WO2013168884A1 - Polymerized toner and method for producing same - Google Patents
Polymerized toner and method for producing same Download PDFInfo
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- WO2013168884A1 WO2013168884A1 PCT/KR2013/001032 KR2013001032W WO2013168884A1 WO 2013168884 A1 WO2013168884 A1 WO 2013168884A1 KR 2013001032 W KR2013001032 W KR 2013001032W WO 2013168884 A1 WO2013168884 A1 WO 2013168884A1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/0802—Preparation methods
- G03G9/0804—Preparation methods whereby the components are brought together in a liquid dispersing medium
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/0819—Developers with toner particles characterised by the dimensions of the particles
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09708—Inorganic compounds
- G03G9/09725—Silicon-oxides; Silicates
Definitions
- 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.
- 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.
- 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.
- 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.
- a 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.
- 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.
- 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.
- dr 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.
- 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
- 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.
- 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.
- 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.
- 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.
- 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.
- the polymerized toner having a specific colloidal silica coated with an external additive on the surface of the toner base particles.
- 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.
- a carrier carrier
- the shape of the toner is divided into spherical balls or potato shaped potatoes and irregular shapes.
- 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.
- 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.
- the ratio of one particle is based on the number of particles.
- 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.
- 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.
- 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.
- 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.
- particle size measurement of the used silica may be performed using a scanning electron microscope (SEM) and a particle size distribution analyzer.
- SEM scanning electron microscope
- 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.
- the shape of the toner is classified into spherical shape, potato, and irregular shape.
- 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.
- 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.
- dimethylsilicone oil, methylphenylsilicone oil, methylhydrogensilicone oil and the like are preferably used from the standpoint of charging stability at high humidity.
- 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.
- 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.
- 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.)
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- the acidic olefin monomer may be an ⁇ , ⁇ -ethylenically unsaturated compound having a carboxyl group, and the like
- 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.
- 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.
- 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.
- the binder resin 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.
- 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.
- the charge control agent 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.
- a problem of broadening the particle size distribution may occur, so that an appropriate content may be used.
- the wax when 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 53 ⁇ 4 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.
- 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.
- 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.
- 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.
- the glass transition temperature 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.
- 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
- 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.
- SBS styrene-butadiene-styrene
- the molecular weight 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.
- the wax component a wax known to be applicable to a polymerized toner can be used without particular limitation.
- 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.
- 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.
- a reaction initiator e.g., a crosslinking agent
- a molecular weight regulator e.g., a molecular weight regulator
- a lubricant eg, oleic acid, stearic acid, etc.
- ⁇ 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.
- an oil-soluble initiator and a water-soluble initiator can be used.
- Azo-based initiators such as azobisisobutyronitrile and azobisvaleronitrile
- Organic peroxides such as benzoyl peroxide and lauroyl peroxide
- water-soluble initiators such as potassium persulfate and ammonium persulfate, etc.
- 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.
- 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 3 ⁇ 4>; 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 3 ⁇ 4>; 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.
- the volume average particle diameter of the toner base particles according to the present invention may be 4 to 10, preferably 5 to 8 ⁇ ⁇ , 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.
- 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.
- the manufacturing conditions for making the pulverized toner spherical can be almost determined depending on the mechanism to be applied.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- the dispersant may be mixed with water to form the aqueous dispersion.
- 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.
- the dispersant serves to stabilize the droplet particles by being uniformly adsorbed on the surface of the droplet.
- 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.
- 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.
- water-soluble organic dispersant examples 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.
- 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.
- 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.
- 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.
- 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).
- specific examples of the binder resin monomer, pigment, pigment stabilizer, charge control agent, and wax contained in the monomer mixture is as described above.
- 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.
- the polymerization reaction can be performed to form spherical toner base particles of an appropriate size.
- a homogenizer may be used to homogenize the monomer mixture and the aqueous dispersion by applying shear force.
- 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.
- Removing the dispersant may include adjusting to a pH suitable for dissolution of the dispersant.
- a water-soluble inorganic acid such as hydrochloric acid or nitric acid
- the dispersant may be dissolved in an aqueous solution and removed from the toner base particles.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- the preparation of the toner base particles used in the present invention is as follows.
- the dispersant At least one of inorganic and water-soluble organic dispersants may be selected and used, and anionic surfactants may be optionally added.
- 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
- 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.
- 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.
- 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.
- Charge binder, pigment, wax, and chain transfer agent are added to the prepared binder resin monomer and stirred to form a monomer mixture.
- a crosslinking agent 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- the monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylnuclear acrylate, and phenyl acrylate.
- 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.
- the acidic olefin monomers may include ⁇ , -ethylenically unsaturated compounds having a carboxyl group, and the like
- 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.
- the content of the charge control agent is preferably 0.01 to 20 parts by weight of the total weight of the monomer mixture.
- 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.
- crosslinking agent examples 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.
- 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.
- 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.
- an oil-soluble initiator and a water-soluble initiator can be used.
- Azo initiators such as azobisisobutyronitrile and azobisdimethylvaleronitrile
- Organic peroxides such as benzoyl peroxide and lauroyl peroxide
- water-soluble initiators such as potassium persulfate and ammonium persulfate, etc.
- 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.
- a basic aqueous solution or an acidic aqueous solution is added to remove the dispersant, washed with water and filtered to separate the 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.
- 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.
- 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
- 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
- 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.
- it causes contamination on the drum surface, but using colloidal silica can improve drum contamination with minimal drum wear.
- 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.
- 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.
- Example 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.
- Example 3 is a SEM photograph of a polymerized toner prepared according to Example 7 of the present invention.
- 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.
- styrene 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.
- 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.
- Table 1 was used as shown in Table 1 below.
- 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 103 ⁇ 4 to 303 ⁇ 4. Had a distribution.
- 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.
- Polymerized toner was prepared in the same manner as in Example 1, except that the type and content of colloidal silica were used differently.
- 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%.
- Example 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.
- 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.
- FIGS. SEM pictures of the polymerized toner prepared in Examples 2, 4 and 7 are shown in FIGS.
- 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.
- 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.
- Example 7 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.
- 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.
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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
【명세서】 【Specification】
【발명의 명칭】 [Name of invention]
증합 토너 및 그의 제조 방법 Stacked toner and its manufacturing method
【기술분야】 Technical Field
본 발명은 전사 사진법 또는 중합 토너, 기존의 분쇄 및 구형화 방법에 의해 사용되는 토너에 관한 것으로, 더욱 상세하게는 외첨제로서 콜로이달 실리카를 사용하여 와이퍼 블레이드 (wiper blade)에서의 클리닝 (cleaning) 기능을 개선하고 PCR, 드럼 또는 전사 벨트 둥의 부품 오염을 현저히 개선할 수 있는 중합 토너 및 그의 제조 방법에 관한 것이다. 【배경기술】 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
토너는 전자 사진 현상 및 정전기적 프린터, 복사기 등에 사용되는 것으로, 피 전사물에 전사 및 정착되어 원하는 패턴을 형성할 수 있는 도료를 말한다. 최근 컴퓨터를 이용한 문서 작성 등아 일반화됨에 따라 프린터와 같은 화상 형성 장치의 수요가 급격히 증가하고 있으며, 이에 따라토너의 사용량 또한 증가되고 있는 실정이다. 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.
일반적으로 프린터에 사용되는 토너는 제조 방법에 따라 기존의 분쇄 방법으로 만든 분쇄 토너와 기계적 구형화와 열풍 구형화 방법을 적용한 구형화 토너 그리고 중합 방법으로 만든 중합 토너로 3 가지로 나누어진다. 각 제조 방법에 따라 토너의 모양이나 구형 정도가 다르며, 토너 내부의 구조와사용된 원료의 분산 정도도 다르다. 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.
최근에는 고해상도와 저온 정착의 성능 개선을 위하여 고해상도를 구현하가 위하여 토너 입도 분포를 작게 만들고 좁은 입경 분포를 가지는 토너를 만들기 위하여 중합 방법으로 토너를 제조하고 있으며 더불어 저온 정착을 가능하도록 하기 위하여 왁스의 함량올 높이고 분자량을 낮추는 방법이 용이한 중합 방법으로 토너를 만들고 있다 . 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.
기존의 제조 방법인 분쇄 토너 제조 방법을 이용하여 입경 분포 개선과 저온 정착을 위하여 분자량을 낮은 수지를 사용하는 방법이 있기는 하지만 중합 방법으로 만든 토너에 비하여 물성이 저하되는 것은 사실이다. 분쇄 토너 방법으로 제조된 토너는 위와 같은 단점은 있지만 특히 현탁 중합 방법으로 제조된 구형의 토너와 다르게 매우 불규칙적인
모양으로 되어 있어 중합 방법으로 제조된 구형 토너 대비 와이퍼 블레이드 (wiper blade)에서 클리닝 (cleaning)이 상대적으로 잘된다. 반대로 중합 방법으로 만든 구형 모양 토너는 클리닝 (cleaning)이 잘되지 않는 문제점을 가지고 있다. 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.
와이퍼 블레이드 (wiper blade)에서의 발생하는 클리닝 문제는 카트리지의 종류 또는 설계에 따라 문제가 심하게 나오기도 한다. 토너에 대전 특성을 부여하기 위한 방법으로 dr. blade를 사용하는 일성분계용 카트리지는 sleeve와 dr. blade 사이를 통과하는 토너들이 과도한 마찰 (friction)로 인하여 사용된 외첨제들이 토너 표면에서 이탈을 많이 하므로 드럼과 와이퍼 블레이드 (wiper blade)간에 마찰 (frict ion)이 과도하게 발생하도록 설계되어 있으며 이로 인하여 종이로 전사되지 못하고 남아있는 토너나 외첨제들을 효과적으로 제거가 가능하다. 그리고 와이퍼 블레이드 (wiper blade)와 드럼간의 강한 마찰력으로 인하여 드럼 마모가 심하게 발생하여 드럼을 장기간 사용하는 것이 어렵다. 드럼과 와이퍼 블레이드 (wiper blade)간의 마찰력을 감소하는 목적으로 윤활제를 첨가하기도 하지만 이로 인하여 추가적인 현상 특성 저하의 원인이 되기도 한다. Dr. blade 대신 캐리어 (carrier )를 사용하는 이성분계용 카트리지는 캐리어 (carrier)와 토너를 믹싱 (mixing)하는 방법으로 토너에 대전 특성을 부여하므로 토너는 과도한 마찰 (frict ion)을 받지 않아 토너 표면에 존재하는 외첨제들이 토너 표면에서 이탈이 일어나지 않으므로 이를 제거하기 위하여 드럼과 와이퍼 블레이드 (wiper blade)간의 마찰 (friction)을 과도하게 할 필요가 없어 와이퍼 블레이드 (wiper blade)가 드럼과의 마찰로 인한 드럼 마모를 최소화하도록 설계가 되어 있다. 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
일성분계용 카트리지와 이성분계 카트리지의 와이퍼 블레이드 (wiper blade)에서 토너나 이탈된 외첨제들이 효과적으로 제거되지 못하면 드럼, PCR 또는 전사 벨트에 오염이 발생하게 된다. 이로 인하여 프린트된 화상에도 BG또는 균일하지 못한 화상이 되어 품질 저하의 원인이 된다. 위에서 설명한 문제는 기존의 불규칙한 모양을 가진 분쇄 토너나 구형화 토너 또는 중합 토너 모두에서 나타나지만 구형으로 만들어진
구형화 토너 또는 중합토너에서 더 심하게 나타난다. 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.
따라서, 클리닝 블레이드에서의 클리닝 성능이 우수할 뿐만 아니라 유동성, 배경오염, 전사효율 등과 같은 토너 및 대전 성능이 우수한 중합 토너 개발에 대한 연구가 필요하다. 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.
