JP5579021B2 - Method for producing toner particles - Google Patents

Description

  The present invention relates to a toner and a toner particle manufacturing method for developing an electrostatic image in an image forming method such as electrophotography, electrostatic printing, and magnetic recording. In particular, the present invention relates to a method for producing toner particles for preventing adhesion of a polymer scale to an inner wall surface of a polymerization vessel when producing toner particles by polymerization.

  As a method for producing toner particles, there is a polymerization method in which a colorant and a charge control agent are included in polymer particles at the stage of polymerizing a polymerizable monomer to form toner particles. For example, in the suspension polymerization method, a polymerizable monomer, a colorant, a release agent and a polymerization initiator, and if necessary, a cross-linking agent, a charge control agent and other additives are uniformly dissolved or dispersed to be polymerizable. A monomer composition is used. This is dispersed in an aqueous medium containing a dispersion stabilizer using an appropriate stirrer, and the polymerizable monomer is polymerized to obtain a suspension of toner particles having a desired particle size. If necessary, the suspension is treated with an acid or alkali to remove the dispersion stabilizer from the surface of the toner particles, and then the aqueous medium is separated in a solid-liquid separation step to obtain toner particles. When it is necessary to further reduce the water content, water is removed from the toner particles by a known drying means.

  The toner particles obtained by these methods that do not depend on the mechanical grinding method are spherical and have a uniform surface. Therefore, the fluidity and transferability are good, and good development characteristics are exhibited even when continuous development is carried out many times, the stress on the toner is small, and the occurrence of filming on the photoreceptor is small. Further, the particle size distribution of the obtained toner particles is sharp, and the yield of toner particles having a desired particle size is high even when a classification step is required.

  In the production of toner by the suspension polymerization method described above, the polymerization step is usually carried out using a polymerization vessel having a stirring means and a heating / cooling means. When the composition adheres, it polymerizes in situ and becomes a scale deposit. The scale deposit remains in the polymerization vessel even after the polymerization process is completed. When this deposit is left untreated, the amount increases each time the number of polymerization steps is repeated. In the case of remarkable adhesion, the heat transfer performance of the polymerization vessel is lowered and the stability of the polymerization reaction is adversely affected. Further, when the scale deposits are peeled off and fall off and mixed into the product toner, they are observed as irregular shaped irregular particles. If the proportion of irregularly shaped particles in the toner increases, the toner characteristics such as triboelectric chargeability and the development characteristics when the image is evaluated are adversely affected, and the product properties are degraded, such as fluctuations in image density, white streaks, and fogging. This is not preferable.

  Further, when the scale deposit grows to a sufficient size and peels / drops off, it may cause clogging or sticking in a piping part or a valve connected to the polymerization vessel. For this reason, the frequent removal operation | work of a deposit | attachment is needed and the fall of the operation rate of a manufacturing apparatus is caused. Furthermore, when the inside of the polymerization vessel is subjected to a surface treatment such as glass lining or fluororesin coating, the treatment surface may be damaged by a work such as chipping, and a repair work may be required. These results in an increase in the cost of the product toner.

  As a method for preventing scale adhesion in such a polymerization reaction, for example, Patent Document 1 discloses that an inorganic dispersed powder layer is formed on a sticky inorganic compound layer in which colloidal silica and alkyl silicate are mixed on the inner wall surface of a polymerization vessel. A method for forming a protective coating has been proposed. However, in this method, repulsion between the inorganic dispersed powder layer and the dispersed droplets of the polymerizable monomer is insufficient, and a satisfactory scale prevention effect cannot be obtained.

  Patent Document 2 discloses a method for preventing adhesion of a polymer scale by applying a scale inhibitor containing a condensation reaction product of an aldehyde compound and a hydroxynaphthalene compound and a vinylphenol polymer to the inner wall of the polymerization vessel. Has been. In this method, the used scale inhibitor may be mixed into the toner particles as a product, and the developability may be adversely affected.

  Patent Document 3 discloses an aqueous dispersion medium containing water or a dispersion stabilizer on the inner wall of the gas phase portion in the polymerization vessel during polymerization as a method for preventing the scale to the gas phase portion and the gas-liquid interface in the polymerization vessel. A method of spraying has been proposed. However, although this method can provide a degree of scale prevention effect in the gas phase part to some extent, it is not possible to obtain any effect in suppressing polymer scale in the polymerization vessel liquid.

  Further, according to Patent Document 4, an aqueous dispersion medium containing a dispersion stabilizer containing a dispersion stabilizer separately prepared in the dispersion of the polymerizable monomer composition and the dispersion of the aqueous dispersion medium containing the dispersion stabilizer on the inner wall of the polymerization vessel. There is disclosed a method for preventing scale by simultaneously feeding a prepared solution mixed with a polymerization vessel into a polymerization vessel. However, the effect of preventing scale generated with temperature rise and / or liquid level drop during polymerization cannot be obtained. Further, according to the examination by the present applicant, this method has not provided a sufficient scale prevention effect.

  On the other hand, several methods for efficiently removing the generated scale deposits have been proposed. For example, a method of spraying a removing agent such as an organic solvent or an alkaline aqueous solution in a polymerization vessel, or filling the polymerization vessel and using heating and stirring together is simple and common. However, in any of these methods, the main point is to dissolve or swell the scale deposits in the liquid, and it takes a certain amount of time to remove all the deposits even when heated. In addition, since the used removal agent is significantly contaminated by the deposits, it is not suitable for reuse as it is, resulting in a large amount of waste liquid being discharged, or it is necessary to take a large regeneration means for the removal agent.

