Method for manufacturing resin particles and method for manufacturing toner particles

Abstract

To provide a dispersion machine which can effectively impart shear force to treated liquid.SOLUTION: A dispersion machine 1 for treating treated liquid by feeding liquid has a rotor 3, a stator 4 facing the rotor, and a shear region 7, wherein the rotor has an annular projection part 5 which is annularly provided with a rotary shaft 2 as a center and a non-projection part 6 other than the annular projection part, the annular projection part has a plurality of slits formed in a centrifugal direction, the non-projection part has smooth parts A composed of smooth surfaces, the stator has smooth parts B facing the smooth parts A with a gap and a supply port 8 for supplying a treated object to the shear region, the shear region is formed by facing the smooth parts and is formed inside the annular projection part, and when an area of the smooth surfaces is represented by R(mm2) and an area of the smooth surfaces is represented by S(mm2), 0.55≤S / R≤0.95 is satisfied.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] This invention relates to the miniaturization, homogenization, dispersion, or dispersion processing of a fluid to be processed. to Dispersing machine Method for producing resin particles and toner particles using the above method This concerns... [Background technology]

[0002] Dispersers are devices that perform emulsification, dispersion, or mixing of fluids to be processed, and various types have been proposed. The demand for uniform processing of materials is increasing in all fields, and proposals are being made for dispersers capable of more precise processing. One method involves partially transferring the material to be processed from a tank to an in-line disperser for treatment. This method is preferred because it allows for efficient dispersion by applying shear to a portion of the material in the disperser. Various shapes of dispersers have been proposed for in-line use. Patent Document 1 describes a disperser in which a rotor equipped with multiple cutter blades and a stator provided around the rotor are arranged concentrically. The stator has multiple slits in its circumferential direction, and as at least the rotor rotates, the fluid to be processed is discharged from the inside to the outside of the stator through the slits, applying a shear force to finen and homogenize it. Patent Document 2 proposes a disperser in which multiple rows of opposing annular teeth are arranged on the rotor and stator, and which is equipped with a mechanism for supplying multiple fluids to be processed. Patent Document 3 proposes a dispersion machine comprising a rotor whose diameter increases in a conical shape from the lower part to the middle part and decreases from the middle part to the upper part, and a stator that houses the rotor and has a desired gap between it and the rotor. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 60-31819 [Patent Document 2] Special Publication No. 4-28409 [Patent Document 3] Patent No. 6448717 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, given the current demands on dispersers, there is a need for dispersers capable of even higher shear treatment of the fluid (liquid) being processed. For example, toner used in electrophotography to develop electrostatic images requires the efficient production of toner particles with small particle size and a sharp particle size distribution using methods such as suspension polymerization in order to exhibit excellent image characteristics. The object of the present invention is to provide a disperser capable of effectively applying shear force to a liquid to be processed in order to meet the above requirements. Furthermore, the object of the present invention is to provide a method for producing resin particles and a method for producing toner particles using the disperser of the present invention. [Means for solving the problem]

[0005] The present invention is a method for producing resin particles using a disperser for processing a liquid to be treated by supplying the liquid to be treated, The disperser comprises a rotor, a stator positioned opposite the rotor, and a shearing region for shearing the liquid to be processed. The rotor has an annular projection provided in an annular shape around the rotor's axis of rotation, and non-protruding parts other than the annular projection. The annular projection has a plurality of slits formed in the centrifugal direction of the annular projection, The non-protruding portion has a smooth portion A which is composed of a smooth surface a, The stator comprises a smooth portion B, which is composed of a smooth surface b that faces the smooth surface a of the smooth portion A with a gap between them, and the workpiece. liquid It has a supply port for supplying to the shear region, The shearing region is formed by the facing of the smooth surface a of the smooth portion A and the smooth surface b of the smooth portion B, and is formed inside the annular protrusion portion. Let the area of the smooth surface a of the smooth portion A be R (mm 2 ), and let the area of the smooth surface b of the smooth portion B be S (mm 2 ). When the relationship between R and S is 0.55 ≦ S / R ≦ 0.95 Satisfying the conditions, When the distance between the portion of the smooth surface a that forms the shear region and the portion of the smooth surface b that forms the shear region is h (mm), then h is 0.6≦h≦3.0 It relates to a method for producing resin particles, characterized by satisfying the above conditions. Further, the present invention includes a granulation step of forming particles of a polymerizable monomer composition containing a polymerizable monomer and a colorant in an aqueous dispersion medium to obtain a dispersion of the particles of the polymerizable monomer composition, After the granulation step, a polymerization step of polymerizing the polymerizable monomer in the particles to obtain a dispersion of toner particles, It is a method for producing toner particles having the above steps, The granulation step is a step of using the above disperser, and relates to a method for producing toner particles.

Effects of the Invention

[0006] According to the present invention, it is possible to provide a disperser capable of effectively applying a shearing force to the fluid to be treated. Furthermore, by providing a method for producing resin particles and a method for producing toner particles using the disperser of the present invention, more uniformly processed resin particles and toner particles can be obtained.

Brief Description of the Drawings

[0007] [Figure 1] It is a schematic view showing an example of the rotor and stator of the disperser of the present invention. [Figure 2] It is a schematic view showing an example of the shearing region 7 formed by the rotor and stator of the disperser of the present invention. [Figure 3] It is a schematic view showing an example of the rotor of the disperser of the present invention as viewed from the supply port 8 side. [Figure 4] It is a schematic diagram showing both the stator in FIG. 1 and the stator viewed from the rotor side. [Figure 5] It is a schematic diagram of the rotor showing the shear region 7 viewed from the rotor side in the direction of the rotation axis of the rotor. [Figure 6] It is a schematic diagram showing an example of the rotor of the disperser of the present invention as viewed from the S field of view in FIG. 3. [Figure 7] It is a schematic diagram showing an example of the rotor of the disperser of the present invention as viewed from the S field of view in FIG. 3. <00001​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​This is a schematic diagram showing the rotor and stator of the disperser used in Comparative Example 2. [Figure 20] Figure 6 is a schematic diagram showing the area Ss of the slit and the area Sp of the annular projection in the rotor. [Figure 21] Figure 7 is a schematic diagram showing the area Ss of the slit and the area Sp of the annular projection in the rotor. [Figure 22] This is a schematic diagram showing a granulation system equipped with a disperser used in the examples or comparative examples. [Modes for carrying out the invention]

[0008] The present invention will be described in detail below.

[0009] [Disperser configuration and toner particle manufacturing] The disperser of the present invention is suitably used for the production of resin particles, wherein the liquid to be processed contains a precursor of resin particles and a liquid that is immiscible with the precursor of resin particles. Examples of such resin particles include toner used in electrophotographic image forming methods, and suspension polymerization is one method of producing them.

[0010] Suspension polymerization is a manufacturing method in which particles of a polymerizable monomer composition containing polymerizable monomers and colorants are formed in an aqueous medium (aqueous dispersion medium), and the polymerizable monomers contained in the particles of the polymerizable monomer composition are polymerized to obtain toner particles.

[0011] The following describes the method for producing toner particles by suspension polymerization, including a detailed explanation of the configuration of the dispersion machine of the present invention, step by step.

[0012] (Preparation process for polymerizable monomer composition) A polymerizable monomer composition containing polymerizable monomers and a coloring agent is prepared. The coloring agent may be dispersed in the polymerizable monomers beforehand using a media stirring mill or the like and then mixed with the other compositions, or it may be dispersed after all the compositions have been mixed.

[0013] (Pelletization process; Dispersion machine use process) A polymerizable monomer composition is added to an aqueous medium containing an inorganic dispersion stabilizer and dispersed to granulate, thereby obtaining a polymerizable monomer composition dispersion. The dispersed droplets of the polymerizable monomer composition dispersion are a major factor in determining the particle size distribution of toner particles. Therefore, the disperser used to form the droplets is required to uniformly apply a high level of shear.

