JP4186735B2 - Toner, toner manufacturing method, two-component developer, and image forming apparatus - Google Patents

Description

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

  In recent years, the electrophotographic apparatus is 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, maintenance-free, and the like. Therefore, a cleaner-less process that collects waste toner during development without cleaning waste toner remaining after transfer, a tandem color process that enables high-speed output of color images, and no fixing oil to prevent offset during fixing In both cases, oilless fixing that achieves both a clear color image having high glossiness and high translucency and non-offset properties is required along with conditions such as good maintenance 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, an image carrier (hereinafter referred to as a photoconductor) is charged by corona discharge using a charging charger, and then a latent image of each color is irradiated onto the photoconductor as an optical signal to form an electrostatic latent image. The latent image is developed by developing with color, for example, yellow toner. Thereafter, a transfer member charged with a polarity opposite to that of the yellow toner is brought into contact with the photosensitive member to transfer the yellow toner image formed on the photosensitive member. The photosensitive member is neutralized after cleaning the toner remaining at the time of transfer, and the development and transfer of the first color toner are completed. Thereafter, the same operation as that of the yellow toner is repeated for toners such as magenta and cyan, and a color image is formed by superimposing the toner images of the respective colors on the transfer body. A four-pass color process in which these superimposed toner images are transferred onto paper charged to a polarity opposite to that of the toner has been put into practical use.

  In addition, a primary transfer in which a plurality of image forming stations having a charger, a photosensitive member, a developing unit, etc. are arranged side by side, and an endless transfer member is brought into contact with the photosensitive member to successively transfer toner of each color sequentially to the transfer member. A secondary transfer process that executes a process to form a multilayer transfer color toner image on a transfer body, and then collectively transfers the multilayer toner image formed on the transfer body onto a transfer medium such as paper or OHP. There have been proposed a tandem color process configured to be executed and a tandem color process in which transfer is continuously performed directly on a paper or OHP transfer medium without using a transfer body.

  In the fixing process, in color images, it is necessary to melt and mix color toners to improve 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 strong cohesive property, so that the toner image during transfer and the tendency of transfer failure are more prominent, making it difficult to achieve both transfer and fixing. When used as two-component development, low-melting-point components of toner adhere to the carrier surface due to collision between particles, friction, mechanical collision such as collision between particles and developer, friction, etc., and heat generated by friction. Spent is likely to occur, which lowers the charging ability of the carrier and hinders the lifetime of the developer.

  For the purpose of providing a long-life coat carrier, Patent Document 1 (Japanese Patent Laid-Open No. Sho 61-80161), Patent Document 2 (Japanese Patent Laid-Open No. 61-80162), and Patent Document 3 (Japanese Patent Laid-Open No. 61-80163) include The carrier core material surface is coated with a resin such as a copolymer of a nitrogen-containing fluorinated alkyl (meth) acrylate and a vinyl monomer or a copolymer of a fluorinated alkyl (meth) acrylate and a nitrogen-containing vinyl monomer. Technology has been proposed. In these, a relatively long-life coat carrier is obtained by coating a copolymer of a nitrogen-containing monomer and a fluorinated monomer or a solvent-soluble fluorine-containing polymer having an imide bond on the surface of the carrier core material. Has been.

  However, since the resin adhesive strength at the adhesive interface with the carrier is weak and the resin strength is insufficient, sufficient impact resistance is not obtained. Further, it is difficult to make the toner negatively charged due to the charging property of fluorine, and there is a problem in that the toner cannot be sufficiently charged, causing image fogging and density unevenness.

  In Patent Document 4 (Japanese Patent No. 2619439) and Patent Document 5 (Japanese Patent No. 2744790), a decrease in toner charge amount in a high humidity atmosphere is prevented, and developer durability is improved. A carrier coated with a silicone resin containing an aminosilane coupling agent has been proposed for the purpose of combining with a toner with limited components, but it is sufficient for preventing toner spent. It wasn't.

  Patent Document 6 (Japanese Patent No. 2801507) proposes a carrier in which a fluorine-substituted alkyl group is introduced into a silicone resin of a coating layer with respect to a positively charged toner. Furthermore, in Patent Document 7 (Japanese Patent Laid-Open No. 2002-23429), a conductive carbon and a cross-linked fluorine-modified silicone resin are used as those that have high development capability in a high-speed process and that do not deteriorate over a long period of time. A coating carrier is proposed. Taking advantage of the excellent charging characteristics of silicone resin, the fluorine-substituted alkyl group provides slipperiness, peelability, water repellency, etc., and prevents wear, peeling, cracks, etc. 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 pulverization / classification in the conventional kneading and pulverization 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. Also, a method for realizing oil-less fixing by blending a release agent such as wax in a resin having a low softening point when the toner is melt-kneaded has been studied. However, there is a limit to the amount of wax that can be blended, and as the amount added increases, the fluidity of the toner decreases, the dropout during transfer increases, the fuser fuses to the photoreceptor, and the spent toner component increases with respect to conventional carriers. The evils of will arise.

