KR101048325B1 - Manufacturing method of polymerized toner - Google Patents

Abstract

Agglomerates formed by mixing colloidal silica and polyvinyl-pyrrolidone as an aqueous dispersant during suspension polymerization are used, and agglomerates of polyvinylpyrrolidone and colloidal silica having a particle diameter of less than 100 nm are compared to the total aggregates. By adjusting to less than or equal to%, the volume average particle diameter (dv) of the toner produced by suspension polymerization is 5 to 10 µm and the volume average particle diameter (dv) / number average particle diameter (dp) is 1.5 or less and small particles having a size of less than 0.5 µm. Polymerized toner particles in which generation of (Emulsion Particle) is suppressed can be prepared.

Polymerized Toner, Aqueous Dispersion, Colloidal Silica, Polyvinylpyrrolidone

Description

Manufacturing Method of Polymerized Toner {Method of Producing Polymerized Toner}

The present invention relates to a method for preparing a polymerized toner, and more particularly, to a method for preparing a polymerized toner using an aqueous dispersion containing 1% or less of aggregates of polyvinylpyrrolidone and colloidal silica having a particle diameter of less than 100 nm. .

Toner is used in electrophotographic development, electrostatic printers, copiers, and the like, and refers to a paint that can be transferred to and fixed on a transfer object to form a desired pattern. Recently, as document creation using a computer is becoming more common, the demand for an image forming apparatus such as a printer is rapidly increasing, and thus the amount of toner is also increasing.

As a method of manufacturing the toner, there are a manufacturing method using pulverization and a manufacturing method using polymerization. The most widely known method of pulverization is a melt-mixing process in which resin and pigment are put together, melt-mixed or extruded, pulverized and classified to produce toner particles. However, the toner particles produced by this process have a problem of poor chargeability or flowability because the toner particles have a very irregular shape such as wide particle size distribution and pointed edges.

In order to solve this problem, a method of producing spherical toner particles by a polymerization method has been proposed. The polymerization method of toner by the polymerization method is known as emulsion polymerization / aggregation method and suspension polymerization method. Since emulsion polymerization method is difficult to control the size distribution of particles and there is a problem in the reproducibility of the quality of the produced toner, Processes by polymerization are preferred.

However, the toner particles formed by the suspension polymerization have a wide distribution of the particle size and partial aggregation of the particles during the polymerization reaction requires a separation process through centrifugation after the polymerization reaction, resulting in a decrease in yield.

In order to solve the above problem, the present invention provides a toner particle having a desirable volume average particle diameter and a narrow size distribution, and does not require partial agglomeration between the particles during the polymerization reaction, so that the centrifugation process is not necessary after the polymerization and the consumption amount is low during printing. It is an object to provide a method for producing particles.

According to the above object, the present invention provides a volume average particle diameter (dv) of 5 to 10 µm and a volume average particle diameter (dv) / number average particle diameter (dp) of 1.5 or less and a size of less than 0.5 µm of the toner produced by suspension polymerization. In order to suppress the formation of the particles of the present invention, there is provided a manufacturing method of a toner, wherein an aggregate formed by mixing colloidal silica and polyvinylpyrrolidone as an aqueous dispersant during suspension polymerization is used.

The present invention provides a toner manufacturing method comprising the following steps.
Dispersing polyvinylpyrrolidone and colloidal silica in an aqueous system, to prepare an aqueous dispersion comprising an aggregate of polyvinylpyrrolidone and colloidal silica having a particle diameter of less than 100 nm in an amount of 1 wt% or less relative to the total aggregate;
Preparing a monomer mixture;
Homogenizing the monomer mixture in the aqueous dispersion to disperse the monomer mixture in the form of fine droplets in the aqueous dispersion; And
Polymerizing the dispersed monomer mixture,

The preparing of the dispersion may include mixing the agglomerates of polyvinylpyrrolidone having a particle diameter of less than 100 nm with colloidal silica by high speed stirring at 11,000 rpm, and removing the supernatant after standing for 10 minutes. It is a manufacturing method of.

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The present invention Removing the aggregates of polyvinylpyrrolidone and colloidal silica of less than 100 nm, wherein the colloidal silica and polyvinylpyrrolidone are mixed under high-speed stirring and the supernatant is removed after a predetermined time period. It provides a method of manufacturing.

