WO2013168884A1

WO2013168884A1 - Polymerized toner and method for producing same

Info

Publication number: WO2013168884A1
Application number: PCT/KR2013/001032
Authority: WO
Inventors: 박주용; 이희제
Original assignee: 주식회사 엘지화학
Priority date: 2012-05-10
Filing date: 2013-02-08
Publication date: 2013-11-14

Abstract

The present invention relates to a toner that is used in a transfer photographic method or a polymerized toner, and an existing pulverization and spheronization method, and more particularly, to a polymerized toner in which colloidal silica, the single particle size of which is between 25 nm and 58 nm and the volume average particle size of which is between 0.06 µm and 0.5 µm is used as an external additive in toner mother particles containing a binder resin, a charge control agent, a pigment, wax and the like, so as to improve a cleaning function of a wiper blade and substantially prevent contamination of components such as a PCR, a drum, or a transfer belt, and to a method for producing same.

Description

【Specification】

[Name of invention]

Stacked toner and its manufacturing method

Technical Field

The present invention relates to a toner used by transfer photographic or polymerized toner, conventional grinding and spheronizing methods, and more particularly, cleaning in a wiper blade using colloidal silica as an external additive. The present invention relates to a polymerized toner capable of improving the function and significantly improving component contamination of a PCR, drum or transfer belt, and a manufacturing method thereof. Background Art

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, the demand for an image forming apparatus such as a printer is rapidly increasing with the generalization of document creation using a computer, and accordingly, the amount of toner usage is also increasing.

In general, the toner used in the printer is classified into three types according to the manufacturing method: a pulverized toner made by a conventional pulverization method, a spheronized toner using a mechanical spheronization and a hot air spheronization method, and a polymerized toner made by a polymerization method. Each manufacturing method differs in the shape and spherical degree of the toner, and also the structure of the toner and the degree of dispersion of the raw materials used.

In recent years, toner has been manufactured in a polymerization method to reduce the toner particle size distribution and to produce a toner having a narrow particle size distribution in order to realize high resolution to improve the performance of high resolution and low temperature fixing. Toner is produced by a polymerization method that is easy to increase in content and lower in molecular weight.

Although there is a method of using a resin having a low molecular weight for improving particle size distribution and fixing at low temperature by using a conventional method for preparing a ground toner, it is true that physical properties are lowered compared to toners made by a polymerization method. The toner prepared by the pulverized toner method has the above disadvantages, but is very irregular unlike the spherical toner prepared by the suspension polymerization method. It is shaped so that the cleaning is relatively good on the wiper blade compared to the spherical toner produced by the polymerization method. On the contrary, spherical toners made by polymerization have a problem of poor cleaning.

Cleaning problems on wiper blades can be very serious, depending on the type or design of the cartridge. As a method for imparting charging characteristics to the toner, dr. One-component cartridges using blades are sleeve and dr. The toner passing between the blades is designed to cause excessive friction between the drum and the wiper blade because the external additives used by the toner are excessively separated from the toner surface due to excessive friction. It is possible to effectively remove toner or external additives remaining on the paper that cannot be transferred to paper. In addition, due to the strong friction between the wiper blade (wiper blade) and the drum, abrasion of the drum occurs badly, making it difficult to use the drum for a long time. Lubricants may be added to reduce the friction between the drum and the wiper blades, but this may cause additional degradation of the development characteristics. Dr. A two-component cartridge that uses a carrier instead of a blade gives charge characteristics to the toner by mixing the carrier with the toner, so the toner does not receive excessive friction and therefore exists on the surface of the toner. The external additives do not occur on the surface of the toner, so there is no need to excessive friction between the drum and the wiper blade to remove it, so that the wiper blade wears the drum due to the friction with the drum. Designed to minimize

If the toner or detached external additives are not effectively removed from the wiper blades of the one-component and two-component cartridges, contamination of the drum, PCR, or transfer belt may occur. As a result, the printed image also becomes a BG or an uneven image, which causes quality deterioration. The problem described above occurs with both conventional irregularly shaped toners, spheronized toners, or polymerized toners. More severe in spherical toner or polymerized toner.

Therefore, research on the development of a toner such as fluidity, background contamination, transfer efficiency, and the like, as well as excellent cleaning performance in a cleaning blade, and polymerization toner having excellent charging performance is required.

[Content of invention]

[Problem to solve]

The present invention is to provide a polymerized toner which is not only excellent in cleaning performance in a cleaning blade but also excellent in toner and charging characteristics such as fluid background contamination, transfer efficiency, and the like, and a method of manufacturing the same. [Measures of problem]

The present invention provides a toner base particle comprising a binder resin, a pigment, a charge control agent, and a wax; And an external system coated on the surface of the toner base particles; wherein the external additive includes colloidal silica having a single particle size of 25 to 58 nm and a volume average particle size of 0.06 to 0.5 // m. Provide a polymerized toner.

The present invention comprises the steps of forming an aqueous dispersion comprising a dispersant; Forming a monomer mixture comprising a binder resin, a pigment, a charge control agent, and a wax; Adding the monomer mixture to the aqueous dispersion and forming toner base particles through suspension polymerization; And coating an external additive on the surface of the toner base particles, wherein the external additive includes colloidal silica having a single particle size of 25 to 58 nm and a volume average particle size of 0.06 to 0.5 mm 3. A method for producing a polymerized toner is provided. Hereinafter, a method of manufacturing a polymerized toner and a polymerized toner manufactured according to the present invention will be described in detail. However, this is presented as an example of the invention, whereby the scope of the invention is not limited, it is apparent to those skilled in the art that various modifications to the embodiments are possible within the scope of the invention.

Unless otherwise stated throughout this specification, "including" or "containing" includes without limitation any component (or component). Reference, and should not be construed to exclude the addition of other components (or components).

According to one embodiment of the invention, there is provided a polymerized toner having a specific colloidal silica coated with an external additive on the surface of the toner base particles. In particular, the polymerized toner may include toner base particles including a binder resin, a pigment, a charge control agent, and a wax; And an external additive coated on the surface of the toner base particles; and the external additive may include colloidal silica having a single particle size of 25 to 58 nm and a volume average particle size of 0.06 to 0.5.

The present inventors use specific colloidal silica in which the particle size is large and particles are confined or fused to spherical mother particles produced by the polymerization method, so that not only the cleaning performance in the cleaning blade but also fluidity, background contamination, transfer efficiency, etc. It has been confirmed that the same toner and charging characteristics can be improved and the present invention has been completed. Accordingly, the polymerized toner of the present invention can be applied to an application field such as the development of an electrophotographic which requires the realization of a uniform image, and by using this, it is possible to obtain an excellent quality print result with high resolution and color realization. In particular, the present invention more seriously occurs the problem of not cleaning in the cartridge using a carrier (carrier) can improve the cleaning (cleaning) performance can effectively improve the parts contamination of the printer.

Depending on the toner manufacturing method, the shape of the toner is divided into spherical balls or potato shaped potatoes and irregular shapes. In addition, depending on the type of toner used, the cartridge is divided into using and not using a carrier. If a cartridge using a carrier rather than the shape of the toner is used, the cleaning of the cleaning wiper may not be performed properly, resulting in toner contamination in the PCR. The polymerized toner of the present invention can significantly improve PCR toner contamination by improving the cleaning performance of the toner by using specific colloidal silica as an external additive to the toner base particles.