[0014] For example, the disperser shown in Figure 1 can be used, but the present invention is not limited to the disperser shown in Figure 1.

[0015] The disperser 1 shown in Figure 1 is equipped with a rotor 3 attached to a rotating shaft 2 and a stator 4 positioned opposite the rotor. The rotor has an annular projection 5 that is provided in an annular shape around the rotor's axis of rotation, and non-projecting parts 6 other than the annular projection. Figure 3 is a schematic diagram of the rotor as seen from the supply port 8 side. The rotor has an annular projection 5 and other non-projecting parts 6. The non-projecting parts 6 have a smooth surface a, and within the smooth surface a there is a smooth part A that excludes the part that constitutes the slit formed by the annular projection. The smooth part A may be a plane or a substantially plane, or it may be composed of multiple planes that are continuously inclined. Furthermore, the annular projection 5 has multiple slits 9 formed in the centrifugal direction of the annular projection.

[0016] On the other hand, Figure 4 is a schematic diagram of the stator as viewed from the direction of the rotor's rotation axis. It has a smooth section B which is composed of a smooth surface b that is opposite to the smooth surface a of the smooth section A with a gap between them. The smooth section B may be a flat plane or a substantially flat plane, or it may be composed of multiple planes that are continuously inclined.

[0017] The supply port 8 is preferably provided on the stator so as to intersect with the rotor's axis of rotation or the extension of the axis of rotation. By providing the supply port in this position, the liquid to be processed supplied from the supply port spreads uniformly across the shear region and is processed accordingly.

[0018] Here, the shear region for shearing the liquid to be processed is the region indicated by reference numeral 7 in Figure 2, which is formed by the opposing smooth surface a of smooth section A and smooth surface b of smooth section B, and is also formed inside the annular projection. Figure 5 is a schematic diagram showing the shear region 7 as seen from the stator side in the direction of rotation of the rotor. The area indicated by the dots where the smooth surface b of the stator and the smooth surface a of the rotor overlap is the shear region 7.

[0019] The inventors have found that in the shear region formed by the opposition of smooth surface a of smooth section A and smooth surface b of smooth section B, a uniform shear force can be applied to the liquid being processed by friction between smooth surface a and smooth surface b. Furthermore, they have found that an even greater shear force can be applied by annular projections provided on the rotor. They have also found that by applying shear force to the liquid being processed uniformly and continuously through the shear region and annular projections, the dispersion capacity of the disperser can be improved.

[0020] On the other hand, there is a disperser, as shown in Figure 18, in which both the rotor 3 and stator 4 have annular projections arranged in an annular shape around the rotor's rotation axis 2, and slits formed by adjacent annular projections. In the case of this disperser, where the annular projections of the rotor and stator are arranged to interlock with each other, the flow of the liquid to be processed becomes complex, and uniform shear is not applied compared to the present invention. Although shear is applied as the liquid to be processed passes between the annular projections, the liquid to be processed flows easily when the slits of the rotor and stator overlap, and flows less easily when the phases of the slits are misaligned, resulting in an unstable liquid flow and an uneven dispersion process.

[0021] As a result of diligent research, the inventors determined that the area of ​​the smooth surface a of the smooth part A is R(mm²). 2 ) and the area of ​​the smooth surface b of the smooth portion B is S(mm 2When this is the case, it was found that the relationship between area R and area S must satisfy 0.55 ≤ S / R ≤ 0.95. Within this range, an area is secured in the shear region that uniformly applies shear to the liquid being treated. In the case of a polymerizable monomer composition and an aqueous medium, a uniform dispersion of the polymerizable monomer composition is obtained in the shear region.

[0022] In the case of 0.55 > S / R, the shearing process in the shear region is not sufficiently performed, and shearing occurs at the annular projection, resulting in uneven shearing, which is undesirable. As a result, the uniformity of the dispersion droplets in the dispersion of the polymerizable monomer composition is lost, and the particle size distribution of the toner particles obtained in subsequent processes deteriorates.

[0023] Attempting to increase the S / R ratio beyond 0.95 is undesirable because it reduces the productivity of the disperser. One method to increase the S / R ratio is to significantly reduce the size of the supply port and increase the area of ​​the smooth surface b of the stator. However, this method results in a larger pressure loss at the supply port due to the smaller size of the supply port. This reduces the processing capacity of the disperser. To avoid reducing processing capacity, the discharge pressure of the pump can be increased, but this also increases the pressure on the wetted parts of the disperser. Therefore, the structure of the disperser must be made capable of withstanding that pressure, which significantly reduces productivity.

[0024] On the other hand, there are methods such as reducing the distance v (see Figure 2) between the annular projection and the stator, but this requires considerable manufacturing precision, which significantly increases the manufacturing cost of the disperser and is therefore undesirable for industrial equipment.

[0025] The shape of the annular projection is not particularly limited, but it is preferably a comb-shaped annular projection having multiple small protrusions, as shown in Figure 6, and the slit 9 is a slit formed between the multiple small protrusions. The shear force applied by the annular projection is applied to the liquid to be processed passing through the slit by the rotation of the rotor. If the annular projection is comb-shaped, the flow of the liquid to be processed from the shear region toward the slit is well maintained, so a more uniform processing is achieved. Figure 6 is a schematic diagram of the rotor shown in Figure 3 as seen from the S field of view.

[0026] Furthermore, when the distance between the portion of smooth surface a that forms a shear region and the portion of smooth surface b that forms a shear region is h (mm), and the centrifugal distance between the annular projection 5 and the stator is v (mm), it is preferable that the relationship between h and v is 0.4 ≤ h / v ≤ 5.0 (see Figure 2). Within this range, the flow of the liquid to be treated from the shear region toward the slit is well maintained, resulting in more uniform processing.

[0027] Furthermore, when the distance between the portion of smooth surface a that forms a shear region and the portion of smooth surface b that forms a shear region is h (mm), and the distance between the multiple slits is K (mm), it is preferable that the relationship between h and K is 0.2 ≤ h / K ≤ 5.0 (see Figures 2, 6, and 7). This range is preferable because it appropriately balances the shear force applied in the shear region with the shear force applied when passing through the slits.

[0028] When the distance between the portion of smooth surface a that forms a shear region and the portion of smooth surface b that forms a shear region is h (mm), and the height of the annular projection is H (mm), it is preferable that the relationship between h and H is 10 ≤ H / h ≤ 60 (see Figure 2). Within this range, the liquid to be treated, which has been processed in the shear region, is processed uniformly without uneven distribution as it passes through the slit.

[0029] In the rotor of the disperser of the present invention, the end of the outermost circumference of the smooth section A can be set to a height approximately midway between the annular projections. Preferably, when the distance between the end of the outermost circumference of the smooth section A and the surface forming the slit on the smooth surface a is D (mm), and the height of the annular projection is H (mm), the relationship between D and H is preferably 0 ≤ D / H ≤ 0.7 (see Figure 16). This range is preferable because it suppresses short paths passing between the stator and the annular projection, allowing the liquid to be processed to pass efficiently through the slit. From this viewpoint, an even more preferable relationship between D and H is 0 ≤ D / H ≤ 0.5. Note that in the configuration of Figure 1, D=0, so D / H=0.

[0030] It is preferable that the opening ratio of the multiple slits on the outer surface of the annular projection is between 10% and 30% of the area. Within this range, the shear force applied by the rotation of the rotor is effectively transmitted to the liquid being processed.