  Therefore, a toner production method using various polymerization methods different from the kneading and pulverization method has been studied. For example, a method for preparing a toner by a suspension polymerization method is described in Patent Document 8 (Japanese Patent Laid-Open No. 62-73276), Patent Document 9 (Japanese Patent Laid-Open No. 5-027476), and the like. However, when toners are prepared using these methods, even if it is attempted to control the particle size distribution of the toner, it is not possible to leave the area of the kneading and pulverization method, and in many cases, further classification operation is required. In addition, since the toner obtained by these methods has a substantially spherical shape, there is a problem in that the toner remaining on the photosensitive member or the like is poorly cleaned and the image quality reliability is impaired.

  In addition, a method for preparing a toner using an emulsion polymerization method includes mixing at least a dispersion obtained by dispersing resin particles obtained by emulsion polymerization, and a colorant particle dispersion containing dispersed colorant particles, and mixing an aqueous medium. In this method, aggregated particles are formed by heating, and the toner is prepared by washing and drying.

  In Patent Document 10 (Japanese Patent Application Laid-Open No. 63-282749), a required amount of a colorant powder, a fixability improver, and a charge control agent are added to a polymer emulsion having an acidic polar group or basic group obtained by emulsion polymerization. When mixed and uniformly dispersed, the primary particles of the polymer, the colorant particles, and the fixing agent particles are aggregated to grow into secondary particles. It is disclosed that when this dispersion is further stirred, the secondary particles aggregate and grow to associated particles having an average particle diameter of 5 to 25 μm.

  Further, in Patent Document 11 (Japanese Patent Laid-Open No. 10-123748), an inner layer that is an associated particle formed by associating secondary particles containing polymer fine particles and a colorant, and an outer layer mainly composed of a polymer. It is disclosed that the particle composition is excellent in low-temperature fixing property and blocking property, and has a narrow particle size distribution so that it can cope with charging characteristics and high image quality and has excellent cleaning properties.

  Further, in Patent Document 12 (Japanese Patent Application Laid-Open No. 10-026842), a fine particle dispersion in which fine particles are dispersed is added and mixed in an aggregated particle dispersion to adhere the fine particles to the aggregated particles. A toner manufacturing method including a second step of forming and a third step of heating and fusing the attached particles is disclosed.

  Japanese Patent Application Laid-Open No. 10-73955 discloses a toner production method in which the concentration of dissociation groups per unit volume in resin particles is lower than the concentration of dissociation groups per unit volume in resin fine particles. It is disclosed. The dissociating group is selected from a carboxyl group, a sulfonic acid group and an ammonium group.

  Patent Document 14 (Japanese Patent Application Laid-Open No. 10-133423) discloses that the molecular weight distribution of the resin in the toner particles by gel permeation chromatography has at least two maxima or shoulders.

  In Patent Document 15 (Japanese Patent Laid-Open No. 10-198070), a resin particle dispersion in which resin particles are dispersed in a polar dispersant, and colorant particles are dispersed in a polar dispersant. A liquid mixture preparing step for preparing a liquid mixture by mixing at least with the colorant particle dispersion liquid, and the polarity of the dispersant contained in the liquid mixture is the same polarity, so that the reliability is excellent in chargeability and color developability. It is disclosed that a toner for developing an electrostatic charge image having high properties can be easily and easily produced.

  In Patent Document 16 (Japanese Patent Laid-Open No. 10-301332), the release agent is 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. In addition, it is disclosed that the resin particles are excellent in fixing property, color developability, transparency, color mixing property and the like by including at least two kinds of resin particles having different molecular weights.

  In Patent Document 17 (Japanese Patent Application Laid-Open No. 11-327201), a toner for developing an electrostatic charge image in which a release agent is disposed in a toner as a release agent layer along the toner surface, a resin fine particle dispersion, Mixing with the colorant dispersion to form aggregated particles, then adding and mixing the dispersion of release agent fine particles, attaching the release agent fine particles to the surface of the aggregated particles, and further dispersing the resin fine particles Add and mix the liquid, adhere the resin particles to the surface of the release agent layer of the agglomerated particles, then heat to a temperature above the glass transition point of the resin particles to fuse and coalesce to form toner particles This suppresses release of the release agent from the toner, is excellent in fixability, chargeability, powder characteristics, and has various characteristics such as chargeability, developability, transferability, fixability, and cleanability. Especially smoothness, transparency, color mixing, It is disclosed that excellent sex.