【발명의 내용】 [Content of invention]
【해결하려는 과제】 [Problem to solve]
본 발명은 클리닝 블레이드에서의 클리닝 성능이 우수할 뿐만 아니라 유동성 배경오염, 전사효율 등과 같은 토너 및 대전 특성 등이 매우 우수한 중합 토너 및 이를 제조하는 제조하는 방법을 제공하고자 한다. 【과제의 해결 수단】 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]
본 발명은 바인더 수지, 안료, 전하조절제, 및 왁스를 포함하는 토너 모입자; 및 상기 토너 모입자 표면에 코팅된 외첨계;를 포함하고, 상기 외첨제로서 단일 입자 크기가 25 내지 58 nm이며 체적평균입경이 0.06 내지 0.5 //m인 콜로이달 실리카 (colloidal silica)를 포함하는 중합 토너를 제공한다. 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.
본 발명은 분산제를 포함하는 수계 분산액을 형성하는 단계; 바인더 수지용 단량체, 안료, 전하 조절제, 및 왁스를 포함하는 단량체 흔합물을 형성하는 단계; 상기 단량체 흔합물을 상기 수계 분산액에 첨가하고 현탁 중합을 통하여 토너 모입자를 형성하는 단계; 및 상기 토너 모입자 표면에 외첨제를 코팅하는 단계 ;를 포함하고, 상기 외첨제로서 단일 입자 크기가 25 내지 58 nm이며 체적평균입경이 0.06 내지 0.5 皿인 콜로이달 실리카 (colloidal silica)를 포함하는 중합토너의 제조 방법을 제공한다. 이하, 발명의 구체적인 구현예에 따른 중합 토너의 제조 방법 및 이에 따라 제조되는 중합 토너에 대하여 상세하게 설명하기로 한다. 다만, 이는 발명의 하나의 예시로서 제시되는 것으로, 이에 의해 발명의 권리범위가 한정되는 것은 아니며, 발명의 권리범위 내에서 구현예에 대한 다양한 변형이 가능함은 당업자에게 자명하다. 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.
본 명세서 전체에서 특별한 언급이 없는 한 "포함" 또는 "함유"라 함은 어떤 구성 요소 (또는 구성 성분)를 별다른 제한 없이 포함함을
지칭하며, 다른 구성 요소 (또는 구성 성분)의 부가를 제외하는 것으로 해석될 수 없다. 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).
발명의 일 구현예에 따르면, 토너 모입자 표면에 특정의 콜로이달 실리카가 외첨제로 코팅된 중합 토너가 제공된다. 특히, 상기 중합 토너는 바인더 수지, 안료, 전하조절제, 및 왁스를 포함하는 토너 모입자; 및 상기 토너 모입자 표면에 코팅된 외첨제;를 포함하고, 상기 외첨제로서 단일 입자 크기가 25 내지 58 nm이며 체적평균입경이 0.06 내지 0.5 인 콜로이달 실리카 (colloidal silica)를 포함할 수 있다. 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.
본 발명자들은, 중합법으로 제조된 구형의 모입자에 입자 사이즈가 크고 입자끼리 서로 웅집 또는 융합되어 있는 특정의 콜로이달 실리카를 사용하여 클리닝 블레이드에서의 클리닝 성능뿐만 아니라 유동성, 배경오염, 전사효율 등가 같은 토너 및 대전 특성이 향상될 수 있음을 확인하고 본 발명을 완성하게 되었다. 이에 따라, 본 발명의 중합 토너는 균일한 화상의 구현을 요구하는 전자 사진의 현상 등의 적용 분야에 적용 가능하고, 이를 이용하면 높은 해상도 및 색상구현도로 뛰어난 품질의 인쇄 결과물을 얻을 수 있다. 특히, 본 발명은 캐리어 (carrier)를 사용하는 카트리지에서 클리닝 (cleaining)이 되지 않는 문제가 더욱 심하게 발생하므로 클리닝 (cleaning) 성능을 개선하여 프린터의 부품 오염을 효과적으로 개선할 수 있다. 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.
토너 제조 방법에 따라 토너의 모양이 공 같은 구형 또는 감자같이 생긴 감자 모양 (potato) 그리고 부정형으로 구분이 된다. 더불어 사용하는 토너의 모양에 따른 종류에 더불어 카트리지도 캐리어 (carrier)를 사용하는 것과 사용하지 않는 것으로 구별된다. 토너의 모양보다는 캐리어 (carrier)를 사용하는 카트리지를 사용할 경우 클리.닝 (cleaning) 와이퍼 (wiper)에서 클리닝 (cleaning)이 제대로 되지 않아 PCR에 토너 오염이 발생하게 된다. 본 발명의 중합 토너는 토너 모입자에 외첨제로서 특정의 콜로이달 실리카를 사용하으로써 토너의 클리닝 (cleaning) 성능을 개선하여 PCR토너 오염을 현저히 개선할 수 있다. 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.
먼저, 본 발명의 중합 토너에서, "콜로이달 실리카' '는 졸-겔 (sol- gel) 방법 등으로 제조된 실리카를 지칭하는 것이며, 상기 콜로이달
실리카는 체적평균입경 0.06 내지 0.5 im (micrometer), 바람직하게는 0.07 내지 0.4 urn, 좀더 바람직하게는 0.08 내지 0.3 가 될 수 있다. 상기 콜로이달 실리카는 클리닝 (cleaning) 개선 측면에서 체적평균입경 0.06 이상이 될 수 있으며, 드럼 마모 감소 측면에서 0.5 이하가 될 수 있다. 상기 콜로이달 실리카는 입자 1개로 되어 있는 비율이 개수 기준으로First, 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% 내지 40%이며, 입자 2개가 서로 융합 (Fused)된 입자의 비율이 10% 내지 30%이며, 입자 3개 이상 융합 (Fused)된 입자의 비율이 10% 내지 30%의 균일한 분포를 갖는 것일 수 있다. 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.
또한, 상기 콜로이달 실리카는 실리카 단일 입자 크기가 25 내지 58 nm(nanometer), 바람직하게는 55 nm 이하, 좀더 바람직하게는 53 nm 이하가 될 수 있다. 이때, 상기 실리카 단일 입자 크기는 전자현미경, 예컨대, 주사전자현미경 (SEM, Scanning Electron Microscope) 및 투과전자현미경 (TEM, Transmission Electron Microscope)을 이용한 방법으로 측정할 수 있으며, 단일 입자의 평균 입경이라고 정의할 수 있다. 본 발명의 콜로이달 실리카를 구성하는 실리카 입자 1개의 단일 입자 크기는 너무 미세한 입자 자체가 부품 오염의 원인이 되는 것을 방지하는 측면에서 25 nm 이상이 될 수 있으며, 부품 오염 개선 효과를 증대하는 측면에서 58 nm 이하가 될 수 있다. 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.
상술한 바와 같이, 입자 사이즈가 크고 입자끼리 서로 웅집 또는 융합되어 있는 콜로이달 실리카의 함량은 토너 모입자 100 중량부에 1.0 증량부 내지 5.0 중량부, 바람직하게는 1.2 중량부 내지 4.0 중량부, 좀더 바람직하게는 1.5 중량부 내지 3.0 중량부로 사용될 수 있다. 상기 콜로이달 실리카는 클리닝 (cleaning) 개선 측면에서 1.0 중량부 이상으로 사용되어야 하며, 드럼 마모 감소 측면에서 5.0 중량부 이하로 사용되어야 한다. 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.
이때, 사용된 실리카의 입도 측정은 주사전자현미경 (SEM: scanning electron microscope) 및 입도 분포 측정기를 이용하여 수행할 수 있다. 또한, 상술한 바와 같은 콜로이달 실리카의 평균입경 범위는 퓨즈드 (fused)된 입자에 대한 것이며, 퓨즈드 (fused)되지 않은 개별 입자만을 사용하였을 때는 클리닝 (cleaning) 개선 효과가 떨어질 수도 있다.
토너 제조 방법에 따라 토너의 모양이 구형, 포테이토, 그리고 부정형으로 구분이 된다. 더불어 사용하는 토너의 모양에 따른 종류에 더불어 카트리지도 캐리어를 사용하는 이성분계 시스템과 캐리어를 사용하지 않는 일성분계 시스템으로 구분된다. 토너의 모양보다는 캐리어를 사용하는 카트리지를 사용할 경우 클리닝 블레이드에서 클리닝이 제대로 되지 않아 PCR에 토너 오염이 발생하게 된다. 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.
토너에 일반적으로 사용하고 있는 입자 사이즈가 작은 50 nm 이하의 소수성 실리카는 소수화 표면 처리 물질 또는 실리카 제조 회사별 대부분의 제품을 사용하여도 클리닝 블레이드에서 클리닝이 제대로 되지 않아 PCR 토너 오염이 발생한다. 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.
상기 클리닝 문제를 해결하기 위해 입자 사이즈가 크고 입자끼리 서로 웅집 또는 융합된 콜로이달 실리카를 사용하면 PCR 토너 오염이 완전히 개선된다. 상기 입자 사이즈가 크고 입자끼리 서로 웅집 또는 융합된 콜로이달 실리카의 함량은 토너 모입자 100 중량부에 대해서 1 중량부 내지 5 중량부가 될 수 있다. 사용 함량이 1 중량부 이하이면 PCR 토너 오염이 완전히 개선되지 않을 수 있으며, 5 중량부 이상 사용하면 코팅되지 않은 실리카들이 많아 드럼 마모가 심하게 발생하거나 정착부를 통해 토너 모입자를 종이에 부착하기 어려울 수 있다. 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.
상기 입자 사이즈가 크고 입자끼리 서로 응집 또는 융합되어 있는 콜로이달 실리카는 실란계 커플링제 또는 실리콘 오일 등을 실리카 입자에 도포 또는 부착하는 표면 처리 등을 사용하여 소수화 처리될 수 있다. 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.
상기 실란계 커플링제는 디메틸디클로로실란, 트리메틸클로로실란, 메틸트리클로로실란, 아릴페닐디클로로실란, 벤질디메틸클로로실란, 브름메틸디클롤로실란, P-클로로페닐트리클로로실란, 3- 클로로프로필트리메톡시, 비닐트리에톡시실란, 비닐트리아세록시실란, 디비닐클로로실란, 및 핵사메틸디실라젠으로 이루어진 군에서 선택된 1종 이상이 사용될 수 있다. 이 중, 드럼과의 부착성 (adhesion) 증진 측면에서 디메틸디클로로실란, 트리메틸클로로실란, 메틸트리클로로실란 등을 사용하는 것이 바람직하다. 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.
상기 실리콘 오일은 디메틸실리콘 오일, 메틸페닐실리콘 오일,
메틸하이드로젠실리콘 오일, 알킬 변성 실리콘 오일, 불소 변성 실리콘 오일, 알코올 변성 실리콘 오일, 아미노 변성 실리콘 오일, 에폭시 변성 실리콘 오일, 에폭시 폴리에이텔 변성 실리콘 오일, 페놀 변성 실리콘 오일 에폭시 변성 실리콘 오일, 카르복시 변성 실리콘 오일, 및 머캅토 변성 실리콘 오일로 이루어진 군에서 선택된 1종 이상이 사용될 수 있다. 이 중, 고습에서의 대전안정성 측면에서 디메틸실리콘 오일, 메틸페닐실리콘 오일, 메틸하이드로젠실리콘 오일 등을 사용하는 것이 바람직하다 . 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.
상기 실리카를 토너 모입자에 부착시키는 방법으로 터빈형 교반기, 헨쉘 믹서, 슈퍼 믹서 등의 일반적인 교반기를 이용하는 방법, 또는 표면 개질기로 불리는 장치 (나라기계제작소사의 "나라 하이브리다이제이숀 시스템") 등올 이용하는 방법이 있다. 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.
