JP2010204435A - Method of manufacturing electrostatic charge image developing toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing electrostatic charge image developing toner, with which even when a small amount of cleaning water is used, and printing is performed in a high-temperature and high-humidity environment (for example, 30°C, 80% RH), separation property of transfer material is satisfactory, and a problem due to toner scattering is not caused even when printing a large number of sheets in a low-temperature and low-humidity environment (for example, 10°C, 20% RH). <P>SOLUTION: The method of manufacturing electrostatic charge image developing toner includes a process of cleaning toner base particles formed in an aqueous medium with cleaning water, wherein the cleaning water contains the net solved component of 0.5 to 1,000.0 mg/L, at 25°C. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing an electrostatic charge image developing toner.

  In recent years, toners that have been wet-granulated instead of toners produced by mechanical grinding are attracting attention because they are advantageous for reducing particle size, sharpening particle size distribution, and introducing a large amount of release agent. . Examples of a method for producing a toner that is granulated in a wet method include an emulsion association method, a suspension polymerization method, a dispersion polymerization method, and a solution suspension method using a separately polycondensed polyester.

  The polymerized toner by the emulsion association method in which the toner base particles are formed through a polymerization process in an aqueous medium can control the particle size and shape of the toner base particles in the manufacturing process, so that the particle size distribution is small and the particle size distribution is sharp. In addition, it is disclosed that a toner having a rounded shape with no corners on the particle surface in which the shape of each toner base particle is uniform can be obtained (see, for example, Patent Document 1).

  Since high-resolution images are expected for toners of this size and shape, for example, a minute dot image of 1200 dpi (dpi represents the number of dots per inch (2.54 cm)) is formed. Considerations for adoption of digital image forming are increasing.

  Toner that is granulated by wet method, toner base particles are formed in an aqueous medium or an organic solvent to form a toner base particle dispersion, and then a separation means typified by a solid-liquid separation device such as a filtration device is used. Thus, the toner base particles are separated from the toner base particle dispersion, and then an external additive is added if necessary. The dispersion liquid in which the toner base particles are dispersed contains impurities such as a surfactant, a free release agent particle released from the toner base particles, or a decomposition product particle thereof. Therefore, when separating the toner base particles from the dispersion liquid, it is necessary to clean the toner base particles so that these impurities do not remain.

  For the purpose of removing impurities from the toner base particles, the toner base particles are separated by separating the toner base particles from the dispersion of the toner base particles by centrifugation, and supplying cleaning water until the electric conductivity of the filtrate falls below a specific value. A technique for cleaning particles is disclosed (for example, see Patent Document 2).

  Also disclosed is a technique for removing impurities by adding a cleaning liquid to a toner base particle from which an aqueous medium has been removed in a container equipped with a stirring blade and a filter and stirring, and then filtering the toner base particle under pressure. (For example, refer to Patent Document 3).

  Further, a method of washing toner base particles with ion-exchanged water in order to wash away the surfactant, dispersion stabilizer, inorganic salt, etc. adhering to the toner base particles is disclosed (for example, see Patent Document 4).

  In addition, in order to wash away the surfactant, dispersion stabilizer, inorganic salt, etc. adhering to the toner base particles, the toner base particles (slurry) have a conductivity of the filtrate by using ion exchange water having an electric conductivity of 1 μS / cm. A method of cleaning until 2 μS / cm is disclosed (for example, refer to Patent Document 5).

JP 2000-214629 A JP 2000-292976 A JP 2001-249490 A JP 2008-233175 A JP 2006-325895 A

  However, the toner for developing an electrostatic charge image (hereinafter, also simply referred to as toner) prepared by washing the toner base particles with ion exchange water (for example, ion exchange water having an electric conductivity of 1 μS / cm) has a high temperature and high temperature. When printing in a humid (for example, 30 ° C, 80% RH) environment, transfer material may be poorly separated, or when a large number of sheets are printed in a low-temperature, low-humidity (for example, 10 ° C, 20% RH) environment, smudges may occur due to toner scattering. Problem occurred.

  Further, the known toner base particle cleaning requires a large amount of cleaning water, which requires a long time for cleaning and has a high manufacturing cost.

  The object of the present invention is that separation of the transfer material is good even when printing is performed in a high temperature and high humidity (for example, 30 ° C., 80% RH) environment, and a large number of sheets are produced in a low temperature and low humidity (for example, 10 ° C., 20% RH) environment It is an object of the present invention to provide a method for producing a toner for developing an electrostatic charge image that does not cause a problem due to toner scattering even after printing.

  The object of the present invention is achieved by adopting the following configuration.

1. In the method for producing a toner for developing an electrostatic charge image, the method includes a step of washing toner base particles formed in an aqueous medium with washing water.
The method for producing a toner for developing an electrostatic charge image, wherein the washing water contains 0.5 to 1000.0 mg / L of total dissolved components at 25 ° C.

  2. 2. The method for producing a toner for developing an electrostatic charge image according to 1 above, wherein the toner base particles are obtained by aggregating and fusing resin particles and colorant particles in an aqueous medium.

  According to the method for producing a toner for developing an electrostatic charge image of the present invention, the transfer material has good separability even when printed in a high temperature and high humidity (for example, 30 ° C., 80% RH) environment, and low temperature and low humidity (for example, 10 ° C., 20%). % RH) Even if a large number of sheets are printed in an environment, there is an excellent effect that a problem due to toner scattering does not occur.

FIG. 4 is a schematic diagram showing a state where a surfactant remaining in toner base particles is replaced with a dissolved component in washing water. It is sectional drawing which shows an example of a rotation cylinder type washing | cleaning apparatus. FIG. 6 is a manufacturing flow diagram (manufacturing process diagram) illustrating an example of a cleaning process for cleaning toner base particles. It is a schematic diagram which shows an example of a monochrome image forming apparatus.

  Since the toner base particles formed in the aqueous medium use a surfactant, a dispersion stabilizer, an inorganic salt, etc. in the step of preparing the toner base particles, the toner base particles include a surfactant, a dispersion stabilizer, an inorganic salt, etc. Is attached. When toner is prepared using toner base particles to which a surfactant, dispersion stabilizer, inorganic salt, etc. are attached, fogging occurs during printing due to the influence of the surfactant, dispersion stabilizer, inorganic salt, etc. Problems such as insufficient image density occur.

  Therefore, it becomes necessary to wash away the surfactant, dispersion stabilizer, inorganic salt, etc. adhering to the toner base particles.

  In known techniques, ion exchange water or pure water is used to wash away the surfactant, dispersion stabilizer, inorganic salt, and the like adhering to the toner base particles.

  However, an electrostatic charge image developing toner (hereinafter also simply referred to as toner) obtained by washing toner base particles with ion-exchanged water or pure water having a small total dissolved component in the washing water has a high temperature and high humidity (for example, 30%). When printing in an environment of 80 ° C. and 80% RH, poor transfer material separation may occur, and when a large number of sheets are printed in a low temperature and low humidity environment (for example, 10 ° C. and 20% RH), contamination of the machine may occur due to toner scattering. It has occurred.

  The inventors of the present invention have considered the above problem because the total dissolved component (the amount of dissolved component) dissolved in the washing water has some influence.

  As a result of various studies, when washing water containing a specific amount of total dissolved components is used for washing toner base particles formed in an aqueous medium, a surfactant or dispersion stabilizer attached to the toner base particles is used. And inorganic salts are easily replaced with dissolved components in the wash water, and surfactants, dispersion stabilizers, inorganic salts, etc. remaining on the toner base particles are removed, and the dissolved components easily adhere to the removed parts. I guess it will be.

  When the total amount of dissolved components in the washing water is small, the amount of dissolved components adhering to the toner particles after drying is reduced, the exposure of the resin surface on the toner particle surface is increased, and the fluidity of some toner in the developing machine is increased. descend. It is considered that toner with insufficient charge is generated due to a decrease in fluidity during printing of a large number of sheets, and the toner with insufficient charge is scattered from the inside of the developing machine, resulting in contamination inside the machine. On the other hand, when there are many total dissolved components in the washing water, the amount of dissolved components adhering to the toner particles after drying increases, and the transfer material is separable in a high temperature and high humidity (for example, 30 ° C., 80% RH) environment. Is thought to worsen.

  Moreover, since the electrical conductivity is affected by the dissolved gas (mainly carbon dioxide), the method for managing the cleaning water disclosed in the disclosure is difficult to manage by using the electrical conductivity. It is considered that there is a problem because the charge amount of toner varies between lots.

  The inventors of the present invention have studied a cleaning water that can achieve the object of the present invention without using a large amount of the cleaning water.

  As a result, when toner base particles are washed with washing water having a total dissolved component of 0.5 to 1000.0 mg / L, preferably 350.0 to 1000.0 mg / L, impurities adhering to the toner base particles (Surfactants, dispersants, inorganic salts, etc.) can be easily replaced with dissolved components, and impurities can be efficiently removed (a small amount of washing water) and remain on the toner base particles without using a large amount of washing water. We found that it is possible to remove impurities and attach new dissolved components.

  It is considered that when washing water having a total dissolved component of 0.5 mg / L or more is used, a small amount of dissolved component is adhered after the removal, and toner scattering can be prevented.