First, in the polymerized toner of the present invention, "colloidal silica"'refers to silica prepared by a sol-gel method or the like, and the colloidal The silica may have a volume average particle diameter of 0.06 to 0.5 im (micrometer), preferably 0.07 to 0.4 urn, and more preferably 0.08 to 0.3. The colloidal silica may have a volume average particle diameter of 0.06 or more in terms of improving cleaning, and may be 0.5 or less in terms of reducing drum wear. In the colloidal silica, the ratio of one particle is based on the number of particles.

30% to 40%, the proportion of particles in which two particles are fused together is 10% to 30%, and the proportion of particles in which three or more particles are fused is 10% to 30%. It may be to have.

In addition, the colloidal silica may have a silica single particle size of 25 to 58 nm (nanometer), preferably 55 nm or less, more preferably 53 nm or less. In this case, the silica single particle size can be measured by an electron microscope, for example, scanning electron microscope (SEM) and transmission electron microscope (TEM), and defined as the average particle diameter of a single particle. can do. The single particle size of one silica particle constituting the colloidal silica of the present invention may be 25 nm or more in terms of preventing excessively fine particles from causing the contamination of the component, and in terms of increasing the effect of improving the component contamination. It can be up to 58 nm.

As described above, the content of the colloidal silica in which the particle size is large and the particles are packed or fused with each other is 1.0 part by weight to 5.0 parts by weight, preferably 1.2 parts by weight to 4.0 parts by weight, 100 parts by weight of the toner base particles, more Preferably 1.5 to 3.0 parts by weight can be used. The colloidal silica should be used in an amount of 1.0 parts by weight or more in terms of improving cleaning and 5.0 parts by weight or less in terms of reducing drum wear.

In this case, particle size measurement of the used silica may be performed using a scanning electron microscope (SEM) and a particle size distribution analyzer. In addition, the range of the average particle diameter of the colloidal silica as described above is for the fused (fused) particles, when the use of only individual particles that are not fused (fused) may reduce the cleaning (improving) effect. According to the toner manufacturing method, the shape of the toner is classified into spherical shape, potato, and irregular shape. In addition to the type of toner used, the cartridge is divided into a two-component system using a carrier and a one-component system not using a carrier. If a cartridge using a carrier rather than the shape of the toner is used, the cleaning blade may not be cleaned properly, resulting in toner contamination in the PCR.

Hydrophobic silicas with a particle size of 50 nm or less commonly used in toners are poorly cleaned on the cleaning blades even when using hydrophobized surface treatment materials or most products by silica manufacturers, resulting in PCR toner contamination.

In order to solve the cleaning problem, the use of colloidal silica in which the particle size is large and the particles are packed or fused with each other completely improves PCR toner contamination. The content of the colloidal silica in which the particle size is large and the particles are packed or fused with each other may be 1 part by weight to 5 parts by weight based on 100 parts by weight of the toner base particles. If the content is less than 1 part by weight, the PCR toner contamination may not be completely improved. If more than 5 parts by weight is used, there is a large amount of uncoated silica, which may result in severe drum wear or difficult to attach toner base particles to the paper through the fixing unit. have.

The colloidal silica in which the particle size is large and the particles are agglomerated or fused with each other can be hydrophobized using a surface treatment for applying or adhering a silane coupling agent or a silicone oil to the silica particles.

The silane coupling agent is dimethyldichlorosilane, trimethylchlorosilane, methyltrichlorosilane, arylphenyldichlorosilane, benzyldimethylchlorosilane, brmethyldichlorolosilane, P-chlorophenyltrichlorosilane, 3-chloropropyltrimethoxy , At least one selected from the group consisting of vinyltriethoxysilane, vinyltriaceoxysilane, divinylchlorosilane, and nuxamethyldisilagen may be used. Among them, it is preferable to use dimethyldichlorosilane, trimethylchlorosilane, methyltrichlorosilane and the like from the viewpoint of improving adhesion with the drum.

The silicone oil is dimethylsilicone oil, methylphenylsilicone oil, Methylhydrogensilicone oil, alkyl modified silicone oil, fluorine modified silicone oil, alcohol modified silicone oil, amino modified silicone oil, epoxy modified silicone oil, epoxy polyether ether modified silicone oil, phenol modified silicone oil epoxy modified silicone oil, carboxy modified Silicone oil, and at least one selected from the group consisting of mercapto modified silicone oil can be used. Among them, dimethylsilicone oil, methylphenylsilicone oil, methylhydrogensilicone oil and the like are preferably used from the standpoint of charging stability at high humidity.

By attaching the silica to the toner base particles, a method using a general stirrer such as a turbine type stirrer, a Henschel mixer, a super mixer, or a device called a surface reformer ("Nara Hybridization System" of Nara Machinery Co., Ltd.) may be used. There is a way.

On the other hand, as the monomer for the binder resin in the toner base particles of the present invention, all monomers used in the toner produced by the polymerization method can be used, and are not particularly limited. Examples of the monomers include styrene monomers, acrylate monomers, methacrylate monomers, diene monomers, and the like, and one or more of them may be used in combination. In addition, an acidic olefin monomer or a basic olefin monomer may be optionally used in combination with the monomer.

The binder resin may include a styrene monomer, an acrylate monomer, a methacrylate monomer, a diene monomer, an acidic olefin monomer and a basic olefin monomer or a mixture thereof and a polymer or a copolymer. However, the present invention is not limited thereto, and various monomers known to be usable for the formation of the toner prepared by the suspension polymerization method may be used without any limitation, and from such monomers, a polymer or a copolymer which becomes a binder resin of the polymerized toner may be formed. Can be.

In addition, the binder resin (a) a styrene monomer; And (b) a polymer or copolymer of at least one monomer selected from the group consisting of an acrylate monomer, a methacrylate monomer and a diene monomer. The polymer is 30 to 95 parts by weight of the monomer of (a) and 100 parts by weight of the monomer of (a) and the monomer of (b) It may include a polymerized 5 to 70 parts by weight of the monomer of (b).

Such polymers may be selected from the group consisting of styrene monomers of (a), (b) acrylate monomers, methacrylate monomers and diene monomers, (c) acidic olefin monomers and basic monomers. It may be a polymerized one or more monomers selected from the group consisting of olefinic monomers. At this time, the mono-decanter of (c) may be polymerized to 0.1 to 30 parts by weight based on 100 parts by weight of the monomer of (a) and the monomer of (b). Styrene monomers for the formation of the binder resin include styrene, monochlorostyrene, methyl styrene, dimethyl styrene, etc. The acrylate monomers are methyl acrylate ethyl acrylate, n- butyl acrylate, isobutyl acryl Acrylate, dodecyl acrylate, 2-ethylnuclear acrylate, and the like. And, methacrylate monomers include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, dodecyl methacrylate, 2-ethylnuclear methacrylate, and the like. The diene monomers include butadiene and isoprene.

