JP2006250975A - Toner, toner manufacturing method, two-component developer, and image forming apparatus - Google Patents

Abstract

Provided is a toner or a two-component developer capable of producing a toner having a small particle size having a sharp particle size distribution without requiring a classification step, extending the life of the toner, and preventing omission and scattering during transfer.
In an aqueous medium, at least a first resin particle dispersion in which first resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and wax particle dispersion in which wax particles are dispersed. The second resin particle dispersion liquid in which the second resin particles are dispersed is added to the core particle dispersion liquid including the core particles produced by mixing and aggregating the liquid, and the mixture is heated and heated. A toner obtained by fusing the second resin particles to the core particles, wherein the pH of the second resin particle dispersion in which the second resin particles are dispersed is adjusted in the range of 3.5 to 9.5. And adding the toner.
[Selection] Figure 1

Description

  The present invention relates to a toner used in a copying machine, a laser printer, plain paper FAX, a color PPC, a color laser printer, a color FAX, and a composite machine thereof, a toner manufacturing method, a two-component developer, and an image forming apparatus.

  In recent years, image forming apparatuses such as printers are shifting from the purpose of office use to personal use, and there is a demand for technology that realizes miniaturization, high speed, high image quality, and maintenance-free. Therefore, a cleaner-less process that collects waste toner during development without cleaning waste toner remaining after transfer in electrophotography, a tandem color process that enables high-speed output of color images, and fixing to prevent offset during fixing Oil-less fixing that achieves both high glossiness and high translucency, a clear color image and non-offset properties without using oil, is required along with conditions such as good maintainability and low ozone exhaust. These functions need to be compatible at the same time, and not only the process but also the improvement in toner characteristics is an important factor.

  In a color printer, in a fixing process, it is necessary to melt and mix color toners in a color image to increase translucency. When toner fusing failure occurs, light scattering occurs on the surface or inside of the toner image, and the original color tone of the toner dye is impaired. In addition, in the overlapping portion, light does not enter the lower layer and color reproducibility deteriorates. . Therefore, it is a necessary condition that the toner has a complete melting characteristic and a translucency that does not disturb the color tone. The need for light transparency on OHP paper is increasing with the increasing number of presentation opportunities in color.

  When a color image is obtained, toner adheres to the surface of the fixing roller to cause an offset, so that a large amount of oil or the like must be applied to the fixing roller, which complicates handling and the configuration of the device. For this reason, in order to reduce the size, maintain maintenance, and reduce the cost of the equipment, it is required to realize oilless fixing that does not use oil during fixing, which will be described later. In order to make this possible, a configuration in which a release agent such as wax is added to a binder resin having sharp melt characteristics is being put into practical use.

  However, the problem with such a toner configuration is that the toner has a high agglomeration characteristic, so that the tendency of toner image disturbance and transfer failure during transfer occurs more significantly, making it difficult to achieve both transfer and fixing. . When used as two-component development, the low melting point component of the toner adheres to the surface of the carrier due to collision between particles, friction, mechanical collision such as collision between particles and developer, friction, etc., or heat generated by friction. Spent is likely to occur, which lowers the charging ability of the carrier and hinders the long life of the developer.

  Patent Document 1 below proposes a carrier in which a fluorine-substituted alkyl group is introduced into a silicone resin of a coating layer for a positively charged toner. Further, Patent Document 2 below proposes a coating carrier containing a conductive carbon and a cross-linked fluorine-modified silicone resin, as it has a high development capability in a high-speed process and does not deteriorate in the long term. Has been. Taking advantage of the excellent charging characteristics of silicone resin, the fluorine-substituted alkyl group provides slipperiness, peelability, water repellency, etc., preventing wear, peeling, cracks, etc., and preventing spelling. However, wear, delamination, cracks, etc. are not satisfactory, and a positively charged toner can provide an appropriate charge amount, but a negatively charged toner is used. The charge amount was too low, and a large amount of reversely charged toner (toner having positive chargeability) was generated, resulting in deterioration such as fogging and toner scattering, and was not durable.

  Various configurations have been proposed for toner. As is well known, the toner for electrostatic charge development used in the electrophotographic method is generally a resin component which is a binder resin, a coloring component consisting of a pigment or a dye, a plasticizer, a charge control agent, and further if necessary. It is comprised by additional components, such as a mold release agent. As the resin component, natural or synthetic resins may be used alone or mixed in a timely manner.

  Then, the above additives are premixed at an appropriate ratio, heated and kneaded by heat melting, finely pulverized by an airflow type impact plate method, and finely classified to complete a toner base. There is also a method in which a toner base is prepared by a chemical polymerization method. Thereafter, an external additive such as hydrophobic silica is added to the toner base to complete the toner. In one-component development, the toner is composed only of toner, but a two-component developer can be obtained by mixing with toner and a carrier composed of magnetic particles.

  However, in the conventional pulverizing / classifying operation in the kneading and pulverizing method, the particle size that can be actually provided economically and in performance is about 8 μm even if the particle size is reduced. At present, methods for producing small-diameter toners by various methods are being studied. In addition, a method for realizing oil-less fixing by blending a release agent such as wax in a low softening resin during melt kneading of the toner has been studied. However, there is a limit to the amount of wax that can be blended, and as the amount added increases, adverse effects such as a decrease in toner fluidity, an increase in voids during transfer, and the occurrence of filming on the photoconductor occur.

  Therefore, a toner production method using various polymerization methods different from the kneading and pulverization method has been studied. For example, when a toner is prepared by a suspension polymerization method, it is difficult to produce a distribution narrower than the particle size distribution of a toner prepared by a kneading and pulverization method, even in an attempt to control the particle size distribution of the toner. Requires operation. Further, since the toner obtained by these methods has a substantially spherical shape, there is a problem that the toner remaining on the photosensitive member or the like is very poorly cleaned and the image quality reliability is impaired.

  In addition, a toner preparation method using an emulsion polymerization method includes a step of forming aggregated particles to prepare an aggregated particle dispersion in a dispersion obtained by dispersing at least resin particles and colorant particles. A resin fine particle dispersion obtained by dispersing resin fine particles is added to and mixed, and the resin fine particles are adhered to the aggregated particles to form the adhered particles, and the adhered particles are heated and fused.

  In the following Patent Document 3, at least a resin particle dispersion obtained by dispersing resin particles in a polar dispersant and a colorant particle dispersion obtained by dispersing colorant particles in a polar dispersant are mixed. A liquid mixture preparation step for preparing a liquid mixture, and by making the polarity of the dispersant contained in the liquid mixture the same polarity, a highly reliable electrostatic image developing toner excellent in chargeability and color development It is disclosed that it can be easily and conveniently manufactured.

  Moreover, in the following Patent Document 4, the release agent contains at least one ester composed of at least one of a higher alcohol having 12 to 30 carbon atoms and a higher fatty acid having 12 to 30 carbon atoms, and the resin particles include: It is disclosed that by including at least two kinds of resin particles having different molecular weights, the fixing property, color developing property, transparency, color mixing property and the like are excellent.

  Release agents include low molecular weight polyolefins such as polyethylene, polypropylene, and polybutene; fatty acid amides such as silicones, oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide, etc .; carnauba wax, rice wax Plant waxes such as candelilla wax, tree wax, jojoba oil, etc .; animal waxes such as beeswax; minerals such as montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, petroleum System waxes and their modifications are disclosed.

  However, if the dispersibility is deteriorated by adding a release agent, color turbidity tends to occur in the toner image melted at the time of fixing. At the same time, the dispersibility of the pigment also deteriorates, and the color developability of the toner becomes insufficient. In addition, when the resin fine particles are further adhered and fused on the surface of the aggregate in the next step, the dispersion of the release agent or the like makes the adhesion of the resin fine particles unstable. Moreover, the release agent once aggregated with the resin is separated and released into the aqueous system. The dispersion of the release agent has a great influence on the agglomeration during mixing and agglomeration due to the polarity and melting point of the wax used. Furthermore, in order to realize oil-less fixing without using oil at the time of fixing, a specific wax is added in a large amount.

  When forming particles by agglomeration reaction in a system in which a fixed amount or more of wax is blended, the particle size becomes coarse with heat treatment time, and it becomes difficult to produce small particle size particles with a narrow particle size distribution.

By using a release agent, it is possible to achieve both oilless fixing, fog reduction during development, and transfer efficiency, but conversely, resin fine particles and pigment fine particles in an aqueous system during production. In the aqueous system, the presence of a floating release agent that is not involved in agglomeration in the aqueous system, and a tendency to coarsen the agglomerated fused particles due to the influence thereof.
Japanese Patent No. 2801507 JP 2002-23429 A JP-A-10-198070 JP-A-10-301332

  The first object of the present invention is to produce a toner having a small particle diameter having a sharp particle size distribution without requiring a classification step. The second purpose is oil-less fixing without using oil on the fixing roller, using a release agent such as wax in the toner to separate the paper from the low-temperature fixing property, high-temperature non-offset property, fixing roller, etc. And storage stability during storage in high temperature conditions. The third object is to provide a long-life two-component developer having high durability that does not deteriorate due to spent even when used in combination with a toner containing a release agent such as wax. A fourth object is to provide an image forming apparatus that prevents high-efficiency by preventing omission and scattering during transfer.

  The toner of the present invention includes at least a first resin particle dispersion in which first resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a wax in which wax particles are dispersed in an aqueous medium. The second resin particle dispersion in which the second resin particles are dispersed is added to the core particle dispersion containing the core particles produced by mixing and agglomerating the particle dispersion, mixing, heating, A toner obtained by fusing the second resin particles to the core particles, wherein the pH of the second resin particle dispersion in which the second resin particles are dispersed is in the range of 3.5 to 9.5. The toner is adjusted to be added.

  The present invention also provides at least a first resin particle dispersion in which first resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a wax in which wax particles are dispersed in an aqueous medium. The second resin particle dispersion in which the second resin particles are dispersed is added to the core particle dispersion containing the core particles produced by mixing and agglomerating the particle dispersion, mixing, heating, A toner obtained by fusing the second resin particles to the core particles, wherein the pH of the second resin particle dispersion in which the second resin particles are dispersed is set to the core in which the core particles are dispersed. It is a toner added by adjusting to the same or lower value than the pH of the particle dispersion.

  The present invention also provides at least a first resin particle dispersion in which first resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a wax in which wax particles are dispersed in an aqueous medium. A second resin in which a second resin particle having a pH adjusted in the range of 3.5 to 9.5 is dispersed in a core particle dispersion containing core particles produced by mixing and agglomerating the particle dispersion. This is a toner production method in which a particle dispersion is added, mixed, and heated to fuse the second resin particles to the core particles.

  The present invention also provides at least a first resin particle dispersion in which first resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a wax in which wax particles are dispersed in an aqueous medium. The second resin particle dispersion in which the second resin particles are dispersed is added to the core particle dispersion containing the core particles produced by mixing and agglomerating the particle dispersion, mixing, heating, A method for producing a toner in which the second resin particles are fused to the core particles, wherein the second resin particle dispersion in which the second resin particles are dispersed has a pH in which the core particles are dispersed. This is a method for producing a toner having a value equal to or lower than the pH of the particle dispersion.

  In addition, the present invention is a two-component developer including a carrier including magnetic particles whose core material surface is coated with a fluorine-modified silicone resin including an aminosilane coupling agent.

  In the toner base particles obtained by further adhering and melting the second resin particles to the core particles obtained by aggregating the first resin particles and the colorant particles in an aqueous system with the above-described configuration, By adjusting the pH of the second resin particle dispersion to a certain range, it is possible to suppress the generation of floating resin particles that do not adhere and melt, suppress the coarsening of the toner base particles, and reduce the size of the toner with a sharp particle size distribution. Base particles can be prepared without a classification step. Also, by adjusting the pH of the second resin particle dispersion to a certain range, the adhesion between the core particles can be adjusted, and the shape of the toner base particles can be controlled when the second resin particles are added. It becomes.

  Furthermore, the storage stability can be maintained while improving the low temperature fixing property / glossiness and the high temperature non-offset property.

  A durable two-component developer that does not deteriorate due to the spent of the carrier can be realized.

  In addition, in a tandem color process that arranges image forming stations that have multiple photoconductors and development sections side by side, and sequentially transfers the toner of each color to the transfer body, it prevents omission and reverse transfer during transfer. High transfer efficiency can be obtained.

  It is possible to provide image formation that enables formation of a color image with high image quality and high reliability without toner scattering and fogging.

(1) Polymerization step The resin particle dispersion is prepared by homopolymerization or copolymerization of a vinyl monomer (vinyl type) by subjecting the vinyl monomer to emulsion polymerization or seed polymerization in a surfactant. Resin) is dispersed in a surfactant to prepare a dispersion. As the means, for example, a high-speed rotating emulsifier, a high-pressure emulsifier, a colloid emulsifier, a ball mill having a medium, a sand mill, a dyno mill, and the like are known per se.

  When the resin in the resin particles is a resin other than the homopolymer or copolymer of the vinyl monomer, if the resin is dissolved in an oily solvent having a relatively low solubility in water, Dissolve the resin in the oily solvent, disperse the fine particles in water together with a surfactant and polymer electrolyte using a disperser such as a homogenizer, and then heat or reduce pressure to evaporate the oily solvent. Thus, a dispersion liquid in which resin particles other than the vinyl resin are dispersed in the surfactant is prepared.

  As polymerization initiators, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2 , 2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile and other azo or diazo polymerization initiators, persulfates (potassium persulfate, ammonium persulfate, etc.), azo compounds (4,4′-azobis-4-cyanovaleric acid and its salt, 2,2′-azobis (2-amidinopropane) salt, etc.), peroxide compounds and the like.

  The colorant particle dispersion is prepared by adding colorant particles in water to which a surfactant has been added and dispersing the particles using the above-described dispersion means.

  The wax particle dispersion is prepared by adding and dispersing wax particles in water to which a surfactant has been added, and dispersing them using an appropriate dispersing means.

  Toners are required to have further low-temperature fixing, high-temperature non-offset property in oilless fixing, releasability, high transparency of color images, and storage stability under a certain high temperature, and must satisfy these simultaneously. I must.

  The toner base particles are prepared by dispersing a first resin particle dispersion in which at least the first resin particles described above are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and wax particles in an aqueous medium. The resulting wax particle dispersion is mixed in an aqueous system and aggregated to produce toner base particles.

  At this time, a first resin particle dispersion in which the first resin particles are dispersed in an aqueous medium, a colorant particle dispersion in which the colorant particles are dispersed, and a wax particle dispersion in which the wax particles are dispersed. Are mixed, the pH of the aqueous medium is adjusted under a certain condition, and a water-soluble inorganic salt is added to produce aggregated particles in which the first resin particles, colorant particles and wax particles are aggregated. Further, at this time, the aqueous medium is heated to a temperature higher than the glass transition temperature (Tg) of the first resin particles and / or higher than the melting point of the wax to be agglomerated particles (also referred to as core particles) at least partially melted. Can be generated).

  When a resin particle dispersion uses a persulfate such as potassium persulfate as a polymerization initiator when polymerizing an emulsion polymerization resin, the residue is decomposed by the heat during the heat aggregation process to change the pH ( Heat treatment at a certain temperature or higher (preferably 80 ° C. or higher in order to sufficiently disperse the residue) for a certain time (preferably about 1 to 5 hours) after emulsion polymerization. It is preferable to apply. Preferably it is 4 or less, More preferably, it is 1.8 or less.

  By adding a water-soluble inorganic salt to this mixed dispersion and heating to a temperature higher than the glass transition temperature (Tg) of the first resin particles and / or higher than the melting point of the wax, toner base particles having a certain particle size are obtained. Generated. At this time, it is preferable to adjust the pH of the mixed dispersion to a range of 9.5 to 12.2 before adding the water-soluble inorganic salt and before heating. The pH can be adjusted by adding 1N NaOH. When the pH is less than 9.5, the formed particles tend to be coarse. On the other hand, if the pH exceeds 12.2, the amount of free wax increases and it becomes difficult to encapsulate the wax uniformly.

  After pH adjustment, a water-soluble inorganic salt is added, and heat treatment is performed to form core particles having a predetermined volume average particle diameter in which at least a part of the first resin particles, colorant particles and wax particles are melted and aggregated. The By maintaining the pH of the liquid when the core particles having the predetermined volume average particle diameter are formed in the range of 7.0 to 9.5, the release of the wax is small, and the narrow particle size distribution in which the wax is included is reduced. Aggregated particles can be formed. The amount of NaOH to be added, the type and amount of flocculant, the pH of the emulsion polymerization resin dispersion, the pH of the colorant dispersion, the pH of the wax dispersion, the heating temperature, and the time are appropriately selected. If the pH of the liquid when the particles are formed is less than 7.0, the aggregated particles tend to be coarse. When the pH exceeds 9.5, the free wax tends to increase due to poor aggregation.

  Next, the second resin particle dispersion in which the second resin particles are dispersed is added to and mixed with the core particle dispersion in which the core particles are dispersed, and at a temperature equal to or higher than the glass transition temperature of the second resin particles. Toner base particles are generated by forming a resin fusion layer for fusing the second resin particles to the core particles by heat treatment.

  A preferred first configuration when the second resin particle dispersion is added to the produced core particle dispersion is that the pH of the second resin particle dispersion in which the second resin particles are dispersed is 3. Adjust to the range of 5-9.5 and add. Thereby, generation | occurrence | production of the floating particle of a 2nd resin particle is reduced, and the uniform adhesion to the core particle surface of a 2nd resin particle can be performed. Moreover, the adhesion to the core particles can be performed quickly, the processing time is shortened, and the productivity can be improved. In addition, when the second resin particles are welded to the core particles, coarsening of the particles due to aggregation of the core particles can be prevented, and a sharp particle size distribution can be formed with a raw particle size.

  The second resin particle dispersion is added as it is when the core particles reach a predetermined particle size. The addition may be batch dropping or sequential dropping, but sequential dropping is preferable. The dropping speed is preferably 1 to 500 g / min. If it is faster than 1 g / min, the particle size distribution tends to be broad. When it is slower than 500 g / min, the particles tend to be coarse.

  When the pH of the second resin particle dispersion is less than 3.5, the second resin particles do not adhere to the surface of the core particles, and the second resin particles remain floating in the aqueous system. It remains cloudy. When the pH of the second resin particle dispersion is higher than 9.5, the core particles are likely to aggregate and cause coarsening of the particles.

  A preferred second configuration when the second resin particle dispersion is added to the generated core particle dispersion is that the pH of the second resin particle dispersion is the same as the core particle dispersion in which the core particles are dispersed. It is the structure which adjusts and adds to the same or lower value than pH of this.

  Thereby, generation | occurrence | production of the floating particle of a 2nd resin particle is reduced, and the uniform adhesion to the core particle surface of a 2nd resin particle can be performed. Moreover, the adhesion to the core particles can be performed quickly, the processing time is shortened, and the productivity can be improved. In addition, when the second resin particles are welded to the core particles, coarsening of the particles due to aggregation of the core particles can be prevented, and a sharp particle size distribution can be formed with a raw particle size. At this time, the minimum pH value is preferably 3.5 or more. This is because if it is less than 3.5, the adhesion of the second resin particles to the surface of the core particles is difficult to proceed. With respect to the range of pH 3.5 to 9.5 of the second resin particle dispersion in which the second resin particles in the first configuration shown above are dispersed, the conditions are narrowed to achieve good particle generation. It is possible. Further, even when the pH of the liquid when the core particles having a predetermined volume average particle diameter are formed becomes a value larger than 9.5, the pH of the second resin particle dispersion liquid of the second configuration is By adjusting to the same or lower value than the pH of the core particle dispersion in which the core particles are dispersed, the generation of floating particles of the second resin particles is reduced, and the second resin particles are uniformly distributed on the core particle surface. Can be attached. Moreover, the adhesion to the core particles can be performed quickly, the processing time is shortened, and the productivity can be improved. In addition, when the second resin particles are welded to the core particles, coarsening of the particles due to aggregation of the core particles can be prevented, and a sharp particle size distribution can be formed with a raw particle size.

  This is because the durability, storage stability, and high temperature non-offset property of the toner are improved. The thickness of the fused resin layer of the second resin particles is preferably 0.5 μm to 2 μm. If it is thinner than this, the effects of storage stability and high-temperature non-offset property cannot be exhibited, and if it is thicker, the low-temperature fixability is hindered.

  As a preferred form, the main component of the surfactant used in preparing the first resin particle dispersion of the core particles is a nonionic surfactant, and the main component of the surfactant used in the colorant dispersion is non-ionic. A configuration in which the main component of the surfactant that is an ionic surfactant and used in the wax dispersion is a nonionic surfactant is preferable. With this configuration, it is possible to eliminate the presence of suspended colorant particles and wax particles that are not involved in aggregation in an aqueous system, and to form core particles having a small particle size, a uniform and sharp particle size distribution in a narrow range. Furthermore, the floating of the second resin particles can be reduced, the adhesion and melting can be made uniform on the core particles, and a sharp particle size distribution can be created.

  At this time, the surfactant of the first resin particle dispersion in which the first resin particles are dispersed is preferably a mixed system of a nonionic surfactant and an ionic surfactant, and the nonionic surfactant is a surfactant. It is preferable to have 60-95 wt% with respect to the whole agent. If the amount is less than 60 wt%, stable aggregated particles cannot be obtained. If it exceeds 95 wt%, the dispersion of the resin particles themselves is not stable.

  Further, as a preferred form, the surfactant used in the first resin particle dispersion is a mixture of a nonionic surfactant and an ionic surfactant, and the surfactant used in the wax dispersion is non-main component. A configuration using only an ionic surfactant is also preferable.

  Further, as a preferred form, the surfactant used in the first resin particle dispersion is a mixture of a nonionic surfactant and an ionic surfactant, and the surfactant used in the colorant dispersion has a non-main component. A configuration in which only the ionic surfactant is used and the main component of the surfactant used in the wax dispersion is only the nonionic surfactant is also preferable.

  When the surfactant used in the first resin particle dispersion is a mixture of a nonionic surfactant and an ionic surfactant, the nonionic surfactant may have 60 to 95 wt% with respect to the total surfactant. preferable. If the amount is less than 60 wt%, stable aggregated particles cannot be obtained. If it exceeds 95 wt%, the dispersion of the resin particles themselves is not stable.

  The surfactant used for the second resin particle dispersion is preferably a mixture of a nonionic surfactant and an ionic surfactant, and the configuration at this time is that the nonionic surfactant is the entire surfactant. On the other hand, it is preferable to have 50 to 95 wt%. If it is less than 50 wt%, it is difficult to promote the adhesion of the second resin particle fine particles to the core particles. If it exceeds 95 wt%, the dispersion of the resin particles themselves is not stable.

  Since the surfactant and the fine particles of the wax have many water molecules and are hydrated to the dispersed particles, the particles are difficult to stick to each other. By adding an electrolyte, water molecules that are hydrated are taken away by the electrolyte, and are easily attached. Furthermore, the particles stick together and grow into larger particles. At this time, when an anionic surfactant is used for dispersion with an ionic surfactant, for example, an anionic system for resin dispersion and an anionic system for wax dispersion, agglomerated particles can be obtained, but when hydrated water molecules are deprived by adding an electrolyte. In addition, particles repelling the wax particles remain, and particles aggregated only with the wax floating alone tend to exist. The presence of particles that do not participate in the aggregation leads to filming on the photosensitive member, a decrease in image density during development, and an increase in fog. In addition, these suspended particles are gradually added to the aggregated particles during the aggregation heating reaction step for a certain time, leading to a factor that the obtained particles become coarse and broad.