The present invention It provides a method for producing a toner, characterized in that the supernatant is 40 to 60 parts by weight based on 100 parts by weight of the total aqueous dispersion.

The present invention The colloidal silica has a volume average particle diameter (dv) of 10 to 30 nm and a volume average particle diameter (dv) / number average particle diameter (dp) of less than 1.5.

The present invention provides a method for producing a toner, wherein the polyvinylpyrrolidone has a molecular weight of 20,000 to 60,000.

The present invention provides a method for producing a toner, wherein the colloidal silica is added in an amount of 5 to 15 parts by weight based on the total monomers.

The present invention adds 1 to 3 parts by weight of the polyvinylpyrrolidone based on the total monomers. It provides a method for producing a toner, characterized in that.

The present invention provides a toner manufacturing method further comprising the step of removing the polyvinylpyrrolidone and colloidal silica.

The present invention provides a method for producing a toner, wherein the polyvinylpyrrolidone and colloidal silica are removed from the toner surface by adding 0.05 to 0.2 N aqueous NaOH solution.

The present invention is the monomer mixture of the aqueous dispersion About 100 parts by weight 1 to 60 parts by weight of the aqueous dispersion is mixed with the monomer mixture, the aromatic vinyl monomer is 30 to 95 parts by weight relative to the total monomers; 5 to 70 parts by weight of one or more monomers selected from the group consisting of acrylate monomers, methacrylate monomers and diene monomers based on the total monomers; 1 to 20 parts by weight of the pigment, based on the total monomers; 0.1 to 30 parts by weight, based on the total monomers of the wax; 0.001 to 10 parts by weight, based on the total monomers, of the crosslinking agent; 0.1 to 20 parts by weight, based on the total monomers, of the charge control agent; And 0.001 to 8 parts by weight of the molecular weight modifier based on the total monomers; It provides a method for producing a toner comprising a.

The present invention provides a method for producing a toner, wherein the monomer mixture further comprises 0.01 to 10 parts by weight based on the total monomers, at least one selected from polyester-based and styrene acrylic polar polymers.

The present invention provides a method for producing a toner, wherein the monomer mixture further comprises 0.1 to 30 parts by weight based on the total monomers of the acidic or basic olefinic monomers.

The present invention provides a method for producing a toner, characterized in that the aromatic vinyl monomer is selected from the group consisting of styrene, monochlorostyrene, methyl styrene, and dimethyl styrene.

The present invention is the acrylate monomer is selected from the group consisting of methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, and 2-ethylhexyl acrylate, methacrylate The monomer is selected from the group consisting of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, dodecyl methacrylate, and 2-ethylhexyl methacrylate. It provides a method for producing a toner, characterized in that is selected from the group consisting of butadiene and isoprene.

The present invention is a petroleum refined wax, wherein the wax comprises paraffin wax, microcrystalline wax, ceresin wax; Natural waxes, including carnuba wax; Or synthetic waxes including ester waxes, polyethylene waxes, and polypropylene waxes.

The present invention provides a method for producing a toner, wherein the molecular weight regulator is at least one selected from mercaptan compounds including t-dodecyl mercaptan and n-dodecyl mercaptan.

The present invention is an inorganic pigment comprising the metal powder pigment, metal oxide pigment, carbon pigment, sulfide pigment, chromium salt pigment, ferrocyanide pigment; Organic pigments including azo pigments, acid dye pigments, basic dye pigments, modal dye pigments, phthalocyanine pigments, quinacridone pigments, and dioxane pigments; Or a mixture thereof.

The present invention, the charge control agent is a cationic charge control agent comprising a high aliphatic metal salt, alkoxy amine, chelate, quaternary ammonium salt, alkylamide, fluorine treatment activator, metal salt of naphthalic acid; Anionic charge control agents comprising chlorinated paraffins, chlorinated polyesters, polyesters containing acids, sulfonylamines of copper phthalocyanine, and styrene-acrylic polymers including sulfonic acid groups; Or a mixture thereof.

In the present invention, the crosslinking agent is divinylbenzene, ethylene dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, 1,6-hexamethylene diacrylate, allyl methacrylate, 1,1, A method for producing a toner, which is selected from the group consisting of 1-trimethylolpropane triacrylate, triallylamine, and tetraallyloxy ethane.