In addition, the acidic olefin monomer may be an α, β-ethylenically unsaturated compound having a carboxyl group, and the like, and the basic olefin monomer may be a methacrylic acid ester or methacrylamide of an aliphatic alcohol having an amine group or a quaternary ammonium group. Type, vinyl amine type, diallyl amine type, ammonium salt thereof and the like can be used.

Meanwhile, in one embodiment of the invention, the toner base particles may include a binder resin, a pigment dispersed in the binder resin, a charge control agent, a wax, and the like, and may further include a pigment stabilizer. And, the toner base particles are 50 to 95% by weight of the binder resin, preferably 60 to 93% by weight, more preferably 70 to 90% by weight; 1 to 20% by weight of pigment, preferably 2 to 15% by weight, more preferably 3 to 10% by weight; 0.1 to 5% by weight of charge control agent, preferably 0.3 to 4% by weight, more preferably 0.5 to 3% by weight; And 0.1 to 30% by weight of wax, preferably 1 to 25% by weight, More preferably 5 to 20% by weight, and may further comprise 0.1 to 20% by weight of pigment stabilizer, preferably 0.2 to 15% by weight, more preferably 0.3 to 10% by weight. By maintaining the content of the binder resin, pigments, charge control agents, waxes, and the like dispersed in the binder resin in the above-described range, it achieves a uniform image and excellent transfer efficiency at the same time the excellent image density of the polymerized toner The offset phenomenon, which is a phenomenon that the toner contaminates the fixing in the process, can be effectively prevented. In particular, if the styrene monomer in the ratio of the monomer is too much Tg is high unsettling occurs on the contrary, if too small Tg is lowered to generate a hot offset (Hot offset) is generally 20% to 30% of the styrene monomer Adjust to content. In the case of the charge control agent (CCA), if the content is less than 0.5%, coagulum is generated due to the decrease in reaction stability, and the triboelectric charging property is insufficient. In the production of the polymerized toner, a problem of broadening the particle size distribution may occur, so that an appropriate content may be used. In addition, when the wax is used in excess of 25% or more, the charging property is reduced due to exposure to the surface of the toner, and when less than 5¾ is used, the toner may be contaminated.

The pigment may be a metal powder pigment, a metal water oxidized pigment, a carbon pigment, a sulfide pigment, a creme salt pigment, a ferrocyanide pigment, an azo pigment, an acid dye pigment, a basic dye pigment, a modal dye type Pigments, phthalocyanine, quinacridone type pigments, dioxane type pigments or combinations thereof. However, the present invention is not limited thereto, and pigments known to be applicable to the polymerized toner may be used without particular limitations.

The charge control agent may include a cationic charge control agent, an anionic charge control agent, or a combination thereof. Examples of the cationic charge tank include nigrosin-type dyes, high aliphatic metal salts, alkoxy amines, chelates, quaternary ammonium salts, alkylamides, fluorine treatment actives, metal salts of naphthalene acid, or mixtures thereof. Regulators include chlorinated paraffins, chlorinated polyesters, polyesters containing acids, sulfonylamines of copper phthalocyanine, sulfonic acid groups or combinations thereof. In addition, it is preferable to use a copolymer having a sulfonic acid group as the charge control agent, more preferably, a copolymer having a sulfonic acid group having a weight average molecular weight of 2,000 to 200,000 may be used, even more preferably. The acid value is 1 to 40 mg KOH / g, the glass transition temperature can be used a copolymer having a sulfonic acid group of 30 to 120 ^° C. If the acid value is less than 1, it does not act as a charge control agent, and if it is 40 or more, it affects the interfacial properties of the monomer mixture to deteriorate the polymerization stability.

In addition, when the glass transition temperature is lower than 30 ^° C, the low glass transition temperature of the charge control agent exposed on the surface may cause friction-melting of the toner to the toner during printing, thereby causing a blocking phenomenon. On the other hand. When the glass transition temperature exceeds 120 ^° C., the surface of the toner is excessively hard, which is undesirable for the coating property and the fixing property. And, if the weight average molecular weight is less than 2,000, the surface concentration is reduced due to high compatibility with the binder resin may not function as a charge control agent, and if more than 200,000, polymerization stability and particle size due to an increase in the viscosity of the monomer mixture due to high molecular weight Not desirable for distribution Specific examples of the copolymer having a sulfonic acid group may include a styrene-acrylic copolymer having a sulfonic acid group, a styrene-methacrylic copolymer having a sulfonic acid group, or a combination thereof, but is not limited thereto.

The pigment stabilizer may be used a styrene-butadiene-styrene (SBS) copolymer having a weight average molecular weight of 2,000 to 200, 000, preferably, the styrene content of the copolymer in the weight ratio of butadiene 10:90 to 90:10 can be used. If the content of styrene exceeds 90%, butadiene blocks are shortened, and the high compatibility with binder resin prevents them from becoming a stabilizer. If the content is less than 10%, the blocks are stabilized, but the length of the short styrene blocks Phenomena do not fully control the action of the pigment to the pigment. In addition, when the molecular weight is less than 2,000, it has a high compatibility with the binder resin and does not function as a pigment. When the molecular weight is more than 200,000, the viscosity of the monomer mixture is so high that the dispersion stability and polymerization stability are deteriorated, and ultimately, the particle size distribution is disadvantageously widened. . As the wax component, a wax known to be applicable to a polymerized toner can be used without particular limitation. For example, the wax component may be petroleum refined wax such as paraffin wax microcrystalline wax or ceresin wax; Natural waxes of carnuba wax; Alternatively, synthetic waxes such as polyester waxes or polyolefin waxes, or mixtures thereof may be used.

Meanwhile, in one embodiment of the invention, the toner base particles may further include at least one additive selected from the group consisting of a reaction initiator, a crosslinking agent, a molecular weight regulator, a lubricant (eg, oleic acid, stearic acid, etc.), and a coupling agent. have. At this time, the toner base particles are 10% by weight or less or from 0.1 to 0.1

10% by weight, preferably 8% by weight or less or 0.3-8% by weight, more preferably 5% by weight or less> or 0.5-5% by weight; 5% by weight or less of the crosslinking agent or 0.01 to 5% by weight, preferably 4% by weight or less, or 0.05 to 4% by weight>, more preferably 3% by weight or less or 0.1 to 3% by weight or 10% by weight or less of a molecular weight modifier or 0.1 to 10% by weight, preferably 8% by weight or less or 0.3 to 8% by weight, more preferably 5% by weight or less or 0.5 to 5% by weight; A suitable amount of lubricant (e.g., oleic acid, stearic acid, etc.), for example, up to 5% by weight or from 0.01 to 5% by weight, preferably up to 4% by weight or from 0.05 to 4% by weight, more preferably up to 3% by weight or 0.1 To 3% by weight of an appropriate amount of coupling agent, such as up to 5% by weight or 0.01 to 5% by weight of the coupling agent, preferably up to 4% by weight or 0.05 to 4% by weight, more preferably up to 3% by weight or 0.1 to 3% by weight ? It may further include one or more.

As the reaction initiator, an oil-soluble initiator and a water-soluble initiator can be used. Specifically, Azo-based 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, Among these, 1 type (s) or 2 or more types can be used in mixture.