  On the other hand, in the wax dispersion using the nonionic surfactant, the water molecules that are hydrated by the addition of the electrolyte are deprived by the electrolyte and are easily adhered to each other. Furthermore, the particles stick together and grow into larger particles. When water molecules that are hydrated are deprived by the addition of electrolyte, they are nonionic, so there is little effect of rebounding wax particles, and the presence of particles that aggregate only floating wax alone is suppressed, and the particle size It is possible to form uniform particles with a sharp distribution.

  Examples of water-soluble inorganic salts include alkali metal salts and alkaline earth metal salts. Examples of the alkali metal include lithium, potassium, and sodium, and examples of the alkaline earth metal include magnesium, calcium, strontium, and barium. Of these, potassium, sodium, magnesium, calcium, and barium are preferable. Examples of the counter ion (anion constituting the salt) of the alkali metal or alkaline earth metal include chloride ion, bromide ion, iodide ion, carbonate ion and sulfate ion.

  Examples of the organic solvent infinitely soluble in water include methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, glycerin, acetone and the like. Among these, alcohols having 3 or less carbon atoms such as methanol, ethanol, 1-propanol, 2-propanol and the like are preferable, and 2-propanol is particularly preferable.

  After forming the adhesion melt layer of the second resin particles on the core particles, the toner base particles can be obtained through any washing step, solid-liquid separation step, and drying step. In this washing step, it is preferable to sufficiently perform substitution washing with ion-exchanged water from the viewpoint of improving the chargeability. There is no restriction | limiting in particular as a separation method in the said solid-liquid separation process, From a viewpoint of productivity, well-known filtration methods, such as a suction filtration method and a pressure filtration method, are mentioned preferably. There is no restriction | limiting in particular as a drying method in the said drying process, Well-known drying methods, such as a flash jet drying method, a fluidized drying method, and a vibration type fluidized drying method, are mentioned preferably from a viewpoint of productivity.

  Examples of nonionic surfactants include higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, fatty acid amide ethylene oxide adducts, and fats and ethylene oxides. Adduct, Polyethylene glycol type nonionic surfactant such as polypropylene glycol ethylene oxide adduct, fatty acid ester of glycerol, fatty acid ester of pentaerythritol, fatty acid ester of sorbitol and sorbitan, fatty acid ester of sucrose, alkyl of other alcohol And polyhydric alcohol type nonionic surfactants such as ethers and fatty acid amides of alkanolamines.

  Polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts and alkylphenol ethylene oxide adducts can be particularly preferably used.

  Examples of the aqueous medium include water such as distilled water and ion exchange water, and alcohols. These may be used individually by 1 type and may use 2 or more types together. The content of the polar surfactant in the dispersant having the polarity cannot be generally defined and can be appropriately selected according to the purpose.

  In the case where a nonionic surfactant and an ionic surfactant are used in combination, examples of the polar surfactant include anions such as sulfate ester, sulfonate, phosphate, and soap. Surfactant, amine surfactant type, quaternary ammonium salt type cationic surfactant and the like.

  Specific examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate and the like.

Specific examples of the cationic surfactant include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like. These may be used individually by 1 type and may use 2 or more types together.
(2-1) Wax In order to improve the separation property from a heating roller of a transfer medium such as a copy sheet on which a low-temperature fixing property, a high-temperature non-offset property or a toner melted at the time of fixing is mounted, a wax is added to the toner. preferable. A single kind of wax can exert a certain effect.

As waxes preferably used, esters comprising a higher alcohol having 16 to 24 carbon atoms and a higher fatty acid having 16 to 24 carbon atoms such as stearyl stearate, palmityl palmitate, behenyl behenate or stearyl montanate,
Esters comprising a higher fatty acid having 16 to 24 carbon atoms such as butyl stearate, isobutyl behenate, propyl montanate or 2-ethylhexyl oleate and a lower monoalcohol,
Montanic acid monoethylene glycol ester, ethylene glycol distearate, monostearic acid glyceride, monobehenic acid glyceride, tripalmitic acid glyceride, pentaerythritol monobehenate, pentaerythritol dilinoleate, pentaerythritol trioleate or pentaerythritol tetrastearate, etc. Esters comprising a higher fatty acid having 16 to 24 carbon atoms and a polyhydric alcohol, or
Higher fatty acids having 16 to 24 carbon atoms and polyhydric alcohols such as diethylene glycol monobehenate, diethylene glycol dibehenate, dipropylene glycol monostearate, distearic diglyceride, tetrastearic acid triglyceride, hexabehenic acid tetraglyceride or decastearic acid decaglyceride Preferable examples include esters composed of multimers.

  In addition, meadowfoam oil or meadowfoam oil derivative, jojoba oil or jojoba oil derivative, carnauba wax, wood wax, beeswax, ozokerite, carnauba wax, canderia wax, ceresin wax or rice wax can also be suitably used.

  In addition, a hydroxy stearic acid derivative, glycerin fatty acid ester, glycol fatty acid ester, or sorbitan fatty acid ester can also be used for cooking.

  Further, fatty acid hydrocarbon waxes such as low molecular weight polypropylene wax, low molecular weight polyethylene wax, polypropylene polyethylene copolymer wax, microcrystalline wax, paraffin wax, and Fischer-to-push wax can also be suitably used.

  The melting point of the wax is preferably 50 to 120 ° C, more preferably 60 to 110 ° C, and still more preferably 65 to 100 ° C. When it is lower than 50 ° C., the storage stability is deteriorated. When the temperature is higher than 120 ° C., the low-temperature fixability and color glossiness are not improved. In addition, the cohesiveness of the wax in the aqueous system decreases, and free particles that do not aggregate in the aqueous system tend to increase.

  The amount of the wax added is preferably 5 to 30 parts by weight with respect to 100 parts by weight of the binder resin. Preferably it is 8-25 weight part, More preferably, 10-20 weight part is preferable. When the amount is less than 5 parts by weight, the effects of low temperature fixing property, high temperature non-offset property and paper separation property are not exhibited. If the amount exceeds 30 parts by weight, it is difficult to control particles having a small particle size.

  In order to uniformly encapsulate the wax in the resin without being desorbed and suspended during mixing and aggregation, the dispersion particle size distribution of the wax, the composition of the wax, and the melting characteristics of the wax are also affected.

  The wax particle dispersion is prepared by heating, melting, and dispersing wax in ion exchange water in an aqueous medium to which a surfactant is added.

  At this time, the dispersed particle diameter of the wax is 20 to 200 nm for the 16% diameter (PR16), 40 to 300 nm for the 50% diameter (PR50), and 84% for the 84% diameter (PR84). ) Is 400 nm or less, PR84 / PR16 is emulsified and dispersed to a size of 1.2 to 2.0, and particles of 200 nm or less are preferably 65% by volume or more and particles exceeding 500 nm are preferably 10% by volume or less.

  Preferably, the 16% diameter (PR16) is 20 to 100 nm, the 50% diameter (PR50) is 40 to 160 nm, and the 84% diameter (PR84) is 260 nm or less when integrated from the small particle diameter side. PR84 / PR16 is 1.2 to 1.8. It is preferable that particles of 150 nm or less are 65 volume% or more and particles exceeding 400 nm are 10 volume% or less.

  More preferably, the 16% diameter (PR16) is 20 to 60 nm, the 50% diameter (PR50) is 40 to 120 nm, and the 84% diameter (PR84) is 220 nm or less when integrated from the small particle diameter side. , PR84 / PR16 is 1.2 to 1.8. It is preferable that particles of 130 nm or less are 65 volume% or more, and particles exceeding 300 nm are 10 volume% or less.

  When the resin particle dispersion, the colorant particle dispersion, and the wax particle dispersion are mixed and aggregated to form aggregated particles, the 50% diameter (PR50) is 20 to 200 nm, so that the wax becomes resin particles. It is easy to be taken in between, preventing aggregation between the waxes itself, and uniform dispersion. Particles that are taken into the resin particles and float in the water can be eliminated.

  Furthermore, when the aggregated particles are heated in an aqueous system to obtain molten aggregated particles, the molten resin particles surround and include the molten wax particles because of the surface tension, and the release agent is included in the resin. It becomes easy.

  PR16 is larger than 160 nm, 50% diameter (PR50) is larger than 200 nm, PR84 is larger than 300 nm, PR84 / PR16 is larger than 2.0, particles of 200 nm or less are larger than 65% by volume and larger than 500 nm When the amount exceeds 10% by volume, the wax is difficult to be taken in between the resin particles, and the agglomeration of only the waxes tends to occur frequently. In addition, particles that are not taken into the resin particles and float in water tend to increase. When the agglomerated particles are heated in an aqueous system to obtain fused agglomerated particles, the molten resin particles are less likely to include the melted wax particles, and the wax is less likely to be included in the resin. In addition, when the resin is adhered and fused, the amount of wax that is exposed and released on the surface of the toner base increases, filming on the photoconductor, increased spent on the carrier, handling characteristics during development, and development memory are generated. It becomes easy.

  When PR16 is smaller than 20 nm, 50% diameter (PR50) is smaller than 40 nm, and PR84 / PR16 is smaller than 1.2, it is difficult to maintain a dispersed state, and reaggregation of wax occurs when left, and particle size distribution. There is a tendency for the storage stability of the to decrease. In addition, the load increases during dispersion, heat generation increases, and productivity tends to decrease.

  In addition, the 50% diameter (PR50) in the volume particle size integration when the wax particles dispersed in the wax particle dispersion are integrated from the small particle size side is the 50% diameter of the resin particles when forming the aggregated particles ( By making it smaller than PR50), the wax is easily taken up between the resin particles, and aggregation between the waxes itself can be prevented, and the dispersion can be performed uniformly. Particles that are taken into the resin particles and float in the water can be eliminated. When the aggregated particles are heated in an aqueous system to obtain molten aggregated particles, the melted resin particles include the melted wax particles because of the surface tension, and the wax is easily included in the resin. More preferably, it is 20% or more smaller than the 50% diameter (PR50) of the resin particles.

  A rotating body in which a wax melt obtained by melting the wax at a wax concentration of 40 wt% or less is rotated at a high speed through a fixed gap with a fixed gap in a medium to which a dispersant maintained at a temperature higher than the melting point of the wax is added. The wax particles can be finely dispersed by emulsifying and dispersing by the action of high shear force generated by the above.

  3 and 4, a gap of about 0.1 mm to 10 mm is provided on the wall of the tank having a constant capacity, and the rotating body is 30 m / s or more, preferably 40 m / s or more, more preferably 50 m / s or more. By rotating at a high speed, a strong shearing force acts on the aqueous system, and an emulsified dispersion having a fine particle size can be obtained. The dispersion can be formed by a treatment time of about 30 seconds to 5 minutes.

  A rotating body that rotates at a speed of 30 m / s or more, preferably 40 m / s or more, more preferably 50 m / s or more, with a gap of about 1 to 100 μm provided to a fixed stationary body as shown in FIGS. By adding a strong shearing force action, a fine dispersion can be created.

  The particle size distribution of fine particles can be made narrower and sharper than a disperser such as a homogenizer. Further, even when left for a long time, the fine particles forming the dispersion do not reaggregate and can maintain a stable dispersion state, and the standing stability of the particle size distribution is improved.

  When the melting point of the wax is high, a molten liquid is prepared by heating in a high pressure state. Also, the wax is dissolved in an oily solvent. This solution is obtained by dispersing fine particles in water together with a surfactant and a polymer electrolyte using the disperser shown in FIGS. 3, 4, 5 and 6, and then evaporating the oily solvent by heating or decompressing. .

The particle size can be measured using a Horiba laser diffraction particle size measuring device (LA920), a Shimadzu laser diffraction particle size measuring device (SALD2100), or the like.
(2-2) Wax Low temperature fixability, high temperature non-offset property, or for improving separation of transfer media such as copy paper carrying toner melted during fixing from a heating roller, etc. A structure in which a plurality of waxes are added is also preferable in order to increase the margin of fixing characteristics that conflict with each other and improve the functionality.

  The wax particle dispersion is prepared by heating, melting, and dispersing wax in ion exchange water in an aqueous medium to which a surfactant is added.

  A preferred first configuration using a plurality of waxes is a configuration in which the wax contains at least a first wax and a second wax, and an endothermic peak temperature of the first wax by the DSC method (referred to as melting point Tm1 (° C.)). The endothermic peak temperature (referred to as the melting point Tm2 (° C)) of the second wax by DSC method is 50 ° C or higher and 50 ° C or lower. A wax having a low melting point makes it possible to achieve both low-temperature fixing properties, and a wax having a high melting point can achieve both high-temperature non-offset properties and poor paper separation.

  In the first configuration preferable as the wax, the melting point Tm1 of the first wax is preferably 55 to 85 ° C, more preferably 60 to 85 ° C, and still more preferably 65 to 75 ° C. When it is lower than 50 ° C., the storage stability is deteriorated. When it is higher than 90 ° C., the low-temperature fixability and color glossiness are not improved. Furthermore, the melting point Tm2 of the second wax is preferably 5 ° C. or higher than the melting point Tm1 of the first wax. The function of the wax can be efficiently separated, and there is an effect of satisfying both low temperature fixing property, high temperature non-offset property and paper separation property. When the temperature is lower than 5 ° C., it is difficult to achieve the effects of achieving both low-temperature fixability, high-temperature non-offset property, and paper separation failure. When the temperature is higher than 50 ° C., the first wax and the second wax are phase-separated and cannot be uniformly taken into the toner particles.

  Furthermore, it is preferable that melting | fusing point Tm2 is 80-120 degreeC as a preferable form of a 2nd wax. More preferably, it is 85-100 degreeC, More preferably, it is preferable that it is 90-100 degreeC. When Tm2 is smaller than 80 ° C., the high temperature non-offset property and the paper separation property are weakened. When it exceeds 120 ° C., the cohesiveness of the wax decreases, and free particles that do not aggregate in the aqueous system increase.

  In the first configuration preferable as the wax, when the toner particles are formed by aggregating the waxes having different melting points with the resin and the colorant in the aqueous system, the first wax and the second wax are separately emulsified and dispersed. When the dispersion is mixed with the resin dispersion and the colorant dispersion and heated and aggregated, due to the difference in the melting speed of the wax, the presence of particles floating without being incorporated into the melt-aggregated particles, which are toner particles, The particle size distribution tends to be broad without agglomeration of the agglomerated particles. In some cases, the wax is uniformly taken into the toner, and it becomes difficult to form particles having a small particle size and a narrow particle size distribution. In addition, the problem that the generated particles rapidly become coarse when the second resin is melted and adhered to the core particles (hereinafter sometimes referred to as shelling) cannot be sufficiently solved.

  Therefore, in the production of the wax particle dispersion, it is preferable that the first wax and the second wax are mixed and emulsified and dispersed. In this method, the first wax and the second wax are heated and emulsified and dispersed in the emulsifying and dispersing apparatus at a constant blending ratio. The charging may be performed separately or simultaneously, but it is preferable that the final dispersion liquid contains the first wax and the second wax in a mixed state.

  Further, as a preferred second configuration using a plurality of waxes, the wax contains at least a first wax and a second wax, and the first wax has a higher alcohol having 16 to 24 carbon atoms and a carbon number. A configuration containing an ester wax composed of at least one of 16 to 24 higher fatty acids and the second wax containing an aliphatic hydrocarbon wax is preferred.

  Further, as a preferred third configuration using a plurality of waxes, the wax contains at least a first wax and a second wax, and the first wax has an iodine value of 25 or less and a saponification value of 30 to 300. A configuration including a wax and the second wax including an aliphatic hydrocarbon wax is preferable.

  Here, in the second configuration and the third configuration preferable as the wax, the endothermic peak temperature (melting point Tm1 (° C.)) of the first wax by DSC method is 50 to 90 ° C., preferably 55 to 85 ° C., More preferably, it is 60-85 degreeC, More preferably, it is 65-75 degreeC. When the temperature is lower than 50 ° C., the storage stability and heat resistance of the toner deteriorate. When it exceeds 90 ° C., the cohesiveness of the wax decreases, and free particles that do not aggregate in the aqueous system increase. Also, low temperature fixability and glossiness are not improved.

  Further, in the second configuration and the third configuration preferable as the wax, the endothermic peak temperature (melting point Tm2 (° C.)) of the second wax by DSC method is 80 to 120 ° C., preferably 85 to 100 ° C. Preferably it is 90-100 degreeC. When the temperature is lower than 80 ° C., the storage stability is deteriorated, and the high temperature non-offset property and the paper separation property are weakened. When it exceeds 120 ° C., the cohesiveness of the wax decreases, and free particles that do not aggregate in the aqueous system increase. In addition, low-temperature fixability and color translucency are hindered.

  In the second or third configuration preferable as the wax, when the aggregated particles are formed together with the resin, the colorant and the aliphatic hydrocarbon wax in the aqueous system, the aliphatic hydrocarbon wax has a compatibility with the resin from the compatibility with the resin. The agglomeration of particles does not easily occur, and the presence of particles floating without the wax being taken into the molten agglomerated particles or the agglomeration of the agglomerated particles does not proceed and the particle size distribution tends to be broad.

  Further, if the temperature and time of the heat treatment are changed in order to suppress the suspended particles and prevent the particle size distribution from becoming broad, the particle diameter becomes coarse. In addition, when the shell is formed, a phenomenon in which the aggregated particles are rapidly coarsened occurs.

  Therefore, by using a wax composed of a first wax containing a specific wax together with a second wax containing a specific aliphatic hydrocarbon wax, the aliphatic hydrocarbon wax is agglomerated. Suppresses the presence of particles floating without being taken into the particles, suppresses the particle size distribution of the agglomerated particles from broadening, and further suppresses the phenomenon of agglomerated particles abruptly coarsening when shelled. .

  During the heat aggregation, the first wax is compatibilized with the resin, so that the aggregation with the aliphatic hydrocarbon wax resin is promoted and uniformly incorporated, and the generation of suspended particles can be prevented. I think that the. Furthermore, the first wax tends to be improved in low-temperature fixability due to partial progress of compatibilization with the resin. Since the aliphatic hydrocarbon wax does not progress in compatibilization with the resin, this wax can exhibit a function of improving the high temperature offset property and the separation property from paper. That is, the first wax has a function as a dispersion aid during the emulsification dispersion treatment of the aliphatic hydrocarbon wax, and further has a function as a low-temperature fixing aid.

  In the second or third configuration preferable as the wax, as described in the preferable first configuration, in the production of the wax particle dispersion, the first wax and the second wax are mixed, emulsified and dispersed. Is preferred. As a result, the presence of particles floating without the wax being incorporated into the aggregated particles is suppressed, and the phenomenon that the aggregated particles are abruptly coarsened when the shell is formed is suppressed. It is possible to produce particles having a narrower particle size distribution.

  Further, in the first, second, or third configuration preferable as a wax, when the weight ratio of the first wax to 100 parts by weight of the wax in the wax particle dispersion is ES1, and the weight ratio of the second wax is FT2, FT2 / ES1 is preferably 0.2 to 10. More preferably, it is the range of 1-9. If it is less than 0.2, that is, if the first wax weight ratio is too large, the effect of high temperature non-offset property cannot be obtained, and the storage stability deteriorates. If the weight ratio is larger than 10, that is, if the weight ratio of the second wax is too large, low-temperature fixing cannot be realized, and the above-described problem that the aggregated particles tend to become coarse cannot be solved. Furthermore, the blending ratio of FT2 being 50 wt% or more is a well-balanced ratio in which low-temperature fixability, high-temperature storage stability and fixing high-temperature non-offset property can be compatible.

  In addition, in the first, second or third constitution preferable as the wax, the dispersion stability is improved by treating the wax, particularly the aliphatic hydrocarbon wax with an anionic surfactant, but the aggregated particles are aggregated. The aggregated particles are coarsened and it is difficult to obtain particles having a sharp particle size distribution.

  Therefore, it is preferable that the wax particle dispersion is prepared by mixing, emulsifying and dispersing the first wax and the second wax with a surfactant mainly composed of a nonionic surfactant. By mixing and dispersing with a surfactant mainly composed of a nonionic surfactant to prepare an emulsified dispersion, aggregation of the wax itself is suppressed and dispersion stability is improved. In the production of agglomerated particles of these waxes with a resin and a colorant dispersion, wax is not liberated and particles having a small particle size and a narrow sharp particle size distribution can be formed.

  In the first, second or third configuration preferable as the wax, the total amount of added wax is preferably 5 to 30 parts by weight with respect to 100 parts by weight of the binder resin. Preferably it is 8-25 weight part, More preferably, 10-20 weight part is preferable. When the amount is less than 5 parts by weight, the effects of low temperature fixing property, high temperature non-offset property and paper separation property are not exhibited. If the amount exceeds 30 parts by weight, it is difficult to control particles having a small particle size.

  The preferred first wax comprises at least one ester composed of at least one of a higher alcohol having 16 to 24 carbon atoms and a higher fatty acid having 16 to 24 carbon atoms. By using this wax, the presence of particles that are suspended without the aliphatic hydrocarbon wax being incorporated into the agglomerated particles is suppressed, the particle size distribution of the agglomerated particles is prevented from becoming broad, and further when shelled. In addition, the phenomenon of agglomerated particles abruptly can be alleviated. Moreover, low temperature fixing can be promoted. The combined use with the second wax prevents high-temperature non-offset property and paper separability as well as coarse particle size, and makes it possible to produce toner base particles having a small particle size and a narrow particle size distribution.

  As alcohol components, in addition to monoalcohols such as methyl, ethyl, propyl or butyl, glycols such as ethylene glycol or propylene glycol or multimers thereof, triols such as glycerin or multimers thereof, and polyhydric alcohols such as pentaerythritol Sorbitan or cholesterol is preferred. When the alcohol component is a polyhydric alcohol, the higher fatty acid may be a mono-substituted product or a poly-substituted product.

Specifically, esters comprising a higher alcohol having 16 to 24 carbon atoms and a higher fatty acid having 16 to 24 carbon atoms, such as stearyl stearate, palmityl palmitate, behenyl behenate or stearyl montanate,
Esters comprising a higher fatty acid having 16 to 24 carbon atoms such as butyl stearate, isobutyl behenate, propyl montanate or 2-ethylhexyl oleate and a lower monoalcohol,
Montanic acid monoethylene glycol ester, ethylene glycol distearate, monostearic acid glyceride, monobehenic acid glyceride, tripalmitic acid glyceride, pentaerythritol monobehenate, pentaerythritol dilinoleate, pentaerythritol trioleate or pentaerythritol tetrastearate, etc. Esters comprising a higher fatty acid having 16 to 24 carbon atoms and a polyhydric alcohol, or
Higher fatty acids having 16 to 24 carbon atoms and polyhydric alcohols such as diethylene glycol monobehenate, diethylene glycol dibehenate, dipropylene glycol monostearate, distearic diglyceride, tetrastearic acid triglyceride, hexabehenic acid tetraglyceride or decastearic acid decaglyceride Preferable examples include esters composed of multimers. These waxes may be used alone or in combination of two or more.

  When the alcohol component and / or the acid component has less than 16 carbon atoms, the function as a dispersion aid is hardly exhibited, and when it exceeds 24, the function as a low-temperature fixing aid is hardly exhibited.