JP-A-5-287564 JP 2006-160960 A JP-A-10-153878 Japanese Patent Laid-Open No. 2003-287928

  An object of the present invention is to provide a method for producing toner particles that solves the above-described problems.

  That is, the present invention relates to a method for producing toner particles by a polymerization method, and suppresses the occurrence of adhesion of a polymer scale on the inner wall of a polymerization vessel when polymerizing dispersed droplets of a polymerizable monomer composition. It is an object of the present invention to provide a method for producing toner particles capable of easily removing the adhered matter on the polymer scale.

As a result of intensive studies on the suppression of the generation of polymer scale during the polymerization step and the removal thereof, the present inventors have found the following method.
(1) Polymerizable a monomer and colorant polymerizable monomer composition and containing not added to the liquid A is an aqueous medium containing an inorganic dispersion stabilizer, the polymerizable monomer in the liquid A in the granulation step, and polymerizable monomer manufacturing method of toner particles to the polymerizable monomer is polymerized contained in particles comprising the polymerization step to obtain toner particles of the composition to form particles of the composition There,
In advance , liquid B, which is a liquid containing a hardly water-soluble inorganic compound , is applied to at least a part of the inner wall of the polymerization vessel used in the polymerization step, and the contents of the polymerization vessel are discharged after the polymerization step is completed. After that, a method for producing toner particles, wherein the inner wall of the polymerization container is brought into contact with liquid C, which is an aqueous solution having a pH of 9 or more.
(2) after said liquid B was applied to at least a portion of the inner wall of the polymerization vessel, the manufacturing method of the toner particles according to the inner wall of the polymerization vessel you warm (1).
(3) The toner particles according to the above inorganic dispersion stabilizer in the liquid A used in the granulation step, the slightly water-soluble inorganic compound in the liquid B is be of the same thing (1) or (2) Manufacturing method.
(4) the concentration of the inorganic dispersion stabilizer in the liquid A and Ca (wt%), when the concentration of the slightly water-soluble inorganic compound in the liquid B was Cb (weight%), Ca and Cb There, 1.0 × Ca ≦ Cb ≦ 40.0 × satisfying the relationship Ca (1) ~ method for producing toner particles according to any one of (3).
(5) such that the slightly water-soluble inorganic compound is present in the surface of the inner wall of the polymerization vessel 0.05 mg / cm ² or more 7.50mg / cm ² or less, in advance, at least the liquid B of the inner wall of the polymerization vessel The method for producing toner particles according to any one of (1) to (4), wherein the toner particles are applied to a part .
(6) The method of producing toner particles according to any one of Ru with a poorly water-soluble metal compound to the hardly water-soluble inorganic compound in the liquid B (1) ~ (5).
(7) The method of producing the toner particles according to any one of the slightly water-soluble inorganic compound in the fluid B Ru with poorly water-soluble phosphoric acid metal salt (1) to (6).
(8) The method of the inner wall of the polymerization vessel in contact with the liquid C is any of Ru methods der stirring while heating it after filling the polymerization vessel with the liquid C (1) ~ (7) 2. A method for producing toner particles according to 1.
(9) The method of producing the toner particles according to any one of the liquid C is Ru aqueous der sodium carbonate (1) to (8).

  According to the present invention, in the polymerization process during the production of the suspension polymerization method toner, it is possible to suppress the generation of the polymer scale generated in the polymerization container and to easily remove the scale even when the scale is generated. It is possible to prevent the irregular shaped particles from being mixed into the product toner. For this reason, when image formation is performed, there is no fluctuation in image density or density unevenness, and a clear and excellent fixing toner can be obtained. In addition, there is no obstruction of heat conduction due to accumulated polymer deposits, and no clogging of pipes due to dropping of polymer deposits. Therefore, frequent removal of polymer deposits is essentially unnecessary, improving productivity. To do.

It is sectional drawing of the suitable superposition | polymerization container used for this invention.

  The present invention can be suitably used for a method for producing toner particles by suspension polymerization. In the suspension polymerization method, a polymerizable monomer composition containing at least a polymerizable monomer and a colorant is added to an aqueous medium, and the polymerizable monomer composition is granulated in the aqueous medium. In this method, toner particles are obtained by forming particles of a monomer composition and polymerizing a polymerizable monomer contained in the particles of the polymerizable monomer composition.

  The method for producing the toner of the present invention by the suspension polymerization method will be described below.

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

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

  Examples of the inorganic dispersion stabilizer include, for example, carbonates such as barium sulfate, calcium sulfate, barium carbonate, calcium carbonate, and magnesium carbonate; aluminum phosphates such as aluminum phosphate, magnesium phosphate, calcium phosphate, barium phosphate, and zinc phosphate. Metal salt; inorganic salt such as calcium metasuccinate, calcium sulfate, barium sulfate; inorganic oxide such as silica, bentonite, alumina; inorganic water such as calcium hydroxide, aluminum hydroxide, magnesium hydroxide, ferric hydroxide Oxides; and the like. These can be used alone or in combination of two or more. These exhibit functions as a dispersion stabilizer by being present as fine particles in an aqueous medium.

(Polymerization process)
By polymerizing the polymerizable monomer in the polymerizable monomer composition dispersion obtained by the granulation step, a polymer fine particle dispersion is obtained. In the polymerization step in the present invention, a general polymerization vessel having a stirring means and adjustable in temperature can be used.

