JP6541464B2 - Method of producing toner particles - Google Patents

Description

  The present invention relates to a toner for visualizing an electrostatic charge image in an image forming method such as electrophotography, electrostatic printing, magnetic recording, and a method of producing toner particles.

  In recent years, as a method of producing toner particles, a proposal regarding a wet toner such as a suspension polymerization method using a polymerizable monomer or the like, an emulsion polymerization / aggregation method, a dissolution suspension method of granulating a binder resin or the like in a solvent Is actively conducted.

  For example, in the suspension polymerization method, the polymerizable monomer, colorant, mold release agent and polymerization initiator, and if necessary, crosslinking agent, charge control agent and other additives are uniformly dissolved or dispersed to be polymerizable. Let it be a monomer composition. The resultant is dispersed in an aqueous medium containing a dispersion stabilizer using a suitable stirrer to polymerize the polymerizable monomer to obtain a suspension of toner particles having a desired particle size.

  In the production of toner by the above-mentioned suspension polymerization method, the polymerization step is usually carried out using a polymerization vessel having stirring means and heating and cooling means, but during polymerization the polymer is formed on the inner wall of the vessel, the surface of stirring means, baffle plate surface etc When the composition adheres, it polymerizes in situ to form a scale (adhesion). The scale remains in the polymerization vessel even after completion of the polymerization process. When this scale is left to stand, its amount increases with the number of polymerization process batches, which lowers the heat transfer performance of the polymerization vessel and adversely affects the stability of the polymerization reaction. Furthermore, the time required for raising the polymerization temperature and for cooling after completion of the polymerization increases with the growth of the scale, which significantly reduces the productivity. The jacket area ratio to the vessel volume decreases as the vessel volume increases, so the larger the vessel volume, the greater the effect of the reduction in heat transfer performance. Therefore, problems such as (1) deterioration in the stability of the polymerization reaction and (2) increase in the time required for temperature rise and cooling become significant as the container volume increases. It is an important issue of In addition, when the scale peels off and falls off and is mixed with the product toner, it is observed as irregular-shaped coarse particles. When the proportion of irregular coarse particles in the toner increases, toner characteristics such as triboelectricity and development characteristics in image evaluation are adversely affected, and fluctuations in image density, generation of white streaks and fogging are observed. It is not preferable because it causes deterioration of properties.

  If the scale grows to a sufficient size and then peels off / drops off, it causes clogging or sticking in the piping part or 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.

  The above suspension polymerization method is different from the above suspension polymerization method in that the toner particle composition such as a binder resin, a colorant, a releasing agent and other additives is a volatile solvent such as a low boiling point organic solvent. Dispersion and dissolution to obtain a toner particle composition. Next, the toner particle composition is granulated in an aqueous medium in which a dispersant is present, and after being formed into droplets, the volatile solvent is removed. In the dissolution and suspension method, the solvent removal step causes the scale of the toner particle composition to grow on the inner wall of the container similarly to the polymerization step of the above-mentioned suspension polymerization method, thereby deteriorating the thermal conductivity of the container, Reduce productivity.

  As a method of preventing such a scale, for example, in Patent Document 1, 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 container to form a scale preventing coating film. Methods for forming have been proposed.

  Patent Document 2 discloses a method for preventing adhesion of polymer scale by applying a scale inhibitor containing a condensation reaction product of an aldehyde compound and a hydroxynaphthalin compound and a vinylphenol polymer to the inner wall of the container. ing.

  In addition, in Patent Document 3, as a method for preventing scale to the gas phase portion and the gas-liquid interface in the container, an aqueous dispersion medium containing water or a dispersion stabilizer is dispersed on the inner wall of the gas phase portion in the polymerization container during polymerization. A method has been proposed.

  Furthermore, according to Patent Document 4, dispersion of the aqueous dispersion medium containing the dispersion stabilizer on the inner wall of the container, and the dispersion medium of the polymerizable monomer composition containing the dispersion stabilizer separately prepared There is disclosed a way to prevent the scale by simultaneously charging the mixed preparation into the container.

  On the other hand, methods for efficiently removing scale deposits that have been generated are also known. For example, a method in which a removal agent such as an organic solvent or an aqueous alkaline solution is sprayed into the polymerization vessel, or a method in which the polymerization vessel is filled with heating and stirring in combination is simple and general. However, all of these methods aim to ensure that the scale is dissolved or swollen in the liquid, and it takes a somewhat long time to remove all the deposits.

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

  Although the means of the said patent documents 1-4 aim at adhesion | attachment suppression by raising the repulsion of an inorganic dispersed powder or a scale inhibiting agent, and a dispersed droplet, in examination of an applicant, with these methods, these methods are carried out. Although certain effects can be obtained, there is room for improvement in the case of continuous production.

  There is also a need for a method that can remove scale in a short time.

  An object of the present invention is to provide a method for producing toner particles in which the problems as described above are solved.

  That is, according to the present invention, in the method for producing toner particles by the suspension polymerization method and the dissolution suspension method, in the polymerization step of polymerizing the dispersed droplets of the polymerizable monomer composition, or the dispersion liquid of the toner particle composition The purpose of the present invention is to provide a method for producing toner particles capable of suppressing the generation of scale deposits on the inner wall of a container and easily removing the generated scale deposits in a solvent removing step of removing solvent from droplets. Do.

  The inventors of the present invention have found out the following methods as a result of intensive studies on suppression of generation of the polymer scale during the polymerization process or generation of the toner composition scale during the solvent removal process, and removal thereof.

The present invention has the following (a) or (b):
(A) A granulating step of dispersing a polymerizable monomer composition containing a polymerizable monomer and a colorant in an aqueous medium to form particles of the polymerizable monomer composition, and the polymerizability A method of producing toner particles, including a polymerization step of polymerizing the polymerizable monomer present in the particles of the monomer composition,
(B) Granulation in which a mixed solution of a toner particle composition containing a binder resin and a colorant and an organic solvent for dissolving the binder resin is dispersed in an aqueous medium to form particles of the mixed solution A method of producing toner particles comprising the steps of: and removing the organic solvent present in the particles of the mixed solution.
A method of producing toner particles, comprising producing toner particles by the method of
Vessel used in the polymerization process in the manufacturing method of the (a), or
The inner wall of the container used in the solvent removal step in the manufacturing method of the (b), after the liquid A containing a poorly water-soluble inorganic compound and a water-soluble inorganic salt is applied, the water-soluble inorganic salt to liquid A dried Deposit, then
In the method (a), the polymerization step,
There lines the solvent removal step in the method of the (b),
The poorly water-soluble inorganic compound is a poorly water-soluble metal salt of phosphoric acid,
In liquid A, the concentration of the water-soluble inorganic salt and B (mass%), when the concentration of the flame-soluble inorganic compound was C (wt%), B and C is represented by the following formula (1) And (2) relationship :
1.3 ≦ B / C ≦ 2.3 Formula (1)
7.0 ≦ C ≦ 15.0 Formula (2)
Is a method for producing toner particles.

  (A) A granulating step of dispersing a polymerizable monomer composition containing a polymerizable monomer and a colorant in an aqueous medium to form particles of the polymerizable monomer composition, and the polymerizability And a polymerization step of polymerizing the polymerizable monomer present in the particles of the monomer composition.

  (B) Granulation in which a mixed solution of a toner particle composition containing a binder resin and a colorant and an organic solvent for dissolving the binder resin is dispersed in an aqueous medium to form particles of the mixed solution The present invention relates to a method for producing toner particles, which comprises the steps of: and removing the organic solvent present in the particles of the mixed solution.

  According to the present invention, it is possible to provide a method for producing toner particles capable of suppressing the generation of scale deposits on the inner wall of a container and easily removing the generated scale deposits.

FIG. 2 is a cross-sectional view of a preferred container of the present invention used in the polymerization step or the solvent removal step.

  The present invention comprises a granulating step of dispersing (a) a polymerizable monomer composition containing a polymerizable monomer and a colorant in an aqueous medium to form particles of the polymerizable monomer composition A method for producing toner particles comprising the step of polymerizing the polymerizable monomer present in the particles of the polymerizable monomer composition, or (b) containing a binder resin and a colorant A granulating step of dispersing a mixed solution of a toner particle composition and an organic solvent for dissolving the binder resin in an aqueous medium to form particles of the mixed solution, and in the particles of the mixed solution And C. removing the organic solvent present. The production method of (a) is a so-called suspension polymerization method, and the production method of (b) is a so-called dissolution suspension method.

  Hereinafter, a method of producing a toner by a suspension polymerization method will be described.

<Step of Preparing Polymerizable Monomer Composition>
A polymerizable monomer composition comprising at least a polymerizable monomer and a colorant is prepared. The colorant may be dispersed in advance in a part of the polymerizable monomers and then mixed with the remaining polymerizable monomers and the like. Alternatively, all the components may be mixed simultaneously to prepare a polymerizable monomer composition.

Granulation process
The polymerizable monomer composition is charged into an aqueous medium containing a dispersion stabilizer, dispersed, granulated, and particles of the polymerizable monomer composition are formed in the aqueous medium. In the granulation step, for example, a vertical stirring tank provided with a stirrer having high shear force can be used. As a stirrer having high shear force, a high shear mixer (manufactured by IKA), T.K. K. Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), T.K. K. A commercially available product such as Philmix (manufactured by Tokushu Kika Kogyo Co., Ltd.) or Creamix (manufactured by Em Technic Co., Ltd.) can be used.

  As a dispersion stabilizer, for example, carbonates such as barium carbonate, calcium carbonate, magnesium carbonate and the like; aluminum phosphate, magnesium phosphate, calcium phosphate, calcium phosphate, barium phosphate, metal phosphate such as zinc phosphate; barium sulfate, calcium sulfate And the like; sulfates such as calcium hydroxide, aluminum hydroxide, magnesium hydroxide, ferric hydroxide metal hydroxides, and the like. These can be used alone or in combination of two or more. These function as dispersion stabilizers by being present as fine particles in an aqueous medium.

<Polymerization process>
By polymerizing the polymerizable monomer in the dispersion of the particles of the polymerizable monomer composition obtained in the granulation step, a dispersion of polymer microparticles is obtained. In the polymerization step in the present invention, a general polymerization vessel which has a stirring means and can be temperature-controlled can be used.