  On the other hand, when wash water having a total dissolved component of 1000.0 mg / L or less is used, a large amount of dissolved component is adhered after removal, and the transfer material is separable even in a high temperature and high humidity (for example, 30 ° C., 80% RH) environment. Believes that it has improved.

  FIG. 1 is a schematic diagram showing how the surfactant remaining in the toner base particles is replaced with dissolved components in the washing water.

  In FIG. 1, (a) is a state in which a surfactant remains on toner base particles, (b) is a state in which a dissolved component is attached to toner base particles, 1 is toner base particles, and 2 is a surfactant. 3 is a dissolved component in the wash water, 4 is a dissolved component, 5 is a combination of a surfactant in the wash water and a dissolved component, and 6 is a surfactant in the wash water.

  As shown in FIG. 1, when the toner base particles in which the surfactant remains are washed with washing water containing the dissolved component, the dissolved component is bonded to the surfactant remaining in the toner base particle. This shows the state where the surfactant is removed from the toner base particles, and the dissolved component adheres to the portion where the surfactant is removed.

  Hereinafter, the present invention will be described in detail.

  First, the total dissolved component referred to in the present invention will be described.

<Total dissolved components>
The total dissolved component referred to in the present invention means the mass of the dissolved component dissolved in 1 L of washing water at 25 ° C.

  In the present invention, the total dissolved component (the mass of the dissolved component) is a value determined by a heat drying method.

  The measurement method by the heat drying method is to collect 2.0 ml of washing water at a temperature of 25 ° C., which has been filtered through a 0.1 μm aperture filter to remove insoluble matter, with a mass of accuracy of ± 10%. Residual solid content after heating in electronic moisture meter MOC-120 using step mode at 60 ° C for 30 minutes, 70 ° C for 30 minutes, 80 ° C for 30 minutes, 90 ° C for 30 minutes, 100 ° C for 30 minutes, 105 ° C for 30 minutes It is the method of calculating | requiring the mass of.

  The dissolved component is an inorganic compound or an organic compound, and examples thereof include salts and nonions by combinations of ions as described below.

Cations (Ca ²⁺ , Mg ²⁺ , Na ⁺ , Fe ²⁺ , Mn ²⁺ etc.)
Anion (HCO ₃ ⁻ , Cl ⁻ , SO ₄ ²⁻ , NO ₃ ⁻ etc.)
(Example: sodium chloride, calcium hydrogen carbonate Ca (HCO ₃ ) ₂ )
Nonion (polyoxyethylene alkyl ether, etc.)
Other organic compounds such as sugars and water-soluble vitamins.

  Preferably, sodium chloride, glucose, sodium dodecyl sulfate, ascorbic acid and the like can be mentioned.

  Next, a method for preparing cleaning water will be described.

<Method for preparing washing water>
The method for preparing the washing water is not particularly limited as long as washing water containing 0.5 to 1000.0 mg / L of the dissolved component is obtained at 25 ° C. As a preferable production method, 0.5 to 1000.0 mg / L of a dissolved component such as a cation, an anion, or nonionic compound is dissolved in 25 ° C. ion-exchanged water that has been filtered to remove insoluble components. A manufacturing method can be given.

  Next, a method for producing the toner of the present invention will be described.

<Method for producing toner>
The method for producing a toner of the present invention is a method of producing toner base particles in an aqueous medium and washing the toner base particles with washing water containing a specific amount of a dissolved component.

As a preferable production method,
Producing a dispersion of toner base particles in an aqueous medium;
A step of solid-liquid separating the toner base particles from the dispersion of the toner base particles;
Contains a specific amount of dissolved component to remove impurities (for example, surfactants, dispersion stabilizers, inorganic salts, etc.) remaining in the solid-liquid separated toner base particles and newly deposit a fixed amount of dissolved component Washing with washing water,
A step of drying the toner base particles after washing, and preparing dried toner base particles;
An example of the method is a method in which an external additive is added to and mixed with dried toner base particles.

  The aqueous medium as used in the field of this invention means the medium which consists of 50-100 mass% of water and 0-50 mass% of water-soluble organic solvents. Preferably, it refers to a medium comprising 90 to 100% by mass of water and 0 to 10% by mass of a water-soluble organic solvent. Examples of the water-soluble organic solvent include methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, tetrahydrofuran, and the like, and an alcohol-based organic solvent that does not dissolve the resin forming the toner base particles is preferable.

  Next, a cleaning method and a cleaning process for cleaning the toner base particles will be described.

  The washing method of the toner base particles is not particularly limited, and examples thereof include a centrifugal separation method, a vacuum filtration method using Nutsche and the like, a filtration method using a filter press and the like.

  As a preferable method for cleaning the toner base particles, a rotating cylindrical cleaning device using a centrifugal separation method can be used.

  FIG. 2 is a cross-sectional view showing an example of a rotating cylindrical cleaning device.

  In FIG. 2, 301 is a main body, 302 is a basket (rotating cylinder), 303 is a basket rotating device, 304 is a scraping device, 305 is a liquid supply pipe, 308 is a liquid discharge port, 310 is a cake discharge port, and 306 is A scraper, 309 is a liquid injection nozzle, and 307 is a filter.

  The rotating cylindrical cleaning device shown in FIG. 2 is of a type that discharges a toner cake from the lower part. A main body 301 includes a basket (rotating cylinder) 302, a basket rotating device 303, a scraping device 304, a liquid supply pipe 305, A liquid discharge port 308 and a cake discharge port 310 are attached. A scraper 306 is mounted on the scraping device 304, a liquid injection nozzle 309 is mounted on the liquid supply pipe 305, and a removable filter 307 is mounted on the basket (rotating cylinder) 302. At the start, the toner base particle dispersion is supplied from the liquid supply pipe 305, and the basket 302 is rotated at a high speed to separate the solid and the liquid, thereby forming a toner cake on the surface of the filter 307. The filtrate is discharged from the liquid discharge port 308.

  Thereafter, in order to wash the toner cake, specific washing water is jetted from the jet nozzle 309 of the liquid supply pipe 305. The toner cake washing water is discharged from a liquid drain port 308.

  Thereafter, the washed toner cake is dehydrated by rotating the basket 302 at a high speed, and then scraped off by the scraper 306 while rotating the basket 302 at a low speed, and discharged from the cake discharge port 310.

  The amount of cleaning water ejected from the ejection nozzle 309 is preferably 1 to 70 times by mass, more preferably 5 to 30 times by mass with respect to the mass of the toner base particles.

  It is preferable to flow a specific washing water of 5 mass times or more of the toner base particle mass to reduce the residual amount of impurities adhering to the toner base particle. Further, it is preferable that the amount of the specific cleaning water flow is 30 mass times or less of the toner base particle mass, so that the cleaning time can be shortened and the production cost can be reduced.

  The acceleration of the basket (rotating cylinder) during cleaning is preferably 500 to 1000G, and more preferably 600 to 800G. When the acceleration is within this range, it is preferable that the washing water can be supplied uniformly over the entire toner cake, and impurities attached to the toner base particles can be removed well.

  The supply amount of cleaning water used for cleaning is preferably within a range in which cleaning water does not stay in the rotary cylindrical cleaning device. If the washing water does not stay, it is preferable that the impurities once separated from the toner base particles do not cause a problem of reattaching to the toner base particles.

  FIG. 3 is a manufacturing flow diagram (manufacturing process diagram) showing an example of a cleaning process for cleaning the toner base particles.

  In FIG. 3, 701 is a tank, 704 is a rotary cylindrical cleaning device, 308 is a discharge port, 306 is a scraping device, 310 is a cake discharge port, 705 is a stock tank, 706 is a drying device, 715 is hot air, 707 is Cyclone 708 represents a toner base particle stock tank.

  This will be described according to the flow shown in FIG. The toner base particle dispersion liquid stocked in the tank 701 is charged into the rotary cylindrical cleaning device 704, and the rotary cylindrical cleaning device is observed while observing the balance between the supply amount of the toner base particle dispersion and the discharge liquid amount from the discharge port 308. The operation of 704 is continued. When a certain amount of solid-liquid separation is completed, the operation is stopped, and washing is performed with washing water containing a specific amount of total dissolved components. Dehydrate after completion of cleaning. Thereafter, the scraper 306 removes the toner cake from the cake discharge port 310. The taken-out toner cake is stored in a stock tank 705, preferably unwound and then sent to a drying device 706, dried by hot air 715, and then toner base particles are collected by a cyclone 707. It is stored in the stock tank 708.

  Next, the method for producing the toner will be described in detail by taking the emulsion association method as an example.

The toner by the emulsion association method is produced through, for example, the following steps.
(1) A step of preparing a dispersion by dissolving or dispersing a release agent in a radical polymerizable monomer (2) A step of preparing a core resin particle by polymerizing a radical polymerizable monomer in the dispersion (3) Step of producing core particles by agglomerating and fusing core resin particles and colorant particles in an aqueous medium (4) Adding core resin particles to the core particle dispersion to obtain core particle surfaces (5) After cooling the toner base particle dispersion, the toner base particles are solid-liquid separated, and the toner base particles are separated from the toner base particles. A cleaning process in which impurities (for example, a surfactant, a dispersion stabilizer, an inorganic salt, etc.) are washed with a washing water containing a specific amount of a dissolved component, and a fixed amount of the dissolved component is adhered. Drying process to dry particles (7) Sometimes with the addition of external additives to toner base particles having a step of preparing a toner.