  The polymerization temperature is 40 ° C. or higher, generally 50 to 90 ° C. The polymerization temperature may be constant throughout, but may be raised in the latter half of the polymerization step for the purpose of obtaining a desired molecular weight distribution. Any stirring means may be used as the stirring means used in the polymerization vessel as long as the dispersed polymerizable monomer composition is floated without stagnation and the temperature in the tank can be kept uniform. As a stirring means, a stirring blade is suitable. For example, a general stirring blade such as a paddle blade, an inclined paddle blade, a three-blade retracted blade, a propeller blade, a disk turbine blade, a helical ribbon blade, an anchor blade, a full zone (shinko pan). Tech), twin star (manufactured by Shinko Pantech), max blend (manufactured by Sumitomo Heavy Industries), supermix (manufactured by Satake Chemical Machinery Co., Ltd.), Hi-F mixer (manufactured by Soken Chemical), and the like.

  An example of a cross-sectional view of a suitable polymerization vessel used in the present invention is shown in FIG. 1, but is not limited thereto.

  In FIG. 1, 1 is a polymerization vessel, 2 is a stirring blade, 3 is a baffle plate, 4 is a stirring motor, 5 is a gas-liquid interface, and 6 is a temperature control jacket.

  Before performing the polymerization step, the inner wall of the polymerization vessel 1 is coated with a liquid (liquid B) containing a hardly water-soluble inorganic compound to coat the inner wall of the polymerization vessel with the hardly water-soluble inorganic compound. After applying the liquid B, it is preferable to dry it. This enhances the adhesion of the poorly water-soluble inorganic compound to the inner wall of the polymerization vessel. In the case where drying is not performed, the adhesiveness of the poorly water-soluble inorganic compound is not sufficient, so that a desired effect cannot be obtained. The drying method is not particularly limited. However, in the case where a jacket for temperature control is provided as in the apparatus shown in FIG. 1, it is effective to dry by heating the inner wall of the polymerization vessel using the jacket. . The polymerization monomer composition dispersion obtained by the granulation step is introduced into a polymerization vessel that has been sufficiently coated with the hardly water-soluble inorganic compound, and the polymerization step is performed. The repulsive force between the inorganic dispersion stabilizer covering the droplets of the polymerizable monomer composition and the poorly water-soluble inorganic compound on the inner wall surface of the polymerization vessel can suppress the adhesion of the polymer scale to the inner wall of the polymerization vessel. it can. Moreover, the adhesion of the scale to the surface of the auxiliary equipment in the polymerization vessel can also be suppressed by performing the same treatment on the surface of the auxiliary equipment such as the stirring device 2 and the baffle 3.

  The liquid component of the liquid B is not particularly limited as long as the hardly water-soluble inorganic compound is insoluble and has volatility. For example, water; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, i Alcohols such as butyl alcohol and t-butyl alcohol can be used. Furthermore, organic solvents, such as acetone, methyl acetate, ethyl acetate, dimethyl sulfoxide, n-hexane, toluene, xylene, can be mentioned. Moreover, these can also be used individually or in combination of 2 or more types. Among those exemplified above, use of water alone or in combination with alcohols is preferable from the industrial and economic viewpoints.

  Examples of the hardly water-soluble inorganic compounds include, for example, carbonates such as barium sulfate, calcium sulfate, barium carbonate, calcium carbonate, and magnesium carbonate; phosphoric acids such as aluminum phosphate, magnesium phosphate, calcium phosphate, barium phosphate, and zinc phosphate Polyvalent metal salts; inorganic salts such as calcium metasuccinate, calcium sulfate and barium sulfate; inorganic oxides such as silica, bentonite and alumina; inorganics such as calcium hydroxide, aluminum hydroxide, magnesium hydroxide and ferric hydroxide A hydroxide; and the like. These poorly water-soluble inorganic compounds can be used alone or in combination of two or more. Of these poorly water-soluble inorganic compounds, poorly water-soluble metal compounds are more preferably used. Furthermore, among them, poorly water-soluble metal phosphates such as aluminum phosphate, magnesium phosphate, calcium phosphate, barium phosphate and zinc phosphate are preferably used.

  Although the slightly water-soluble inorganic compound as the inorganic dispersion stabilizer and the slightly water-soluble inorganic compound contained in the liquid B may be different from each other, from the viewpoint of simplifying the process of removing the dispersion stabilizer after polymerization. It is preferable to use a combination of those soluble in acid or alkali. Furthermore, it is preferable to use a hardly water-soluble inorganic compound having the same composition.

  The dispersion stabilizer used in the granulation step in which the polymerizable monomer composition is performed in an aqueous dispersion medium is preferably an inorganic dispersion stabilizer. Electrostatic repulsion due to the inorganic dispersion stabilizer that collects in the dispersed droplets of the polymerizable monomer composition and the poorly water-soluble inorganic compound that adheres to the inner wall of the polymerization vessel suppresses the adhesion of the dispersed droplets to the inner wall of the polymerization vessel. The Thereby, a scale can be suppressed effectively.

  When a water-soluble polymer is used as a dispersion stabilizer, a sufficient repulsive force is not generated between the dispersed droplets and the polymerization vessel, so that the effect of preventing adhesion of the polymer scale is not satisfactory.

  The liquid B can be applied to the inner wall of the polymerization vessel as long as it can be uniformly applied. For example, the liquid B is sprayed using a shower nozzle or a spray nozzle. The polymerization vessel is filled with the liquid B and then discharged. For example, a method of applying with a brush.