  The polymerization temperature is 40 ° C. or higher, generally 50 to 90 ° C. The polymerization temperature may be constant throughout, but the temperature may be raised in the latter half of the polymerization step for the purpose of obtaining a desired molecular weight distribution. The stirring means used for the polymerization vessel may be any means capable of suspending the dispersed polymerizable monomer composition without retaining it and keeping the temperature in the tank 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, three receding blades, a propeller blade, a disc turbine blade, a helical ribbon blade, an anchor blade, a full zone Made by Tech Co., Ltd., Twin Star (made by Shinko Pantech Co., Ltd.), Max Blend (made by Sumitomo Heavy Industries, Ltd.), Supermix (made by Satake Chemical Machinery Industries), Hi-F mixer (made by Soken Chemical Co., Ltd.) and the like.

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

  In FIG. 1, 1 is a container, 2 is a stirring blade, 3 is a baffle plate, 4 is a stirring motor, 5 is a gas-liquid interface, 6 is a temperature control jacket, 7 is a polymerization container thermometer, and 8 is a jacket thermometer , 9 is a container discharge valve, 10 is a shower nozzle, and 11 is a liquid A supply line.

  It is important to apply a liquid containing a water-soluble inorganic salt and a hardly water-soluble inorganic compound (hereinafter referred to as “liquid A”) on the inner wall surface of the container 1 before performing the polymerization step. The application of the liquid A to the inner wall of the container may be applied to the area in contact with the medium introduced into the container, but is preferably applied to the entire inner wall. However, only a part (for example, the bottom) may be used.

  The method of applying the liquid A to the inner wall of the container 1 may be any method as long as the liquid A can be uniformly applied, for example, spraying using a shower nozzle or a spray nozzle, filling the container with the liquid A and discharging it, printing The method of painting with etc. is mentioned.

  After applying the liquid A, it is preferable to heat or dry it. Thereby, the viscosity of the liquid A is increased, the adhesion of the poorly water-soluble inorganic compound to the inner wall of the container 1 in the liquid A is increased, and the adhesion suppressing effect is enhanced.

  Further, it is preferable to heat or dry the liquid A to reduce the moisture content of the liquid A, and to precipitate the water-soluble inorganic salt on the application surface of the liquid A applied to the inner wall of the container. When the water-soluble inorganic salt is not dissolved in the liquid A, when the liquid A is dried, the poorly water-soluble inorganic compounds mutually repel each other due to electrostatic repulsion, and thus the adhesion preventing layer having many voids Become. On the other hand, when the water-soluble inorganic salt is dissolved in the liquid A, the water-soluble inorganic salt is precipitated and disposed in the gaps of the poorly water-soluble inorganic compound, and therefore the poorly water-soluble inorganic compound and the water solubility are small. An anti-adhesion layer of the mixed crystal of the inorganic salt is formed. As the number of voids in the anti-adhesion layer increases, the deposit enters the voids, and the adhesion preventing effect is reduced. In that respect, the anti-adhesion layer proposed in the present invention containing the poorly water-soluble inorganic compound and the precipitated water-soluble inorganic salt has a very high adhesion prevention effect because it has fewer voids than in the prior art.

  Furthermore, on the surface of the antiadhesive layer containing the poorly water-soluble inorganic compound and the precipitated water-soluble inorganic salt, the water-soluble inorganic salt gradually dissolves in water during the polymerization. Therefore, since the vicinity of the surface in contact with water is structurally brittle, the poorly water-soluble inorganic compound is also gradually peeled off from the surface during stirring. That is, since a novel antiadhesive layer always appears during polymerization, even if adhesion is generated on the antiadhesive layer, the dissolution of the water-soluble inorganic substance on the surface of the antiadhesive layer and the peeling of the hardly water-soluble inorganic compound occur. Since the deposit is also removed, the adhesion suppressing effect does not decrease, and the very excellent adhesion suppressing effect is exhibited.

  Although the method of drying the applied liquid A is not particularly limited, it is effective to heat and dry the inner wall of the container 1 by using the jacket 6 for temperature control as in the apparatus shown in FIG. . Further, for the stirring device 2 without the jacket and the baffle 3, a method by blowing dry air or warm air is effective.

  The polymerizable monomer composition dispersion obtained in the granulation step is introduced into the container 1 in which the poorly water-soluble inorganic compound and the precipitated water-soluble inorganic salt have been coated with a small amount of voids, and the polymerization step is performed. The adhesion of the polymer scale to the inner wall of the container 1 is suppressed by the repulsion between the inorganic dispersion stabilizer covering the droplets of the polymerizable monomer composition and the hardly water-soluble inorganic compound on the inner wall surface of the container 1 it can. Also, even if adhesion is generated on the adhesion prevention layer during polymerization, the water-soluble inorganic salt on the surface of the adhesion prevention layer is dissolved as described above and adhesion is removed together with the adhesion prevention layer, and a new adhesion prevention layer always appears The effect does not decrease.

Assuming that the concentration of the water-soluble inorganic salt in the liquid A is B (mass%) and the concentration of the poorly water-soluble inorganic compound is C (mass%), B and C have a relationship of the following formulas (1) and (2) It is preferable to satisfy
1.3 ≦ B / C ≦ 2.3 Formula (1)
7.0 ≦ C ≦ 15.0 Formula (2)
When B / C is less than 1.3, the deposition ratio of the water-soluble inorganic salt in the antiadhesive layer containing the poorly water-soluble inorganic compound and the precipitated water-soluble inorganic salt is insufficient. Therefore, even if the water-soluble inorganic salt of the antiadhesive layer dissolves during polymerization, the strength of the antiadhesive layer is structurally not sufficiently lowered, so the poorly water-soluble inorganic compound is difficult to peel off, and the antiadhesive effect is , Not enough.

  When B / C is larger than 2.3, the deposition ratio of the water-soluble inorganic salt in the antiadhesive layer containing the poorly water-soluble inorganic compound and the precipitated water-soluble inorganic salt becomes too high. Therefore, the adhesion prevention layer becomes brittle with the dissolution of the water-soluble inorganic salt during polymerization, and the adhesion prevention layer is partially peeled off or the surface of the container itself is exposed before the polymerization is completed. The effect is not enough.

  When the concentration of the poorly water-soluble inorganic compound (C) is less than 7.0% by mass, the poorly water-soluble inorganic compounds are separated from each other, and the repulsive force between the poorly water-soluble inorganic compounds becomes weak. Therefore, when the water-soluble inorganic salt is added, the repelling effect of the charge double layer of the poorly water-soluble inorganic compound is canceled out, the poorly water-soluble inorganic compound is easily aggregated, and the adhesion preventing effect as the poorly water-soluble inorganic compound is reduced. It is not preferable because it

  When the concentration of the poorly water-soluble inorganic compound (C) is more than 15.0% by mass, the viscosity of the liquid (A) is large, uniform application to the inner wall of the container is difficult, application unevenness easily occurs, and the unevenness is large. Is not preferable because the adhesion preventing effect is reduced.

  As the liquid component (medium) in the liquid A, those in which the poorly water-soluble inorganic compound is insoluble and the solubility of the water-soluble inorganic salt is large are preferable, and water is particularly preferable. In addition, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, i-butyl alcohol, t-butyl alcohol etc. can be added to water as long as the solubility of the water-soluble inorganic salt is not affected. The following alcohols may be added.

  As the poorly water-soluble inorganic compound contained in the liquid A, a hardly water-soluble metal salt such as aluminum phosphate, magnesium phosphate, calcium phosphate, barium phosphate, zinc phosphate, etc. Poorly water-soluble metal hydroxides such as calcium hydroxide, aluminum hydroxide, magnesium hydroxide and ferric hydroxide; and hardly water-soluble metal carbonates such as barium carbonate, calcium carbonate and magnesium carbonate.

  The water-soluble inorganic salt contained in the liquid A preferably has high solubility in water and is easily soluble. Specifically, metal chlorides such as potassium chloride, sodium chloride, calcium chloride and magnesium chloride; metal hydroxides such as potassium hydroxide and sodium hydroxide; carbonates such as potassium carbonate and sodium carbonate; sodium hydrogen phosphate And phosphates such as sodium dihydrogen phosphate; and the like. Among the above-exemplified compounds, metal chlorides such as potassium chloride, sodium chloride, calcium chloride, magnesium chloride and the like having little change in pH when the water-soluble inorganic salt is dissolved in the liquid A are preferable.

  It is preferable that the above-described inner wall surface of the container, the stirring blade, the baffle plate and the like liquid contact portion be made of glass lining. This is because the silicon present on the surface of the glass lining and the sparingly water-soluble inorganic compound in the liquid A cause a structural electrical interaction, thereby strengthening the fixing effect.

<Distillation process>
If necessary, in order to remove volatile impurities such as unreacted polymerizable monomers and byproducts, a part of the aqueous medium may be distilled off by a distillation process after completion of the polymerization. The distillation step can be carried out at normal pressure or under reduced pressure.

<Washing process, solid-liquid separation process and drying process>
The polymer particle dispersion can also be treated with acid or alkali for the purpose of removing the dispersion stabilizer attached to the polymer particle surface. After this, the polymer particles are separated from the liquid phase by a general solid-liquid separation method, but water is added again to completely remove the acid or alkali and the dispersion stabilizer component dissolved therein. Wash. This washing step is repeated several times, and after sufficient washing, solid-liquid separation is again carried out to obtain toner particles. The obtained toner particles are dried by known drying means, if necessary.

<Classification process>
The toner particles thus obtained have a sufficiently sharp particle size as compared with the conventional pulverized toner, but if a sharper particle size is required, it is desirable to perform classification using an air classifier or the like. It is also possible to separate and remove particles that deviate from the particle size distribution of.

  Next, an example in which the present invention is used in a method for producing a toner by a dissolution suspension method will be described.