한편, 본 발명의 토너 모입자에 바인더 수지용 단량체는 중합법으로 제조되는 토너에 사용되는 모든 단량체를 사용할 수 있으며 특별히 제한되지 않는다. 단량체의 예로는 스티렌계 단량체, 아크릴레이트계 단량체, 메타크릴레이트계 단량체, 또는 디엔계 단량체 등을 들 수 있으며, 이들 중에서 1종 이상을 흔합하여 사용할 수 있다. 또한, 상기 단량체에 선택적으로 산성 올레핀계 단량체 또는 염기성 올레핀계 단량체를 1종 이상 흔합하여 사용할 수도 있다. 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.
상기 바인더 수지는 스티렌계 단량체, 아크릴레이트계 단량체, 메타크릴레이트계 단량체, 디엔계 단량체, 산성 올레핀계 단량체 및 염기성 올레핀계 단량체 또는 이들의 흔합물와 중합체 또는 공중합체를 포함할 수 있다. 다만, 이에 한정되는 것은 아니며, 현탁중합법으로 제조되는 토너의 형성을 위하여 사용 가능한 것으로 알려진 다양한 단량체를 별다른 제한 없이 사용할 수 있으며, 이러한 단량체로부터 중합 토너의 바인더 수지로 되는 중합체 또는 공중합체를 형성할 수 있다. 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.
또한, 상기 바인더 수지는 (a) 스티렌계 단량체; 및 (b) 아크릴레이트계 단량체, 메타크릴레이트계 단량체 및 디엔계 단량체로 이루어진 군에서 선택된 1종 이상 선택된 단량체의 중합체 또는 공중합체를 포함할 수 있다. 상기 중합체는, 상기 (a)의 단량체 및 (b)의 단량체를 합한 100 중량부에 대하여, 상기 (a)의 단량체의 30 내지 95 중량부와 상기
(b)의 단량체의 5 내지 70 중량부를 중합한 것을 포함할 수 있다. 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).
이러한 중합체는 상기 (a)의 스티렌계 단량체와, (b) 아크릴레이트계 단량체, 메타크릴레이트계 단량체 및 디엔계 단량체로 이루어진 군에서 1종 이상 선택된 단량체와, (c) 산성 올레핀계 단량체 및 염기성 올레핀계 단량체로 이루어진 군에서 선택된 1종 이상의 단량체의 중합한 것으로 될 수 있다. 이 때, 상기 (c)의 단탈체는 상기 (a)의 단량체 및 (b)의 단량체를 합한 100 중량부에 대하여 0.1 내지 30 중량부로 중합될 수 있다. 상기 바인더 수지의 형성을 위한 스티렌계 단량체로는 스티렌, 모노클로로스티렌, 메틸스티렌, 디메틸스티렌 등이 있으며, 상기 아크릴레이트계 단량체로는 메틸아크릴레이트 에틸아크릴레이트, n- 부틸아크릴레이트, 이소부틸아크릴레이트, 도데실 아크릴레이트, 2- 에틸핵실아크릴레이트 등이 있다. 그리고, 메타크릴레이트계 단량체로는 메틸 메타크릴레이트, 에틸메타크릴레이트, n-부틸 메타크릴레이트, 이소부틸 메타크릴레이트, 도데실 메타크릴레이트, 2-에틸핵실 메타크릴레이트 등이 있으며, 상기 디엔계 단량체로는 부타디엔, 이소프렌 등이 있다. 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.
또한, 상기 산성 올레핀계 단량체로는 카르복실기를 가진 α,β- 에틸렌 불포화 화합물 등을 사용할 수 있고, 염기성 올레핀계 단량체로는 아민기나 4차 암모늄기를 가진 지방족 알콜의 메타크릴산 에스테르계, 메타크릴 아미드계, 비닐 아민계, 디알릴 아민계나 이의 암모늄염 등을 사용할 수 있다. 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.
한편, 발명의 일 구현예에서, 상기 토너 모입자는 바인더 수지, 및 상기 바인더 수지에 분산된 안료, 전하 조절제, 및 왁스 등을 포함할 수 있으며, 추가로 안료안정제를 포함할 수도 있다. 그리고, 이러한 토너 모입자는 바인더 수지 50 내지 95 증량 %, 바람직하게는 60 내지 93 증량 %, 좀더 바람직하게는 70 내지 90 중량 %; 안료 1 내지 20 중량 %, 바람직하게는 2 내지 15 중량 ¾, 좀더 바람직하게는 3 내지 10 중량 %; 전하 조절제 0.1 내지 5 중량 %, 바람직하게는 0.3 내지 4 중량 %, 좀더 바람직하게는 0.5 내지 3 중량 %; 및 왁스 0.1 내지 30 중량 %, 바람직하게는 1 내지 25 중량 %,
좀더 바람직하게는 5 내지 20 중량 %를 포함할 수 있으며, 추가로 안료안정제 0.1 내지 20 중량 %, 바람직하게는 0.2 내지 15 중량 %, 좀더 바람직하게는 0.3 내지 10 중량 %를 포함할 수 있다. 상기 바인더 수지, 및 상기 바인더 수지에 분산된 안료, 전하 조절제, 및 왁스 등의 함량을 상술한 바와 같은 범위로 유지함으로써, 중합 토너의 우수한 화상 농도로 균일한 화상과 우수한 전사효율을 구현함 동시에 정착 과정에서 토너가 정착를을 오염시키는 현상인 오프셋 현상 등올 효과적으로 방지할 수 있다. 특히, 상기 단량체의 비율에서 스티렌계 단량체가 너무 많으면 Tg가 높아서 미 정착이 발생하며 반대로 너무 작으면 Tg가 낮아져 핫-오프셋 (Hot offset)이 발생하므로 일반적으로 스티렌계 단량체가 20% 내지 30%의 함량으로 조절한다. 전하조절제 (CCA)의 경우는 함량이 0.5% 이하이면 반웅 안정성의 저하로 웅집 (coagulum)이 많이 발생하고 마찰 대전 특성이 부족하게 되、어 현상 특성이 저하되며, 반대로 4% 이상 너무 사용하게 되면 중합 토너 제조시 입도 분포가 넓어지는 (broad) 문제가 발생하게 되므로 적절한 함량을 사용할 수 있다. 또한, 왁스 (wax)는 25% 이상 과량 사용하면 토너 표면으로 노출되어 대전 특성이 저하되며, 5¾ 이하를 사용하면 토너가 오염이 되는 현상이 발생하게 될 수 있다. 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.
상기 안료는 금속분말형 안료, 금속물산화형 안료, 카본형 안료, 황화물형 안료, 크름염형 안료, 페로시아니드형 안료, 아조형 안료, 산성염료형 안료, 염기 성염료형 안료, 모단트염료형 안료, 프탈로시아닌, 퀴나크리돈형 안료, 디옥산형 안료 또는 이들의 흔합물을 포함한다. 다만, 이에 한정되는 것은 아니고, 중합 토너에 적용할 수 있는 것으로 알려진 안료는 별 다른 제한 없이 사용할 수 있다. 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.
상기 전하조절제로는 양이온성 전하조절제, 음이온성 전하조절제, 또는 이들의 흔합물을 포함할 수 있다. 상기 양이온성 전하조 ^제로는 니그로신형 염료, 고지방족의 금속염, 알콕시 아민, 킬레이트, 4차 암모늄염, 알킬아미드, 불소 처리 활성제, 나프탈렌산의 금속염 또는 이들의 흔합물 등이 있고, 상기 음이온성 전하조절제로는 염소화된 파라핀, 염소화된 폴리에스테르, 산을 함유한 폴리에스테르, 구리 프탈로시아닌의 설포닐아민, 설폰산기 또는 이들의 흔합물 등이 있다.
또한, 상기 전하조절제로 설폰산기를 갖는 공중합체를 사용하는 것이 바람직한데, 보다 바람직하게는 중량평균분자량이 2, 000 내지 200 ,000인 설폰산기를 갖는 공중합체를 사용할 수 있으며, 보다 더 바람직하게는 산가가 1 내지 40 mg KOH/g이고, 유리전이온도는 30 내지 120 °C인 설폰산기를 갖는 공중합체를 사용할 수 있다. 상기 산가가 1 미만이면 전하조절제의 역할을 하지 못하며, 40 이상이면 단량체 흔합물의 계면특성에 영향을 미쳐 중합안정성을 악화시킨다. 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.
또한, 상기 유리전이온도가 30 °C 미만이면 표면에 노출되어 있는 전하조절제의 낮은 유리전이온도로 인해 프린팅시 토너 대 토너의 마찰- 용융을 발생시켜 블록킹 현상을 유발할 수 있다. 반면에. 상기 유리전이온도가 120 °C 초과하면 토너의 표면을 과도로 단단하게 하여 코팅성 및 정착성의 물성에 바람직하지 못하다. 그리고, 상기 중량평균분자량이 2,000 미만이면 바인더 수지와의 높은 상용성으로 표면 농도가 저하되어 전하조절제의 기능을 하지 못할 수 있으며, 200,000 이상이면 높은 분자량으로 인한 단량체 흔합물의 점도 증가로 중합 안정성과 입도 분포에 바람직하지 못하다. 상기 설폰산기를 갖는 공중합체의 구체적인 예로는 설폰산기를 갖는 스티렌-아크릴계 공중합체, 설폰산기를 갖는 스틸렌 -메타크릴계 공중합체 또는 이들의 흔합물을 들 수 있으나, 이에 한정되는 것은 아니다. 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.
상기 안료안정제는 2,000 내지 200, 000의 중량평균분자량을 갖는 스티렌 -부타디엔-스티렌 (SBS) 공중합체를 사용할 수 있으며, 바람직하게는, 상기 공중합체중 스티렌 함량 대 부타디엔의 함량이 중량비로 10:90 내지 90 :10인 것을 사용할 수 있다. 스티렌의 함량이 90%을 초과하면 부타디엔의 블록의 길이가 짧아져 바인더 수지와의 높은 상용성으로 안정제 역할을 층분히 하지 못하며, 10% 미만이면 안정제 역할을 층분히 하지만 짧은 스티렌 블록의 길이로 말미암아 안료 대 안료의 작용을 충분히 제어하지 못하는 현상을 보인다. 또한, 분자량이 2,000 미만이면 바인더 수지와의 높은 상용성으로 안료로서의 기능을 하지 못하며, 200,000 이상이면 단량체 흔합물의 점도를 너무 높여 분산안정성과 중합안정성을 악화시키며 궁극적으로 입도 분포를 넓게 하는 단점을 보인다.
상기 왁스 성분은, 중합 토너에 적용할 수 있는 것으로 알려진 왁스는 별다른 제한 없이 사용할 수 있다. 예컨대, 상기 왁스 성분으로는 파라핀 왁스 미정질 왁스 (microcrystalline wax), 또는 세레신 왁스 등의 석유 정제 왁스; 카르누바 왁스 둥의 천연 왁스; 또는 폴리에스테르계 왁스 또는 폴리올레핀계 왁스 등의 합성 왁스 또는 이들의 흔합물을 1종 이상 사용할 수 있다. 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.
한편, 발명의 일 구현 예에서, 상기 토너 모입자는 반응개시게, 가교제, 분자량 조절제, 활제 (예, 올레인산, 스테아린산 등), 및 커플링제로 이루어진 군에서 선택된 1종 이상의 첨가제를 더 포함할 수 있다. 이 때, 상기 토너 모입자는 반웅개시제 10 증량 % 이하 또는 0.1 내지 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 중량 %, 바람직하게는 8중량 % 이하 또는 0.3 내지 8 중량 %, 좀더 바람직하게는 5 중량 ¾> 이하 또는 0.5 내지 5 중량 %; 상기 가교제 5 중량 % 이하 또는 0.01 내지 5 중량 %, 바람직하게는 4 중량 ¾ 이하 또는 0.05 내지 4 중량 ¾>, 좀더 바람직하게는 3 중량 % 이하 또는 0.1 내지 3 중량^ 또는 분자량 조절제 10 중량 % 이하 또는 0.1 내지 10 중량 %, 바람직하게는 8 중량 % 이하 또는 0.3 내지 8 중량 %, 좀더 바람직하게는 5 중량 ¾ 이하 또는 0.5 내지 5 중량 %; 적량의 활제 (예, 올레인산, 스테아린산 등), 예컨대, 활제 5 중량 % 이하 또는 0.01 내지 5 중량 %, 바람직하게는 4 중량 % 이하 또는 0.05 내지 4 중량 %, 좀더 바람직하게는 3 중량 % 이하 또는 0.1 내지 3 중량 적량의 커플링제, 예컨대, 커플링제 5 중량 % 이하 또는 0.01 내지 5 중량 %, 바람직하게는 4 중량 % 이하 또는 0.05 내지 4 중량 %, 좀더 바람직하게는 3 중량 % 이하 또는 0.1 내지 3 중량? 등을 1종 이상으로 더 포함할 수 있다. 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.