The crosslinking agent is divinylbenzene, ethylene dimethacrylate, ethylene glycol Dimethacrylate, diethylene glycol diacrylate, 1,6-nuxa methylene diacrylate, allyl methacrylate, 1,1,1-trimethylolpropane triacrylate, triallylamine, tetraallyloxyethane or these It may include a mixture of.

The molecular weight modifier may include t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl meraptan, carbon tetrachloride or a combination thereof.

As the lubricant and the coupling agent, those known to be applicable to the production of the polymerized toner may be used without particular limitation.

Polymerized toner of the present invention is a binder resin 50 to 95 weight ¾>; Pigments 1 to 20 weight percent; 0.1-5% increase in charge control agent; 0.1 to 30% by weight wax; Plasticizer 0.1 to 5 weight ¾>; And a reaction agent, a crosslinking agent, a molecular weight adjusting agent, a lubricant, and a coupling agent may include 10 wt% or less or 0.01 to 10 wt%, respectively.

In addition, in one embodiment of the invention, the volume average particle diameter of the toner base particles according to the present invention may be 4 to 10, preferably 5 to 8 β η, more preferably 6 to 7 mi. The volume average particle size of the toner base particles may be 4 or more in terms of image density and scattering prevention, and the volume average particle size of the toner base particles may be 10 or less in terms of reducing consumption.

On the other hand, in another embodiment of the present invention, the present invention provides a spheronized toner using colloidal silica as an external additive. The spheronized toner includes an external additive coated on the surface of the toner base particles, and as the external additive, a colloidal silica having a single particle size of 25 to 58 nm and a volume average particle size of 0.06 to 0.5 / mm3 is used. It may include.

The spheronized toner of the present invention can use colloidal silica as an external additive to improve the cleaning function on the wiper blade and to significantly improve component contamination such as PCR, drums or transfer belts.

The spheronized toner may be prepared by sphering the toner after preparing the pulverized toner. As the method of spherical pulverized toner, mechanical spherical method and high temperature hot air are used. have. Mechanically spherical has the advantage that it can be manufactured in various shapes such as potato model and spherical shape, but there is a disadvantage in that the production of toner in spherical form is low in the hour / spherical process using silver hot air. While it has the advantage of making spherical toner, it is difficult to make potato toner. For reference, the manufacturing conditions for making the pulverized toner spherical can be almost determined depending on the mechanism to be applied.

In this way, the present invention can be applied to spheronized toner, and can improve the cleaning function on a wiper blade regardless of polymerized toner or spherical toner, and to improve PCR, drum or transfer belt. Excellent effect of improving component contamination can be realized. Therefore, the present invention is applicable not only to polymerized toner but also to spheronized toner manufactured in spherical form. In addition, the present invention can also be effectively applied to spheronized toners prepared in a potato shape. Meanwhile, according to another embodiment of the present invention, a method of manufacturing the polymerized toner may be provided. In particular, the method for producing the polymerized toner comprises the steps of forming an aqueous dispersion comprising a dispersant; Forming a monomer mixture comprising a binder resin, a pigment, a charge control agent, and a wax; Adding the monomer mixture to the aqueous dispersion and forming toner base particles through suspension polymerization; And coating an external additive on the surface of the toner base particles; and as the external additive, a colloidal silica having a single particle size of 25 to 58 nm and a volume average particle size of 0.06 to 0.5 may be used. .

The "colloidal silica" refers to a silica prepared by a sol-gel method or the like, wherein the colloidal silica has a particle ratio of 30% to 40% by number, particle 2 The proportion of particles in which the dogs are fused with each other is 10% to 30%, and the proportion of particles in which three or more particles are fused is 10% to 30% with a uniform distribution.

The colloidal silica may have a volume average particle diameter of 0.06 to 0.5 urn, preferably 0.07 to 0.4} M, and more preferably 0.08 to 0.3. Can be. The colloidal silica may have a volume average particle diameter of 0.06 urn or more in terms of improving cleaning, and may be 0.5 m or less in terms of reducing drum wear.

On the other hand, specific examples of the colloidal silica usable in the present invention are as described above.

The present inventors use specific colloidal silica in which the particle size is large and the particles are packed or fused with each other to the spherical mother particles prepared by the polymerization method, so that not only the cleaning performance in the cleaning blade but also fluidity, background contamination, transfer efficiency, etc. It was confirmed that the same toner and a polymerized toner having improved charging characteristics could be prepared, and thus the present invention was completed. Applying the polymerized toner prepared in this way can increase the glossiness of the printed result, and thus can be effectively applied to fields such as photo printing requiring high resolution and color realization. In another embodiment of the invention, the dispersant may be mixed with water to form the aqueous dispersion. In order to homogenize such an aqueous dispersion, agitation or shearing may be applied. Specifically, the forming of the aqueous dispersion may include mixing potassium phosphate and calcium chloride aqueous solution to obtain potassium phosphate in the form of crystals on the aqueous solution. The potassium phosphate may be used as a dispersant, and the aqueous dispersion may have a form in which potassium phosphate crystals are uniformly dispersed in water.

The dispersant prevents coarsening between particles such as monomers or pigments for binder resin present in the form of droplets in the aqueous medium, and allows the particles to be uniformly dispersed. In addition, the dispersant serves to stabilize the droplet particles by being uniformly adsorbed on the surface of the droplet. In addition, such a dispersant may be solubilized by acid, alkyl: alkali treatment, or hot water washing after completion of the polymerization reaction in the aqueous medium, and may be separated from the toner base particles.

The dispersant includes an inorganic dispersant, an organic dispersant, an anionic surfactant or a combination thereof. Such a dispersant may be applied in an amount of 1 to 5 parts by weight, preferably 2 to 4 parts by weight, and more preferably 2.5 to 3.5 parts by weight, based on 100 parts by weight of the monomer mixture.

Specific examples of the inorganic dispersant include calcium phosphate, hydrogen phosphate, calcium dihydrogen phosphate, hydroxy apatite, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, Calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina or combinations thereof.

Specific examples of the water-soluble organic dispersant include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxy propyl cellulose and ethyl cellulose. cellulose, carboxyl methyl cellulose and its sodium salt, polyacrylic acid And salts thereof, starch or a combination thereof.

Specific examples of the anionic surfactants include fatty acid salts, alkyl sulfate ester salts, alkylaryl sulfate ester salts, dialkyl sulfosuccinate salts, alkyl phosphates, and mixtures thereof.

A more preferable example of the said dispersing agent is a calcium phosphate. The chamo phosphate may be obtained in the form of crystals in an aqueous solution by mixing an aqueous sodium phosphate solution with a chamomile chloride solution, and the aqueous dispersion may be in a form in which calcium phosphate crystals are uniformly dispersed in water.

On the other hand, the monomer mixture may be formed by mixing and dissolving the binder resin monomer, pigment, pigment stabilizer, charge control agent and wax and the like, and homogenized in the aqueous dispersion using a homogenizer.

The binder resin monomer may include a styrene monomer, an acrylate monomer, a methacrylate monomer, a diene monomer, an acidic olefin monomer, a basic olefin monomer, or a mixture thereof.