Hereinafter, each step will be described.
(1) Step of preparing a dispersion In this step, a wax is dispersed or dissolved in a radical polymerizable monomer, and a solution of the radical polymerizable monomer mixed with the wax is prepared.
(2) Step of producing a dispersion of core resin particles In a preferred example of this step, a radical in which a wax is dissolved or dispersed in an aqueous medium containing a surfactant having a critical micelle concentration (CMC) or less. A polymerizable monomer solution is added, mechanical energy is applied to form droplets, then a water-soluble radical polymerization initiator is added, and the polymerization reaction proceeds in the droplets. An oil-soluble polymerization initiator may be contained in the droplet. In such a polymerization process, it is essential to apply a mechanical energy to forcibly emulsify (form droplets). Examples of the mechanical energy applying means include strong stirring such as homomixer, ultrasonic wave, and manton gorin or ultrasonic vibration energy applying means.

  The core resin particle may be a particle having a multilayer resin layer by producing core polymer particles and performing multistage polymerization on the surface thereof.

  10-1000 nm is preferable and, as for the number average primary particle diameter of the resin particle for cores, 30-300 nm is more preferable.

  This number average primary particle diameter is a value measured using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.).

Through this step, core resin particles containing wax are obtained.
(3) Step of producing core particles In this step, core particles are produced by aggregating and fusing the core resin particles. As a method for aggregating and fusing the core resin particles, a salting out / fusing method is preferable. In the agglomeration / fusion step, internal additive particles such as wax particles and charge control agents can be agglomerated and fused together with the core resin particles and the colorant particles.

  In this case, “salting out / fusion” means that aggregation and fusion are advanced in parallel, and when the particles grow to a desired particle size, an aggregation terminator is added to stop the particle growth, and further necessary. The heating for controlling the particle shape according to the above is performed continuously.

  The colorant particles can be produced by dispersing the colorant in an aqueous medium. The dispersion treatment of the colorant is performed in a state where the surfactant concentration is set to a critical micelle concentration (CMC) or more in water. The disperser used for the dispersion treatment of the colorant is not particularly limited, but preferably an ultrasonic disperser, a mechanical homogenizer, a pressure disperser such as a manton gorin or a pressure homogenizer, a sand grinder, a Getzmann mill, a diamond fine mill, or the like. A medium type disperser is mentioned. Examples of the surfactant used include the same surfactants as those described above. The colorant may be surface-modified. In the surface modification method of the colorant, the colorant is dispersed in a solvent, the surface modifier is added to the dispersion, and the system is reacted by raising the temperature. After completion of the reaction, the colorant is separated by filtration, washed and filtered with the same solvent, and dried to obtain a colorant (pigment) treated with the surface modifier.

  The salting-out / fusion method, which is a preferred agglomeration and fusion method, comprises an alkali metal salt, an alkaline earth metal salt, a trivalent salt, or the like in water in which core resin particles and colorant particles are present. A salting-out agent is added as a flocculant having a critical aggregation concentration or higher, and then heated to a temperature that is higher than the glass transition point of the core resin particles and higher than the melting peak temperature (° C.) of the mixture. This is a step of performing fusion at the same time as the analysis proceeds. Here, the alkali metal salt and the alkaline earth metal salt which are salting-out agents include lithium, potassium, sodium and the like as the alkali metal, and examples of the alkaline earth metal include magnesium, calcium, strontium and barium. Preferably, potassium, sodium, magnesium, calcium, and barium are used.

The range of the addition temperature is not higher than the glass transition point of the resin, but is generally 5 to 55 ° C, preferably 10 to 45 ° C.
(4) Step of preparing toner base particles In this step, the resin particle dispersion for shell is added to the core particle dispersion to agglomerate and fuse the shell resin particles to the surface of the core particles. A toner base particle is produced by forming a shell layer composed of resin particles for the shell.

The core particle dispersion is added to the shell resin particle dispersion while maintaining the temperature in the first ripening step, and the shell resin particles are slowly applied to the core particle surface over several hours while continuing the heating and stirring. The toner base particles are formed by coating. The heating and stirring time is preferably 1 to 7 hours, particularly preferably 3 to 5 hours.
(5) Cooling Step / Solid-Liquid Separation / Washing Step The cooling step is a step of cooling the dispersion of the toner base particles. As a cooling treatment condition, cooling is performed at a cooling rate of 1 to 20 ° C./min. The cooling treatment method is not particularly limited, and examples thereof include a method of cooling the outside of the reaction vessel by flowing a refrigerant through a cooling pipe, and a method of cooling by directly introducing cold water into the reaction system.

In the solid-liquid separation / washing step, a solid-liquid separation process for solid-liquid separation of the toner base particles from the dispersion of the toner base particles cooled to a predetermined temperature in the above-described step, and a solid-liquid separated toner cake (wet state) And a cleaning process in which impurities such as surfactants are washed with washing water containing a specific amount of dissolved components, and a fixed amount of dissolved components are adhered. Is done.
(6) Drying step The drying step is a step of drying the washed toner cake to obtain dried toner base particles. Dryers used in this process include spray dryers, vacuum freeze dryers, vacuum dryers, stationary shelf dryers, mobile shelf dryers, fluidized bed dryers, rotary dryers, stirring dryers, etc. Is preferably used. The moisture content of the dried toner base particles is preferably 3.0% by mass or less, and more preferably 1.5% by mass or less. When the toner base particles that have been dried are aggregated with weak interparticle attractive forces, the aggregate may be crushed. Here, as the crushing treatment apparatus, a mechanical crushing apparatus such as a jet mill, a Henschel mixer, a coffee mill, or a food processor can be used.
(7) Step for Producing Toner This step is a step for producing a toner by mixing an external additive with dried toner base particles.

  As an external additive mixing device, a mechanical mixing device such as a Henschel mixer or a coffee mill can be used.

  Next, members used for producing the toner according to the present invention will be described.

<Members used to produce toner>
(Binder resin)
The core resin that forms the core particles and the shell resin that forms the shell layer are preferably styrene-acrylic copolymer resins. In addition, as a monomer for producing the resin A forming the core particle, a polymerizable monomer that lowers the glass transition point (Tg) of a copolymer such as propyl acrylate, propyl methacrylate, butyl acrylate, and 2-ethylhexyl acrylate Is preferably copolymerized. In addition, as a monomer for producing a shell resin for forming a shell layer, a copolymerizable monomer that raises the glass transition point (Tg) of a copolymer such as styrene, methyl methacrylate, or methacrylic acid is copolymerized. It is preferable to do.

  Each resin constituting the toner according to the present invention will be described in more detail.

  As the resin for the core resin shell, a polymer obtained by polymerizing a polymerizable monomer as described below can be used.

  The resin according to the present invention contains a polymer obtained by polymerizing at least one polymerizable monomer as a constituent component. Examples of the polymerizable monomer include styrene, o-methylstyrene, m- Methylstyrene, p-methylstyrene, α-methylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-tert-butylstyrene, p Styrene or styrene derivatives such as -n-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, methyl methacrylate, ethyl methacrylate, methacryl N-butyl acid, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, Methacrylate derivatives such as n-octyl acrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, methyl acrylate, ethyl acrylate, acrylic Acrylate derivatives such as isopropyl acid, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, phenyl acrylate, Olefins such as ethylene, propylene, isobutylene, halogenated vinyls such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, vinylidene fluoride, vinyl propionate, vinyl acetate , Vinyl esters such as vinyl benzoate, vinyl ethers such as vinyl methyl ether and vinyl ethyl ether, vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl hexyl ketone, N-vinyl carbazole, N-vinyl indole, N There are N-vinyl compounds such as vinylpyrrolidone, vinyl compounds such as vinylnaphthalene and vinylpyridine, and acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide. These vinyl monomers can be used alone or in combination.

  Further, it is more preferable to use a combination of monomers having an ionic dissociation group as the polymerizable monomer constituting the resin. For example, those having a substituent such as a carboxyl group, a sulfonic acid group, a phosphoric acid group as a constituent group of the monomer, preferably acrylic acid, methacrylic acid, maleic acid, itaconic acid, cinnamic acid, fumaric acid, Maleic acid monoalkyl ester, itaconic acid monoalkyl ester, styrene sulfonic acid, allyl sulfosuccinic acid, 2-acrylamido-2-methylpropane sulfonic acid, acid phosphooxyethyl methacrylate, 3-chloro-2-acid phosphooxypropyl methacrylate Etc.

  Furthermore, multifunctional such as divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, etc. It is also possible to use a crosslinkable resin by using a functional vinyl.

(Coloring agent)
As the colorant used in the present invention, carbon black, dyes, pigments and the like can be arbitrarily used. As the carbon black, channel black, furnace black, acetylene black, thermal black, lamp black and the like are used.

