JP2007183679A - Toner for electrostatic image development, method for manufacturing toner for electrostatic image development and method for fixing toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerized toner excellent in low-temperature fixability and hot offset resistance, having good OHP transparency and excellent also in charging property. <P>SOLUTION: The toner for electrostatic image development is obtained by sticking or fixing resin fine particles on particle aggregates containing at least polymer primary particles, wherein the amount of a tetrahydrofuran-insoluble component in the polymer primary particles is 15-80% and the toner contains a wax having a melting point of 30-100°C. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an electrostatic charge developing toner used in electrophotographic copying machines and printers. More specifically, the present invention relates to a charge developing toner produced by an emulsion polymerization aggregation method.

  Toner for electrostatic charge development that has been widely used in electrophotography in the past is a mixture of a styrene / acrylate copolymer containing a colorant such as carbon black or pigment, a charge control agent and / or a magnetic material. It has been produced by melting and kneading with a machine, and then pulverizing and classifying. However, the conventional toner obtained by the melt-kneading / pulverization method as described above has a limit in controlling the particle size of the toner, and substantially manufactures a toner having an average particle size of 10 μm or less, particularly 8 μm or less with a high yield. However, it was difficult to achieve the high resolution required for electrophotography in the future.

In order to achieve low-temperature fixability, a method of blending a wax having a low softening point in the toner during kneading has been proposed, but in the kneading / pulverization method, blending of about 5% is the limit, A toner exhibiting sufficient low-temperature fixing performance and sufficient OHP transparency could not be obtained. Japanese Patent Laid-Open No. 63-186253 (Patent Document 1) proposes a method for producing a toner by emulsion polymerization / aggregation in order to overcome the problem of particle size control and achieve high resolution. However, even in this method, there is a limit to the amount of wax that can be introduced in the coagulation step, and a sufficient improvement effect has not been obtained with respect to low-temperature fixability. Japanese Patent Laid-Open No. 9-190012 (Patent Document 2) proposes a method for producing a toner by an emulsion polymerization / aggregation method comprising crosslinked primary particles in order to suppress the gloss of an image. However, in this method, sufficient OHP transparency cannot be obtained, and OHP transparency is not sufficient.
JP-A 63-186253 Japanese Patent Laid-Open No. 9-190012

  An object of the present invention is to provide a novel toner that overcomes the drawbacks of conventionally used electrostatic charge developing toners and satisfies high resolution, low-temperature fixability, offset resistance, and OHP transparency.

  As a result of intensive studies on the above problems, the present inventors have found that a particle aggregate obtained by coaggregating a wax emulsion and a crosslinked polymer primary particle, or a crosslinked polymer primary obtained by emulsion polymerization using a wax emulsion as a seed. The inventors have found that the above problems can be solved by encapsulating resin fine particles in particle aggregates using particles, and have reached the present invention.

  That is, the gist of the present invention is that, in an electrostatic charge developing toner obtained by adhering or fixing resin fine particles to a particle aggregate containing at least polymer primary particles, the tetrahydrofuran insoluble content of the polymer primary particles is 15% to 80%. And the toner contains a wax having a melting point of 30 to 100 ° C.

  Another aspect of the present invention is an electrostatic charge developing toner obtained by attaching or fixing resin fine particles to a particle aggregate containing at least polymer primary particles, wherein the toner has a tetrahydrofuran insoluble content of 12% to 80%, and The toner is an electrostatic charge developing toner characterized by containing a wax having a melting point of 30 to 100 ° C.

  Another gist of the present invention is that a monomer mixture containing at least one polyfunctional monomer is polymerized by emulsion polymerization to form polymer primary particles, and this is co-aggregated with a wax having a melting point of 30 to 100 ° C. to obtain an average volume. The present invention relates to a method for producing a toner for developing an electrostatic charge image, characterized in that a particle aggregate having a particle diameter of 3 to 10 μm is formed, and resin fine particles are adhered or fixed to the particle aggregate.

  Another gist of the present invention is that a monomer mixture containing at least one polyfunctional monomer is polymerized by emulsion polymerization using wax fine particles having a melting point of 30 to 100 ° C. as seeds to form polymer primary particles, which are aggregated. The present invention relates to a method for producing a toner for developing an electrostatic charge image, characterized in that a particle aggregate having an average volume particle diameter of 3 to 10 μm is formed, and resin fine particles are adhered or fixed to the particle aggregate. According to another aspect of the present invention, there is provided a toner fixing method, wherein the toner for developing an electrostatic image is fixed by a fixing device having a fixing roller having a rubber hardness of 90 or less.

  Hereinafter, the present invention will be described in detail. The toner for developing an electrostatic charge image of the present invention is produced by producing polymer primary particles by an emulsion polymerization method, the polymer primary particles, a colorant, and other additives such as a charge control agent and a fluidizing agent as required. Is formed by adhering or fixing resin fine particles to the resin, and the toner contains a low-melting-point wax, and the polymer primary particles are crosslinked. To do.

  As the wax used in the present invention, any known wax can be used as long as it has a low melting point of 30 to 100 ° C. Specifically, low molecular weight polyethylene, low molecular weight polypropylene, copolymerization can be used. Olefin wax such as polyethylene, paraffin wax, behenyl behenate, montanate ester, ester wax having a long chain aliphatic group such as stearyl stearate, plant wax such as hydrogenated castor oil carnauba wax, distearyl ketone, etc. Long chain alkyl group ketones, alkyl group silicones, higher fatty acids such as stearic acid, long chain fatty acid alcohols, fatty acid polyhydric alcohols such as pentaerythritol, and their partial esters, oleic acid amides, stearic acid amides, etc. Higher fatty acid amide, aliphatic carbo Saccharides esters of acid.

  The melting point of the wax used is 30 to 100 ° C., preferably 40 ° C. or higher, more preferably 50 ° C. or higher, 90 ° C. or lower, more preferably 80 ° C. or lower. When the melting point exceeds 100 ° C., the effect of low-temperature fixing becomes poor. Furthermore, ester waxes having a long-chain aliphatic group are preferred. Among ester waxes, those having an aliphatic group having 10 to 30 carbon atoms are more preferred, and the number of carbon atoms in the entire molecule is preferably 20 to 60. These waxes may be used not only alone but also in combination. In particular, when an ester wax is used, it is preferable to use a mixture of a plurality of esters having different carbon numbers.

  The wax fine particles used in the present invention are obtained by emulsifying the wax in the presence of at least one emulsifier selected from known cationic surfactants, anionic surfactants, and nonionic surfactants.

  In the present invention, these wax fine particles are used for resin seed polymerization. Or it co-aggregates with the said wax microparticles | fine-particles and the polymer primary particle dispersion and colorant microparticles | fine-particles which are demonstrated below.

  Specific examples of the cationic surfactant used as the emulsifier include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl ammonium bromide and the like. Specific examples of the anionic surfactant include fatty acid soaps such as sodium stearate and sodium dodecanoate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, and sodium lauryl sulfate.

  Specific examples of nonionic surfactants include dodecyl polyoxyethylene ether, hexadecyl polyoxyethylene ether, nonylphenyl polyoxyethylene ether, lauryl polyoxyethylene ether, sorbitan monooleate polyoxyethylene ether, monodecanoyl salt. Examples include sugars.