The present invention provides a method for producing a toner, wherein the monomer mixture further comprises 0.01 to 5.00 parts by weight of the reaction initiator based on the total monomers.

The present invention An azo initiator including azobisisobutyronitrile and azobisvaleronitrile as the reaction initiator; Organic peroxides, including benzoyl peroxide, and lauroyl peroxide; And a water-soluble initiator containing potassium persulfate and ammonium persulfate.
The present invention provides a method for producing a toner, wherein the monomer mixture and the aqueous dispersion are sheared with a homogenizer to disperse the monomer mixture in the form of fine droplets in the aqueous dispersion and polymerize the dispersed monomer mixture with gentle stirring. do.

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The present invention provides a method for producing polymerized toner particles in which formation of emulsion particles is suppressed after polymerization and low in consumption.

The toner provided by the present invention is prepared through the following aqueous dispersion preparation, monomer mixture preparation and suspension polymerization steps.

(1) Aqueous Dispersion Preparation Step

5-15 parts by weight of colloidal silica is added to the aqueous system based on the total amount of monomers. In this case, when the colloidal silica is less than 5 parts by weight based on the total monomers, the monomer mixture is not dispersed and stabilized as fine droplets during homogenization (homogenization), and when the colloidal silica is more than 15 parts by weight based on the total monomers, the aqueous system is used. Increased viscosity results in a wider size distribution of fine droplets of the monomer mixture during homogenization (homogenization), resulting in a volume average particle diameter (dv) / number average particle diameter (dp) of greater than 1.5, which is desirable. You will not. When the volume average particle diameter (dv) / number average particle diameter (dp) of the toner produced is more than 1.5, the consumption amount of the toner increases and the image becomes uneven. Add 1 to 3 parts by weight of polyvinylpypylidone based on the total monomers To prepare an aqueous dispersion. At this time, when polyvinylpyrrolidone is added in an amount less than 1 part by weight based on the total monomers, colloidal silica aggregated by polyvinylpypylidone, which serves as a dispersant, is formed. When polyvinylpyrrolidone is added in excess of 3 parts by weight based on the total monomers, colloidal silica is agglomerated and the remaining polyvinylpypylidone acts as an independent dispersant. However, additional toner particles may be produced which are much smaller than the expected size of the toner particles.

The colloidal silica preferably has a volume average particle diameter (dv) of 10 to 30 nm and a volume average particle diameter (dv) / number average particle diameter (dp) of less than 1.5. In this case, when the volume average particle diameter (dv) of the colloidal silica is less than 10 nm, the aggregated size is smaller than expected when aggregated by polyvinyl-pyrrolidone and smaller than expected when used as a dispersant. Forms toner particles of size. When the volume average particle diameter (dv) of colloidal silica is more than 30 nm, when agglomerated by polyvinyl-pyrrolidone, the agglomerated size is larger than expected and larger than expected when used as a dispersant. Forms toner particles of size. When the volume average particle diameter (dv) / number average particle diameter (dp) of colloidal silica is 1.5 or more, the size of the aggregated colloidal silica when it is aggregated by polyvinylpyrrolidone is wide and the monomer When fine droplets are produced through homogenization of the mixture (homogenization), the size distribution is wide and consequently the volume average particle diameter (dv) / number average particle diameter (dp) of the toner particles is not preferable, which is undesirable.

The polyvinyl pyrrolidone (Polyvinyl-pyrrolidone) is preferably a molecular weight of 20,000 ~ 60,000. If the molecular weight of polyvinyl-pyrrolidone is less than 20,000, it is difficult to agglomerate colloidal silica, and if the molecular weight of polyvinyl-pyrrolidone exceeds 60,000, it is aggregated by raising the pH after polymerization. In the step of dispersing the washed colloidal silica again, the aggregated colloidal silica is not dispersed again, which is difficult to wash.

In an aqueous dispersion comprising an aggregate of polyvinylpyrrolidone and colloidal silica, it is preferable to include an aggregate of polyvinylpyrrolidone and colloidal silica having a particle diameter of less than 100 nm in an amount of 1% or less relative to the total aggregate.