<Toner particle composition preparation process>
As a method of preparing a toner particle mixture in which a toner particle composition such as resin and colorant is dissolved or dispersed in an organic solvent, the resin, colorant and the like are gradually added while stirring in the organic solvent. , May be dissolved or dispersed. However, when using a pigment as a coloring agent, or adding a substance that is difficult to dissolve in an organic solvent, such as a mold release agent or a charge control agent, make the particles smaller before adding to the organic solvent. Is preferred. At the time of dispersion, a known disperser such as a bead mill or a disc mill can be used.

Granulation process
The toner particle composition obtained in the above step is dispersed in an aqueous medium containing at least a surfactant or an inorganic dispersion stabilizer to prepare a dispersion of the toner particle composition. When a modified resin having an isocyanate group at the end of the toner particle composition is added, an active hydrogen group-containing compound is added, and the active hydrogen group-containing compound can react with the active hydrogen group-containing compound in an aqueous medium. The dispersion liquid of the toner particle composition may be formed while the binder resin is produced by reacting a modified resin having such a site. As an apparatus used at a granulation process, it can carry out by the paddle type stirring tank which installed the stirrer which has high shear force like the suspension polymerization method mentioned above, for example. As a stirrer having high shear force, a high shear mixer (manufactured by IKA), T.K. K. Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), T.K. K. A commercially available product such as Philmix (manufactured by Tokushu Kika Kogyo Co., Ltd.) or Creamix (manufactured by Em Technic Co., Ltd.) can be used.

  As the surfactant, anionic surfactants such as alkyl benzene sulfonate, α-olefin sulfonate, phosphate ester, alkyl amine salt, amino alcohol fatty acid derivative, polyamine fatty acid derivative, amine salt type such as imidazoline, Alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, alkyl dimethyl benzyl ammonium salts, pyridinium salts, alkyl isoquinolinium salts, quaternary ammonium salt type cationic surfactants such as benzethonium chloride, fatty acid amide derivatives, polyhydric alcohols Nonionic surfactants such as derivatives, eg amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaines It is.

  As the inorganic dispersion stabilizer, for example, carbonates such as barium carbonate, calcium carbonate, magnesium carbonate etc .; aluminum phosphate, magnesium phosphate, calcium phosphate, calcium phosphate, barium phosphate, metal phosphates such as zinc phosphate; barium sulfate, sulfate Sulfates such as calcium; calcium hydroxide, aluminum hydroxide, magnesium hydroxide, metal hydroxides of ferric hydroxide; and the like can be mentioned.

<Solvent removal (solvent removal) process>
In order to remove the organic solvent from the obtained dispersion of the toner particle composition, a method of gradually raising the temperature while stirring the entire system to completely evaporate and remove the organic solvent in the droplets is adopted. it can. Alternatively, the dispersion of the toner particle composition may be depressurized with stirring to evaporate and remove the organic solvent.

Aging Process
When a modified resin having an isocyanate group at the end is added, a ripening step may be carried out in order to advance the isocyanate elongation / crosslinking reaction. The ripening time is usually 10 minutes to 40 hours, preferably 2 to 24 hours. The reaction temperature is usually 0 to 65 ° C, preferably 35 to 50 ° C.

  An example of a cross-sectional view of a container suitable for the present invention used in the desolvation step and the ripening step is shown in FIG. 1, but it is not limited thereto.

  The desolvation step and the ripening step may be carried out in the same vessel or in separate vessels. By applying a liquid (a liquid A) containing a poorly water-soluble inorganic compound and a water-soluble inorganic salt to the inner wall surface of the container 1 in advance, the inner wall of the container 1 is made of a mixed crystal of the poorly water-soluble inorganic compound and the water-soluble inorganic salt precipitated. Coated with the anti-adhesion layer. The method of applying the liquid A is the same as the method in the above-mentioned suspension polymerization method.

  Thereafter, the dispersion of the toner particle composition prepared in the granulation step is transferred into the container 1, and the desolvation step and the ripening step are performed under the conditions described above.

<Washing process, solid-liquid separation process, drying process and classification process>
About the above-mentioned process, the same operation as the method in the above-mentioned suspension polymerization method may be performed.

<Polymerizable monomer>
As a polymerizable monomer suitably used for the toner of the present invention, a vinyl-based polymerizable monomer capable of radical polymerization is used. As the vinyl-based polymerizable monomer, monofunctional or polyfunctional monomers can be used. Examples of monofunctional polymerizable monomers include the following.

  Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p- n-Hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, styrene derivatives such as p-phenylstyrene; methyl acrylate Ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-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 methyl methacrylate; methylene aliphatic monocarboxylic acid esters, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and vinyl formate such as vinyl formate; vinyl methyl ether, vinyl ethyl ether Vinyl ethers such as vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

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

  In the present invention, the above-described monofunctional polymerizable monomers are used alone or in combination of two or more, or the above-mentioned monofunctional polymerizable monomer and multifunctional polymerizable monomer are used in combination. . Among the above-mentioned monomers, it is preferable to use styrene or a styrene derivative alone or as a mixture, or a mixture thereof with other monomers from the viewpoint of the development characteristics and durability of the toner.

<Colorant>
The colorants preferably used in the present invention include the following organic pigments or dyes, and inorganic pigments.

  Copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds and basic dye lake compounds can be used as organic pigments or organic dyes as cyan colorants.

  Specifically, the following may be mentioned. C. I. Pigment blue 1, C.I. I. Pigment blue 7, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. Pigment blue 66. Examples of the organic pigment or organic dye as a magenta colorant include the following. Condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds.

  Specifically, the following may be mentioned. C. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment violet 19, C.I. I. Pigment red 23, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 150, C.I. I. Pigment red 166, C.I. I. Pigment red 169, C.I. I. Pigment red 177, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 254. As organic pigments or organic dyes as yellow-based colorants, compounds represented by condensation azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds and allylamide compounds are used.

  Specifically, the following may be mentioned. C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 176, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 181, C.I. I. Pigment yellow 191, C.I. I. Pigment yellow 194. As a black coloring agent, carbon black and those toned in black using the above-mentioned yellow-based / magenta-based / cyan-based coloring agent are used.

  These colorants can be used alone, in a mixture, or in the form of a solid solution. The colorant used in the toner of the present invention is selected in terms of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in the toner.

  The colorant is preferably used in an amount of 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin (or polymerizable monomer).

  In selecting a colorant, it is necessary to pay attention to the polymerization inhibition and the aqueous phase migration of the colorant. In particular, many dyes and carbon blacks have polymerization inhibitory properties, so care must be taken when used. Preferably, these should be subjected to surface modification, for example, hydrophobization treatment with a substance having no polymerization inhibition. As a method of surface-treating a dye, there is mentioned a method of polymerizing a polymerizable monomer in the presence of the dye in advance, and the obtained colored polymer is added to a raw material for toner such as a polymerizable monomer composition. . Furthermore, as for carbon black, in addition to the same treatment as the above-described dye, graft treatment may be performed with a substance that reacts with the surface functional group of carbon black, such as polyorganosiloxane.

<Release agent>
As the releasing agent used in the present invention, a wax in a solid state at room temperature may be sufficient in terms of the blocking resistance of the toner, the durability to many sheets, the low temperature fixing property and the offset resistance.

  The following may be mentioned as waxes. Paraffin wax, polyolefin wax, microcrystalline wax, polymethylene wax such as Fischer-Tropsch wax, amide wax, higher fatty acid, long chain alcohol, ester wax and graft compounds thereof, and block compounds thereof. It is preferable that these have low molecular weight components removed and that the maximum endothermic peak of the endothermic curve obtained by the differential scanning calorimeter be sharp. In order to improve the translucency of the image fixed on the OHP, in particular, a linear ester wax is suitably used. The linear ester wax is preferably contained in an amount of 1 to 40 parts by mass, more preferably 4 to 30 parts by mass, with respect to 100 parts by mass of the binder resin (or polymerizable monomer).

  In the present invention, a second release agent having a melting point of less than 80 ° C. can be used in combination in order to increase the plasticity of the toner particles and to improve the fixability in the low temperature range. As the second mold 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 wax of a montan derivative is preferably used. It is more preferable to previously remove impurities such as liquid fatty acid from these waxes.

<Charge control agent>
The toner produced by the present invention may contain a charge control agent. Known charge control agents can be used. For example, as what controls the toner to be negatively chargeable, the following can be mentioned. Organometallic compounds and chelate compounds are effective, and monoazo dye metal compounds, acetylacetone metal compounds, aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters and phenol derivatives such as bisphenol Kind. Further, the following may be mentioned. Urea derivatives, metal-containing salicylic acid compounds, quaternary ammonium salts, calixarenes, silicon compounds, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-acrylic-sulfonic acid copolymers, nonmetal carboxylic acids Compound.

  Examples of the toner that controls the toner to be positively charged include the following. Nigrosine and modified fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate; onium salts such as phosphonium salts and lakes of these pigments, tri Phenylmethane dyes and their lake pigments (as lakeing agents, phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, or ferrocyanide), higher fatty acids 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 preferably used in an amount of 0.01 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass, with respect to 100 parts by mass of the binder resin (or polymerizable monomer).

<Polymerization initiator>
As a polymerization initiator which can be used for this invention, there is an azo polymerization initiator. The following may be mentioned as the azo polymerization initiator. 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis -4-Methoxy-2,4-dimethyl valeronitrile, azobismethyl butyronitrile.

  Organic peroxide initiators can also be used. Examples of the organic peroxide initiator include the following. Benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, tert-butyl-peroxypivalate.

  In addition, 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 of persulfates (sodium salt, potassium salt, ammonium salt and the like), and oxidizing metal salts such as tetravalent cerium salt. As reducing substances, reducing metal salts (divalent iron salts, monovalent copper salts, trivalent chromium salts), ammonia, lower amines (amines having 1 to 6 carbon atoms such as methylamine and ethylamine), hydroxyl Amino compounds such as amines, sodium thiosulfate, sodium hydrosulfite, sodium bisulfite, sodium sulfite, reducing sulfur compounds such as sodium formaldehyde sulfoxylate, lower alcohols (having 1 to 6 carbon atoms), ascorbic acid or salts thereof, And lower aldehydes (C1-C6). The initiator is selected with reference to a 10-hour half-life temperature and used alone or in combination. The addition amount of the polymerization initiator varies depending on the target 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 crosslinking 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.