In addition, the binder resin monomers are (a) styrene-based monomers; And (b) at least one monomer selected from the group consisting of an acrylate monomer, a methacrylate monomer and a diene monomer. The binder resin monomer is 30 to 95 parts by weight of the monomer of (a) and 5 to 70 of the monomer of (b) with respect to 100 parts by weight of the monomer of (a) and the monomer of (b). It may include parts by weight.

In addition, the binder resin monomer is a monomer selected from the group consisting of styrene monomer of (a), (b) acrylate monomer, methacrylate monomer and diene monomer, (c) acidic olefin It may include one or more monomers selected from the group consisting of monomers and basic olefinic monomers. In this case, the monomer of (c) may be included in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the monomer of (a) and the monomer of (b). On the other hand, specific examples of the binder resin monomer, pigment, pigment stabilizer, charge control agent, and wax contained in the monomer mixture is as described above. In addition, the monomer mixture is 50 to 95% by weight of the monomer for binder resin, 1 to 20% by weight of pigment, 0.1 to 5% by weight of charge control agent, and 0.1 wax It may include from 30% by weight, in addition may include a pigment stabilizer and specific examples and content ranges are as described above.

Toner base particles may be formed by mixing the monomer mixture with the aqueous dispersion and suspending polymerizing. More specifically, the forming of the toner base particles may include adding the monomer mixture to the aqueous dispersion; Applying a shear force to the aqueous dispersion and the monomer mixture to homogenize the monomer mixture in the form of droplets in the aqueous dispersion; And suspension polymerizing the homogenized monomer mixture. As described above, the monomer mixture and the aqueous dispersion may be homogenized using a homogenizer.

By uniformly dispersing the monomer mixture in the form of fine water droplets (droplets) in the aqueous dispersion, the polymerization reaction can be performed to form spherical toner base particles of an appropriate size. For dispersion in the form of such fine droplets (droplets), a homogenizer may be used to homogenize the monomer mixture and the aqueous dispersion by applying shear force. Specifically, the monomer mixed with the aqueous dispersion using a homogenizer is used. The mixture may be homogenized at a speed of 5,000 rpm to 20,000 rpm, preferably 8,000 rpm to 17,000 rpm to disperse the monomer mixture in the form of fine droplets in the aqueous dispersion.

The suspension polymerization may be carried out at 60 to 90 ^° C for 8 to 20 hours. As a more preferred example, the suspension polymerization may be carried out at 50 to 70 ^° C for 8 to 12 hours after the suspension polymerization reaction, the temperature is raised to 80 to 110 ^° C and the reaction may proceed for 30 minutes to 4 hours.

On the other hand, in another embodiment of the invention the step of removing the dispersant; And drying the toner base particles.

Removing the dispersant may include adjusting to a pH suitable for dissolution of the dispersant. By adding a water-soluble inorganic acid such as hydrochloric acid or nitric acid to the dispersion in which the toner base particles are produced, and adjusting the pH to 2 or less, preferably 1.5 or less, the dispersant may be dissolved in an aqueous solution and removed from the toner base particles. In this dispersant removal step, After the adjustment, the mixture is stirred for at least 5 hours to further dissolve the dispersant, and then a toner slurry containing less than 50% by weight of water can be obtained using a filtration device. In addition, in the step of removing the dispersant, a step of homogenizing the solution by applying a shear force to a homogenizer and a separation step using a centrifugal separator may be applied. After the dispersant removal step described above, the dispersant may be more efficiently removed by repeating the removal of water using a filter device and the addition of excess distilled water several times.

The drying of the toner base particles includes putting a toner cake from which the dispersant is removed into a vacuum oven and vacuum drying at room temperature. However, the present invention is not limited thereto, and a drying method known to be commonly used in the preparation of the polymerized toner may be used without particular limitation. In addition, in another embodiment of the invention, the toner base particles include the step of coating an external additive on the surface, and in particular, the toner base particles by using the colloidal silica and hydrophobic silica as an external scavenger in a predetermined range. Coating on the surface. The coating step of the external additive may be performed by using a Henschel mixer and adding the external additive to the toner base particles, followed by ^' high-speed stirring. The silica may be used without particular limitation as is known to be usable for the polymerized toner. For example, a method of attaching the silica to the toner base particles using a general stirrer such as a turbine type stirrer, a Henschel mixer, a super mixer, or an apparatus called a surface reformer ("Nara Hybridization System" of Nara Machinery Co., Ltd.) The method using etc. can be applied.

The monomer mixture may further include adding at least one additive selected from the group consisting of a reaction initiator, a crosslinking agent, a lubricant, a molecular weight regulator, and a coupling agent. Specific examples and preferred content ranges of such additives are as described above.

On the other hand, according to a preferred embodiment of the present invention, the preparation of the toner base particles used in the present invention is as follows.

(1) Step 1: Preparing Aqueous Dispersion

Dissolve the dispersant in distilled water to prepare an aqueous dispersion. The dispersant At least one of inorganic and water-soluble organic dispersants may be selected and used, and anionic surfactants may be optionally added.

At this time, the dispersant is an inorganic dispersant selected from the group consisting of calcium phosphate salt, magnesium salt, hydrophilic silica, hydrophobic silica and colloidal silica; Or from the group consisting of polyoxyethylene alkyl ether, polyoxyalkylene alkyl phenol ether, sorbitan fatty acid ester, polyoxy alkylene fatty acid ester, glycerin fatty acid ester, polyvinyl alcohol, alkyl cellulose and polyvinyl pyrrolidone Nonionic polymer dispersing agent chosen from more than 1 type; And polyacrylamides, polyvinyl amines, polyvinyl amine N-oxides, polyvinyl ammonium salts, polydialkyldiallyl ammonium salts, polyacrylic acids, polystyrene sulfonic acids, polyacrylates, pulleysulfonic acid salts and pulleyaminoalkyl acrylates. It can be used alone or in combination of one or more of the ionic polymer dispersant selected from one or more, and the content thereof is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the entire aqueous solution.

If the content of the dispersant is less than 0.01 parts by weight, the reaction stability is broken during suspension polymerization, and if the content of the dispersant is more than 10 parts by weight, the formation of subgroups (emulsion dog particles) increases, and the toner base particle size is smaller than desired. Because it can be formed.

On the other hand, the anionic surfactant may be selected from the group consisting of fatty acid salts, alkyl sulfate ester salts, alkyl aryl sulfate ester salts, dialkyl sulfosuccinate salts, alkyl phosphates, etc., the content of the entire aqueous solution When viewed at 100 parts by weight, it is preferably 0.001 to 20 parts by weight. If the content is less than 0.001 part by weight, the reaction stability may be adversely affected during suspension polymerization. If the content is 20 parts by weight or more, the formation of side reactants (emulsion particles) is increased, and the toner base particle size is larger than that desired. This is because it can be formed small.

(2) second step: monomer mixture preparation step

In this step, a binder resin monomer, a charge control agent, a pigment, a wax-o-gas fine chain transfer agent, and the like are mixed to prepare a monomer mixture as a polymerization raw material. Be prepared.

First, an aromatic vinyl monomer, acrylate monomer, methacrylate monomer or a common combined diene monomer alone or ^"at least one, and stirred to prepare a monomer binder Souza. Charge binder, pigment, wax, and chain transfer agent are added to the prepared binder resin monomer and stirred to form a monomer mixture.