  Further, the preferred first wax composition includes a wax having an iodine value of 25 or less and a saponification value of 30 to 300. By using together with the second wax, coarsening of the particle size is prevented, and toner base particles having a small particle size and a narrow particle size distribution can be generated. By defining the iodine value, the effect of improving the dispersion stability of the wax can be obtained, the formation of aggregated particles with the resin and colorant particles can be made uniform, and the formation of particles with a small particle size and a narrow particle size distribution is possible. . However, if the iodine value is larger than 25, the dispersion stability is too good, and the formation of aggregated particles with the resin and colorant particles cannot be performed uniformly, and there is a tendency for the floating particles of the wax to increase. It tends to be a broad particle size distribution. If the floating particles remain in the toner, filming of the photoreceptor or the like is caused. The repulsion due to the charge effect of the toner is difficult to be mitigated during the multi-layer transfer of the toner in the primary transfer. When the saponification value is less than 30, the presence of unsaponifiable matter and hydrocarbons increases, and formation of uniform aggregated particles having a small particle size becomes difficult. The filming of the photosensitive member and the charging property of the toner are deteriorated, and the charging property during continuous use is reduced. When it becomes larger than 300, suspended matter in the water system increases. The repulsion due to the charge action of the toner is less likely to be alleviated. In addition, fog and toner scattering increase.

  It is preferable that the heat loss at 220 ° C. of the wax having prescribed iodine value and saponification value is 8% by weight or less. When the loss on heating exceeds 8% by weight, the glass transition point of the toner is lowered, and the storage stability of the toner is impaired. It adversely affects the development characteristics and causes fogging and photoconductor filming. The particle size distribution of the generated toner becomes broad.

Molecular weight characteristics in gel permeation chromatography (GPC) of waxes with prescribed iodine value and saponification value, number average molecular weight is 100 to 5000, weight average molecular weight is 200 to 10,000, and ratio of weight average molecular weight to number average molecular weight (weight average molecular weight / Number average molecular weight) is 1.01 to 8, the ratio of Z average molecular weight to number average molecular weight (Z average molecular weight / number average molecular weight) is 1.02 to 10, and the molecular weight is 5 × 10 ² to 1 × 10 ⁴ . It preferably has at least one molecular weight maximum peak. More preferably, the number average molecular weight is 500-4500, the weight average molecular weight is 600-9000, the ratio of weight average molecular weight to number average molecular weight (weight average molecular weight / number average molecular weight) is 1.01-7, Z average molecular weight and number average. The molecular weight ratio (Z average molecular weight / number average molecular weight) is 1.02 to 9, more preferably the number average molecular weight is 700 to 4000, the weight average molecular weight is 800 to 8000, and the ratio of the weight average molecular weight to the number average molecular weight (weight average). (Molecular weight / number average molecular weight) is 1.01 to 6, and the ratio of Z average molecular weight to number average molecular weight (Z average molecular weight / number average molecular weight) is 1.02 to 8.

When the number average molecular weight is smaller than 100, the weight average molecular weight is smaller than 200, and the molecular weight maximum peak is located in a range smaller than 5 × 10 ² , the storage stability is deteriorated. Further, the handling property in the developing device is lowered, and the toner density uniformity is inhibited. This causes toner photoconductor filming. The particle size distribution of the generated toner becomes broad.

The number average molecular weight is greater than 5000, the weight average molecular weight is greater than 10,000, the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is greater than 8, and the ratio of the Z average molecular weight to the number average molecular weight (Z When the average molecular weight / number average molecular weight) is larger than 10 and the molecular weight maximum peak is located in a range larger than the region of 1 × 10 ⁴ , the releasing action is weakened and the low-temperature fixability is lowered. It becomes difficult to reduce the particle size of the generated particles when the emulsified dispersed particles of wax are generated.

  Further, a material having a volume increase rate of 2 to 30% at a change of 10 ° C. at a temperature equal to or higher than the melting point of the wax having prescribed iodine value and saponification value is preferable. When it changes from solid to liquid when it melts with heat during fixing, the adhesion between the toners is further strengthened, the fixing property is further improved, and the releasability from the fixing roller is also improved. Offset property is also improved.

  As the first wax, materials such as a meadow foam oil derivative, carnauba wax derivative, jojoba oil derivative, wood wax, beeswax, ozokerite, carnauba wax, canderia wax, ceresin wax or rice wax are also preferred, and these Derivatives are also preferably used. One type or a combination of two or more types can be used.

  As the meadow foam oil derivative, meadow foam oil fatty acid, metal salt of meadow foam oil fatty acid, meadow foam oil fatty acid ester, hydrogenated meadow foam oil or meadow foam oil triester can be preferably used. An emulsified dispersion having a small particle size and a uniform particle size distribution can be prepared. It is a preferable material that is effective for low-temperature fixability in oilless fixing, prolonging the life of the developer, and improving transferability. These can be used alone or in combination of two or more.

  The meadow foam oil fatty acid obtained by saponification and decomposition of meadow foam oil is preferably composed of a fatty acid having 4 to 30 carbon atoms. As the metal salt, metal salts such as sodium, potassium, calcium, magnesium, barium, zinc, lead, manganese, iron, nickel, cobalt or aluminum can be used. High temperature non-offset property is good.

  Meadowfoam oil fatty acid esters include, for example, esters such as methyl, ethyl, butyl, glycerin, pentaerythritol, polypropylene glycol, or trimethylolpropane, and in particular, meadow foam oil fatty acid pentaerythritol monoester, meadowfoam oil fatty acid pentaerythritol triester. Ester or meadow foam oil fatty acid trimethylolpropane ester is preferred. Effective for low-temperature fixability.

  Hydrogenated Meadowfoam oil is obtained by hydrogenating Meadowfoam oil to make unsaturated bonds saturated bonds. Low temperature fixability and glossiness can be improved.

  Furthermore, an esterification reaction product of a meadow foam fatty acid and a polyhydric alcohol such as glycerin, pentaerythritol, trimethylolpropane, or the like is obtained by using tolylene diisocyanate (TDI), diphenylmethane-4,4′-diisocyanate (MDI), or the like. An isocyanate polymer of a meadow foam oil fatty acid polyhydric alcohol ester obtained by crosslinking with isocyanate can also be preferably used. The spent property to the carrier is small and the life of the two-component developer can be extended.

  As jojoba oil derivatives, jojoba oil fatty acid, metal salt of jojoba oil fatty acid, jojoba oil fatty acid ester, hydrogenated jojoba oil, jojoba oil triester, maleic acid derivative of epoxidized jojoba oil, isocyanate of jojoba oil fatty acid polyhydric alcohol ester Polymers and halogenated modified jojoba oil can also be preferably used. An emulsified dispersion having a small particle size and a uniform particle size distribution can be prepared. Easy mixing and dispersion of resin and wax. It is a preferable material that is effective for low-temperature fixability in oilless fixing, prolonging the life of the developer, and improving transferability. These can be used alone or in combination of two or more.

  Jojoba oil fatty acid obtained by saponifying and decomposing jojoba oil consists of fatty acids having 4 to 30 carbon atoms. As the metal salt, metal salts such as sodium, potassium, calcium, magnesium, barium, zinc, lead, manganese, iron, nickel, cobalt, and aluminum can be used. High temperature non-offset property is good.

  Examples of jojoba oil fatty acid esters include methyl, ethyl, butyl, glycerin, pentaerythritol, polypropylene glycol, trimethylolpropane and the like, and in particular, jojoba oil fatty acid pentaerythritol monoester, jojoba oil fatty acid pentaerythritol triester, jojoba Oil fatty acid trimethylolpropane ester and the like are preferable. Effective for low-temperature fixability.

  Hydrogenated jojoba oil is obtained by hydrogenating jojoba oil to make unsaturated bonds saturated bonds. Low temperature fixability and glossiness can be improved.

  Furthermore, an esterification reaction product of jojoba oil fatty acid and a polyhydric alcohol such as glycerin, pentaerythritol, trimethylolpropane, tolylene diisocyanate (TDI), diphenylmethane-4,4′-disicocyanate (MDI), etc. An isocyanate polymer of jojoba oil fatty acid polyhydric alcohol ester obtained by crosslinking with the above isocyanate can also be preferably used. The spent property to the carrier is small and the life of the two-component developer can be extended.

  The saponification value refers to the number of milligrams of potassium hydroxide required to saponify 1 g of a sample. This is the sum of acid value and ester value. To determine the saponification value, a sample is saponified in an alcohol solution of about 0.5 N potassium hydroxide, and then excess potassium hydroxide is titrated with 0.5 N hydrochloric acid.

  The iodine value refers to the amount of halogen absorbed when halogen is allowed to act on a sample, and expressed in terms of g relative to 100 g of the sample. It is the number of grams of iodine absorbed, and the higher this value, the higher the degree of unsaturation of the fatty acid in the sample. Add iodine and mercury (II) chloride alcohol solution or iodine glacial acetic acid solution to chloroform or carbon tetrachloride solution of the sample, and titrate the remaining iodine without reacting with sodium thiosulfate standard solution to absorb iodine Calculate the amount.

  For the measurement of the loss on heating, the weight of the sample cell is precisely weighed to 0.1 mg (W1 mg), 10 to 15 mg of the sample is put in this, and it is precisely weighed to 0.1 mg (W2 mg). The sample cell is set on a differential thermobalance, and the measurement is started with a weighing sensitivity of 5 mg. After the measurement, the weight loss when the sample temperature reaches 220 ° C. is read to 0.1 mg by the chart (W3 mg). The apparatus is TGD-3000 manufactured by Vacuum Riko, the heating rate is 10 ° C./min, the maximum temperature is 220 ° C., the holding time is 1 min, and the heating loss (%) = W 3 / (W 2 −W 1) × 100. .

  In addition, instead of the wax described above as the first wax, or in combination with a hydroxystearic acid derivative, glycerin fatty acid ester, glycol fatty acid ester or sorbitan fatty acid ester material is also preferable, and one or a combination of two or more types is used. Is also effective. Uniform emulsification-dispersed small particle size particles can be prepared, and when used together with the second wax, coarsening of the particle size can be prevented, and toner base particles having a small particle size and a narrow particle size distribution can be generated.

  Oilless fixing having low temperature fixing, high glossiness, and translucency can be realized. In addition, the life of the developer can be extended along with the oilless fixing.

  As a derivative of hydroxystearic acid, methyl 12-hydroxystearate, butyl 12-hydroxystearate, propylene glycol mono12-hydroxystearate, glycerin mono12-hydroxystearate or ethylene glycol mono12-hydroxystearate is suitable. Material. It has low-temperature fixability, oil separability improvement effect, and photoconductor filming prevention effect in oilless fixing.

  Glycerin fatty acid esters include glycerol stearate, glycerol distearate, glycerol tristearate, glycerol monopalmitate, glycerol dipalmitate, glycerol tripalmitate, glycerol behenate, glycerol dibehenate, glycerol tribehenate, glycerol monomyristate Glycerin dimyristate or glycerin trimyristate is a suitable material. It has the effect of alleviating cold offset at low temperatures and preventing deterioration of transferability in oilless fixing.

  As the glycol fatty acid ester, propylene glycol fatty acid esters such as propylene glycol monopalmitate and propylene glycol monostearate, and ethylene glycol fatty acid esters such as ethylene glycol monostearate and ethylene glycol monopalmitate are suitable materials. Low temperature fixability, good slippage during development, and has the effect of preventing carrier spent.

  As sorbitan fatty acid esters, sorbitan monopalmitate, sorbitan monostearate, sorbitan tripalmitate, and sorbitan tristearate are suitable materials. Furthermore, materials such as stearic acid ester of pentaerythritol and mixed esters of adipic acid and stearic acid or oleic acid are preferable, and one kind or a combination of two or more kinds can be used. It has the effect of improving the separability of paper in oilless fixing and the effect of preventing photoconductor filming.

  As the second wax, a fatty acid hydrocarbon wax such as a low molecular weight polypropylene wax, a low molecular weight polyethylene wax, a polypropylene polyethylene copolymer wax, a microcrystalline wax, a paraffin wax, or a Fisher to push wax can be suitably used.

  As the second wax, a modified wax obtained by reacting a long-chain alkyl alcohol with an unsaturated polyvalent carboxylic acid or an anhydride thereof and a synthetic hydrocarbon wax is also preferably used.

  The carbon number of the long-chain alkyl group of the modified second wax is preferably 4 to 30, and the acid value is preferably 10 to 80 mgKOH / g. A wax obtained by reacting a long-chain alkylamine with an unsaturated polyvalent carboxylic acid or its anhydride and an unsaturated hydrocarbon wax, or a long-chain fluoroalkyl alcohol and an unsaturated polycarboxylic acid or its anhydride and an unsaturated Waxes obtained by reaction with hydrocarbon waxes can also be suitably used. The effects include the enhancement of the releasing action by the long chain alkyl group, the improvement of the dispersion phase with the resin by the ester group, and the improvement of durability and offset property by the vinyl group.

In the molecular weight distribution in GPC of this modified second wax, the weight average molecular weight is 1000 to 6000, the Z average molecular weight is 1500 to 9000, and the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is 1.1 to 3.8, the ratio of the Z average molecular weight to the number average molecular weight (Z average molecular weight / number average molecular weight) is 1.5 to 6.5, 1 × 10 ^{3 to} 3 × 10 ⁴ in at least one region It has a molecular weight maximum peak, an acid value of 10 to 80 mgKOH / g, a melting point of 80 to 120 ° C., and a penetration at 25 ° C. of 4 or less. More preferably, the weight average molecular weight is 1000 to 5000, the Z average molecular weight is 1700 to 8000, the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is 1.1 to 2.8, and the Z average molecular weight is The number average molecular weight ratio (Z average molecular weight / number average molecular weight) is at least one molecular weight maximum peak in the region of 1.5 to 4.5, 1 × 10 ³ to 1 × 10 ⁴ , and the acid value is 10 to 50 mgKOH. / G, melting point 85-100 ° C., more preferably weight average molecular weight 1000-2500, Z average molecular weight 1900-3000, ratio of weight average molecular weight to number average molecular weight (weight average molecular weight / number average molecular weight) is 1. .2~1.8, Z average molecular weight to number average molecular weight ratio (Z average molecular weight / number average molecular weight) of at least one of the regions of 1.7~2.5,1 × ^{10 3} ~3 × ¹⁰ 3 Has a molecular weight maximum peak, acid value 35~50mgKOH / g, a melting point of 90 to 100 ° C..

  There is no improvement in the high temperature non-offset property in oilless fixing and the deterioration of storage stability. In an image in which three layers of color toner are formed on a thin paper, it is particularly effective for improving the paper separation from the fixing roller and the fixing belt.

  By using it in combination with a carrier, it is possible to suppress the generation of spent as well as oil-less fixing, to extend the life of the developer, and to achieve both fixing ability and development stability.

Here, when the carbon number of the long-chain alkyl of the modified wax is smaller than 4, the releasing action is weakened, and the separation property and the high temperature non-offset property are deteriorated. When the carbon number of the long-chain alkyl is larger than 30, the mixed aggregation property with the resin is deteriorated and the dispersibility is lowered. When the acid value is smaller than 10 mgKOH / g, the charge amount during long-term use of the toner is reduced. When the acid value is greater than 80 mgKOH / g, the moisture resistance decreases, and the fogging under high humidity increases. If it is high, it is difficult to reduce the particle size of the produced particles when the emulsified dispersed particles are produced. When the melting point is lower than 80 ° C., the storage stability of the toner is lowered and the high temperature non-offset property is deteriorated. When the melting point is higher than 120 ° C., the low-temperature fixability becomes weak and the color glossiness is deteriorated. It becomes difficult to reduce the particle size of the generated particles when the emulsified dispersed particles are generated. When the penetration at 25 ° C. is larger than 4, the toughness is lowered and the photoreceptor filming occurs during long-term use. Weight average molecular weight smaller than 1000, Z average molecular weight smaller than 1500, Weight average molecular weight / number average molecular weight smaller than 1.1, Z average molecular weight / number average molecular weight smaller than 1.5, molecular weight maximum peak Is located in a range smaller than 1 × 10 ³ , the storage stability of the toner is lowered, and filming occurs on the photosensitive member and the intermediate transfer member. Further, the handling property in the developing device is lowered, and the uniformity of the toner density is lowered. The particle size distribution of the produced particles at the time of producing the emulsified dispersed particles becomes a load. The weight average molecular weight is greater than 6000, the Z average molecular weight is greater than 9000, the weight average molecular weight / number average molecular weight is greater than 3.8, the Z average molecular weight / number average molecular weight is greater than 6.5, and the molecular weight maximum When the peak is located in a range larger than the region of 3 × 10 ⁴ , the mold release action is weakened and the high temperature non-offset property is lowered. It becomes difficult to reduce the particle size of the generated particles when the emulsified dispersed particles are generated.

Alcohols used in the modified second wax include octanol (C ₈ H ₁₇ OH), dodecanol (C ₁₂ H ₂₅ OH), stearyl alcohol (C ₁₈ H ₃₇ OH), nonacosanol (C ₂₉ H ₅₉ OH) or Those having an alkyl chain of 4 to 30 carbon atoms such as pentadecanol (C ₁₅ H ₃₁ OH) can be used. Moreover, N-methylhexylamine, nonylamine, stearylamine, nonadecylamine, etc. can be used conveniently as amines. As the fluoroalkyl alcohol, 1-methoxy- (perfluoro-2-methyl-1-propene), hexafluoroacetone, 3-perfluorooctyl-1,2-epoxypropane or the like can be preferably used.

  As the unsaturated polyvalent carboxylic acid or anhydride thereof used for the modified second wax, one or two of maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, or citraconic anhydride is used. It can be used above. Of these, maleic acid and maleic anhydride are more preferable. As the unsaturated hydrocarbon wax, ethylene, propylene, α-olefin and the like can be suitably used.

Unsaturated polyhydric carboxylic acid or its anhydride is polymerized with alcohol or amine, and this is then added to synthetic hydrocarbon wax in the presence of dicrummi peroxide or tertiary butyl peroxyisopropyl monocarbonate. Can be obtained.
(3) Resin Examples of the resin fine particles of the toner of the present embodiment include a thermoplastic binder resin. Specifically, styrenes such as styrene, parachlorostyrene, or α-methylstyrene, acrylic acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, lauryl acrylate, or 2-ethylhexyl acrylate , Methacrylic monomers such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, or 2-ethylhexyl methacrylate, ethylenic polymers such as acrylic acid, methacrylic acid, or sodium styrenesulfonate. Vinyl nitriles such as saturated acid monomers, acrylonitrile or methacrylonitrile, vinyl ethers such as vinyl methyl ether or vinyl isobutyl ether, vinyl kets such as vinyl methyl ketone, vinyl ethyl ketone or vinyl isopropenyl ketone S, ethylene, propylene, or homopolymers, such as monomers such as olefins, such as butadiene, or monomers thereof can be given two or more combinations copolymer or a mixture thereof.

  Furthermore, epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, etc., non-vinyl condensation resins, or a mixture of them with the vinyl resin, or a vinyl monomer in the presence of these resins Examples thereof include a graft polymer obtained by polymerizing a polymer.

  Among these resins, vinyl resins are particularly preferable. In the case of a vinyl resin, it is advantageous in that a resin particle dispersion can be easily prepared by emulsion polymerization or seed polymerization using an ionic surfactant or the like. Examples of the vinyl monomer include acrylic acid, methacrylic acid, maleic acid, cinnamic acid, fumaric acid, vinyl sulfonic acid, ethylene imine, vinyl pyridine, vinyl amine, and other vinyl polymer acids and vinyl polymer bases. The monomer used as a raw material is mentioned. The liquid concentration of the resin particles in the resin particle dispersion is 5 to 50% by weight, preferably 10 to 30% by weight.

  The first resin constituting the core particles in order to eliminate the presence of floating particles in the formation of aggregated particles (sometimes referred to as core particles) by agglutination reaction with wax and colorant, and to form particles with a sharp particle size distribution The glass transition point of the particles is preferably 45 ° C to 60 ° C and the softening point is 90 ° C to 140 ° C. More preferably, the glass transition point is 45 ° C to 55 ° C, the softening point is 90 ° C to 135 ° C, and still more preferably, the glass transition point is 45 ° C to 52 ° C, and the softening point is 90 ° C to 130 ° C. preferable.

  Moreover, as a preferable structure of the first resin particles, the weight average molecular weight (Mw) is 10,000 to 60,000, and the ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.5 to 6. Some configurations are preferred. It is preferable that the weight average molecular weight (Mw) is 10,000 to 50,000 and the ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.5 to 3.9. More preferably, the weight average molecular weight (Mw) is 10,000 to 30,000, and the ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.5 to 3.

  When the glass transition point of the first resin particles is lower than 45 ° C., the core particles are coarsened. Storage stability and heat resistance are reduced. If it is higher than 55 ° C., the low-temperature fixability deteriorates. When Mw is smaller than 10,000, the core particles are coarsened. Storage stability and heat resistance are reduced. If it exceeds 60,000, the low-temperature fixability deteriorates. When Mw / Mn is larger than 6, the shape of the core particle is not stable, irregular shapes and irregularities remain on the particle surface, and the surface smoothness is inferior.

  The core particles can be prevented from being coarsened by the configuration including the first resin particles and the wax, and particles having a narrow particle size distribution can be efficiently generated.

  In addition, low-temperature fixability is possible, and further, there is an effect that the image gloss can be made constant by reducing the change of the image gloss to the fixing temperature. Normally, since the glossiness of an image increases as the fixing temperature rises, the glossiness of the image fluctuates due to fluctuations in the fixing temperature, and it is necessary to control the fixing temperature severely. However, with this configuration, the effect of little fluctuation in image gloss can be obtained even when the fixing temperature varies.

  Also preferred is a structure in which the second resin particles are fused to the core particles to form a resin fusion layer, and the resin has a glass transition point of 45 ° C. to 65 ° C. and a softening point of 140 ° C. ˜180 ° C., weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is 50,000 to 500,000, ratio Mw / Mn of weight average molecular weight (Mw) to number average molecular weight (Mn) is 2 to 10 The structure which is is preferable. More preferably, the glass transition point is 50 ° C to 65 ° C, the softening point is 145 ° C to 180 ° C, Mw is 80,000 to 500,000, and Mw / Mn is 2 to 7. More preferably, the glass transition point is 50 ° C to 60 ° C, the softening point is 150 ° C to 180 ° C, the Mw is 120,000 to 500,000, and the Mw / Mn is 2 to 5.

  The aim is to improve the durability, high-temperature offset resistance, and separability by promoting thermal fusion of the core particle surfaces and increasing the softening point. If the glass transition point of the second resin particles is lower than 45 ° C., secondary aggregation tends to occur. Moreover, storage stability deteriorates. When the temperature is higher than 65 ° C., the heat fusion property to the surface of the core particle is deteriorated, and the uniform adhesion is deteriorated. When the softening point of the second resin particles is lower than 140 ° C., durability, high-temperature offset resistance and separability are deteriorated. When it is higher than 180 ° C., glossiness and translucency are lowered. By making Mw / Mn small and making the molecular weight distribution close to monodisperse, it is possible to uniformly heat-bond the second resin particles to the surface of the core particles.

  When the Mw of the second resin particles is smaller than 50,000, durability, high temperature non-offset property, and paper separation property are deteriorated. If it exceeds 500,000, the low-temperature fixability, glossiness, and translucency are lowered.

  The first resin particles are preferably 60 wt% or more, more preferably 70 wt% or more, and still more preferably 80 wt% or more based on the total toner resin.

  The molecular weights of the resin, wax, and toner are values measured by gel permeation chromatography (GPC) using several types of monodisperse polystyrene as standard samples.

  The apparatus is HLC8120GPC series manufactured by Tosoh Corporation, the column is TSKgel super HM-H H4000 / H3000 / H2000 (6.0 mm ID-150 mm × 3), eluent THF (tetrahydrofuran), flow rate 0.6 mL / min, sample concentration 0 .1%, injection amount 20 μL, detector RI, measurement temperature 40 ° C., pre-measurement treatment was performed by dissolving the sample in THF and allowing it to stand overnight, followed by filtration with a 0.45 μm membrane filter to remove additives such as silica. The resin component is measured. The measurement conditions are conditions in which the molecular weight distribution of the target sample is included in a range in which the logarithm of the molecular weight and the count number are linear in a calibration curve obtained with several types of monodisperse polystyrene standard samples.

