizable monomer, a colorant, a release agent and a polymerization initiator, and further, if necessary, a crosslinking agent, a charge control agent and other additives. It is set as a containing composition. This is dispersed in an aqueous medium containing a dispersion stabilizer using an appropriate stirrer, and the polymerizable monomer is polymerized to obtain a suspension of toner particles having a desired particle size.
The toner particles produced in this way have a very sharp particle size distribution, so that not only high developability can be realized, but also the yield is high, so that it is excellent from the viewpoint of productivity.

However, in the process of obtaining toner particles, particles (fine particles) much smaller than the toner particle diameter are generated. When toner containing fine particles is used for electrophotography, it is fixed or fused to a member in the cartridge. When the fixed or fused fine particles are separated from the members in the cartridge and mixed into the toner, development streaks and fogging may occur.
For these reasons, there is a need for a method for producing toner particles that suppresses the formation of fine particles.

  As a method of suppressing the production of fine particles, there is a method of reducing the stirring power in the reaction step before the colorant-containing composition is polymerized. By reducing the stirring power, droplets of a fine colorant-containing composition that becomes microparticles after polymerization generated in the step before the reaction step, and droplets of a colorant-containing composition that are appropriately sized as toner particles Increased contact opportunities with For this reason, the droplets of the minute colorant-containing composition can be united with the appropriate colorant-containing composition.

  However, in the method of lowering the stirring power, bubbles are generated due to the decomposition of the polymerization initiator, or the dissolved gas in the liquid decreases in solubility as the liquid temperature increases, and bubbles are formed. And since these bubbles may overflow from a reaction container, manufacture is difficult by the method of making stirring power low. Further, heat radiation is hindered by bubbles accumulated on the liquid surface, and adverse effects directly related to toner quality such as fluctuation of the molecular weight of the obtained polymer are easily caused.

  As a method for suppressing foaming, Patent Document 1 discloses a technique of installing a turbine blade in a tank gas phase portion and mechanically defoaming, and Patent Document 2 attempts to defoam by reducing the pressure with a vacuum pump. Technology is disclosed.

JP-A-9-75610 Japanese Patent No. 5586552

However, in the method disclosed in Patent Document 1, since the stirring blade for defoaming is exposed from the liquid surface, adhesion occurs on the stirring blade, and the defoaming performance is reduced due to the deposit. Productivity is not high.
In the method disclosed in Patent Document 2, the running cost is increased by the vacuum pump, or the production conditions are restricted due to the fluctuation of the boiling point under reduced pressure.
As described above, with the conventional technology, it is difficult to achieve both the suppression of fine particles and the suppression of bubbles while suppressing the influence on toner performance and productivity.

  The present invention has been made in view of the above problems, and provides a toner particle manufacturing method that can obtain a toner having excellent developability, suppress the generation of fine particles, and suppress foaming. For the purpose.

According to one aspect of the present invention, there is provided a method for producing toner particles comprising a step of stirring a dispersion using a stirring device,
The stirring device includes a container, a rotating shaft suspended in the container, and a plurality of paddle blades provided in multiple stages on the rotating shaft,
In the maximum diameter blade having the maximum diameter among the plurality of paddle blades, a portion giving the maximum diameter exists above the center in the height direction of the maximum diameter blade,
The maximum diameter of the maximum diameter blade is D1 (m), the blade height of the maximum diameter blade is H1 (m), and the lowermost portion of the maximum diameter blade and the position of H1 × 0.2 above the lowermost portion When the maximum diameter between them is D2 (m), the D1 and the D2 satisfy the relationship of the following formula (1),
When the maximum blade diameter of the lower blade provided below the maximum diameter blade is D3 (m), the D1 and the D3 satisfy the relationship of the following formula (2),
The distance from the lowermost part of the inner surface of the container to the liquid level of the dispersion in a stationary state is H2 (m), and the distance from the lowermost part of the inner surface of the container to the uppermost part of the maximum diameter blade is H3 (m). Then, a method for producing toner particles in which H2 and H3 satisfy the relationship of the following formula (3) is provided.
1.1 × D2 ≦ D1 Formula (1)
1.1 × D3 ≦ D1 ≦ 1.5 × D3 Formula (2)
0.6 × H2 ≦ H3 ≦ H2 Formula (3)

According to another aspect of the invention,
A stirring device for stirring the dispersion in the process of producing toner particles,
The stirring device includes a container, a rotating shaft suspended in the container, and a plurality of paddle blades provided in multiple stages on the rotating shaft,
In the maximum diameter blade having the maximum diameter among the plurality of paddle blades, a portion giving the maximum diameter exists above the center in the height direction of the maximum diameter blade,
The maximum diameter of the maximum diameter blade is D1 (m), the blade height of the maximum diameter blade is H1 (m), and the lowermost portion of the maximum diameter blade and the position of H1 × 0.2 above the lowermost portion When the maximum diameter between them is D2 (m), the D1 and the D2 satisfy the relationship of the following formula (1),
When the maximum blade diameter of the lower blade provided below the maximum diameter blade is D3 (m), the D1 and the D3 satisfy the relationship of the following formula (2),
The distance from the lowermost part of the inner surface of the container to the liquid level of the dispersion in a stationary state is H2 (m), and the distance from the lowermost part of the inner surface of the container to the uppermost part of the maximum diameter blade is H3 (m). Then, a stirrer in which the H2 and the H3 satisfy the relationship of the following formula (3) is provided.
1.1 × D2 ≦ D1 Formula (1)
1.1 × D3 ≦ D1 ≦ 1.5 × D3 Formula (2)
0.6 × H2 ≦ H3 ≦ H2 Formula (3)

  According to one aspect of the present invention, there is provided a method for producing toner particles having excellent developability and production stability, wherein the production of toner particles is less likely to generate fine particles and less foam. It becomes possible.

It is the schematic which shows an example of the stirring apparatus which can be applied to this invention. It is the schematic which shows an example of the stirring apparatus which can be applied to this invention. It is the schematic which shows another example of the stirring apparatus which can be applied to this invention. It is the schematic which shows another example of the stirring apparatus which can be applied to this invention. It is the schematic which shows another example of the stirring apparatus which can be applied to this invention.