  Concentration Ca (mass%) of the inorganic dispersion stabilizer with respect to the aqueous dispersion medium (liquid A) containing the inorganic dispersion stabilizer and the concentration Cb of the poorly water-soluble inorganic compound with respect to the liquid (liquid B) containing the poorly water-soluble inorganic compound % By mass) preferably satisfies the relationship of 1.0Ca ≦ Cb ≦ 40.0Ca.

  When the concentration Cb (mass%) of the poorly water-soluble inorganic compound with respect to the liquid B is smaller than 1.0Ca, the repulsive force with the dispersion stabilizer covering the periphery of the dispersion droplet of the polymerizable monomer composition is small and sufficient. It is difficult to obtain the effect. When the concentration Cb (mass%) is larger than 40.0Ca, a part of the hardly water-soluble inorganic compound on the inner wall of the polymerization vessel migrates into the polymerizable monomer composition dispersion, and the polymerizable monomer composition dispersion The droplet size distribution may be disturbed and the resulting image characteristics of the toner particles may be adversely affected. Moreover, it is not preferable for increasing the load in the subsequent process.

It is preferred that the hardly water-soluble inorganic compound to the polymerization vessel inner wall surface is present at a density of 0.05 mg / cm ² or more 7.50mg / cm ² or less. When the concentration is less than 0.05 mg / cm ² , a portion in which the hardly water-soluble inorganic compound does not exist partially occurs, and electrostatic repulsive force on the droplet of the polymerizable monomer composition of the hardly water-soluble inorganic compound is reduced. This is not preferable because the scale adhesion suppressing effect is small. When it is larger than 7.50 mg / cm ² , cracks are generated in the layer of the hardly water-soluble inorganic compound, and the layer is easily peeled off. The peeled layer of the hardly water-soluble inorganic compound moves into the polymerizable monomer composition dispersion liquid, disturbs the distribution of droplet diameters of the polymerizable monomer composition dispersion liquid, and the resulting toner Particle image characteristics may be adversely affected. Moreover, it is not preferable for increasing the load in the subsequent process. Moreover, when the layer of a hardly water-soluble inorganic compound is too thick, the heat transfer efficiency of the polymerization vessel is lowered.

  After the completion of the polymerization step, after the contents of the polymerization container (polymer fine particle dispersion) are discharged, the scale deposits can be completely removed by bringing the liquid C having a pH of 9 or more into contact with the inner wall of the polymerization container. As a method of bringing the liquid C into contact, any method such as a method of spraying with a spray nozzle or a shower nozzle, a method of filling the polymerization vessel with the liquid C can be used, but in the case of a polymerization vessel as shown in FIG. A method of stirring after the polymerization vessel is filled with the liquid C is preferable from the viewpoint of detergency. Further, at this time, the cleaning property is further improved by heating the liquid C. If the temperature at which the liquid C is heated is higher than room temperature, a certain degree of effect can be obtained, but if the temperature is 50 ° C. or higher, the effect becomes more remarkable.

  The liquid C only needs to have a pH of 9 or more, and sodium hydroxide, sodium carbonate, sodium metasilicate, tribasic sodium phosphate and the like can be used. Sodium carbonate is particularly preferable from the viewpoint of handling.

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

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

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

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

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

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

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

[Colorant]
The following are mentioned as a coloring agent used by this invention. Carbon black; I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Modern Tread 30, C.I. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modern Blue 7, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I. I. Dyes such as Basic Green 6: yellow lead, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow NCG, tartrazine lake, molybdenum orange, permanent orange GTR, benzidine orange G, cadmium red, Permanent Red 4R, Watching Red Calcium Salt, Brilliant Carmine 3B, Fast Violet B, Methyl Violet Lake, Bitumen, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Quinacridone, Rhodamine Lake, Phthalocyanine Blue, Fast Sky Blue, Pigment Green B, Pigments such as Malachite Green Lake and Final Yellow Green G.

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

  These colorants are preferably used in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

[Release agent]
As the release agent used in the present invention, a wax in a solid state at room temperature may be used in terms of toner blocking resistance, multi-sheet durability, low-temperature fixability, and offset resistance.

  Examples of the wax include the following. Polymethylene waxes such as paraffin wax, polyolefin wax, microcrystalline wax, Fischer-Tropsch wax, amide wax, higher fatty acid, long chain alcohol, ester wax and graft compounds thereof, and block compounds thereof. These are preferably removed from the low molecular weight component and have a sharp maximum endothermic peak in the endothermic curve obtained by a differential scanning calorimeter. In order to improve the translucency of the image fixed on the OHP, a linear ester wax is particularly preferably used. The linear ester wax may be contained in an amount of 1 to 40 parts by weight, more preferably 4 to 30 parts by weight, based on 100 parts by weight of the polymerizable monomer.

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

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

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

  These charge control agents are used in an amount of 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymerizable monomer.

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

  An organic peroxide initiator can also be used. The following are mentioned as an organic peroxide type | system | group initiator. Benzoyl peroxide, lauroyl peroxide, di-α-cumyl peroxide, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, bis (4-t-butylcyclohexyl) peroxydicarbonate, 1, 1-bis (t-butylperoxy) cyclododecane, t-butylperoxymaleic acid, bis (t-butylperoxy) isophthalate, methyl ethyl ketone peroxide, tert-butylperoxy-2-ethylhexanoate, diisopropyl Peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide.