  The weight average particle diameter of the wax fine particles is preferably 0.01 μm or more, more preferably 0.03 μm or more, and particularly preferably 0.05 μm or more. Further, it is preferably 3 μm or less, more preferably 1 μm or less, and particularly preferably 0.8 μm or less. When the average particle diameter of the wax emulsion is larger than 3 μm, the average particle diameter of the polymer particles obtained by seed polymerization becomes too large, so that it is unsuitable for applications requiring high resolution as a toner. On the other hand, when the average particle size of the emulsion is smaller than 0.01 μm, the wax content in the polymer primary particles after seed polymerization becomes too low, and the effect of the wax becomes poor.

  The wax is usually 1 part by weight or more, preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and usually 40 parts by weight or less, preferably 35 parts by weight or less, more preferably 100 parts by weight of the binder resin. Is used at 30 parts by weight or less. If the amount of the wax having a melting point of 30 to 100 ° C. is within the above range, a wax having a melting point of 100 ° C. or more may be shared. In addition, components other than wax, such as pigments, charge control agents, etc., may be used as seeds at the same time within the scope of the present invention.

  In seed emulsion polymerization in the presence of a wax emulsion, a monomer having a polar group (a monomer having a Bronsted acidic group or a monomer having a basic functional group) and another monomer are added in succession. Polymerization proceeds in the contained emulsion. At this time, the monomers may be added separately, or a plurality of monomers may be mixed and added in advance. Further, it is possible to change the monomer composition during the monomer addition. The monomer may be added as it is, or may be added as an emulsion mixed and adjusted in advance with water or a surfactant.

  In proceeding with the seed emulsion polymerization, a certain amount of emulsifier may be added to the wax emulsion. Further, the addition timing of the polymerization initiator may be any before the monomer addition, at the same time as the monomer addition, after the monomer addition, or may be a combination of these addition methods. The polymer primary particles obtained as described above are polymer particles substantially including a wax, and the morphology thereof takes any form such as a core-shell type, a phase separation type, and an occlusion type. It may be a mixture of these forms. Particularly preferred is the core-shell type.

  Examples of the monomer having a Bronsted acidic group used in the present invention include monomers having a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and cinnamic acid, and monomers having a sulfonic acid group such as sulfonated styrene. , Etc. Examples of the monomer having a Bronsted basic group include monomers having an amino group such as aminostyrene, dimethylaminoethyl acrylate and diethylaminoethyl methacrylate, and nitrogen-containing heterocyclic ring-containing monomers such as vinylpyridine.

  Other comonomers include styrenes such as styrene, methyl styrene, chlorostyrene, dichlorostyrene, p-tert-butyl styrene, p-butyl styrene, p-nonyl styrene, methyl acrylate, ethyl acrylate, propyl acrylate , Butyl acrylate, isobutyl acrylate, hydroxyethyl acrylate, ethyl hexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, hydroxyethyl methacrylate, ethyl hexyl methacrylate, etc. ( Examples include acrylamide such as (meth) acrylic acid ester and acrylic acid dimethylamide. Of these, styrene and butyl acrylate are particularly preferable.

  In the present invention, a polyfunctional monomer is used as a polymerization component together with the above-described monomer to crosslink the resin, and the degree of crosslinking of the polymer primary particles is controlled so that the tetrahydrofuran insoluble content is 15 to 80%. The tetrahydrofuran insoluble content is preferably 20% or more, more preferably 30% or more. Moreover, since it is preferably 70% or less, and more preferably 60% or less, such control is performed. Here, the tetrahydrofuran-insoluble content is an index representing the degree of crosslinking, and the larger the tetrahydrofuran-insoluble content, the higher the degree of crosslinking of the resin. If the degree of crosslinking is too low, offset is likely to occur, and if it is too high, OHP transparency decreases.

  The polyfunctional monomer used in the present invention means a monomer having at least two ethylenic double bonds having radical polymerizability in the molecule. Examples of the polyfunctional monomer used in the present invention include divinylbenzene, hexanediol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol acrylate. Etc. A monomer having a reactive group in a pendant group, such as glycidyl methacrylate, methylol acrylamide, or acrolein, can be used. Of these, divinylbenzene and hexanediol diacrylate are preferred. The blending ratio of such a polyfunctional monomer in the monomer mixture is preferably 0.005% by weight or more, more preferably 0.1% by weight or more, and particularly preferably 0.3% by weight or more. Preferably it is 5 weight% or less, More preferably, it is 3 weight% or less, Most preferably, it is 1 weight% or less.

  In the present invention, the colorant primary particles are aggregated simultaneously with the polymer primary particles and the wax particles or simultaneously with the polymer primary particles encapsulating the wax to form a particle aggregate to form a toner core material. The colorant to be used may be an inorganic pigment, an organic pigment, an organic dye, or a combination thereof.

  Specific examples of the colorant used in the colorant primary particles include carbon black, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa yellow, rhodamine dyes, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallyl. Any known dyes and pigments such as methane dyes, monoazo dyes, disazo dyes, and condensed azo dyes can be used alone or in combination. In the case of a full color toner, it is preferable to use benzidine yellow for yellow, monoazo and condensed azo dyes, magenta for quinacridone and monoazo dyes, and cyan for phthalocyanine blue. The colorant is preferably used in an amount of 3 parts by weight or more, more preferably 5 parts by weight or more, preferably 20 parts by weight or less, and more preferably 10 parts by weight or less with respect to 100 parts by weight of the binder resin. These colorants are also emulsified in water in the presence of an emulsifier and used in the form of an emulsion. The average particle size is preferably 0.01 to 3 μm.

  As the charge control agent, any known one can be used alone or in combination. In consideration of color toner adaptability (the charge control agent itself is colorless or light and there is no color tone problem on the toner), the quaternary ammonium salt compound is positively charged and the salicylic acid or alkylsalicylic acid chromium is negatively charged. , Metal salts with zinc, aluminum, etc., metal complexes, metal salts of benzylic acid, metal complexes, amide compounds, phenol compounds, naphthol compounds, phenolamide compounds, 4,4′-methylenebis [2- [N- (4- Hydroxynaphthalene compounds such as chlorophenyl) amido] -3-hydroxynaphthalene] are preferred. The amount used may be determined by the desired charge amount of the toner, but is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, and particularly preferably 1 part by weight with respect to 100 parts by weight of the binder resin. The amount is preferably 10 parts by weight or less, more preferably 8 parts by weight or less, and particularly preferably 5 parts by weight or less.

  In the present invention, as a method of incorporating a charge control agent into the toner, when obtaining the polymer primary particles, the charge control agent is used alone or seeded simultaneously with the wax, or the charge control agent is dissolved or dissolved in the monomer or the wax. It may be used in a dispersed manner, or the primary particles of the charge control agent may be aggregated simultaneously with the primary particles of the polymer to form a particle aggregate, and may be used as a toner, but before or simultaneously with the step of attaching or fixing the resin fine particles or It is preferable to adhere or fix the primary particles of the charge control agent after the step. In this case, the charge control agent is also used as an emulsion (primary particles of the charge control agent) having an average particle diameter of 0.01 to 3 μm in water.

  Next, a feature of the present invention is that toner particles are formed by further coating (adhering or fixing) resin fine particles to the above-mentioned particle aggregate in which the degree of cross-linking of the polymerized primary particles is 15 to 80% in terms of tetrahydrofuran insolubles. is there. The resin fine particles preferably have a volume average particle size of 0.02 μm or more, more preferably 0.05 μm or more, and preferably 2 μm or less, more preferably 1.5 μm or less. The thing obtained by superposing | polymerizing the monomer similar to the monomer used for can be used. The resin fine particles are dispersed in water or a liquid mainly composed of water with an emulsifier (the above-mentioned surfactant) and used as an emulsion, but it is preferable to use resin fine particles obtained by an emulsion polymerization method. Resin fine particles obtained by emulsion polymerization using the wax fine particles as a seed are also preferably used.