[0031] Here, as shown in Figure 7, if the slit is surrounded by a rotor component, the opening portion is defined as the slit area Ss(mm²) as shown in Figure 21. 2 ) and the area of ​​the annular projection is Sp(mm 2 ) . In the case of an annular projection that is a comb-shaped annular projection having multiple small protrusions, as shown in Figure 6, the area of ​​the slit Ss (mm²) is defined as the straight line connecting the points where the distance between adjacent small protrusions and the stator is narrowest, as shown in Figure 20, and the area enclosed by the rotor members. 2 ) and the area of ​​the annular projection is the shaded area Sp(mm 2 )

[0032] The aperture ratio is calculated using the following formula (1). Opening ratio (area %) = Slit area Ss ÷ {(Slit area Ss) + (Area of ​​annular projection Sp)} ... Equation (1)

[0033] It is preferable that the distance h (mm) between the portion of smooth surface a that forms a shear region and the portion of smooth surface b that forms a shear region is 0.6 ≤ h ≤ 3.0 (see Figure 2). Within this range, the shear force in the dispersion process can be suitably generated.

[0034] In the granulation process, the granulation system shown in Figure 22 can be used, but the present invention is not limited to the granulation system shown in Figure 22. The liquid to be treated is a mixture of an aqueous medium containing an inorganic dispersion stabilizer and a polymerizable monomer composition. The temperature of the liquid to be treated can be selected as appropriate, but it may be heated to prevent precipitation of the polymerizable monomer composition, etc. The liquid to be treated is sent from the tank 14 to the disperser 1 of the present invention by a liquid delivery means (pump) 10. The liquid to be treated after being processed by the disperser 1 is sent to the tank 14. A dispersion of the polymerizable monomer composition is obtained by performing this dispersion process for a predetermined time. It is preferable to stir the liquid to be treated by the stirring mechanism 15 in the tank 14 so that the ratio of the aqueous dispersion medium to the polymerizable monomer composition can be kept constant and the liquid can be sent to the disperser.

[0035] Here, when performing shear treatment with a disperser using the granulation system shown in Figure 22, it is preferable that the number of passes calculated from the mass W (kg) of the mixed liquid of the aqueous dispersion medium and the polymerizable monomer composition, the circulation flow rate α (kg / min), and the processing time T (min) be 3 or more and 8 or less, more preferably 4 or more and 6 or less. The number of passes is calculated using the following formula (2). Number of passes = (α × T) ÷ W ... Equation (2)

[0036] Examples of inorganic dispersion stabilizers include 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; and metal hydroxides such as calcium hydroxide, aluminum hydroxide, magnesium hydroxide, and ferric hydroxide. These can be used individually or in combination of two or more. They exert their function as dispersion stabilizers by existing as poorly water-soluble inorganic fine particles in an aqueous medium.

[0037] (Reaction process) A dispersion of toner particles is obtained by polymerizing the polymerizable monomers in the polymerizable monomer composition dispersion obtained as described above. A general-purpose stirring tank with temperature control can be used for the reaction step in the present invention.

[0038] Polymerization is carried out at temperatures of 40°C or higher, generally between 50°C and 90°C. The polymerization temperature can be kept constant throughout the process, but it may be increased in the later stages of the polymerization process to obtain a desired molecular weight distribution.

[0039] Any type of stirring blade can be used for stirring, as long as it can keep the polymerizable monomer composition dispersion suspended without stagnation and maintain a uniform temperature in the tank. Examples of stirring blades or stirring means include general stirring blades such as paddle blades, inclined paddle blades, three-blade swept blades, propeller blades, disc turbine blades, helical ribbon blades and anchor blades, as well as "Fullzone" (manufactured by Shinko Pantech Co., Ltd.), "Twinstar" (manufactured by Shinko Pantech Co., Ltd.), "Maxblend" (manufactured by Sumitomo Heavy Industries Co., Ltd.), "Supermix" (manufactured by Satake Chemical Machinery Industry Co., Ltd.) and "Hi-F Mixer" (manufactured by Soken Chemical Co., Ltd.).

[0040] (Washing process, solid-liquid separation process) To remove the dispersion stabilizer adhering to the surface of the toner particles, the toner particle dispersion is treated with an acid or alkali. After this, the polymer particles are separated from the liquid phase by a general solid-liquid separation method. However, to completely remove the acid or alkali and the dispersion stabilizer components dissolved in them, the toner particles are washed again with water. This washing process is repeated several times until sufficient washing is achieved, after which solid-liquid separation is performed again to obtain wet toner particles.

[0041] (drying process) The resulting wet toner particles are dried to remove any water and aqueous media they contain. Various drying methods can be used in the general drying process, including vacuum drying, fluidized bed drying, and airflow drying.

[0042] (Classification process) After drying, the desired toner particles are obtained by classifying them using an air classifier or similar device to achieve the required particle size distribution.

[0043] (External addition process) Toner can be obtained by mixing toner particles with an external additive for the purpose of imparting various properties to the toner particles.

[0044] [Toner composition materials] Examples of binder resins for toners include styrene-acrylic copolymers. These styrene-acrylic copolymers are copolymers of styrene monomers and acrylic monomers (acrylic acid or methacrylic acid and their alkyl esters).

[0045] Here, the styrene-acrylic copolymer may be contained in the binder resin in a state consisting solely of the styrene-acrylic copolymer, or it may be contained in the binder resin in the state of a block copolymer, graft copolymer, or mixture thereof with other polymers.

[0046] Furthermore, the content of styrene-acrylic polymer in the binder resin is 50% by mass or more, and preferably 80% by mass or more and 100% by mass or less. The inclusion of a styrene-acrylic copolymer in the binder resin improves the toner's developing characteristics and durability.

[0047] In addition to the styrene-acrylic copolymer, other known resins or polymers used in toners can be used as the binder resin.

[0048] Examples of styrene monomers include the following:

[0049] Styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, divinylbenzene, etc.

[0050] The styrene monomer can be used individually, or two or more types selected from among them can be used in combination.

[0051] Examples of the acrylic monomer include the following:

[0052] Alkyl acrylates such as 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, n-nonyl acrylate, n-decyl acrylate, and n-dodecyl acrylate; Alkyl methacrylates such as 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, n-decyl methacrylate, and n-dodecyl methacrylate; Acrylic acid diesters such as diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, and 1,6-hexanediol diacrylate; Acrylic acid, methacrylic acid, etc.

[0053] While one type of acrylic monomer can be used, two or more types selected from these can also be used in combination.

[0054] The glass transition temperature (Tg) of the binder resin can be set to a desired range by adjusting the polymerization ratio of the styrene monomer and the acrylic monomer. Specifically, the polymerization ratio (styrene monomer:acrylic monomer) of the styrene monomer and the acrylic monomer is preferably 65:35 to 100:0 by mass, and more preferably 70:30 to 85:15. The glass transition temperature (Tg) of the binder resin is preferably 25°C or higher and 65°C or lower.

[0055] Various types of polymerization initiators can be used in the manufacturing of toner particles, including peroxide-based polymerization initiators and azo-based polymerization initiators.

[0056] Examples of organic peroxide polymerization initiators include peroxyesters, peroxydicarbonates, dialkylperoxides, peroxyketals, ketone peroxides, hydroperoxides, and diacylperoxides.

[0057] Specific examples of organic peroxide polymerization initiators include peroxyesters such as t-butyl peroxyacetate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-hexyl peroxyacetate, t-hexyl peroxypivalate, t-hexyl peroxyisobutyrate, t-butyl peroxyisopropyl monocarbonate, and t-butyl peroxy-2-ethylhexyl monocarbonate; Examples include diacyl peroxides such as benzoyl peroxide; peroxydicarbonates such as diisopropyl peroxydicarbonate; peroxyketals such as 1,1-di-t-hexyl peroxycyclohexane; dialkyl peroxides such as di-t-butyl peroxide; and others such as t-butyl peroxyallyl monocarbonate.

[0058] Examples of inorganic peroxide polymerization initiators include persulfates and hydrogen peroxide.