  Further, in Patent Document 18 (Japanese Patent Laid-Open No. 11-2922), a release agent is emulsified by discharge collision at high pressure, and the particle size of the release agent is 0.4 μm or less and 0.8 μm or more is 5 particles. It is described that the release of the release agent can be prevented and the OHP permeability is increased by the composition of less than or equal to%.

  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.

  Further, in order to realize oilless fixing without using oil at the time of fixing, a specific wax is added in a large amount. And when it fuse | melts with resin from which melting | fusing point, a softening point, and viscoelasticity differ, it becomes difficult to unite | combine, maintaining a uniform state, when uniting by heating. In particular, it is possible to achieve both oil-less fixing, fogging during development, and transfer efficiency by using a release agent having a certain acid value and functional group. In the aqueous system, uniform mixing and aggregation with resin fine particles and pigment fine particles are hindered, and there is a tendency to increase the presence of a floating release agent that is not involved in aggregation in the aqueous system, and also in the pigment.

In addition, in an emulsifying disperser such as a homogenizer, the ultimate particle diameter of a release agent or the like is limited to several hundred nanometers. Further, in order to form a uniform particle size distribution by reducing the particle size of the toner, it is necessary to form a dispersion having a fine particle size in the release agent itself. However, the particle size distribution of the dispersion is an important factor, and when the particles are simply refined, coarse particles exist separately in a floating state without being mixed and agglomerated when mixed and agglomerated with the resin dispersion and pigment dispersion. Particles tend to adhere to the stirring shaft and the wall surface during melting, resulting in decreased productivity.
JP 61-80161 A JP 61-80162 A JP 61-80163 A Japanese Patent No. 2619439 Japanese Patent No. 2744790 Japanese Patent No. 2801507 JP 2002-23429 A JP-A-62-73276 JP-A-5-27476 JP-A-63-282749 JP-A-10-123748 JP-A-10-26842 JP-A-10-73955 Japanese Patent Laid-Open No. 10-133423 JP-A-10-198070 JP-A-10-301332 JP 11-327201 A Japanese Patent Laid-Open No. 11-2922

  The object of the present invention is to eliminate the presence of a floating release agent that is not involved in aggregation in an aqueous system, and also to eliminate the presence of a floating pigment in the pigment to achieve uniform mixing and aggregation. It aims at preventing scattering and realizing good color reproducibility.

  It is an object of the present invention to produce a toner having a small particle size having a sharp particle size distribution without a classification step.

  An object of the present invention is to realize an oilless fixing that exhibits high translucency and high glossiness by using a release agent such as wax in a toner in an oilless fixing toner that does not use oil in a fixing roller.

  An object of the present invention is to provide a long-life toner and a two-component developer having high durability that do not deteriorate due to spent even when used in combination with a toner containing a release agent such as wax.

  Another object of the present invention is to improve the cleaning properties of the toner on the photosensitive member and the transfer member, and prevent the occurrence of filming.

  Further, to provide a toner and a two-component developer that improve toner image quality by reducing the particle size of the toner and suppress the lowering of the fluidity of the toner so that the toner can be supplied, mixed with the carrier, and charged. It is in.

  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 is possible to eliminate voids, reverse transfer, and scattering during transfer. An object of the present invention is to provide an image forming apparatus capable of preventing and obtaining high transfer efficiency.

  Another object of the present invention is to provide a toner and a two-component developer that can satisfy the above-mentioned problems comprehensively.

  In view of the above-mentioned problems, the configuration of the present invention is such that, in an aqueous medium, at least a resin particle dispersion in which resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a small particle size in a volume particle size distribution 16% diameter (PR16) is 20 to 200 nm, 50% diameter (PR50) is 40 to 300 nm, 84% diameter (PR84) is 400 nm or less, and PR84 / PR16 is 1. An inorganic toner having an average particle diameter of 6 nm to 20 nm is formed on a toner base produced by mixing and aggregating a release agent particle dispersion liquid in which release agent particles of 2 to 2.0 are dispersed and mixed in an aqueous system and heating. 0.5 to 2.5 parts by weight of fine powder with respect to 100 parts by weight of the toner base, 1.0 to 3.5 parts by weight of inorganic fine powder with an average particle diameter of 20 nm to 200 nm with respect to 100 parts by weight of the toner base, A toner additive treatment.