  The resin fine particle may also be a crosslinked resin using the above-mentioned polyfunctional monomer. However, when fixing with a relatively soft member, it is preferable that the degree of crosslinking of the resin fine particle is small, specifically, THF insoluble. The content is preferably 0 to 15%, more preferably 0 to 10%.

  The amount of the resin fine particles to be coated is preferably 1 part by weight or more, more preferably 3 parts by weight or more, particularly preferably 5 parts by weight or more with respect to 100 parts by weight of the resin constituting the particle aggregate. The amount is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, and particularly preferably 12 parts by weight or less. Further, the particle aggregate may be fused at a temperature equal to or higher than the glass transition point of the polymer primary particles before or after the resin particles are coated on the particle aggregate.

  Further, the toner of the present invention can be used together with additives such as a fluidizing agent, if necessary. Specific examples of such fluidizing agents include fine particles such as hydrophobic silica, titanium oxide, and aluminum oxide. A powder may be mentioned, and is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, preferably 5 parts by weight or less, more preferably 3 parts by weight with respect to 100 parts by weight of the binder resin. Used in the following ranges.

  In the toner of the present invention produced using each of the components described above, a resin in which polymer primary particles are crosslinked is used. However, the wax is almost dissolved in tetrahydrofuran, and the resin fine particles preferably have a low degree of crosslinking. Because it is used, it is almost dissolved. On the other hand, the colorant usually does not dissolve in tetrahydrofuran, and the charge control agent may or may not dissolve in tetrahydrofuran. However, since the charge control agent is usually used in a small proportion relative to other components, these are taken into consideration. Then, when the insoluble content of tetrahydrofuran as a toner is measured, about 12 to 80% is insoluble. Further, the tetrahydrofuran insoluble content of the toner is preferably 15% or more, more preferably 20% or more, and preferably 70% or less, more preferably 60% or less.

  Further, the toner of the present invention includes an inorganic fine powder such as magnetite, ferrite, cerium oxide, strontium titanate, and conductive titania, a resistance adjuster such as styrene resin and acrylic resin, and a lubricant as an internal or external additive. Used. The amount of these additives to be used may be appropriately selected depending on the desired performance, and is usually about 0.05 to 10 parts by weight with respect to 100 parts by weight of the binder resin.

  The electrostatic charge developing toner of the present invention may be used in any form of a two-component developer or a non-magnetic one-component developer. When used as a two-component developer, the carrier may be a magnetic substance such as iron powder, magnetite powder, ferrite powder, or a known material such as a mono or magnetic carrier having a resin coating on the surface thereof. As the coating resin of the resin coating carrier, generally known styrene resin, acrylic resin, styrene acrylic copolymer resin, silicone resin, modified silicone resin, fluororesin, or a mixture thereof can be used.

  Next, a suitable fixing device that can be used for fixing the toner of the present invention will be described. As shown in FIG. 1, the fixing device typically includes an upper fixing member and a lower fixing member, and has a heating device inside the upper or lower fixing member. In the fixing device shown here, the upper fixing member (the member that contacts the recording paper surface on which the toner is placed) is a fixing roller, and the lower fixing member is a pressure roller.

  The fixing roller has an elastic layer on a cylindrical metal core having a heat source on the inside, and further has a release layer on the elastic layer. The material of the cylindrical cored bar is not particularly limited, but metals such as aluminum, iron, and stainless steel are usually used. As the heat source provided inside the cored bar, any heat source conventionally used in the fixing roller may be used. For example, a heater lamp or the like can be used. As the material of the elastic layer, a known rubber material can be used as long as it has heat resistance enough to withstand continuous use at the fixing temperature, and a material having good thermal conductivity is preferable. Specific examples include silicone rubbers such as RTV silicone, LTV silicone, and HTV silicone, fluorine rubber, butadiene rubber, and isoprene rubber. In order to reduce the hardness of the fixing roller, an elastic body made of a relatively soft material such as silicone rubber may be provided. To increase the hardness of the fixing roller, the elasticity of a relatively hard material may be used. It is also possible to provide a body or no elastic body.

  The thickness of the coating layer is usually 10 μm or more, preferably 12 μm or more, and m is usually 200 μm or less, preferably 100 μm or less, particularly preferably 50 μm or less. Preferred fluororesins used for the coating layer include polytetrafluoroethylene (PTFE) resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) resin paint, or tetrafluoroethylene-hexafluoropropylene copolymer (FEP). Resin. The coating layer can also be used by mixing with other resins compatible with these fluororesins, but preferably the fluororesin is 50% by weight or more, more preferably 70% by weight or more of the entire coating layer. .

  Further, an elastic body layer, a coating layer, and a heater may be provided also on the pressure roller side. In a preferred embodiment of the present invention, the width of the fixing nip pressed by the fixing roller 71 and the pressure roller 72 is preferably 3 mm or more, more preferably 4 mm or more, and preferably 30 mm or less, more preferably 20 mm or less. It is. The nip passing speed of the recording paper is preferably 70 mm / second or more, more preferably 100 mm / second or more, and particularly preferably 120 mm / second or more. The upper limit of the speed is not particularly limited, but is usually 500 mm / min or less due to apparatus limitations.

  The toner of the present invention uses a crosslinked resin as the polymer primary particles constituting the toner core material (particle aggregate). Therefore, the toner surface has a relatively soft structure with respect to the inside of the toner. . Accordingly, the case where the hardness of the fixing roller is relatively soft is more effective for fixing the toner of the present invention. Specifically, it is preferable that the rubber hardness of the surface of the fixing roller is 90 or less. Here, the rubber hardness represents a rubber hardness measured in accordance with Japan Rubber Association Standard SRIS 0101. The rubber hardness on the surface of the fixing roller is more preferably 85 or less, and particularly preferably 80 or less.

  The present invention will be specifically described below with reference to examples. In the following examples, “parts” means “parts by weight”. The average particle diameter, molecular weight, glass transition point (Tg), fixing temperature width, and charge amount of the polymer particles were measured by the following methods.

Average particle diameter: Measured with LA-500 manufactured by Horiba, Microtrac UPA manufactured by Nikkiso Co., Ltd., or Coulter Counter Multisizer type II (abbreviated as Coulter Counter) manufactured by Coulter.
Weight average molecular weight: Measured by gel permeation chromatography (GPC). (Solvent: THF, calibration curve: standard polystyrene)
Glass transition point (Tg): Measured with DSC7 manufactured by PerkinElmer.

  The tetrahydrofuran insoluble matter indicating the degree of crosslinking of the polymer primary particles was measured by dissolving 1 g of the polymer primary particles in 100 g of tetrahydrofuran at 25 ° C. for 24 hours and filtering the residual amount. The tetrahydrofuran insoluble matter in the toner was measured by quantifying the residual amount when 1 g of the toner was dissolved in 100 g of tetrahydrofuran at 25 ° C. for 24 hours and filtered.