  The wax obtained by the reaction with a long-chain alkyl alcohol, an unsaturated polyvalent carboxylic acid or an anhydride thereof, and a synthetic hydrocarbon wax was measured using a GPC-150C manufactured by WATERS as an apparatus and a Shodex HT-806M (8. 0 mm ID-30 cm × 2), eluent is o-dichlorobenzene, flow rate is 1.0 mL / min, sample concentration is 0.3%, injection volume is 200 μL, detector is RI, measurement temperature is 130 ° C., In the pretreatment for measurement, the sample was dissolved in a solvent and then filtered through a 0.5 μm sintered metal filter. The measurement conditions are conditions in which the molecular weight distribution of the target sample is included in a range in which the logarithm of the molecular weight and the count number are linear in a calibration curve obtained with several types of monodisperse polystyrene standard samples.

The softening point of the binder resin was about 9.8 with a plunger while heating a 1 cm ³ sample at a heating rate of 6 ° C./min with a constant-load extrusion capillary rheometer flow tester (CFT500) manufactured by Shimadzu Corporation. Applying a load of × 10 ⁵ N / m ² and extruding from a die with a diameter of 1 mm and a length of 1 mm, the piston stroke begins to rise from the relationship between the temperature rise characteristic of the plunger stroke and temperature. The temperature is the outflow start temperature (Tfb), 1/2 of the difference between the lowest value of the curve and the end point of the outflow, and the temperature at the point where the minimum value of the curve is added is the melting temperature (softening point) in the 1/2 method. Tm).

In addition, the glass transition point of the resin was measured by using a differential scanning calorimeter (Shimadzu DSC-50), heated to 100 ° C., allowed to stand at that temperature for 3 minutes, and then cooled to room temperature at a cooling rate of 10 ° C./min. When the thermal history is measured by heating at a heating rate of 10 ° C./min, the maximum slope between the baseline extension line below the glass transition point and the peak rising portion to the peak apex is shown. Says the temperature at the intersection with the tangent.
The melting point of the endothermic peak by DSC of the wax was 5 ° C / min using a differential scanning calorimeter (Shimadzu DSC-50), heated to 200 ° C, rapidly cooled to 10 ° C for 5 minutes, then allowed to stand for 15 minutes. The temperature was raised at ° C./min, and the endothermic (melting) peak was obtained. The amount of sample put into the cell was 10 mg ± 2 mg.
(4) Charge Control Agent The charge control agent is preferably an acrylic sulfonic acid polymer, and a vinyl copolymer of a styrene monomer and an acrylic acid monomer having a sulfonic acid group as a polar group. In particular, a copolymer with acrylamido-2-methylpropanesulfonic acid can exhibit preferable characteristics. By using it in combination with a carrier to be described later, the handling property in the developing device is improved and the uniformity of the toner density is improved. Further, development memory can be suppressed.

  These are prepared by creating a dispersion of a styrene acrylamide-2-methylpropane sulfonic acid copolymer produced by emulsion polymerization, and adding the second resin particle dispersion described above to the core particle dispersion. Therefore, the charge control function can be exhibited by adding it to the toner surface.

  As a preferable material, a metal salt of a salicylic acid derivative is used. With this configuration, it is possible to prevent image disturbance due to charging during fixing. This seems to be the effect of the functional group having the acid value of the wax and the charging polarity of the metal salt. In addition, it is possible to prevent a decrease in charge amount during continuous use.

  These are melted in a resin monomer (for example, a styrene monomer is preferable) at the time of emulsion polymerization, and the monomer is emulsion polymerized to prepare a resin fine particle dispersion to which CCA is added.

The addition amount is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the resin. More preferably, it is 0.1-2 weight part, More preferably, it is 0.5-1.5 weight part. When the amount is less than 0.1 parts by weight, the charging effect is lost. If it exceeds 5 parts, the dispersion will not be uniform. Color turbidity in color images is noticeable.
(5) Pigment As the colorant (pigment) used in the present embodiment, carbon black, iron black, graphite, nigrosine, and an azo dye metal complex can be preferably used as the black pigment. Examples of yellow pigments include C.I. I. Acetoacetic acid arylamide monoazo yellow pigments such as C.I. Pigment Yellow 1, 3, 74, 97 or 98; I. Acetoacetic acid arylamide disazo yellow pigments such as C.I. Pigment Yellow 12, 13, 14, and 17; I. Solven Yellow 19, 77, 79 or C.I. I. Disperse Yellow 164 is blended, and C.I. I. Benzimidazolone pigments of CI Pigment Yellow 93, 180 and 185 are preferred. Examples of magenta pigments include C.I. I. Red pigments such as CI Pigment Red 48, 49: 1, 53: 1, 57, 57: 1, 81, 122, 5; I. Red dyes such as Solvent Red 49, 52, 58 and 8 can be preferably used. Examples of cyan pigments include C.I. I. A blue dyed pigment of phthalocyanine and its derivatives such as Pigment Blue 15: 3 can be preferably used. The addition amount is preferably 3 to 8 parts by weight with respect to 100 parts by weight of the binder resin.

The median diameter of each particle is usually 1 μm or less, preferably 0.01 to 1 μm. When the median diameter exceeds 1 μm, the particle size distribution of the finally obtained toner for developing an electrostatic charge image is broadened, or free particles are generated, which easily deteriorates performance and reliability. On the other hand, when the median diameter is within the above range, there are no disadvantages, and the uneven distribution among the toners is reduced, the dispersion in the toner is improved, and the variation in performance and reliability is advantageous. The median diameter can be measured using, for example, a Horiba laser diffraction particle size measuring instrument (LA920).
(6) External additive In this embodiment, inorganic fine powder is mixed and added as an external additive. External additives include silica, alumina, titanium oxide, zirconia, magnesia, ferrite, magnetite and other metal oxide fine powders, barium titanate, calcium titanate, titanates such as strontium titanate, barium zirconate, zircon Zirconates such as calcium acid and strontium zirconate, or mixtures thereof are used. The external additive is hydrophobized as necessary.

  As the silicone oil-based material to be treated by the external additive, those shown in (Chemical Formula 1) are preferable.

  For example, dimethyl silicone oil, methyl hydrogen silicone oil, methyl phenyl silicone oil, cyclic dimethyl silicone oil, epoxy modified silicone oil, carboxyl modified silicone oil, carbinol modified silicone oil, methacryl modified silicone oil, mercapto modified silicone oil, polyether modified An external additive treated with at least one of silicone oil, methylstyryl-modified silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, amino-modified silicone oil and chlorophenyl-modified silicone oil is preferably used. Examples thereof include SH200, SH510, SF230, SH203, BY16-823 or BY16-855B manufactured by Toray Dow Corning Silicone.

  For the treatment, the external additive and the material such as silicone oil are mixed with a mixer such as a Henschel mixer (FM20B manufactured by Mitsui Mining Co., Ltd.), the method of spraying a silicone oil-based material on the external additive, and the silicone oil as a solvent. There is a method of preparing by dissolving or dispersing a system material, mixing with an external additive, and then removing the solvent. The silicone oil-based material is preferably blended in an amount of 1 to 20 parts by weight with respect to 100 parts by weight of the external additive.

  As silane coupling agents, dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, hexamethyldisilazane, allylphenyldichlorosilane, benzylmethylchlorosilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, Vinyltriacetoxysilane, divinylchlorosilane, dimethylvinylchlorosilane, or the like can be preferably used. The silane coupling agent treatment is a dry treatment in which the vaporized silane coupling agent is reacted with the external additive made into a cloud by stirring or the like, or a silane coupling agent in which the external additive is dispersed in a solvent is dropped. It is processed by a wet method or the like.

  It is also preferable to treat the silicone oil-based material after the silane coupling treatment.

  The external additive having positive electrode chargeability is treated with aminosilane, amino-modified silicone oil or epoxy-modified silicone oil represented by the following formula (Chemical Formula 2).

  Moreover, in order to improve hydrophobic treatment, the combined use of treatment with hexamethyldisilazane, dimethyldichlorosilane, or other silicone oil is also preferable. For example, it is preferable to treat with at least one of dimethyl silicone oil, methylphenyl silicone oil, and alkyl-modified silicone oil.

  Moreover, it is also preferable to treat the surface of the external additive with one or more selected from the group of fatty acid esters, fatty acid amides, fatty acids and fatty acid metal salts (hereinafter referred to as fatty acids). Surface-treated silica or titanium oxide fine powder is more preferable.

  Examples of fatty acids or fatty acid metal salts include caprylic acid, capric acid, undecylic acid, lauric acid, myristylic acid, parimitic acid, stearic acid, behenic acid, montanic acid, laccellic acid, oleic acid, erucic acid, sorbic acid, linoleic acid, etc. Is mentioned. Of these, fatty acids having 12 to 22 carbon atoms are preferred.

Moreover, as a metal which comprises a fatty-acid metal salt, aluminum, zinc, calcium, magnesium, lithium, sodium, lead, or barium is mentioned, Among these, aluminum, zinc, or sodium is preferable. Particularly preferred are aluminum distearate (Al (OH) (C ₁₇ H ₃₅ COO) ₂ ) or aluminum monostearate (Al (OH) ₂ (C ₁₇ H ₃₅ COO)), etc. Is preferred. Having an OH group can prevent overcharging and suppress poor transfer. Further, it is considered that the processability with the external additive is improved during the treatment.

  The aliphatic amide has 16 to 24 carbon atoms such as palmitic acid amide, palmitoleic acid amide, stearic acid amide, oleic acid amide, arachidic acid amide, eicosenoic acid amide, behenic acid amide, erucic acid amide, or ligrinoceric acid amide. Saturated or monovalent unsaturated aliphatic amides are preferably used.

  Examples of fatty acid esters include esters comprising higher alcohols having 16 to 24 carbon atoms and higher fatty acids having 16 to 24 carbon atoms such as stearyl stearate, palmityl palmitate, behenyl behenate or stearyl montanate, butyl stearate, Esters consisting of higher fatty acids having 16 to 24 carbon atoms and lower monoalcohols such as isobutyl behenate, propyl montanate or 2-ethylhexyl oleate, or fatty acid pentaerythritol monoester, fatty acid pentaerythritol triester, or fatty acid trimethylol Propane ester or the like is preferably used.

  Materials such as hydroxystearic acid derivatives, polyhydric alcohol fatty acid esters such as glycerin fatty acid ester, glycol fatty acid ester or sorbitan fatty acid ester are preferred, and one kind or a combination of two or more kinds can also be used.

  As a preferred form of the surface treatment, it is also preferred that the surface of the external additive to be treated is treated with a coupling agent and / or polysiloxane such as silicone oil and then treated with a fatty acid or the like. This is because a uniform treatment is possible as compared with the case where the fatty acid of the hydrophilic silica is simply treated, and the toner can be highly charged and the fluidity when added to the toner is improved. In addition, the above-described effects can be obtained even in a configuration in which fatty acid or the like is treated together with a coupling agent and / or silicone oil.

  Dissolve fatty acid in a hydrocarbon-based organic solvent such as toluene, xylene, hexane or isopar, and mix it with an external additive such as silica, titanium oxide, alumina, etc. It is produced by adhering to the surface and subjecting it to a surface treatment, and then removing the solvent and performing a drying treatment.

  The mixing ratio of the polysiloxane and the fatty acid is preferably 1: 2 to 20: 1. When the ratio is higher than 1: 2, the amount of charge of the external additive is increased, and the image density is lowered and charge-up is likely to occur in two-component development. When the amount of fatty acid or the like is less than 20: 1, the effect on the transfer loss and reverse transferability is lowered.

  At this time, the ignition loss of the external additive whose surface is treated with a fatty acid or the like is preferably 1.5 to 25 wt%. More preferably, it is 5-25 wt%, More preferably, it is 8-20 wt%. When the amount is less than 1.5 wt%, the function of the treating agent is not sufficiently exhibited, and the effect of improving the chargeability and transferability does not appear. When it exceeds 25 wt%, an untreated agent is present, which adversely affects developability and durability.

  Unlike the conventional pulverization method, the surface of the toner base particles produced according to the present invention is formed from only a resin, which is advantageous in terms of charge uniformity. This is because compatibility with the external additive used is important.

  A configuration in which 1 to 6 parts by weight of an external additive having an average particle diameter of 6 nm to 200 nm is externally added to 100 parts by weight of the toner base particles is preferable. When the average particle diameter is smaller than 6 nm, the floating particles and the filming on the photoreceptor are likely to occur. The occurrence of reverse transcription during transcription cannot be suppressed. When it is larger than 200 nm, the fluidity of the toner is deteriorated. When the amount is less than 1 part by weight, the fluidity of the toner is deteriorated. The occurrence of reverse transcription during transcription cannot be suppressed. When the amount is more than 6 parts by weight, filming on the suspended particles and the photosensitive member tends to occur. High temperature non-offset property is deteriorated.

  Further, an external additive having an average particle diameter of 6 nm to 20 nm is added to 0.5 to 2.5 parts by weight with respect to 100 parts by weight of the toner base particles, and an external additive having an average particle diameter of 20 nm to 200 nm is added to 100 parts by weight of the toner base particles. On the other hand, a configuration in which at least 0.5 to 3.5 parts by weight is externally added is also preferable. By using an external additive that is functionally separated by this configuration, the charge imparting property and the charge retention property are improved, and a margin can be further taken against reverse transfer, dropout, and toner scattering during transfer. At this time, the ignition loss of the external additive having an average particle diameter of 6 nm to 20 nm is preferably 0.5 to 20 wt%, and the ignition loss of the average particle diameter of 20 nm to 200 nm is preferably 1.5 to 25 wt%. By increasing the loss on ignition with an average particle size of 20 nm to 200 nm more than the loss on ignition of an external additive with an average particle size of 6 nm to 20 nm, it is effective for reverse transfer during transfer and voiding. Is demonstrated.

  By specifying the loss on ignition of the external additive, a margin can be taken against reverse transfer, dropout, and scattering during transfer. It is possible to improve the handling property in the developing unit and increase the uniformity of the toner density. Moreover, development memory generation can be suppressed.

  If the loss on ignition with an average particle diameter of 6 nm to 20 nm is less than 0.5 wt%, the transfer margin for reverse transfer and voids becomes narrow. If it exceeds 20 wt%, the surface treatment becomes uneven, and variations in charging occur. The loss on ignition is preferably 1.5 to 17 wt%, more preferably 4 to 10 wt%.

  If the loss on ignition with an average particle size of 20 nm to 200 nm is less than 1.5 wt%, the transfer margin for reverse transfer and hollow out becomes narrow. If it exceeds 25 wt%, the surface treatment becomes uneven, resulting in uneven charging. The loss on ignition is preferably 2.5 to 20 wt%, more preferably 5 to 15 wt%.

  Further, an external additive having an average particle diameter of 6 nm to 20 nm and an ignition loss of 0.5 to 20 wt% is 0.5 to 2 parts by weight with respect to 100 parts by weight of the toner base particles, and the average particle diameter is 20 nm to 100 nm. The external additive having an ignition loss of 1.5 to 25 wt% is 0.5 to 3.5 parts by weight with respect to 100 parts by weight of the toner base particles, the average particle diameter is 100 nm to 200 nm, and the ignition loss is 0.1. A configuration in which at least 0.5 to 2.5 parts by weight of the external additive of 10 wt% to 100 parts by weight of the toner base particles is externally added is also preferable. The structure of the external additive with the function of specifying the average particle size and loss on ignition improves the charge imparting property, charge retention, reverse transfer during transfer, and improvement of voids. Effective for removal.

  Further, an external additive having a positive charge property with an average particle diameter of 6 nm to 200 nm and an ignition loss of 0.5 to 25 wt% is further added to 0.2 to 1.5 parts by weight based on 100 parts by weight of the toner base particles. A configuration in which external processing is performed is also preferable.

  The effect of adding an external additive having a positive charging property can prevent the toner from being overcharged during long-term continuous use, thereby further extending the developer life. Furthermore, the effect of suppressing scattering during transfer due to overcharging can also be obtained. In addition, the spent on the carrier can be prevented. If the amount is less than 0.2 parts by weight, it is difficult to obtain the effect. If it exceeds 1.5 parts by weight, fogging during development increases. The ignition loss is preferably 1.5 to 20 wt%, more preferably 5 to 19 wt%.

  For drying loss (%), about 1 g of a sample is placed in a container that has been dried, allowed to cool, and precisely weighed in advance, and weighed accurately. Dry in a hot air dryer (105 ° C ± 1 ° C) for 2 hours. After cooling in a desiccator for 30 minutes, the weight is precisely weighed and calculated from the following formula.

  Loss on drying (%) = [Loss on drying (g) / Sample amount (g)] × 100.

  For ignition loss, about 1 g of a sample is placed in a magnetic crucible that has been dried, allowed to cool, and precisely weighed in advance, and weighed accurately. Ignite for 2 hours in an electric furnace set to 500 ° C. After standing to cool in a desiccator for 1 hour, its weight is precisely weighed and calculated from the following formula.

  Loss on ignition (%) = [Loss on ignition (g) / Sample amount (g)] × 100.

  Moreover, it is preferable that the water | moisture-content adsorption amount of the processed external additive is 1 wt% or less. Preferably it is 0.5 wt% or less, More preferably, it is 0.1 wt% or less, More preferably, it is 0.05 wt% or less. When the content is more than 1 wt%, chargeability is deteriorated and filming on the photoconductor during durability is caused. The water adsorption amount was measured with a continuous vapor adsorption device (BELSORP18: Nippon Bell Co., Ltd.) for the water adsorption device.

  For the determination of the degree of hydrophobicity, 0.2 g of the product to be tested is weighed into 50 ml of distilled water charged in a 250 ml beaker. At the tip, methanol is dropped from a burette that is invaded in the liquid until the total amount of the external additive is wet. At that time, slowly stir slowly with an electromagnetic stirrer. The degree of hydrophobicity is calculated by the following equation from the amount of methanol a (ml) essential for complete wetting.

Hydrophobicity = (a / (50 + a)) × 100 (%).
(7) Toner powder physical properties In this embodiment, toner base particles containing a binder resin, a colorant and a wax have a volume average particle diameter of 3 to 7 μm and a toner particle diameter of 2.52 to 4 μm in the number distribution. Toner having a mother particle content of 10 to 75% by number, a toner particle size of 25 to 75% by volume in a volume distribution of 4 to 6.06 μm, and a toner particle size of 8 μm or more in a volume distribution Toner containing 5% by volume or less of mother particles and having a particle size of 4 to 6.06 μm in the volume distribution, V46 being the volume percent of the mother particles having a particle size of 4 to 6.06 μm in the number distribution When the number% of the base particles is P46, P46 / V46 is in the range of 0.5 to 1.5, the variation coefficient in the volume average particle size is 10 to 25%, and the variation coefficient in the number particle size distribution is 10 to 10. 28% Is preferred.
Preferably, the toner base particles have a volume average particle size of 3 to 6.5 μm, the content of toner base particles having a particle size of 2.52 to 4 μm in the number distribution is 20 to 75% by number, and 4 to 6 in the volume distribution. Toner base particles having a particle size of 0.06 μm are 35 to 75% by volume, toner base particles having a particle size of 8 μm or more in the volume distribution are contained in 3% by volume or less, and 4 to 6. When the volume% of toner base particles having a particle size of 06 μm is V46 and the number% of toner base particles having a particle size of 4 to 6.06 μm in the number distribution is P46, P46 / V46 is 0.5. The coefficient of variation in the volume average particle diameter is preferably 10 to 20%, and the coefficient of variation of the number particle size distribution is preferably 10 to 23%.

  More preferably, the toner base particles have a volume average particle size of 3 to 5 μm, the content of toner base particles having a particle size of 2.52 to 4 μm in the number distribution is 40 to 75% by number, and 4 to 6 in the volume distribution. The toner base particles having a particle size of 0.06 μm are 45 to 75% by volume, the toner base particles having a particle size of 8 μm or more in the volume distribution are contained in 3% by volume or less, and 4 to 6. When the volume% of toner base particles having a particle diameter of 06 μm is V46 and the number% of toner base particles having a particle diameter of 4 to 6.06 μm in the number distribution is P46, P46 / V46 is 0.5. It is preferable that the variation coefficient in the volume average particle size is 10 to 15% and the variation coefficient of the number particle size distribution is 10 to 18%.

  It is possible to prevent high-resolution image quality, and also prevent reverse transfer and dropout in tandem transfer, and achieve both oil-less fixing. The fine powder in the toner affects toner fluidity, image quality, storage stability, filming on the photosensitive member, developing roller, and transfer member, aging characteristics, transferability, particularly multi-layer transfer in the tandem system. Furthermore, it affects the non-offset property, glossiness and translucency in oilless fixing. In a toner containing a wax such as a wax for realizing oil-less fixing, the amount of fine powder affects the compatibility with tandem transferability.

  When the volume average particle size exceeds 7 μm, it is impossible to achieve both image quality and transfer. When the volume average particle size is less than 3 μm, it becomes difficult to handle toner particles during development.

  If the content of toner base particles having a particle diameter of 2.52 to 4 μm in the number distribution is less than 10% by number, it is impossible to achieve both image quality and transfer. When it exceeds 75% by number, it becomes difficult to handle the toner base particles during development. In addition, filming on the photosensitive member, the developing roller, and the transfer member is likely to occur. Furthermore, fine powder tends to be offset because of its high adhesion to the heat roller. Further, in the tandem system, toner aggregation tends to be strong, and transfer failure of the second color is likely to occur during multilayer transfer. An appropriate range is required.

  If toner base particles having a particle size of 4 to 6.06 μm in the volume distribution exceed 75% by volume, it is impossible to achieve both image quality and transfer. When it is less than 30% by volume, the image quality is deteriorated.

  When toner mother particles having a particle size of 8 μm or more in the volume distribution are contained exceeding 5% by volume, the image quality is deteriorated. Causes transfer failure.

  When the volume% of toner base particles having a particle diameter of 4 to 6.06 μm in the volume distribution is V46, and the number% of toner base particles having a particle diameter of 4 to 6.06 μm in the number distribution is P46, When P46 / V46 is less than 0.5, the amount of fine powder present becomes excessive, resulting in poor fluidity, poor transferability, and poor background fog. When it is larger than 1.5, there are many large particles and the particle size distribution becomes broad, so that high image quality cannot be achieved.

  The purpose of defining P46 / V46 can be used as an index for making the toner particles small and narrowing the particle size distribution.

  The coefficient of variation is the standard deviation of the toner particle size divided by the average particle size. This is based on the particle diameter measured using a Coulter counter (Coulter). The standard deviation is expressed as the square root of the value obtained by dividing the square of the difference from the average value of each measured value when (n-1) is measured when n particle systems are measured.

  In other words, the coefficient of variation represents the extent of the particle size distribution, and if the coefficient of variation of the volume particle size distribution is less than 10% or the coefficient of variation of the number particle size distribution is less than 10%, it is difficult to produce, This will increase costs. When the variation coefficient of the volume particle size distribution is larger than 25% or the variation coefficient of the number particle size distribution is larger than 28%, the particle size distribution becomes broad, the toner cohesion becomes stronger, and the filming and transfer to the photosensitive member are performed. It is difficult to collect residual toner in a defective and cleaner-less process.