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

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

[Polar resin]
In the case of a polymerization method using an aqueous medium such as suspension polymerization, the inclusion of a release agent can be promoted by adding a polar resin to the polymerizable monomer composition. When a polar resin is present in a polymerizable monomer composition suspended in an aqueous medium, the polar resin tends to migrate to the vicinity of the interface between the aqueous medium and the polymerizable monomer composition due to the difference in affinity for water. Therefore, polar resin is unevenly distributed on the toner surface. As a result, the toner particles have a core-shell structure, and the inclusion property of the release agent is improved even when a large amount of the release agent is contained.

  As such a polar resin, a saturated or unsaturated polyester resin is particularly preferable because the fluidity of the polar resin itself can be expected when it is unevenly distributed on the toner surface to form a shell.

  As the polyester-based resin, those obtained by condensation polymerization of the following acid component monomers and alcohol component monomers can be used. The following are mentioned as an acid component monomer. Terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, camphoric acid, cyclohexanedicarboxylic acid, trimellit acid. Examples of alcohol component monomers include the following. Alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane, and Polyalkylene glycols, bisphenol A, hydrogenated bisphenol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, glycerin, trimethylolpropane, pentaerythritol.

[External additive]
In the production method of the present invention, an external additive can be used for the purpose of imparting various properties to the toner. The external additive preferably has a particle size of 1/10 or less of the average particle size of the toner particles from the viewpoint of durability when added to the toner. Examples of the external additive include the following. Metal oxides such as aluminum oxide, titanium oxide, strontium titanate, cerium oxide, magnesium oxide, chromium oxide, tin oxide, zinc oxide; nitrides such as silicon nitride; carbides such as carbide silicon carbide; calcium sulfate, barium sulfate, Inorganic metal salts such as calcium carbonate; fatty acid metal salts such as zinc stearate and calcium stearate; carbon black, silica.

  These external additives are used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of toner particles. The external additives may be used singly or in combination of two or more, but those subjected to hydrophobic treatment are more preferable.

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

  These magnetic materials have a volume average particle diameter (Dv) of 0.5 μm or less, preferably about 0.1 to 0.5 μm.

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

  The content of the magnetic substance in the toner is 20 to 200 parts by weight, particularly preferably 40 to 150 parts by weight, based on 100 parts by weight of the polymerizable monomer. .

In addition, it is preferable that the magnetic material has a saturation magnetization (σs) of 50 to 200 Am ² / kg and a residual magnetization (σr) of 2 to 20 Am ² / kg when 800 kA / m is applied. The magnetic properties of the magnetic material are measured using an oscillating magnetometer VSM P-1-10 (manufactured by Toei Kogyo Co., Ltd.) at a room temperature of 25 ° C. and an external magnetic field of 79.6 kA / m.

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

  As described above, the toner produced according to the present invention can be used as either a one-component or two-component developer.

  In the case of a magnetic toner containing a magnetic material in the toner as a one-component developer, a method of transporting or charging the magnetic toner using a magnet built in the developing sleeve is used. When non-magnetic toner containing no magnetic material is used, there is a method in which a blade and a fur brush are used to forcibly frictionally charge with a developing sleeve and the toner is attached to the sleeve to be conveyed.

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

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

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

  The average particle size of these carriers is preferably 10 to 100 μm, more preferably 20 to 50 μm.

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

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

  The measurement method used in the present invention will be described below.

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

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, dedicated software was set up as follows.

  On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.

  In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

The specific measurement method is as follows.
1) About 200 ml of the electrolytic solution is placed in a 250 ml round bottom beaker made exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.
3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.
4) The beaker of 2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
5) In a state where the electrolytic aqueous solution in the beaker of 4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
6) Into the round bottom beaker of 1) installed in the sample stand, the electrolyte solution of 5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. The measurement is performed until the number of measured particles reaches 50,000.
7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. When the graph / volume% is set in the dedicated software, the “average diameter” on the “Analysis / volume statistics (arithmetic average)” screen is the weight average particle diameter (D4), and the graph / number% in the dedicated software. The “average diameter” on the “analysis / number statistics (arithmetic mean)” screen is the number average particle diameter (D1).

(2) Calculation method of sharpness of particle size distribution The sharpness of the particle size distribution was evaluated by determining D4 / D1 using the above-mentioned weight average particle diameter (D4) and number average particle diameter (D1). The closer the D4 / D1 is to 1, the sharper the particle size distribution.

(3) Calculation Method of Amount of Coarse Powder The volume-based coarse particle amount (volume%) in the toner is calculated by analyzing the data after measuring the Multisizer 3 described above.

  The volume percentage of particles of 10.0 μm or more in the toner is calculated by the following procedure. First, graph / volume% is set with dedicated software, and the measurement result chart is displayed as volume%. Then, check “>” in the particle size setting portion on the “format / particle size / particle size statistics” screen, and enter “10” in the particle size input section below. When the “analysis / volume statistic (arithmetic average)” screen is displayed, the numerical value of the “> 10 μm” display portion is the volume% of particles of 10.0 μm or more in the toner. The volume percentage of 10 μm or more at this time was defined as the amount of coarse powder.

(4) Calculation Method of Scale Adhesion Rate The mass of the polymerization vessel is W ₀ , and the mass obtained by performing the polymerization reaction n times in the same polymerization vessel, washing with water and drying is W. When the total solid content mass calculated from the toner particle manufacturing recipe is M, the adhesion rate is:
Scale adhesion rate (%) = (W−W ₀ ) / M / n × 100
Is calculated by

  The image evaluation method performed in the embodiment of the present invention and its judgment criteria will be described below.