When the aqueous dispersion of colloidal silica and polyvinylpyrrolidone is added with HCl under high speed stirring to adjust the pH to 2 or less, aggregates of colloidal silica and polyvinylpyrrolidone are formed. Colloidal silica and polyvinylpyrrolidone mixed under high-speed agitation of about 11,000 rpm can remove colloidal silica / polyvinylpyrrolidone aggregates of less than 100 nm by removing the supernatant after about 10 minutes of stirring. . In this case, by removing 40 to 60, preferably 50 parts by weight of the supernatant with respect to 100 parts by weight of the total aqueous dispersion, the aggregate of polyvinylpyrrolidone and colloidal silica having a particle diameter of less than 100 nm may be included as 1% or less of the total aggregate. Can be.

In the case of containing 1% or more of agglomerates of colloidal silica and polyvinylpyrrolidone having a particle diameter of less than 100 nm, small toner particles of less than 0.5 μm are produced, which is not preferable.

Further, toner particles of uniform size can be formed when the volume average particle diameter (dv) / number average particle diameter (dp) of the aggregate of colloidal silica and polyvinylpyrrolidone is 1.5 or less.

(2) step of preparing polymerized toner

The monomer mixture is prepared as follows.

As the monomer, an aromatic vinyl monomer, an acrylate monomer, a methacrylate monomer, a diene monomer, or a mixture thereof can be used, and optionally an acidic or basic olefin monomer can be used.

30 to 95 parts by weight of the aromatic vinyl monomer based on the total monomers; 5 to 70 parts by weight of one or more monomers selected from the group consisting of acrylate monomers, methacrylate monomers and diene monomers based on the total monomers; And optionally 0.1 to 30 parts by weight of an acidic or basic olefinic monomer, based on the total monomers; 1 to 20 parts by weight of the pigment, based on the total monomers; 0.1 to 30 parts by weight, based on the total monomers of the wax; 0.001 to 10 parts by weight, based on the total monomers, of the crosslinking agent; 0.1 to 20 parts by weight, based on the total monomers, of the charge control agent; And a monomer complex comprising 0.001 to 8 parts by weight, based on the total monomers, of the molecular weight modifier. Per 100 parts by weight Prepare from 1 to 60 parts by weight and mix with an aqueous dispersion to form a mixture.

The toner core is polymerized by applying a shear force to the mixture with a homogenizer.

In addition, optionally, one or more selected from polyester-based and styrene-acrylic polar polymers may be added to the monomer in an amount of 0.01 to 10 parts by weight based on the total monomers.

Styrene, monochlorostyrene, methyl styrene, dimethyl styrene, etc. can be used as an aromatic vinylic monomer, It is preferable to use these at 30-95 weight part with respect to monomer total.

As the acrylate monomer, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, and the like can be used. As the methacrylate monomer, methyl Methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, etc. can be used, and butadiene, isoprene, etc. Can be used. It is preferable that at least one of the acrylate monomer, the methacrylate monomer and the diene monomer is used at 5 to 70 parts by weight based on the total monomers.

As the acidic olefinic monomer, an α, β-ethylene compound having a carboxyl group may be used, and as the basic olefinic monomer, methacrylic acid ester type, methacrylic amide type, vinyl amine of an aliphatic alcohol having an amine group or a quaternary ammonium group Type, diallyl amine type, ammonium salt thereof, etc. can be used.

When using one or more of the acidic or basic olefinic monomers, it is preferable to use 0.1 to 30 parts by weight based on the total monomers.

As said wax, Petroleum refined wax, such as a paraffin wax, a microcrystal wax, a ceresin wax; Natural waxes such as carnuba wax; Or synthetic waxes such as ester waxes, polyethylene waxes, and polypropylene waxes. The wax is preferably used in 0.1 to 30 parts by weight based on the total monomers.

As the molecular weight regulator, one or more mercaptan-based compounds such as t-dodecyl mercaptan and n-dodecyl mercaptan may be used, and these molecular weight regulators are preferably used in an amount of 0.001 to 8 parts by weight based on the total monomers. .

The pigments include inorganic pigments such as metal powder type pigments, metal oxide type, carbon type, sulfide type, chromium salt type and ferrocyanide type, azo type, acid dye type, basic dye type, modal dye type, phthalocyanine and quina. Organic pigments such as credon type and dioxane type or mixtures thereof can be used, and are used in an amount of 1 to 20 parts by weight based on the total monomers.