DETAILED DESCRIPTION Exemplary embodiments for carrying out the present invention will be described in detail below with reference to the drawings. However, the description of this embodiment does not limit the technical scope of the present invention to the following embodiment.
As a method for producing a toner that can be suitably used in the present invention, there are a suspension polymerization method, a dissolution suspension method using separately polycondensed polyester, and the like. It can be applied to the production of other various polymerization toners.
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.

The suspension polymerization method is a method in which particles of a polymerizable monomer composition containing a polymerizable monomer and a colorant are formed in an aqueous medium, and a polymerizable monomer contained in the particles of the polymerizable monomer composition is formed. In this method, toner particles are obtained by polymerizing a monomer.
Hereinafter, a method for producing toner particles by suspension polymerization will be described step by step.

(Preparation process of polymerizable monomer composition)
A polymerizable monomer composition containing 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 and dispersed to obtain granules, thereby obtaining a dispersion of the polymerizable monomer composition. The granulation step can be performed, for example, in a vertical stirring tank provided with a stirrer having a high shearing force. Although it does not specifically limit as a stirrer which has a high shear force, For example, the following commercially available things can be used. High shear mixer (manufactured by IKA), T.K. K. Homomixer (manufactured by PRIMIX Corporation), T. K. Fill mix (manufactured by Primics), Claremix (manufactured by M Technique).

  Examples of the inorganic dispersion stabilizer include the following. 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; sulfates such as barium sulfate and calcium sulfate; calcium hydroxide , Aluminum hydroxide, magnesium hydroxide, ferric hydroxide metal 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)
A dispersion of toner particles is obtained by adding a polymerization initiator to the polymerizable monomer composition dispersion obtained as described above and polymerizing the polymerizable monomer. In the polymerization step in the present invention, a general stirring tank capable of adjusting the 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.

As the stirring device used in the method for producing toner particles of the present invention, a stirring device as shown in FIGS. 1A and 1B is preferably used.
The stirrer includes a reaction vessel 1, a rotary shaft 5 suspended inside the reaction vessel 1, and a plurality of paddle blades (for example, the largest diameter blade 2 and the lower blade 3) provided in multiple stages on the rotation shaft 5. ). By having a plurality of paddle blades in multiple upper and lower stages, the convection of the entire inside of the container becomes good and the effect of entraining bubbles in the liquid is obtained.
In the maximum diameter blade having the maximum diameter among the plurality of paddle blades, the portion that gives the maximum diameter exists above the center in the height direction of the maximum diameter blade,
The maximum diameter of the maximum diameter blade is set to D1 (m), the blade height of the maximum diameter blade is set to H1 (m), and between the lowermost portion of the maximum diameter blade and the upper H1 × 0.2 position of the lowermost portion. When the maximum diameter is D2 (m), the D1 and the D2 must satisfy the relationship of the following formula (1).
1.1 × D2 ≦ D1 Formula (1)
Since the upper part of the maximum diameter blade is wide, the entrainment of bubbles in the liquid becomes good. Since the lower part of the maximum diameter blade is narrow, the shearing force, which is one of the factors that increase the fine particles, is suppressed.

When the maximum blade diameter of the lower blade provided below the maximum diameter blade is D3 (m), it is necessary that D1 and D3 satisfy the relationship of the following formula (2).
1.1 × D3 ≦ D1 ≦ 1.5 × D3 Formula (2)
If it is in the above range, the balance between the discharge amount of the maximum diameter blade and the discharge amount of the lower blade is appropriate, and the factor of increasing the fine particles while maintaining the convection in the container for entraining the bubbles in the liquid One shearing force is suppressed.

When the dispersion is added to the container, the distance from the bottom of the inner surface of the container to the liquid surface of the stationary dispersion is H2 (m), and the distance from the bottom of the inner surface of the container to the top of the largest diameter blade Is H3 (m), the H2 and the H3 must satisfy the relationship of the following formula (3).
0.6 × H2 ≦ H3 ≦ H2 Formula (3)
If it is in the above range, the distance from the top of the largest diameter blade that entrains bubbles in the liquid to the liquid surface is appropriate,
1) can maintain convection entraining bubbles in the liquid, and
2) Adhering to the stirring blade generated when the stirring blade is higher than the liquid level, splashing into the gas phase in the container, bubbling caused by stirring the liquid level, and fine particles due to excessive stirring Can be suppressed.

  The shape of the maximum diameter blade is preferably a substantially trapezoid whose upper base is longer than the lower base. Since the upper part of the maximum diameter blade having the effect of entraining bubbles in the liquid is wide, entrainment of bubbles from the liquid surface becomes good. Since the lower part of the maximum diameter blade is narrow, the shearing force that causes the increase of fine particles is suppressed. However, each side of the maximum diameter blade does not necessarily have to be a straight line, and may have a shape having a curve, a depression, or the like.

The number of paddle blades is not particularly limited, but two paddle blades are preferable. If the paddle blades are two paddle blades, the shear force, which is one of the factors that increase the fine particles, can be suppressed to the minimum necessary while maintaining the convection in the container for entraining the bubbles in the liquid.
It is preferable that the lower blade is provided below the largest blade. By providing the lower blade below the largest blade, the upper and lower convection generated by the largest blade is transferred without interruption, and the entrainment of bubbles from the liquid surface is improved.

It is preferable that the diameter D1 (m) of the uppermost portion of the maximum diameter blade and the height H1 (m) of the maximum diameter blade satisfy the relationship of the following formula (4).
0.5 × D1 ≦ H1 ≦ 1.5 × D1 Formula (4)
If H1 is in the above range, entrainment of bubbles from the liquid surface is good.

  In any two adjacent paddle blades in the upper and lower sides, the upper paddle blade may be provided so as to precede the rotational direction at an intersecting angle α1 of 10 degrees or more and 90 degrees or less with respect to the lower paddle blade. preferable. Within the above range, the downward flow from the upper paddle blade to the lower paddle blade is efficiently generated, the convection inside the container is good, and the entrainment of bubbles from the liquid surface is good.