LASER JET2300 was used as the image forming apparatus. Here, a process speed was set to 150 mm / sec, and a development bias in which an alternating electric field of 1.6 kVpp and a frequency of 2200 Hz was superimposed on a DC voltage Vdc of −430 V was used. Under these conditions, an image endurance test of 6,000 sheets was performed in an intermittent mode on an image with an A-point of 8 points and a printing rate of 4% in a normal temperature and humidity environment (23 ° C., 60% RH). It was. As the recording medium, A4 75 g / m ² paper was used.

(5) Image density The image density formed a solid image portion, and the density of this solid image was measured with a Macbeth reflection densitometer (manufactured by Macbeth).

(6) Fog A white image was output, and the reflectance was measured using a REFECTMETER MODEL TC-6DS manufactured by Tokyo Denshoku. On the other hand, the reflectance of the transfer paper (standard paper) before white image formation was measured in the same manner. As the filter, a green filter was used for black and magenta toners, an amber filter was used for cyan toners, and a blue filter was used for yellow toners. The fog was calculated from the reflectance before and after the white image output using the following formula.
Fog (reflectance) (%) = reflectance of standard paper (%)-reflectance of white image sample (%)

The obtained fog value was evaluated in five steps according to the following evaluation criteria.
A: Very good level (less than 0.5%)
B: Good level (0.5% or more and less than 1.0%)
C: No problem level (1.0% or more and less than 2.0%)
D: Acceptable level (2.0% or more and less than 3.0%)
E: Bad level (3.0% or more)

<Example 1>
(Preparation of liquid A)
720 parts by mass of ion-exchanged water and 450 parts by mass of 0.1 mol / liter-Na ₃ PO ₄ aqueous solution were charged into a _4- liter separable flask for 2 liters equipped with Claremix (M Technique Co., Ltd.), 15000 rpm And warmed to 60 ° C. A liquid A containing 0.56% by mass of calcium phosphate was obtained by adding 67.6 parts by mass of a 1.0 mol / liter-CaCl ₂ aqueous solution.

(Preparation and application of liquid B)
1354 parts by mass of 0.5 mol / liter-Na ₃ PO ₄ aqueous solution was stirred at 15000 rpm and heated to 60 ° C. To this, 380 parts by mass of a 3.0 mol / liter-CaCl ₂ aqueous solution was added to obtain a liquid containing calcium phosphate. The liquid B was concentrated by removing a part of the water to obtain a liquid B having a calcium phosphate concentration of 10.00% by mass, which is a poorly water-soluble inorganic compound.

A 2 liter four-neck separable flask was heated in a hot water bath at 60 ° C., and the liquid B prepared above was placed in the flask and brought into contact with the inner wall. After the excess liquid B was removed from the polymerization vessel, the inside of the flask was dried in a 60 ° C. hot water bath to fix calcium phosphate to the flask surface. The density (mg / cm ² ) of calcium phosphate calculated from the difference in mass of the flask before and after fixing calcium phosphate and the surface area of the inner wall of the flask was calculated. Table 1 shows the concentration Ca of the liquid A, the concentration Cb of the liquid B, and the density of the hardly water-soluble inorganic compound fixed to the flask.

(Preparation of polymerizable monomer composition)
Styrene 74 parts by mass n-butyl acrylate 26 parts by mass divinylbenzene 0.5 parts by mass saturated polyester resin 10 parts by mass (polycondensate of bisphenol A and terephthalic acid, Mn = 10000, Mw / Mn = 2.6, acid value = 12mgKOH / g, Tg = 72 ° C)
E-88 (manufactured by Orient Chemical Industry Co., Ltd.) 2 parts by mass negative charge control agent T-77 (manufactured by Hodogaya Chemical) 1.5 parts by mass hydrophobized magnetic iron oxide 90 parts by mass Dissolved in and dispersed. 10 parts by weight of paraffin wax (maximum endothermic peak at DSC of 78 ° C.) was added and mixed and dissolved, and 7.0 parts by weight of a polymerization initiator t-butyl-oxy-2-ethylhexanoate was dissolved to be polymerizable. A monomer composition was obtained.

(Granulation process)
The polymerizable monomer composition is charged into the liquid A, stirred at 15000 rpm for 10 minutes in Claremix (manufactured by M Technique Co., Ltd.) in an N ₂ atmosphere at 60 ° C., granulated, and polymerized. A body composition dispersion was obtained.

(Polymerization process)
The polymerizable monomer composition dispersion prepared above is transferred to the above-described separable flask to which calcium phosphate is fixed, and the rotational speed of a stirrer equipped with a propeller stirring blade is increased to 200 rpm and the temperature is raised to 70 ° C. 4 Polymer fine particle dispersion was obtained by performing time polymerization.

(Washing with liquid C)
After discharging the polymer fine particle dispersion from the separable flask, the separable flask was sufficiently washed with ion-exchanged water. The separable flask was filled with an aqueous sodium carbonate solution (liquid C) whose concentration was adjusted to pH 12, and stirred for 1 hour while heating at 85 ° C. The liquid C was discharged and thoroughly washed with ion exchange water, and then the separable flask was dried and weighed. Using this separable flask, the scale deposition rate was determined from the weight increase of the separable flask after repeating the above steps seven times. The results are shown in Table 2.

(Washing, filtration, drying and classification processes)
Dilute hydrochloric acid was added to the suspension obtained by the seventh polymerization reaction to dissolve calcium phosphate. This was subjected to pressure filtration for solid-liquid separation, then re-dispersed with ion exchange water 3 times the mass of the solid content, pressure filtered again to reduce the water content to 10% or less, and then 40 ° C. The toner particles were obtained by drying in a constant temperature bath. Table 2 shows the results of measuring the weight average particle diameter (D4), the sharpness of the particle size distribution, and the amount of coarse powder of the obtained toner particles.