<Binder resin>
There is no restriction | limiting in particular as binder resin, It can select suitably from well-known things. Moreover, what is obtained by polymerizing said polymerizable monomer can be used. Specifically, for example, styrenes such as styrene and chlorostyrene; monoolefins such as ethylene, propylene, butylene and isoprene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate and vinyl butyrate; methyl acrylate Α-Methylene aliphatic monocarboxylic acid esters such as ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and dodecyl methacrylate; vinyl Vinyl ethers such as methyl ether, vinyl ethyl ether and vinyl butyl ether; homopolymers or copolymers of vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone, and the like.

As a polymer of the said styrene or its substituted thing, a polystyrene, poly p-chlorostyrene, polyvinyl toluene, etc. are mentioned, for example. Examples of the styrene-based copolymer include styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyl toluene copolymer, styrene-vinyl naphthalene copolymer, styrene-methyl acrylate copolymer Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene -Acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.

  Particularly representative binding resins include, for example, polystyrene resins, polyester resins, styrene-alkyl acrylate copolymers, styrene-alkyl methacrylate copolymers, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, styrene -A maleic anhydride copolymer, a polyethylene resin, a polypropylene resin etc. are mentioned. These may be used alone or in combination of two or more.

<Organic solvent>
The organic solvent used in the dissolution and suspension method of the present invention is preferably volatile having a boiling point of less than 100 ° C., from the viewpoint of facilitating the subsequent removal of the solvent. Examples of such an organic solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, Ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. When the resin to be dissolved or dispersed in an organic solvent is a resin having a polyester skeleton, an ester-based solvent such as methyl acetate, ethyl acetate or butyl acetate or a ketone-based solvent such as methyl ethyl ketone or methyl isobutyl ketone dissolves Among them, methyl acetate, ethyl acetate and methyl ethyl ketone are particularly preferable because of their high solvent removability.

<Modified resin added to organic solvent>
The modified resin (hereinafter sometimes referred to as "prepolymer") used in the dissolution and suspension method of the present invention is not particularly limited as long as it has at least a site capable of reacting with the active hydrogen group-containing compound. Instead, they can be appropriately selected from known resins and the like, and examples thereof include polyol resins, polyacrylic resins, polyester resins, epoxy resins, derivative resins thereof, and the like.

  These may be used alone or in combination of two or more. Among these, polyester resins are particularly preferable in terms of high fluidity and transparency at the time of melting.

  There is no restriction | limiting in particular as a site | part which can react with the active hydrogen group containing compound in the said prepolymer, Although it can select suitably from well-known substituents etc., For example, an isocyanate group, an epoxy group, carboxylic acid, an acid A chloride group etc. are mentioned.

  These may be contained singly or in combinations of two or more. Of these, isocyanate groups are particularly preferred.

<Active hydrogen group-containing compound>
The active hydrogen group-containing compound used in the dissolution and suspension method of the present invention is used as an extender, crosslinking agent, etc. when the modifying resin capable of reacting with the active hydrogen group-containing compound undergoes elongation reaction, crosslinking reaction, etc. in an aqueous medium. Works.

  The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected according to the purpose. For example, a polymer capable of reacting with the active hydrogen group-containing compound is the isocyanate group In the case of containing polyester prepolymers, amines are preferable in that they can be made to have high molecular weight by reaction with isocyanate group-containing polyester prepolymers such as extension reaction and crosslinking reaction.

  There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be used alone or in combination of two or more. Among these, alcoholic hydroxyl groups are particularly preferred.

<External additive>
In the production method of the present invention, an external additive can be used for the purpose of imparting various characteristics to the toner. The external additive preferably has a particle diameter of 1/10 or less of the average particle diameter of the toner particles from the viewpoint of durability when added to the toner. The external additives 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 silicon carbide carbide; calcium sulfate, barium sulfate, Inorganic metal salts such as calcium carbonate; fatty acid metal salts such as zinc stearate, calcium stearate; carbon black, silica.

  The external additive is used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, with respect to 100 parts by mass of toner particles. The external additive may be used alone or in combination of two or more, but it is more preferable to use a hydrophobic treatment.

<Magnetic material>
The manufacturing method of the present invention is also applicable to a method of manufacturing 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, magnetic materials contained in the magnetic toner include iron oxides such as magnetite, hematite and ferrite; metals such as iron, cobalt and nickel or these metals and aluminum, cobalt, lead, magnesium, tin and the like Alloys of metals such as zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium and mixtures thereof.

  As these magnetic materials, particles having a volume average particle diameter (Dv) of 0.5 μm or less, preferably about 0.1 to 0.5 μm are preferable.

  The volume average particle size (Dv) of the magnetic particles is a circle having a magnification of 10,000 to 40,000 and a projected area of 100 magnetic members in the field of view using a transmission electron microscope (TEM). The equivalent diameter is determined, and the volume average particle diameter is calculated based on it.

  The content of the magnetic self-proportion in the toner is 20 to 200 parts by mass with respect to 100 parts by mass of the polymerizable monomer, and particularly preferably 40 to 150 parts by mass with respect to 100 parts by mass of the polymerizable monomer. Good.

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

Hydrophobizing agent
It is also preferable to hydrophobize the surface of the magnetic material in order to improve the dispersibility of these magnetic materials in toner particles. Coupling agents such as silane coupling agents and titanium coupling agents are used in the hydrophobization treatment. Among them, 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, hydroxypropyl trimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane.

  The toner produced by the present invention can be used as either a one-component or two-component developer as described above.

  In the case of a magnetic toner in which a magnetic material is contained in toner as a one-component developer, a method of transporting or charging the magnetic toner using a magnet incorporated in a developing sleeve is used. When nonmagnetic toner containing no magnetic material is used, there is a method of using a blade and a fur brush to forcibly carry out frictional charging in the developing sleeve and adhere the toner on the sleeve.

  When the toner obtained by the production method of the present invention is used as a two-component developer, it is used as a developer together with the toner using a carrier. The carrier to be used in the present invention is not particularly limited, and is constituted in a single or complex ferrite state mainly composed of iron, copper, zinc, nickel, cobalt, manganese and chromium atoms.

  Carrier shape is also important from the viewpoint that saturation magnetization and electric resistance can be controlled in a wide range, and it is preferable to select, for example, spherical, flat, or amorphous, and further to control fine structure of carrier surface state, for example, surface unevenness. In general, a method of coating a resin after generating carrier core particles in advance by baking and granulating the above-mentioned metal compound is used. From the point of view of reducing the load of the carrier on the toner, after kneading the metal compound and the resin, pulverizing and classifying it to obtain a low density dispersed carrier, and further, directly kneading the metal compound and the polymerizable monomer It is also possible to use a method of suspension polymerization in an aqueous medium to obtain a spherically dispersed polymerization carrier.

  The particle size of the carrier was measured using a laser diffraction type particle size distribution measuring apparatus (Helloss <HELOS>) manufactured by Synpatec Co., Ltd. and equipped with a dry type dispersing machine (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.

  The mixing ratio of the carrier to the toner in the present invention when preparing a two-component developer is usually 2% to 15% by mass, preferably 4% to 13% by mass as the toner concentration in the developer. The result is obtained. If the toner concentration is less than 2% by mass, the image density is low and it becomes impractical to use. If it exceeds 15% by mass, fogging and scattering inside the machine are likely to increase, and image deterioration and developer consumption increase tend to occur.

  The measuring method of the physical property in this invention is described below.

<Method of measuring weight average particle diameter (D4), number average particle diameter (D1)>
The weight average particle diameter (D4) and the number average particle diameter (D1) of the toner are calculated as follows. As a measuring apparatus, a precise particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) having a 100 μm aperture tube and using a pore electrical resistance method is used. The setting of measurement conditions and the analysis of measurement data use the attached special software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.). The measurement is performed with 25,000 channels of effective measurement channels.

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

  In addition, before performing measurement and analysis, setting of dedicated software was performed as follows.

  In the "Change Standard Measurement Method (SOM)" screen of the special software, set the total count number in the control mode to 50000 particles, set the number of measurements once, and the Kd value "standard particle 10.0 μm" (Beckman Coulter Inc. Make the obtained value. The threshold and noise level are automatically set by pressing the "Threshold / noise level measurement button". Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check “Aperture tube flush after measurement”.

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

The specific measurement method is as follows.
1) Put about 200 ml of the electrolytic aqueous solution in a 250 ml round bottom beaker for Multisizer 3 only, set it on a sample stand, and stir the stirrer rod at 24 rotations / sec counterclockwise. Then, dirt and air bubbles in the aperture tube are removed by the "aperture flush" function of special software.
2) Put about 30 ml of the electrolytic aqueous solution into a 100 ml flat bottom beaker made of glass. Among them, “contaminone N” (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH 7 precision measuring instrument cleaning consisting of organic builders as a dispersing agent, Wako Pure Chemical Industries, Ltd. Add about 0.3 ml of a diluted solution obtained by diluting about 3 times by mass with deionized water.
3) Two oscillators with an oscillation frequency of 50 kHz are incorporated 180 degrees out of phase, and an ultrasonic dispersator "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios Co., Ltd.) having an electrical output of 120 W is prepared. About 3.3 liters of ion exchange 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) Place the beaker of 2) into the beaker fixing hole of the ultrasonic disperser, and operate the ultrasonic disperser. Then, the height position of the beaker is adjusted so that the resonance state of the liquid surface of the electrolytic aqueous solution in the beaker is maximized.
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 little by little to the electrolytic aqueous solution and dispersed. Then, ultrasonic dispersion processing is continued for another 60 seconds. In addition, in ultrasonic dispersion, the water temperature of the water tank is appropriately adjusted so as to be 10 ° C. or more and 40 ° C. or less.
6) In the round bottom beaker of the above 1) placed in the sample stand, the electrolyte aqueous solution of the above 5) in which the toner is dispersed using a pipette is dropped to adjust the measurement concentration to about 5%. Then, measurement is performed until the number of measurement particles reaches 50,000.
7) Analyze the measured data with the dedicated software attached to the device to calculate the weight average particle size (D4) and the number average particle size (D1). The "average diameter" on the "Analytical / volume statistics (arithmetic mean)" screen is the weight average particle size (D4) when the graph / volume% is set in the special software, and the graph / number% in the special software The “average diameter” on the “Analysis / number statistics (arithmetic mean)” screen when setting “1” is the number average particle diameter (D1).

EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but these do not limit the present invention at all. Examples 8 and 12 to 17 are reference examples.

Example 1
(Preparation of Liquid A)
As a poorly water-soluble inorganic compound, a commercially available 10.0 mass% calcium phosphate colloid solution (manufactured by Taihei Kagaku Sangyo: TCP-10U pH: 7.5) was adjusted to a concentration of 30.0 mass% using a decanter centrifugal settler. Next, calcium chloride (dihydrate, manufactured by Kishida Chemical: special grade) and ion-exchanged water are added as a water-soluble inorganic salt to a 30.0 mass% calcium phosphate colloidal solution, the calcium phosphate concentration is 10.0 mass%, the water-soluble inorganic The liquid A was adjusted so that the relationship between the salt concentration (B) mass% and the hardly water-soluble inorganic compound concentration (C) was 1.7. Thereafter, while uniformly stirring, the temperature was raised to 60 ° C. to obtain a liquid A. The pH of liquid A was measured, and it remained at 7.5.

(Application of liquid A)
After raising the temperature inside the jacket 6 to 60 ° C in advance, 40 kg of liquid A is shown in FIG. The liquid A was supplied from the liquid A supply line 14 of 1 into the interior of the container 1, and the entire inner wall of the container 1 was contacted and coated. After that, the inner wall of the container 1 was dried for 1 hour by heat transfer from the jacket 6, and calcium phosphate was fixed inside the container 1 while precipitating the water-soluble inorganic salt in the liquid A.

(Production of Toner Particles 1)
Toner particles 1 were produced by the following procedure. The materials were prepared at the following ratios such that the total amount of the aqueous medium and the polymerizable monomer composition was 500 kg.

(Preparation of aqueous medium)
To 330 parts by mass of ion-exchanged water, 5.0 parts by mass of Na ₃ PO _{4 and} 2.0 parts by mass of 10% hydrochloric acid are added, and stirring is performed at 3,000 s ⁻¹ using a high shear mixer (manufactured by IKA) While making the jacket 6 warm water flow, it was heated to 60.degree. An aqueous solution prepared by dissolving 3.0 parts by mass of CaCl _{2 in} 20 parts by mass of ion exchange water was added thereto to prepare a 0.6 mass% calcium phosphate aqueous medium having a pH of 5.2.

(Preparation of Polymerizable Monomer Composition)
The following materials were dissolved at 100 s ⁻¹ with a propeller stirrer to prepare a solution.
Styrene 75.0 parts by mass n-butyl acrylate 25.0 parts by mass Sulfonic acid group-containing resin (Acribase FCA-1001-NS, manufactured by Fujikura Kasei)
3.0 parts by mass styrene-methacrylic acid-methyl methacrylate-α-methylstyrene copolymer
20.0 parts by mass (Styrene / methacrylic acid / methyl methacrylate / α-methylstyrene = 80.85 / 2.50 / 1.65 / 15.0, Mp = 19,700, Mw = 7,900, TgB = 96 ° C, acid value = 12.0 mg KOH / g, Mw / Mn = 2.1)
Next, the following materials were added to the above solution.
C. I. Pigment red 122 8.0 parts by weight of a negative charge control agent (Bontron E-88, manufactured by Orient Chemical Co., Ltd.) 1.0 parts by weight of a hydrocarbon wax having a melting point of 77 ° C. (HNP-51, manufactured by Nippon Seiwa Co., Ltd.) 0 parts by mass The above mixture was heated to a temperature of 60 ° C., and then stirred at 9,000 s ⁻¹ with a TK homomixer (manufactured by Tokushu Kika Kogyo) for dissolution and dispersion.

  Into this, 9.0 parts by mass of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

(Granulation process)
The above polymerizable monomer composition is put into the above aqueous medium and stirred for 10 minutes at 3000 s ^-1 using a high shear mixer (manufactured by IKA) at a temperature of 60 ° C. to disperse the polymerizable monomer composition. I got a liquid.

(Polymerization process)
After completion of the granulation step, the dispersion liquid of the polymerizable monomer composition is continued to be temperature-controlled at 60 ° C. The mixture was transferred to container 1 of ¹ and stirring was started at 80 s ⁻¹ , and after raising the temperature to 70 ° C., reaction was performed at 70 ° C. for 5 hours. Subsequently, the temperature in the jacket 6 was set to 95 ° C., the temperature in the container 1 was raised to 85 ° C., and the reaction was further carried out at 80 ° C. for 5 hours to produce toner particles 1. At this time, the time required to raise the temperature from 70 ° C. to 85 ° C. was 50 minutes. After completion of the polymerization reaction, the slurry containing the toner particles 1 was cooled to 35 ° C. and transferred to the distillation step.

  As a result of visual observation of the inner wall of the container 1, it was confirmed that no scale deposits remained on the inner wall of the container 1, and the anti-adhesion layer consisting of the poorly water-soluble inorganic compound was slightly adhered to the entire inner surface of the container. The anti-adhesion layer is apparently thinner than before the polymerization, and it seems that it peeled off together with the dissolution of the water-soluble inorganic substance. In addition, it is considered that no adhesion was generated at all because the adhesion-preventing layer was gradually peeled off to always reveal a new adhesion-preventing layer.

  After repeating the above steps 10 batches using the container 1, when the inside of the container 1 was visually confirmed, no scale deposit was observed on the inner wall of the container 1 at all, and the scale deposit was growing. It was confirmed that there was not. In addition, the rate of increase in scale was determined from the time spent for raising the temperature from 70 ° C. to 85 ° C. for the first and tenth batches. The rail increase rate is described below. The results are shown in Table 1.

<Calculation method of scale increase rate>
In the polymerization step or the solvent removal step / aging step, the amount of increase in the time required for raising the temperature in the vessel along with the growth of scale deposits is calculated. After cleaning the inside of the container, the time required for temperature increase / decrease in temperature in the first batch polymerization step or solvent removal step / aging step is t1 in the same vessel, the nth batch polymerization step or solvent removal step / aging step The time required for the temperature rise / drop of temperature is taken as tn.

The rate of increase in scale is
Scale increase rate (%) = (tn−t1) / t1 × 100
Calculated by

  The larger the increase, the worse the adhesion is, which is not preferable because it causes a decrease in productivity and an adverse effect on quality. In particular, if the increase exceeds 30%, the productivity is greatly affected, which is not preferable. Furthermore, it is not preferable because it is a major cause of molecular weight fluctuation.

Example 2
(Preparation of Liquid A)
As a poorly water-soluble inorganic compound, a commercially available 10.0 mass% calcium phosphate colloid solution (manufactured by Taihei Kagaku Sangyo: TCP-10U pH: 7.5) was adjusted to a concentration of 30.0 mass% using a decanter centrifugal settler. Next, calcium chloride (dihydrate made by Kishda Chemical: special grade) and ion-exchanged water are added as a water-soluble inorganic salt to a 30.0 wt% calcium phosphate colloid solution, and the calcium phosphate concentration is 13.0 wt%, the water-soluble inorganic salt concentration The liquid A was adjusted so that the relationship between (B) mass% and the hardly water-soluble inorganic compound concentration (C) is 2.0. Thereafter, while uniformly stirring, the temperature was raised to 60 ° C. to obtain a liquid A. The pH of liquid A was measured, and it remained at 7.5.

  Production of toner particles 2 was performed in the same manner as in Example 1 except for the above.

  After repeating the above steps 10 batches using this container 1, when the inside of the container 1 was visually confirmed, no adhesion was generated on the inner wall of the container as in Example 1. The results are shown in Table 1.

Example 3
(Preparation of Liquid A)
As a poorly water-soluble inorganic compound, a commercially available 10.0 mass% calcium phosphate colloid solution (manufactured by Taihei Kagaku Sangyo: TCP-10U pH: 7.5) was adjusted to a concentration of 30.0 mass% using a decanter centrifugal settler. Next, calcium chloride (dihydrate, manufactured by Kishida Chemical Co., Ltd .: special grade) and ion-exchanged water are added as a water-soluble inorganic salt to a 30.0 mass% calcium phosphate colloid solution, the concentration of calcium phosphate is 7.0 mass%, water-soluble inorganic The liquid A was adjusted so that the relationship between the salt concentration (B) mass% and the hardly water-soluble inorganic compound concentration (C) was 1.3. Thereafter, while uniformly stirring, the temperature was raised to 60 ° C. to obtain a liquid A. The pH of liquid A was measured, and it remained at 7.5.

  Production of toner particles 3 was performed in the same manner as in Example 1 except for the above.

  After repeating the above steps 10 batches using this container 1, when the inside of the container 1 was visually confirmed, no adhesion was generated on the inner wall of the container as in Example 1. The results are shown in Table 1.

Example 4
(Preparation of Liquid A)
As a poorly water-soluble inorganic compound, a commercially available 10.0 mass% calcium phosphate colloid solution (manufactured by Taihei Kagaku Sangyo: TCP-10U pH: 7.5) was adjusted to a concentration of 30.0 mass% using a decanter centrifugal settler. Next, as a water soluble inorganic salt, calcium chloride (dihydrate made by Kishda Chemical: special grade) and ion exchange water are added to a 30.0 mass% calcium phosphate colloidal solution, and the calcium phosphate concentration is 15.0 mass%, water soluble inorganic The liquid A was adjusted so that the relationship between the salt concentration (B) mass% and the hardly water-soluble inorganic compound concentration (C) was 1.3. Thereafter, while uniformly stirring, the temperature was raised to 60 ° C. to obtain a liquid A. The pH of liquid A was measured, and it remained at 7.5.

  The toner particles 4 were produced in the same manner as in Example 1 except for the above.

  After repeating the above steps 10 batches using this container 1, when the inside of the container 1 was visually confirmed, no adhesion was generated on the inner wall of the container as in Example 1. The results are shown in Table 1.