When the inner diameter of the container is D4 (m), it is preferable that the D4 and the D1 satisfy the relationship of the following formula (5).
0.50 × D4 ≦ D1 ≦ 0.95 × D4 Formula (5)
If D1 is 0.50 × D4 or more, sufficient stirring ability for entraining bubbles on the liquid surface can be obtained. If D1 is 0.95 × D4 or less, an appropriate clearance is maintained between the container and the stirring blade, an excessive shearing force is not applied to the dispersion, and the increase in fine particles is minimized.

When the blade height of the lower blade is H4 (m), it is preferable that the H1 and the H4 satisfy the relationship of the following formula (6).
H4 ≦ H1 Formula (6)
If H1 is equal to or higher than H4, the height of the lower blade that increases the fine particles is the minimum necessary, and an excessive shear force is not given to the dispersion, and the increase of the fine particles is minimized.

In any paddle blade adjacent in the vertical direction, when the distance from the lowermost portion of the upper paddle blade to the uppermost portion of the lower paddle blade is H5 (m), D4 and H5 are expressed by the following formula (7). It is preferable to satisfy the relationship.
H5 ≦ 0.2 × D4 Formula (7)
If it is within the above range, the distance from the lowermost part of the upper wing to the uppermost part of the lower wing is appropriate, the downward flow from the upper wing to the lower wing is efficiently generated, and the convection inside the container is good, The entrainment of bubbles from the liquid surface is good.

When P (W) is the power when stirring the dispersion with the stirrer and V (m ³ ) is the volume of the dispersion added to the stirrer, P and V have the relationship of the following formula (8): It is preferable to satisfy.
10 ≦ P / V ≦ 600 Formula (8)
If it is in the said range, the favorable bubble entrainment effect can be acquired, suppressing the shear force which increases a microparticle.

A baffle may be installed inside the container to further improve the convection of the dispersion. Various shapes such as a flat plate, a cylinder, and an ellipse are applicable as the shape of the baffle.
An auxiliary wing may be attached to the lower part of the largest diameter blade as shown in FIG. By attaching the auxiliary wing, the liquid flow from the upper wing to the lower wing becomes better. As the shape of the auxiliary wing, various shapes such as a flat plate, a cylinder, and an ellipse are applicable.

(Organic volatile component removal 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 process, solid-liquid separation process and drying process)
In order to remove the dispersion stabilizer adhering to the surface of the toner particles, the toner particle dispersion is treated with an acid or an alkali. Thereafter, the toner 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, the toner particles are washed again with water. 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.

(Classification process)
The toner particles obtained in this way have a sufficiently sharp particle size as compared with conventional pulverized toners. However, when a sharper particle size is required, the toner particles are classified by an air classifier or the like. Particles deviating from the particle size distribution can be separated and removed.

(Polymerizable monomer)
As the polymerizable monomer used in the present invention, for example, 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; Vinyl esters such as methylene aliphatic monocarboxylic acid ester, 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.

  Examples of the polyfunctional polymerizable monomer include the following. 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, tetramethylolmethane 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 used in the present invention include the following organic pigments or dyes and inorganic pigments.

As the organic pigment or organic dye as the 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 colorants are used.

These colorants can be used alone or in combination and further in the form of a solid solution. The colorant is selected from the viewpoints of hue angle, saturation, brightness, light resistance, dispersibility in the toner, and the like.
The usage-amount of a coloring agent is 1 mass part or more and 20 mass parts or less normally with respect to 100 mass parts of polymerizable monomers.

<Release agent>
As the release agent used in the present invention, for example, 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 paraffin wax, polyolefin wax, microcrystalline wax, Fischer-Tropsch wax, amide wax, higher fatty acid, long chain alcohol, and ester wax.

<Charge control agent>
A well-known thing can be utilized as a charge control agent used for this invention.
Examples of controlling the toner to be negatively charged include the following. Organic metal compounds and chelate compounds are effective, monoazo dye metal compounds, acetylacetone metal compounds, aromatic hydroxycarboxylic acids, aromatic mono and polycarboxylic acids and their metal salts, anhydrides, esters, bisphenol and other phenol derivatives 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 and 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.
The use amount of these charge control agents is preferably 0.01 parts by mass or more and 20 parts by mass or less, and more preferably 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.

  Also. When a compound having a salicylic acid skeleton is contained as a charge control agent, the effect of the present invention is great. Furthermore, in the present invention, when the toner particles contain a charge control resin having a structure represented by the following formula (9), the effects of the present invention are remarkably exhibited.

[In the formula (9), R ² are each independently a hydroxyl group, a carboxyl group, having 1 to 18 alkyl group carbon atoms, or represents a 1 to 18 alkoxy group carbon atoms. R ³ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms. j represents an integer of 1 to 3, and i represents an integer of 0 to 3. ]

The structure represented by the above formula (9) has a structure in which an aromatic ring and a salicylic acid structure are bonded via an alkyl ether advantageous for electron conduction. This large conjugated structure extending from the salicylic acid structure plays a role in holding the charge generated by frictional charging inside the molecule while minimizing the influence of external temperature and humidity, and in order to stably apply the charge of the toner The charging property is favorable, which is preferable. However, since the aromatic ring and the salicylic acid structure act as a surfactant and easily foam, the effect of the present invention is greatly manifested.
The charge control resin may be a polymer having a monomer unit represented by the following formula (10).

[In the formula (10), R ⁴ are each independently a hydroxyl group, a carboxyl group, having 1 to 18 alkyl group carbon atoms, or represents a 1 to 18 alkoxy group carbon atoms. R ⁵ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and R ⁶ represents a hydrogen atom or a methyl group. l represents an integer of 1 to 3, and k represents an integer of 0 to 3. ]

<Polymerization initiator>
Examples of the polymerization initiator used in the present invention include azo polymerization initiators and organic peroxide 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.

  Examples of the organic peroxide polymerization initiator include the following. Benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, tert-butyl-peroxypivalate.

  These polymerization initiators can be used alone or in combination, and a chain transfer agent, a polymerization inhibitor and the like can be further added and used to control the degree of polymerization of the polymerizable monomer. When a polymerization initiator is used, there is a substance that generates gas along with its decomposition, and bubbles may be generated in the liquid. In addition, in the polymerization process, bubbles may also be generated in the liquid by cavitation by stirring, entrainment of the gas phase part, bubbling of dissolved gas accompanying an increase in liquid temperature, gas generation by reaction, and the like. Bubbles generated in the liquid rise over time, and the problem becomes apparent.