(Image evaluation)
A toner was prepared by mixing 100 parts by mass of the toner particles with 1.0 part by mass of hydrophobic silica fine powder having a BET specific surface area of 120 m ² / g using a Henschel mixer (Mitsui Miike Chemical Co., Ltd.). . Table 2 shows the results of evaluation of image density and fog on the obtained toner.

<Example 2>
Toner particles were obtained in the same manner as in Example 1 except that a sodium hydroxide aqueous solution adjusted to pH 12 was used as liquid C. Table 1 shows the concentration Ca of the liquid A, the concentration Cb of the liquid B, and the density of the hardly water-soluble inorganic compound fixed to the flask. Table 2 shows the evaluation of scale adhesion rate, weight average particle diameter (D4) of toner particles, sharpness of particle size distribution, coarse powder amount, image density, and fog.

<Example 3>
Toner particles were obtained in the same manner as in Example 1 except that 2 L of liquid C heated to 85 ° C. was sprayed on the inner wall of the separable flask. Table 1 shows the concentration Ca of the liquid A, the concentration Cb of the liquid B, and the density of the hardly water-soluble inorganic compound fixed to the flask. Table 2 shows the evaluation of scale adhesion rate, weight average particle diameter (D4) of toner particles, sharpness of particle size distribution, coarse powder amount, image density, and fog.

<Example 4>
A magnesium hydroxide colloidal solution (liquid A) is prepared by dropping an aqueous solution in which 9 parts by mass of sodium hydroxide is dissolved in 59 parts by mass of ion-exchanged water into an aqueous solution in which 11 parts by mass of magnesium chloride is dissolved in 1159 parts by mass of ion-exchanged water. Then, toner particles were obtained in the same manner as in Example 1 except that the liquid A was concentrated so that the magnesium hydroxide concentration was 10% by mass and the liquid B was used. Table 1 shows the concentration Ca of the liquid A, the concentration Cb of the liquid B, and the density of the hardly water-soluble inorganic compound fixed to the flask. Table 2 shows the evaluation of scale adhesion rate, weight average particle diameter (D4) of toner particles, sharpness of particle size distribution, coarse powder amount, image density, and fog.

<Example 5>
Implemented except that commercially available colloidal silica (Snowtex 20 manufactured by Nissan Chemical Industries, Ltd.) was diluted to 0.56% by mass to give liquid A, and the same colloidal silica was diluted to 10% to give liquid B. Toner particles were obtained in the same manner as in Example 1. Table 1 shows the concentration Ca of the liquid A, the concentration Cb of the liquid B, and the density of the hardly water-soluble inorganic compound fixed to the flask. Table 2 shows the evaluation of scale adhesion rate, weight average particle diameter (D4) of toner particles, sharpness of particle size distribution, coarse powder amount, image density, and fog.

<Example 6>
1354 parts by mass of 0.05 mol / liter-Na ₃ PO ₄ aqueous solution was stirred at 15,000 rpm with Claremix (manufactured by M Technique) and heated to 60 ° C., and 380 masses of 0.3 mol / liter-CaCl ₂ aqueous solution was added thereto. Toner particles were obtained in the same manner as in Example 1 except that part B was added to obtain liquid B. Table 1 shows the concentration Ca of the liquid A, the concentration Cb of the liquid B, and the density of the hardly water-soluble inorganic compound fixed to the flask. Table 2 shows the evaluation of scale adhesion rate, weight average particle diameter (D4) of toner particles, sharpness of particle size distribution, coarse powder amount, image density, and fog.

<Example 7>
Toner particles were obtained in the same manner as in Example 1 except that the liquid B was prepared in the same manner as in Example 1 and then concentrated until the calcium phosphate concentration was 22.0% by mass. Table 1 shows the concentration Ca of the liquid A, the concentration Cb of the liquid B, and the density of the hardly water-soluble inorganic compound fixed to the flask. Table 2 shows the evaluation of scale adhesion rate, weight average particle diameter (D4) of toner particles, sharpness of particle size distribution, coarse powder amount, image density, and fog.

<Example 8>
1354 parts by mass of 0.04 mol / liter-Na ₃ PO ₄ aqueous solution was stirred at 15000 rpm and heated to 60 ° C., and 380 masses of 0.25 mol / liter-CaCl ₂ aqueous solution was added thereto. Toner particles were obtained in the same manner as in Example 1 except that part B was added to obtain liquid B. Table 1 shows the concentration Ca of the liquid A, the concentration Cb of the liquid B, and the density of the hardly water-soluble inorganic compound fixed to the flask. Table 2 shows the evaluation of scale adhesion rate, weight average particle diameter (D4) of toner particles, sharpness of particle size distribution, coarse powder amount, image density, and fog.

<Example 9>
Toner particles were obtained in the same manner as in Example 1 except that the liquid B was prepared in the same manner as in Example 1 and then concentrated until the calcium phosphate concentration was 23.0% by mass. Table 1 shows the concentration Ca of the liquid A, the concentration Cb of the liquid B, and the density of the hardly water-soluble inorganic compound fixed to the flask. Table 2 shows the evaluation of scale adhesion rate, weight average particle diameter (D4) of toner particles, sharpness of particle size distribution, coarse powder amount, image density, and fog.