  The particle size distribution is measured by using a Coulter Counter TA-II type (Coulter Counter Co., Ltd.) and connecting an interface (manufactured by Nikkaki Co., Ltd.) for outputting the number distribution and volume distribution and a personal computer. The electrolyte solution is a surfactant (sodium lauryl sulfate) added to a concentration of 1%. About 2 mg of the toner to be measured is added to about 50 ml. The electrolyte solution in which the sample is suspended is dispersed for about 3 minutes with an ultrasonic disperser. And an aperture of 70 μm was used with a Coulter counter TA-II type. In the 70 μm aperture system, the particle size distribution measurement range is 1.26 μm to 50.8 μm, but the region less than 2.0 μm is not practical because the measurement accuracy and measurement reproducibility are low due to the influence of external noise and the like. Therefore, the measurement area was set to 2.0 μm to 50.8 μm.

Further, the degree of compression is calculated from the static bulk density and the dynamic bulk density, which is one of the indicators of toner fluidity. The fluidity of the toner is affected by the particle size distribution of the toner, the toner particle shape, the external additive, and the type and amount of the wax. When the toner particle size distribution is narrow and the amount of fine powder is small, the toner surface has few irregularities and the shape is nearly spherical, the amount of external additive added is large, or the particle size of the external additive is small, the degree of compression is small. The fluidity of the toner becomes higher. The degree of compression is preferably 5 to 40%. More preferably, it is 10 to 30%. It is possible to achieve both oilless fixing and tandem multi-layer transfer. If it is less than 5%, the fixability is lowered, and the translucency is particularly likely to deteriorate. Toner scattering tends to increase from the developing roller. Transferability greater than 40% is lowered, and tandem-type deficiency occurs and transfer failure occurs.
(8) Carrier As the carrier of the present embodiment, a carrier containing magnetic particles whose core material surface is coated with a fluorine-modified silicone resin containing an aminosilane coupling agent is preferably used.

  More preferably, the carrier is a composite magnetic particle having at least magnetic particles and a binder resin, the magnetic particle surface of which is coated with a resin made of a fluorine-modified silicone resin containing an aminosilane coupling agent. used.

  A thermosetting resin is preferable as the binder resin constituting the magnetic particles. Thermosetting resins include phenolic resins, epoxy resins, polyamide resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, xylene resins, acetoguanamine resins, furan resins, silicone resins, polyimide resins, urethane resins. These resins may be used alone or in combination of two or more, but preferably contain at least a phenol resin.

The composite particles in the present invention are preferably spherical particles having an average particle diameter of preferably 10 to 50 μm, more preferably 10 to 40 μm, still more preferably 10 to 30 μm, and most preferably 15 to 30 μm. Further, the specific gravity is 2.5 to 4.5, particularly 2.5 to 4.0, and the BET specific surface area by nitrogen adsorption of the carrier is preferably 0.03 to 0.3 m ² / g. When the average particle diameter of the carrier is less than 10 μm, the abundance ratio of the fine particles is high in the carrier particle distribution, and the carrier particles have a low magnetization per carrier particle, so that the carrier is easily developed on the photoreceptor. On the other hand, when the average particle of the carrier exceeds 50 μm, the specific surface area of the carrier particle becomes small and the toner holding force becomes weak, so that toner scattering occurs. In addition, a full color with many solid portions is not preferable because the reproduction of the solid portions is particularly poor.

  A conventional carrier having ferrite-based core particles has a large specific gravity of 5 to 6 and a particle diameter of 50 to 80 μm, so the BET specific surface area is small, and the mixing property when stirring with toner is small. However, when the toner is replenished, the charge rising property is insufficient and a large amount of toner is consumed, and when a large amount of toner is replenished, there is a tendency that a lot of fog occurs. If the density ratio between the toner and the carrier is not controlled within a narrow range, it is difficult to achieve both the image density, fogging and toner scattering reduction.

  However, the use of a carrier having a large specific surface area value makes it difficult to control the toner density because the image quality is hardly deteriorated even if the density ratio between the toner and the carrier is controlled in a wide range. Further, the mixing property with the toner can be more uniformly mixed, and when the toner is replenished, it has a good charge rising property, and the density ratio between the toner and the carrier can be controlled in a wider range. Image quality is hardly deteriorated, and both image density, fogging, and toner scattering can be reduced.

At this time, assuming that the specific surface area value of the toner is TS (m ² / g) and the specific surface area value of the carrier is CS (m ² / g), the TS / CS satisfies the relationship of 2 to 110, thereby stabilizing the image quality. Can be planned. Preferably it is 2-50, More preferably, it is 2-30. If it is less than 2, carrier adhesion tends to occur. On the other hand, if it is larger than 110, the density ratio between the toner and the carrier for reducing the image density, fogging and toner scattering is reduced, and the image quality is liable to deteriorate. A conventional carrier having ferrite-based core particles has a small specific surface area, and a conventional pulverized toner has an irregular shape and a large specific surface area.

  Composite magnetic particles are produced by reacting and curing phenols and aldehydes in the presence of magnetic particles and a basic catalyst while stirring the phenols and aldehydes in an aqueous medium. It can manufacture by the method of producing | generating the magnetic particle containing these.

  The average particle diameter of the obtained composite magnetic particles can be controlled by adjusting the stirring blade peripheral speed of the stirring device so that appropriate shearing and compaction are applied depending on the amount of water used.

  Production of composite particles using an epoxy resin as a binder resin is, for example, a method in which bisphenols, epihalohydrin, and lipophilic inorganic compound particle powder are dispersed in an aqueous medium and reacted in an alkaline aqueous medium. Can be mentioned.

  In the present invention, the content ratio between the magnetic fine particles of the composite magnetic particles and the binder resin is preferably 1 to 20% by mass of the binder resin and 80 to 99% by mass of the magnetic particles. When the content of the magnetic particles is less than 80 wt%, the saturation magnetization value becomes small, and when it exceeds 99 wt%, the binding between the magnetic particles by the phenol resin tends to be weak. Considering the strength of the composite magnetic particles, it is preferably 97 wt% or less.

  Magnetic fine particles include spinel ferrite such as magnetite and gamma iron oxide, and magnetoplumbites such as spinel ferrite and barium ferrite containing one or more metals other than iron (Mn, Ni, Zn, Mg, Cu, etc.). Type ferrite, fine particle powder of iron or alloy having an oxide layer on the surface can be used. The shape may be any of granular, spherical and acicular. In particular, when high magnetization is required, ferromagnetic fine particle powder such as iron can be used. However, considering chemical stability, magnetoplumbites such as spinel ferrite and barium ferrite containing magnetite and gamma iron oxide It is preferable to use ferromagnetic fine particle powder of type ferrite. By appropriately selecting the type and content of the ferromagnetic fine particle powder, composite particles having a desired saturation magnetization can be obtained.

In measurement under a magnetic field of 1000 oersted (79.57 kA / m), the strength of magnetization is 30 to 70 Am ² / kg, preferably 35 to 60 Am ² / kg, and the residual magnetization (σr) is 0.1 to 20 Am ² / kg, preferably 0.1 to 10 Am ² / kg, specific resistance value of 1 × 10 ⁶ to 1 × 10 ¹⁴ Ωcm, preferably 5 × 10 ^{6 to} 5 × 10 ¹³ Ωcm, more preferably 5 It is preferably × 10 ^{6 to} 5 × 10 ⁹ Ωcm.

  In the carrier production method according to the present invention, phenols and aldehydes are reacted in an aqueous medium in the presence of a basic catalyst in the presence of magnetic particles and a suspension stabilizer.

  As phenols used here, in addition to phenol, alkylphenols such as m-cresol, p-tert-butylphenol, o-propylphenol, resorcinol, bisphenol A, and a part or all of the benzene nucleus or alkyl group are included. Although the compound which has phenolic hydroxyl groups, such as halogenated phenol substituted by the chlorine atom or the bromine atom, is mentioned, Among these, phenol is the most preferable. When a compound other than phenol is used as the phenol, particles are difficult to form, or even if particles are formed, they may have an indeterminate shape. Therefore, phenol is most preferable in view of shape.

  The aldehydes used in the method for producing composite particles in the present invention include formaldehyde and furfural in the form of either formalin or paraformaldehyde, and formaldehyde is particularly preferable.

  Moreover, as resin used for the resin coating layer of this invention, a fluorine-modified silicone resin is essential. The fluorine-modified silicone resin is preferably a crosslinkable fluorine-modified silicone resin obtained from a reaction between a perfluoroalkyl group-containing organosilicon compound and polyorganosiloxane. The compounding ratio of the polyorganosiloxane and the perfluoroalkyl group-containing organosilicon compound is 3 parts by weight or more and 20 parts by weight or less of the perfluoroalkyl group-containing organosilicon compound with respect to 100 parts by weight of the polyorganosiloxane. Is preferred. Compared to the conventional coating on ferrite core particles, the adhesiveness of the composite magnetic particles in which the magnetic particles are dispersed in the curable resin is strengthened, and the effect of improving the durability is exhibited together with the chargeability described later.

  The polyorganosiloxane preferably exhibits at least one repeating unit selected from the following formulas (Formula 3) and (Formula 4).

Examples of the organosilicon compound containing a perfluoroalkyl group include CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , C ₄ F ₉ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , C ₈ F _{17 CH 2 CH 2 Si (OCH 3} ) 3, C 8 F 17 CH 2 CH 2 Si (OC 2 H 5) 3, (CF 3) 2 CF (CF 2) 8 CH 2 CH 2 Si (OCH 3) 3 , etc. In particular, those having a trifluoropropyl group are preferred.

  Moreover, in this embodiment, an aminosilane coupling agent is contained in the coating resin layer. As this aminosilane coupling agent, known ones may be used. For example, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, octadecylmethyl [3- (trimethoxy Cyril) propyl] ammonium chloride (from the top SH6020, SZ6023, AY43-021: trade names manufactured by Toray Dow Corning Silicone), KBM602, KBM603, KBE903, KBM573 (trade names manufactured by Shin-Etsu Silicone), etc. Primary amines are preferred. A secondary or tertiary amine substituted with a methyl group, ethyl group, phenyl group or the like is weak in polarity and has little effect on the charge rising characteristics with the toner. When the amino group is an aminomethyl group, aminoethyl group, or aminophenyl group, the most advanced silane coupling agent is a primary amine, but the amino group in a linear organic group extending from the silane. Does not contribute to the charge start-up characteristics with the toner and, conversely, is affected by moisture at high humidity, so it has the charge imparting ability with the initial toner due to the state-of-the-art amino group, but it has the charge imparting ability during printing durability. It will eventually drop and its life will be short.

  Therefore, by using such an aminosilane coupling agent and a fluorine-modified silicone resin in combination, negative chargeability can be imparted to the toner while ensuring a sharp charge amount distribution, and the toner is replenished. The toner has a quick charge rising property and can reduce the toner consumption. Furthermore, the aminosilane coupling agent expresses an effect like a crosslinking agent, improves the degree of crosslinking of the fluorine-modified silicone resin layer as the base resin, further improves the coating resin hardness, Separation and the like can be reduced, the spent resistance is improved, the decrease in charge imparting ability is suppressed, the charge is stabilized, and the durability is improved. In particular, in the toner configuration in which the resin fused layer is formed by fusing the second resin particles to the core particles, the charge rising property is improved, the fog is reduced, the uniformity of the solid image is improved, and the character skipping at the time of transfer is performed. In addition, the void is improved, the handling property in the developing device is improved, and so-called development memory in which a history remains after collecting a solid image can be reduced.

  The use ratio of the aminosilane coupling agent is 5 to 40% by weight, preferably 10 to 30% by weight, based on the resin. If the amount is less than 5% by weight, the effect of the aminosilane coupling agent is not obtained. If the amount exceeds 40% by weight, the degree of crosslinking of the resin coating layer becomes too high, and the charge-up phenomenon is likely to occur. May cause image defects.

Further, in order to prevent charge-up in order to stabilize charging, the resin coating layer can contain conductive fine particles. Conductive fine particles include oil furnace carbon and acetylene black carbon black, semiconductive oxides such as titanium oxide and zinc oxide, powder surfaces such as titanium oxide, zinc oxide, barium sulfate, aluminum borate and potassium titanate. Examples thereof include tin oxide, carbon black, and those coated with metal, and those having a specific resistance of 10 ¹⁰ Ω · cm or less are preferable. The content in the case of using conductive fine particles is preferably 1 to 15% by weight. If the conductive fine particles are contained in a certain amount with respect to the resin coating layer, the filler effect increases the hardness of the resin coating layer by the filler effect. However, if the content exceeds 15% by weight, the formation of the resin coating layer is inhibited. However, it causes a decrease in adhesion and hardness. Further, the excessive content of the conductive fine particles in the full color developer causes the color stain of the toner transferred and fixed on the paper surface.

  The method for forming the coating layer on the composite magnetic particles is not particularly limited. For example, a known coating method, for example, an immersion method in which a powder that is a composite magnetic particle is immersed in a solution for forming a coating layer, or for forming a coating layer. Spray method of spraying the solution onto the surface of the composite magnetic particles, fluidized bed method of spraying the solution for forming the coating layer in a state where the composite magnetic particles are suspended by the flowing air, and the solution for forming the composite magnetic particles and the coating layer in a kneader coater In addition to wet coating methods such as the kneader coater method to remove the solvent, the powdered resin and composite magnetic particles are mixed at high speed, and the frictional heat is used to fuse the resin powder onto the surface of the composite magnetic particles. Any of these can be applied, and in the coating of a fluorine-modified silicone resin containing an aminosilane coupling agent in the present invention, wet coating is possible. The law is particularly preferably used.

  The solvent used in the coating layer forming coating solution is not particularly limited as long as it dissolves the coating resin, and can be selected so as to be compatible with the coating resin used. In general, for example, aromatic hydrocarbons such as toluene and xylene, ketones such as acetone and methyl ethyl ketone, and ethers such as tetrahydrofuran and dioxane can be used.

  The resin coating amount is preferably 0.2 to 6.0% by weight, more preferably 0.5 to 5.0% by weight, still more preferably 0.6 to 4.0% by weight, and 0.0% by weight based on the composite magnetic particles. 7 to 3% by weight. If the coating amount of the resin is less than 0.2% by weight, a uniform coating cannot be formed on the surface of the composite magnetic particles, and the influence of the characteristics of the composite magnetic particles is greatly affected, and the fluorine-modified silicone of the present invention The effect of the resin and the aminosilane coupling agent cannot be fully exhibited. When the content exceeds 6.0% by weight, the coating layer becomes too thick, and the composite magnetic particles are granulated, and uniform composite magnetic particles tend not to be obtained.

Thus, after coating the fluorine-modified silicone resin containing an aminosilane coupling agent on the surface of the composite magnetic particles, it is preferable to perform a baking treatment. The means for performing the baking process is not particularly limited, and may be either an external heating system or an internal heating system, for example, a fixed or fluid electric furnace, a rotary kiln electric furnace, or a burner furnace. Or it may be baked by microwave. However, with regard to the temperature of the baking treatment, in order to efficiently express the effect of the fluorine silicone that improves the spent resistance of the resin coating layer, the treatment is preferably performed at a high temperature of 200 to 350 ° C., more preferably 220-280 ° C. The treatment time is preferably 1.5 to 2.5 hours. When the treatment temperature is low, the hardness of the coating resin itself is lowered. If the processing temperature is too high, charge reduction occurs.
(9) Two-component development In the development process, an AC bias is applied between the photosensitive member and the developing roller together with a DC bias. The frequency at that time is 1 to 10 kHz, the AC bias is 1.0 to 2.5 kV (pp), and the peripheral speed ratio between the photoconductor and the developing roller is 1: 1.2 to 1: 2. It is preferable. More preferably, the frequency is 3.5 to 8 kHz, the AC bias is 1.2 to 2.0 kV (pp), and the peripheral speed ratio between the photosensitive member and the developing roller is 1: 1.5 to 1: 1. .8. More preferably, the frequency is 5.5 to 7 kHz, the AC bias is 1.5 to 2.0 kV (pp), and the peripheral speed ratio between the photosensitive member and the developing roller is 1: 1.6 to 1: 1. .8.

  With this development process configuration and the use of the toner or the two-component developer of this embodiment, a high image density can be obtained, fogging can be reduced, and dots can be faithfully reproduced. Both high-quality images and oilless fixability can be achieved.

  If the frequency is less than 1 kHz, dot reproducibility deteriorates and halftone reproducibility deteriorates. When the frequency is higher than 10 kHz, the development region cannot be followed and the effect does not appear. In this frequency range, in the two-component development using a high resistance carrier, it works to reciprocate between the carrier and the toner rather than between the developing roller and the photosensitive member, and has the effect of slightly releasing the toner from the carrier. Good reproducibility and halftone reproducibility are achieved, and a high image density can be obtained.

When the AC bias is smaller than 1.0 kV (pp), the effect of suppressing charge-up cannot be obtained, and when the AC bias is larger than 2.5 kV (pp), the fog increases. If the peripheral speed ratio between the photoconductor and the developing roller is smaller than 1: 1.2 (the developing roller becomes slow), it is difficult to obtain image density. When the peripheral speed ratio between the photosensitive member and the developing roller is larger than 1: 2 (the developing roller speed is increased), toner scattering increases.
(10) Tandem color process In order to form a color image at high speed, this embodiment has a plurality of toner image forming stations including a photoconductor, a charging means, and a toner carrier, and a static image formed on the image carrier. A primary transfer process in which a toner image obtained by developing an electrostatic latent image is transferred to the transfer member by bringing an endless transfer member into contact with the image carrier is sequentially executed, and a multilayer image is formed on the transfer member. A transfer process configured to execute a secondary transfer process in which a multi-layer toner image formed on the transfer body is then collectively transferred to a transfer medium such as paper or OHP. When the distance from the first primary transfer position to the second primary transfer position is d1 (mm) and the peripheral speed of the photosensitive member is v (mm / s), the transfer position satisfies d1 / v ≦ 0.65. In the configuration that takes the configuration, This is intended to achieve both downsizing of the printer and printing speed. In order to realize a reduction in size that can process 20 sheets per minute (A4) or more and the machine can be used for SOHO, it is essential to have a configuration in which a plurality of toner image forming stations are short and the process speed is increased. is there. In order to achieve both a reduction in size and a printing speed, a configuration in which the above value is 0.65 or less is considered a minimum.

  However, when the configuration between the toner image forming stations is short, for example, the time from the primary transfer of the yellow toner of the first color to the primary transfer of the next magenta toner of the second color is extremely short. There is almost no charge relaxation or charge relaxation of the transferred toner, and when transferring the magenta toner onto the yellow toner, the magenta toner is repelled by the charge action of the yellow toner, the transfer efficiency decreases, The problem of hollowing out occurs. Further, during the primary transfer of the cyan toner of the third color, the cyan toner splatters, transfer defects, and transfer omissions occur remarkably when transferred onto the previous yellow and magenta toners. Furthermore, during repeated use, toner of a specific particle size is selectively developed, and if the fluidity of each toner particle differs greatly, the chance of frictional charging differs, resulting in variation in charge amount and further deterioration in transferability. Will be invited.

Therefore, by using the toner or the two-component developer of the present embodiment, the charge distribution is stabilized, the toner can be prevented from being overcharged, and the fluidity fluctuation can be suppressed. For this reason, it is possible to prevent transfer efficiency from being lowered, character dropout during transfer, and reverse transfer without sacrificing fixing characteristics.
(11) Oilless Color Fixation In this embodiment, the present invention is suitably used for an electrophotographic apparatus having a fixing process having an oilless fixing configuration in which oil is not used as a toner fixing unit. As the heating means, electromagnetic induction heating is a preferable configuration from the viewpoint of shortening the warm-up time and saving energy. A heating and pressurizing unit having at least a magnetic field generating unit, a rotary heating member having at least a heat generation layer and a release layer generated by electromagnetic induction, and a rotary pressurizing member forming a fixed nip with the rotary heating member; In this configuration, a transfer medium such as copy paper on which toner is transferred is passed between the rotary heating member and the rotary pressure member, and is fixed. As a feature thereof, the warm-up time of the rotary heating member is very fast compared to the case where a conventional halogen lamp is used. For this reason, since the copying operation is started in a state where the temperature of the rotary pressure member is not sufficiently raised, low temperature fixing and a wide range of offset resistance are required.

  As a configuration, a configuration using a fixing belt in which a heating member and a fixing member are separated is also preferably used. As the belt, a heat resistant belt such as a nickel electroformed belt or a polyimide belt having heat resistance and deformability is preferably used. In order to improve releasability, it is preferable to use silicone rubber, fluororubber, or fluororesin as the surface layer.

  In such fixing, conventionally, release oil has been applied to prevent offset. It is no longer necessary to apply release oil with toner having releasability without using oil. However, if the release oil is not applied, it is easy to be charged, and if an unfixed toner image comes close to the heating member or the fixing member, toner jump may occur due to the influence of charging. It tends to occur especially at low temperatures and low humidity.

  Therefore, by using the toner of this embodiment, low temperature fixing and a wide range of offset resistance can be realized without using oil, and high color translucency can be obtained. Further, the toner can be prevented from being overcharged, and toner flying due to the charging action with the heating member or the fixing member can be suppressed.

(Example of carrier core material production)
A 1 liter flask was charged with 52 g of phenol, 75 g of 37% formalin, 400 g of spherical magnetite particles having an average particle size of 0.24 μm, 15 g of 28% ammonia water, 1.0 g of calcium fluoride and 50 g of water while stirring. After raising the temperature to 85 ° C. for 60 minutes, the composite magnetic particles composed of phenol resin and spherical magnetite particles were generated by reacting and curing at the same temperature for 120 minutes.

  Next, after the contents in the flask were cooled to 30 ° C., 0.5 liter of water was added thereto, the supernatant was removed, and the lower layer precipitate was washed with water and air-dried. Subsequently, this was dried at 50-60 degreeC under pressure reduction (5 mmHg or less), and the composite magnetic particle (carrier core material A) was obtained.

  A 1 liter flask was charged with 50 g of phenol, 65 g of 37% formalin, 450 g of spherical magnetite particles having an average particle size of 0.24 μm, 15 g of 28% ammonia water, 1.0 g of calcium fluoride and 50 g of water while stirring. After raising the temperature to 85 ° C. for 60 minutes, the composite magnetic particles composed of phenol resin and spherical magnetite particles were generated by reacting and curing at the same temperature for 120 minutes.

  Next, after the contents in the flask were cooled to 30 ° C., 0.5 liter of water was added thereto, the supernatant was removed, and the lower layer precipitate was washed with water and air-dried. Subsequently, this was dried at 50-60 degreeC under pressure reduction (5 mmHg or less), and the composite magnetic particle (carrier core material B) was obtained.

  A 1 liter flask is charged with 47.5 g of phenol, 62 g of 37% formalin, 480 g of spherical magnetite particles having an average particle size of 0.24 μm, 15 g of 28% ammonia water, 1.0 g of calcium fluoride and 50 g of water, and stirred. Then, the temperature was raised to 85 ° C. over 60 minutes, and then reacted and cured at the same temperature for 120 minutes to produce composite magnetic particles composed of phenol resin and spherical magnetite particles.

  Next, after the contents in the flask were cooled to 30 ° C., 0.5 liter of water was added thereto, the supernatant was removed, and the lower layer precipitate was washed with water and air-dried. Next, this was dried at 50 to 60 ° C. under reduced pressure (5 mmHg or less) to obtain composite magnetic particles (carrier core material C).

As the core material d, ferrite particles having an average particle diameter of 50 μm and a saturation magnetization of 65 Am ² / kg when the applied magnetic field is 238.74 kA / m (3000 oersted) are used.
(Carrier production example 1)
Next, R ₁ and R ₂ represented by the following formula (Chemical Formula 5) are methyl groups, that is, (CH ₃ ) ₂ SiO _2/2 unit is 15.4 mol%, and R ₃ represented by the following Formula (Chemical Formula 6) is A fluorine-modified silicone resin was obtained by reacting 250 g of a polyorganosiloxane having a methyl group, that is, 84.6 mol% of CH ₃ SiO _3/2 units, and 21 g of CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ . Further, 100 g of the fluorine-modified silicone resin in terms of solid content and 10 g of aminosilane coupling agent (γ-aminopropyltriethoxysilane) were weighed and dissolved in 300 cc of toluene solvent.