  A redox polymerization 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 bisulfite, sodium sulfite, sodium formaldehyde sulfoxylate and other reducing sulfur compounds, lower alcohols (1 to 6 carbon atoms), ascorbic acid or salts thereof, And lower aldehyde (C1-6). The polymerization 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.

<External additive>
An external additive can be added to the toner particles obtained by the production method of the present invention for the purpose of improving various powder characteristics. 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, and 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 and silica.

  The content of these external additives is preferably from 0.01 to 10 parts by weight, more preferably from 0.05 to 5 parts by weight, based on 100 parts by weight of the toner particles. These external additives may be used alone or in combination. These external additives are more preferably hydrophobized.

<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. Examples of the magnetic material used in the present invention include the following. Iron oxides such as magnetite, hematite, ferrite; metals such as iron, cobalt, nickel or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, Alloys of metals such as selenium, titanium, tungsten, vanadium and mixtures thereof.

  The content of these magnetic materials is preferably 20 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer, and 40 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. Is more preferable.

When a magnetic material is used in the present invention, the surface of the magnetic material is preferably subjected to a hydrophobic treatment in order to improve the dispersibility of the magnetic material in the toner particles. 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. Examples of the silane coupling agent include the following. Vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxy Silane, hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane.
Hereinafter, various methods for measuring toner particles obtained by the suspension polymerization method will be described.

  The present invention will be specifically described with reference to the following examples. Unless otherwise specified, all parts and% in the examples and comparative examples are based on mass.

[Example 1]
A toner was manufactured according to the following procedure.

(Synthesis example of monomer A)
18 g of 2,4-dihydroxybenzoic acid, which is a salicylic acid intermediate, was dissolved in 150 mL of methanol. To this solution, 36.9 g of potassium carbonate was added and heated to 65 ° C. A solution in which 18.7 g of 4- (chloromethyl) styrene and 100 mL of methanol were mixed and dissolved was prepared, and this solution was added dropwise to the salicylic acid intermediate solution and reacted at a temperature of 65 ° C. for 3 hours. The obtained reaction solution was cooled and then filtered, and methanol in the filtrate was distilled off under reduced pressure to obtain a precipitate. The precipitate was dispersed in 1.50 L of water at pH = 2, and extracted by adding ethyl acetate. Then, after washing with water, it was dried with magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain a precipitate. The precipitate was washed with hexane and then recrystallized with toluene / ethyl acetate to obtain 20.1 g of monomer A having a structure represented by the following formula (11).

<Synthesis of charge control resin B>
12.00 g of monomer A represented by formula (11) and 88.00 g of styrene were dissolved in 40.00 mL of N, N-dimethylformamide (DMF), stirred for 1 hour, and then heated to 110 ° C. Dissolved solution obtained by stirring a solution prepared by adding 3.50 g of tert-butyl peroxyisopropyl monocarbonate (trade name: Perbutyl I, manufactured by NOF Corporation) in 40.00 mL of toluene in this reaction solution for 1 hour. Was dripped. The reaction was further carried out at 110 ° C. for 4 hours under introduction of nitrogen. Then, it cooled and it was dripped at methanol 1.00L, and the deposit was obtained. The obtained precipitate was dissolved in 120 mL of THF (tetrahydrofuran) and then added dropwise to 1.80 L of methanol to precipitate a white precipitate, which was filtered and dried at 90 ° C. under reduced pressure. Thus, charge control resin B was obtained from monomer A and styrene.

The composition analysis of the obtained charge control resin B was performed using ¹ H-NMR described later, and it was confirmed that the monomer A was polymerized. Further, the acid value of the charge control resin B is 24.8 mgKOH / g, the weight average molecular weight Mw = 28,500, and Mw / Mn = 2.2, and the formula (11) derived from the monomer A from the acid value. It was confirmed that the structure represented was 442 μmol / g.

(Structural analysis of charge control resin B and monomer A)
The structures of the charge control resin B and the monomer A were determined using a nuclear magnetic resonance apparatus ( ¹ H-NMR), and the composition ratio was calculated.
The apparatus used is described below.
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Frequency range: 10,500Hz
Integration count: 64 times Measurement temperature: 30 ° C

50 mg of a sample was placed in a sample tube having an inner diameter of 5 mm, and deuterated chloroform (CDCl ₃ ) was added as a solvent. The sample tube was placed in a constant temperature bath at 40 ° C., and the sample was dissolved to prepare a measurement sample. It measured on the said conditions using the said measurement sample.
In addition, the molar content of the structure represented by the formula (9) in the charge control resin B was calculated by the above acid value measurement in addition to the above nuclear magnetic resonance apparatus.
Specifically, the structure of the monomer contained in the charge control resin B was analyzed using a nuclear magnetic resonance apparatus, and the constituent monomer was identified. Next, from the above acid value measurement, it was quantified from the relationship between the structure represented by the formula (9) contained in the charge control resin B and the acid value, and calculated as the molar content.

<Molecular weight measurement of resin>
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the charge control resin B were calculated in terms of polystyrene using gel permeation chromatography (GPC).
When measuring the molecular weight of a resin having an acid group, the column elution rate also depends on the amount of the acid group, so a sample with an acid group capped in advance was prepared.
Methyl esterification is preferred for capping, and a commercially available methyl esterifying agent was used. Specifically, a method of treating with trimethylsilyldiazomethane was used.
The molecular weight was measured by GPC as follows.

The resin was added to THF (tetrahydrofuran), and the solution which was allowed to stand at room temperature for 24 hours was filtered through a solvent-resistant membrane filter “Mysholy Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. Obtained.
In the sample solution, the amount of THF was adjusted so that the concentration of the resin was 0.8% by mass. In addition, when the resin is difficult to dissolve in THF, a basic solvent such as N, N-dimethylformamide (DMF) can be used.
Using the sample solution, measurement was performed under the following conditions.

Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven columns of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Oven temperature: 40.0 ° C
Sample injection volume: 0.10 mL

In calculating the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts.
Standard polystyrene samples for preparing calibration curves are trade names “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, manufactured by Tosoh Corporation. F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ".