Charge control agents include cationic charge regulators such as high aliphatic metal salts, alkoxy amines, chelates, quaternary ammonium salts, alkylamides, fluorine treatment actives, and metal salts of naphthalene acid, or polyesters including chlorinated paraffins, chlorinated polyesters, and acids. , Anionic charge control agents such as sulfonylamine of copper phthalocyanine and styrene-acrylic polymers including sulfonic acid groups, or mixtures thereof, are preferably used in an amount of 0.1 to 20 parts by weight based on the total monomers.

As the crosslinking agent, divinylbenzene, ethylene dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, 1,6-hexamethylene diacrylate, allyl methacrylate, 1,1,1-trimethylol Propane triacrylate, triallylamine, tetraallyloxyethane and the like are used, and it is preferable to use 0.001 to 10 parts by weight based on the total monomers.

The monomer mixture of the present invention may further comprise a reaction initiator. As the reaction initiator, an oil-soluble initiator and a water-soluble initiator can be used. Specifically, Azo initiators, such as azobisisobutyronitrile and azobisvaleronitrile; Organic peroxides such as benzoyl peroxide and lauroyl peroxide; Generally used water-soluble initiators, such as potassium persulfate and ammonium persulfate, etc. can be used. The reaction initiator is preferably used in an amount of 0.01 to 5.00 parts by weight based on the total monomers, more preferably 0.1 to 2.0 parts by weight.

(3) Suspension polymerization stage

The monomer mixture is mixed with the aqueous dispersion to polymerize the monomer under suitable suspension polymerization conditions generally known.

(4) colloidal silica and poly (vinyl-pyrrolidone) removal step

In the solution containing the polymerized toner prepared above, the dispersant is first removed from the toner by a suitable method. In the case of using agglomerated colloidal silica as an aqueous dispersant, by adding a 0.05-0.2 N NaOH aqueous solution to raise the pH to 5 or more, the agglomerated colloidal silica is dispersed in the water and the agglomerated colloidal silica is removed from the toner surface. It is possible to do Colloidal silica and polyvinylpyrrolidone may be separated from the toner through a separation and cleaning process using a filter device, a filter press device, or the like.

In order to describe the present invention in more detail, the following examples are described, but the present invention is not limited thereto.

Example 1

(Production of Polymerized Toner)

10 parts by weight of a colloidal silica having a particle diameter of 20 nm and a dv / dp of 1.2 as a dispersant in 400 parts by weight of ion-exchanged water was dispersed at room temperature based on the total amount of the monomer mixture, and a polyvinylpypylidone having a molecular weight of 30,000 (Polyvinyl-pyrrolidone). ) Was added 2 parts by weight based on the total amount of the monomer mixture and then at 400 rpm for 10 minutes at room temperature. After stirring, at 11,000 rmp HCl aqueous solution was added with high speed stirring to adjust the pH to 2, and then stirred for 20 minutes to prepare an aqueous dispersion composed of colloidal silica and polyvinylpyrrolidone flocculant. At this time, in order to remove agglomerates of colloidal silica and polyvinylpyrrolidone having a size of less than 100 nm, the stirring was stopped and allowed to stand for 10 minutes, and then 50 parts by weight of the supernatant of the entire aqueous dispersion was removed based on 100 parts by weight of the total aqueous dispersion. It heated up at ° C.
160 parts by weight of styrene, 36 parts by weight of n-butyl acrylate and 4 parts by weight of acrylic acid were used as monomers, 4 parts by weight of allyl methacrylate as a crosslinking agent, 0.4 parts by weight of n-dodecyl mercaptan as a molecular weight modifier, and a sulfonic acid group After fully dissolving 1 part by weight of the styrene-acrylic polymer charge control agent included, 10 parts by weight of the pigment was stirred at 2,000 rpm with a bead mill for 2 hours, and beads were removed to finally prepare 215.02 parts by weight of the monomer and pigment mixture.
The mixture was heated to 70 ° C. in a water bath and stirred for 20 minutes by adding 5 parts by weight of a wax having a Tm of 100 ° C., and homogenizing at 13000 rpm using an aqueous dispersion and a homogenizer. The monomer mixture was dispersed in the form of fine droplets in the dispersion, and then reacted with a paddle type stirrer at 200 rpm for 15 hours to prepare a polymerized toner.