상기 반응개시제로는 유용성 개시제와 수용성 개시제를 사용할 수 있다. 구체적으로는 아조비스이소부티로니트릴, 아조비스발레로니트릴 등의 아조계 개시제; 벤조일퍼옥사이드, 라우로일퍼옥사이드 등의 유기 퍼옥사이드; 과황산칼륨, 과황산암모늄 등의 일반적으로 쓰이는 수용성 개시제 등을 사용할 수 있으며, 이 중에서 1종 또는 2종 이상을 흔합하여 사용할 수도 있다. 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.
상기 가교제는 디비닐벤젠, 에틸렌 디메타크릴레이트, 에틸렌글리콜
디메타크릴레이트, 디에틸렌글리콜 디아크릴레이트, 1,6-핵사메틸렌 디아크릴레이트, 알릴 메타크릴레이트, 1,1,1-트리메틸올프로판 트리아크릴레이트, 트리알릴아민, 테트라알릴옥시에탄 또는 이들의 흔합물을 포함할 수 있다. 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.
상기 분자량 조절제로는 t-도데실 메르캅탄, n-도데실 메르갑탄, n- 옥틸메르갑탄, 사염화탄소 또는 이들의 흔합물을 포함할 수 있다. The molecular weight modifier may include t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl meraptan, carbon tetrachloride or a combination thereof.
상기 활제 및 커플링제로는 중합 토너 제조에 적용될 수 있는 것으로 알려진 것은 별다른 제한 없이 사용 가능하다. 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.
본 발명의 중합 토너는 바인더 수지 50 내지 95 중량 ¾>; 안료 1 내지 20 중량 %; 전하 조절제 0.1 내지 5 증량 %; 왁스 0.1 내지 30 증량 %; 가소제 0.1 내지 5 중량 ¾>; 및 반웅 개시제, 가교제, 분자량조절제, 활제, 및 커플링제로 이루어진 군에서 선택된 1종 이상의 첨가제 각각 10 중량 % 이하 또는 0.01 내지 10 중량 %를 포함할 수 있다. 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.
또한, 발명의 일 구현예에서, 본 발명에 따른 상기 토너 모입자의 체적평균 입경은 4 내지 10 이며, 바람직하게는 5 내지 8 βη, 좀더 바람직하게는 6 내지 7 mi가 될 수 있다. 이러한 토너 모입자의 체적평균입경은 화상 농도 및 비산 방지 측면에서 4 이상이 될 수 있으며, 상기 토너 모입자의 체적평균입경은 소모량 절감 측면에서 10 이하가 될 수 있다. 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.
한편, 발명의 다른 일 구현예에서, 본 발명은 외첨제로서 콜로이달 실리카를 사용하는 구형화 토너를 제공한다. 상기 구형화 토너는 상기 토너 모입자 표면에 코팅된 외첨제를 포함하고, 상기 외첨제로서 단일 입자 크기가 25 내지 58 nm이며 체적평균입경이 0.06 내지 0.5 /皿인 콜로이달 실리카 (colloidal silica)를 포함할 수 있다. 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.
본 발명의 구형화 토너는 외첨제로서 콜로이달 실리카를 사용하여 와이퍼 블레이드 (wiper blade)에서의 클리닝 (cleaning) 기능올 개선하고 PCR, 드럼 또는 전사 벨트 등의 부품 오염을 현저히 개선할 수 있다. 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.
상기 구형화 토너는 분쇄 토너를 제조한 후에, 토너를 구형화하는 단계를 통해 제조될 수 았다. 이렇게 분쇄 토너를 구형화 하는 방법으로는 기계적인 방법으로 구형을 하는 방법과 고온의 열풍을 이용하는 방법이
있다. 기계적으로 구형화를 하면 감자 모형과 구형의 여러가지 모양으로 제조하는 것이 가능한 장점이 있으나 구형으로 토너를 제조하려면 시간당 생산량이 적다는 단점이 있다/고은의 열풍을 이용하여 구형화를 하면 짧은 시간에 공 모양의 구형 토너를 만드는 장점이 있는 반면 감자 모양의 토너를 만드는 것이 어렵다. 참고로, 분쇄 토너를 구형으로 만드는 제조 조건은 적용하는 기계 장치에 따라 거의 정해질 수 있다. 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.
이와 같은 방법으로 구형화 토너에도 본 발명을 적용할 수 있으며, 중합 토너 또는 구형화 토너에 관계 없이 와이퍼 블레아드 (wiper blade)에서의 클리닝 (cleaning) 기능을 개선하고 PCR, 드럼 또는 전사 벨트 등의 부품 오염을 개선하는 우수한 효과를 구현할 수 있다. 그러므로, 중합 토너 뿐만 아니라 구형으로 제조된 구형화 토너인 경우에도 적용이 된다. 또한, 감자 모양으로 제조된 구형화 토너인 경우에도 역시 본 발명을 효과적으로 적용할 수 있다. 한편, 발명의 다른 일 구현예에 따르면, 상기 중합 토너를 제조하는 방법이 제공될 수 있다. 특히, 상기 중합 토너의 제조 방법은 분산제를 포함하는 수계 분산액을 형성하는 단계; 바인더 수지용 단량체, 안료, 전하 조절제, 및 왁스를 포함하는 단량체 흔합물을 형성하는 단계; 상기 단량체 흔합물을 상기 수계 분산액에 첨가하고 현탁 중합을 통하여 토너 모입자를 형성하는 단계; 및 상기 토너 모입자 표면에 외첨제를 코팅하는 단계;를 포함하고, 상기 외첨제로서 단일 입자 크기가 25 내지 58 nm이며 체적평균입경이 0.06 내지 0.5 인 콜로이달 실리카 (colloidal silica)를 사용할 수 있다. 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. .
상기 "콜로이달 실리카 "는 졸-겔 (sol-gel) 방법 등으로 제조된 실리카를 지칭하는 것이며, 상기 콜로이달 실리카는 입자 1개로 되어 있는 비율이 개수 기준으로 30% 내지 40%이며, 입자 2개가 서로 융합 (Fused)된 입자의 비율이 10% 내지 30%이며, 입자 3개 이상 융합 (Fused)된 입자의 비율이 10% 내지 30%의 균일한 분포를 갖는 것일 수 있다. 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.
상기 콜로이달 실리카는 체적평균입경 0.06 내지 0.5 urn, 바람직하게는 0.07 내지 0.4 }M, 좀더 바람직하게는 0.08 내지 0.3 가 될
수 있다. 상기 콜로이달 실리카는 클리닝 (cleaning) 개선 측면에서 체적평균입경 0.06 urn 이상이 될 수 있으며, 드럼 마모 감소 측면에서 0.5 m 이하가 될 수 있다. 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.
또한, 상기 콜로이달 실리카는 실리카 단일 입자 크기가 25 내지 58 nm(nanometer), 바람직하게는 55 nm 이하, 좀더 바람직하게는 53 nm 이하가 될 수 있다. 이때, 상기 실리카 단일 입자 크기는 전자현미경, 예컨대, 주사전자현미경 (SEM, Scanning Electron Microscope) 및 투과전자현미경 (TEM, Transmission Electron Microscope)을 이용한 방법으로 측정할 수 있으며, 단일 입자의 평균 입경이라고 정의할 수 있다. 본 발명의 콜로이달 실리카를 구성하는 실리카 입자 1개의 단일 입자 크기는 너무 미세한 입자 자체가 부품 오염의 원인이 되는 것을 방지하는 측면에서 25 nm 이상이 될 수 있으며, 부품 오염 개선 효과를 증대하는 측면에서 58 nm 이하가 될 수 있다. 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.
상술한 바와 같이, 입자 사이즈가 크고 입자끼리 서로 웅집 또는 융합되어 있는 콜로이달 실리카의 함량은 토너 모입자 100 중량부에 1.0 증량부 내지 5.0 중량부, 바람직하게는 1.2 중량부 내지 4.0 중량부, 좀더 바람직하게는 1.5 중량부 내지 3.0 중량부로 사용될 수 있다. 상기 콜로이달 실리카는 클리닝 (cleaning) 개선 측면에서 1.0 중량부 이상으로 사용되어야 하며, 드럼 마모 감소 측면에서 5.0 중량부 이하로 사용되어야 한다. 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.
한편, 본 발명에서 사용 가능한 콜로이달 실리카에 대한 구체적인 예에 관해서는 상술한 바와 같다. On the other hand, specific examples of the colloidal silica usable in the present invention are as described above.
본 발명자들은 중합법으로 제조된 구형의 모입자에 입자 사이즈가 크고 입자끼리 서로 웅집 또는 융합되어 있는 특정의 콜로이달 실리카를 사용함으로써, 클리닝 블레이드에서의 클리닝 성능뿐만 아니라 유동성, 배경오염, 전사효율 등가 같은 토너 및 대전 특성이 향상된 중합 토너를 제조할 수 있음을 확인하고 본 발명을 완성하게 되었다. 이렇게 제조되는 중합 토너를 적용하면 인쇄결과물의 광택도를 높일 수 있기 때문에 높은 해상도 및 색상 구현도를 요구하는 사진 인쇄 등의 분야에 효과적으로 적용할 수 있다.
발명의 다른 일 구현예에서는, 분산제를 물에 흔합하여 상기 수계 분산액을 형성할 수 있다. 이러한 수계 분산액을 균질화시키기 위하여 교반하는 단계 또는 전단력을 가하는 단계를 적용할 수 있다. 구체적으로, 상기 수계 분산액을 형성하는 단계는 인산 나트륨 수용액과 염화 칼슘 수용액을 흔합하여 수용액 상에서 결정의 형태인 인산 칼륨을 얻는 단계를 포함할 수 있다. 이러한 인산 칼륨은 분산제로 사용될 수 있으며, 상기 수계 분산액은 물에 인산 칼륨 결정이 균일하게 분산되어 있는 형태일 수 있다. 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.
상기 분산제는 수계 매체 내에서 액적 형태로서 존재하고 있는 바인더 수지용 단량체 또는 안료 등의 입자 사이의 웅집을 방지하고, 이러한 입자들이 균일하게 분산할 수 있게 한다. 또한, 상기 분산제는 액적 표면에 균일하게 흡착하여 이러한 액적 입자를 안정화시키는 역할을 한다. 그리고, 이러한 분산제는 수계 매체 내에서 중합 반응 종료 후에 산이나 알킬:리 (alkali) 처리, 또는 온수 세척 등을 통하여 가용화되고, 토너 모입자로부터 분리될 수 있다. 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.
상기 분산제는 무기 분산제, 유기 분산제 , 음이온성 계면활성제 또는 이들의 흔합물을 포함한다. 이러한 분산제는 상기 단량체 흔합물 100중량부에 대하여 1 내지 5증량부, 바람직하게는 2 내지 4 중량부, 좀더 바람직하게는 2.5 내지 3.5 중량부로 적용될 수 있다. 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.