  The carrier core material A10 kg was coated by using the immersion drying type coating apparatus and stirring the coating resin solution for 20 minutes. Thereafter, baking was performed at 260 ° C. for 1 hour to obtain carrier A1.

The carrier A1 is a spherical particle having a spherical magnetite particle content of 80.4% by mass, an average particle diameter of 30 μm, a specific gravity of 3.05, a magnetization value of 61 Am ² / kg, and a volume resistivity of 3 × 10 ⁹ Ωcm, specific surface area was 0.098 m ² / g.
(Carrier production example 2)
Production Example 1, except that using a carrier core _B, and changes the _{CF 3 CH 2 CH 2 Si (} OCH 3) 3 to _{C 8 F 17 CH 2 CH 2} Si (OCH 3) 3 is as in Preparation Example 1 Carrier B1 was obtained in the same process.

The carrier B1 is a spherical particle having a spherical magnetite particle content of 88.4% by mass, an average particle diameter of 45 μm, a specific gravity of 3.56, a magnetization value of 65 Am ² / kg, and a volume resistivity of 8 × 10 ¹⁰ Ωcm, specific surface area 0.057 m ² / g.
(Carrier production example 3)
In Production Example 1, the same procedure as in Production Example 1 was conducted except that carrier core material C was used and conductive carbon (EC made by Ketjen Black International Co., Ltd.) was dispersed in a ball mill in an amount of 5 wt% based on the resin solid content. Carrier C1 was manufactured in the process.

The carrier C1 is a spherical particle having a spherical magnetite particle content of 92.5% by mass, an average particle diameter of 48 μm, a specific gravity of 3.98, a magnetization value of 69 Am ² / kg, and a volume resistivity of 2 × 10 ⁷ Ωcm, specific surface area was 0.043 m ² / g.
(Carrier Production Example 4)
In Production Example 1, Carrier A2 was produced in the same process as Production Example 1 except that the amount of aminosilane coupling agent added was changed to 30 g.

The carrier A2 is a spherical particle having a spherical magnetite particle content of 80.4% by mass, an average particle diameter of 30 μm, a specific gravity of 3.05, a magnetization value of 61 Am ² / kg, and a volume resistivity of 2 × 10 ¹⁰ Ωcm, specific surface area 0.01 m ² / g.
(Carrier Comparative Example 5)
Except having changed the addition amount of the aminosilane coupling agent into 50g, the core material was manufactured in the process similar to the manufacture example 1, it coated, and carrier a1 was obtained.
(Carrier Comparative Example 6)
100 g of straight silicone (SR-2411 manufactured by Toray Dow Corning Co., Ltd.) as a solid content was weighed as a coating resin and dissolved in 300 cc of a toluene solvent. Coating was performed on the ferrite particles d10 kg by using an immersion drying type coating apparatus and stirring the coating resin solution for 20 minutes. Thereafter, baking was performed at 210 ° C. for 1 hour to obtain a carrier d2. The average particle diameter was 80 μm, the specific gravity was 5.5, the magnetization value was 75 Am ² / kg, the volume resistivity was 2 × 10 ¹² Ωcm, and the specific surface area was 0.024 m ² / g.
(Carrier Comparative Example 7)
100 g of an acrylic modified silicone resin (KR-9706, manufactured by Shin-Etsu Chemical Co., Ltd.) as a solid content was weighed and dissolved in a 300 cc toluene solvent. Coating was performed on the ferrite particles d10 kg by using an immersion drying type coating apparatus and stirring the coating resin solution for 20 minutes. Thereafter, baking was performed at 210 ° C. for 1 hour to obtain a carrier d3. The average particle size was 80 μm, the specific gravity was 5.5, the magnetization value was 75 Am ² / kg, the volume resistivity was 2 × 10 ¹¹ Ωcm, and the specific surface area was 0.022 m ² / g.
(Example 1)
Next, examples of the toner of the present invention will be described, but the present invention is not limited to these examples.
[Creation of resin dispersion]
Table 1 shows the characteristics of the resin used. Mn is a number average molecular weight, Mw is a weight average molecular weight, Mz is a Z average molecular weight, Mp is a molecular weight peak value, Tm (° C.) is a softening point, and Tg (° C.) is a glass transition point. Styrene, n-butyl acrylate, and acrylic acid indicate the amount (g).

(1) Preparation of Resin Particle Dispersion RL1 A monomer liquid composed of 240.1 g of styrene, 59.9 g of n-butyl acrylate, and 4.5 g of acrylic acid was added to 440 g of ion-exchanged water and a nonionic surfactant. (Sanyo Kasei Co., Ltd .: Nonipol 400) 7.5 g, anionic surfactant (Sanyo Kasei Kogyo Co., Ltd .: S20-F, 20% concentration aqueous solution) 22.5 g, dodecanethiol 6 g, carbon tetrabromide 0 g After dispersion, 4.5 g of potassium persulfate was added thereto, and emulsion polymerization was performed at 75 ° C. for 4 hours. Thereafter, aging treatment is further performed at 90 ° C. for 2 hours, and resin particles having Mn of 7200, Mw of 13800, Mz of 20500, Mp of 10800, Tm of 98 ° C., Tg of 52 ° C., and median diameter of 0.14 μm are dispersed. A resin particle dispersion RL1 was prepared. The pH of the resin dispersion at this time was 1.8.
(2) Preparation of Resin Particle Dispersion RL2 A monomer liquid consisting of 230.1 g of styrene, 69.9 g of n-butyl acrylate, and 4.5 g of acrylic acid was added to 440 g of ion-exchanged water and a nonionic surfactant. (Sanyo Kasei Co., Ltd .: Nonipol 400) 7.5 g, anionic surfactant (Sanyo Kasei Kogyo Co., Ltd .: S20-F, 20% concentration aqueous solution) 22.5 g, dodecanethiol 6 g, carbon tetrabromide 0 g After dispersion, 4.5 g of potassium persulfate was added thereto, and emulsion polymerization was performed at 75 ° C. for 4 hours. Thereafter, aging treatment is further performed at 90 ° C. for 5 hours, and resin particles having Mn of 7500, Mw of 17600, Mz of 30100, Mp of 18500, Tm of 106 ° C., Tg of 47 ° C., and median diameter of 0.18 μm are dispersed. A resin particle dispersion RL2 was prepared. The pH of the resin dispersion at this time was 1.9.
(3) Preparation of Resin Particle Dispersion RL3 A monomer liquid composed of 230.1 g of styrene, 69.9 g of n-butyl acrylate, and 4.5 g of acrylic acid was added to 440 g of ion-exchanged water in a nonionic surfactant. (Sanyo Kasei Co., Ltd .: Nonipol 400) 9 g, anionic surfactant (Sanyo Kasei Kogyo Co., Ltd .: S20-F, 20% strength aqueous solution) 15 g, dodecanethiol 1.5 g, carbon tetrabromide 0 g dispersed. Then, 4.5 g of potassium persulfate was added thereto, and emulsion polymerization was performed at 75 ° C. for 4 hours. Thereafter, aging treatment is further performed at 90 ° C. for 4 hours, and resin particles having Mn of 15300, Mw of 51400, Mz of 87400, Mp of 31400, Tm of 126 ° C., Tg of 54 ° C., and median diameter of 0.18 μm are dispersed. A resin particle dispersion RL2 was prepared. The pH of the resin dispersion at this time was 1.8.
(4) Preparation of resin particle dispersion RH1 A monomer liquid consisting of 230.1 g of styrene, 69.9 g of n-butyl acrylate, and 4.5 g of acrylic acid was added to 440 g of ion-exchanged water, and a nonionic surfactant. (Sanyo Kasei Co., Ltd .: Nonipol 400) 4.5 g, anionic surfactant (Sanyo Kasei Kogyo Co., Ltd .: S20-F, 20% strength aqueous solution) 37.5 g, dodecanethiol 1.5 g, carbon tetrabromide 0 g Then, 1.5 g of potassium persulfate was added thereto, and emulsion polymerization was performed at 75 ° C. for 4 hours. Thereafter, aging treatment is further performed at 90 ° C. for 4 hours, and resin particles having Mn of 14300, Mw of 51400, Mz of 189000, Mp of 58000, Tm of 144 ° C., Tg of 58 ° C., and a median diameter of 0.14 μm are dispersed. A resin particle dispersion RH1 was prepared. The pH of the resin dispersion at this time was 2.0.
(5) Preparation of resin particle dispersion RH2 A monomer liquid composed of 176 g of styrene, 64 g of n-butyl acrylate, and 3.6 g of acrylic acid was added to 350 g of ion-exchanged water (Sanyo Kasei Co., Ltd.). Manufactured by Nonipol 400) 2.4 g, anionic surfactant (Sanyo Kasei Kogyo Co., Ltd .: S20-F, 20% strength aqueous solution) 36 g, dodecanethiol 0 g, carbon tetrabromide 0 g was dispersed. 2.4 g of potassium sulfate was added and emulsion polymerization was performed at 80 ° C. for 4 hours. Thereafter, aging treatment is further performed at 90 ° C. for 2 hours, and resin particles having Mn of 23400, Mw of 208500, Mz of 493200, Mp of 89100, Tm of 170 ° C., Tg of 58 ° C., and median diameter of 0.18 μm are dispersed. A resin particle dispersion RH2 was prepared. The pH of the resin dispersion at this time was 1.8.
(6) Preparation of resin particle dispersion rl4 A monomer liquid consisting of 192 g of styrene, 48 g of n-butyl acrylate, and 3.6 g of acrylic acid was added to 350 g of ion-exchanged water (Sanyo Kasei Co., Ltd.). Manufactured by Nonipol 400) 3.6 g, anionic surfactant (Sanyo Kasei Kogyo Co., Ltd .: S20-F, 20% strength aqueous solution) 30 g, dodecanethiol 12 g, carbon tetrabromide 2.4 g, and dispersed. 2.4 g of potassium persulfate was added thereto, and emulsion polymerization was carried out at 70 ° C. for 5 hours. Thereafter, aging treatment is further performed at 80 ° C. for 2 hours, and resin particles having Mn of 4100, Mw of 7600, Mz of 43,000, Mp of 7000, Tm of 89 ° C., Tg of 39 ° C., and median diameter of 0.18 μm are dispersed. A resin particle dispersion rl4 was prepared. At this time, the pH of the resin dispersion was 1.7.
(7) Preparation of resin particle dispersion rl5 A monomer liquid consisting of 230.1 g of styrene, 69.9 g of n-butyl acrylate, and 4.5 g of acrylic acid was added to 440 g of ion-exchanged water, and a nonionic surfactant. (Sanyo Kasei Co., Ltd .: Nonipol 400) 4.5 g, anionic surfactant (Sanyo Kasei Kogyo Co., Ltd .: S20-F, 20% strength aqueous solution) 37.5 g, dodecanethiol 1.5 g, carbon tetrabromide 0 g Then, 1.5 g of potassium persulfate is added thereto, emulsion polymerization is performed at 75 ° C. for 5 hours, and then aging treatment is further performed at 80 ° C. for 2 hours. Mn is 8900, Mw is 61200, Mz is 108400. A resin particle dispersion rl5 was prepared in which resin particles having a Mp of 52800, a Tm of 142 ° C., a Tg of 57 ° C., and a median diameter of 0.16 μm were dispersed. The pH of the resin dispersion at this time was 1.8.
(8) Preparation of resin particle dispersion rh3 A monomer liquid composed of 204 g of styrene, 36 g of n-butyl acrylate, and 3.6 g of acrylic acid was placed in 350 g of ion-exchanged water (Sanyo Kasei Co., Ltd.). Dispersed using 7.2 g of nonipol 400), 12 g of an anionic surfactant (manufactured by Sanyo Kasei Kogyo Co., Ltd .: S20-F, 20% strength aqueous solution), 12 g of dodecanethiol, and 2.4 g of carbon tetrabromide. To this, 2.4 g of potassium persulfate was added, and emulsion polymerization was performed at 75 ° C. for 5 hours. Thereafter, aging treatment is further performed at 80 ° C. for 2 hours, and resin particles having Mn of 2600, Mw of 28300, Mz of 96200, Mp of 2700, Tm of 135 ° C., Tg of 43 ° C., and median diameter of 0.18 μm are dispersed. A resin particle dispersion rh3 was prepared. The pH of the resin dispersion at this time was 2.0.
(9) Preparation of resin particle dispersion rh4 A monomer liquid consisting of 204 g of styrene, 36 g of n-butyl acrylate, and 2.4 g of acrylic acid was added to 350 g of ion-exchanged water (Sanyo Kasei Co., Ltd.). Manufactured by Nonipol 400) 6 g, anionic surfactant (manufactured by Sanyo Chemical Industries, Ltd .: S20-F, 20% strength aqueous solution) 18 g, dodecanethiol 0 g, carbon tetrabromide 0 g, and potassium persulfate 2.4 g is added, emulsion polymerization is performed at 80 ° C. for 5 hours, and then aging treatment is further performed at 90 ° C. for 2 hours. Mn is 18600, Mw is 238700, Mz is 529000, Mp is 163600, Tm is 182 ° C. A resin particle dispersion rh4 in which resin particles having a Tg of 67 ° C. and a median diameter of 0.16 μm are dispersed was prepared. The pH of the resin dispersion at this time was 2.1.
(Example 2)
[Creation of pigment dispersion]
Table 2 shows the pigments used.

(1) Preparation of Colorant Particle Dispersion Liquid PM1 20 g of magenta pigment (Clariant's PERMANENT RUINE F6B), 2 g of nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd .: Elminol NA400), and 78 g of ion-exchanged water were mixed. Dispersion was carried out for 20 minutes at an oscillation frequency of 30 kHz using a sonic disperser to prepare a colorant particle dispersion PM1 in which colorant particles having a median diameter of 0.12 μm were dispersed.
(2) Preparation of Colorant Particle Dispersion PC1 20 g of cyan pigment (KETBLUE111 manufactured by Dainippon Ink & Chemicals), 2 g of nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd .: Erminol NA400), and 78 g of ion-exchanged water are mixed. Dispersion was performed for 20 minutes at an oscillation frequency of 30 kHz using a sonic disperser to prepare a colorant particle dispersion PC1 in which colorant particles having a median diameter of 0.12 μm were dispersed.
(3) Preparation of colorant particle dispersion PY1 20 g of yellow pigment (PY74 manufactured by Sanyo Dye), 2 g of nonionic surfactant (manufactured by Sanyo Kasei Co., Ltd .: Erminol NA400), and 78 g of ion-exchanged water are mixed and ultrasonically mixed. Using a disperser, dispersion was performed at an oscillation frequency of 30 kHz for 20 minutes to prepare a colorant particle dispersion PY1 in which colorant particles having a median diameter of 0.12 μm were dispersed.
(4) Preparation of Colorant Particle Dispersion PB1 20 g of black pigment (MA100S manufactured by Mitsubishi Chemical Corporation), 2 g of nonionic surfactant (manufactured by Sanyo Kasei Co., Ltd .: Erminol NA400), and 78 g of ion-exchanged water are mixed and ultrasonically mixed. Using a disperser, dispersion was performed at an oscillation frequency of 30 kHz for 20 minutes to prepare a colorant particle dispersion PB1 in which colorant particles having a median diameter of 0.12 μm were dispersed.
Example 3
[Creation of wax dispersion]
(Table 3), (Table 4), (Table 5), and (Table 6) show the wax used and the properties of the wax. Tmw (° C.) represents the melting point, and Ck (wt%) represents the loss on heating. In the cumulative volume particle size distribution from the small particle size side, PR16 indicates a 16% diameter, PR50 indicates a 50% diameter, and PR84 indicates an 84% diameter. Numerical values in parentheses in (Table 6) indicate the blending ratio of the wax.

(1) Preparation of Wax Particle Dispersion WA1 FIG. 3 is a schematic view of a stirring and dispersing apparatus, and FIG. 4 is a view seen from above. Reference numeral 801 denotes an outer tank, in which cooling water is injected from 808 and discharged from 807. Reference numeral 802 denotes a dam plate that stops the liquid to be processed, and a hole is formed in the central portion. Reference numeral 803 denotes a rotating body that rotates at a high speed and is fixed to the shaft 806 and can rotate at a high speed. A hole of about 1 to 5 mm is formed on the side surface of the rotating body, and the liquid to be processed can be moved. The tank is 120 ml, and about half of the liquid to be treated is charged. The speed MAX of the rotating body can be up to 50 m / s. The diameter of the rotating body is 52 mm, and the inner diameter of the tank is 56 mm. Reference numeral 804 denotes a raw material inlet for continuous processing. Sealed during high-pressure processing or batch processing.

In a state of normal pressure in the tank, 67 g of ion-exchanged water, 2 g of a nonionic surfactant (manufactured by Sanyo Kasei Co., Ltd .: Elminol NA400), 1 g of nonionic surfactant (New Coal 565C, manufactured by Nippon Emulsifier Co., Ltd.) The wax (W-1) 5 g and the second wax (W-11) 25 g were charged, the speed of the rotating body was 30 m / s for 5 min, and then the rotation speed was increased to 50 m / s for 2 min. A wax particle dispersion WA1 was formed.
(2) Preparation of Wax Particle Dispersion WA2 67 g of ion-exchanged water and a nonionic surfactant (manufactured by Sanyo Kasei Co., Ltd.) under the same conditions as (1) except that the inside of the tank was pressurized to 0.4 MPa. : Erminol NA400) 3 g, first wax (W-2) 10 g and second wax (W-12) 20 g were charged, the speed of the rotating body was 30 m / s for 3 min, and then the rotating speed was 50 m / s. And treated for 2 minutes to form a wax particle dispersion WA2.
(3) Preparation of Wax Particle Dispersion WA3 67 g of ion-exchanged water and nonionic surfactant (Newcol manufactured by Nippon Emulsifier Co., Ltd.) were used under the same conditions as in (1) except that the tank was pressurized to 0.4 MPa. 565C) 2.5 g, anionic surfactant (SCF manufactured by Sanyo Chemical Industries, Ltd.) 0.5 g, 15 g of the first wax (W-3) and 15 g of the second wax (W-13), The speed was increased at 20 m / s for 3 minutes, and then the rotational speed was increased to 45 m / s, followed by treatment for 2 minutes, whereby a wax particle dispersion WA3 was formed.
(4) Preparation of wax particle dispersion WA4
Under the same conditions as (1), 67 g of ion-exchanged water, 3 g of nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd .: Elminol NA400), 10 g of the first wax (W-4) and the second wax (W -11) 20 g was charged, the speed of the rotating body was 3 m at 30 m / s, and then the rotating speed was increased to 50 m / s, followed by 2 min treatment to form a wax particle dispersion WA4.
(5) Preparation of Wax Particle Dispersion WA5 FIG. 5 is a schematic view of a stirring and dispersing apparatus, and FIG. 6 is a top view. Reference numeral 850 denotes a raw material inlet, and reference numeral 852 denotes a fixed body having a floating structure. A narrow gap of about 1 μm to 10 μm is formed by the pressing force of the spring 851 and the pushing force of the rotating body 853 and the high speed rotating force. Reference numeral 854 denotes a shaft connected to a motor (not shown). The raw material charged from 850 receives a strong shearing force between the gap between the stationary body and the rotating body, and is dispersed into fine particles in the liquid. The processed raw material liquid is discharged from 856. FIG. 6 shows a view from above. The discharged raw material liquid 855 is blown radially and collected in a sealed container. The outer diameter of the rotating body is 100 mm.

  The raw material liquid is pre-dispersed with a wax and a surfactant in an aqueous medium that has been preliminarily heated under pressure, and is added through an inlet 850 and instantly refined. The supply amount was 1 kg / h, and the rotating body was rotated at a maximum speed of 100 m / s.

Charged with 67 g of ion-exchanged water, 3 g of nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd .: Elminol NA400), 6 g of the first wax (W-5) and 24 g of the second wax (W-12) and rotated. The body speed was 100 m / s and the supply rate was 1 kg / h, and a wax particle dispersion WA5 was formed.
(6) Preparation of wax particle dispersion WA6
Under the same conditions as in (1), 67 g of ion-exchanged water, 3 g of a nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd .: Elminol NA400), 5 g of the first wax (W-6) and the second wax (W -11) 25 g were charged, and the speed of the rotating body was 3 minutes at 20 m / s, and then the rotational speed was increased to 50 m / s, followed by treatment for 2 minutes to form a wax particle dispersion WA6.
(7) Preparation of wax particle dispersion WA7 67 g of ion-exchanged water and a nonionic surfactant (manufactured by Sanyo Kasei Co., Ltd.) under the same conditions as in (1) except that the inside of the tank was pressurized to 0.4 MPa. : 3 g of Erminol NA400), 7.5 g of the first wax (W-7) and 22.5 g of the second wax (W-12) were charged, the speed of the rotating body was 3 min at 20 m / s, and then the rotating speed Was increased to 50 m / s and treated for 2 min to form a wax particle dispersion WA7.
(8) Preparation of wax particle dispersion WA8
Under the same conditions as in (5), 67 g of ion-exchanged water, 3 g of a nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd .: Elminol NA400), 15 g of the first wax (W-8) and the second wax (W -13) 15 g was charged, the speed of the rotating body was 100 m / s, and the supply rate was 1 kg / h, and a wax particle dispersion WA8 was formed.
(9) Preparation of wax particle dispersion WA9
Under the same conditions as in (1), 67 g of ion-exchanged water, 3 g of a nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd .: Elminol NA400), 15 g of the first wax (W-9) and the second wax (W -11) 15 g were charged, the speed of the rotating body was 3 minutes at 20 m / s, and then the rotational speed was increased to 50 m / s, followed by treatment for 2 minutes to form a wax particle dispersion WA9.
(10) Preparation of wax particle dispersion WA10 67 g of ion-exchanged water and nonionic surfactant (manufactured by Sanyo Kasei Co., Ltd.) under the same conditions as (1) except that the inside of the tank was pressurized to 0.4 MPa. : Elginol NA400) 3 g, first wax (W-10) 10 g and second wax (W-12) 20 g were charged, the speed of the rotating body was 30 m / s for 3 min, and then the rotating speed was 50 m / s. And treated for 2 minutes to form a wax particle dispersion WA10.
(11) Preparation of wax particle dispersion WA11
Under the same conditions as in (1), 67 g of ion-exchanged water, 3 g of a nonionic surfactant (manufactured by Sanyo Kasei Co., Ltd .: Elminol NA400) and 30 g of wax (W-1) were charged, and the speed of the rotating body was 30 m / Then, the rotation speed was increased to 50 m / s for 3 minutes, and the treatment was performed for 2 minutes to form a wax particle dispersion WA11.
(12) Preparation of wax particle dispersion WA12
Under the same conditions as in (1), 67 g of ion-exchanged water, 2.5 g of nonionic surfactant (New Coal 565C manufactured by Nippon Emulsifier Co., Ltd.), 0.5 g of anionic surfactant (SCF manufactured by Sanyo Chemical Industries Co., Ltd.), wax ( W-2) 30 g was charged, the speed of the rotating body was 3 minutes at 20 m / s, and then the rotational speed was increased to 45 m / s, followed by treatment for 2 minutes to form a wax particle dispersion WA12.
(13) Preparation of wax particle dispersion WA13
Under the same conditions as in (1), 67 g of ion-exchanged water, 3 g of a nonionic surfactant (manufactured by Sanyo Kasei Co., Ltd .: Elminol NA400) and 30 g of wax (W-6) were charged, and the speed of the rotating body was 30 m / Then, the rotation speed was increased to 50 m / s for 3 minutes, and the treatment was performed for 2 minutes, whereby a wax particle dispersion WA13 was formed.
(14) Preparation of wax particle dispersion WA14
Under the same conditions as in (5), 67 g of ion-exchanged water, 3 g of a nonionic surfactant (manufactured by Sanyo Kasei Co., Ltd .: Elminol NA400) and 30 g of wax (W-7) were charged, and the speed of the rotating body was 100 m / s, the supply rate was 1 kg / h, and a wax particle dispersion WA14 was formed.
(15) Preparation of wax particle dispersion WA15
Under the same conditions as in (1), 67 g of ion-exchanged water, 3 g of a nonionic surfactant (manufactured by Sanyo Kasei Co., Ltd .: Elminol NA400) and 30 g of wax (W-11) were charged, and the speed of the rotating body was 20 m / Then, the rotation speed was increased to 50 m / s for 3 minutes, and the treatment was performed for 2 minutes to form a wax particle dispersion WA15.
(16) Preparation of Wax Particle Dispersion WA16 67 g of ion-exchanged water and nonionic surfactant (manufactured by Sanyo Kasei Co., Ltd.) under the same conditions as (1) except that the inside of the tank was pressurized to 0.4 MPa. : 3 g of Erminol NA400) and 30 g of wax (W-12) were charged, the speed of the rotating body was 3 min at 20 m / s, and then the rotating speed was increased to 50 m / s, followed by 2 min processing to form a wax particle dispersion WA16. It was.
(17) Preparation of wax particle dispersion WA17 67 g of ion-exchanged water and nonionic surfactant (manufactured by Sanyo Kasei Co., Ltd.) under the same conditions as in (1) except that the inside of the tank was pressurized to 0.4 MPa. : 3 g of Erminol NA400) and 30 g of wax (W-13) were charged, the rotating body was processed at a speed of 100 m / s, and the supply rate was 1 kg / h, and a wax particle dispersion WA17 was formed.
Example 4
[Create toner base]
The composition of the produced toner is shown in (Table 7). d50 (μm) represents the volume average particle diameter of the toner base particles.