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(Measurement of the amount of particles)

After the reaction was allowed to settle for 1 day, after separation by sedimentation with normal toner particles of 5 to 10 μm and fine particles of less than 0.5 μm, the supernatant was collected, dried and weighed. The fraction of the total reactants of the particles was measured.

(Cleaned by centrifuge)

NaOH aqueous solution was added to the toner synthesized above, and the concentration of NaOH was adjusted to 0.1N to remove silica from the surface of the toner. The silica was removed from the reaction product by centrifugation-decontamination-redispersion twice with distilled water at 3,000 rpm for 15 minutes using a centrifuge (Beckman J2-21M, Rotor JA-14). Finally, water was removed through filtering, the toner cake was put in a vacuum oven, and vacuum dried at room temperature for 48 hours to prepare a toner.

(Measurement of the size of colloidal silica / polyvinylpyrrolidone aggregates and toner particles)

The size and shape of the prepared colloidal silica / polyvinylpyrrolidone aggregates and toner particles were all measured using a multisizer cooler counter.

(Consumption of Toner)

Fill the surface-treated toner with the HP4600 printer (Hewlett-Packard) printer cartridge feeder, measure the entire weight of the feeder, print 1,000 square sheets of 19cm wide and 1.5cm long on A4 paper, and then measure the feeder weight again to reduce the toner consumption. Calculated.

Consumption (g) = feed weight before 1,000 sheets print-feed weight after 1,000 sheets print

[Example 2]

In Example 1, a polymerized toner was obtained in the same manner as in Example 1 except that polyvinyl-pyrrolidone having a molecular weight of 40,000 was added. The evaluation results are shown in Table 1.

Example 3

In Example 1, a polymerization toner was obtained in the same manner as in Example 1 except that colloidal silica having a particle size of 25 nm and polyvinylyl-pyrrolidone having a molecular weight of 40,000 were added to the aqueous dispersion. The evaluation results are shown in Table 1.

Example 4

In Example 1, a polymerized toner was obtained in the same manner as in Example 1 except that 7 parts by weight of colloidal silica was added to the aqueous dispersion and polyvinylyl-pyrrolidone having a molecular weight of 40,000 was added. The evaluation results are shown in Table 1.

Example 5

In Example 1, a polymerized toner was obtained in the same manner as in Example 1 except that 12 parts by weight of colloidal silica was added to the aqueous system and polyvinylyl-pyrrolidone having a molecular weight of 40,000 was added. The evaluation results are shown in Table 1.

Comparative Example 1

In Example 1, the polymerized toner was obtained in the same manner as in Example 1 except that the colloidal silica and polyvinylpyrrolidone aggregates were prepared and then the aggregates having a size of less than 100 nm were not removed. The evaluation results are shown in Table 1.

Comparative Example 2

In Example 1, after preparing colloidal silica and polyvinylpyrrolidone aggregates, the aggregates having a size of less than 100 nm were not sufficiently removed so that the fraction of aggregates having a size of less than 100 nm compared to the total aggregates was 5%. In the same manner, a polymerized toner was obtained. The evaluation results are shown in Table 1.

The toner particles produced by the method of the present invention exhibited desirable volume average particle diameters and narrow size distributions, produced little particles, and consumed less when printed.

Claims (23)