[0059] Examples of azo polymerization initiators include 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonnitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, and dimethyl-2,2'-azobis(2-methylpropionate).

[0060] Furthermore, if necessary, two or more of these polymerization initiators can be used simultaneously.

[0061] The amount of polymerization initiator used is preferably 0.10 parts by mass or more and 20.0 parts by mass or less per 100.0 parts by mass of polymerizable monomer.

[0062] (Polar resin) The toner particles may also contain a polar resin. Examples of polar resins include polyester resins. By using a polyester resin as the polar resin, the lubricating properties of the resin itself can be expected when the resin is unevenly distributed on the surface of the toner particles and forms a shell.

[0063] Polyester resins include condensation polymers of alcohol monomers and carboxylic acid monomers.

[0064] Examples of alcohol monomers include the following:

[0065] Alkylene oxide adducts of bisphenol A such as polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(3.3)-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene(2.0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(2.0)-polyoxyethylene(2.0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(6)-2,2-bis(4-hydroxyphenyl)propane; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,4-Butenediol, 1,5-Pentanediol, 1,6-Hexanediol, 1,4-Cyclohexanedimethanol, Dipropylene glycol, Polyethylene glycol, Polypropylene glycol, Polytetramethylene glycol, Bisphenol A, Hydrogenated bisphenol A, Sorbitol, 1,2,3,6-Hexanetetrol, 1,4-Sorbitan, Pentaerythritol, Dipentaerythritol, Tripentaerythritol, 1,2,4-Butanetriol, 1,2,5-Pentanetriol, Glycerol, 2-Methylpropanetriol, 2-Methyl-1,2,4-Butanetriol, Trimethylolethane, Trimethylolpropane, 1,3,5-Trihydroxymethylbenzene.

[0066] On the other hand, examples of carboxylic acid monomers include the following:

[0067] Aromatic dicarboxylic acids or their anhydrides, such as phthalic acid, isophthalic acid, and terephthalic acid; alkyl dicarboxylic acids or their anhydrides, such as succinic acid, adipic acid, sebacic acid, and azelaic acid; succinic acid or its anhydrides substituted with alkyl or alkenyl groups having 6 to 18 carbon atoms; unsaturated dicarboxylic acids or their anhydrides, such as fumaric acid, maleic acid, and citraconic acid.

[0068] In addition, the following monomers can also be used.

[0069] Polyhydric alcohols such as sorbitol, sorbitan, and oxyalkylene ethers of novolac-type phenolic resins; polyhydric carboxylic acids such as trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and its anhydride.

[0070] Among these, a condensate polymer of a bisphenol derivative represented by the following formula (I) and a divalent or higher carboxylic acid is preferred because it has good electrostatic properties.

[0071] Examples of divalent or greater carboxylic acids include fumaric acid, maleic acid, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, and their acid anhydrides, as well as their lower alkyl esters.

[0072] [ka] (In the formula, R represents an ethylene group or a propylene group, x and y are integers greater than or equal to 1, and the average value of x + y is between 2 and 10.)

[0073] The content of the polar resin is preferably 1.0 part by mass or more and 20.0 parts by mass or less, and more preferably 2.0 parts by mass or more and 10.0 parts by mass or less, per 100.0 parts by mass of the binder resin or polymerizable monomer that produces the binder resin.

[0074] (Coloring agent) The toner particles may contain a coloring agent. Examples of the coloring agent include various conventionally known dyes and pigments.

[0075] Examples of black colorants include carbon black, magnetic materials, or materials colored black using the yellow, magenta, and cyan colorants listed below.

[0076] Examples of yellow colorants include monoazo compounds, disazo compounds, condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, examples include CI Pigment Yellow 74, 93, 95, 109, 111, 128, 155, 174, 180, and 185.

[0077] Examples of magenta colorants include monoazo compounds, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolon compounds, thioindigo compounds, and perylene compounds. Specifically, examples include CI Pigment Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, and CI Pigment Violet 19.

[0078] Examples of cyanide colorants include copper phthalocyanine compounds and their derivatives, anthraquinone compounds, and basic dye lake compounds. Specifically, examples include CI Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and 66.

[0079] This toner can be used as a magnetic toner. In that case, the toner particles should contain a magnetic material. In this case, the magnetic material can also serve as a colorant.

[0080] Examples of the magnetic material include iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel; or alloys and mixtures thereof with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium.

[0081] The colorant may be selected from the viewpoints of hue angle, chroma, lightness, lightfastness, OHP transparency, and dispersibility in toner particles. The colorant can be used alone, in combination, or even in a solid solution state.

[0082] The content of the colorant is preferably 1.0 part by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin or the polymerizable monomer that forms the binder resin.

[0083] (Wax) The wax used in the present invention is not particularly limited, and known waxes can be used. However, from the viewpoint of compatibility with the styrene-acrylic copolymer contained in the binder resin, an ester wax, which is a condensate of an alcohol component and a carboxylic acid component, is preferably used. 3 ) 1 / 2 or more and 9.00 (cal / cm 3 ) <00S0012>or less is preferable.

[0084] [[ID=2S]] From the viewpoint of compatibility with the styrene-acrylic copolymer contained in the binder resin, an ester wax, which is a condensate of an alcohol component and a carboxylic acid component, is preferably used as the wax.

[0085] In the present invention, the wax is not particularly limited as long as it satisfies the above relationship. However, from the viewpoints of compatibility with the styrene-acrylic copolymer contained in the binder resin and release property during fixing, an ester wax is preferable. Also, a monofunctional or bifunctional ester wax is more preferable because it has better plasticity.

[0086] Monofunctional or bifunctional ester waxes include esters of monohydric or dihydric linear saturated alcohols with monohydric linear saturated fatty acids, or esters of monohydric or dihydric linear saturated fatty acids with monohydric linear saturated alcohols.

[0087] Monohydric straight-chain saturated alcohols include, but are not limited to, alcohols with 6 to 24 carbon atoms, such as the following compounds: For example, hexanol, heptanol, octanol, nonyl alcohol, decanol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, and behenyl alcohol.

[0088] Divalent straight-chain saturated alcohols include diols with 6 to 24 carbon atoms, and examples of such compounds include, but are not limited to, the following: 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, 1,20-icosanediol, 1,22-docosanediol, and 1,24-tetracosanediol.

[0089] Monounsaturated straight-chain saturated fatty acids with 8 to 24 carbon atoms are used, and the following compounds can be cited, but are not limited to, examples of which include hexanoic acid, octicic acid, nonylic acid, decanoic acid, dodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid.

[0090] Divalent straight-chain saturated fatty acids include dicarboxylic acids with 8 to 24 carbon atoms, and the following compounds are examples, but are not limited to these. Examples include suberic acid, sebacic acid, dodecanediic acid, tetradecanediic acid, hexadecanedioic acid, octadecanediic acid, eicosanedioic acid, docosanedioic acid, and tetracosanedioic acid.

[0091] The above wax is preferably used in an amount of 1.0 part by mass or more and 30.0 parts by mass or less per 100.0 parts by mass of the binder resin.

[0092] The toner particles may also contain hydrocarbon wax in addition to ester wax.

[0093] Examples of hydrocarbon waxes include aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; and waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene or acrylic acid.

[0094] The hydrocarbon wax content is preferably 0.5 parts by mass or more and 5.0 parts by mass or less per 100 parts by mass of the binder resin.

[0095] The melting points of ester waxes and hydrocarbon waxes are preferably 30°C to 130°C, and more preferably 60°C to 100°C. Exhibiting these thermal properties makes it easier to ensure both low-temperature fixability and heat-resistant storage of the resulting toner.