  As the dye, C.I. I. Solvent Red 1, 49, 52, 58, 63, 111, 122, C.I. I. Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162, C.I. I. Solvent Blue 25, 36, 60, 70, 93, 95, etc. can be used, and mixtures thereof can also be used. Examples of the pigment include C.I. I. Pigment Red 5, 48: 1, 53: 1, 57: 1, 122, 139, 144, 149, 166, 177, 178, 222, C.I. I. Pigment Orange 31 and 43, C.I. I. Pigment Yellow 14, 17, 93, 94, 138, 156, 158, 180, 185, C.I. I. Pigment green 7, C.I. I. Pigment Blue 15: 3, 60, etc. can be used, and a mixture thereof can also be used. The number average primary particle size varies depending on the type, but is preferably about 10 to 200 nm.

(Wax (release agent))
Examples of waxes that can be used in the present invention include conventionally known waxes. Preferably, polyolefin waxes such as polyethylene wax and polypropylene wax, long chain hydrocarbon waxes such as paraffin wax and sazol wax, dialkyl ketone waxes such as distearyl ketone, carnauba wax, montan wax, trimethylolpropane tribe. Henates, pentaerythritol tetramyristate, pentaerythritol tetrastearate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, behenate behenate, 1,18-octadecanediol distearate, Ester waxes such as tristearyl trimellitic acid and distearyl maleate, ethylenediamine dibehenyl amide, tris trimellitic acid Amide wax such as allyl amide and the like.

  The melting point of the wax is preferably 40 to 160 ° C, more preferably 50 to 120 ° C, and still more preferably 60 to 90 ° C. By setting the melting point within the above range, the heat-resistant storage property of the toner is secured, and stable toner image formation can be performed without causing cold offset or the like even when fixing at a low temperature. Further, the wax content in the toner is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass.

  The polymerization initiator, chain transfer agent, and surfactant that can be used in the toner production method will be described.

(Radical polymerization initiator)
The resin constituting the core particles and the shell layer constituting the toner according to the present invention is produced by polymerizing the polymerizable monomer described above. The radical polymerization initiators usable in the present invention are as follows. There is. Preferably, the oil-soluble polymerization initiator includes 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1 -Carbonitrile), azo or diazo polymerization initiators such as 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl Peroxycarbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis- (4 4-t-butylperoxycyclohexyl) propane, Squirrel - like the like (t-butylperoxy) polymeric initiator having a side chain a peroxide-based polymerization initiator or a peroxide, such as triazines.

  Moreover, when forming resin by an emulsion polymerization method, a water-soluble radical polymerization initiator can be used. Examples of the water-soluble polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, azobisaminodipropane acetate, azobiscyanovaleric acid and its salts, hydrogen peroxide and the like.

  For the purpose of adjusting the molecular weight of the resin, a commonly used chain transfer agent can be used.

  The chain transfer agent is not particularly limited, and examples thereof include mercaptans such as octyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, n-octyl-3-mercaptopropionate, terpinolene, carbon tetrabromide and α-methyl. Styrene dimer or the like is used.

(Dispersion stabilizer)
In addition, a dispersion stabilizer can be used in order to appropriately disperse the polymerizable monomer and the like in the reaction system. Dispersion stabilizers include tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate , Bentonite, silica, alumina and the like. Furthermore, those generally used as surfactants such as polyvinyl alcohol, gelatin, methylcellulose, sodium dodecylbenzenesulfonate, ethylene oxide adduct, and higher alcohol sodium sulfate can be used as the dispersion stabilizer.

  The surfactant used in the present invention will be described.

  In order to perform polymerization using the above-mentioned radical polymerizable monomer, it is necessary to perform oil droplet dispersion in an aqueous medium using a surfactant. Although it does not specifically limit as surfactant which can be used in this case, The following ionic surfactant can be mentioned as an example of a suitable thing.

  Examples of ionic surfactants include sulfonates (sodium dodecylbenzenesulfonate, sodium arylalkylpolyethersulfonate, 3,3-disulfonediphenylurea-4,4-diazo-bis-amino-8-naphthol-6). -Sodium sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-6-sodium sulfonate, etc.) Sulfate esters (sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, etc.), fatty acid salts (sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, Potassium phosphate, calcium oleate and the like).

  Nonionic surfactants can also be used. Preferably, polyethylene oxide, polypropylene oxide, a combination of polypropylene oxide and polyethylene oxide, ester of polyethylene glycol and higher fatty acid, alkylphenol polyethylene oxide, ester of higher fatty acid and polyethylene glycol, ester of higher fatty acid and polypropylene oxide, polyoxyethylene alkyl Examples include ethers and sorbitan esters.

(External additive)
The toner used in the present invention is prepared by adding particles such as inorganic fine particles and organic fine particles having a number average primary particle size of 4 to 800 nm as external additives (= external additives) to the toner base particles. .

  By adding the external additive, the fluidity and chargeability of the toner are improved, and the cleaning property is improved. The type of external additive is not particularly limited, and examples thereof include the following inorganic fine particles, organic fine particles, and lubricants.

  A conventionally well-known thing can be used as an inorganic fine particle. Preferably, silica, titania, alumina, strontium titanate fine particles and the like can be used. These inorganic fine particles may be hydrophobized if necessary. Specific examples of the silica fine particles include commercially available products R-805, R-976, R-974, R-972, R-812, R-809 manufactured by Nippon Aerosil Co., Ltd., HVK-2150, H- manufactured by Hoechst. 200, commercial products TS-720, TS-530, TS-610, H-5, MS-5 and the like manufactured by Cabot Corporation.

  As titania fine particles, for example, commercially available products T-805 and T-604 manufactured by Nippon Aerosil Co., Ltd., commercially available products MT-100S, MT-100B, MT-500BS, MT-600, MT-600SS, JA- 1. Commercial products TA-300SI, TA-500, TAF-130, TAF-510, TAF-510T manufactured by Fuji Titanium Co., Ltd. Commercial products IT-S, IT-OA, IT-OB, IT- manufactured by Idemitsu Kosan Co., Ltd. OC etc. are mentioned.

  Examples of the alumina fine particles include commercial products RFY-C and C-604 manufactured by Nippon Aerosil Co., Ltd. and commercial products TTO-55 manufactured by Ishihara Sangyo Co., Ltd.

  As the organic fine particles, spherical organic fine particles having a number average primary particle diameter of about 10 to 2000 nm can be used. Preferably, a homopolymer such as styrene or methyl methacrylate or a copolymer thereof can be used.

  In addition, a lubricant can be used to further improve the cleaning property and the transfer property. Examples of the lubricant include metal salts of the following higher fatty acids. That is, salts of zinc stearate, aluminum, copper, magnesium, calcium, etc., zinc oleate, salts of manganese, iron, copper, magnesium, etc., zinc palmitate, salts of copper, magnesium, calcium, etc., linoleic acid And salts of zinc and calcium of ricinoleic acid.

  The addition amount of these external additives and lubricants is preferably 0.1 to 10.0% by mass with respect to the whole toner. Examples of methods for adding external additives and lubricants include methods using various known mixing devices such as a turbuler mixer, a Henschel mixer, a nauter mixer, and a V-type mixer.

<Developer>
The toner produced by the toner production method of the present invention can be used as a non-magnetic one-component developer or a two-component developer toner. The two-component developer is obtained by mixing a carrier and a toner.

  The mixing ratio of the carrier and the toner is preferably 3 to 10 parts by mass of toner with respect to 100 parts by mass of the carrier. The method for mixing the carrier and the toner is not particularly limited, and can be mixed using a known mixer.

  The carrier used for the two-component developer is preferably a coating carrier in which magnetic particles are coated with a resin, or a resin dispersion type carrier in which magnetic particles are dispersed in a resin. The resin composition for coating is not particularly limited, and for example, olefin resin, styrene resin, styrene-acrylic resin, silicon resin, ester resin, or fluorine-containing polymer resin is used. Moreover, it does not specifically limit as resin for comprising a resin dispersion type carrier, A well-known thing can be used, For example, a styrene-acrylic-type resin, a polyester resin, a fluorine resin, a phenol resin etc. are used. be able to.

As the magnetic particles, known materials typified by iron, ferrite, and magnetite can be used, and ferrite particles or magnetite particles are particularly preferable. The median diameter (D ₅₀ ) based on the volume of the carrier is preferably 15 to 100 μm, more preferably 20 to 80 μm.

The measurement of the median diameter (D ₅₀ ) based on the volume of the carrier can be measured using a laser diffraction particle size distribution measuring device “HELOS” (manufactured by Sympathec).

The initial resistance of the carrier is preferably 1 × 10 ^{8 to} 3 × 10 ¹⁰ Ωcm, and more preferably 2 × 10 ⁸ to 1 × 10 ¹⁰ Ωcm.

  Next, the image forming apparatus will be described.

<Image forming apparatus>
Examples of the image forming apparatus used in the present invention include a monochrome image forming apparatus and a color image forming apparatus.

  FIG. 3 is a schematic diagram illustrating an example of a monochrome image forming apparatus.

  The monochrome image forming apparatus shown in FIG. 3 is a digital image forming apparatus, and includes an image reading unit A, an image processing unit B, an image forming unit C, and a transfer material conveying unit D as a transfer material conveying unit. Yes.