Dispersing polyvinylpyrrolidone and colloidal silica in an aqueous system, to prepare an aqueous dispersion comprising an aggregate of polyvinylpyrrolidone and colloidal silica having a particle diameter of less than 100 nm in an amount of 1 wt% or less relative to the total aggregate; Preparing a monomer mixture; Homogenizing the monomer mixture in the aqueous dispersion to disperse the monomer mixture in the form of fine droplets in the aqueous dispersion; And Polymerizing the dispersed monomer mixture, The preparing of the dispersion may include mixing the agglomerates of polyvinylpyrrolidone having a particle diameter of less than 100 nm with colloidal silica by high speed stirring at 11,000 rpm, and removing the supernatant after standing for 10 minutes. Manufacturing method. delete delete The method of claim 1, wherein the supernatant is 40 to 60 parts by weight based on 100 parts by weight of the total aqueous dispersion. The method of claim 1, wherein the colloidal silica has a volume average particle diameter (dv) of 10 to 30 nm and a volume average particle diameter (dv) / number average particle diameter (dp) of less than 1.5. The method of claim 1, wherein the polyvinylpyrrolidone has a molecular weight of 20,000 to 60,000. The method of claim 1, wherein the colloidal silica is added in an amount of 5 to 15 parts by weight based on the total monomers. The method of claim 1, wherein the polyvinylpyrrolidone is added in an amount of 1 to 3 parts by weight based on the total monomers. The method of claim 1, further comprising removing the polyvinylpyrrolidone and colloidal silica. 10. The method of claim 9, wherein polyvinylpyrrolidone and colloidal silica are removed from the toner surface by adding 0.05 to 0.2 N aqueous NaOH solution. The dispersion of claim 1 wherein the monomer mixture is About 100 parts by weight 1 to 60 parts by weight of the aqueous dispersion is mixed with the monomer mixture, the aromatic vinyl monomer is 30 to 95 parts by weight relative to the total monomers; 5 to 70 parts by weight of one or more monomers selected from the group consisting of acrylate monomers, methacrylate monomers and diene monomers based on the total monomers; 1 to 20 parts by weight of the pigment, based on the total monomers; 0.1 to 30 parts by weight, based on the total monomers of the wax; 0.001 to 10 parts by weight, based on the total monomers, of the crosslinking agent; 0.1 to 20 parts by weight, based on the total monomers, of the charge control agent; And 0.001 to 8 parts by weight of the molecular weight modifier based on the total monomers; Toner manufacturing method comprising the. 12. The method of claim 11, wherein the monomer mixture further comprises 0.01 to 10 parts by weight based on the total monomers, at least one selected from the group consisting of polyester and styrene acrylic polar polymers. 12. The method of claim 11, wherein the monomer mixture further comprises 0.1 to 30 parts by weight of an acidic or basic olefinic monomer based on the total monomers. 12. The method of claim 11, wherein the aromatic vinyl monomer is selected from the group consisting of styrene, monochlorostyrene, methyl styrene, and dimethyl styrene. The method of claim 11, wherein the acrylate monomer is selected from the group consisting of methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, and 2-ethylhexyl acrylate, The methacrylate monomer is selected from the group consisting of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, dodecyl methacrylate, and 2-ethylhexyl methacrylate, and diene The monomer is selected from the group consisting of butadiene and isoprene. 12. The method of claim 11, wherein the wax is petroleum refined wax including paraffin wax, microcrystalline wax, ceresin wax; Natural waxes, including carnuba wax; Or synthetic waxes including ester waxes, polyethylene waxes, and polypropylene waxes. 12. The method of claim 11, wherein the molecular weight modifier is at least one selected from mercaptan compounds including t-dodecyl mercaptan and n-dodecyl mercaptan. 12. The method of claim 11, wherein the pigment is an inorganic pigment including a metal powder pigment, a metal oxide pigment, a carbon pigment, a sulfide pigment, a chromium salt pigment, and a ferrocyanide pigment; Organic pigments including azo pigments, acid dye pigments, basic dye pigments, modal dye pigments, phthalocyanine pigments, quinacridone pigments, and dioxane pigments; Or a mixture thereof. 12. The method of claim 11, wherein the charge control agent includes a cationic charge control agent including a high aliphatic metal salt, alkoxy amine, chelate, quaternary ammonium salt, alkylamide, fluorine treatment active agent, metal salt of naphthalene acid; Anionic charge control agents comprising chlorinated paraffins, chlorinated polyesters, polyesters containing acids, sulfonylamines of copper phthalocyanine, and styrene-acrylic polymers including sulfonic acid groups; Or a mixture thereof. The method of claim 11, wherein the crosslinking agent is divinylbenzene, ethylene dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, 1,6-hexamethylene diacrylate, allyl methacrylate, 1 And 1,1-trimethylolpropane triacrylate, triallylamine, and tetraallyloxy ethane. 12. The method of claim 11, wherein the monomer mixture further comprises 0.01 to 5.00 parts by weight of the reaction initiator relative to the total monomers. 22. The composition of claim 21, wherein the reaction initiator comprises: an azo initiator comprising azobisisobutyronitrile and azobisvaleronitrile; Organic peroxides, including benzoyl peroxide, and lauroyl peroxide; And a water-soluble initiator containing potassium persulfate and ammonium persulfate. delete