[0096] (Charge control agent) The toner particles may contain a charge control agent. Examples of such charge control agents include the following:

[0097] Organometallic compounds, chelate compounds, monoazometallic compounds, acetylacetone metal compounds, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, quaternary ammonium salts, calixarenes, silicon compounds, nonmetallic carboxylic acid compounds and their derivatives, sulfonic acid groups, sulfonic acid bases, or sulfonic acid ester groups having sulfonic acid resins.

[0098] Specifically, the following are examples of charge control agents for negative charging.

[0099] Metal compounds of aromatic carboxylic acids, such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, and dicarboxylic acid; polymers or copolymers having sulfonic acid groups, sulfonic acid bases, or sulfonic acid ester groups; metal salts or metal complexes of azo dyes or azo pigments; boron compounds, silicon compounds, calixarenes, etc.

[0100] On the other hand, the following are examples of charge control agents for positive charging.

[0101] Quaternary ammonium salts, high molecular weight compounds having quaternary ammonium salts in their side chains; guanidine compounds; nigrosine compounds; imidazole compounds, etc.

[0102] Of these, charge control agents for negative charging are often used.

[0103] Furthermore, examples of polymers or copolymers having a sulfonic acid group, a sulfonic acid base, or a sulfonic acid ester group include monopolymers of sulfonic acid group-containing vinyl monomers such as styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, vinyl sulfonic acid, and methacrylic sulfonic acid, or copolymers of other vinyl monomers with the sulfonic acid group-containing vinyl monomer.

[0104] The content of the charge control agent is preferably 0.01 parts by mass or more and 20.0 parts by mass or less, and more preferably 0.1 parts by mass or more and 10.0 parts by mass or less, per 100.0 parts by mass of the binder resin or polymerizable monomer that produces the binder resin.

[0105] (External additive) From the viewpoint of improving image quality, it is preferable that the toner contains an external additive to the toner particles.

[0106] Examples of external additives include inorganic microparticles such as silica microparticles, titanium dioxide microparticles, and aluminum oxide microparticles.

[0107] It is preferable that the inorganic fine particles are hydrophobized with a hydrophobic agent such as a silane coupling agent, silicone oil, or a mixture thereof.

[0108] The content of the external additive is preferably 0.1 parts by mass or more and 5.0 parts by mass or less per 100.0 parts by mass of toner particles, and more preferably 0.1 parts by mass or more and 3.0 parts by mass or less.

[0109] [Methods for measuring various physical properties] The following describes the calculation and measurement methods for each physical property value specified in the present invention and in the embodiments described later.

[0110] <Method for measuring volume-average median diameter (Dv50) and number-average median diameter (Dn50)> The volume-average median diameter (Dv50) and number-average median diameter (Dn50) of toner particles are calculated as follows. The measurement device used is the "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter), a precision particle size distribution analyzer using the pore electrical resistance method with a 100 μm aperture tube. The included dedicated software, "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter), is used to set the measurement conditions and analyze the measurement data. The measurement is performed using 25,000 effective measurement channels.

[0111] The electrolytic aqueous solution used for measurement is prepared by dissolving special grade sodium chloride in deionized water to a concentration of approximately 1% by mass; for example, "ISOTON II" (manufactured by Beckman Coulter) can be used.

[0112] Furthermore, before performing the measurements and analysis, the dedicated software was configured as follows.

[0113] In the "Change Standard Measurement Method (SOMME)" screen of the dedicated software, set the total count in control mode to 50,000 particles, the number of measurements to 1, and the Kd value to the value obtained using "Standard Particle 10.0 μm" (manufactured by Beckman Coulter). Press the "Measure Threshold / Noise Level Button" to automatically set the threshold and noise level. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check "Flush aperture tube after measurement".

[0114] In the "Pulse to Particle Size Conversion Settings" screen of the dedicated software mentioned above, set the bin spacing to logarithmic particle size, the particle size bins to 256 particle size bins, and the particle size range from 2 μm to 60 μm.

[0115] The specific measurement method is as follows: (1) Pour approximately 200 ml of the electrolytic solution into a 250 ml round-bottom glass beaker specifically designed for the Multisizer 3, set it on the sample stand, and stir the mixture with the stirrer rod at 24 revolutions per second in a counterclockwise direction. Then, use the "Aperture Flash" function of the dedicated software to remove any dirt and air bubbles from inside the aperture tube. (2) Place approximately 30 ml of the electrolytic aqueous solution into a 100 ml flat-bottomed glass beaker. Add approximately 0.3 ml of a diluted solution of "Contaminon N" (a 10% by mass aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) diluted to approximately 3 times its original volume with deionized water as a dispersant. (3) Prepare an "Ultrasonic Dispension System Tetra150" (manufactured by Nikko Bios Co., Ltd.) ultrasonic disperser with an electrical output of 120W, which incorporates two oscillators with an oscillation frequency of 50kHz with a phase difference of 180 degrees. Add approximately 3.3 liters of deionized water to the water tank of the ultrasonic disperser, and add approximately 2 ml of Contaminon N to this water tank. (4) Place the beaker from (2) into the beaker fixing hole of the ultrasonic disperser and operate the ultrasonic disperser. Then, adjust the height of the beaker so that the resonance state of the liquid surface of the electrolytic aqueous solution inside the beaker is maximized. (5) While irradiating the electrolytic aqueous solution in the beaker described in (4) with ultrasound, add approximately 10 mg of toner to the electrolytic aqueous solution in small amounts and disperse it. Continue the ultrasonic dispersion treatment for another 60 seconds. During ultrasonic dispersion, adjust the water temperature in the tank to be between 10°C and 40°C as appropriate. (6) Using a pipette, the electrolyte aqueous solution from (5) containing the dispersed toner is dropped into the round-bottom beaker from (1) placed in the sample stand, and the concentration is adjusted to approximately 5%. The measurement is then carried out until the number of particles measured reaches 50,000. (7) The measurement data is analyzed using the dedicated software attached to the device to calculate the volume-average median diameter (Dv50) and the number-average median diameter (Dn50).

[0116] <Calculation of particle size distribution> The particle size distribution was indicated by the value derived from the following calculation formula (2). Volume-average median diameter (Dv50) ÷ Number-average median diameter (Dn50) ... Equation (2) The above index indicates that the closer the value is to 1, the sharper the granularity distribution. Hereafter, this index will be referred to as "Dv50 / Dn50".

[0117] <Method for measuring peak molecular weight (Mp) and weight-average molecular weight (Mw)> The peak molecular weight (Mp) and weight-average molecular weight (Mw) of crystalline materials, resins, and toners are measured using gel permeation chromatography (GPC) as follows: First, the sample to be measured is dissolved in tetrahydrofuran (THF) at room temperature. If it is difficult to dissolve, it is heated to a temperature of 35°C or lower. Then, the resulting solution is filtered through a solvent-resistant membrane filter, "Myshoridisk" (manufactured by Tosoh Corporation), with a pore diameter of 0.2 μm to obtain the sample solution. The sample solution is adjusted so that the concentration of components soluble in THF is 0.8% by mass. This sample solution is then measured under the following conditions. Equipment: High-speed GPC system "HLC-8220GPC" [manufactured by Tosoh Corporation] Column: LF-604, double column [Manufactured by Showa Denko Corporation] Eluent:THF Flow rate: 0.6mL / min Oven temperature: 40℃ Sample injection volume: 0.020 mL For calculating the molecular weight of the sample, a molecular weight calibration curve created using standard polystyrene resin (product names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation) is used.

[0118] <Method for measuring the melting point (Tm)> The melting point of crystalline materials (crystalline resins or waxes) is measured using a differential scanning calorimeter (DSC) Q2000 (TA Instruments) under the following conditions. Heating rate: 10℃ / min Measurement start temperature: 20℃ Measurement end temperature: 180℃ The temperature correction for the device's detection unit uses the melting points of indium and zinc, while the heat of fusion of indium is used for heat quantity correction. Specifically, approximately 5 mg of the sample is accurately weighed, placed in an aluminum pan, and measured once. An empty aluminum pan is used as a reference. The peak temperature of the maximum endothermic peak at that time is taken as the melting point.