<Measurement of acid value of resin>
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value in the present invention was measured according to JIS K 0070-1992. Specifically, it measured according to the following procedures.
Titration was performed using a 0.1 mol / L potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.). The factor of the potassium hydroxide ethyl alcohol solution was determined using a potentiometric titrator (potentiometric titrator AT-510 manufactured by Kyoto Electronics Industry Co., Ltd.).

Specifically, 100 mL of 0.100 mol / L hydrochloric acid was placed in a 250 mL tall beaker, titrated with a potassium hydroxide ethyl alcohol solution, and determined from the amount of potassium hydroxide ethyl alcohol solution required for neutralization. As 0.100 mol / L hydrochloric acid, one prepared according to JIS K 8001-1998 was used.
The measurement conditions for the acid value measurement are shown below.

Titration apparatus: potentiometric titration apparatus AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.)
Electrode: Composite glass electrode double junction type (Kyoto Electronics Industry Co., Ltd.)
Titrator control software: AT-WIN
Titration analysis software: Tview
The titration parameters and control parameters at the time of titration were as follows.

<Titration parameter>
Titration mode: Blank titration Titration style: Total titration Maximum titration: 20 mL
Waiting time before titration: 30 seconds Titration direction: Automatic

<Control parameters>
End point determination potential: 30 dE
End point determination potential value: 50 dE / dmL
End point detection judgment: Not set Control speed mode: Standard gain: 1
Data collection potential: 4 mV
Data collection titration: 0.1 mL

<Measurement of acid value>
0.100 g of the measurement sample was precisely weighed in a 250 mL tall beaker, and 150 mL of a mixed solution of toluene and ethanol (3: 1) was added and dissolved over 1 hour. Titration was performed using a potassium hydroxide ethyl alcohol solution using a potentiometric titrator.

<Measurement of acid value Blank test>
Titration similar to the above operation was performed except that no sample was used (that is, only a mixed solution of toluene and ethanol (3: 1) was used).
The obtained result was substituted into the following formula to calculate the acid value.
A = [(C−B) × f × 5.611] / S
Here, A: acid value (mgKOH / g), B: addition amount (mL) of potassium hydroxide ethyl alcohol solution in blank test, C: addition amount (mL) of potassium hydroxide ethyl alcohol solution in final test, f : Factor of potassium hydroxide ethyl alcohol solution, S: Sample (g).

(Preparation process of pigment dispersion composition)
With respect to 23.0 parts by mass of styrene, C.I. I. 1.88 parts by mass of Pigment Yellow 155 and 0.58 parts by mass of a charge control agent (Bontron E88; manufactured by Orient Chemical Co., Ltd.) were prepared. These were introduced into an attritor (manufactured by Nippon Coke Kogyo Co., Ltd.) and stirred at 200 rpm at a temperature of 25 ° C. for 300 minutes using zirconia beads having a radius of 5.00 mm to prepare a pigment dispersion composition.

(Preparation process of colorant-containing composition)
The following materials were put in the same container and mixed and dispersed at a peripheral speed of 20 m / sec using a TK homomixer (manufactured by Primix Co., Ltd.).
-Pigment dispersion composition 25.02 parts by mass-Styrene 15.34 parts by mass-N-butyl acrylate 9.59 parts by mass-Polyester resin 1.92 parts by mass-Styrene-methacrylic acid-methyl methacrylate-α-methylstyrene copolymer Coalescence
5.75 parts by mass (styrene / methacrylic acid / methyl methacrylate / α-methylstyrene = 80.85 / 2.50 / 1.65 / 15.0, main peak molecular weight Mp = 19,700, Mw = 7,900, Glass transition temperature Tg = 96 ° C., acid value = 12.0 mg KOH / g, Mw / Mn = 2.1)
・ Sulfonic acid group-containing resin (Acrybase FCA-1001-NS, manufactured by Fujikura Kasei Co., Ltd.)
0.05 part by mass, charge control resin B 0.20 part by mass

  Further, after heating to 60 ° C., 4.79 parts by mass of hydrocarbon wax (HNP-9; manufactured by Nippon Seiwa Co., Ltd.) was added, and the mixture was dispersed and mixed for 30 minutes. -Azobis (2, 4- dimethyl valeronitrile) 4.31 mass part was melt | dissolved, and the coloring agent containing composition was prepared.

(Preparation process of aqueous dispersion medium)
To the granulation tank, 129.71 parts by mass of ion-exchanged water, 2.51 parts by mass of sodium phosphate dodecahydrate, and 1.13 parts by mass of 10% by mass hydrochloric acid were prepared to prepare an aqueous sodium phosphate solution. Warmed to ° C. 1.46 parts by mass of calcium chloride dihydrate was dissolved in 10.20 parts by mass of ion-exchanged water to obtain an aqueous calcium chloride solution. A calcium chloride aqueous solution was added to the above-mentioned sodium phosphate aqueous solution, and the mixture was stirred for 30 minutes at a peripheral speed of 25 m / sec using a TK homomixer (manufactured by Primix Co., Ltd.).

(Granulation process)
A colorant-containing composition is put into an aqueous dispersion medium, and the temperature is 60 ° C. under a nitrogen atmosphere. The mixture was stirred with a homomixer at a peripheral speed of 25 m / sec for 20 minutes to obtain a dispersion of a colorant-containing composition.

(Reaction process)
The dispersion of the colorant-containing composition was transferred to another stirring vessel, heated to a temperature of 73 ° C. while being stirred with a stirring blade, and reacted for 4 hours. Thereafter, the temperature was further raised to 85 ° C. and reacted for 2 hours to obtain a dispersion of toner particles.

  The stirring container used was a container, a rotating shaft suspended inside the container, and two paddle blades provided on the rotating shaft in two upper and lower stages. Since the paddle blade located in the upper stage has the largest diameter among the two-stage stirring blades, it is referred to as the largest diameter blade. The paddle wing located at the lower stage is referred to as the lower wing.