The melting point of the wax was measured using a DSC-20 (manufactured by Seiko) at a heating rate of 10 ° C / min. The temperature at the top of the peak showing the maximum endotherm in the DSC curve was taken as the melting point of the wax.
Fixing temperature range: Recording paper carrying an unfixed toner image was prepared, the temperature of the fixing roller was changed from 100 to 220 ° C., conveyed to the fixing nip portion, and the fixing state when discharged was observed. A fixing temperature region was defined as a temperature region in which no offset was generated on the fixing roller during fixing and the toner on the recording paper after fixing was sufficiently adhered to the recording paper. The fixing roller (heating roller) of the fixing device is made of aluminum as a core metal, 1.5 mm thick dimethyl-based low-temperature vulcanized silicone rubber having a rubber hardness of 3 ° according to JIS-A standard as an elastic layer, and PFA (release layer). (Tetetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) having a thickness of 50 μm is used. The rubber hardness of the surface of the fixing roller measured in accordance with Japan Rubber Association Standard SRIS 0101 was 80. Evaluation was performed with a nip width of 4 mm without application of silicone oil. The fixing speed was 120 mm / sec and 30 mm / sec.

  The OHP transparency is evaluated by using the above fixing roller, fixing to an OHP film under the conditions of oilless, 30 mm / sec, 180 ° C., and using a spectrophotometer for cyan, 480 nm and 620 nm transmittances for magenta The transmittances of 700 nm and 560 nm were measured, and in the case of yellow, the transmittances of 680 nm and 400 nm were measured, and the difference was used as a value.

  Charge amount: The toner is put into a non-magnetic one-component developer tank (Casio ColorPagePrestoN4 developer tank or Kyushu Matsushita Phaser550 developer tank), and after rotating the roller a certain number of times, the toner on the roller is sucked. The charge amount per unit weight was determined from the charge amount and the weight of the sucked toner.

  (Preparation of Wax Dispersion) As 100 parts of the wax dispersion, 30 parts of behenyl behenate was emulsified by applying high-pressure shear in the presence of 1.67 parts of sodium dodecylbenzenesulfonate to obtain an ester wax dispersion. The obtained dispersion had a solid content concentration of 30%, and the average particle size measured by UPA was 220 nm. (This is wax dispersion A)

  As 100 parts of the wax dispersion, 30 parts of behenyl behenate was emulsified by high-pressure shearing in the presence of 0.23 part of sodium dodecylbenzenesulfonate to obtain an ester wax dispersion. The obtained dispersion had a solid content concentration of 30%, and the average particle size measured by UPA was 400 nm. (This is wax dispersion B)

  Dehydrated water 68.33 parts, ester mixture mainly composed of behenyl behenate (Unistar M-2222SL, manufactured by NOF Corporation) and ester mixture mainly composed of stearyl stearate (UNISTAR M9766, manufactured by NOF Corporation) 7: 3 mixture 30 1 part of sodium dodecylbenzenesulfonate (Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., 66% active ingredient) was mixed and emulsified by applying high-pressure shearing at 90 ° C. to obtain a dispersion of ester wax fine particles. . The average particle diameter of the ester wax fine particles measured by LA-500 was 340 nm. (This is wax dispersion C)

  68.33 parts of demineralized water, 30 parts of stearic ester of pentaerythritol (Unistar H476, manufactured by NOF Corporation), 1.67 parts of sodium dodecylbenzenesulfonate (Neogen SC, manufactured by Daiichi Kogyo Seiyaku, 66% active ingredient) The mixture was emulsified by applying high-pressure shear at 90 ° C. to obtain a dispersion of ester wax fine particles. The average particle diameter of the ester wax fine particles measured by LA-500 was 350 nm. (This is the wax dispersion D)

  (Preparation of polymer primary particle dispersion) 35 parts of the following amount of wax dispersion A and demineralized water 400 in a glass reactor equipped with a stirrer, a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device The temperature was raised to 90 ° C. under a nitrogen stream. Thereafter, the following monomers, an aqueous emulsifier solution and an initiator were added, and emulsion polymerization was performed for 6.5 hours.

[Table 1]
(Monomers)
Styrene 79 parts butyl acrylate 21 parts acrylic acid 3 parts octanethiol 0.38 parts hexanediol diacrylate (HDDA) 0.7 parts (emulsifier aqueous solution)
10% sodium dodensylbenzenesulfonate (S-DBS) aqueous solution
1 part demineralized water 25 parts (initiator)
8% aqueous hydrogen peroxide solution 10.6 parts 8% aqueous ascorbic acid solution 10.6 parts

  After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The resulting polymer dispersion had a weight average molecular weight of 98,000, an average particle size measured by UPA of 190 nm, and Tg of 57 ° C. When the cross section of the obtained emulsion was observed with TEM, it was observed that the wax was encapsulated with the resin (this is the polymer primary particle dispersion A). The tetrahydrofuran insoluble content of the polymer primary particles was 40%.

  A milky white polymer dispersion was obtained in the same manner as the polymer primary particle dispersion A except that the wax dispersion B was used in place of the wax dispersion A and the monomers were changed as follows. The obtained polymer dispersion had a weight average molecular weight of 71,000, an average particle size measured by UPA of 179 nm, and Tg of 48 ° C. (This is referred to as polymer primary particle dispersion B). The tetrahydrofuran insoluble content of the polymer primary particles was 55%.

[Table 2]
(Monomers)
Styrene 64 parts butyl acrylate 36 parts acrylic acid 3 parts trichlorobromomethane 0.5 part divinylbenzene 1 part

  A milky white polymer dispersion was obtained in the same manner as the polymer primary particle dispersion B except that 67 parts of styrene and 33 parts of butyl acrylate were changed. The obtained polymer dispersion had a weight average molecular weight of 52,000, an average particle size measured by UPA of 205 nm, and Tg of 51 ° C. (This is the polymer primary particle dispersion C.) The tetrahydrofuran insoluble content of the polymer primary particles was 70%.

  A milky white polymer dispersion was obtained in the same manner as the polymer primary particle dispersion B except that 72 parts of styrene and 28 parts of butyl acrylate were changed. The obtained polymer dispersion had a weight average molecular weight of 44,000, an average particle size measured by UPA of 158 nm, and Tg of 55 ° C. (This is referred to as polymer primary particle dispersion D). The tetrahydrofuran insoluble content of the polymer primary particles was 75%.

  A reactor (volume 60 liters, inner diameter 400 mm) equipped with a stirrer (three blades), a heating / cooling device, a concentrating device, and each raw material / auxiliary charging device 28 parts wax dispersion C, 15% neogen SC aqueous solution 1 .2 parts and 393 parts of demineralized water were added, the temperature was raised to 90 ° C. under a nitrogen stream, and 1.6 parts of an 8% aqueous hydrogen peroxide solution and 1.6 parts of an 8% ascorbic acid aqueous solution were added. Thereafter, a mixture of the following monomers / emulsifier aqueous solution was added over 5 hours from the start of polymerization, and an initiator aqueous solution was added over 6 hours from the start of polymerization, and the mixture was further maintained for 30 minutes.

[Table 3]
[Monomers]
79 parts of styrene (5530 g)
Butyl acrylate 21 parts Acrylic acid 3 parts Octanethiol 0.38 part 2-Mercaptoethanol 0.01 part Hexanediol diacrylate 0.9 part [Emulsifier aqueous solution]
15% Neogen SC aqueous solution 1 part Demineralized water 25 parts
[Initiator aqueous solution]
8% hydrogen peroxide aqueous solution 9 parts 8% ascorbic acid aqueous solution 9 parts

  After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The weight-average molecular weight of the polymer soluble in THF was 119,000, the average particle size measured by UPA was 189 nm, and Tg was 57 ° C. (this is referred to as polymer primary particle dispersion E). The THF insoluble content of the polymer primary particles was 52%.