[0119] <Measurement of glass transition temperature (Tg)> The glass transition temperature of amorphous resin is the temperature (°C) at the point where a line equidistant in the vertical direction from the line extending the baseline before and after the change in specific heat occurs, in the reversing heat flow curve obtained by differential scanning calorimetry in the melting point measurement method described above, intersects with the curve of the step-like change portion of the glass transition in the reversing heat flow curve.

[0120] [Configurations included in embodiments of the present invention] This embodiment includes the following configuration. (Configuration 1) A disperser for processing a liquid to be processed by supplying the liquid to be processed. Method for manufacturing resin particles using And, The disperser comprises a rotor, a stator positioned opposite the rotor, and a shearing region for shearing the liquid to be processed. The rotor has an annular projection provided in an annular shape around the rotor's axis of rotation, and non-protruding parts other than the annular projection. The annular projection has a plurality of slits formed in the centrifugal direction of the annular projection, The non-protruding portion has a smooth portion A which is composed of a smooth surface a, The stator has a smoothing section B which is composed of a smoothing surface b which is opposed to the smoothing surface a of the smoothing section A with a gap between them, and a supply port for supplying the material to be processed to the shearing region. The shear region is formed by the opposing smooth surface a of the smooth portion A and the smooth surface b of the smooth portion B, and is formed on the inside of the annular projection. The area of ​​the smooth surface a of the smooth portion A is R(mm 2 ) and the area of ​​the smooth surface b of the smooth portion B is S(mm 2 When this is the case, the relationship between R and S is, 0.55 ≤ S / R ≤ 0.95 Features that satisfy Method for manufacturing resin particles . (Configuration 2) The annular projection is a comb-shaped annular projection having a plurality of small protrusions, The plurality of slits are slits formed between the plurality of small protrusions. As described in Configuration 1 Method for manufacturing resin particles . (Configuration 3) When the distance between the portion of the smooth surface a that forms the shear region and the portion of the smooth surface b that forms the shear region is h (mm), and the distance between the annular projection and the stator in the centrifugal direction is v (mm), the relationship between h and v is, 0.4 ≤ h / v ≤ 5.0 Configuration 1 or 2 that satisfies the conditions described above Method for manufacturing resin particles . (Configuration 4) When the distance between the portion of the smooth surface a that forms the shear region and the portion of the smooth surface b that forms the shear region is h (mm), and the distance between the plurality of slits is K (mm), the relationship between h and K is, 0.2 ≤ h / K ≤ 5.0 One of the configurations 1 to 3 that satisfies the conditions described above. Method for manufacturing resin particles . (Configuration 5) When the distance between the portion of the smooth surface a that forms the shear region and the portion of the smooth surface b that forms the shear region is h (mm), and the height of the annular projection is H (mm), the relationship between h and H is, 10 ≤ H / h ≤ 60 One of the configurations 1 to 4 that satisfies the conditions described above. Method for manufacturing resin particles . (Configuration 6) The configuration according to any of Configurations 1 to 5, wherein the opening ratio of the plurality of slits on the outer circumferential surface of the annular projection is 10 area % or more and 30 area % or less. Method for manufacturing resin particles . (Configuration 7) When the distance between the portion of the smooth surface a that forms the shear region and the portion of the smooth surface b that forms the shear region is h (mm), 0.6 ≤ h ≤ 3.0 One of the configurations 1 to 6 that satisfies the conditions described above. Method for manufacturing resin particles . (Configuration 8) The supply port is provided on the stator so as to intersect with the rotation axis of the rotor or the extension of the rotation axis, as in any of Configurations 1 to 7. Method for manufacturing resin particles . (composition 9 ) before The liquid to be treated contains a precursor of resin particles and a liquid that is immiscible with the precursor of resin particles. One of the components described in 1 to 8 A method for manufacturing resin particles. (composition 10 A granulation step to form particles of a polymerizable monomer composition containing a polymerizable monomer and a coloring agent in an aqueous dispersion medium to obtain a dispersion of the polymerizable monomer composition particles, Following the granulation step, a polymerization step is performed to polymerize the polymerizable monomer in the particles to obtain a dispersion of toner particles. A method for producing toner particles having the following characteristics: The granulation step is a step that uses a disperser described in any of configurations 1 to 8. A method for manufacturing toner particles. [Examples]

[0121] The present invention will be specifically explained by the following examples. The method for producing toner particles is described below. Examples 26 and 28 are for reference only. Unless otherwise specified, all values ​​in the examples and comparative examples are based on mass.

[0122] [Example 1] Toner particles were manufactured using the following procedure.

[0123] (Pigment dispersion composition preparation process) 15.9 parts of styrene were mixed with 2.95 parts of CIPigment Blue 15:3, manufactured by Dainichi Seika Co., Ltd. Furthermore, 0.324 parts of a charge control agent (Bontron E88; manufactured by Orient Chemical Industry Co., Ltd.), 0.075 parts of an aluminum salicylate compound, and 0.36 parts of a sulfonic acid group-containing resin (Acrybase FCA-1001-NS; manufactured by Fujikura Kasei Co., Ltd.) were prepared. These were introduced into an attritor (manufactured by Nippon Coke Co., Ltd.) and stirred at 200 rpm at 25°C for 300 minutes using 3.0 mm diameter zirconia beads to prepare a pigment dispersion composition.

[0124] (Preparation process for polymerizable monomer composition) The following materials were placed in the same container and mixed and dispersed using a TK Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at a peripheral speed of 20 m / s. • Pigment dispersion composition 17.89 parts • Styrene 8.59 parts n-butyl acrylate 8.75 parts • Polyester resin 1 1.30 parts (Mw=11000, Tg=76℃, acid value=5.3mgKOH / g) • Styrene-methacrylate-methyl methacrylate-α-methylstyrene copolymer 4.59 copies (Styrene / methacrylic acid / methyl methacrylate / α-methylstyrene = 80.85 / 2.50 / 1.65 / 15.0, Mp = 19700, Mw = 7900, Tg = 96℃, acid value = 12.0 mgKOH / g, Mw / Mn = 2.1) Furthermore, after heating to 60°C, • Hydrocarbon wax (HNP-51; manufactured by Nippon Seiro Co., Ltd.) 3.24 parts • Ethylene glycol distearate 0.97 parts • Dibehenyl adipic acid 1.30 parts The mixture was added and dispersed and mixed for 30 minutes.

[0125] (Aqueous dispersion medium preparation process) As shown in Figure 22, 81.25 parts of deionized water, 1.51 parts of sodium phosphate dodecahydrate, and 0.725 parts of 10% by mass hydrochloric acid were added to a granulation tank to prepare an aqueous sodium phosphate solution, which was then heated to 60°C. 0.88 parts of calcium chloride dihydrate were dissolved in 5.85 parts of deionized water to obtain an aqueous calcium chloride solution. The aqueous calcium chloride solution was added to the aforementioned aqueous sodium phosphate solution and stirred for 30 minutes at a peripheral speed of 25 m / s using a Clearmix (manufactured by M-Technique Co., Ltd.) to prepare a dispersion of poorly water-soluble inorganic fine particles.