  The upper part of the image reading unit A is provided with automatic document feeding means for automatically conveying the document. The document placed on the document placing table 11 is separated and conveyed by the document conveying roller 12 at the reading position 13a. The image is read. The document after the document reading is completed is discharged onto the document discharge tray 14 by the document transport roller 12.

  On the other hand, the image of the original when placed on the platen glass 13 is read at a speed v of the first mirror unit 15 including the illumination lamp and the first mirror constituting the scanning optical system, and the V-shaped first image is located. Reading is performed by the movement of the second mirror unit 16 including the two mirrors and the third mirror in the same direction at the speed v / 2.

  The read image is formed on the light receiving surface of the image sensor CCD, which is a line sensor, through the projection lens 17. The line-shaped optical image formed on the image sensor CCD is sequentially photoelectrically converted into an electric signal (luminance signal) and then A / D converted, and the image processing unit B performs processing such as density conversion and filter processing. Then, the image data is temporarily stored in the memory.

  In the image forming unit C, as an image forming unit, a drum-shaped photoconductor 21 as an image carrier, a charging means (charging step) 22 for charging the photoconductor 21 on the outer periphery thereof, and a surface potential of the charged photoconductor. Potential detecting means 220 for detecting the toner, developing means (developing process) 23, transfer / conveying belt device 45 serving as a transferring means (transfer process), cleaning device (cleaning process) 26 for the photosensitive member 21, and light discharging means (light discharging process). PCL (precharge lamps) 27 are arranged in the order of operation. Further, on the downstream side of the developing means 23, a reflection density detecting means 222 for measuring the reflection density of the patch image developed on the photosensitive member 21 is provided. The photosensitive member 21 is driven and rotated in the clockwise direction shown in the figure.

  After the rotating photosensitive member 21 is uniformly charged by the charging unit 22, an image based on an image signal called from the memory of the image processing unit B by an exposure optical system as an image exposure unit (image exposure step) 30 is used. Exposure is performed. The exposure optical system as the image exposure means 30 as the writing means uses a laser diode (not shown) as a light source, and the optical path is bent by the reflection mirror 32 via the rotating polygon mirror 31, the fθ lens 34, and the cylindrical lens 35, and main scanning is performed. Therefore, image exposure is performed on the photoconductor 21 at the position Ao, and an electrostatic latent image is formed by rotation (sub-scanning) of the photoconductor 21. In an example of this embodiment, the character portion is exposed to form an electrostatic latent image.

  In the image forming apparatus, a semiconductor laser or a light emitting diode can be used as an image exposure light source when an electrostatic latent image is formed on a photoconductor. By using these image exposure light sources, the exposure dot diameter in the writing principal direction is narrowed down to 10 to 80 μm, and digital exposure is performed on the photosensitive member, whereby from 400 dpi (dpi: the number of dots per 2.54 cm) to 2500 dpi. High-resolution electrophotographic images can be obtained.

The exposure dot diameter refers to the length of the exposure beam along the main scanning direction (Ld: measured at the maximum length) in a region where the intensity of the exposure beam is 1 / e ² or more of the peak intensity.

The light beams used have a solid scanner such as the scanning optical system and LED using a semiconductor laser, there is a Gaussian distribution and Lorentz distribution, etc. also the light intensity distribution is in each 1 / e ² or more regions of peak intensity The exposure dot diameter is used.

  The electrostatic latent image on the photoconductor 21 is reversely developed by the developing unit 23, and a visible toner image is formed on the surface of the photoconductor 21.

  In the transfer material transport unit D, paper feed units 41 (A), 41 (B), and 41 (C) are provided below the image forming unit as transfer material storage means in which transfer materials P of different sizes are stored. Further, a manual paper feeding unit 42 for manually feeding paper is provided on the side, and the transfer material P selected from any of them is fed along the transport path 40 by the guide roller 43 and fed. The transfer material P is temporarily stopped by a pair of paper feed registration rollers 44 that correct the inclination and bias of the transfer material P, and then re-feeded. The transport path 40, the pre-transfer roller 43a, and the paper feed path 46 are transferred. The toner image on the photosensitive member 21 is transferred to the transfer material P while being transferred to the transfer conveyance belt 454 of the transfer conveyance belt device 45 by the transfer electrode 24 and the separation electrode 25 at the transfer position Bo. Is, the transfer material P is separated from the photosensitive member 21 surface, it is conveyed to the fixing unit 50 by the transfer conveyor belt device 45. A separation claw 29 is provided as an auxiliary member for separating the transfer material P from the surface of the photoreceptor 21.

  The fixing unit 50 includes a fixing roller 51 and a pressure roller 52. By passing the transfer material P between the fixing roller 51 and the pressure roller 52, the toner is fixed by heating and pressing. After the toner image is fixed, the transfer material P is discharged onto the paper discharge tray 64.

  The above describes the state of image formation on one side of the transfer material. However, in the case of double-sided copying, the paper discharge switching member 170 is switched, the transfer material guide 177 is opened, and the transfer material P is indicated by a broken arrow. Conveyed in the direction.

  Further, the transfer material P is transported downward by the transport mechanism 178 and is switched back by the transfer material reversing unit 179, and the rear end portion of the transfer material P becomes the leading end portion and transported into the duplex copying paper supply unit 130. The

  The transfer material P moves a conveyance guide 131 provided in the duplex copying paper supply unit 130 in the paper supply direction, refeeds the transfer material P by the paper supply roller 132, and guides the transfer material P to the conveyance path 40. .

  Again, as described above, the transfer material P is conveyed in the direction of the photosensitive member 21, the toner image is transferred to the back surface of the transfer material P, fixed by the fixing unit 50, and then discharged onto the discharge tray 64.

  As the image forming apparatus, the above-described photosensitive member and components such as a developing device and a cleaning device may be integrally combined as a process cartridge, and this unit may be configured to be detachable from the apparatus main body. Further, at least one of a charger, an image exposure device, a developing device, a transfer or separation device, and a cleaning device is integrally supported together with a photosensitive member to form a process cartridge, and a single unit that is detachable from the apparatus main body. It is good also as a structure which can be attached or detached using guide means, such as a rail of an apparatus main body.

<Transfer material>
The transfer material used in the present invention is a support for holding a toner image, and is usually called an image support, a transfer material, or transfer paper. Preferred examples include various kinds of transfer materials such as plain paper from thin paper to thick paper, coated printing paper such as art paper and coated paper, commercially available Japanese paper and postcard paper, plastic film for OHP, and cloth. However, it is not limited to these.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, the aspect of this invention is not limited to this.

<Preparation of washing water>
First, the following washing water was prepared.

<Preparation of washing water 1-5>
The well water was filtered with a filter having an opening of 0.1 μm to remove insoluble matters, and then ion exchange water was produced through an ion exchange device.

  In addition, the total melt | dissolution component of the obtained ion exchange water was 0.02 mg / L.

  Sodium chloride was added and dissolved in this ion-exchanged water to prepare “washing water 1 to 5” having different total dissolved components at 25 ° C. as follows.

Washing water 1: total dissolved component is 400.0 mg / L
Washing water 2: Total dissolved component is 0.7 mg / L
Washing water 3: Total dissolved component is 960.0 mg / L
Washing water 4: Total dissolved component is 1200.0 mg / L
Washing water 5: Total dissolved component is 0.3 mg / L
<Preparation of washing water 6>
The water as prepared using the ion exchanger (total dissolved component is 0.02 mg / L) is referred to as “washing water 6”.

<Preparation of washing water 7, 8, 9, 10, 11>
Sodium chloride used in the preparation of washing water 1 was changed to glucose (manufactured by Wako Pure Chemical Industries, Ltd.), and total dissolved components were 500.0 mg / L, 0.7 mg / L, 960.0 mg / L, Adjusted to 1200.0 mg / L and 0.4 mg / L to prepare “washing water 7”, “washing water 8”, “washing water 9”, “washing water 10”, and “washing water 11”. .

<Preparation of washing water 12, 13, 14, 15, 16>
Sodium chloride used in the preparation of the washing water 1 was changed to sodium dodecyl sulfate (Wako Grade 1: Wako Pure Chemical Industries, Ltd.), and the total dissolved components were 500.0 mg / L, 0.7 mg / L, It is adjusted to 960.0 mg / L, 1200.0 mg / L, and 0.4 mg / L, and “washing water 12”, “washing water 13”, “washing water 14”, “washing water 15”, “washing” Water 16 "was prepared.

<Preparation of washing water 17, 18, 19, 20, 21>
Sodium chloride used in the preparation of washing water 1 was changed to ascorbic acid (manufactured by Wako Pure Chemical Industries, Ltd.), and the total dissolved components were 500.0 mg / L, 0.7 mg / L, and 960.0 mg / L, respectively. , 1200.0 mg / L, 0.4 mg / L, and prepare “washing water 17”, “washing water 18”, “washing water 19”, “washing water 20”, and “washing water 21”. did.

<Production of toner>
The toner is prepared by preparing a dispersion of toner base particles in an aqueous medium, separating the toner base particles from the dispersion of the toner base particles to form a toner cake, washing the toner cake with washing water, drying and removing the toner cake. It was prepared by adding an additive.