On the other hand, it is preferable to further add a crosslinking agent to the monomer mixture. This is because, when the toner is prepared by adding a crosslinking agent to the monomer mixture, it is advantageous to prevent puncturing between the toners and to improve storage.

On the other hand, the monomer for the binder resin in the present invention can be used all monomers used in the toner produced by the polymerization method is not particularly limited. Examples of the monomers include styrene monomers, acrylate monomers, methacrylate monomers, diene monomers, and the like, and one or more of them may be used in combination. In addition, an acidic olefin monomer or a basic olefin monomer may be optionally used in combination with the monomer.

The binder resin may include a polymer or copolymer of a styrene monomer, an acrylate monomer, a methacrylate monomer, a diene monomer, an acidic olefin monomer, and a basic olefin resin or a mixture thereof. However, the present invention is not limited thereto, and various monomers known to be usable for the formation of the toner prepared by the suspension polymerization method may be used without particular limitation, and from such monomers, a polymer or a copolymer which becomes the binder resin of the polymerized toner may be formed. Can be.

In addition, the binder resin (a) a styrene monomer; And (b) a polymer or copolymer of at least one monomer selected from the group consisting of an acrylate monomer, a methacrylate monomer and a diene monomer. The polymer is polymerized with 30 to 95 parts by weight of the monomer of (a) and 5 to 70 parts by weight of the monomer of (b) based on 100 parts by weight of the monomer (a) and the monomer of (b). It may include one. This content range is for adjusting the glass transition temperature of the polymerized toner, When containing less than 30 parts by weight of the monomer of (a) the glass transition temperature is too low may cause an offset phenomenon, when it exceeds 95 parts by weight, the glass transition temperature may be too high to fixability.

Such a polymer is a monomer selected from the group consisting of the styrene monomer of (a), (b) an acrylate monomer, a methacrylate monomer and a diene monomer, (C) an acidic olefin monomer, and It may be a polymerized one or more monomers selected from the group consisting of basic olefin monomers. At this time, the monomer of (c) may be polymerized to 0.1 to 30 parts by weight based on 100 parts by weight of the monomer of (a) and the monomer of (b). Styrene monomers for the formation of the binder resin include styrene, monochlorostyrene, methyl styrene, dimethyl styrene and the like. Examples of the monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylnuclear acrylate, and phenyl acrylate. And, as the methacrylate monomer, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, dodecyl methacrylate, octyl methacrylate, 2-ethylnuclear methacrylate The diene monomers include butadiene, isoprene and the like. The acrylate-based monomers, methacrylate-based monomers, diene-based monomers may be used alone or in combination of one or more, the content thereof is preferably 5 to 70 parts by weight based on the total weight of the monomer mixture. In this way, the content is limited in order to adjust the glass transition temperature of the toner to an appropriate level as in the case of the styrene monomer.

In addition, the acidic olefin monomers may include α, -ethylenically unsaturated compounds having a carboxyl group, and the like, and the basic olefin resins may include methacrylic acid esters or methacrylamides of aliphatic alcohols having amine groups or quaternary ammonium groups. Vinyl amine type, diallyl amine type, ammonium salt thereof, etc. can be used, It can be used individually or in mixture of 1 or more types. Its content is preferably 0.1 to 20 parts by weight based on the total weight of the monomer mixture. Acidic olefinic monomers and basic olefinic monomers If it is added to improve the charging property of the surface exceeds 20 parts by weight, the reaction stability deteriorates during toner polymerization, and the toner base particles may agglomerate with each other.

The charge control agent is at least one cation selected from the group consisting of nigrosine dyes, nigro-type electron accepting dyes, high aliphatic metal salts, alkoxy amines, chelates, quaternary ammonium salts, alkylamides, fluorine treatment actives and metal salts of naphthalic acid Sex charge regulators; Or at least one anionic charge selected from the group consisting of electron acceptor organic complexes, chlorinated paraffins, chlorinated polyesters, polyesters containing acids, sulfonylamines of copper phthalocyanine and styrene-acryl-based polymers including sulfonic acid groups Modulators may be used, and at least one of them may be selected, and these may be used alone or in combination. At this time, the content of the charge control agent is preferably 0.01 to 20 parts by weight of the total weight of the monomer mixture. When the content of the charge control agent is less than 0.01 parts by weight may not have a sufficient charge density required for printing, when the amount exceeds 20 parts by weight may cause a phenomenon in which the amount of charge is rather reduced.

The pigments include inorganic dyes selected from the group consisting of metal powder pigments, metal water oxidized pigments, carbon pigments, sulfide pigments, chromium salt pigments, and ferrocyanide pigments; Or an organic dye selected from the group consisting of azo pigments, acid dye pigments, basic dye pigments, modant dye pigments, phthalocyanine, quinacridone pigments, and dioxane pigments; It can select and use 1 or more types from among. The content of the pigment is preferably 1 to 20 parts by weight based on the total amount of the monomer mixture. When the pigment is less than 1 part by weight, it may be difficult to achieve a desired color in a sufficient amount, and when the pigment is more than 20 parts by weight, dispersion between the monomer and the pigment may not be effectively performed.

The wax may be petroleum refined wax, natural wax, synthetic wax, or the like. Petroleum refined waxes include paraffin wax, microcrystalline wax and ceresin wax. Natural waxes include carnauba wax, synthetic waxes include polyester waxes, Polyolefin waxes such as polyethylene and polypropylene, and the like, but are not particularly limited thereto. The waxes may be used alone or in combination of one or more, the content of the wax is preferably 0.01 to 30 parts by weight based on the total weight of the monomer mixture.

The chain transfer agent may use at least one of t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl metgatan, carbon tetrachloride, carbon tetrabromide, and the like. The content of the chain transfer agent is preferably about 0.01 to 10 parts by weight based on the whole monomer mixture.

Examples of the crosslinking agent include divinylbenzene, ethylene dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, 1,6-nuclear methylene diacrylate, allyl methacrylate, 1,1,1-trimethyl Epropane triacrylate, triallylamine, tetraallyloxyethane or a mixture thereof may be used, and the content thereof is preferably 0.001 to 10 parts by weight based on the total weight of the monomer mixture. When the content of the crosslinking agent is less than 0.001 part by weight, it may be difficult to expect the effect of improving the storage properties, and when the content of the crosslinking agent exceeds 10 parts by weight, gelation may occur inside the toner, which may cause a problem of inferior fixability of the toner during printing.

(3) third step: suspension polymerization step

The polymerization initiator is added to the monomer mixture prepared in the second step, and the monomer mixture is added to the aqueous dispersion prepared in the first step. The aqueous dispersion containing the monomer mixture is subjected to shearing force by suspension polymerization.

As the polymerization initiator, an oil-soluble initiator and a water-soluble initiator can be used. Specifically, Azo initiators, such as azobisisobutyronitrile and azobisdimethylvaleronitrile; 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, Among these, 1 type (s) or 2 or more types can be used in mixture. The content of the polymerization initiator is preferably 0.01 to 5 parts by weight based on the whole monomer mixture. If the content is less than 0.01 parts by weight may cause miso material, 5 This is because the reaction rate is too fast when the weight part is exceeded, which may cause a problem in that the reaction stability is lowered.