상기 무기 분산제의 구체적인 예로는 인산 칼슘, 인산수소칼슴, 인산이수소 칼슘, 히드록시 아파타이트 (hydroxy apatite), 인산 마그네슘, 인산 알루미늄, 인산 아연, 탄산칼슘, 탄산마그네슘, 수산화칼슘, 수산화마그네슘, 수산화 알미늄, 메타 규산 칼슘, 황산칼슘, 황산바륨, 벤토나이트 (bentonite), 실리카 (silica), 알루미나 (alumina) 또는 이들의 흔합물 등이 있다. 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.
상기 수용성 유기 분산제의 구체적인 예로는 폴리비닐 알코올 (polyvinyl alcohol), 젤라틴 (gelatin) , 메틸 셀를로오스 (methyl cellulose), 메틸 히드록시 프로필 셀를로오스 (methyl hydroxy propyl cellulose), 에틸셀를로오스 (ethyl cellulose), 카르복실 메틸 샐를로오스 (carboxyl methyl cellulose) 및 그의 나트륨염, 폴리 아크릴산
및 그의 염, 전분 (starch) 또는 이들의 흔합물 등이 있다. 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.
상기 음이온성 계면활성제의 구체적인 예로는 지방산염, 알킬 황산에스테르염, 알킬아릴 황산에스테르염, 디알킬설포숙신산염, 알킬 인산염 또는 이들의 흔합물 등이 있다. 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.
상기 분산제의.보다 바람직한 예로 인산 칼^을 들 수 있다. 이러한 인산 칼슴은 인산 나트륨 수용액과 염화 칼슴 수용액을 흔합하여 수용액 상에서 결정의 형태로 얻어질 수 있으며, 상기 수계 분산액은 인산 칼슘 결정이 물에 균일하게 분산되어 있는 형태일 수 있다. 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.
한편, 상기 단량체 흔합물은 상기 바인더 수지용 단량체, 안료, 안료안정제, 전하 조절제 및 왁스 등을 흔합하고 층분히 녹여서 형성될 수 있으며, 호모게나이저를 이용하여 수계 분산액에 균질화될 수 있다. 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.
상기 바인더 수지용 단량체는 스티렌계 단량체, 아크릴레이트계 단량체, 메타크릴레이트계 단량체, 디엔계 단량체, 산성 올레핀계 단량체, 염기성 올레핀계 단량체 또는 이들의 흔합물을 포함할 수 있다. 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.
또한, 상기 바인더 수지용 단량체는 (a) 스티렌계 단량체; 및 (b) 아크릴레이트계 단량체, 메타크릴레이트계 단량체 및 디엔계 단량체로 이루어진 군에서 선택된 1종 이상 선택된 단량체를 포함할 수 있다. 상기 바인더 수지용 단량체는 상기 (a)의 단량체 및 (b)의 단량체를 합한 100 중량부에 대하여, 상기 (a)의 단량체의 30 내지 95 중량부와, 상기 (b)의 단량체의 5 내지 70 중량부를 포함할 수 있다. 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.
또한, 상기 바인더 수지용 단량체는 (a)의 스티렌계 단량체와, (b) 아크릴레이트계 단량체, 메타크릴레이트계 단량체 및 디엔계 단량체로 이루어진 군에서 1종 이상 선택된 단량체와, (c) 산성 올레핀계 단량체 및 염기성 을레핀계 단량체로 이루어진 군에서 선택된 1종 이상의 단량체를 포함할 수 있다. 이때, 상기 (c)의 단량체는 상기 (a)의 단량체 및 (b)의 단량체를 합한 100 중량부에 대하여 0.1 내지 30 중량부로 포함될 수 있다. 한편, 상기 단량체 흔합물에 포함되는 바인더 수지용 단량체, 안료, 안료안정제, 전하 조절제, 및 왁스의 구체적인 예에 관해서는 상술한 바와 같다. 그리고, 상기 단량체 흔합물은 바인더 수지용 단량체 50 내지 95 중량 %, 안료 1 내지 20 중량 %, 전하조절제 0.1 내지 5 중량 %, 및 왁스 0.1
내지 30 중량 %를 포함할 수 있으며, 이외에 추가로 안료안정제를 포함할 수 있으며 구체적인 예와 함량 범위는 상술한 바와 같다. 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.
상기 단량체 흔합물을 상기 수계 분산액에 흔합하고 현탁 중합함으로써 토너 모입자를 형성할 수 있는데, 보다 구체적으로, 상기 토너 모입자를 형성하는 단계는, 상기 단량체 흔합물을 상기 수계 분산액에 첨가하는 단계; 상기 수계 분산액 및 단량체 흔합물에 전단력을 가하여 상기 단량체 흔합물을 수계 분산액에 액적 형태로 균질화하는 단계; 및 상기 균질화된 단량체 흔합물을 현탁 중합하는 단계를 포함할 수 있다. 그리고, 상술한 바와 같이, 상기 단량체 흔합물 및 수계 분산액은 호모게나이저를 이용하여 균질화시킬 수 있다. 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.
상기 수계 분산액에 상기 단량체 흔합물을 미세한 물방물 (액적) 형태로 균일하게 분산하여 중합 반웅을 진행하면 적절한 크기의 구형 토너 모입자를 형성할 수 있다. 이러한 미세한 물방울 (액적) 형태의 분산을 위하여, 호머게나이저를 이용하여 상기 단량체 흔합물과 수계 분산액에 전단력을 가해 균질화시킬 수 있는데, 구체적으로, 호모게나이저를 이용하여 상기 수계 분산액과 흔합된 단량체 흔합물을 5,000 rpm 내지 20,000 rpm, 바람직하게는 8,000 rpm 내지 17,000 rpm의 속도로 균질화하여 상기 단량체 흔합물을 상기 수계 분산액 내에서 미세 액적 형태로 분산시킬 수 있다. 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.
상기 현탁 중합은 60 내지 90 °C에서 8 내지 20 시간 동안 이루어 질 수 있다. 보다 바람직한 예로, 상기 현탁 중합은 50 내지 70 °C에서 8 내지 12 시간 동안 현탁 중합 반웅을 진행한 후, 80 내지 110 °C로 승온한 후 30 분 내지 4 시간 동안 반응을 진행할 수 있다. 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.
한편, 발명의 다른 일 구현 예에서는 상기 분산제를 제거하는 단계; 및 상기 토너 모입자를 건조하는 단계를 더 포함할 수 있다. On the other hand, in another embodiment of the invention the step of removing the dispersant; And drying the toner base particles.
상기 분산제를 제거하는 단계는, 분산제의 용해에 적합한 pH로 조절하는 단계를 포함할 수 있다. 상기 토너 모입자가 생성된 분산액에 염산 또는 질산 등의 수용성 무기산을 첨가하여 pH를 2 이하, 바람직하게는 1.5 이하로 조정함으로써, 상기 분산제를 수용액상으로 용해시켜 토너 모입자로부터 제거할 수 있다. 이러한 분산제 제거 단계에서는 pH를 적절히
조절한 후 5 시간 이상 교반하여 상기 분산제가 층분히 용해하도록 한 후, 여과 장치를 이용하여 50 중량 % 미만의 물을 포함하는 토너 슬러리를 얻을 수 있다. 또한, 상기 분산제를 제거하는 단계에서는 호모게나이저로 전단력을 가하여 용액을 균질화시키는 단계 및 원심분리장치를 이용한 분리 단계를 적용할 수 있다. 그리고, 상술한 분산제 제거 단계 이후에, 필터 장치를 이용한 수분 제거 및 과량의 증류수 첨가를 수회에 걸쳐 반복하는 과정을 통하여 분산제를 더욱 효율적으로 제거할 수 있다. 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.
상기 토너 모입자를 건조하는 단계는 분산제가 제거된 토너 케익 (cake)을 진공 오븐에 넣고 상온에서 진공 건조하는 단계를 포함한다. 다만, 이에 한정되는 것은 아니고, 중합토너의 제조 단계에서 통상적으로 사용되는 것으로 알려진 건조 방법을 별다른 제한 없이 사용할 수 있다. 또한, 발명의 다른 일 구현예에서, 상기 토너 모입자는 표면에 외첨제를 코팅하는 단계를 포함하며, 특히, 외참제로서 상기 콜로이달 실리카 및 소수성 실리카를 소정의 범위로 흔합 사용하여 토너 모입자 표면에 코팅한다. 이러한 외첨제의 코팅 단계는 헨쉘 믹서를 사^해 상기 토너 모입자에 외첨제를 첨가한 후,' 고속 교반하는 방법으로 진행할 수 있다. 상기 실리카는 중합 토너에 사용 가능한 것으로 알려진 것을 별다른 제한 없이 사용할 수 있다. 예컨대, 상기 실리카를 토너 모입자에 부착시키는 방법으로 터빈형 교반기, 헨쉘 믹서, 슈퍼 믹서 등의 일반적인 교반기를 이용하는 방법, 또는 표면 개질기로 불리는 장치 (나라기계제작소사의 "나라 하이브리다이제이숀 시스템") 등을 이용하는 방법을 적용할 수 있다. 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.
상기 단량체 흔합물은 반응 개시제, 가교제, 활제, 분자량 조절제, 및 커플링제로 이루어진 군에서 선택된 1종 이상의 첨가제를 추가적으로 첨가하는 단계를 포함할 수 있다. 이러한 첨가제의 구체적인 예 및 바람직한 함량 범위는 상술한 바와 같다. 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.
한편, 본 발명의 바람직한 일 구현예 따르면, 본 발명에 사용되는 토너 모입자의 제조는 하기 방법과 같다 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) 제 1 단계: 수계 분산액 준비 단계 (1) Step 1: Preparing Aqueous Dispersion
증류수에 분산제를 녹여 수계 분산액을 준비한다. 상기 분산제는
무기 분산제 또는 수용성 유기 분산제 중에서 1종 이상 선택하여 사용할 수 있으며, 선택적으로 음이온성 계면활성제를 첨가할 수도 있다. 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.
이때, 상기 분산제는 인산칼슘염, 마그네슴염, 친수성 실리카, 소수성 실리카 및 콜로이달 실리카로 이루어진 군으로부터 1종 이상 선택되는 무기 분산제; 또는 폴리옥시에틸렌 알킬에테르, 폴리옥시알킬렌 알킬 페놀에테르, 소르비탄 지방산 에스테르, 폴리옥시 알킬렌 지방산 에스테르, 글리세린 지방산 에스테르, 폴리비닐 알코을, 알킬 셀를로오스 및 폴리비닐 피롤리돈으로 이루어진 군으로부터 1종 이상 선택되는 비이온성 고분자 분산제 ; 및 폴리아크릴 아미드, 폴리비닐 아민, 폴리비닐 아미 N-옥사이드, 폴리비닐 암모늄염, 폴리디알킬디알릴 암모늄염, 폴리아크릴산, 폴리스티렌 설폰산, 폴리아크릴산염, 풀리설폰산염 및 풀리아미노알킬 아크릴산염으로 이루어진 군으로부터 1종 이상 선택되는 이온성 고분자 분산제를 단독으로 또는 1종 이상 흔합하여 사용할 수 있으며, 그 함량은 수용액 전체를 100 증량부로 보았을 때, 0.01 내지 10 중량부인 것이 바람직하다. 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.
분산제의 함량이 0.01 중량부 미만인 경우에는 현탁 중합시 반응 안정성이 깨지며, 10 중량부를 초과하는 경우에는 부반웅물 (에멀견 입자)의 형성이 증가하고, 토너 모입자 크기가 목적하는 것보다 작게 형성될 수 있기 때문이다. 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.