<Preparation of toner base particle dispersion>
(Preparation of toner base particle dispersion 1 (example of emulsion association method))
[Preparation of core resin particle 1]
As described below, the first-stage polymerization, the second-stage polymerization, and then the third-stage polymerization were performed to produce “core resin particles 1” having a multilayer structure.

(1) First-stage polymerization 4 parts by mass of anionic surfactant (Structural Formula 1) shown below in a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introduction apparatus are added to 3040 parts by mass of ion-exchanged water. The dissolved surfactant solution was charged, and the internal temperature was raised to 80 ° C. while stirring at a stirring speed of 230 rpm under a nitrogen stream.

(Structural Formula 1) C ₁₀ H ₂₁ (OCH ₂ CH ₂ ) ₂ SO ₃ Na
To this surfactant solution, an initiator solution in which 10 parts by mass of a polymerization initiator (potassium persulfate: KPS) was dissolved in 400 parts of ion-exchanged water was added, the temperature was adjusted to 75 ° C., 480 parts by mass of styrene, A monomer mixture composed of 250 parts by mass of n-butyl acrylate, 68 parts by mass of methacrylic acid, and 20 parts by mass of n-octyl-3 mercaptopropionate was added dropwise over 1 hour, and this system was added at 75 ° C. for 2 hours. Then, polymerization (first stage polymerization) was performed by heating and stirring to prepare resin particles. This is designated as “resin particle A1”.

(2) Second stage polymerization (formation of intermediate layer)
In a flask equipped with a stirrer, 208 parts by mass of styrene, 158 parts by mass of n-butyl acrylate, 26 parts by mass of methacrylic acid, and 5.9 parts by mass of n-octyl mercaptan were added to the paraffin as wax. 112 parts by mass of wax “HNP-33” (manufactured by Nippon Seiki Co., Ltd.) was added, and the mixture was heated to 90 ° C. and dissolved to prepare a monomer solution.

  On the other hand, a surfactant solution in which 3 parts by mass of an anionic surfactant (Structural Formula 1) is dissolved in 1151 parts by mass of ion-exchanged water is heated to 76 ° C., and a monomer solution is added to the surfactant solution. After that, the wax monomer solution was mixed and dispersed for 15 minutes by a mechanical disperser “CLEARMIX” (manufactured by M Technique Co., Ltd.) having a circulation path, and a dispersion containing emulsified particles having a dispersed particle diameter of 250 nm Was made.

  Next, an initiator solution in which 9.7 parts by mass of potassium persulfate was dissolved in 184 parts by mass of ion-exchanged water was added to the dispersion, and the system was polymerized by heating and stirring at 82 ° C. for 60 minutes. Two-stage polymerization) was performed to obtain resin particles. This resin particle is referred to as “resin particle A2”.

(3) Third stage polymerization (formation of outer layer)
An initiator solution in which 11.4 parts by mass of potassium persulfate is dissolved in 216 parts by mass of ion-exchanged water is added to the “resin particles A2” obtained as described above, and styrene is added at a temperature of 82 ° C. A monomer mixed solution consisting of 357 parts by mass, 250 parts by mass of n-butyl acrylate, 23 parts by mass of methacrylic acid, and 8.2 parts by mass of n-octyl mercaptan was added dropwise over 85 minutes. After completion of the dropwise addition, the temperature was raised to 93 ° C. and the mixture was heated and stirred for 65 minutes to perform polymerization (third stage polymerization), and then cooled to 28 ° C. to produce “core resin particles 1”.

[Production of Resin Particle 1 for Shell]
A stainless steel kettle (SUS kettle) equipped with a stirrer, temperature sensor, cooling pipe, and nitrogen introducing device was charged with a surfactant solution in which 1.53 parts by mass of sodium dodecyl sulfate was dissolved in 2975 parts by mass of ion-exchanged water, and nitrogen was added. The liquid temperature was raised to 80 ° C. while stirring at a stirring speed of 230 rpm under an air stream.

  To this surfactant solution, a polymerization initiator solution in which 10 parts by mass of potassium persulfate was dissolved in 195 parts by mass of ion-exchanged water was added and the temperature was adjusted to 80 ° C. Then, the following monomer mixture was added dropwise over 180 minutes. The system was polymerized by heating and stirring at 80 ° C. for 1 hour to produce “shell resin particles 1”.

[Preparation of dispersion of colorant particles]
90 parts by mass of the anionic surfactant (1) was dissolved in 1600 parts by mass of ion-exchanged water with stirring. While stirring this solution, 400 parts by mass of carbon black “Regal 330” (Cabot Corporation) was gradually added, and then dispersed using a stirring device “Cleamix” (M Technique Co.). A “colorant particle dispersion” was prepared.

  The particle diameter of the colorant particles in this “colorant particle dispersion” was 110 nm as measured using an electrophoretic light scatterometer (ELS-800: manufactured by Otsuka Electronics Co., Ltd.).

[Preparation of core particle 1]
415.4 parts by mass of “core resin particles 1” (in terms of solid content), 880 parts by mass of ion-exchanged water, and 149 parts by mass of “dispersion of colorant particles”, a temperature sensor, a cooling tube, and a nitrogen introduction device The mixture was stirred in a reaction vessel equipped with a stirrer. After preparing the temperature in the container at 20 ° C., a 5 mol / liter sodium hydroxide aqueous solution was added to this solution to adjust the pH to 10.5.

Next, an aqueous solution in which 70 parts by mass of magnesium chloride hexahydrate was dissolved in 70 parts by mass of ion-exchanged water was added over 10 minutes at 30 ° C. with stirring. After leaving for 3 minutes, the stirring speed was gradually lowered. In this state, the particle size of the core particles was measured with “Coulter Counter 3” (manufactured by Coulter Co.). When the particle median system (D ₅₀ ) reached 6.0 μm, the stirring speed was returned to the sodium chloride 14 An aqueous solution in which 6 parts by mass is dissolved in 58.4 parts by mass of ion-exchanged water is added to stop the growth of the particle size, and further, as an aging treatment, the mixture is heated and stirred for 1 hour at a liquid temperature of 40 ° C. Continued to produce “core particle 1”.

[Preparation of toner base particle dispersion 1]
96 parts by mass (in terms of solid content) of “core resin particle 1” is added to 564 parts by mass (in terms of solid content) at 40 ° C., and the temperature is raised to 60 ° C. while stirring is continued for 1 hour. By heating, the “shell resin particles 1” were fused to the surface of the “core particles 1”.

  Here, an aqueous solution in which 58 parts by mass of sodium chloride was dissolved in 234 parts by mass of ion-exchanged water was added to complete the shelling, and the fusion was continued by heating and stirring at a liquid temperature of 60 ° C. for 1 hour. Then, it was cooled to 30 ° C. under the condition of 8 ° C./min to prepare “Toner Base Particle Dispersion 1”.

(Preparation of toner base particle dispersion 2 (example of emulsion association method))
(Preparation of resin particle dispersion)
370 parts by mass of styrene, 30 parts by mass of n-butyl acrylate, 8 parts by mass of acrylic acid, 24 parts by mass of dodecanethiol, and 4 parts by mass of carbon tetrabromide were mixed and dissolved in a nonionic surfactant “nonylphenyl” 6 parts by weight of ether and 10 parts by weight of the anionic surfactant “sodium dodecylbenzenesulfonate” were emulsion-polymerized in a flask dissolved in 550 parts by weight of ion-exchanged water, and mixed slowly for 10 minutes. 50 parts by mass of ion-exchanged water in which part by mass was dissolved was added. After carrying out nitrogen substitution, the inside of the flask was stirred and heated in an oil bath until the contents reached 70 ° C., and emulsion polymerization was continued for 5 hours. As a result, “resin fine particle dispersion 2” in which resin particles having a volume average particle diameter = 150 nm, a glass transition temperature = 58 ° C., and a weight average molecular weight = 11500 was dispersed was obtained. The solid content concentration of this dispersion was 40% by mass.

(Preparation of colorant dispersion)
Colorant “Regal 330” 60 parts by weight Nonionic surfactant “Noniphenyl ether” 5 parts by weight Ion-exchanged water 240 parts by weight After the above components are dissolved and mixed, the homogenizer “Ultra Tarrax T50” (manufactured by IKA Corporation) Was then stirred for 10 minutes, followed by dispersion treatment with a mechanical disperser to prepare “Colorant Dispersion 2” in which colorant particles having a volume average particle size of 250 nm were dispersed.

(Preparation of release agent dispersion)
Paraffin wax (melting point 97 ° C.) 100 parts by weight Cationic surfactant “alkyl ammonium salt” 5 parts by weight Ion-exchanged water 240 parts by weight The above components are mixed in a round stainless steel flask with a homogenizer “Ultra Turrax T50” (IKA The product was dispersed for 10 minutes using a pressure discharge type homogenizer, and “release agent dispersion 2” in which release agent particles having a volume average particle size of 550 nm were dispersed was prepared.