[0126] (granulation process) A polymerizable monomer composition was added to the aqueous dispersion medium in the granulation tank shown in Figure 22, and stirred for 2 minutes at a peripheral speed of 20 m / s using Creamix (manufactured by M-Technique Co., Ltd.) at a temperature of 60°C and under a nitrogen atmosphere. The mixture of the aqueous dispersion medium and polymerizable monomer composition from the granulation tank was then sent to an external circulation path and to the disperser of the present invention. The rotor of the disperser was rotated at a peripheral speed of 40 m / s to apply shear to the mixture of the aqueous dispersion medium and polymerizable monomer composition, and the mixture was returned to the granulation tank. The secondary pressure of the disperser was set to 0.25 MPa. The primary pressure was 0.17 MPa. The processing time in the disperser was 45 minutes, with 5 passes. This obtained a dispersion of the polymerizable monomer composition.

[0127] The configuration requirements for the distributed system used are shown in Table 1.

[0128] (Reaction process) The dispersion of the polymerizable monomer composition was transferred to another tank, and 9.0 parts of t-butyl peroxypivalate, a polymerization initiator, were added while stirring with a paddle blade. The temperature was then raised to 73°C and the reaction was carried out for 4 hours. After that, the temperature was further raised to 90°C and the reaction was carried out for 2 hours to obtain a dispersion of toner particles.

[0129] (Washing / filtration / drying process) After cooling the toner particle dispersion, hydrochloric acid was added to adjust the pH to 1.2, and the mixture was stirred for 1 hour. The toner particle dispersion was then filtered, and the filtrate was washed and filtered with an equal volume of water to obtain wet toner particles.

[0130] The obtained wet toner particles were air-dried in a constant temperature bath at 35°C for 3 days to obtain toner particle 1.

[0131] For the obtained toner particles 1, the "Dv50 / Dn50" index, which is an indicator of the sharpness of the particle size distribution, was 1.11. The results, along with the evaluation rank according to the evaluation criteria below, are shown in Table 2. (Evaluation Criteria) A: Dv50 / Dn50 is 1.15 or less B: Dv50 / Dn50 is between 1.15 and 1.20. C:Dv50 / Dn50 is between 1.20 and 1.25. D:Dv50 / Dn50 is over 1.25

[0132] [Examples 2-4] Except for adjusting the opening of the supply port, the relationship S / R between the area R (mm) of the smooth surface a of smooth section A in the shear region and the area S (mm) of the smooth surface b of smooth section B was changed, and toner particles 2 to 4 were obtained under the same conditions and methods as in Example 1.

[0133] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 2-4.

[0134] [Example 5] Except for adjusting the opening of the supply port to set the relationship S / R between the area R (mm) of the smooth surface a of smooth section A in the shear region and the area S (mm) of the smooth surface b of smooth section B to 0.95, toner particles 5 were obtained under the same conditions and methods as in Example 1.

[0135] In the granulation process, the pressure on the primary side of the disperser was 0.05 MPa higher compared to Example 1. Flow rate pulsation was also observed. This is thought to be due to the reduced opening of the supply port, and is considered to be the limit for stable operation of the disperser.

[0136] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 5.

[0137] [Example 6] Toner particles 6 were obtained under the same conditions and methods as in Example 1, except that the shape of the disperser's rotor, as shown in Figure 7, was a rotor in which parts of adjacent annular protrusions were connected. The number of slits was adjusted to maintain the same aperture ratio.

[0138] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 6.

[0139] [Examples 7-10] Except for changing the relationship h / v between the distance h (mm) between the portion forming the shear region of smooth surface a and the portion forming the shear region of smooth surface b, and the distance v (mm) between the annular projection and the stator in the centrifugal direction, toner particles 7 to 10 were obtained under the same conditions and methods as in Example 1.

[0140] Compared to Example 1, when increasing h / v, the centrifugal distance v(mm) between the annular projection and the stator was decreased. Compared to Example 1, when decreasing h / v, the centrifugal distance v(mm) between the annular projection and the stator was increased.

[0141] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 7-10.

[0142] [Examples 11-14] Toner particles 11 to 14 were obtained under the same conditions and methods as in Example 1, except that the relationship h / K between the distance h (mm) between the shear region-forming portion of smooth surface a and the shear region-forming portion of smooth surface b, and the distance K (mm) between the multiple slits was changed. The change in h / K was made by changing the distance K (mm) between the multiple slits, and the aperture ratio was adjusted by changing the number of slits.

[0143] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 11-14.

[0144] [Example 15] Toner particles 15 were obtained under the same conditions and methods as in Example 1, except that the distance h (mm) between the portion forming the shear region of smooth surface a and the portion forming the shear region of smooth surface b was set to 3.0 mm.

[0145] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 15.

[0146] [Examples 16, 17] Toner particles 16 and 17 were obtained under the same conditions and methods as in Example 15, except that the distance h (mm) between the portion of smooth surface a that forms a shear region and the portion of smooth surface b that forms the same shear region, and the relationship H / h between the height of the annular projection and H (mm) were changed. The change in H / h was made by changing the height H (mm) of the annular projection.

[0147] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 16 and 17.

[0148] [Example 18] Toner particles 18 were obtained under the same conditions and methods as in Example 1, except that the distance h (mm) between the portion forming the shear region of smooth surface a and the portion forming the shear region of smooth surface b was set to 1.0 mm.

[0149] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 18.

[0150] [Examples 19, 20] Toner particles 19 and 20 were obtained under the same conditions and methods as in Example 18, except that the distance h (mm) between the portion forming the shear region of smooth surface a and the portion forming the shear region of smooth surface b, and the relationship H / h between the height of the annular projection and H (mm) were changed. The change in H / h was achieved by changing the height H (mm) of the annular projection.

[0151] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 19 and 20.

[0152] [Examples 21-24] Toner particles 21 to 24 were obtained under the same conditions and methods as in Example 1, except that the aperture ratio was changed by multiple slits on the outer surface of the annular projection. The aperture ratio was adjusted by the number of slits.

[0153] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 21-24.

[0154] [Example 25] Toner particles 25 were obtained under the same conditions and methods as in Example 1, except that the height H (mm) of the annular projection was changed and H / h was set to 10.

[0155] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 25.

[0156] [Examples 26, 27] Except for changing the distance h (mm) between the portion of smooth surface a that forms a shear region and the portion of smooth surface b that forms a shear region, toner particles 26 and 27 were obtained under the same conditions and methods as in Example 25.

[0157] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 26 and 27.

[0158] [Example 28] Toner particles 28 were obtained under the same conditions and methods as in Example 1, except that the distance h (mm) between the portion of smooth surface a that forms a shear region and the portion of smooth surface b that forms a shear region was changed.

[0159] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 28.

[0160] [Example 29] In Example 1, the center of the supply port coincided with the extension of the rotation axis. However, as shown in Figures 8 and 9, the position of the supply port was changed so that the center of the supply port 8 did not coincide with the extension of the rotation axis C, and the extensions of the supply port and the rotation axis intersected. Otherwise, toner particles 29 were obtained under the same conditions and methods as in Example 1.

[0161] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 29.

[0162] [Example 30] In contrast to Embodiment 1, where the center of the supply port coincides with the extension of the rotation axis, toner particles 30 were obtained under the same conditions and methods as in Embodiment 1, except that the supply port was provided at a position where the extension of the supply port 8 and the rotation axis C do not intersect, as shown in Figures 10 and 11.

[0163] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 30.

[0164] [Example 31] As shown in Figures 12 and 13, the annular projections 5 are arranged in two concentric stages, and the outermost annular projection has the same shape as in Example 1. Except that the outer circumference of the inner annular projection was set to be 70% of the rotor diameter, toner particles 31 were obtained under the same conditions and methods as in Example 1.

[0165] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 31.

[0166] [Example 32] Toner particles 32 were obtained under the same conditions and methods as in Example 31, except that the relationship S / R between the area R (mm) of the smooth surface a of smooth section A and the area S (mm) of the smooth surface b of smooth section B in the shear region was changed by adjusting the opening of the portion continuous with the supply port.

[0167] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 32.