한편, 상기 음이온 계면활성제로는 지방산염 , 알킬 황산 에스테르염, 알킬 아릴 황산 에스테르염, 디알킬 설포숙신산염, 알킬 인산염 등으로 이루어진 군에서 1종 이상 선택하여 사용할 수 있으며, 그 함량은 수용액 전체를 100 중량부로 보았올 때, 0.001 내지 20 중량부인 것이 바람직하다. 상기 함량이 0.001 중량부 미만일 경우에는 현탁 중합시 반응 안정성이 좋지 않은 영향을 미칠 수 있으며, 20 중량부 이상일 경우에는 부반응물 (에멀젼 입자)의 형성이 증가하고, 토너 모입자 크기가 목적하는 것보다 작게 형성될 수 있기 때문이다. 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) 제 2 단계 : 단량체 흔합물 준비 단계 (2) second step: monomer mixture preparation step
이 단계에서는 바인더 수지 단량체, 전하조절제, 안료, 왁스오가스 미 사슬 이동제 등을 흔합하여 중합 원료가 되는 단량체 흔합물을
준비하도록 한다 . 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.
먼저, 방향족 비닐계 단량체, 아크릴레이트계 단량체, 메타크릴레이트계 단량체 또는 디엔계 단량체를 단독 또는' 1종 이상 흔합하고, 교반하여 바인더 수자 단량체를 준비한다. 준비된 바인더 수지 단량체에 전하조절제, 안료, 왁스, 및 사슬이동제를 넣고 교반하여 단량체 흔합물을 만든다. 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.
한편, 상기 단량체 흔합물에 가교제를 더 첨가하는 것이 바람직하다. 단량체 흔합물에 가교제를 첨가하여 토너를 제조할 경우, 토너 간의 웅집이 방지되어 보존성이 개선된다는 장점이 있기 때문이다. 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.
한편, 본 발명에서 바인더 수지용 단량체는 중합법으로 제조되는 토너에 사용되는 모든 단량체를 사용할 수 있으며 특별히 제한되지 않는다. 단량체의 예로는 스티렌계 단량체, 아크릴레이트계 단량체, 메타크릴레이트계 단량체, 또는 디엔계 단량체 등을 들 수 있으며, 이들 중에서 1종 이상을 흔합하여 사용할 수 있다. 또한, 상기 단량체에 선택적으로 산성 올레핀계 단량체 또는 염기성 올레핀계 단량체를 1종 이상 흔합하여 사용할 수도 있다. 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.
상기 바인더 수지는 스티렌계 단량체, 아크릴레이트계 단량체, 메타크릴레이트계 단량체, 디엔계 단량체, 산성 올레핀계 단량체 및 염기성 을레핀계 단량체 또는 이들의 흔합물의 중합체 또는 공중합체를 포함할 수 있다. 다만, 이에 한정되는 것은 아니며, 현탁중합법으로 제조되는 토너의 형성을 위하여 사용 가능한 것으로 알려진 다양한 단량체를 별다른 제한 없이 사용할 수 있으며, 이러한 단량체로부터 중합 토너의 바인더 수지로 되는 중합체 또는 공중합체를 형성할 수 있다. 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.
또한, 상기 바인더 수지는 (a) 스티렌계 단량체; 및 (b) 아크릴레이트계 단량체, 메타크릴레이트계 단량체 및 디엔계 단량체로 이루어진 군에서 선택된 1종 이상 선택된 단량체의 중합체 또는 공중합체를 포함할 수 있다. 상기 중합체는, 상기 (a)의 단량체 및 (b)의 단량체를 합한 100 중량부에 대하여, 상기 (a)의 단량체의 30 내지 95 중량부와 상기 (b)의 단량체의 5 내지 70 중량부를 중합한 것을 포함할 수 있다. 이러한 함량 범위는 중합된 토너의 유리전이온도를 맞추기 위한 것으로, 상기
(a)의 단량체를 30 중량부 미만으로 포함하는 경우에는 유리전이온도가 너무 낮게 나와 오프셋 현상이 발생할 수 있으며, 95 중량부를 초과하는 경우에는 유리전이온도가 너무 높아져 정착성이 저하될 수 있다. 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.
이러한 증합체는 상기 (a)의 스티렌계 단량체와, (b) 아크릴레이트계 단량체, 메타크릴레이트계 단량체 및 디엔계 단량체로 이루어진 군에서 1종 이상 선택된 단량체와, (C) 산성 올레핀계 단량체 및 염기성 올레핀계 단량체로 이루어진 군에서 선택된 1종 이상의 단량체의 중합한 것으로 될 수 있다. 이 때, 상기 (c)의 단량체는 상기 (a)의 단량체 및 (b)의 단량체를 합한 100 중량부에 대하여 0.1 내지 30 중량부로 중합될 수 있다. 상기 바인더 수지의 형성을 위한 스티렌계 단량체로는 스티렌, 모노클로로스티렌, 메틸스티렌, 디메틸스티렌 등이 있으며, 상기 아크릴레이트계 . 단량체로는 메틸아크릴레이트, 에틸아크릴레이트, n- 부틸아크릴레이트, 이소부틸아크릴레이트, 도데실 아크릴레이트, 옥틸 아크릴레이트, 2-에틸핵실아크릴레이트, 페닐 아크릴레이트 등이 있다. 그리고, 메타크릴레이트계 단량체로는 메틸 메타크릴레이트, 에틸메타크릴레이트, n-부틸 메타크릴레이트, 이소부틸 메타크릴레이트, 도데실 메타크릴레이트, 옥틸 메타크릴레이트, 2-에틸핵실 메타크릴레이트 등이 있으며, 상기 디엔계 단량체로는 부타디엔, 이소프렌 등이 있다. 상기 아크릴레이트계 단량체, 메타크릴레이트계 단량체, 디엔계 단량체는 단독 또는 1종 이상 흔합하여 사용할 수 있으며, 그의 함량은 단량체 흔합물 전체 중량을 기준으로 5 내지 70 중량부인 것이 바람직하다. 이처럼 함량을 한정하는 것은 스티렌계 단량체의 경우와 마찬가지로 토너의 유리전이온도를 적정 수준으로 맞추기 위함이다. 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.
또한, 상기 산성 올레핀계 단량체로는 카르복실기를 가진 α , - 에틸렌 불포화 화합물 등을 사용할 수 있고, 염기성 을레핀계 단량체로는 아민기나 4차 암모늄기를 가진 지방족 알콜의 메타크릴산 에스테르계, 메타크릴 아미드계 비닐 아민계, 디알릴 아민계나 이의 암모늄염 등을 사용할 수 있는데, 이를 단독 또는 1종 이상 흔합하여 사용할 수 있다. 그의 함량은 단량체 흔합물 전체 중량 ο르 기준으로 0.1 내지 20 중량부인 것이 바람직하다. 산성 올레핀계 단량체와 염기성 을레핀계 단량체는
표면의 대전 특성을 향상시키기 위해 첨가되는 것으로 20 중량부를 넘어서게 되면 토너 중합시 반응 안정성이 나빠져 토너 모입자들이 서로 응집하는 현상이 발생할 수 있다. 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.
상기 전하 조절제는 니그로신형 염료, 니그로형의 전자 받게 염료, 고지방족의 금속염, 알콕시 아민, 킬레이트, 4차 암모늄염, 알킬아미드, 불소 처리 활성제 및 나프탈렌산의 금속염으로 이루어진 군으로부터 선택되는 1종 이상의 양이온성 전하 조절제; 또는 전자 받게 유기착물, 염소화된 파라핀, 염소화된 폴리에스테르, 산을 함유한 폴리에스테르, 구리 프탈로시아닌의 설포닐아민 및 설폰산기를 포함한 스티렌-아크뮐계 고분자로 이루어진 군으로부터 선택되는 1종 이상의 음이온성 전하 조절제를 사용할 수 있으며, 이 중에서 1종 이상 선택되며 이들을 단독 또는 1종 이상 흔합하여 사용할 수 있다. 이때 상기 전하조절제의 함량은 단량체 흔합물 전체 중량의 0.01 내지 20 중량부인 것이 바람직하다. 상기 전하조절제의 함량이 0.01 중량부 미만인 경우에는 프린팅시 필요한 층분한 전하밀도를 가지지 못할 수 있고, 20 중량부를 초과하는 경우에는 오히려 전하량이 떨어지는 현상이 발생할 수 있다. 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.
상기 안료는 금속분말형 안료, 금속물산화형 안료, 카본형 안료, 황화물형 안료, 크롬염형 안료, 및 페로시아니드형 안료 등으로 이루어진 군에서 선택된 무기 염료; 또는 아조형 안료, 산성 염료형 안료, 염기성 염료형 안료, 모단트 염료형 안료, 프탈로시아닌, 퀴나크리돈형 안료, 및 디옥산형 안료로 이루어진 군에서 선택된 유기 염료; 중에서 1종 이상을 선택하여 사용할 수 있다. 상기 안료의 함량은 단량체 흔합물 전체 증량을 기준으로 1 내지 20 중량부가 바람직하다. 상기 안료가 1 중량부 미만인 경우에는 원하는 색을 층분히 구현하기 어려울 수 있으며, 20 중량부를 초과하는 경우에는 단량체와 안료 사이의 분산이 효과적으로 이뤄지지 않을 수 있다. 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.
상기 왁스는 석유 정제 왁스, 천연 왁스, 합성 왁스 등을 사용할 수 있다. 석유 정제 왁스에는 파라핀 왁스, 미정질 왁스 (microcrystalline wax), 세레신 왁스 (Ceresin wax) 등이 있으며, 천연 왁스에는 카르누바 왁스 (Carnauba wax) 등이 있고, 합성 왁스에는 폴리에스테르계 왁스,
폴리에틸렌이나 폴리프로필렌 등의 폴리을레핀계 왁스 등이 있으며, 특별히 이에 한정되는 것은 아니다. 상기 왁스들은 단독 또는 1종 이상 흔합하여 사용될 수 있으며, 상기 왁스의 함량은 단량체 흔합물 전체 중량을 기준으로 0.01내지 30중량부인 것이 바람직하다. 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.
상기 사슬 이동제는 t-도데실 메르캅탄, n-도데실 메르캅탄, n-옥틸 메트갑탄, 사염화탄소, 및 사브름화탄소 등을 1종 이상 사용할 수 있다. 상기 사슬 이동제의 함량은 단량체 흔합물 전체에 대하여 0.01 내지 10 중량부 정도인 것이 바람직하다. 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.
상기 가교제로는 디비닐벤젠, 에틸렌 디메타크릴레이트, 에틸렌글리콜 디메타크릴레이트, 디에틸렌글리콜 디아크릴레이트, 1,6- 핵사메틸렌 디아크릴레이트, 알릴 메타크릴레이트, 1,1,1-트리메틸을프로판 트리아크릴레이트, 트리알릴아민, 테트라알릴옥시에탄 또는 이들의 흔합물 등을 사용될 수 있으며, 그의 함량은 단량체 흔합물 전체 중량을 기준으로 0.001 내지 10 중량부인 것이 바람직하다. 상기 가교제의 함량이 0.001 중량부 미만인 경우에는 보존성 향상의 효과를 기대하기 어려울 수 있으며, 10 중량부를 초과하는 경우에는 토너 내부에 겔화가 일어나 프린팅시 토너의 정착성이 떨어지는 문제가 발생할 수 있다. 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) 제 3단계: 현탁 중합 단계 (3) third step: suspension polymerization step
상기 제 2단계에서 준비한 단량체 흔합물에 중합개시제를 넣고, 상기 단량체 흔합물을 상기 제 1단계에서 준비한 수계 분산액에 투입한다. 상기 단량체 흔합물을 포함하는 수계 분산액에 전단력을 부여하여 현탁중합시킨다. 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.