(Preparation of aggregated particles)
Resin fine particle dispersion 2 234 parts by weight Release agent dispersion 2 40 parts by weight Polyaluminum chloride 1.8 parts by weight Ion-exchanged water 600 parts by weight The above components were mixed in a round stainless steel flask with a homogenizer “Ultra Turrax T50” ( IKA Co., Ltd.) was mixed and dispersed, and then heated to 55 ° C. while stirring the inside of the flask in an oil bath for heating. After maintaining at 55 ° C. for 30 minutes, it was confirmed that aggregated particles having a volume-based median diameter (D ₅₀ ) of 4.8 μm were formed in the solution. Further, when the temperature of the heating oil bath was raised and held at 56 ° C. for 2 hours, the median diameter (D ₅₀ ) on the volume basis was 5.9 μm. Thereafter, 32 parts by mass of “resin fine particle dispersion 2” is added to the dispersion containing the aggregated particles, and then the temperature of the heating oil bath is raised to 55 ° C. and held for 30 minutes to prepare “aggregated particles 2”. did. After adding 1 mol / L sodium hydroxide to the dispersion containing the “aggregated particles 2” and adjusting the pH of the system to 5.0, the stainless steel flask was sealed with a magnetic seal and stirring was continued. While heating to 95 ° C. and holding for 6 hours, “Toner Base Particle Dispersion 2” having a volume-based median diameter (D ₅₀ ) of 6.0 μm was produced.

(Preparation of toner base particle dispersion 3 (example of polyester association method))
[Preparation of polyester resin]
715.0 parts by weight of dimethyl terephthalate, 95.8 parts by weight of sodium dimethyl 5-sulfoisophthalate, 526.0 parts by weight of propanediol, 48.0 parts by weight of diethylene glycol, and 247.1 parts by weight of dipropylene glycol Then, 1.5 parts by mass of butyltin hydroxide catalyst was placed in a polycondensation reactor. The mixture was heated to 190 ° C. and slowly raised to about 200-202 ° C. while collecting methanol by-product in the distillation receiver. Next, the temperature was raised to about 210 ° C. while reducing the pressure from atmospheric pressure to about 1067 Pa over about 4.5 hours. The product was taken out to prepare “Polyester Resin 3” having a glass transition temperature of 53.8 ° C.

[Preparation of polyester resin emulsion]
Next, 168 parts by mass of the above-mentioned “polyester resin 3” was added to 1,232 parts by mass of deionized water and stirred at 92 ° C. for 2 hours to prepare “polyester resin emulsion 3”.

[Meeting process]
1,400 parts by weight of “Polyester resin emulsion 3” and 14.22 parts by weight of “Regal 330” were added to the reactor to prepare “Emulsion / Dispersion 3”.

  Next, zinc acetate was dissolved in deionized water to prepare a 5 mass% zinc acetate solution. This solution was placed in a reservoir placed on a balance and connected to a pump capable of accurately supplying a zinc acetate solution at 0.01-9.9 ml / min. The amount of zinc acetate required for emulsion association is 10% of the resin mass in the emulsion.

After “Emulsion / Dispersion 3” was heated to 56 ° C., the zinc acetate solution was pumped at 9.9 ml / min to initiate association. When 60% by weight of the total amount of zinc acetate (205 parts by weight in a 5% by weight solution) is added, the pump addition rate is reduced to 1.1 ml / min and the amount of zinc acetate is equal to 10% by weight of the resin in the emulsion. The addition was continued until it reached 335 parts by mass with a 5% by mass solution, and the mixture was stirred at 80 ° C. for 9 hours to prepare “Toner Base Particle Dispersion 3” having a median diameter (D ₅₀ ) of 5.9 μm on a volume basis.

(Preparation of toner base particle dispersion 4 (example of suspension polymerization method))
165 parts by mass of styrene, 35 parts by mass of n-butyl acrylate, 10 parts by mass of “Regal 330”, 2 parts by mass of metal compound of di-t-butylsalicylate, 8 parts by mass of styrene-methacrylic acid copolymer, paraffin wax (mp = 70 The solution in which 20 parts by mass was mixed was heated to 60 ° C., and uniformly dissolved and dispersed at a rotational speed of 12000 rpm using a “TK homomixer” (manufactured by Tokushu Kika Kogyo Co., Ltd.). To this was added 10 parts by mass of 2,2′-azobis (2,4-valeronitrile) as a polymerization initiator to prepare “polymerizable monomer composition 4”. Next, 450 parts by mass of 0.1 M sodium phosphate aqueous solution was added to 710 parts by mass of ion-exchanged water, and 68 parts by mass of 1.0 M calcium chloride was gradually added while stirring at 13,000 rpm using a “TK homomixer”. “Suspension 4” in which tricalcium was dispersed was prepared. The “polymerizable monomer composition 4” is added to this “suspension 4” and stirred for 20 minutes at a rotational speed of 10,000 rpm using a “TK homomixer”. Granulated. Then, it was made to react at 75-95 degreeC for 5 to 15 hours using the reaction apparatus. The tricalcium phosphate was dissolved and removed with hydrochloric acid to prepare “toner base particle dispersion 4” having a median diameter (D ₅₀ ) of 6.2 μm on a volume basis.

(Preparation of toner base particle dispersion 5 (example of dissolution suspension method))
(Preparation of pigment dispersion)
50 parts by mass of polyester resin (Tg: 60 ° C., softening point: 98 ° C., weight average molecular weight: 9500)
Legal 330 50 parts by mass Ethyl acetate 100 parts by mass A container obtained by adding glass beads to the dispersion having the above material composition was attached to a sand mill disperser. While cooling around the vessel, the dispersion was carried out for 8 hours in a high-speed stirring mode, and then diluted with ethyl acetate to prepare “Pigment Dispersion Liquid 5” having a pigment concentration of 15 mass%.

(Preparation of micronized wax dispersion)
Paraffin wax (melting point: 85 ° C.) 15 parts by mass Toluene 85 parts by mass The above materials were put into a disperser equipped with a stirring blade and having a function of circulating a heat medium around the container. The temperature was gradually raised while stirring at 83 rpm, and finally the mixture was stirred for 3 hours while maintaining at 100 ° C. Next, while continuing stirring, the mixture was cooled to room temperature at a rate of about 2 ° C. per minute to precipitate finely divided wax. This wax dispersion was dispersed again at a pressure of 550 × 10 ⁵ Pa using a high-pressure emulsifier “APV Gorin homogenizer” (manufactured by APV Gorin Co., Ltd.). At the same time, the particle size of the wax was measured and found to be 0.69 μm. The prepared fine particle wax dispersion was diluted with ethyl acetate so that the mass concentration of the wax was 15% by mass to prepare “fine particle wax dispersion 5”.

(Preparation of oil phase)
85 parts by mass of polyester resin (Tg: 60 ° C., softening point: 98 ° C., weight average molecular weight: 9500)
Pigment dispersion 5 (pigment concentration 15% by mass) 50 parts by mass Fine particle wax dispersion 5 (wax concentration 15% by mass) 33 parts by mass Ethyl acetate 32 parts by mass The polyester resin in the material composition was sufficiently dissolved. After confirmation, this solution was put into a homomixer “ACE Homogenizer” (manufactured by Nippon Seiki Co., Ltd.) and stirred at 16000 rpm for 2 minutes to prepare a uniform “oil phase 5”.

(Preparation of aqueous phase)
Calcium carbonate (average particle size: 0.03 μm) 60 parts by mass Pure water 40 parts by mass An aqueous calcium carbonate solution obtained by stirring the above materials with a ball mill for 4 days was referred to as “aqueous phase (calcium carbonate aqueous solution) 5”. When the average particle diameter of calcium carbonate was measured using “Laser diffraction / scattering particle size distribution measuring apparatus A-700” (manufactured by Horiba, Ltd.), it was about 0.08 μm.

Carboxymethylcellulose 2 parts by mass Pure water 98 parts by mass An aqueous solution of carboxymethylcellulose obtained by stirring the above materials with a ball mill was designated as “aqueous phase (carboxymethylcellulose aqueous solution) 5”.

(Preparation of spherical particles)
Oil phase 5 55 parts by mass Aqueous phase (calcium carbonate aqueous solution) 5 15 parts by mass Aqueous phase (carboxymethylcellulose aqueous solution) 5 30 parts by mass The above materials were put into a “colloid mill” (manufactured by Nippon Seiki Co., Ltd.). Emulsification was performed at 5 mm, 9400 rpm for 40 minutes. Next, the emulsion was put into a rotary evaporator, and the solvent was removed under reduced pressure at room temperature of 4,000 Pa for 3 hours.

Thereafter, 12 mol / L hydrochloric acid was added until the pH reached 2, and calcium carbonate was removed from the toner base particles. Thereafter, 10 mol / L sodium hydroxide was added until the pH reached 10, and stirring was continued for 1 hour while stirring in an ultrasonic cleaning tank, and a “toner base material having a median diameter (D ₅₀ ) of 6.0 μm on a volume basis was determined. A particle dispersion 5 ”was prepared.