Example 5
(Preparation of Liquid A)
As a poorly water-soluble inorganic compound, a commercially available 10.0 mass% calcium phosphate colloid solution (manufactured by Taihei Kagaku Sangyo: TCP-10U pH: 7.5) was adjusted to a concentration of 30.0 mass% using a decanter centrifugal settler. Next, calcium chloride (dihydrate, manufactured by Kishida Chemical Co., Ltd .: special grade) and ion-exchanged water are added as a water-soluble inorganic salt to a 30.0 mass% calcium phosphate colloid solution, the concentration of calcium phosphate is 7.0 mass%, water-soluble inorganic The liquid A was adjusted so that the relationship between the salt concentration (B) mass% and the hardly water-soluble inorganic compound concentration (C) is 2.3. Thereafter, while uniformly stirring, the temperature was raised to 60 ° C. to obtain a liquid A. The pH of liquid A was measured, and it remained at 7.5.

  The toner particles 5 were produced in the same manner as in Example 1 except for the above.

  After repeating the above steps 10 batches using this container 1, when the inside of the container 1 was visually confirmed, no adhesion was generated on the inner wall of the container as in Example 1. The results are shown in Table 1.

Example 6
(Preparation of Liquid A)
As a poorly water-soluble inorganic compound, a commercially available 10.0 mass% calcium phosphate colloid solution (manufactured by Taihei Kagaku Sangyo: TCP-10U pH: 7.5) was adjusted to a concentration of 30.0 mass% using a decanter centrifugal settler. Next, as a water soluble inorganic salt, calcium chloride (dihydrate made by Kishda Chemical: special grade) and ion exchange water are added to a 30.0 mass% calcium phosphate colloidal solution, and the calcium phosphate concentration is 15.0 mass%, water soluble inorganic The liquid A was adjusted so that the relationship between the salt concentration (B) mass% and the hardly water-soluble inorganic compound concentration (C) is 2.3. Thereafter, while uniformly stirring, the temperature was raised to 60 ° C. to obtain a liquid A. The pH of liquid A was measured, and it remained at 7.5.

  The toner particles 6 were produced in the same manner as in Example 1 except for the above.

  After repeating the above steps 10 batches using this container 1, when the inside of the container 1 was visually confirmed, no adhesion was generated on the inner wall of the container as in Example 1. The results are shown in Table 1.

Example 7
(Preparation of Liquid A)
As a poorly water-soluble inorganic compound, a commercially available 10.0 mass% calcium phosphate colloid solution (manufactured by Taihei Kagaku Sangyo: TCP-10U pH: 7.5) was adjusted to a concentration of 30.0 mass% using a decanter centrifugal settler. Then, add sodium dihydrogenphosphate (manufactured by Kishida Chemical Co., Ltd .: special grade) and ion-exchanged water as a water-soluble inorganic salt to a 30.0 mass% calcium phosphate colloid solution, and the calcium phosphate concentration is 7.0 mass%, a water-soluble inorganic salt The liquid A was adjusted so that the relationship between the concentration (B) mass% and the hardly water-soluble inorganic compound concentration (C) is 1.3. Thereafter, while uniformly stirring, the temperature was raised to 60 ° C. to obtain a liquid A. The pH of liquid A was measured and found to be 4.7.

  The toner particles 7 were produced in the same manner as in Example 1 except for the above.

  The above steps were repeated 10 batches using this container 1, and the inside of the container 1 was visually checked. As a result, it was confirmed that adhesion was partially generated on the inner wall of the container. The results are shown in Table 1.

Example 8
(Preparation of Liquid A)
An equivalent to Example 3 was made.

(Application of liquid A)
After the inside of the jacket 6 was heated up to 60 ° C. in advance, 40 kg of liquid A was supplied from the liquid A supply line 14 of FIG. 1 into the inside of the container 1 to contact the entire inner wall of the container 1 for coating. Thereafter, the granulation liquid was immediately received and polymerization was started.

  The toner particles 8 were produced in the same manner as in Example 3 except for the above.

  After repeating the above steps 10 batches using this container 1, when the inside of the container 1 was visually confirmed, it was confirmed that adhesion was generated on the entire inner wall of the container on the entire surface of the container. The results are shown in Table 1.

Example 9
(Preparation of Liquid A)
A thing equivalent to Example 4 was created.

(Application of liquid A)
After the inside of the jacket 6 was heated up to 60 ° C. in advance, 40 kg of liquid A was supplied from the liquid A supply line 14 of FIG. 1 into the inside of the container 1 to contact the entire inner wall of the container 1 for coating. Thereafter, the granulation liquid was immediately received and polymerization was started.

  The toner particles 9 were produced in the same manner as in Example 4 except for the above.

  After repeating the above steps 10 batches using this container 1, when the inside of the container 1 was visually confirmed, it was confirmed that adhesion was generated on the entire inner wall of the container on the entire surface of the container. The results are shown in Table 1.

Example 10
(Preparation of Liquid A)
An equivalent of Example 5 was made.

(Application of liquid A)
After the inside of the jacket 6 was heated up to 60 ° C. in advance, 40 kg of liquid A was supplied from the liquid A supply line 14 of FIG. 1 into the inside of the container 1 to contact the entire inner wall of the container 1 for coating. Thereafter, the granulation liquid was immediately received and polymerization was started.

  Production of toner particles 10 was performed in the same manner as in Example 5 except for the above.

  After repeating the above steps 10 batches using this container 1, when the inside of the container 1 was visually confirmed, it was confirmed that adhesion was generated on the entire inner wall of the container on the entire surface of the container. The results are shown in Table 1.

Example 11
(Preparation of Liquid A)
A thing equivalent to Example 6 was created.

(Application of liquid A)
After the inside of the jacket 6 was heated up to 60 ° C. in advance, 40 kg of liquid A was supplied from the liquid A supply line 14 of FIG. 1 into the inside of the container 1 to contact the entire inner wall of the container 1 for coating. Thereafter, the granulation liquid was immediately received and polymerization was started.

  The toner particles 11 were produced in the same manner as in Example 6 except for the above.

  After repeating the above steps 10 batches using this container 1, when the inside of the container 1 was visually confirmed, it was confirmed that adhesion was generated on the entire inner wall of the container on the entire surface of the container. The results are shown in Table 1.

Example 12
(Preparation of Liquid A)
As a poorly water-soluble inorganic compound, commercially available magnesium hydroxide (manufactured by Kamijima Chemical Industries, Ltd .: # 200) was diluted with ion exchange water to obtain a 30.0 mass% magnesium hydroxide colloidal solution (pH: 10.3). Next, as a water soluble inorganic salt, calcium chloride (dihydrate made by Kishida Chemical: special grade) and ion exchanged water are added to a 30.0 mass% magnesium hydroxide colloid solution, and the concentration of magnesium hydroxide is 7.0 mass%. The liquid A was adjusted so that the relationship between the water-soluble inorganic salt concentration (B) mass% and the hardly water-soluble inorganic compound concentration (C) is 1.3. Thereafter, while uniformly stirring, the temperature was raised to 40 ° C. to obtain a liquid A. When the pH of liquid A was measured, it remained at 10.3.

(Application of liquid A)
After the inside of the jacket 6 was heated up to 40 ° C. in advance, 40 kg of liquid A was supplied from the liquid A supply line 14 of FIG. 1 into the inside of the container 1, and the entire inner wall of the container 1 was contacted and coated. After that, the inner wall of the container 1 was dried for 1 hour by heat transfer from the jacket 6, and magnesium hydroxide was fixed inside the container 1 while depositing the water-soluble inorganic salt in the liquid A.

(Production of Toner Particles 12)
Toner particles 12 were produced by the following procedure. The materials were adjusted at the following ratios so that the total amount of the aqueous medium and the polymerizable monomer composition was 500 kg.

(Preparation of aqueous medium)
To 330 parts by mass of ion-exchanged water, 5.0 parts by mass of Na ₃ PO _{4 and} 2.0 parts by mass of 10% hydrochloric acid are added, and stirring is performed at 3,000 s ⁻¹ using a high shear mixer (manufactured by IKA) While making the jacket 6 warm water flow, it was heated to 60.degree. An aqueous solution prepared by dissolving 3.0 parts by mass of CaCl 2 in 20 parts by mass of ion exchanged water is added thereto, and after 30 minutes, a 48.5% by mass aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, Sanyo Chemical Industries, Ltd. 15 parts by mass of industrial product) and 30 parts by mass of ethyl acetate were added, and the liquid temperature was cooled to 40 ° C. to prepare an aqueous medium.

(Create master batch)
C. I. Pigment red 122 45 parts by mass · unmodified polyester resin A (SREL 0-005, manufactured by Sanyo Chemical Industries, Ltd.) 60 parts by mass The above materials are kneaded at 150 ° C. for 30 minutes using a two-roll mill, rolled and cooled and crushed by a pulperizer I got a masterbatch.

(Synthesis of Intermediate Polyester and Prepolymer)
-Bisphenol A ethylene oxide 2 mol adduct-682 parts by mass-Bisphenol A propylene oxide 2 mol adduct-81 parts by mass-Terephthalic acid 283 parts by mass-Trimellitic anhydride 22 parts by mass-Dibutyltin oxide 2 parts by mass It was put into a vessel, and reacted under normal pressure at 230 ° C. for 8 hours. Then, it was reacted at a reduced pressure of 10 to 15 mmHg for 5 hours to synthesize an intermediate polyester.

Then
Intermediate polyester 410 parts by mass Isophorone diisocyanate 89 parts by mass Ethyl acetate 500 parts by mass were added and reacted at 100 ° C. for 5 hours to synthesize a prepolymer.

(Synthesis of ketimine)
In a reaction vessel, 170 parts of isophorone diamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound.

(Preparation of wax dispersion)
Unmodified polyester resin (Sanyo Chemical Industries, Ltd., SREL 0-005) 100 parts by mass Paraffin wax (Nippon Seiwa Co., Ltd., HPE-11) 90 parts by mass Maleic acid-modified paraffin wax (manufactured by Chukyo Yushi Co., Ltd., P- 166) 10 parts by weight of ethyl acetate 400 parts by weight were stirred for 10 minutes using a propeller blade, dispersed, and dispersed for 8 hours using a Dyno mill to obtain a wax dispersion.