  A reactor (volume 60 liters, inner diameter 400 mm) equipped with a stirrer (three blades), a heating / cooling device, a concentrating device, and each raw material / auxiliary charging device 28 parts wax dispersion C, 15% neogen SC aqueous solution 1 .2 parts and 393 parts of demineralized water were added, the temperature was raised to 90 ° C. under a nitrogen stream, and 1.6 parts of an 8% aqueous hydrogen peroxide solution and 1.6 parts of an 8% ascorbic acid aqueous solution were added. Thereafter, a mixture of the following monomers / emulsifier aqueous solution was added over 5 hours from the start of polymerization, and an initiator aqueous solution was added over 6 hours from the start of polymerization, and the mixture was further maintained for 30 minutes.

[Table 4]
[Monomers]
Styrene 79 parts butyl acrylate 21 parts acrylic acid 3 parts bromotrichloromethane 0.45 parts 2-mercaptoethanol 0.01 parts hexanediol diacrylate 0.9 parts [emulsifier aqueous solution]
15% Neogen SC aqueous solution 1 part Demineralized water 25 parts [Initiator aqueous solution]
8% hydrogen peroxide aqueous solution 9 parts 8% ascorbic acid aqueous solution 9 parts

  After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The polymer had a THF-soluble component weight-average molecular weight of 148,000, an average particle size measured by UPA of 207 nm, and Tg of 55 ° C. (this is referred to as polymer primary particle dispersion F). The THF insoluble content of the polymer primary particles was 60%.

  A reactor equipped with a stirrer (full zone blade), heating / cooling device, concentrating device, and each raw material / auxiliary charging device (volume: 2 liters, inner diameter: 120 mm) was charged with 35 parts of wax dispersion and 397 parts of demineralized water, and nitrogen. The temperature was raised to 90 ° C. under an air stream, and 1.6 parts of an 8% aqueous hydrogen peroxide solution and 1.6 parts of an 8% ascorbic acid aqueous solution were added. Thereafter, a mixture of the following monomers / emulsifier aqueous solution was added over 5 hours from the start of polymerization, and an initiator aqueous solution was added over 6 hours from the start of polymerization, and the mixture was further maintained for 30 minutes.

[Table 5]
[Monomers]
79 parts of styrene (237g)
Butyl acrylate 21 parts Acrylic acid 3 parts Octanethiol 0.38 part 2-mercaptoethanol 0.01 part Hexanediol diacrylate 0.9 part
[Emulsifier aqueous solution]
15% Neogen SC aqueous solution 1 part Demineralized water 25 parts
[Initiator aqueous solution]
8% hydrogen peroxide aqueous solution 9 parts 8% ascorbic acid aqueous solution 9 parts

  After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The weight-average molecular weight of the THF-soluble polymer was 139,000, the average particle size measured by UPA was 201 nm, and Tg was unclear, but it was estimated to be between 60 and 65 ° C. (this Is a polymer primary particle dispersion G). The THF insoluble content of the polymer primary particles was 53%.

  (Preparation of resin fine particle dispersion) 4.3 parts of 10% S-DBS aqueous solution and 400 parts of demineralized water were added to a glass reactor equipped with a stirrer, heating / cooling device, concentration device, and raw material / auxiliary charging device. The temperature was raised to 90 ° C. under a nitrogen stream. Thereafter, the following monomers, an aqueous emulsifier solution and an initiator were added, and emulsion polymerization was performed for 6.5 hours.

[Table 6]
(Monomers)
Styrene 79 parts butyl acrylate 21 parts acrylic acid 3 parts trichlorobromomethane 0.5 part (emulsifier aqueous solution)
10% S-DBS aqueous solution 2.2 parts demineralized water 25 parts (initiator)
8% aqueous hydrogen peroxide solution 10.6 parts 8% aqueous ascorbic acid solution 10.6 parts

  After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The obtained polymer dispersion had a weight average molecular weight of 60,000, an average particle size measured by UPA of 154 nm, and Tg of 65 ° C. (This is referred to as resin fine particle dispersion A.)

  5 parts of 15% Neogen SC aqueous solution and 372 parts of demineralized water were added to a reactor (capacity 60 liters, inner diameter 400 mm) equipped with a stirrer (three blades), heating / cooling device, concentrating device, and raw material / auxiliary charging device. The temperature was raised to 90 ° C. under a nitrogen stream, and 1.6 parts of an 8% aqueous hydrogen peroxide solution and 1.6 parts of an 8% ascorbic acid aqueous solution were added. Thereafter, a mixture of the following monomers / emulsifier aqueous solution was added over 5 hours from the start of polymerization, and an initiator aqueous solution was added over 6 hours from the start of polymerization, and the mixture was further maintained for 30 minutes.

[Table 7]
[Monomers]
88 parts of styrene (6160g)
Butyl acrylate 12 parts Acrylic acid 2 parts Bromotrichloromethane 0.5 part 2-mercaptoethanol 0.01 part Hexanediol diacrylate 0.4 part
[Emulsifier aqueous solution]
15% Neogen SC aqueous solution 2.5 parts Demineralized water 24 parts
[Initiator aqueous solution]
8% hydrogen peroxide aqueous solution 9 parts 8% ascorbic acid aqueous solution 9 parts

  After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The polymer had a THF-soluble component weight-average molecular weight of 54,000, an average particle size measured by UPA of 83 nm, and Tg of 85 ° C. (this is referred to as resin fine particle dispersion B).

  6 parts of 15% Neogen SC aqueous solution and 372 parts of demineralized water in a reactor (volume 2 liters, 120 mm inner diameter) equipped with a stirrer (three receding blades), heating / cooling device, concentrating device, and raw material / auxiliary charging device Was heated to 90 ° C. under a nitrogen stream, and 1.6 parts of an 8% aqueous hydrogen peroxide solution and 1.6 parts of an 8% aqueous ascorbic acid solution were added. Thereafter, a mixture of the following monomers / emulsifier aqueous solution was added over 5 hours from the start of polymerization, and an initiator aqueous solution was added over 6 hours from the start of polymerization, and the mixture was further maintained for 30 minutes.

[Table 8]
[Monomers]
Styrene 88 parts (308 g)
Butyl acrylate 12 parts Acrylic acid 2 parts Bromotrichloromethane 0.5 part 2-mercaptoethanol 0.01 part Hexanediol diacrylate 0.4 part
[Emulsifier aqueous solution]
15% Neogen SC aqueous solution 3 parts Demineralized water 23 parts [Initiator aqueous solution]
8% hydrogen peroxide aqueous solution 9 parts 8% ascorbic acid aqueous solution 9 parts

  After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The polymer had a THF-soluble component weight-average molecular weight of 57,000, an average particle size measured by UPA of 56 nm, and Tg of 84 ° C. (this is referred to as polymer primary particle dispersion C).