상기 중합 개시제로는 유용성 개시제와 수용성 개시제를 사용할 수 있다. 구체적으로는 아조비스이소부티로니트릴, 아조비스디메틸발레로니트릴 등의 아조계 개시제; 벤조일퍼옥사이드, 라우로일퍼옥사이드 등의 유기 퍼옥사이드; 과황산칼륨, 과황산암모늄 등의 일반적으로 쓰이는 수용성 개시제 등을 사용할 수 있으며, 이 중에서 1종 또는 2종 이상을 흔합하여 사용할 수도 있다. 상기 중합 개시제의 함량은 단량체 흔합물 전체에 대하여 0.01 내지 5 중량부인 것이 바람직하다. 상기 함량이 0.01 중량부 미만인 경우 미반을 물질이 발생할 수 있으며, 5
중량부를 초과하는 경우에는 반응 속도가 너무 빨라 반웅 안정성이 저하되는 문제가 발생할 수 있기 때문이다. 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) 제 4 단계 : 분산제 분리 및 건조 단계 (4) 4th step: dispersant separation and drying step
중합이 완료되면, 분산제의 종류에 따라 염기성 수용액이나 산성 수용액을 첨가하여 분산제를 제거하고, 물로 세척하고 필터링하여 분산제를 분리한다. 예를 들어, 콜로이달 실리카를 수계 분산제로 사용하는 경우에는 농도가 0.05 내지 0. N인 NaOH를 첨가함으로써, 콜로이달 실리카를 제거할 수 있다. 분산제가 토너와 완전히 분리될 때까지 상기 과정을 반복한다. 분산제가 토너와 완전히 분리되면, 토너 모입자를 진공 오븐에 넣어 상온에서 48 시간 건조하여 최종 토너 모입자를 얻는다. 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.
본 발명의 토너 제조 방법과 같이, 바인더 수지 단량체, 전하조절제, 안료, 왁스 등을 포함하여 이루어지는 토너 모입자에 입자 사이즈가 크고 입자끼리 서로 웅집 또는 융합되어 있는 콜로이달 실리카와 입자 사이즈가 작은 소수성 실리카를 흔합 사용함으로써 토너 모입자의 표면 전하량이 균일하고 시간이 경과하여도 전하량이 일정하게 유지되어 클리닝 블레이드에서의 클리닝 성능 뿐만 아니라 유동성, 배경오염, 전사효율 등과 같은 토너 및 대전 특성이 향상된 토너를 제조할 수 있다. 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.
한편, 본 발명에 따른 중합 토너는 좁은 입경 분포와 함께 높은 화상농도와 우수한 전사효율로 균일한 화상 구현이 가능한 우수한 물성을 갖는 것이 될 수 있다. 특히, 토너와 사용된 다른 외첨제들의 특성에 따라 드럼 표면에서 오염의 원인으로 작용하지만 콜로이달 실리카를 사용할 경우 최소한의 드럼 마모로 드럼 오염을 개선할 수 있다. 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.
본 발명에 있어서 상기 기재된 내용 이외의 사항은 필요에 따라 가감이 가능한 것이므로, 본 발명에서는 특별히 한정하지 아니한다. 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.
【발명의 효과】 【Effects of the Invention】
본 발명은 특정의 콜로이달 실리카를 외첨제로 포함함으로써 와이퍼 블레이드 (wiper blade)에서의 클리닝 (cleaning) 성능이 대폭 향상된 중합 토너 및 이의 제조 방법을 제공한다. 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.
특히, 본 발명에 따른 중합 토너는 현탁 중합법 (suspension)으로 만든 구형의 토너 모입자 (core)를 사용하고 캐리어 (carrier)를 사용하는 2
성분계 카트리지에서 심하게 발생하는 PCR, 드럼 등의 부품 오염으로 발생하던 BG도 개선되었으며 더불어 전사효율 등의 측면에서도 매우 우수한 성능을 발휘할 수 있다. 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.
【도면의 간단한 설명】 [Brief Description of Drawings]
도 1은 본 발명의 실시예 2에 따라 제조된 중합 토너의 SEM 사진을 나타낸 것이다. 1 is a SEM photograph of a polymerized toner prepared according to Example 2 of the present invention.
도 2는 본 발명의 실시예 4에 따라 제조된 중합 토너의 S01 사진을 나타낸 것이다. Figure 2 shows a S01 picture of the polymerized toner prepared according to Example 4 of the present invention.
도 3은 본 발명의 실시예 7에 따라 제조된 중합 토너의 SEM 사진을 나타낸 것이다. 3 is a SEM photograph of a polymerized toner prepared according to Example 7 of the present invention.
【발명을 실시하기 위한 구체적인 내용】 [Specific contents to carry out invention]
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다. 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.
[실시예 1] Example 1
토너 모입자의 제조 Preparation of Toner Base Particles
내용적 3,000 mL의 반응기에 증류수 2,000 g과 분산제로서 콜로이달 실리카 48.8 g을 녹이고, 온도를 반웅 온도인 70 °C로 높인 수계 분산액을 준비하였다. 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.
다른 용기에 스티렌 720 g과, n-부틸 아크릴레이트 160 g, 및 알릴메타크릴레이크 18 g, 및 카본 블랙 45 g을 넣고, 비드밀로 2,000 rpm의 속도로 2 시간 동안 교반한 후, 비들르 제거하여 단량체 흔합물 500 g을 준비하였다. 준비한 흔합물을 70 °C로 물 중탕하여 온도를 높인 후, 설폰산기를 포함한 스티렌-아크릴계 고분자 전하조절제 4.5 g, 파라핀 왁스 23 g을 넣고, 20 분 동안 교반하면서 층분히 녹였다. 층분히 녹인 단량체 흔합물에 중합개시제인 아조비스이소부티로니트릴 8.5 g을 넣고 3분 동안 교반시켜 반웅물을 준비하였다. 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.
반응물을 수계 분산액에 투입하고 호모게나이저로 10,000 rpm의 속도로 20 분 동안 교반하면서 반웅을 지속시켰다. 20 분 후에 일반
교반기로 500 rpm의 속도로 20 시간 동안 교반하여 현탁 중합 반응을 실시한 후, 합성된 토너를 물로 세정하고 필터링하는 과정을 층분히 반복하여 분산제를 제거하고 진공 건조하여 토너 모입자를 제조하였다. 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.
외첨제 코팅 External additive coating
상기와 같이 제조한 토너 모입자 100 중량부에 대하여, 하기 표 1에 나타낸 바와 같이 체적평균입경 0.2-0.3 jam을 갖는 콜로이달 실리카 (실리카 단일 입자 크기 40~53 nm)를 다음과 같은 함량으로 사용하여 헨쉘 믹서기로 5,000 rpm 속도로 7 분 동안 흔합하고 교반하여, 토너 모입자 표면에 외첨제를 코팅하였다. 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.
이때, 상기 콜로이달 실리카는 "균일한 분포"를 갖는 것으로, 입자 In this case, the colloidal silica has a "uniform distribution", particles
1개로 되어 있는 비율이 30%~40%이며, 입자 2개가 서로 융합 (Fused)된 입자의 비율이 10%~30%이며, 입자 3개 이상 융합 (Fused)된 입자의 비율이 10¾~30¾의 분포를 갖는 것이었다. 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.
[실시예 2~3] [Examples 2-3]
하기 표 1에 나타낸 바와 같이, 상기 콜로이달 실리카의 함량을 각각 As shown in Table 1, respectively, the content of the colloidal silica
3 중량부 및 5 중량부로 달리하여 사용한 것을 제외하고는, 실시예 1과 동일한 방법으로 중합토너를 제조하였다. 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.
[실시예 4~8] EXAMPLES 4-8
하기 표 1에 나타낸 바와 같.이, 콜로이달 실리카의 종류 및 함량을 달리하여 사용한 것을 제외하고는, 실시예 1과 동일한 방법으로 중합 토너를 제조하였다. 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.
여기서, 상기 콜로이달 실리카는 "불균일한 분포"를 갖는 것으로, 입자 1개로 되어 있는 비율이 30% 미만 또는 4 초과이며, 입자 2개가 서로 융합 (Fused)된 입자의 비율이 10% 미만 또는 30% 초과이며, 입자 3개 이상 융합 (Fused)된 입자의 비율이 10% 미만 또는 30% 초과의 분포를 갖는 것이었다. 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%.
[비교예 1~26] [Comparative Examples 1 ~ 26]
하기 표 1에 나타낸 바와 같이, 콜로이달 실리카의 종류 및 함량을 달리하여 사용한 것을 제외하고는, 실시예 1과 동일한 방법으로 중합
토너를 제조하였다. 상기 실시예 1~8 및 비교예 1~26에 따라 제조된 중합 토너에 대하여 다음과 같은 방법으로 PCR 토너 오염, 전사효율, 화상오염도 (BG: background) 등을 평가하였다. 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.
PCR토너 오염 평가 PCR Toner Contamination Assessment
PCR 부품의 토너 오염이 발생하는 것을 비교하기 위하여 레이져 프린터용 카트리지 (C2200, 제조사: Xerox)에 사용되는 카트리지를 이용하였다. 이 카트리지는 캐리어 (carrier)를 사용하며 약 70 g의 캐리어 (carrier)가 들어있으며 더불어 일부 토너가 캐리어 (carrier )와 같이 카트리지 내부에 있는 상태로 되어 있다. 이 상태에서 토너를 추기로 보급하여 실험을 진행하였다. PCR 오염 정도는 토너를 약 70 g 정도 보급한 후에 20 g 정도를 소모하여 카트리지 내부에 캐리어 (carrier)와 같이 남아 있던 토너를 완전히 소모시킨 다음, 카트리지의 PCR을 다시 청소한 후에 A4의 5% 커버리지 패턴 (coverage pattern)으로 500 매 정도 소모한 다음 PCR에 토너가 오염되는 정도를 비교하여 토너의 클리닝 (cleaning) 성능이 효과적으로 개선되었는지를 비교하였다. 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: PCR오염 양호 (오염 발생 전혀 없음) A: Good PCR contamination (no pollution)
B: PCR오염 조금 양호 (5¾> 미만 발생) B: Slightly good PCR contamination (less than 5¾>)
C: PCR오염 발생띠 20% 발생) C: 20% occurrence of PCR contamination band)
D: PCR오염 심하게 발생 (20%~60% 발생) 상기 실시예 1~8 및 비교예 1~26에 따라 제조된 중합 토너에서 사용된 외첨제로서 콜로이달 실리카의 구체적인 종류와 토너 모입자 100 중량부에 대한 함량은 하기 표 1에 나타낸 바와 같다. 또한, 상술한 바와 같은 방법으로 측정한 중합 토너의 PCR 오염 평가 결과를 하기 표 1에 함께 나타내었다. 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.
상술한 바와 같은 PCT 토너 오염 평가와 함께, 중합 토너에 대한 전사효율 및 화상오염도 (BG: background)를 평가한 결과, 본 발명에 따른 실시예 1~8의 경우에 85% 이상 또는 90% 이상의 우수한 전사 효율이 얻을 수 있었으며, 비화상부분에서 전혀 화상오염이 나타나지 않음을 확인하였다. 그러나, 비교예 1~26의 경우에는 PCT 토너 오염에 따라 전사효율이 70% 이하로 현저히 떨어지며, 비화상 부분에서의 BG는 PCT이 오염된 토너들이 흔합된 색상으로, 예컨대, 열은 갈색 등으로 화상오염이 나타남을 확인하였다. 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.
또한, 실시예 2, 4, 7에 따라 제조된 중합 토너에 대한 SEM 사진을 도 1~3에 나타내었다. 도 1~3에 나타낸 바와 같이, 콜로이달 실리카의 융합 (fusion) 정도에 따라 토너 표면에 도포되어 있는 상태를 확인할 수 있다. 특히, 도 3에 나타난 바와 같이, 콜로이달 실리카의 입도 분포가 매우 좁은 (narrow) TG-C190의 경우 (실시예 7)는 토너 표면에 도포되어 있는 정도가 매우 균일한 것을 알 수 있다. 다만, 콜로이달 실리카의 융합 (fusion) 정도가 충분치 않은 TG-C190의 경우 (실시예 7) 또는 실리카 입자의 융합 (fusion)이 너무 많은 SAKAI 1의 경우 (실시예 4)에 비해,
실리카 입자가 층분히 융합 (fusion)이 되어 있어 실리카 분포가 균일한 실시예 2의 경우에 좀더 우수한 PCR 토너 오염 개선 , 즉, 클리닝 (cleaning) 개선 효과를 구현할 수 있음을 알 수 있다. 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.