(Preparation of toner base particle dispersion 6 (example of continuous emulsion dispersion method))
[Synthesis of Polyether Resin (A)]
In a high-pressure reactor equipped with a stirrer, a nitrogen inlet tube, a thermometer, a raw material inlet, etc., 0.5 parts by mass of potassium hydroxide and 200 parts by mass of toluene as a solvent were placed, and the pressure in the system was 10 × 10 ^5. Pa, maintaining the temperature at 40 ° C., a mixture of 10.8 parts by mass of propylene oxide and 89.2 parts by mass of styrene oxide was injected little by little, and the state of molecular weight change was traced by end group determination, The reaction was terminated when the number average molecular weight reached 7,000. The total amount of the monomer injected at this time was 8.64 parts by mass of propylene oxide and 71.4 parts by mass of styrene oxide. Toluene and unreacted monomers were distilled off from the resulting polymer solution under a reduced pressure of 4,000 Pa to obtain “polyether resin (A)”.

[Synthesis of polyester resin (B) having no ether bond]
In a flask having an internal volume of 5 liters equipped with a stirrer, a nitrogen introduction tube, a thermometer, and a rectifying column, 67.85 parts by mass of terephthalic acid, 3.34 parts by mass of neopentyl glycol, 25.58 parts by mass of propylene glycol, 3.22 parts by mass of trimethylolpropane and 0.3 parts by mass of dibutyltin oxide were added, and the reaction was allowed to stir at 240 ° C. under a nitrogen stream. The reaction was terminated when the softening point by the ring and ball method reached 130 ° C. to obtain “polyester resin (B)”. The obtained “polyester resin (B)” was a light yellow solid, and the weight average molecular weight in terms of polystyrene by GPC measurement was 96,000.

Coloring of 18 parts by weight of “polyether resin (A)”, 72 parts by weight of “polyester resin (B)” and 10 parts by weight of “Regal 330” heated to 180 ° C. using a biaxial continuous kneader. The resin melt was transferred to a rotary continuous dispersion apparatus “Cabitron CD1010” (manufactured by Eurotech Co., Ltd.) at a rate of 100 parts by mass per minute. Separately prepared aqueous medium tank is filled with 0.37 mass% diluted ammonia water diluted with ion-exchanged water and heated at 150 ° C. with a heat exchanger at a rate of 0.1 liter per minute. The colored resin melt is transferred to the Cavitron at the same time, and a dispersion liquid having a temperature of 160 ° C. in which the colored resin spherical fine particles are dispersed is obtained under the operating conditions of a rotor rotation speed of 7500 rpm and a pressure of 5 × 10 ⁵ Pa. After cooling to a temperature of 40 ° C. in 10 seconds, “toner base particle dispersion 6” having a volume-based median diameter (D ₅₀ ) of 5.9 μm was produced.

<Preparation of Toner 1>
(Formation of toner cake 1)
The “toner base particle dispersion 1” produced above was subjected to solid-liquid separation with a rotating cylindrical cleaning device “MARK III model number 60 × 40” (manufactured by Matsumoto Kikai Co., Ltd.) to form “toner cake 1”.

(Cleaning of toner cake 1)
The cleaning of the toner cake 1 is performed by spraying “washing water 1”, which is 11 mass times the toner base particle mass, from the spray nozzle attached to the rotating cylindrical cleaning device in the above rotating cylindrical cleaning device. The toner cake was washed with water.

(Drying of toner cake 1)
Next, the toner cake was scraped off by a scraper inserted into the machine, discharged from the machine, and stored in a container. Thereafter, the toner cake was supplied little by little to “Flash Jet Dryer” (manufactured by Seishin Enterprise Co., Ltd.) and dried until the water content of the toner base particles became 0.5% by mass to produce “Toner Base Particles 1”. .

(Mixing of external additives)
100 parts by mass of the “toner base particles 1” produced above are 0.8 parts by mass of rutile titanium oxide (volume average particle diameter = 20 nm) and 1.8 parts by mass of spherical monodispersed silica (volume average particle diameter = 127 nm). And blended for 15 minutes with a “Henschel mixer” (circumferential speed 30 m / s) (manufactured by Mitsui Miike Chemical Co., Ltd.). Thereafter, coarse particles were removed using a filter having an opening of 45 μm to prepare “Toner 1”.

<Preparation of Toner 2-6>
The washing water 1 used in the preparation of the toner 1 is changed to “washing water 2 to 6”, and the amount of each washing water is 33 times, 7 times, 7 times, 12 times, and 33 times times the toner base particle weight. “Toners 2 to 6” were prepared in the same manner as “Toner 1” except that

<Preparation of Toners 7 to 11>
The toner base particles 1 used in the preparation of the toner 1 were changed to “toner base particles 2 to 6”, and the amount of the washing water 1 was changed from 11 to 12 times the same as “toner 1”. “Toners 7 to 11” were produced.

<Preparation of Toners 12 to 16>
“Toners 12 to 15” were prepared in the same manner except that the cleaning water 1 used in the preparation of the toner 7 was changed to “washing water 7 to 11” and the amount of cleaning water was changed to 27 times the mass of the toner base particles. .

<Preparation of Toners 17 to 21>
“Toners 17 to 21” were produced in the same manner except that the washing water 1 used in the production of the toner 8 was changed to “washing water 12 to 16” and the amount of washing water was changed to 58 times the mass of the toner base particle mass. . <Preparation of Toners 22 to 26>
“Toners 22 to 26” were prepared in the same manner except that the cleaning water 1 used in preparation of the toner 9 was changed to “washing water 17 to 21” and the amount of cleaning water was changed to 22 times the mass of the toner base particles. .

  Table 1 shows the toner base particles, cleaning water, and the amount of cleaning water used for toner preparation (mass multiple of toner base particle mass).

<< Preparation of developer >>
100 parts by mass of “ferrite carrier” having a volume average particle diameter of 60 μm coated with a silicone resin and 6 parts by mass of the toner prepared above were sequentially mixed for 5 minutes with a V-type mixer to prepare “Developers 1 to 11”. .

<Evaluation>
As an image forming apparatus for evaluation, a high-speed image forming apparatus “bizhub PRO 1050 (manufactured by Konica Minolta Business Technologies)” was prepared.

  The evaluation was performed by sequentially loading the “toner 1 to 26” and “two-component developer 1 to 26” prepared above, and an original image (thin line image, halftone image, (A4 size image) in which a white background image and a solid image are each divided into quarters).

<Separability of transfer material>
For the separation property of the transfer material, an evaluation device was prepared by removing the separation claw 29 for separating the transfer material P from the surface of the photoreceptor 21, and A4 quality fine paper (64 g / mm) in a high temperature and high humidity (30 ° C., 80% RH) environment. m ² ) was laterally fed and when 100 sheets of a solid image were printed on the front end portion of the print 5 cm, evaluation was performed in a state where the transfer material was wound around the photosensitive member. In the evaluation, ◎, ○, and Δ are acceptable.

Evaluation Criteria A: No winding of 100 sheets occurred and no transfer material adhered to the photoconductor and no lifting phenomenon was observed. O: No winding of 100 sheets occurred, but the transfer material adhered to the photoconductor. Lifting phenomenon was observed in 1 to 3 sheets Δ: No winding occurred in all 100 sheets, but the phenomenon that the transfer material adhered to the photoreceptor and lifted was observed in 4 or more sheets ×: The transfer material was a photoreceptor Winding occurred.

<Toner scattering (filter adhesion)>
Toner scattering is performed by printing 100,000 sheets in a low-temperature, low-humidity (10 ° C., 20% RH) environment, and measuring the amount of toner adhered to the exhaust filter used as the characteristic value of “toner scattering” when the printing of 100,000 sheets is completed. evaluated. In the evaluation of toner scattering, a filter adhesion amount of 60 mg or less is accepted.

<Toner spillage, dirt inside the machine due to toner scattering>
To prevent spilling and scattering of toner in the machine, print 100,000 sheets in a low-temperature, low-humidity (10 ° C, 20% RH) environment, and visually observe the spillage and contamination of the machine due to toner scattering when the printing of 100,000 sheets is completed. evaluated. In addition, ◎ and ○ are acceptable for toner spillage and toner contamination due to toner scattering.

Evaluation criteria:
◎: Toner spillage and toner smudge due to toner scattering are hardly seen ○: Toner spillage and toner smudge due to toner scattering are relatively minor ×: Toner spillage and toner splatter smudge due to toner scattering A level at which dirt defects are recognized and cause practical problems.

  Table 2 shows the evaluation results.

  As shown in Table 2, “Examples 1 to 17” corresponding to the present invention obtained good results for any of the evaluation items. On the other hand, in “Comparative Examples 1 to 9” outside the present invention, there was a problem in any of these evaluation items, and it was confirmed that the effects of the present invention were not expressed.

301 Main body 302 Basket 303 Basket rotating device 304 Scraping device 305 Liquid supply pipe 306 Scraper 307 Filter 308 Liquid discharge port 309 Injection nozzle 310 Cake discharge port

Claims (2)

In the method for producing a toner for developing an electrostatic charge image, the method includes a step of washing toner base particles formed in an aqueous medium with washing water.
The method for producing a toner for developing an electrostatic charge image, wherein the washing water contains 0.5 to 1000.0 mg / L of total dissolved components at 25 ° C. 2. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the toner base particles are obtained by aggregating and fusing resin particles and colorant particles in an aqueous medium.

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