The diameter D1 of the uppermost portion of the maximum diameter blade was set to 0.455 (m). The diameter D2 of the portion located 0.073 (m) above the lowest part of the maximum diameter blade was 0.228 (m). The diameter D3 of the lower blade was set to 0.350 (m). The inner diameter D4 of the container was 0.650 (m).
The blade height H1 of the largest diameter blade was set to 0.364 (m). The distance H2 from the bottom surface inside the tank to the liquid level of the dispersion of the colorant-containing composition in a stationary state was set to 1.100 (m). The distance H3 from the lowermost part inside the tank to the uppermost part of the largest diameter blade was set to 0.880 (m). The blade height H4 of the lower blade was set to 0.121 (m). The distance H5 from the lowermost portion of the largest diameter blade to the uppermost portion of the lower blade was set to 0.065 (m).
The maximum diameter blade is provided so as to precede the rotational direction R1 with respect to the lower blade at an intersecting angle α1 = 50 (°).

A torque detector “TH-1205” (manufactured by Ono Sokki Co., Ltd.) was installed between the electric motor for agitator and the rotating shaft, and “TS-2800” (manufactured by Ono Sokki Co., Ltd.) and “TS-0283” (The torque and the rotation speed n (rpm) at the time of stirring were measured with Ono Sokki Co., Ltd.). After operating the stirring blade for 1 minute, 60 torque values per second output from “TS-0283” were collected, and the average value T (N · m) was used as the stirring torque. The power value P (W) of the stirrer was obtained from the following formula (12).
P = 2 × π × T × n / 60 Formula (12)
P / V (W / m ³ ) is calculated from the calculated power value P (W) and the volume V (m ³ ) of the dispersion of the colorant-containing composition, and P / V = 300 (W / m ^3). ), The number of rotations of the stirrer was appropriately adjusted.

  Two cylindrical baffles were inserted into the stirring vessel from above the vessel. The columnar baffles were arranged axially relative to the rotation axis at a position 0.030 (m) closer to the center of the container from the wall surface of the container. The cylindrical baffle was fixed to the container ceiling. The diameter of the cylindrical baffle was 0.030 (m), and the length was 0.800 (m) downward from the surface of the dispersion of the colorant-containing composition in a stationary state.

As shown in FIG. 1B, two strip plates 7 were attached as auxiliary blades to the lowermost portion of the largest diameter blade. The shape of the strip-shaped plate 7 was 0.060 (m) in width and 0.100 (m) in height. The attachment position of the strip-shaped plate 7 was as follows.
Vertical direction The uppermost part of the strip-shaped plate 7 is in contact with the lowermost part of the largest diameter blade 2.
Horizontal direction The outermost peripheral part of the strip-shaped plate 7 (the part farthest from the rotating shaft 5 when attached) and the outermost peripheral part of the lowermost part of the maximum diameter blade 2 (the farthest away from the rotating shaft 5 when attached) Is substantially the same.

(Organic volatile substance removal process)
The dispersion was transferred to another container, heated to 95 ° C. with stirring, held for 2 hours, and then cooled to 30 ° C.

(Washing / filtration / drying process)
After cooling the dispersion that had undergone the organic volatile matter removal step, hydrochloric acid was added to adjust the pH to 1.4, and the mixture was stirred for 2 hours. Thereafter, the dispersion was separated by filtration, washed with water, and dried at a temperature of 40 ° C. for 48 hours to obtain toner particles.

(External addition process)
1.0 mass part (number average particle diameter of primary particles: 7 nm) of hydrophobic silica fine powder surface-treated with dimethyl silicone oil is mixed with FM mixer (manufactured by Nippon Coke Industries Co., Ltd.) with respect to 100.0 mass parts of toner particles. ) For 10 minutes to obtain a toner.

<Measurement method of volume-based median diameter (Dv50), number-based median diameter (Dn50)>
The volume-based median diameter (Dv50) and the number-based median diameter (Dn50) of the toner particles 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. For setting of measurement conditions and analysis of measurement data, attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. 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 (SOMME)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman -Set the value obtained using Coulter Co., Ltd. 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 dedicated to 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 placed in 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 is added.

(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 Tetra 150” (manufactured by Nikki Bios Co., Ltd.) with an electrical output of 120 W is prepared. . About 3.3 L of ion exchange water is placed in the water tank of the ultrasonic disperser, and about 2 mL of the above-mentioned Contaminone N is added 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. 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 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) To 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 volume-based median diameter (Dv50) and the number-based median diameter (Dn50) are calculated.

<Calculation of particle size distribution>
The closer the ratio of Dv50 to Dn50 (Dv50 / Dn50) is to 1, the sharper the particle size distribution. As described above, if the particle size distribution is sharp, high developability can be realized and the yield is high, which is excellent from the viewpoint of productivity.

<Measurement method of fine particle ratio>
The fine particle ratio of the toner particles was measured with a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during calibration.

  The specific measurement method is as follows. First, about 20 mL of ion-exchanged water from which impure solids and the like are previously removed is placed in a glass container. About 0.2 mL of a diluted solution obtained by diluting the above-mentioned Contaminone N with ion-exchanged water about 3 times by mass as a dispersant is added thereto. Further, about 0.02 g of a measurement sample is added, and dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC. As the ultrasonic disperser, a desktop ultrasonic washer disperser (for example, “VS-150” manufactured by Vervo Crea Co., Ltd.) having an oscillation frequency of 50 kHz and an electric output of 150 W is used. Ion exchange water is put, and about 2 mL of the above-mentioned Contaminone N is added to this water tank.

  For the measurement, the flow type particle image analyzer equipped with “LUCPLFLN” (magnification 20 ×, numerical aperture 0.40) as an objective lens was used, and particle sheath “PSE-900A” (Sysmex Corporation) was used as the sheath liquid. Made). The dispersion prepared in accordance with the above procedure is introduced into the flow type particle image analyzer, and 2,000 toner particles are measured in the HPF measurement mode and in the total count mode. Then, the binarization threshold at the time of particle analysis is set to 85%, the analysis particle diameter is set to the particle perimeter length, limited to 6.332 μm or more and less than 400.0 μm, and the abundance ratio of particles less than 6.332 μm is defined as the fine particle ratio. did.