한편, 상기 표 1에 나타난 바와 같이, 본 발명에 따라 외첨제로서 입자 사이즈가 크고 입자가 서로 웅집 또는 융합된 콜로이달 실리카를 소정의 함량 범위로 사용한 실시예 1 내지 8와 외첨제의 종류 및 함량을 변화시킨 비교예 1 내지 26을 비교해 보면, 실시예 1 내지 8이 클리닝 블레이드에서의 클리닝 성능 등 측면에서 비교예 1 내지 26에 비해 우수하다는 것을 알 수 있다. 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.
이와 같이, 토너 표면에 존재하는 콜로이달 실리카가 너무 적은 경우에는 클리닝 (cleaning) 개선 효과가 적으며, 이를 과량 사용하면 토너 표면에 존재하지 않고 이탈되어 또다른 문제를 유발시킨다. 결과적으로 콜로이달 실리카로 제조된 실리카 입자의 크기가 0.1 m 보다 큰 입도 분포를 가져야 하며 입자간의 융합 (fusion) 정도가 균일하여야 클리닝 개선 효과가 탁월하다는 것을 확인하였다.
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
【청구항 1] [Claim 1]
바인더 수지, 안료, 전하조절제, 및 왁스를 포함하는 토너 모입자; 상기 토너 모입자 표면에 코팅된 외첨제 ; Toner base particles including binder resins, pigments, charge control agents, and waxes; An external additive coated on the surface of the toner base particles;
를 포함하고, 상기 외첨제로서 단일 입자 크기가 25 내지 58 nm이며 체적평균입경이 0.06 내지 0.5 인 콜로이달 실리카 (colloidal silica)를 포함하는 중합토너 . 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.
【청구항 2】 [Claim 2]
제 1항에 있어서, The method of claim 1,
상기 토너 모입자 100 증량부에 대하여 상기 콜로이달 실리카를 1.0 내지 5.0 중량부의 함량으로 포함하는 중합토너 . 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.
【청구항 3】 [Claim 3]
제 1항에 있어서, The method of claim 1,
상기 콜로이달 실리카 (colloidal silica)는 입자 1개로 되어 있는 비율이 개수 기준으로 30% 내지 40%이며, 입자 2개가 서로 융합 (fused)된 입자의 비율이 10% 내지 30¾이며, 입자 3개 이상 융합 (fused)된 입자의 비율이 10%내지 30%의 분포를 갖는 것인 중합토너. 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%.
【청구항 4】 [Claim 4]
게 1항에 있어서, According to claim 1,
상기 콜로이달 실리카 (colloidal silica)는 실란계 커플링제 또는 실리콘 오일로 소수화 처리된 것인 중합 토너. Wherein the colloidal silica is hydrophobized with a silane coupling agent or silicone oil.
【청구항 5】 [Claim 5]
제 4항에 있어서, The method of claim 4,
상기 실란계 커플링제는 디메틸디클로로실란, 트리메틸클로로실란, 메틸트리클로로실란, 아릴페닐디클로로실란, 벤질디메틸클로로실란, 브롬메틸디클를로실란, p—클로로페닐트리클로로실란, 3- 클로로프로필트리메톡시, 비닐트리에톡시실란, 비닐트리아세톡시실란, 디비닐클로로실란, 및 핵사메틸디실라젠으로 이루어진 군에서 선택된 1종 이상인 중합 토너 .
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.
【청구항 6] [Claim 6]
제 4항에 있어서, The method of claim 4,
상기 실리콘 오일은 디메틸실리콘 오일, 메틸페닐실리콘 오일, 메틸하이드로젠실리콘 오일, 알킬 변성 실리콘 오일, 불소 변성 실리콘 오일, 알코을 변성 실리콘 오일, 아미노 변성 실리콘 오일, 에폭시 변성 실리콘 오일, 에폭시 폴리에이텔 변성 실리콘 오일, 페놀 변성 실리콘 오일, 에폭시 변성 실리콘 오일, 카르복시 변성 실리콘 오일, 및 머갑토 변성 실라콘 오일로 이루어진 군에서 선택된 1종 이상인 중합 토너. 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.
【청구항 7】 [Claim 7]
제 1항에 있어서, The method of claim 1,
상기 바인더 수지는 스티렌계 단량체, 아크릴레이트계 단량체, 메타크릴레이트계 단량체, 디엔계 단량체, 산성 올레핀계 단량체 및 염기성 을레핀계 단량체로 이루어진 군에서 1종 이상 선택된 단량체의 중합체를 포함하는 중합 토너 . 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.
【청구항 8】 [Claim 8]
제 1항에 있어서, The method of claim 1,
상기 전하조절제는 니그로신형 염료, 고지방족의 금속염, 알콕시 아민, 킬레이트, 4차 암모늄염, 알킬아미드, 불소 처리 활성제 및 나프탈렌산의 금속염으로 이루어진 군으로부터 선택되는 1종 이상의 양이온성 전하 조절제; 또는 염소화된 파라핀, 염소화된 폴리에스테르, 산을 함유한 폴리에스테르, 구리 프탈로시아닌의 설포닐아민 및 설폰산기를 포함한 스티렌-아크릴계 고분자로 이루어진 군으로부터 선택되는 1종 이상의 음이온성 전하 조절제를 포함하는 중합 토너 . 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. .
【청구항 9】 [Claim 9]
제 1항에 있어서, The method of claim 1,
상기 안료는 금속분말형 안료, 금속물산화형 안료, 카본형 안료, 황화물형 안료, 크롬염형 안료, 페로시아니드형 안료, 아조형 안료, 산성염료형 안료, 염기 성염료형 안료, 모단트염료형 안료, 프탈로시아닌, 퀴나크리돈형 안료, 및 디옥산형 안료로 이루어진 군에서 선택된 1종 이상을 포함하는 중합토너 .
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.
【청구항 10] [Claim 10]
제 1항에 있어서, The method of claim 1,
상기 왁스는 파라핀 왁스, 미정질 왁스 (microcrystalline wax), 세레신 왁스 (Ceresin wax), 카르누바 왁스 (Carnauba wax), 폴리에스테르계 왁스, 폴리올레핀계 '왁스로 이루어진 군에서 선택된 1종 이상인 중합 토너. 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.
【청구항 11】 [Claim 11]
제 1항에 있어서, . The method of claim 1 wherein.
상기 토너 모입자는 바인더 수지 50 내지 95 중량 %, 안료 1 내지 20 중량 %, 전하 조절제 0.1 내지 5 중량 %, 및 왁스 0.1 내지 30 중량 %를 포함하는 중합 토너 . 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.
【청구항 12】 [Claim 12]
제 1항에 있어서, The method of claim 1,
상기 토너 모입자는 반웅 개시제, 가교제, 분자량조절제, 활제, 및 커플링제로 이루어진 군에서 선택된 1종 이상의 첨가제를 더 포함하는 중합 토너ᅳ 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.
【청구항 13】 [Claim 13]
제 12항에 있어서, The method of claim 12,
상기 토너 모입자는 바인더 수지 50 내지 95 중량 ¾; 안료 1 내지 20 중량 %; 전하 조절제 0.1 내지 5 중량 %; 왁스 0.1 내지 30 중량 ¾; 및 반웅 개시제, 가교제, 분자량조절제, 활제, '및 커플링제로 이루어진 군에서 선택된 1종 이상의 첨가제 10중량 ¾ 이하를 포함하는 중합 토너 . 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.
【청구항 14] [Claim 14]
분산제를 포함하는 수계 분산액을 형성하는 단계; Forming an aqueous dispersion comprising a dispersant;
바인더 수지용 단량체, 안료, 전하 조절제, 및 왁스를 포함하는 단량체 흔합물을 형성하는 단계; Forming a monomer mixture comprising a binder resin, a pigment, a charge control agent, and a wax;
상기 단량체 흔합물을 상기 수계 분산액에 첨가하고 현탁 중합을 통하여 토너 모압자를 형성하는 단계; 및 Adding the monomer mixture to the aqueous dispersion and forming a toner mother pressure through suspension polymerization; And
상기 토너 모입자 표면에 외첨제를 코팅하는 단계; Coating an external additive on the surface of the toner base particles;
를 포함하고, 상기 외첨제로서 단일 입자 크기가 25 내지 58 nm이며 체적평균입경이 0.06 내지 0.5 /m인 콜로이달 실리카 (col loidal silica)를
포함하는 중합 토너의 제조 방법. 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.
【청구항 15] [Claim 15]
제 14항에 있어서, The method of claim 14,
상기 현탁 중합은 50 내지 70 °C에서 8 내지 12 시간 동안 반응시키는 단계 및 80 내지 100 °C로 승온한 후 30 분 내지 4 시간 동안 반응시키는 단계를 포함하는 중합 토너의 제조 방법. 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.
【청구항 16】 [Claim 16]
제 14항에 있어서, The method of claim 14,
상기 분산제는 무기분산제, 수용성 유기 고분자 분산제 및 음이온성 계면활성제로 이루어진 군으로부터 선택된 1종 이상을 포함하는 중합 토너의 제조 방법 . Wherein the dispersant comprises at least one selected from the group consisting of inorganic dispersants, water-soluble organic polymer dispersants, and anionic surfactants.
【청구항 17】 [Claim 17]
제 14항에 있어서, The method of claim 14,
상기 단량체 흔합물은 반응 개시제, 가교제, 분자량조절제, 활제, 및 커플링제로 이루어진 군에서 선택된 1종 이상의 첨가제를 더 포함하는 중합 토너의 제조 방법 . 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.
【청구항 18] [Claim 18]
제 14항에 있어서, The method of claim 14,
상기 토너 모입자를 형성하는 단계는, Forming the toner base particles,
상기 단량체 흔합물을 상기 수계 분산액에 첨가하는 단계; Adding the monomer mixture to the aqueous dispersion;
상기 수계 분산액 및 단량체 흔합물에 전단력을 가하여 상기 단량체 흔합물을 수계 분산액에 액적 형태로 균질화하는 단계; 및 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
상기 균질화된 단량체 흔합물을 현탁 중합하는 단계 Suspension polymerizing the homogenized monomer mixture
를 포함하는 것인 중합 토너의 제조 방법 .
Method for producing a polymerized toner comprising a.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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JP2007099582A (en) * | 2005-10-07 | 2007-04-19 | Shin Etsu Chem Co Ltd | Highly hydrophobic spherical sol-gel silica fine particle, method for producing the same, toner external additive for electrostatic charge image development composed of the fine particle, and developer using the toner external additive |
JP2007334118A (en) * | 2006-06-16 | 2007-12-27 | Aimekkusu:Kk | Toner for electrostatic image development |
JP2010128216A (en) * | 2008-11-27 | 2010-06-10 | Nippon Zeon Co Ltd | Toner for electrostatic charge image development and image forming method |
-
2013
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007099582A (en) * | 2005-10-07 | 2007-04-19 | Shin Etsu Chem Co Ltd | Highly hydrophobic spherical sol-gel silica fine particle, method for producing the same, toner external additive for electrostatic charge image development composed of the fine particle, and developer using the toner external additive |
KR100703972B1 (en) * | 2006-01-10 | 2007-04-09 | 주식회사 씨아이티 | Polymerized toner and fabricating method thereof |
JP2007334118A (en) * | 2006-06-16 | 2007-12-27 | Aimekkusu:Kk | Toner for electrostatic image development |
JP2010128216A (en) * | 2008-11-27 | 2010-06-10 | Nippon Zeon Co Ltd | Toner for electrostatic charge image development and image forming method |
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