(Preparation of Toner Particle Composition)
150 parts by mass of masterbatch, 700 parts by mass of resin A (non-modified polyester resin A), 850 parts by mass of ethyl acetate are put into a container in which a stirring rod and a thermometer are set, and a TK homomixer (manufactured by Tokushu Kika Co., The mixture was mixed for 10 minutes at 9,000 rpm.

  Thereafter, while cooling the container, the rotational speed of the TK homomixer was set to 1,000 rpm, and the solution was stirred until the liquid temperature reached 40 ° C.

  After the liquid temperature reached 40 ° C., 200 parts of the wax dispersion was added while cooling the container, and mixing and stirring were performed while adjusting the number of rotations so that the liquid temperature did not exceed 45 ° C.

  Further, 194 parts by mass of prepolymer and 6 parts by mass of ketimine compound were added, and the mixture was stirred for 30 seconds at a rotational speed of 5,000 rpm to obtain a toner particle composition.

(Granulation)
The materials were adjusted at the following ratio so that the total amount of granulated slurry was 600 kg.

Aqueous medium: 60 parts of each of the toner composition mixed solution is charged into a container containing 140 parts by mass, and mixed for 10 minutes at 3,000 s ^-1 using a high shear mixer (manufactured by IKA) to disperse the toner particle composition I got a liquid.

(Desolvation, aging)
After completion of the granulation step, the dispersion of the toner particle composition was transferred to the container of FIG. 1 in which the temperature control was continued at 40 ° C., and stirring was started at 50 seconds ^-1 to remove the solvent for 10 hours. Subsequently, the temperature in the jacket was set to 90 ° C., the temperature in the container 1 was raised to 60 ° C., and aging was further performed at 60 ° C. for 5 hours to produce toner particles 12. At this time, the time required to raise the temperature from 40 ° C. to 60 ° C. was 30 minutes. After completion of the solvent removal / aging step, the slurry containing toner particles 12 was transferred to the next step.

  As a result of visual observation of the inner wall of the container 1, it was confirmed that no scale deposits remained on the inner wall of the container 1, and magnesium hydroxide, which is an inorganic dispersion stabilizer, was slightly adhered to the entire inner surface of the container. The layer of magnesium hydroxide is thinner than before the polymerization, and it seems to have come off in place with the dissolution of the water-soluble mineral. Also, it is considered that no adhesion was generated because the calcium phosphate layer peels off at a place, and a new anti-adhesion layer always appears.

  After repeating the above steps 10 batches using the container 1, when the inside of the container 1 was visually confirmed, no scale deposit was observed on the inner wall of the container 1 at all, and the scale deposit was growing. It was confirmed that there was not. Moreover, the scale increase rate was calculated | required from the time spent heating up from 40 degreeC to 60 degreeC of a 1st batch and a 10th batch. The results are shown in Table 1.

Example 13
(Preparation of Liquid A)
As a poorly water-soluble inorganic compound, commercially available magnesium hydroxide (manufactured by Kamijima Chemical Industries, Ltd .: # 200) was diluted with ion exchange water to obtain a 30.0 mass% magnesium hydroxide colloidal solution (pH: 10.3). Next, as a water soluble inorganic salt, calcium chloride (dihydrate: manufactured by Kishida Chemical Co., Ltd .: special grade) and ion exchanged water are added to a 30.0 mass% magnesium hydroxide colloid solution, and the concentration of magnesium hydroxide is 15.0 mass%. The liquid A was adjusted so that the relationship between the water-soluble inorganic salt concentration (B) mass% and the hardly water-soluble inorganic compound concentration (C) is 1.3. Thereafter, while uniformly stirring, the temperature was raised to 40 ° C. to obtain a liquid A. When the pH of liquid A was measured, it remained at 10.3.

  The toner particles 13 were produced in the same manner as in Example 12 except for the above.

  After repeating the above steps 10 batches using this container 1, when the inside of the container 1 was visually confirmed, no adhesion was generated on the inner wall of the container as in Example 12. The results are shown in Table 1.

Example 14
(Preparation of Liquid A)
As a poorly water-soluble inorganic compound, commercially available magnesium hydroxide (manufactured by Kamijima Chemical Industries, Ltd .: # 200) was diluted with ion exchange water to obtain a 30.0 mass% magnesium hydroxide colloidal solution (pH: 10.3). Next, as a water soluble inorganic salt, calcium chloride (dihydrate made by Kishida Chemical: special grade) and ion exchanged water are added to a 30.0 mass% magnesium hydroxide colloid solution, and the concentration of magnesium hydroxide is 7.0 mass%. The liquid A was adjusted so that the relationship between the water-soluble inorganic salt concentration (B) mass% and the hardly water-soluble inorganic compound concentration (C) is 2.3. Thereafter, while uniformly stirring, the temperature was raised to 40 ° C. to obtain a liquid A. When the pH of liquid A was measured, it remained at 10.3.

  The toner particles 14 were produced in the same manner as in Example 12 except for the above.

  After repeating the above steps 10 batches using this container 1, when the inside of the container 1 was visually confirmed, no adhesion was generated on the inner wall of the container as in Example 12. The results are shown in Table 1.

Example 15
(Preparation of Liquid A)
As a poorly water-soluble inorganic compound, commercially available magnesium hydroxide (manufactured by Kamijima Chemical Industries, Ltd .: # 200) was diluted with ion exchange water to obtain a 30.0 mass% magnesium hydroxide colloidal solution (pH: 10.3). Next, as a water soluble inorganic salt, calcium chloride (dihydrate: manufactured by Kishida Chemical Co., Ltd .: special grade) and ion exchanged water are added to a 30.0 mass% magnesium hydroxide colloid solution, and the concentration of magnesium hydroxide is 15.0 mass%. The liquid A was adjusted so that the relationship between the water-soluble inorganic salt concentration (B) mass% and the hardly water-soluble inorganic compound concentration (C) is 2.3. Thereafter, while uniformly stirring, the temperature was raised to 40 ° C. to obtain a liquid A. When the pH of liquid A was measured, it remained at 10.3.

  The toner particles 15 were produced in the same manner as in Example 12 except for the above.

  After repeating the above steps 10 batches using this container 1, when the inside of the container 1 was visually confirmed, no adhesion was generated on the inner wall of the container as in Example 12. The results are shown in Table 1.

Example 16
(Preparation of Liquid A)
As a poorly water-soluble inorganic compound, commercially available magnesium hydroxide (manufactured by Kamijima Chemical Industries, Ltd .: # 200) was diluted with ion exchange water to obtain a 30.0 mass% magnesium hydroxide colloidal solution (pH: 10.3). Subsequently, sodium dihydrogenphosphate (manufactured by Kishida Chemical Co., Ltd .: special grade) and ion-exchanged water are added as a water-soluble inorganic salt to a 30.0 mass% magnesium hydroxide colloid solution, and the concentration of magnesium hydroxide is 7.0 mass%, The liquid A was adjusted so that the relationship between the water-soluble inorganic salt concentration (B) mass% and the hardly water-soluble inorganic compound concentration (C) becomes 1.3. Thereafter, while uniformly stirring, the temperature was raised to 40 ° C. to obtain a liquid A. It was 9.5 when the pH of the liquid A was measured.

  The toner particles 16 were produced in the same manner as in Example 12 except for the above.

  The above steps were repeated 10 batches using this container 1, and the inside of the container 1 was visually checked. As a result, it was confirmed that adhesion was partially generated on the inner wall of the container. The results are shown in Table 1.

Example 17
(Preparation of Liquid A)
An equivalent of Example 12 was made.

(Application of liquid A)
After raising the temperature inside the jacket 6 to 40 ° C in advance, 40 kg of liquid A is shown in FIG. The liquid A was supplied from the liquid A supply line 14 of 1 into the interior of the container 1, and the entire inner wall of the container 1 was contacted and coated. After that, the granulation liquid was immediately received, and the solvent removal step was started.

  The toner particles 17 were produced in the same manner as in Example 12 except for the above.

  After repeating the above steps 10 batches using this container 1, when the inside of the container 1 was visually confirmed, it was confirmed that adhesion was generated on the entire inner wall of the container on the entire surface of the container. The results are shown in Table 1.

Comparative Example 1
(Preparation of Liquid A)
As a poorly water-soluble inorganic compound, a commercially available 10.0 mass% calcium phosphate colloid solution (manufactured by Taihei Kagaku Sangyo: TCP-10U pH: 7.5) was adjusted to a concentration of 30.0 mass% using a decanter centrifugal settler. Then, add sodium dihydrogenphosphate (manufactured by Kishida Chemical Co., Ltd .: special grade) and ion-exchanged water as a water-soluble inorganic salt to a 30.0 mass% calcium phosphate colloid solution, and the calcium phosphate concentration is 4.0 mass%, a water-soluble inorganic salt The liquid A was adjusted so that the relationship between the concentration (B) mass% and the hardly water-soluble inorganic compound concentration (C) was 1.0. Thereafter, while uniformly stirring, the temperature was raised to 60 ° C. to obtain a liquid A. The pH of liquid A was measured and found to be 4.7.

(Application of liquid A)
After the inside of the jacket 6 was heated up to 60 ° C. in advance, 40 kg of liquid A was supplied from the liquid A supply line 14 of FIG. 1 into the inside of the container 1 to contact the entire inner wall of the container 1 for coating. After that, the granulation liquid was immediately received and polymerization was started.

  The toner particles 18 were produced in the same manner as in Example 1 except for the above.

  After repeating the above steps 10 batches using this container 1, when the inside of the container 1 was visually confirmed, it was confirmed that adhesion was generated on the entire inner wall of the container. The results are shown in Table 1.