  (Preparation of Colorant Fine Particle Dispersion) To 65 parts of demineralized water, 30 parts of Pigment Blue 15: 3 and 5 parts of polyoxyethylene nonylphenyl ether were added and dispersed with a sand grinder mill to obtain a colorant fine particle dispersion. . The resulting dispersion had a solid content concentration of 35%, and the average particle size measured by UPA was 150 nm. (This is the colorant fine particle dispersion A)

  207.5 parts of Pigment Red 238 and 2.5 parts of dodecylbenzenesulfonate were added to 77.5 parts of demineralized water and dispersed for 6 hours in a sand grinder mill to obtain a colorant fine particle dispersion. The resulting dispersion had a solid content of 20%, and the average particle size measured by UPA was 180 nm. (This is the colorant fine particle dispersion B)

  To 73 parts of demineralized water, 20 parts of Pigment Yellow 74 and 7 parts of polyoxyethylene nonylphenyl ether were added and dispersed in a sand grinder mill for 6 hours to obtain a colorant fine particle dispersion. The resulting dispersion had a solid content of 20%, and the average particle size measured by UPA was 300 nm. (This is the colorant fine particle dispersion C.)

  Pigment Blue 15: 3 aqueous dispersion (EP-700 Blue GA, manufactured by Dainichi Seika Co., Ltd., solid content 35%) The average particle size measured by UPA was 150 nm (this is referred to as Colorant Fine Particle Dispersion D) .

  20 parts of Pigment Yellow 74, 7 parts of polyoxyethylene alkylphenyl ether, and 73 parts of demineralized water were dispersed in a sand grinder mill to obtain a colorant fine particle dispersion. The average particle diameter measured by UPA was 211 nm (this is referred to as “colorant fine particle dispersion E”).

  (Preparation of Charge Control Agent Fine Particle Dispersion) To 76 parts of demineralized water, 20 parts of charge control agent 4,4′-methylenebis [2- [N- (4-chlorophenyl) amido] -3-hydroxynaphthalene], and alkylnaphthalene 4 parts of a sulfonate was added and dispersed by a sand grinder mill to obtain a charge control agent fine particle dispersion. The resulting dispersion had a solid content concentration of 24% and an average particle size measured by UPA of 200 nm. (This is the charge control agent fine particle dispersion A)

[Example 1]
Polymer primary particle dispersion A 90 parts (as solids)
Resin fine particle dispersion A 10 parts (as solid content)
Colorant fine particle dispersion A 6.7 parts (as solid content)
Charge control agent fine particle dispersion 2 parts (as solids)
Sodium dodecylbenzenesulfonate aqueous solution
0.5 parts (as solids)

  The above components were mixed in the following order. A sodium dodecylbenzenesulfonate aqueous solution was added to the polymer primary particle dispersion A and mixed uniformly, and then the colorant fine particle dispersion A was added and mixed uniformly. While stirring the mixed dispersion thus obtained with an anchor blade with a baffle, an aqueous aluminum sulfate solution was added at 30 ° C. (0.6 parts as a solid content). The average particle diameter of the mixed dispersion after addition of the aqueous aluminum sulfate solution was 2 μm. Thereafter, the temperature was raised to 55 ° C. with stirring and held for 1 hour, and further heated to 58 ° C. and held for 1 hour. Thereafter, the charge control agent fine particle dispersion A, the resin fine particle dispersion A, and an aluminum sulfate aqueous solution (0.1 part as solid content) were added in this order. After holding for 1 hour and a half, 10% S-DBS aqueous solution (3 parts as a solid content) was added, and then the temperature was raised to 95 ° C. and held for 4 hours. Thereafter, it was cooled, washed with filtered water with a Kiriyama funnel, and freeze-dried to obtain a toner (this toner is referred to as “toner A”).

  To 100 parts of toner, 0.6 part of silica having a hydrophobic surface treatment was mixed and stirred to obtain a developing toner (this is called developing toner A). The obtained toner A had a volume average particle diameter of 7.4 μm as measured by a Coulter counter. Moreover, the ratio of volume particle diameter of 5 μm or less is 1.7%, the ratio of 15 μm or more is 0.3%, and the ratio of volume average particle diameter to number average particle diameter is 1.09. It was narrow and good. This toner had a tetrahydrofuran insoluble content of 75%.

  When the fixing property of the developing toner A was evaluated, the toner was fixed at 180 to 220 ° C. at a fixing speed of 120 mm / sec and fixed at 150 to 180 ° C. at a fixing speed of 30 mm / sec. The OHP transparency was 60%. The charge amount of the toner A measured by ColorPagePrest was −8 μC / g, and the charge amount of the developing toner A was −18 μC / g.

[Example 2]
A toner B and a developing toner B were obtained in the same manner as in Example 1 except that the colorant fine particle dispersion A was changed to the colorant fine particle dispersion B. The volume average particle diameter of toner B is 7.5 μm, the ratio of the volume particle diameter of 5 μm or less is 1.5%, and the ratio of 15 μm or more is 0.2%. The ratio was 1.11 and the particle size distribution was very narrow and good. This toner had an insoluble content of tetrahydrofuran of 60%.

  When the fixing property of the developing toner B was evaluated, it was fixed at 200 to 220 ° C. at a fixing speed of 120 mm / sec and fixed at 160 to 190 ° C. at a fixing speed of 30 mm / sec. The OHP transparency was 50%. The charge amount of the toner B measured by ColorPagePrest was −20 μC / g, and the charge amount of the developing toner B was −25 μC / g.

[Example 3]
A toner C and a developing toner C were obtained in the same manner as in Example 1 except that the colorant fine particle dispersion A was changed to the colorant fine particle dispersion C. The volume average particle diameter of the toner C is 7.6 μm, the ratio of the volume particle diameter of 5 μm or less is 1.5%, the ratio of 15 μm or more is 0%, and the ratio of the volume average particle diameter to the number average particle diameter is The particle size distribution was very narrow and good. This toner had an insoluble content of tetrahydrofuran of 80%.

  When the fixing property of the developing toner C was evaluated, the toner was fixed at 160 to 220 ° C. at a fixing speed of 120 mm / sec and fixed at 140 to 190 ° C. at a fixing speed of 30 mm / sec. The OHP transparency was 65%. The charge amount of the toner C measured by ColorPagePrest was −3 μC / g, and the charge amount of the developing toner C was −21 μC / g.

[Example 4]
Polymer primary particle dispersion B 100 parts (as solids)
Resin fine particle dispersion A 21 parts (as solid content)
Colorant fine particle dispersion A 6.7 parts (as solid content)
Charge control agent fine particle dispersion 0.1 part (as solid content)

  The above components were mixed in the following order. The colorant fine particle dispersion A was added to the polymer primary particle dispersion B and mixed uniformly. While stirring the obtained mixed dispersion with an anchor blade, an aqueous NaCl solution was added at 20 ° C. (10 parts as a solid content). Thereafter, the temperature was raised to 45 ° C. with stirring and held for 1 hour, further raised to 95 ° C. and held for 5 hours, and then cooled to obtain toner particles.

  100 parts of the toner particles were charged and stirred in a glass reactor equipped with a stirrer, a heating / cooling device, a concentrating device, and raw material / auxiliary charging devices. The charge control agent fine particle dispersion A and the resin fine particle dispersion A were added thereto and held at 45 ° C. for 2 hours. Thereafter, it was cooled, washed with filtered water with a Kiriyama funnel, and freeze-dried to obtain a toner (this toner is referred to as toner D).

  To 100 parts of toner, 0.6 part of silica having a hydrophobic surface treatment was mixed and stirred to obtain a developing toner (this is called developing toner D). The obtained toner D had a volume average particle diameter of 7.1 μm. The ratio of the volume average particle size to the number average particle size was 1.2, and the particle size distribution was very narrow and good. This toner had an insoluble content of tetrahydrofuran of 60%.