(4) 4th step: dispersant separation and drying step

Upon completion of the polymerization, depending on the type of dispersant, a basic aqueous solution or an acidic aqueous solution is added to remove the dispersant, washed with water and filtered to separate the dispersant. For example, when colloidal silica is used as the aqueous dispersant, the colloidal silica can be removed by adding NaOH having a concentration of 0.05 to 0.0 N. The process is repeated until the dispersant is completely separated from the toner. When the dispersant is completely separated from the toner, the toner base particles are put in a vacuum oven and dried at room temperature for 48 hours to obtain the final toner base particles.

As in the toner manufacturing method of the present invention, colloidal silica in which the particle size is large and the particles are coarsely or fused to each other in a toner base particle including a binder resin monomer, a charge control agent, a pigment, a wax, and the like, and a hydrophobic silica having a small particle size By using a mixture of toner base particles, the surface charge of the toner base particles is uniform and the charge is kept constant over time, thereby producing toners having improved cleaning properties and charging characteristics such as fluidity, background contamination, transfer efficiency, etc. can do.

On the other hand, the polymerized toner according to the present invention may have excellent physical properties capable of realizing a uniform image with a high image density and excellent transfer efficiency with a narrow particle size distribution. In particular, depending on the characteristics of the toner and other external additives used, it causes contamination on the drum surface, but using colloidal silica can improve drum contamination with minimal drum wear.

In the present invention, matters other than those described above can be added or subtracted as necessary, and therefore the present invention is not particularly limited.

【Effects of the Invention】

The present invention provides a polymerized toner that significantly improves the cleaning performance in a wiper blade by including certain colloidal silica as an external additive, and a method of manufacturing the same.

In particular, the polymerized toner according to the present invention uses a spherical toner core made by suspension polymerization and uses a carrier. The BG, which is caused by the contamination of components such as PCR and drums, which are severely generated in the component cartridge, has also been improved, and it can also show excellent performance in terms of transfer efficiency.

[Brief Description of Drawings]

1 is a SEM photograph of a polymerized toner prepared according to Example 2 of the present invention.

Figure 2 shows a S01 picture of the polymerized toner prepared according to Example 4 of the present invention.

3 is a SEM photograph of a polymerized toner prepared according to Example 7 of the present invention.

[Specific contents to carry out invention]

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

Example 1

Preparation of Toner Base Particles

2,000 g of distilled water and 48.8 g of colloidal silica as a dispersant were dissolved in a reactor having a volume of 3,000 mL, and an aqueous dispersion was prepared in which the temperature was raised to 70 ^° C., a reaction temperature.

Into another vessel, 720 g of styrene, 160 g of n-butyl acrylate, 18 g of allyl methacrylate, and 45 g of carbon black were added, stirred with a bead mill at a speed of 2,000 rpm for 2 hours, and then removed. 500 g of the monomer mixture were prepared. The prepared mixture was heated in 70 ^° C. to increase the temperature, and 4.5 g of styrene-acrylic polymer charge control agent including sulfonic acid group and 23 g of paraffin wax were added thereto, and the mixture was dissolved for 20 minutes while stirring. 8.5 g of azobisisobutyronitrile, which is a polymerization initiator, was added to the monomer mixture that was dissolved, and the mixture was stirred for 3 minutes to prepare a semi-aqueous product.

The reaction was introduced into an aqueous dispersion and reaction continued while stirring for 20 minutes at a speed of 10,000 rpm with a homogenizer. Normal after 20 minutes After performing a suspension polymerization reaction by stirring at a speed of 500 rpm for 20 hours with a stirrer, the synthesized toner was washed with water and filtered repeatedly to remove the dispersant and vacuum-dried to prepare toner base particles.

External additive coating

For 100 parts by weight of the toner base particles prepared as described above, colloidal silica (silica single particle size 40-53 nm) having a volume average particle diameter of 0.2-0.3 jam was used as shown in Table 1 below. Was mixed and stirred for 7 minutes at a speed of 5,000 rpm with a Henschel blender to coat the external additive on the surface of the toner base particles.

In this case, the colloidal silica has a "uniform distribution", particles

The ratio of one is 30% to 40%, the proportion of particles in which two particles are fused together is 10% to 30%, and the proportion of particles in which three or more particles are fused is 10¾ to 30¾. Had a distribution.

[Examples 2-3]

As shown in Table 1, respectively, the content of the colloidal silica

Polymerized toner was prepared in the same manner as in Example 1, except that 3 parts by weight and 5 parts by weight were used differently.

EXAMPLES 4-8

As shown in Table 1 below. Polymerized toner was prepared in the same manner as in Example 1, except that the type and content of colloidal silica were used differently.

Here, the colloidal silica has a "non-uniform distribution", and the ratio of one particle is less than 30% or more than 4, and the ratio of particles in which two particles are fused to each other is less than 10% or 30%. More than 3, and the proportion of particles fused at least 3 particles had a distribution of less than 10% or more than 30%.

[Comparative Examples 1 ~ 26]

As shown in Table 1, the polymerization was carried out in the same manner as in Example 1, except that the type and content of colloidal silica were used differently. Toner was prepared. PCR toner contamination, transfer efficiency, image contamination (BG) background, and the like were evaluated for the polymerized toner prepared according to Examples 1 to 8 and Comparative Examples 1 to 26 as follows.

PCR Toner Contamination Assessment

The cartridge used in the laser printer cartridge (C2200, manufacturer: Xerox) was used to compare the occurrence of toner contamination of the PCR components. The cartridge uses a carrier and contains about 70 g of carrier, with some toner inside the cartridge as a carrier. In this state, the toner was replenished to further experiments. PCR contamination consumed about 20 g after about 70 g of toner was used up to completely consume the toner remaining as a carrier inside the cartridge, and then 5% coverage of A4 after cleaning the PCR of the cartridge again. About 500 sheets were consumed in a pattern and then the degree of contamination of the toner by PCR was compared to see whether the cleaning performance of the toner was effectively improved.

A: Good PCR contamination (no pollution)

B: Slightly good PCR contamination (less than 5¾>)

C: 20% occurrence of PCR contamination band)

D: PCR contamination is severely generated (20% to 60% occurs) Specific types of colloidal silica and 100 weight of toner base particles as external additives used in the polymerized toner prepared according to Examples 1 to 8 and Comparative Examples 1 to 26. The content of parts is shown in Table 1 below. In addition, the results of PCR contamination evaluation of the polymerized toner measured by the method as described above are shown in Table 1 together.

[Table 1]

As a result of evaluating the transfer efficiency and the image contamination (BG: background) for the polymerized toner together with the above-described PCT toner contamination evaluation as described above, in the case of Examples 1 to 8 according to the present invention, it was excellent in at least 85% or at least 90%. Transfer efficiency was obtained, and it was confirmed that no image contamination appeared in the non-image part. However, in the case of Comparative Examples 1 to 26, the transfer efficiency is significantly lowered to 70% or less according to PCT toner contamination, and the BG in the non-image part is a color in which PCT-contaminated toners are mixed, for example, heat is brown or the like. It was confirmed that burn contamination appeared.