<Example 10>
Toner particles were obtained in the same manner as in Example 1 except that the same liquid B as in Example 4 was used. Table 1 shows the concentration Ca of the liquid A, the concentration Cb of the liquid B, and the density of the hardly water-soluble inorganic compound fixed to the flask. Table 2 shows the evaluation of scale adhesion rate, weight average particle diameter (D4) of toner particles, sharpness of particle size distribution, coarse powder amount, image density, and fog.

<Example 11>
Toner particles were obtained in the same manner as in Example 1 except that the liquid B was applied to the inner wall of the separable flask and then not dried. Table 1 shows the concentration Ca of the liquid A, the concentration Cb of the liquid B, and the density of the hardly water-soluble inorganic compound fixed to the flask. Table 2 shows the evaluation of scale adhesion rate, weight average particle diameter (D4) of toner particles, sharpness of particle size distribution, coarse powder amount, image density, and fog.

<Example 12>
Toner particles were obtained in the same manner as in Example 1 except that a sodium carbonate aqueous solution whose concentration was adjusted to pH 9 was used as liquid C. Table 1 shows the concentration Ca of the liquid A, the concentration Cb of the liquid B, and the density of the hardly water-soluble inorganic compound fixed to the flask. Table 2 shows the evaluation of scale adhesion rate, weight average particle diameter (D4) of toner particles, sharpness of particle size distribution, coarse powder amount, image density, and fog.

<Example 13>
Toner particles were obtained in the same manner as in Example 1 except that a sodium carbonate aqueous solution whose concentration was adjusted to pH 14 was used as liquid C. Table 1 shows the concentration Ca of the liquid A, the concentration Cb of the liquid B, and the density of the hardly water-soluble inorganic compound fixed to the flask. Table 2 shows the evaluation of scale adhesion rate, weight average particle diameter (D4) of toner particles, sharpness of particle size distribution, coarse powder amount, image density, and fog.

<Comparative Example 1>
Toner particles were obtained in the same manner as in Example 1 except that a sodium carbonate aqueous solution whose concentration was adjusted to pH 8 was used as liquid C. Table 1 shows the concentration Ca of the liquid A, the concentration Cb of the liquid B, and the density of the hardly water-soluble inorganic compound fixed to the flask. Table 2 shows the evaluation of scale adhesion rate, weight average particle diameter (D4) of toner particles, sharpness of particle size distribution, coarse powder amount, image density, and fog.

<Comparative example 2>
Toner particles were obtained by the same method as in Example 1 except that washing with liquid C was not performed after the polymerization step. Table 1 shows the concentration Ca of the liquid A, the concentration Cb of the liquid B, and the density of the hardly water-soluble inorganic compound fixed to the flask. Table 2 shows the evaluation of scale adhesion rate, weight average particle diameter (D4) of toner particles, sharpness of particle size distribution, coarse powder amount, image density, and fog.

1 Polymerization vessel, 2 stirring blade, 3 baffle plate, 4 stirring motor, 5 gas-liquid interface, 6 jacket for temperature control

Claims (9)

A polymerizable monomer and a polymerizable monomer composition having containing a colorant, in addition to the liquid A is an aqueous medium containing an inorganic dispersion stabilizer, the polymerizable monomer composition in the liquid A a granulation step, and polymerizable monomer manufacturing method of toner particles to the polymerizable monomer is polymerized contained in particles comprising the polymerization step to obtain toner particles of the composition forming the particle,
In advance , liquid B, which is a liquid containing a hardly water-soluble inorganic compound , is applied to at least a part of the inner wall of the polymerization vessel used in the polymerization step, and the contents of the polymerization vessel are discharged after the polymerization step is completed. After that, a method for producing toner particles, wherein the inner wall of the polymerization container is brought into contact with liquid C, which is an aqueous solution having a pH of 9 or more. Wherein after the liquid B was applied to at least a portion of the inner wall of the polymerization vessel, the manufacturing method of the toner particles according to the inner wall of the polymerization vessel 請 Motomeko 1 you warm. And the inorganic dispersion stabilizer in the liquid A used in the granulation step, the manufacturing method of the toner particles according to 請 Motomeko 1 or 2 wherein the slightly water-soluble inorganic compound be of the same ones in the liquid B. When the concentration of the inorganic dispersion stabilizer in the liquid A and Ca (wt%), the concentration of the slightly water-soluble inorganic compound in the liquid B was Cb (weight%), Ca and Cb are
1.0 × Ca ≦ Cb ≦ 40.0 × Ca
Method for producing toner particles according to any one of the relationship of 請 Motomeko 1-3 satisfying. So that the slightly water-soluble inorganic compound is present in the surface of the inner wall of the polymerization vessel 0.05 mg / cm ² or more 7.50mg / cm ² or less, in advance, the liquid B in at least a part of the inner wall of the polymerization vessel method for producing toner particles according to any one of claims 1 to 4 for coating. Method for producing toner particles according to any one of the slightly water-soluble inorganic compound ~ 請 Motomeko 1 Ru with hardly water-soluble metal compound to compound 5 in the liquid B. Method for producing toner particles according to any one of the flame 請 Motomeko that the water-soluble inorganic compound Ru with poorly water-soluble phosphoric acid metal salt 1 to 6 in the liquid B. The method of the inner wall of the polymerization vessel in contact with the liquid C is described the polymerization vessel in any one of 請 Motomeko 1-7 how Ru der stirring while heating it after filling with the liquid C Toner particle manufacturing method. Method for producing toner particles according to any one of the liquid C is 請 Motomeko 1-8 Ru aqueous sodium carbonate der.

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