  When the fixing property of the developing toner D was evaluated, it was fixed at 110 to 200 ° C. at a fixing speed of 120 mm / sec, and the OHP transparency was 73%. The charge amount of the developing toner D measured by Phaser was −20 μC / g.

[Example 5]
A toner E and a developing toner E were obtained in the same manner as in Example 4 except that the polymer primary particle dispersion B was changed to the polymer primary fine particle dispersion C. The volume average particle diameter of the toner E is 6.8 μm, the ratio of the volume average particle diameter to the number average particle diameter is 1.05, and the particle diameter distribution is very narrow and good. This toner had an insoluble content of tetrahydrofuran of 70%.

  When the fixing property of the developing toner E was evaluated, it was fixed at 115 to 200 ° C. at a fixing speed of 120 mm / sec, and the charge amount of the developing toner E measured by Phaser was −19 μC / g.

[Example 6]
A toner F and a developing toner F were obtained in the same manner as in Example 4 except that the polymer primary particle dispersion B was changed to the polymer primary particle dispersion D and the resin particle dispersion A was changed to 10 parts. . The volume average particle diameter of the toner F is 6.3 μm, the ratio of the volume average particle diameter to the number average particle diameter is 1.04, and the particle diameter distribution is very narrow and good. The toner had an insoluble content of tetrahydrofuran of 82%.

  When the fixing property of the developing toner F was evaluated, it was fixed at 120 to 200 ° C. at a fixing speed of 120 mm / sec, and the charge amount of the developing toner F measured by Phaser was −27 μC / g.

[Comparative Example 1]
A toner G and a developing toner G were obtained in the same manner as in Example 3 except that the resin fine particle dispersion A was not added. The volume average particle diameter of the toner G was 7.1 μm. When the fixing property of the developing toner G was evaluated, the toner was fixed at 138 to 200 ° C. at a fixing speed of 120 mm / sec and fixed at 112 to 182 ° C. at a fixing speed of 30 mm / sec. The toner G was not negatively charged as measured by ColorPagePrest. The charge amount of the developing toner G was −1 μC / g.

[Comparative Example 2]
A toner H and a developing toner H were obtained in the same manner as in Example 6 except that the resin fine particle dispersion A was not added. The volume average particle diameter of the toner H is 6.0 μm. The ratio of the volume average particle diameter to the number average particle diameter was 1.02. When the fixing property of the developing toner H was evaluated, it was fixed at 120 to 200 ° C. at a fixing speed of 120 mm / sec. As a result of measurement with Phaser, the developing toner H was not negatively charged.

[Comparative Example 3]
In Example 1, a toner J and a developing toner J were obtained in the same manner as in Example 1 except that divinylbenzene was not used in preparing the polymer primary particle dispersion. The volume average particle diameter of the toner J was 6.5 μm. The ratio of the volume average particle diameter to the number average particle diameter was 1.02. Further, the tetrahydrofuran insoluble content of the toner was 5.5%. When the fixing property of the developing toner J was evaluated, fixing was performed at 170 to 180 ° C. at a fixing temperature width of 120 mm / sec. When measured by Phaser, the charge amount of the developing toner J was −19 μC / g.

[Table 9]
[Example 7]
104 parts of polymer primary particle dispersion E (71 g: as solid content)
Resin fine particle dispersion B 6 parts (as solids)
Colorant fine particle dispersion D 6.7 parts (as solid content)
Charge control agent fine particle dispersion A 2 parts (as solid content)
0.5 parts of 15% Neogen SC aqueous solution (as solids)

  Using each of the above components, a toner was produced by the following procedure. The polymer primary particle dispersion and 15% Neogen SC aqueous solution were charged into a reactor (capacity 1 liter, anchor blade with baffle) and mixed uniformly, and then the colorant fine particle dispersion was added and mixed uniformly. While stirring the obtained mixed dispersion, an aqueous aluminum sulfate solution was added dropwise (0.6 parts as a solid content). Thereafter, while stirring, the temperature was raised to 51 ° C. over 20 minutes and held for 1 hour, and further heated to 58 ° C. over 6 minutes and held for 1 hour. A charge control agent fine particle dispersion, a resin fine particle dispersion, and an aluminum sulfate aqueous solution (0.07 parts as solid content) were added in this order, and the temperature was raised to 60 ° C. over 10 minutes and held for 30 minutes. After adding 15% Neogen SC aqueous solution (3 parts as solid content), the temperature was raised to 95 ° C. over 35 minutes and held for 3.5 hours. Thereafter, the mixture was cooled, filtered, washed with water, and dried to obtain a toner (toner K). To 100 parts of the toner, 0.6 part of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (developing toner K).

  The volume average particle diameter of the developing toner K by Coulter counter is 7.2 μm, the ratio of the volume particle diameter of 5 μm or less is 35%, the ratio of 15 μm or more is 0.5%, and the ratio of the volume average particle diameter to the number average particle diameter Was 1.12. The 50% circularity was 0.97. The fixing property of the developing toner K was fixed at 170 to 220 ° C. at a fixing speed of 120 mm / S, and fixed at 130 to 220 ° C. at a fixing speed of 30 mm / S. The OHP permeability was 70%. The charge amount of the toner K was −7 μC / g, and the charge amount of the developing toner K was −15 μC / g. The THF insoluble content of the toner was 33%.

[Table 10]
[Example 8]
Polymer primary particle dispersion F 105 parts (as solids)
Resin fine particle dispersion B 5 parts (as solid content)
Colorant fine particle dispersion E 6.7 parts (as solid content)
Charge control agent fine particle dispersion A 2 parts (as solid content)

  Using each of the above components, a toner was produced by the following procedure. The polymer primary particle dispersion and the colorant fine particle dispersion were charged into a reactor (volume: 1 liter, anchor blade with baffle) and mixed uniformly. While stirring the obtained mixed dispersion, an aqueous aluminum sulfate solution was added dropwise (0.6 parts as a solid content). Thereafter, while stirring, the temperature was raised to 51 ° C. over 25 minutes and held for 1 hour, and further heated to 59 ° C. over 8 minutes and held for 40 minutes. A charge control agent fine particle dispersion, a resin fine particle dispersion, and an aqueous aluminum sulfate solution (0.07 parts as a solid content) were added in this order, and the temperature was raised to 61 ° C. over 15 minutes and held for 30 minutes. After adding 15% neogen SC aqueous solution (3.8 parts as a solid content), the temperature was raised to 96 ° C. over 30 minutes and held for 4 hours. Thereafter, the mixture was cooled, filtered, washed with water, and dried to obtain a toner (toner L). To 100 parts of toner-2, 0.6 parts of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (developing toner L).

  The volume average particle diameter of the developing toner L by Coulter counter is 7.5 μm, the ratio of 5 μm or less of the volume particle diameter is 1.6%, the ratio of 15 μm or more is 0.7%, the volume average particle number and the number average particle diameter The ratio was 1.14. The 50% circularity was 0.96. The fixing property of the developing toner L was fixed at 150 to 220 ° C. at a fixing speed of 120 mm / S, and fixed at 130 to 220 ° C. at a fixing speed of 30 mm / S. The charge amount of the toner L was −4 μC / g, and the charge amount of the developing toner L was −3 μC / g. The THF insoluble content of the toner was 55%.