(1) Preparation of toner base M1 In a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter, 2000 ml, 204 g of the first resin particle dispersion RL1, 45 g of the colorant particle dispersion PM1, wax 85 g of the dispersion WA1 was added, 500 ml of ion-exchanged water was added, and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T25) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 2.7.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11.8, and then 317 g of a 23% strength magnesium sulfate aqueous solution was added and stirred for 10 min. Thereafter, the temperature was raised from 20 ° C. to 90 ° C. at a rate of 1 ° C./min, followed by heat treatment for 3 hours to obtain core particles. The obtained core particle dispersion had a pH of 9.2.

  Thereafter, with the water temperature kept at 90 ° C., 165 g of the second resin particle dispersion RH1 having a pH adjusted to 8.5 was added at a dropping rate of 5 g / min. Heat treatment was performed for 1.5 hours to obtain particles in which the second resin particles were fused.

  After cooling, the product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid drier to obtain a toner base M1 having a volume average particle size of 4.1 μm and a coefficient of variation of 18.7.

  At this time, when the pH of the second resin particle dispersion to be dropped was adjusted to 9.7, the core particles were agglomerated with each other, and the generated particles were coarsened to a volume average particle size of 12 μm or more. .

  Conversely, when the second resin particle dispersion is dropped while maintaining the pH without adjusting the pH, the second resin particles do not adhere to the core particles at all, and only the second resin particles are aggregated to produce a volume. The coefficient of variation was 40 or more and the particle size distribution was quite broad, and the dispersion remained cloudy.

  Further, when the pH of the second resin particle dispersion is adjusted to 3.2 and the second resin particle dispersion is added dropwise, the adhesion of the second resin particles to the core particles does not easily proceed, and the core particles It took time to fuse the second resin particles to 5 hours or more. The volume variation coefficient at that time was 32, which was a fairly broad particle size distribution.

  In addition, when the pH of the mixed dispersion obtained by adding 500 ml of ion exchange water to the first resin particle dispersion, the colorant particle dispersion, and the wax dispersion WA is lower than 9.5, the formation is performed. The formed core particles were coarsened, and the volume average particle size was coarsened to a size of 15 μm or more. When the pH was 12.5, the amount of free wax increased, making it difficult to encapsulate the wax uniformly. The dispersion remained cloudy.

If the pH of the liquid when the core particles are formed is higher than 9.5, aggregation is poor and free wax and free colorant particles increase in an aqueous system that does not participate in aggregation.
(2) Preparation of toner base M2 In a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter, 2000 ml, 204 g of the first resin particle dispersion RL1, 45 g of the colorant particle dispersion PM1, and wax 80 g of the dispersion liquid WA2 was added, 500 ml of ion-exchanged water was added, and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T25) to prepare a mixed particle dispersion liquid. The pH of the obtained mixed dispersion was 1.8.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 9.7, and 312 g of a 23% strength magnesium sulfate aqueous solution was added thereto, followed by stirring for 10 minutes. Thereafter, the temperature was raised from 20 ° C. to 90 ° C. at a rate of 1 ° C./min, followed by heat treatment for 3 hours to obtain core particles. The obtained core particle dispersion had a pH of 7.2.

  Thereafter, with the water temperature kept at 90 ° C., 165 g of the second resin particle dispersion RH1 adjusted to pH 6.8 was added at a dropping rate of 5 g / min. Heat treatment was performed for 1.5 hours to obtain particles in which the second resin particles were fused.

Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid-type dryer, resulting in a volume average particle size of 6.8 μm and a coefficient of variation of 21.1. Toner base M2 was obtained.
(3) Preparation of toner base M3 In a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter, 2000 ml, 204 g of the first resin particle dispersion RL1, 31 g of the colorant particle dispersion PM1, and wax 40 g of the dispersion WA3 was added, 330 ml of ion-exchanged water was added, and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T25) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 3.2.
Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11, and then 261 g of a 23% strength magnesium sulfate aqueous solution was added, followed by stirring for 10 minutes. Thereafter, the temperature was raised from 20 ° C. to 90 ° C. at a rate of 1 ° C./min, followed by heat treatment for 3 hours to obtain core particles. The obtained core particle dispersion had a pH of 8.4.

  Thereafter, 50 g of the second resin particle dispersion RH2 whose pH was adjusted to 7.9 was added at a dropping rate of 1 g / min while the water temperature was kept at 90 ° C., and the condition was 95 ° C. after completion of the dropping. Heat treatment was performed for 2 hours to obtain particles in which the second resin particles were fused.

Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. The toner base thus obtained was dried at 40 ° C. for 6 hours with a fluid dryer, and the volume average particle diameter was 4.6 μm and the coefficient of variation was 17.1. A toner base M3 was obtained.
(4) Preparation of toner base M4 A 2000 ml four-necked flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter was charged with 204 g of the first resin particle dispersion RL1 and 31 g of the colorant particle dispersion PM1 and wax. 40 g of dispersion WA4 was added, 330 ml of ion-exchanged water was added, and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T25) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 3.8.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11.9, and then 261 g of a 23% strength magnesium sulfate aqueous solution was added and stirred for 10 min. Thereafter, the temperature was raised from 20 ° C. to 90 ° C. at a rate of 1 ° C./min, followed by heat treatment for 3 hours to obtain core particles. The obtained core particle dispersion had a pH of 9.3.

  Thereafter, 50 g of the second resin particle dispersion RH2 having a pH adjusted to 6.0 was added at a dropping rate of 1 g / min while the water temperature was kept at 90 ° C., and the condition was 95 ° C. after completion of the dropping. Heat treatment was performed for 2 hours to obtain particles in which the second resin particles were fused.

Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours with a fluid dryer to obtain a toner base M4 having a volume average particle size of 3.9 μm and a coefficient of variation of 18.2.
(5) Preparation of toner base M5 In a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod and a pH meter, 2000 ml, 204 g of the first resin particle dispersion RL2 and 42 g of the colorant particle dispersion PM1 are waxed. 90 g of particle dispersion WA5 was added, 500 ml of ion-exchanged water was added, and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T50) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 2.2.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 9.7, and then 319 g of a 23% strength magnesium sulfate aqueous solution was added, followed by stirring for 10 minutes. Thereafter, the temperature was raised from 20 ° C. to 90 ° C. at a rate of 1 ° C./min, followed by heat treatment for 3 hours to obtain core particles. The resulting core particle dispersion had a pH of 7.

  Thereafter, 145 g of the second resin particle dispersion RH1 adjusted to pH 5 was added at a dropping rate of 10 g / min while maintaining the water temperature at 90 ° C. Heat treatment was performed for 5 hours to obtain particles in which the second resin particles were fused.

Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid drier to obtain a toner base M5 having a volume average particle diameter of 6.7 μm and a coefficient of variation of 15.8.
(6) Preparation of toner matrix M6 In a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter, 2000 ml, 204 g of the first resin particle dispersion RL2, 42 g of the colorant particle dispersion PM1, and wax 50 g of particle dispersion WA6 was added, 450 ml of ion-exchanged water was added, and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T50) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 3.8.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11.8, and then 281 g of a 23% strength magnesium sulfate aqueous solution was added and stirred for 10 minutes. Thereafter, the temperature was raised from 20 ° C. to 90 ° C. at a rate of 1 ° C./min, followed by heat treatment for 3 hours to obtain core particles. The obtained core particle dispersion had a pH of 9.2.

  Thereafter, 145 g of the second resin particle dispersion RH1 adjusted to pH 5 was added at a dropping rate of 5 g / min while maintaining the water temperature at 90 ° C. Heat treatment was performed for 5 hours to obtain particles in which the second resin particles were fused.

Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid drier to obtain a toner base M6 having a volume average particle size of 4.2 μm and a coefficient of variation of 18.9.
(7) Preparation of toner base M7 In a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter, 2000 ml, 204 g of the first resin particle dispersion RL2, 32 g of the colorant particle dispersion PM1, and wax 60 g of particle dispersion WA7 was added, 360 ml of ion-exchanged water was added, and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T25) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 1.8.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 9.7, and then 281 g of a 23% strength magnesium sulfate aqueous solution was added and stirred for 10 min. Thereafter, the temperature was raised from 20 ° C. to 90 ° C. at a rate of 1 ° C./min, followed by heat treatment for 3 hours to obtain core particles. The obtained core particle dispersion had a pH of 7.2.

  Thereafter, 60 g of the second resin particle dispersion RH2 having a pH adjusted to 4.5 was added at a dropping rate of 10 g / min with the water temperature kept at 90 ° C., and the condition was 95 ° C. after completion of the dropping. Heat treatment was performed for 2 hours to obtain particles in which the second resin particles were fused.

Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours with a fluid dryer to obtain a toner base M7 having a volume average particle size of 5.9 μm and a coefficient of variation of 19.1.
(8) Preparation of toner base M8 In a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter, 2000 ml, 204 g of the first resin particle dispersion RL2, 32 g of the colorant particle dispersion PM1, and wax 40 g of particle dispersion WA8 and 350 ml of ion-exchanged water were added and mixed for 10 min using a homogenizer (manufactured by IKA: Ultra Turrax T25) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 2.1.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11.2, and then 262 g of a 23% strength magnesium sulfate aqueous solution was added and stirred for 10 minutes. Thereafter, the temperature was raised from 20 ° C. to 90 ° C. at a rate of 1 ° C./min, followed by heat treatment for 3 hours to obtain core particles. The obtained core particle dispersion had a pH of 8.5.

  Thereafter, 60 g of the second resin particle dispersion RH2 adjusted to pH 8 with the water temperature kept at 90 ° C. was added at a dropping rate of 1 g / min, and after completion of the dropping, the condition was 95 ° C. for 2 hours. Heat treatment was performed to obtain particles in which the second resin particles were fused.

Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid drier to obtain a toner base M8 having a volume average particle diameter of 5 μm and a coefficient of variation of 16.2.
(9) Preparation of toner base M9 In a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter, 2000 ml, 204 g of the first resin particle dispersion RL3, 45 g of the colorant particle dispersion PM1, and wax 90 g of particle dispersion WA9 was added, 500 ml of ion-exchanged water was added, and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T50) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 2.8.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11.9, and then 322 g of a 23% strength magnesium sulfate aqueous solution was added and stirred for 10 min. Thereafter, the temperature was raised from 20 ° C. to 90 ° C. at a rate of 1 ° C./min, followed by heat treatment for 3 hours to obtain core particles. The obtained core particle dispersion had a pH of 9.3.

  Thereafter, with the water temperature kept at 90 ° C., 165 g of the second resin particle dispersion RH1 adjusted to pH 6 was added at a dropping rate of 5 g / min. Heat treatment was performed for 5 hours to obtain particles in which the second resin particles were fused.

Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid drier to obtain a toner base M9 having a volume average particle size of 4.1 μm and a coefficient of variation of 18.6.
(10) Preparation of toner base M10 In a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod and a pH meter, 2000 ml, 204 g of the first resin particle dispersion RL3, 32 g of the colorant particle dispersion PM1, and wax 40 g of particle dispersion WA10 was added, 350 ml of ion-exchanged water was added, and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T50) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 1.9.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 9.7, and then 262 g of a 23% strength magnesium sulfate aqueous solution was added, followed by stirring for 10 minutes. Thereafter, the temperature was raised from 20 ° C. to 90 ° C. at a rate of 1 ° C./min, followed by heat treatment for 3 hours to obtain core particles. The resulting core particle dispersion had a pH of 7.

  Thereafter, 60 g of the second resin particle dispersion RH2 having a pH adjusted to 4 was added at a dropping rate of 5 g / min while maintaining the water temperature at 90 ° C., and after completion of dropping, the condition was maintained at 95 ° C. for 2 hours. Heat treatment was performed to obtain particles in which the second resin particles were fused.

Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid drier to obtain a toner base M10 having a volume average particle size of 6.7 μm and a coefficient of variation of 20.7.
(11) Preparation of toner base M11 In a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter, 2000 ml, 204 g of the first resin particle dispersion RL2 and 45 g of the colorant particle dispersion PM1 are waxed. 50 g of the dispersion WA11 was added, 450 ml of ion-exchanged water was added, and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T25) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 2.5.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11.8, and then 284 g of a 23% strength magnesium sulfate aqueous solution was added and stirred for 10 minutes. Thereafter, the temperature was raised from 20 ° C. to 90 ° C. at a rate of 1 ° C./min, followed by heat treatment for 3 hours to obtain core particles. The obtained core particle dispersion had a pH of 9.2.

  Thereafter, with the water temperature kept at 90 ° C., 165 g of the second resin particle dispersion RH2 whose pH was adjusted to 8.8 was added at a dropping rate of 5 g / min. Heat treatment was performed for 1.5 hours to obtain particles in which the second resin particles were fused.

  After cooling, the product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid drier to obtain a toner base M11 having a volume average particle size of 4.1 μm and a coefficient of variation of 18.6.

  At this time, when the pH of the second resin particle dispersion to be dropped was adjusted to 9.7, the core particles were agglomerated and the generated particles were coarsened to a volume average particle size of 14 μm or more.

  Conversely, when the second resin particle dispersion is dropped while maintaining the pH without adjusting the pH, the second resin particles do not adhere to the core particles at all, and only the second resin particles are aggregated to produce a volume. The coefficient of variation was 43 or more and the particle size distribution was quite broad, and the dispersion remained cloudy.

  Further, when the pH of the second resin particle dispersion is adjusted to 3.4 and the second resin particle dispersion is dropped, the adhesion of the second resin particles to the core particles does not easily proceed, and the core particles It took time to fuse the second resin particles to the substrate, and it took more than 6 hours. The volume variation coefficient at that time was 35 and the particle size distribution was quite broad.

  When the pH of the mixed dispersion obtained by adding 500 ml of ion exchange water to the first resin particle dispersion, the colorant particle dispersion, and the wax dispersion WA is lower than 9.5 The formed core particles were coarsened and the volume average particle size was coarsened to a size of 16 μm or more. When the pH was 12.5, the amount of free wax increased, making it difficult to encapsulate the wax uniformly. The dispersion remained cloudy.

When the pH of the liquid when the core particles were formed was higher than 9.5, aggregation was poor and free wax and free colorant particles increased in an aqueous system that did not participate in aggregation.
(12) Preparation of toner base M12 A 2000 ml four-necked flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter is charged with 204 g of the first resin particle dispersion RL2 and 45 g of the colorant particle dispersion PM1 and wax. 50 g of the dispersion WA12 was added, 450 ml of ion-exchanged water was added, and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T25) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 1.8.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 9.7, and then 284 g of a 23% strength magnesium sulfate aqueous solution was added, followed by stirring for 10 minutes. Thereafter, the temperature was raised from 20 ° C. to 90 ° C. at a rate of 1 ° C./min, followed by heat treatment for 3 hours to obtain core particles. The obtained core particle dispersion had a pH of 7.2.

  Thereafter, with the water temperature kept at 90 ° C., 165 g of the second resin particle dispersion RH2 adjusted to pH 4 was added at a dropping rate of 5 g / min. Heat treatment was performed for 5 hours to obtain particles in which the second resin particles were fused.

Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid dryer, and the volume average particle diameter was 5.8 μm and the coefficient of variation was 17.1. Toner base M12 was obtained.
(13) Preparation of toner base M13 In a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter, 2000 ml, 204 g of the first resin particle dispersion RL2, 37 g of the colorant particle dispersion PM1, and wax 85 g of the dispersion WA3 was added, 400 ml of ion-exchanged water was added, and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T25) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 2.8.
Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11, and then 310 g of a 23% strength magnesium sulfate aqueous solution was added and stirred for 10 min. Thereafter, the temperature was raised from 20 ° C. to 90 ° C. at a rate of 1 ° C./min, followed by heat treatment for 3 hours to obtain core particles. The obtained core particle dispersion had a pH of 8.4.

  Thereafter, 100 g of the second resin particle dispersion RH2 whose pH was adjusted to 8.0 with the water temperature kept at 90 ° C. was added at a dropping rate of 5 g / min. Heat treatment was performed for 1.5 hours to obtain particles in which the second resin particles were fused.

Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid drier, resulting in a volume average particle size of 5.4 μm and a coefficient of variation of 19.8. Toner base M13 was obtained.
(14) Preparation of toner base M14 In a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter, 2000 ml, 204 g of the first resin particle dispersion RL2, 37 g of the colorant particle dispersion PM1, and wax 85 g of the dispersion WA14 was added, 400 ml of ion-exchanged water was added, and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T25) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 2.8.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11.9, and then 310 g of a 23% strength magnesium sulfate aqueous solution was added and stirred for 10 min. Thereafter, the temperature was raised from 20 ° C. to 90 ° C. at a rate of 1 ° C./min, followed by heat treatment for 3 hours to obtain core particles. The obtained core particle dispersion had a pH of 9.3.

  Thereafter, 100 g of the second resin particle dispersion RH2 having a pH adjusted to 9.1 was added at a dropping rate of 1 g / min while the water temperature was kept at 90 ° C. Heat treatment was performed for 1.5 hours to obtain particles in which the second resin particles were fused.

Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid drier to obtain a toner base M14 having a volume average particle size of 3.8 μm and a coefficient of variation of 21.8.
(15) Preparation of toner matrix M15 In a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod and a pH meter, 2000 ml, 204 g of the first resin particle dispersion RL1, 42 g of the colorant particle dispersion PM1, and wax 65 g of particle dispersion WA15 was added, 450 ml of ion-exchanged water was added, and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T50) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 2.2.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 9.7, and then 295 g of a 23% strength magnesium sulfate aqueous solution was added, followed by stirring for 10 minutes. Thereafter, the temperature was raised from 20 ° C. to 90 ° C. at a rate of 1 ° C./min, followed by heat treatment for 3 hours to obtain core particles. The resulting core particle dispersion had a pH of 7.

  Thereafter, 145 g of a second resin particle dispersion RH1 having a pH adjusted to 3.8 was added at a dropping rate of 10 g / min while the water temperature was kept at 90 ° C., and the condition was 95 ° C. after completion of the dropping. Heat treatment was performed for 2 hours to obtain particles in which the second resin particles were fused.

Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid drier to obtain a toner base M15 having a volume average particle size of 6.4 μm and a coefficient of variation of 18.8.
(16) Preparation of toner base M16 In a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod and a pH meter, 2000 ml, 204 g of the first resin particle dispersion RL1, 42 g of the colorant particle dispersion PM1, and wax 65 g of particle dispersion WA16 was added, 450 ml of ion-exchanged water was added, and mixed for 10 min using a homogenizer (manufactured by IKA: Ultra Turrax T50) to prepare a mixed particle dispersion. The resulting mixed dispersion had a pH of 2.3.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11.8, and then 295 g of a 23% strength magnesium sulfate aqueous solution was added and stirred for 10 min. Thereafter, the temperature was raised from 20 ° C. to 90 ° C. at a rate of 1 ° C./min, followed by heat treatment for 3 hours to obtain core particles. The obtained core particle dispersion had a pH of 9.2.

  Thereafter, 145 g of the second resin particle dispersion RH1 adjusted to pH 5 with the water temperature kept at 90 ° C. was added at a dropping rate of 5 g / min, and after completion of the dropping, the condition was 95 ° C. for 2 hours. Heat treatment was performed to obtain particles in which the second resin particles were fused.

Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid drier to obtain a toner base M16 having a volume average particle size of 4.2 μm and a coefficient of variation of 16.2.
(17) Preparation of toner base M17 In a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter, 2000 ml, 204 g of the first resin particle dispersion RL1, 42 g of the colorant particle dispersion PM1, and wax 65 g of particle dispersion WA17 was added, 450 ml of ion exchange water was added, and mixed for 10 min using a homogenizer (manufactured by IKA: Ultra Turrax T25) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 1.8.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 9.7, and then 295 g of a 23% strength magnesium sulfate aqueous solution was added, followed by stirring for 10 minutes. Thereafter, the temperature was raised from 20 ° C. to 90 ° C. at a rate of 1 ° C./min, followed by heat treatment for 3 hours to obtain core particles. The obtained core particle dispersion had a pH of 7.2.

  Thereafter, 145 g of the second resin particle dispersion RH1 having a pH adjusted to 4 was added at a dropping rate of 10 g / min while maintaining the water temperature at 90 ° C., and after completion of dropping, the condition was 95 ° C. for 2 hours. Heat treatment was performed to obtain particles in which the second resin particles were fused.

Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid drier to obtain a toner base M17 having a volume average particle diameter of 6.8 μm and a coefficient of variation of 16.0.
Table 8 shows the external additives used in this example. The amount of charge was measured by the blow-off method of frictional charging with an uncoated ferrite carrier. In an environment of 25 ° C. and 45 RH%, 50 g of carrier and 0.1 g of silica or the like are mixed in a 100 ml polyethylene container, stirred for 5 minutes and 30 minutes at a speed of 100 min ⁻¹ by longitudinal rotation, and 0.3 g is collected. Then, nitrogen gas was blown for 1 minute with 1.96 × 10 ⁴ (Pa).

  For negative chargeability, the 5-minute value is preferably −100 to −800 μC / g, and the 30-minute value is preferably −50 to −600 μC / g. Highly charged silica can function with a small amount of addition.

  Table 9 shows the toner material composition used in this example. Other black toner, cyan toner, and yellow toner used PB1, PC1, and PY1 as pigments, and other compositions were the same as the magenta toner composition.

The external additive indicates a blending amount (parts by weight) with respect to 100 parts by weight of the toner base. In the external addition process (Henschel mixer FM20B, manufactured by Mitsui Mining Co., Ltd.), stirring blade Z0S0 type, rotation speed 2000 min ⁻¹ , treatment time 5 min, and input amount 1 kg were performed.