  In measurement, automatic focus adjustment is performed using standard latex particles (for example, “RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5100A” manufactured by Duke Scientific) diluted with ion-exchanged water before starting the measurement. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.

  In the examples of the present application, a flow-type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, was used. Proof of calibration except that the analysis particle diameter is limited to a particle circumference length of 6.332 μm or more and less than 400.0 μm, and the analysis particle diameter is limited to a circle equivalent diameter (number) of 4.044 μm or more and less than 100.0 μm. Measurements were taken under the measurement and analysis conditions.

<Evaluation of fine particle ratio>
Table 1 shows the evaluation rank of the fine particle ratio.

<Heap accumulation height>
In order to evaluate the degree of foaming, the height at which bubbles are deposited is measured. First of all, the liquid level position in a state where foaming is not performed is measured. For the measurement, a metal rod is vertically inserted into the reaction vessel from the inspection port 4 of the reaction vessel 1 to reach below the liquid level. At this time, the metal bar is marked at a position where the height of the inspection port 4 can be recognized. Since the portion that reaches below the liquid level is colored with the colorant on the metal rod, the distance T0 from the inspection port 4 to the liquid level is determined by measuring the length from the marked position to the top of the colored portion. Can be sought.

  Further, in the process where foaming is a problem, the position of the foam is measured. In the process where foaming is a problem, when the metal rod is inserted by the same method as the method for measuring the liquid level, the metal rod is colored according to the height at which bubbles are deposited. By measuring the length from the top of the colored portion to the marked position, the distance T1 from the inspection port to the top of the bubble can be determined. The height at which the bubbles are deposited can be obtained from the difference between T0 and T1.

In the polymerization process, bubbles were generated in the liquid as the polymerization initiator was decomposed. When the foam height by foaming became the highest, the foam height was measured according to the method for measuring the foam height described above.
When the dispersion of the colorant-containing composition was transferred to the stirring vessel, the distance from the liquid level of the dispersion of the colorant-containing composition before stirring to the inspection port of the stirring vessel was 1.2 (m).
Table 3 shows the evaluation results such as the physical property values of the toner particles obtained in Example 1 and the height of accumulated bubbles.

[Examples 2 to 5]
Toners of Examples 2 to 5 were obtained by the same conditions and methods as in Example 1 except that the rotational speed of the stirring blade was adjusted so that the (P / V) was a value shown in Table 2.

[Examples 6 to 7]
Toners of Examples 6 to 7 were obtained by the same conditions and methods as in Example 1 except that H5 was changed to the values shown in Table 2.

[Examples 8 to 9]
Toners of Examples 8 to 9 were obtained under the same conditions and method as in Example 1 except that H4 was changed to the values shown in Table 2.

Example 10
A toner of Example 10 was obtained by the same conditions and method as in Example 1 except that D1, D2, D3, H1, and H4 were changed to the values shown in Table 2.

Example 11
The toner of Example 11 was obtained by the same conditions and method as in Example 10 except that the cylindrical baffle was removed from the container.

[Examples 12 to 14]
Toners of Examples 12 to 14 were obtained by the same conditions and methods as in Example 11 except that D1, D2, D3, H1 and H4 were changed to the values shown in Table 2.

[Examples 15 to 18]
Toners of Examples 15 to 18 were obtained under the same conditions and method as in Example 1 except that α1 was set to the value shown in Table 2.

[Examples 19 to 22]
Toners of Examples 19 to 22 were obtained under the same conditions and method as in Example 10 except that H1 and H4 were changed to the values shown in Table 2.

Example 23
A toner was obtained by the same conditions and method as in Example 1 except that each of the largest diameter blade and the lower blade was replaced with three paddle blades.

Example 24
A toner was obtained by the same conditions and method as in Example 1 except that the strip-shaped plate as an auxiliary blade was removed from the maximum diameter blade.

Example 25
As shown in FIG. 2, a toner was obtained by the same conditions and method as in Example 24, except that R chamfering was performed on the left and right corners of the uppermost portion of the maximum diameter blade.
The distance H6 from the top of the largest diameter blade to the center of the R chamfer is 0.050 (m), the distance D5 from the center of the rotating shaft to the center of the R chamfer is 0.400 (m), and the radius of the R chamfer R2 was set to 0.050 (m).

Example 26
A toner was obtained by the same conditions and method as in Example 24 except that D2 = 0.114 (m).

[Examples 27 to 28]
Toners of Examples 27 to 28 were obtained under the same conditions and method as in Example 1 except that H3 was changed to the value shown in Table 2.

[Examples 29 to 30]
Toners of Examples 29 to 30 were obtained under the same conditions and method as in Example 1 except that D3 was set to the values shown in Table 2.

Example 31
A toner was obtained under the same conditions and method as in Example 1 except that D2 was changed to the value shown in Table 2.

[Example 32]
As shown in FIG. 3, (31) two paddle blades having a diameter D6 = 0.200 (m) and a height H7 = 0.030 (m) on the rotating shaft below the lower blade (hereinafter, the lowermost blade) Attached). (32) The distance from the lowermost part of the lower wing to the uppermost part of the lowermost wing was set to H8 = 0.065 (m). (33) The lowermost lower blade was attached to the lower blade so as to recede in the rotation direction R1 at an intersecting angle α2 = 25 (°). A toner was obtained by the same conditions and method as in Example 1 except for the above (31) to (33).

Example 33
As shown in FIG. 4, (41) a two-paddle blade (hereinafter, second lower stage) having a diameter D7 = 0.200 (m) and a height H9 = 0.030 (m) on the rotating shaft below the largest diameter blade. It is also described as a wing.) (42) The distance H10 = 0.020 (m) from the lowermost part of the largest diameter blade to the uppermost part of the second lower blade. (43) The second lower blade was attached so as to recede in the rotation direction R1 at an intersecting angle α3 = 25 (°) with respect to the largest-diameter blade. A toner was obtained by the same conditions and method as in Example 1 except for the above (41) to (43).

Example 34
A toner was obtained under the same conditions and method as in Example 27 except that the charge control resin B was not added in the colorant-containing composition preparation step.

[Comparative Example 1]
A toner was obtained by the same conditions and method as in Example 1 except that H3 = 0.550 (m). When the temperature in the container reached 73 ° C., bubbles overflowed from the container, and the operation was stopped.