Comparative Example 2
(Preparation of Liquid A)
As a poorly water-soluble inorganic compound, a commercially available 10.0 mass% calcium phosphate colloid solution (manufactured by Taihei Kagaku Sangyo: TCP-10U pH: 7.5) was adjusted to a concentration of 30.0 mass% using a decanter centrifugal settler. Then, add sodium dihydrogenphosphate (manufactured by Kishida Chemical Co., Ltd .: special grade) and ion-exchanged water as a water-soluble inorganic salt to a 30.0 mass% calcium phosphate colloid solution, and the calcium phosphate concentration is 17.0 mass%, water-soluble inorganic salt The liquid A was adjusted so that the relationship between the concentration (B) mass% and the hardly water-soluble inorganic compound concentration (C) was 1.0. Thereafter, while uniformly stirring, the temperature was raised to 60 ° C. to obtain a liquid A. The pH of liquid A was measured and found to be 4.7.

  The toner particles 19 were produced in the same manner as in Comparative Example 1 except for the above.

  After repeating the above steps 10 batches using this container 1, when the inside of the container 1 was visually confirmed, it was confirmed that adhesion was generated on the entire inner wall of the container. The results are shown in Table 1.

Comparative Example 3
(Preparation of Liquid A)
As a poorly water-soluble inorganic compound, a commercially available 10.0 mass% calcium phosphate colloid solution (manufactured by Taihei Kagaku Sangyo: TCP-10U pH: 7.5) was adjusted to a concentration of 30.0 mass% using a decanter centrifugal settler. Then, add sodium dihydrogenphosphate (manufactured by Kishida Chemical Co., Ltd .: special grade) and ion-exchanged water as a water-soluble inorganic salt to a 30.0 mass% calcium phosphate colloid solution, and the calcium phosphate concentration is 4.0 mass%, a water-soluble inorganic salt The liquid A was adjusted so that the relationship between the concentration (B) mass% and the hardly water-soluble inorganic compound concentration (C) was 2.5. Thereafter, while uniformly stirring, the temperature was raised to 60 ° C. to obtain a liquid A. It was 4.5 when pH of liquid A was measured.

  The toner particles 20 were produced in the same manner as in Comparative Example 1 except for the above.

  After repeating the above steps 10 batches using this container 1, when the inside of the container 1 was visually confirmed, it was confirmed that adhesion was generated on the entire inner wall of the container. The results are shown in Table 1.

Comparative Example 4
(Preparation of Liquid A)
As a poorly water-soluble inorganic compound, a commercially available 10.0 mass% calcium phosphate colloid solution (manufactured by Taihei Kagaku Sangyo: TCP-10U pH: 7.5) was adjusted to a concentration of 30.0 mass% using a decanter centrifugal settler. Then, add sodium dihydrogenphosphate (manufactured by Kishida Chemical Co., Ltd .: special grade) and ion-exchanged water as a water-soluble inorganic salt to a 30.0 mass% calcium phosphate colloid solution, and the calcium phosphate concentration is 17.0 mass%, water-soluble inorganic salt The liquid A was adjusted so that the relationship between the concentration (B) mass% and the hardly water-soluble inorganic compound concentration (C) was 2.5. Thereafter, while uniformly stirring, the temperature was raised to 60 ° C. to obtain a liquid A. It was 4.5 when pH of liquid A was measured.

  The toner particles 21 were produced in the same manner as in Comparative Example 1 except for the above.

  After repeating the above steps 10 batches using this container 1, when the inside of the container 1 was visually confirmed, it was confirmed that adhesion was generated on the entire inner wall of the container. The results are shown in Table 1.

Comparative Example 5
(Preparation of Liquid A)
As a poorly water-soluble inorganic compound, commercially available magnesium hydroxide (manufactured by Kamijima Chemical Industries, Ltd .: # 200) was diluted with ion exchange water to obtain a 30.0 mass% magnesium hydroxide colloidal solution (pH: 10.3). Next, sodium dihydrogen phosphate (manufactured by Kishida Chemical Co., Ltd .: special grade) and ion exchange water are added as a water-soluble inorganic salt to a 30.0 mass% magnesium hydroxide colloid solution, and the magnesium hydroxide concentration is 4.0 mass%, The liquid A was adjusted so that the relationship between the water-soluble inorganic salt concentration (B) mass% and the hardly water-soluble inorganic compound concentration (C) would be 1.0. Thereafter, while uniformly stirring, the temperature was raised to 40 ° C. to obtain a liquid A. It was 8.9 when pH of liquid A was measured.

(Application of liquid A)
After raising the temperature inside the jacket 6 to 40 ° C in advance, 40 kg of liquid A is shown in FIG. The liquid A was supplied from the liquid A supply line 14 of 1 into the interior of the container 1, and the entire inner wall of the container 1 was contacted and coated. After that, the granulation liquid was immediately received, and the solvent removal step was started.

The toner particles 22 were produced by the same method as in Example 12 except for the above.
After repeating the above steps 10 batches using this container 1, when the inside of the container 1 was visually confirmed, it was confirmed that adhesion was generated on the entire inner wall of the container. The results are shown in Table 1.

Comparative Example 6
(Preparation of Liquid A)
As a poorly water-soluble inorganic compound, commercially available magnesium hydroxide (manufactured by Kamijima Chemical Industries, Ltd .: # 200) was diluted with ion exchange water to obtain a 30.0 mass% magnesium hydroxide colloidal solution (pH: 10.3). Next, sodium dihydrogen phosphate (manufactured by Kishida Chemical Co., Ltd .: special grade) and ion exchange water are added as a water-soluble inorganic salt to a 30.0 mass% magnesium hydroxide colloid solution, and the magnesium hydroxide concentration is 17.0 mass%, The liquid A was adjusted so that the relationship between the water-soluble inorganic salt concentration (B) mass% and the hardly water-soluble inorganic compound concentration (C) would be 1.0. Thereafter, while uniformly stirring, the temperature was raised to 40 ° C. to obtain a liquid A. It was 8.9 when pH of liquid A was measured.

  The toner particles 23 were produced in the same manner as in Comparative Example 5 except for the above.

  After repeating the above steps 10 batches using this container 1, when the inside of the container 1 was visually confirmed, it was confirmed that adhesion was generated on the entire inner wall of the container. The results are shown in Table 1.

Comparative Example 7
(Preparation of Liquid A)
As a poorly water-soluble inorganic compound, commercially available magnesium hydroxide (manufactured by Kamijima Chemical Industries, Ltd .: # 200) was diluted with ion exchange water to obtain a 30.0 mass% magnesium hydroxide colloidal solution (pH: 10.3). Next, sodium dihydrogen phosphate (manufactured by Kishida Chemical Co., Ltd .: special grade) and ion exchange water are added as a water-soluble inorganic salt to a 30.0 mass% magnesium hydroxide colloid solution, and the magnesium hydroxide concentration is 4.0 mass%, The liquid A was adjusted so that the relationship between the water-soluble inorganic salt concentration (B) mass% and the hardly water-soluble inorganic compound concentration (C) was 2.5. Thereafter, while uniformly stirring, the temperature was raised to 40 ° C. to obtain a liquid A. It was 8.1 when pH of liquid A was measured.

  Production of toner particles 24 was performed in the same manner as in Comparative Example 5 except for the above.

  After repeating the above steps 10 batches using this container 1, when the inside of the container 1 was visually confirmed, it was confirmed that adhesion was generated on the entire inner wall of the container. The results are shown in Table 1.

Comparative Example 8
(Preparation of Liquid A)
As a poorly water-soluble inorganic compound, commercially available magnesium hydroxide (manufactured by Kamijima Chemical Industries, Ltd .: # 200) was diluted with ion exchange water to obtain a 30.0 mass% magnesium hydroxide colloidal solution (pH: 10.3). Next, sodium dihydrogen phosphate (manufactured by Kishida Chemical Co., Ltd .: special grade) and ion exchange water are added as a water-soluble inorganic salt to a 30.0 mass% magnesium hydroxide colloid solution, and the magnesium hydroxide concentration is 17.0 mass%, The liquid A was adjusted so that the relationship between the water-soluble inorganic salt concentration (B) mass% and the hardly water-soluble inorganic compound concentration (C) was 2.5. Thereafter, while uniformly stirring, the temperature was raised to 40 ° C. to obtain a liquid A. It was 8.1 when pH of liquid A was measured.

  The toner particles 25 were produced in the same manner as in Comparative Example 5 except for the above.

  After repeating the above steps 10 batches using this container 1, when the inside of the container 1 was visually confirmed, it was confirmed that adhesion was generated on the entire inner wall of the container. The results are shown in Table 1.

Reference Signs List 1 container 2 stirring blade 3 baffle plate 4 stirring motor 5 air-liquid interface 6 jacket for temperature control 7 polymerization container thermometer 8 jacket thermometer 9 container discharge valve 10 shower nozzle 11 liquid A supply line

Claims (2)

Following (a) or (b) :
(A) A granulating step of dispersing a polymerizable monomer composition containing a polymerizable monomer and a colorant in an aqueous medium to form particles of the polymerizable monomer composition, and the polymerizability A method of producing toner particles, including a polymerization step of polymerizing the polymerizable monomer present in the particles of the monomer composition,
(B) Granulation in which a mixed solution of a toner particle composition containing a binder resin and a colorant and an organic solvent for dissolving the binder resin is dispersed in an aqueous medium to form particles of the mixed solution A method of producing toner particles comprising the steps of: and removing the organic solvent present in the particles of the mixed solution.
A method of producing toner particles, comprising producing toner particles by the method of
Vessel used in the polymerization process in the manufacturing method of the (a), or
The inner wall of the container used in the solvent removal step in the manufacturing method of the (b), after the liquid A containing a poorly water-soluble inorganic compound and a water-soluble inorganic salt is applied, the water-soluble inorganic salt to liquid A dried Deposit, then
In the method (a), the polymerization step or
There lines the solvent removal step in the method of the (b),
The poorly water-soluble inorganic compound is a poorly water-soluble metal salt of phosphoric acid,
In liquid A, the concentration of the water-soluble inorganic salt and B (mass%), when the concentration of the flame-soluble inorganic compound was C (wt%), B and C is represented by the following formula (1) And (2) relationship :
1.3 ≦ B / C ≦ 2.3 Formula (1)
7.0 ≦ C ≦ 15.0 Formula (2)
A method of producing toner particles, characterized in that The method for producing toner particles according to claim 1, wherein the water-soluble inorganic salt is calcium chloride or sodium dihydrogen phosphate.

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