In addition, SEM pictures of the polymerized toner prepared in Examples 2, 4 and 7 are shown in FIGS. As shown in Figs. 1 to 3, it is possible to confirm the state applied to the surface of the toner according to the degree of fusion of the colloidal silica. In particular, as shown in FIG. 3, in the case of TG-C190 having a very narrow particle size distribution of colloidal silica (Example 7), the degree of coating on the surface of the toner is very uniform. However, compared to the case of TG-C190 (Example 7) where the degree of fusion of colloidal silica is not sufficient (Example 7) or the case of SAKAI 1 having too much fusion of silica particles (Example 4), It can be seen that the silica particles are fused to each other, and thus, in the case of Example 2 having a uniform silica distribution, a better PCR toner contamination improvement, that is, a cleaning (improving) cleaning effect can be realized.

On the other hand, as shown in Table 1, according to the present invention Examples 1 to 8 and the type and content of the external additive using a colloidal silica in which the particle size is large and the particles are packed or fused with each other in a predetermined content range according to the present invention Comparing Comparative Examples 1 to 26 in which the above was changed, it can be seen that Examples 1 to 8 are superior to Comparative Examples 1 to 26 in terms of cleaning performance in the cleaning blade.

As such, when there is too little colloidal silica present on the surface of the toner, there is little effect of improving the cleaning, and when it is used excessively, it does not exist on the surface of the toner and is released, causing another problem. As a result, the size of the silica particles made of colloidal silica should have a particle size distribution larger than 0.1 _m , and it was confirmed that the cleaning improvement effect was excellent when the degree of fusion between the particles was uniform.

Claims

[Patent Claims]

[Claim 1]

Toner base particles including binder resins, pigments, charge control agents, and waxes; An external additive coated on the surface of the toner base particles;

Polymerized toner comprising a colloidal silica having a single particle size of 25 to 58 nm and a volume average particle size of 0.06 to 0.5 as the external additive.

[Claim 2]

The method of claim 1,

A polymerized toner containing the colloidal silica in an amount of 1.0 to 5.0 parts by weight based on 100 parts by weight of the toner base particles.

[Claim 3]

The method of claim 1,

The colloidal silica (colloidal silica) is a ratio of one particle is 30% to 40% based on the number, the ratio of two particles are fused to each other (10% to 30¾), three or more particles fused Polymerized toner, wherein the proportion of fused particles has a distribution of 10% to 30%.

[Claim 4]

According to claim 1,

Wherein the colloidal silica is hydrophobized with a silane coupling agent or silicone oil.

[Claim 5]

The method of claim 4,

The silane coupling agent is dimethyldichlorosilane, trimethylchlorosilane, methyltrichlorosilane, arylphenyldichlorosilane, benzyldimethylchlorosilane, bromine methyldichlorosilane, p—chlorophenyltrichlorosilane, 3-chloropropyltrime A polymerized toner which is at least one selected from the group consisting of methoxy, vinyltriethoxysilane, vinyltriacetoxysilane, divinylchlorosilane, and nuxamethyldisilagen.

[Claim 6]

The method of claim 4,

The silicone oil is dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, alkyl modified silicone oil, fluorine modified silicone oil, alcohol modified silicone oil, amino modified silicone oil, epoxy modified silicone oil, epoxy polyether modified silicone oil Phenolic modified silicone oil, epoxy modified silicone oil, carboxy modified silicone oil, and mercury-modified silacone oil.

[Claim 7]

The method of claim 1,

The binder resin is a polymerized toner containing a polymer of at least one monomer selected from the group consisting of styrene monomers, acrylate monomers, methacrylate monomers, diene monomers, acidic olefin monomers, and basic olefinic monomers.

[Claim 8]

The method of claim 1,

The charge control agent includes at least one cationic charge control agent selected from the group consisting of nigrosine dyes, high aliphatic metal salts, alkoxy amines, chelates, quaternary ammonium salts, alkylamides, fluorine treatment actives and metal salts of naphthalene acid; Or at least one anionic charge control agent selected from the group consisting of chlorinated paraffins, chlorinated polyesters, polyesters containing acids, sulfonylamines of copper phthalocyanine and styrene-acrylic polymers containing sulfonic acid groups. .

[Claim 9]

The method of claim 1,

The pigments include metal powder pigments, metal water oxidized pigments, carbon pigments, sulfide pigments, chromium salt pigments, ferrocyanide pigments, azo pigments, acid dye pigments, basic dye pigments, and mordant dyes. Polymerized toner containing at least one selected from the group consisting of pigments, phthalocyanine, quinacridone pigments, and dioxane pigments.

[Claim 10]

The method of claim 1,

The wax is at least one selected from the group consisting of paraffin wax, microcrystalline wax, ceresin wax, carnauba wax, polyester wax, and polyolefin wax.

[Claim 11]

The method of claim 1 wherein.

The toner base particles may include 50 to 95 wt% of binder resin, 1 to 20 wt% of pigment, 0.1 to 5 wt% of charge control agent, and 0.1 to 30 wt% of wax.

[Claim 12]

The method of claim 1,

The toner base particles may further include at least one additive selected from the group consisting of a reaction initiator, a crosslinking agent, a molecular weight adjusting agent, a lubricant, and a coupling agent.

[Claim 13]

The method of claim 12,

The toner base particles are 50 to 95 weight ¾ of the binder resin; 1 to 20 wt% pigment; 0.1 to 5 wt% charge control agent; Wax 0.1-30 weight ¾; And banung initiator, crosslinking agent, chain transfer agent, a lubricant, a ^', and the coupling agent at least one additive selected from the group consisting of 10 polymerized toner containing by weight less than ¾.

[Claim 14]

Forming an aqueous dispersion comprising a dispersant;

Forming a monomer mixture comprising a binder resin, a pigment, a charge control agent, and a wax;

Adding the monomer mixture to the aqueous dispersion and forming a toner mother pressure through suspension polymerization; And

Coating an external additive on the surface of the toner base particles;

And, as the external additive, a colloidal silica having a single particle size of 25 to 58 nm and a volume average particle diameter of 0.06 to 0.5 / m. The manufacturing method of the polymeric toner containing.

[Claim 15]

The method of claim 14,

The suspension polymerization is a method for producing a polymerized toner comprising the step of reacting at 50 to 70 ^° C for 8 to 12 hours and the reaction for 30 minutes to 4 hours after heating up to 80 to 100 ^° C.

[Claim 16]

The method of claim 14,

Wherein the dispersant comprises at least one selected from the group consisting of inorganic dispersants, water-soluble organic polymer dispersants, and anionic surfactants.

[Claim 17]

The method of claim 14,

The monomer mixture further comprises at least one additive selected from the group consisting of a reaction initiator, a crosslinking agent, a molecular weight regulator, a lubricant, and a coupling agent.

[Claim 18]

The method of claim 14,

Forming the toner base particles,

Adding the monomer mixture to the aqueous dispersion;

Applying a shear force to the aqueous dispersion and the monomer mixture to homogenize the monomer mixture in the form of droplets in the aqueous dispersion; And

Suspension polymerizing the homogenized monomer mixture

Method for producing a polymerized toner comprising a.