[0168] [Example 33] As shown in Figures 14 and 15, the annular projection on the outermost circumference of the rotor used in Example 31 was eliminated, leaving only the inner annular projection. Furthermore, by adjusting the opening of the portion continuous with the supply port, the relationship S / R between the area R (mm) of the smooth surface a of smooth section A and the area S (mm) of the smooth surface b of smooth section B in the shear region became 0.60 with this device configuration.

[0169] Otherwise, toner particles 33 were obtained under the same conditions and methods as in Example 1.

[0170] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 33.

[0171] [Example 34] Toner particles 34 were obtained under the same conditions and methods as in Example 33, except that the relationship S / R between the area R (mm) of the smooth surface a of smooth section A and the area S (mm) of the smooth surface b of smooth section B in the shear region was changed by adjusting the opening of the portion continuous with the supply port.

[0172] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 34.

[0173] [Example 35] As shown in Figures 16 and 17, toner particles 35 were obtained under the same conditions and methods as in Example 1, except that a rotor was provided in which the relationship between the distance D (mm) between the outermost edge of the smooth portion A and the surface constituting the slit on the smooth surface a and the height H (mm) of the annular projection was 0.3.

[0174] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 35.

[0175] [Example 36] As shown in Figures 16 and 17, toner particles 36 were obtained under the same conditions and methods as in Example 1, except that a rotor was provided in which the relationship between the distance D (mm) between the outermost edge of the smooth portion A and the surface constituting the slit on the smooth surface a and the height H (mm) of the annular projection was 0.5.

[0176] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 36.

[0177] [Example 37] As shown in Figures 16 and 17, toner particles 37 were obtained under the same conditions and methods as in Example 1, except that a rotor was provided in which the relationship between the distance D (mm) between the outermost edge of the smooth portion A and the surface constituting the slit on the smooth surface a and the height H (mm) of the annular projection was 0.7.

[0178] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles.

[0179] [Example 38] As shown in Figures 16 and 17, toner particles 38 were obtained under the same conditions and methods as in Example 1, except that a rotor was provided in which the relationship between the distance D (mm) between the outermost edge of the smooth portion A and the surface constituting the slit on the smooth surface a and the height H (mm) of the annular projection was 0.8.

[0180] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 38.

[0181] [Example 39] Toner particles 39 were obtained under the same conditions and method as in Example 37, except that the number of passes was set to 6.

[0182] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 39.

[0183] [Example 40] Toner particles 40 were obtained under the same conditions and methods as in Example 38, except that the number of passes was set to 6.

[0184] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 40.

[0185] [Comparative Example 1] A disperser was used in which the annular projections of the rotor and the stator were fitted together, with the annular projections of the rotor and the stator being fitted together, as shown in Figure 18. The h / v, h / K, H / h, and aperture ratio of each annular projection were the same as those of the annular projection in Example 1. Otherwise, toner particles 41 were obtained under the same conditions and methods as in Example 1.

[0186] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 41.

[0187] [Comparative Example 2] A disperser equipped with a rotor without annular protrusions, as shown in Figure 19, was used. Otherwise, toner particles 42 were obtained under the same conditions and methods as in Example 1.

[0188] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 42.

[0189] [Comparative Example 3] Toner particles 43 were obtained under the same conditions and methods as in Example 1, except that the opening of the portion continuous with the supply port was adjusted so that the relationship S / R between the area R (mm) of the smooth surface a of smooth section A in the shear region and the area S (mm) of the smooth surface b of smooth section B was set to 0.50.

[0190] Table 1 shows the configuration requirements of the disperser in the granulation process, and Table 2 shows the particle size distribution of the obtained toner particles 43.

[0191] [Table 1]

[0192] [Table 2] [Explanation of symbols]

[0193] 1: Disperser, 2: Rotating shaft, 3: Rotor, 4: Stator, 5: Annular projection, 6: Non-projecting part, 7: Shear region, 8: Supply port, 9: Slit, 10: Pump, 11: Pressure gauge, 12: Valve, 13: Flow meter, 14: Tank, 15: Agitation mechanism, a: Smooth surface a, A: Smooth part A, b: Smooth surface b, B: Smooth part B, C: Rotor rotation shaft, h: Spacing h of parts forming the shear region, v: Centrifugal distance v between the annular projection and the stator, K: Slit spacing K, S: S field of view (field of view direction relative to the rotor in Figures 6, 7, 20, 21), Ss: Slit area Ss, Sp: Annular projection area Sp

Claims

1. A method for producing resin particles using a disperser for processing a liquid to be treated by supplying the liquid to be treated, The disperser comprises a rotor, a stator positioned opposite the rotor, and a shearing region for shearing the liquid to be processed. The rotor has an annular projection provided in an annular shape around the rotor's axis of rotation, and non-protruding parts other than the annular projection. The annular projection has a plurality of slits formed in the centrifugal direction of the annular projection, The non-protruding portion has a smooth portion A which is composed of a smooth surface a. The stator has a smooth section B which is composed of a smooth surface b which is opposed to the smooth surface a of the smooth section A with a gap between them, and a supply port for supplying the liquid to be processed to the shear region. The shear region is formed by the opposing smooth surface a of the smooth portion A and the smooth surface b of the smooth portion B, and is formed on the inside of the annular projection. The area of ​​the smooth surface a of the smooth portion A is R (mm 2 ) and the area of ​​the smooth surface b of the smooth portion B is S (mm²) 2 When this is the case, the relationship between R and S is, 0.55 ≤ S / R ≤ 0.95 Satisfying the conditions, When the distance between the portion of the smooth surface a that forms the shear region and the portion of the smooth surface b that forms the shear region is h (mm), then h is 0.6 ≤ h ≤ 3.0 A method for producing resin particles, characterized by satisfying the requirements.

2. The aforementioned annular projection is a comb-shaped annular projection having a plurality of small protrusions, The plurality of slits are slits formed between the plurality of small protrusions. A method for producing resin particles according to claim 1.

3. When the distance between the portion of the smooth surface a that forms the shear region and the portion of the smooth surface b that forms the shear region is h (mm), and the distance between the annular projection and the stator in the centrifugal direction is v (mm), the relationship between h and v is, 0.4 ≤ h / v ≤ 5.0 A method for producing resin particles according to claim 1 or 2, which satisfies the requirements.

4. When the distance between the portion of the smooth surface a that forms the shear region and the portion of the smooth surface b that forms the shear region is h (mm), and the distance between the plurality of slits is K (mm), the relationship between h and K is, 0.2 ≤ h / K ≤ 5.0 A method for producing resin particles according to claim 1 or 2, which satisfies the requirements.

5. When the distance between the portion of the smooth surface a that forms the shear region and the portion of the smooth surface b that forms the shear region is h (mm), and the height of the annular projection is H (mm), the relationship between h and H is, 10 ≤ H / h ≤ 60 A method for producing resin particles according to claim 1 or 2, which satisfies the requirements.

6. A method for producing resin particles according to claim 1 or 2, wherein the opening ratio due to the plurality of slits on the outer circumferential surface of the annular projection is 10 area % or more and 30 area % or less.

7. The method for producing resin particles according to claim 1 or 2, wherein the supply port is provided on the stator such that it intersects with the rotation axis of the rotor or an extension of the rotation axis.

8. The method for producing resin particles according to claim 1 or 2, wherein the liquid to be treated contains a precursor of resin particles and a liquid that is immiscible with the precursor of resin particles.

9. A granulation step to form particles of a polymerizable monomer composition containing a polymerizable monomer and a coloring agent in an aqueous dispersion medium to obtain a dispersion of the polymerizable monomer composition particles, Following the granulation step, a polymerization step is performed to polymerize the polymerizable monomer in the particles to obtain a dispersion of toner particles. A method for producing toner particles having the following characteristics: The granulation step is a step using the disperser described in claim 1. A method for manufacturing toner particles.

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