[Table 11]
[Example 9]
Polymer primary particle dispersion E 104 parts (as solids)
Resin fine particle dispersion B 6 parts (as solids)
Colorant fine particle dispersion B 6.7 parts (as solid content)
Charge control agent fine particle dispersion A 2 parts (as solid content)
0.65 parts of 15% neogen SC aqueous solution (as solids)

  Using each of the above components, a toner was produced by the following procedure. The polymer primary particle dispersion and 15% Neogen SC aqueous solution were charged into a reactor (capacity 1 liter, anchor blade with baffle) and mixed uniformly, and then the colorant fine particle dispersion was added and mixed uniformly. While stirring the obtained mixed dispersion, an aqueous aluminum sulfate solution was added dropwise (0.8 parts as a solid content). Thereafter, while stirring, the temperature was raised to 51 ° C. over 15 minutes and held for 1 hour, and further heated to 59 ° C. over 6 minutes and held for 20 minutes. A charge control agent fine particle dispersion, a resin fine particle dispersion, and an aluminum sulfate aqueous solution (0.09 parts as a solid content) were added in this order, and the mixture was held at 59 ° C. for 20 minutes. After adding 15% Neogen SC aqueous solution (3.7 parts as solid content), the temperature was raised to 95 ° C. over 25 minutes, and further 15% Neogen SC aqueous solution (0.7 parts as solid content) was added. For 3.5 hours. Thereafter, the resultant was cooled, filtered, washed with water, and dried to obtain a toner (toner M). To 100 parts of this toner, 0.6 part of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (developing toner M).

  The volume average particle diameter of the developing toner M measured by Coulter counter is 7.8 μm, the ratio of the volume particle diameter of 5 μm or less is 2.1%, the ratio of 15 μm or more is 2.1%, the volume average particle diameter and the number average particle diameter The ratio was 1.15. The 50% circularity was 0.97. The fixing property of the developing toner M was fixed at 160 to 220 ° C. at a fixing speed of 120 mm / S, and fixed at 120 to 220 ° C. at a fixing speed of 30 mm / S. The charge amount of the toner M was −17 μC / g, and the charge amount of the developing toner M was −17 μC / g. The THF insoluble content of the toner was 48%.

[Table 12]
[Example 10]
105 parts of polymer primary particle dispersion G (71 g: as solid content)
Resin fine particle dispersion C 5 parts (as solid content)
Colorant fine particle dispersion D 6.7 parts (as solid content)
Charge control agent fine particle dispersion A 2 parts (as solid content)
0.5 parts of 15% Neogen SC aqueous solution (as solids)

  Using each of the above components, a toner was produced by the following procedure. The polymer primary particle dispersion and 15% neogen SC aqueous solution were charged into a reactor (capacity 1 liter, anchor blade with baffle), mixed uniformly, then added with colorant fine particle dispersion, and mixed uniformly. While stirring the obtained mixed dispersion, an aqueous aluminum sulfate solution was added dropwise (0.53 parts as a solid content). Thereafter, while stirring, the temperature was raised to 50 ° C. over 25 minutes and held for 1 hour, and further heated to 63 ° C. over 35 minutes and held for 20 minutes. A charge control agent fine particle dispersion, a resin fine particle dispersion, and an aqueous aluminum sulfate solution (0.07 parts as solid content) were added in this order, and the temperature was raised to 65 ° C. over 10 minutes and held for 30 minutes. After adding 15% Neogen SC aqueous solution (3 parts as solid content), the temperature was raised to 96 ° C. over 30 minutes and held for 5 hours. Thereafter, the mixture was cooled, filtered, washed with water, and dried to obtain a toner (toner N). To 100 parts of this toner, 0.6 part of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (developing toner N).

  The volume average particle diameter of the developing toner N by Coulter counter is 7.9 μm, the ratio of the volume particle diameter of 5 μm or less is 2%, the ratio of 15 μm or more is 1.5%, and the ratio of the volume average particle diameter to the number average particle diameter Was 1.20. The 50% circularity was 0.95. The fixing property of the developing toner N was fixed at 170 to 220 ° C. at a fixing speed of 120 mm / S, and fixed at 130 to 220 ° C. at a fixing speed of 30 mm / S. The OHP permeability was 70%. The charge amount of the toner N was −9 μC / g, and the charge amount of the developing toner N was −15 μC / g. The THF insoluble content of the toner was 40%.

  According to the present invention, it is possible to provide a polymerized toner having a sufficient non-offset region even in the heating roller fixing method, having good OHP transparency and excellent chargeability. The polymerized toner of the present invention has a small particle size and a sharp particle size distribution, and is suitable for high-resolution image formation.

FIG. 3 is a schematic view of details of a fixing device used in the present invention.

Explanation of symbols

71 Upper fixing member (fixing roller)
72 Lower fixing member (pressure roller)
71a Cover layer 71b Elastic layer 71c Cylindrical core 71d Heater lamp T Toner P Recording paper

Claims (13)

  In a toner for developing an electrostatic charge image in which resin fine particles are adhered or fixed to a particle aggregate containing at least polymer primary particles, the tetrahydrofuran insoluble content of the polymer primary particles is 15% to 80%, and the toner has a melting point. An electrostatic charge image developing toner comprising a wax at 30 to 100 ° C.   2. The electrostatic image developing toner according to claim 1, wherein resin particles not containing wax adhere or adhere to the surface of the particle aggregate containing wax.   3. The electrostatic image developing toner according to claim 1, wherein the monomer constituting the polymer primary particles has a Bronsted acidic group or a Bronsted basic group.   4. The electrostatic image developing toner according to claim 1, wherein the wax has a melting point of 40 to 90.degree.   5. The electrostatic image developing toner according to claim 1, wherein the wax is contained in an amount of 1 to 40 parts by weight with respect to 100 parts by weight of the binder resin.   The toner for developing an electrostatic charge image according to any one of claims 1 to 5, wherein the primary particle of the polymer has an insoluble content in tetrahydrofuran of 30 to 75%.   The electrostatic image developing toner according to claim 1, wherein the polyfunctional monomer is 0.005 to 5 wt% in the monomer constituting the polymer primary particles.   In an electrostatic image developing toner obtained by adhering or fixing resin fine particles to a particle aggregate containing at least polymer primary particles, the toner has a tetrahydrofuran insoluble content of 12% to 80%, and the toner has a melting point of 30 to 100. A toner for developing an electrostatic image, characterized by containing a wax at 0 ° C.   The toner for developing an electrostatic image according to claim 8, wherein the tetrahydrofuran insoluble content of the resin fine particles is 0 to 15% by weight.   A monomer mixture containing at least one polyfunctional monomer is polymerized by emulsion polymerization to form polymer primary particles, and this and a wax having a melting point of 30 to 100 ° C. are co-aggregated to form particle aggregates having an average volume particle size of 3 to 10 μm. A method for producing a toner for developing an electrostatic charge image, wherein the toner particles are aggregated, and resin fine particles are adhered or fixed to the particle aggregate.   A monomer mixture containing at least one polyfunctional monomer is polymerized by emulsion polymerization using wax fine particles having a melting point of 30 to 100 ° C. as seeds to form polymer primary particles, which are aggregated to have an average volume particle size of 3 to 10 μm. A method for producing a toner for developing an electrostatic charge image, comprising: adhering or fixing resin fine particles to the particle aggregate.   The method for producing a toner for developing an electrostatic charge image according to claim 10 or 11, wherein the ratio of the polyfunctional monomer when the monomer mixture is polymerized by an emulsion polymerization method is 1 to 30% by weight in the total monomers.   10. A toner fixing method, wherein the toner for developing an electrostatic charge image according to claim 1 is fixed by a fixing device having a fixing roller having a rubber hardness of 90 or less.

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