  FIG. 1 is a cross-sectional view showing a configuration of an image forming apparatus for forming a full-color image used in this embodiment. In FIG. 1, the outer casing of the color electrophotographic printer is omitted. The transfer belt unit 17 includes a transfer belt 12, a first color (yellow) transfer roller 10Y made of an elastic body, a second color (magenta) transfer roller 10M, a third color (cyan) transfer roller 10C, and a fourth color (black). Transfer roller 10K, drive roller 11 made of aluminum roller, second transfer roller 14 made of elastic body, second transfer driven roller 13, belt cleaner blade 16 for cleaning the toner image remaining on the transfer belt 12, and opposed to the cleaner blade A roller 15 is provided at a position to be used. At this time, the distance from the first color (Y) transfer position to the second color (M) transfer position is 70 mm (second color (M) transfer position to third color (C) transfer position, third color (C). The fourth color (K) transfer position is the same distance from the transfer position), and the peripheral speed of the photoconductor is 125 mm / s.

The transfer belt 12 is used by kneading a conductive filler in an insulating polycarbonate resin and forming a film with an extruder. In the present example, a film obtained by adding 5 parts by weight of conductive carbon (for example, ketjen black) to 95 parts by weight of polycarbonate resin (for example, Iupilon Z300, manufactured by Mitsubishi Gas Chemical) as the insulating resin was used. Further, the surface is coated with a fluororesin, the thickness is about 100 μm, the volume resistance is 10 ⁷ to 10 ¹² Ω · cm, and the surface resistance is 10 ⁷ to 10 ¹² Ω / □. This is also for improving dot reproducibility. This is to effectively prevent slack and charge accumulation due to long-term use of the transfer belt 12, and the coating of the surface with a fluororesin is effective for toner filming on the surface of the transfer belt after long-term use. This is to prevent it. If the volume resistance is less than 10 ⁷ Ω · cm, retransfer is likely to occur, and if it is greater than 10 ¹² Ω · cm, the transfer efficiency deteriorates.

The first transfer roller is a carbon conductive urethane foam roller having an outer diameter of 8 mm, and the resistance value is 10 ² to 10 ⁶ Ω. During the first transfer operation, the first transfer roller 10 is pressed against the photoreceptor 1 with a pressing force of 1.0 to 9.8 (N) via the transfer belt 12, and the toner on the photoreceptor is transferred onto the belt. Is done. If the resistance value is smaller than 10 ² Ω, retransfer is likely to occur. Larger transfer defects are more likely to occur than 10 ⁶ Ω. If it is less than 1.0 (N), transfer defects occur, and if it is greater than 9.8 (N), transfer character omission occurs.

The second transfer roller 14 is a carbon conductive foamed urethane roller having an outer diameter of 10 mm, and the resistance value is 10 ² to 10 ⁶ Ω. The second transfer roller 14 is pressed against the transfer roller 13 via the transfer belt 12 and a transfer medium 19 such as paper or OHP. The transfer roller 13 is configured to be driven to rotate by the transfer belt 12. In the second transfer, the second transfer roller 14 and the counter transfer roller 13 are pressed against each other with a pressing force of 5.0 to 21.8 (N), and the toner is transferred from the transfer belt onto the recording material 19 such as paper. The If the resistance value is smaller than 10 ² Ω, retransfer is likely to occur. Larger transfer defects are more likely to occur than 10 ⁶ Ω. If it is smaller than 5.0 (N), transfer failure occurs. If it is larger than 21.8 (N), the load increases and jitter tends to occur.

  Four sets of image forming units 18Y, 18M, 18C, and 18K for each color of yellow (Y), magenta (M), cyan (C), and black (B) are arranged in series as shown in the figure.

  Each of the image forming units 18Y, 18M, 18C, and 18K is composed of the same constituent members except for the developer contained therein, so that the Y image forming unit 18Y will be described to simplify the description, and the units for other colors The description of is omitted.

  The image forming unit is configured as follows. 1 is a photosensitive member, 3 is a pixel laser signal light, 4 is a developing roller having an outer diameter of 10 mm made of aluminum having a magnet having a magnetic force of 1200 gauss, and is opposed to the photosensitive member with a gap of 0.3 mm. Rotate in the direction of. 6 is a stirring roller that stirs the toner and carrier in the developing device and supplies them to the developing roller. The composition ratio of the carrier and the toner is read by a magnetic permeability sensor (not shown) and is supplied from a toner hopper (not shown) in a timely manner. A metal magnetic blade 5 regulates the magnetic brush layer of the developer on the developing roller. The developer amount is 150 g. The gap was 0.4 mm. Although the power supply is omitted, a DC voltage of −500 V and an AC voltage of 1.5 kV (pp) and a frequency of 6 kHz are applied to the developing roller 4. The peripheral speed ratio between the photoreceptor and the developing roller was 1: 1.6. The mixing ratio of toner and carrier was 93: 7, and the developer amount in the developing unit was 150 g.

  A charging roller 2 having an outer diameter of 10 mm made of epichlorohydrin rubber is applied with a DC bias of -1.2 kV. The surface of the photoreceptor 1 is charged to −600V. 8 is a cleaner, 9 is a waste toner box, and 7 is a developer.

  The paper is transported from below the transfer unit 17 so that the paper 19 is fed by a paper feed roller (not shown) to the nip portion where the transfer belt 12 and the second transfer roller 14 are pressed. A conveyance path is formed.

  The toner on the transfer belt 12 is transferred to the paper 19 by +1000 V applied to the second transfer roller 14, and includes a fixing roller 201, a pressure roller 202, a fixing belt 203, a heating medium roller 204, and an induction heater unit 205. It is conveyed to the fixing unit and fixed there.

  FIG. 2 shows the fixing process. A belt 203 is placed between the fixing roller 201 and the heat roller 204. A predetermined load is applied between the fixing roller 201 and the pressure roller 202, and a nip is formed between the belt 203 and the pressure roller 202. An induction heater unit 205 including a ferrite core 206 and a coil 207 is provided on the outer peripheral surface of the heat roller 204, and a temperature sensor 208 is provided on the outer surface.

  The belt has a structure in which 30 μm of Ni is used as a base, silicone rubber is 150 μm thereon, and further, PFA tube is 30 μm.

  The pressure roller 202 is pressed against the fixing roller 201 by a pressure spring 209. The recording material 19 having the toner 210 moves along the guide plate 211.

  A fixing roller 201 as a fixing member is a silicone rubber having a rubber hardness (JIS-A) of 20 degrees according to JIS standard on the surface of an aluminum hollow roller metal core 213 having a length of 250 mm, an outer diameter of 14 mm, and a thickness of 1 mm. An elastic layer 214 having a thickness of 3 mm is provided. A silicone rubber layer 215 is formed thereon with a thickness of 3 mm and has an outer diameter of about 20 mm. It receives a driving force from a driving motor (not shown) and rotates at 125 mm / s.

  The heat roller 204 is a hollow pipe having a thickness of 1 mm and an outer diameter of 20 mm. The surface temperature of the fixing belt was controlled to 170 ° using a thermistor.

  The pressure roller 202 as a pressure member has a length of 250 mm and an outer diameter of 20 mm. This is provided with a 2 mm thick elastic layer 217 made of silicone rubber having a rubber hardness (JIS-A) of 55 degrees according to JIS standards on the surface of a hollow roller metal core 216 made of aluminum having an outer diameter of 16 mm and a thickness of 1 mm. . The pressure roller 202 is rotatably installed, and a nip width of 5.0 mm is formed between the pressure roller 202 and the fixing roller 201 by a spring-loaded spring 209 on one side 147N.

  The operation will be described below. In the full color mode, all of the first transfer rollers 10 of Y, M, C, and K are pushed up and press the photoreceptor 1 of the image forming unit via the transfer belt 12. At this time, a DC bias of +800 V is applied to the first transfer roller. An image signal is sent from the laser beam 3 and is incident on the photoreceptor 1 whose surface is charged by the charging roller 2 to form an electrostatic latent image. The toner on the developing roller 4 that rotates in contact with the photoreceptor 1 visualizes the electrostatic latent image formed on the photoreceptor 1.

  At this time, the image forming speed of the image forming unit 18Y (125 mm / s equal to the peripheral speed of the photoconductor) and the moving speed of the transfer belt 12 are 0.5 to 1.5% slower than the transfer belt speed. Is set to

  In the image forming process, the Y signal light 3Y is input to the image forming unit 18Y, and image formation with Y toner is performed. Simultaneously with the image formation, the first transfer roller 10Y causes the Y toner image to be transferred from the photoreceptor 1Y to the transfer belt 12. At this time, a DC voltage of +800 V was applied to the first transfer roller 10Y.

  With a time lag between the first color (Y) first transfer and the second color (M) first transfer, M signal light 3M is input to the image forming unit 18M, and image formation with M toner is performed. Simultaneously with the image formation, the M toner image is transferred from the photosensitive member 1M to the transfer belt 12 by the action of the first transfer roller 10M. At this time, the first color (Y) toner is formed and the M toner is transferred. Similarly, image formation with C (cyan) and K (black) toners is performed, and a YMCK toner image is formed on the transfer belt 12 by the action of the first transfer rollers 10C and 10B simultaneously with the image formation. This is a so-called tandem method.

  On the transfer belt 12, toner images of four colors are positioned and overlapped to form a color image. After the transfer of the final B toner image, the four color toner images are collectively transferred to the paper 19 fed from a paper feed cassette (not shown) at the same time by the action of the second transfer roller 14. At this time, the transfer roller 13 was grounded, and a DC voltage of +1 kV was applied to the second transfer roller 14. The toner image transferred to the paper was fixed by a pair of fixing rollers 201 and 202. The paper was then discharged out of the apparatus through a pair of discharge rollers (not shown). The residual transfer toner remaining on the intermediate transfer belt 12 was cleaned by the action of the cleaning blade 16 to prepare for the next image formation.

  Table 10 shows the results of image output using the electrophotographic apparatus shown in FIG. Filming of toner on the photoreceptor when 100,000 sheets running durability test is performed on A4 size paper, transition of image density before and after running test, fog in non-image area, solid image uniformity, transfer The state of sex (such as voids) was evaluated.

The charge amount is measured by the blow-off method of frictional charging with the ferrite carrier. Under an environment of 25 ° C. and a relative humidity of 45% RH, 0.3 g of a sample for durability evaluation was collected and blown with nitrogen gas 1.96 × 10 ⁴ (Pa) for 1 minute.

  When an image was produced using a developer, a high-density image with a high image density of 1.3 or higher was obtained with a high resolution, with no non-image area fogging, no toner scattering, etc. It was. Further, even in a long-term durability test of 100,000 A4 sheets, both the fluidity and the image density showed a stable characteristic with little change. In addition, the uniformity when the entire solid image was taken at the time of development was also good. There is no development memory.

  Even during continuous use, no abnormal image of the vertical muscles occurred. There is almost no spent toner component on the carrier. There was little change in carrier resistance and a decrease in charge amount, good charge rising property upon rapid toner replenishment, and no phenomenon of fog increase under a high humidity environment. Also, when used for a long time, a high saturation charge amount was obtained and could be maintained for a long time. Fluctuations in charge amount under low temperature and low humidity hardly occur. Further, even if the mixing ratio of the toner and the carrier is changed to 5 to 20 wt%, the image density and the image quality such as the background fog are hardly changed, and a wide toner density control can be performed.

  Also, in the transfer, the void is at a level that causes no problem in practical use, and the transfer efficiency is about 95%. Further, the filming of the toner on the photosensitive member and the transfer belt was at a level where there was no practical problem. There was no defective cleaning of the transfer belt. In addition, toner disturbance and toner skip at the time of fixing hardly occur. Also, in the full-color image in which the three colors overlap, no transfer failure occurred, and no paper wrapping around the fixing belt occurred during fixing.

  Table 11 shows the fixability, offset property, high-temperature storage stability, and paper wrapping property around the fixing belt in a full-color image.

In a fixing device using a solid image with an adhesion amount of 1.2 mg / cm ^{2 at} a process speed of 125 mm / s and a belt not coated with oil, OHP transmittance (fixing temperature 160 ° C.), minimum fixing temperature, and offset generation at high temperature The temperature was evaluated. The OHP transmittance was measured with a spectrophotometer U-3200 (Hitachi, Ltd.) for the transmittance of 700 nm light. Storage stability shows the result after standing at 55 ° C. for 24 hours.

  In the toners TM1 to TM17, no OHP jam occurred at the fixing nip portion. In a full-color image of plain paper, no offset occurred at 200,000 sheets. Even if the oil is not applied with a silicone or fluorine-based fixing belt, no belt surface deterioration phenomenon is observed. The OHP translucency was 80% or more, and the non-offset temperature range was obtained in a wide range in the fixing roller not using oil. In addition, almost no aggregation was observed in the storage stability at 55 ° C. for 24 hours (◯ level).

  Table 12 shows the glossiness of the solid image portion at that time with respect to the fixing temperature (° C.). The glossiness was Horiba Gross Checker IG320.

  The TM1 to TM17 toners are characterized by little change in image gloss even when the fixing temperature changes.

  The present invention is useful not only for an electrophotographic system using a photoconductor but also for a system in which a paper or a toner containing a conductive material is directly deposited on a substrate as a wiring pattern.

Sectional drawing which shows the structure of the image forming apparatus used in one Example of this invention Sectional drawing which shows the structure of the fixing unit used in one Example of this invention. Schematic of the stirring and dispersing apparatus used in one embodiment of the present invention The top view of the stirring and dispersing device used in one embodiment of the present invention Schematic of the stirring and dispersing apparatus used in one embodiment of the present invention The top view of the stirring and dispersing device used in one embodiment of the present invention

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Charging roller 3 Laser signal light 4 Developing roller 5 Blade 10 1st transfer roller 12 Transfer belt 13 Drive tension roller 14 2nd transfer roller 17 Transfer belt unit 18B, 18C, 18M, 18Y Image forming unit 18 Image forming unit Group 201 Fixing roller 202 Pressure roller 203 Fixing belt 205 Induction heater section 206 Ferrite core 207 Coil 801 Outer tank 802 Dam plate 803 Rotating body 806 Shaft 807 Cooling water discharge port 808 Cooling water inlet 850 Raw material inlet 852 Fixed body 853 Rotation Body 854 Shaft 856 Raw material discharge

Claims (25)

In an aqueous medium, at least the first resin particle dispersion in which the first resin particles are dispersed, the colorant particle dispersion in which the colorant particles are dispersed, and the wax particle dispersion in which the wax particles are dispersed are mixed. Then, the second resin particle dispersion in which the second resin particles are dispersed is added to the core particle dispersion containing the core particles produced by agglomeration, mixed, heated, and then the second resin particles. A toner obtained by fusing to the core particles,
A toner, wherein the second resin particle dispersion in which the second resin particles are dispersed is adjusted to have a pH of 3.5 to 9.5. In an aqueous medium, at least the first resin particle dispersion in which the first resin particles are dispersed, the colorant particle dispersion in which the colorant particles are dispersed, and the wax particle dispersion in which the wax particles are dispersed are mixed. Then, the second resin particle dispersion in which the second resin particles are dispersed is added to the core particle dispersion containing the core particles produced by agglomeration, mixed, heated, and then the second resin particles. A toner obtained by fusing to the core particles,
The second resin particle dispersion in which the second resin particles are dispersed is adjusted to have a pH that is the same or lower than the pH of the core particle dispersion in which the core particles are dispersed. toner. The toner according to claim 1, wherein the wax particle dispersion is prepared by emulsifying and dispersing with a surfactant mainly composed of a nonionic surfactant. The main component of the surfactant used in the first resin dispersion and / or the second resin dispersion is a nonionic surfactant, and the main component of the surfactant used in the colorant dispersion is a nonionic surfactant. The toner according to claim 1, wherein the toner is a non-ionic surfactant as a main component of the surfactant used in the wax dispersion. The surfactant used for the first resin dispersion and / or the second resin dispersion is a mixture of a nonionic surfactant and an ionic surfactant, and the surfactant used for the wax dispersion is nonionic. Surfactant only,
The mixing ratio of the surfactant used in the first resin dispersion is such that the nonionic surfactant has 60 wt% or more based on the total surfactant, and the surfactant used in the second resin dispersion. The toner according to claim 1, wherein the mixing ratio of the agent is such that the nonionic surfactant has 50 wt% or more based on the total amount of the surfactant. The surfactant used for the first resin dispersion and / or the second resin dispersion is a mixture of a nonionic surfactant and an ionic surfactant, and the surfactant used for the wax dispersion is nonionic. Only the surfactant, the main component of the surfactant used in the colorant dispersion is only a nonionic surfactant,
The mixing ratio of the surfactant used in the resin dispersion is such that the nonionic surfactant has 60 wt% or more based on the total amount of the surfactant, and the surfactant used in the second resin dispersion is mixed. The toner according to claim 1, wherein the nonionic surfactant has a ratio of 50 wt% or more based on the total amount of the surfactant. In an aqueous medium, at least the first resin particle dispersion in which the first resin particles are dispersed, the colorant particle dispersion in which the colorant particles are dispersed, and the wax particle dispersion in which the wax particles are dispersed are mixed. The second resin particle dispersion in which the second resin particles whose pH is adjusted to the range of 3.5 to 9.5 is dispersed in the core particle dispersion containing the core particles formed by aggregation is added. The toner is produced by mixing, heating, and fusing the second resin particles to the core particles. In an aqueous medium, at least the first resin particle dispersion in which the first resin particles are dispersed, the colorant particle dispersion in which the colorant particles are dispersed, and the wax particle dispersion in which the wax particles are dispersed are mixed. Then, the second resin particle dispersion in which the second resin particles are dispersed is added to the core particle dispersion containing the core particles produced by agglomeration, mixed, heated, and then the second resin particles. Is a method for producing a toner that is fused to the core particles,
The pH of the second resin particle dispersion in which the second resin particles are dispersed is equal to or lower than the pH of the core particle dispersion in which the core particles are dispersed. Production method. The pH of the first resin particle dispersion in which the first resin particles are dispersed, the colorant particle dispersion in which the colorant particles are dispersed, and the wax particle dispersion in which the wax particles are dispersed is 9.5 to 12.2. The toner production method according to claim 7, wherein the toner is adjusted to a range of 10 to 10. 9. The method for producing a toner according to claim 7, wherein the wax particle dispersion is prepared by emulsifying and dispersing with a surfactant mainly composed of a nonionic surfactant. The main component of the surfactant used in the first resin dispersion and / or the second resin dispersion is a nonionic surfactant, and the main component of the surfactant used in the colorant dispersion is a nonionic surfactant. 9. The method for producing a toner according to claim 7, wherein the surfactant used in the wax dispersion is a nonionic surfactant. The surfactant used for the first resin dispersion and / or the second resin dispersion is a mixture of a nonionic surfactant and an ionic surfactant, and the surfactant used for the wax dispersion is nonionic. Surfactant only,
The mixing ratio of the surfactant used in the first resin dispersion is such that the nonionic surfactant has 60 wt% or more based on the total surfactant, and the surfactant used in the second resin dispersion. The method for producing a toner according to claim 7 or 8, wherein the mixing ratio of the agent is such that the nonionic surfactant has 50 wt% or more based on the entire surfactant. The surfactant used for the first resin dispersion and / or the second resin dispersion is a mixture of a nonionic surfactant and an ionic surfactant, and the surfactant used for the wax dispersion is nonionic. Only the surfactant, the main component of the surfactant used in the colorant dispersion is only a nonionic surfactant,
The mixing ratio of the surfactant used in the first resin dispersion is such that the nonionic surfactant has 60 wt% or more based on the total surfactant, and the surfactant used in the second resin dispersion. The method for producing a toner according to claim 7 or 8, wherein the mixing ratio of the agent is such that the nonionic surfactant has 50 wt% or more based on the entire surfactant. An inorganic fine powder having an average particle diameter in the range of 6 nm to 200 nm is added to the toner base according to claim 1 or 2 and the manufactured toner base according to claim 7 or 8 in an amount of 1 to 6 weights with respect to 100 parts by weight of the toner base. A two-component developer comprising: a toner added in a range of a part; and a carrier including magnetic particles coated with a fluorine-modified silicone resin including at least a surface of a core material containing an aminosilane coupling agent. The inorganic fine powder having an average particle diameter of 6 nm to 20 nm is 0.5 to 2.5 parts by weight based on 100 parts by weight of the toner base, and the inorganic fine powder having an average particle diameter of 20 nm to 200 nm is based on 100 parts by weight of the toner base. The two-component developer according to claim 14, wherein 0.5 to 3.5 parts by weight are externally added. An inorganic fine powder having an average particle diameter of 6 nm to 20 nm and an ignition loss of 0.5 to 20 wt% is 0.5 to 2.5 parts by weight with respect to 100 parts by weight of the toner base, an average particle diameter of 20 nm to 200 nm, strong 15. The two-component developer according to claim 14, wherein an inorganic fine powder having a heat loss of 1.5 to 25 wt% is externally added to 0.5 to 3.5 parts by weight with respect to 100 parts by weight of the toner base. The two-component developer according to claim 14, wherein the carrier coating resin contains 5 to 40 parts by weight of an aminosilane coupling agent in 100 parts by weight of the coating resin. The two-component developer according to claim 14, wherein the coating resin layer contains 1 to 15 parts by weight of conductive fine powder with respect to 100 parts by weight of the coating resin. The two-component developer according to claim 14, wherein the coating resin is 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the carrier core material. A crosslinkable fluorine-modified silicone obtained by a reaction in which the fluorine-modified silicone resin is a reaction in which the organosilicon compound containing a perfluoroalkyl group is 3 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the polyorganosiloxane. The two-component developer according to claim 14, which is a silicone resin. The two-component developer according to claim 14, wherein the fluorine-modified silicone resin is a crosslinkable fluorine-modified silicone resin obtained from a reaction between a perfluoroalkyl group-containing organosilicon compound and polyorganosiloxane. The organosilicon compound containing a perfluoroalkyl group is CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , C ₄ F ₉ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , C ₈ F ₁₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , C ₈ F ₁₇ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ , (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH ₂ Si (OCH ₃ ) _3, etc. The two-component developer according to claim 21, wherein the two-component developer is at least one. The two-component developer according to claim 21, wherein the polyorganosiloxane is at least one selected from the following (Chemical Formula 1) and (Chemical Formula 2).

At least a magnetic field generating means, a heating member having a rotating action having at least a heat generating layer and a release layer that generate heat by electromagnetic induction, and a pressure member having a rotating action that forms a fixed nip with the heating member. The toner according to claim 1, the toner produced by the method according to claim 7, or the two-component according to claim 14, comprising a heating and pressurizing unit, between the heating member and the pressure member. An image forming apparatus comprising a fixing process in which a transfer medium onto which toner in a developer is transferred is fixed. And a plurality of toner image forming stations including at least an image carrier, a charging unit for forming an electrostatic latent image on the image carrier and a toner carrier, and an electrostatic latent image formed on the image carrier. The toner according to claim 1 or 2, the toner produced by the method according to claim 7 or 8, or the toner in the two-component developer according to claim 14, which visualizes the electrostatic latent image. A primary transfer process in which an image is transferred to the transfer body by bringing an endless transfer body into contact with the image carrier is sequentially performed to form a multilayer transfer toner image on the transfer body, and then A transfer system configured to execute a secondary transfer process in which a multi-layer toner image formed on the transfer body is collectively transferred to a transfer medium, and the transfer process starts from a first primary transfer position; Second primary transfer position , Or the distance from the second primary transfer position to the third primary transfer position, or the distance from the third primary transfer position to the fourth primary transfer position, d1 (mm), and the peripheral speed of the photoconductor An image forming apparatus characterized by satisfying the condition of d1 / v ≦ 0.65 (sec) where v is (mm / s).

Images