[Comparative Example 2]
A toner was obtained under the same conditions and method as in Example 1 except that H3 = 1.210 (m). When the inside of the container was confirmed during operation, the liquid surface was violently disturbed by the maximum diameter blade, and bubbles were generated.

[Comparative Example 3]
A toner was obtained by the same conditions and method as in Example 1 except that D3 = 0.455 (m).

[Comparative Example 4]
A toner was obtained by the same conditions and method as in Example 1 except that D3 = 0.284 (m).
When the temperature in the container reached 73 ° C., bubbles overflowed from the container, and the operation was stopped.

[Comparative Example 5]
A toner was obtained by the same conditions and method as in Example 1 except that D2 = 0.455 (m).

[Comparative Example 6]
A toner was obtained by the same conditions and method as in Example 1 except that the lower blade was removed.
When the temperature in the container reached 73 ° C., bubbles overflowed from the inspection port of the container, and the operation was stopped.

  Table 3 shows the evaluation results of the physical properties of the toner particles obtained in Examples 2-34 and Comparative Examples 1-6, the height of the generated bubbles, and the like.

1: Reaction vessel 2: Maximum diameter blade 3: Lower blade 4: Inspection port 5: Rotating shaft 6: Cylindrical baffle 7: Strip plate (auxiliary blade)
D1, D2, D3: Blade diameter D3: Inner diameter of container
H1, H4: Blade height H2: Liquid surface height H3: Stirring blade height H5: Interblade distance α1: Crossing angle

Claims (11)

A method for producing toner particles comprising a step of stirring a dispersion using a stirring device,
The stirring device includes a container, a rotating shaft suspended in the container, and a plurality of paddle blades provided in multiple stages on the rotating shaft,
In the maximum diameter blade having the maximum diameter among the plurality of paddle blades, a portion giving the maximum diameter exists above the center in the height direction of the maximum diameter blade,
The maximum diameter of the maximum diameter blade is D1 (m), the blade height of the maximum diameter blade is H1 (m), and the lowermost portion of the maximum diameter blade and the position of H1 × 0.2 above the lowermost portion When the maximum diameter between them is D2 (m), the D1 and the D2 satisfy the relationship of the following formula (1),
When the maximum blade diameter of the lower blade provided below the maximum diameter blade is D3 (m), the D1 and the D3 satisfy the relationship of the following formula (2),
The distance from the lowermost part of the inner surface of the container to the liquid level of the dispersion in a stationary state is H2 (m), and the distance from the lowermost part of the inner surface of the container to the uppermost part of the maximum diameter blade is H3 (m). The toner particle manufacturing method is characterized in that the H2 and the H3 satisfy the relationship of the following formula (3).
1.1 × D2 ≦ D1 Formula (1)
1.1 × D3 ≦ D1 ≦ 1.5 × D3 Formula (2)
0.6 × H2 ≦ H3 ≦ H2 Formula (3)   The method for producing toner particles according to claim 1, wherein the shape of the maximum diameter blade is a substantially trapezoid whose upper base is longer than the lower base.   The method for producing toner particles according to claim 1, wherein the paddle blade is a two-paddle blade.   The method for producing toner particles according to claim 1, wherein the lower blade is provided below the largest blade. The method for producing toner particles according to claim 1, wherein the D1 and the H1 satisfy the relationship of the following formula (4).
0.5 × D1 ≦ H1 ≦ 1.5 × D1 Formula (4)   The upper paddle blade in any two adjacent paddle blades in the vertical direction is provided so as to precede the rotation direction at an intersecting angle α1 of 10 degrees or more and 90 degrees or less with respect to the lower paddle blade. The method for producing toner particles according to any one of 1 to 5. The method for producing toner particles according to any one of claims 1 to 6, wherein when the inner diameter of the container is D4 (m), the D4 and the D1 satisfy a relationship of the following formula (5).
0.50 × D4 ≦ D1 ≦ 0.95 × D4 Formula (5) The method for producing toner particles according to any one of claims 1 to 7, wherein when the blade height of the lower blade is H4 (m), the H1 and the H4 satisfy a relationship of the following formula (6).
H4 ≦ H1 Formula (6) In any two two-paddle blades adjacent in the vertical direction, when the distance from the lowermost portion of the upper two-paddle blade to the uppermost portion of the lower two-paddle blade is H5 (m), D4 and H1 Satisfying the relationship of the following formula (7), the method for producing toner particles according to claim 1.
H5 ≦ 0.2 × D4 Formula (7) When the power when stirring the dispersion with the stirring device is P (W) and the volume of the dispersion added to the stirring device is V (m3), P and V are expressed by the following formula ( The method for producing toner particles according to any one of claims 1 to 9, which satisfies the relationship 8).
10 ≦ P / V ≦ 600 Formula (8) A stirring device for stirring the dispersion in the process of producing toner particles,
The stirring device includes a container, a rotating shaft suspended in the container, and a plurality of paddle blades provided in multiple stages on the rotating shaft,
In the maximum diameter blade having the maximum diameter among the plurality of paddle blades, a portion giving the maximum diameter exists above the center in the height direction of the maximum diameter blade,
The maximum diameter of the maximum diameter blade is D1 (m), the blade height of the maximum diameter blade is H1 (m), and the lowermost portion of the maximum diameter blade and the position of H1 × 0.2 above the lowermost portion When the maximum diameter between them is D2 (m), the D1 and the D2 satisfy the relationship of the following formula (1),
When the maximum blade diameter of the lower blade provided below the maximum diameter blade is D3 (m), the D1 and the D3 satisfy the relationship of the following formula (2),
The distance from the lowermost part of the inner surface of the container to the liquid level of the dispersion in a stationary state is H2 (m), and the distance from the lowermost part of the inner surface of the container to the uppermost part of the maximum diameter blade is H3 (m). The stirring apparatus is characterized in that the H2 and the H3 satisfy the relationship of the following formula (3).
1.1 × D2 ≦ D1 Formula (1)
1.1 × D3 ≦ D1 ≦ 1.5 × D3 Formula (2)
0.6 × H2 ≦ H3 ≦ H2 Formula (3)

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