  Further, the constitution of the present invention is such that, in an aqueous medium, at least a resin particle dispersion in which resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a volume particle size distribution from the small particle size side. In the cumulative volume particle size distribution when integrated, the 16% diameter (PR16) is 20 to 200 nm, the 50% diameter (PR50) is 40 to 300 nm, the 84% diameter (PR84) is 400 nm or less, and PR84 / PR16 is 1.2 to A release agent particle dispersion having 2.0 release agent particles dispersed therein, in the presence of a water-soluble inorganic salt, the pH of the aqueous medium is 8 or more, and the temperature of the aqueous medium is the melting point of the release agent, An inorganic fine powder having an average particle size of 6 nm to 20 nm is applied to a toner base having a volume average particle size of 3 to 8 μm and a coefficient of variation of 25 or less obtained by heating to a temperature above the glass transition point of the resin fine particles and aggregating and associating. An inorganic fine powder having an average particle diameter of 0.5 to 2.5 parts by weight with respect to 100 parts by weight of the toner base and an average particle size of 20 to 200 nm was externally added to 1.0 to 3.5 parts by weight with respect to 100 parts by weight of the toner base. Toner.

  Further, the constitution of the present invention is such that, in an aqueous medium, at least a resin particle dispersion in which resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a volume particle size distribution from the small particle size side. In the cumulative volume particle size distribution when integrated, the 16% diameter (PR16) is 20 to 200 nm, the 50% diameter (PR50) is 40 to 300 nm, the 84% diameter (PR84) is 400 nm or less, and PR84 / PR16 is 1.2 to A release agent particle dispersion having 2.0 release agent particles dispersed therein, in the presence of a water-soluble inorganic salt, the pH of the aqueous medium is 8 or more, and the temperature of the aqueous medium is the melting point of the release agent, The resin fine particles are heated to a temperature equal to or higher than the glass transition point of the resin fine particles to cause aggregation and association, and further, the dispersion in which the aggregation and association particles thus aggregated are dispersed are mixed with the resin particle dispersion in which the resin particles are dispersed. Clump The inorganic fine powder having an average particle diameter of 6 nm to 20 nm is added to 100 parts by weight of the toner base on a toner base having a volume average particle diameter of 3 to 8 μm and a coefficient of variation of 25 or less. A toner obtained by externally adding 1.0 to 3.5 parts by weight of inorganic fine powder having an average particle diameter of 20 to 200 nm with respect to 100 parts by weight of the toner base.

  In addition, the configuration of the present invention includes, in an aqueous medium, at least a resin particle dispersion in which resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a dispersant in the resin particle dispersion. A release agent particle dispersion in which release agent particles are dispersed with a dispersant having an opposite polarity and a dispersant having the same polarity as that of the release agent particle dispersion are blended, mixed and agglomerated, and heated for a certain time. And a toner base externally treated by aggregation and aggregation, wherein the release agent particles have a 16% diameter in the volume particle size distribution when the volume particle size distribution is integrated from the small particle size side. (PR16) is 20 to 200 nm, 50% diameter (PR50) is 40 to 300 nm, 84% diameter (PR84) is 400 nm or less, and PR84 / PR16 is 1.2 to 2.0. 3-8μm, change A coefficient of 25 or less, and the external addition treatment is performed at 0.5 to 2.5 parts by weight of an inorganic fine powder having an average particle diameter of 6 nm to 20 nm with respect to 100 parts by weight of the toner base, and an average particle diameter of 20 nm to 200 nm. This is a toner for treating 1.0 to 3.5 parts by weight of a certain inorganic fine powder with respect to 100 parts by weight of the toner base.

  In addition, the configuration of the present invention includes, in an aqueous medium, at least a resin particle dispersion in which resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a dispersant in the resin particle dispersion. A release agent particle dispersion in which release agent particles are dispersed with a dispersant having an opposite polarity and a dispersant having the same polarity as that of the release agent particle dispersion are blended, mixed and agglomerated, and heated for a certain time. Then, a dispersion liquid in which the aggregated and aggregated aggregated particles are dispersed and a resin particle dispersion in which resin particles are dispersed are mixed to adhere and fuse the resin particles to the surface of the aggregated aggregated particles. In the toner obtained by external addition to the toner base, the 16% diameter (PR16) is 20 to 200 nm in the volume particle size cumulative distribution when the release agent particles are integrated from the small particle size side in the volume particle size distribution. 50% diameter (PR 0) is 40 to 300 nm, 84% diameter (PR84) is 400 nm or less, PR84 / PR16 is 1.2 to 2.0, the volume average particle diameter of the toner is 3 to 8 μm, and the coefficient of variation is 25 or less. In the external addition treatment, the inorganic fine powder having an average particle diameter of 6 nm to 20 nm is 0.5 to 2.5 parts by weight with respect to 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 used as the toner. The toner is 1.0 to 3.5 parts by weight with respect to 100 parts by weight of the base.

  Further, the structure of the present invention is a release agent melt obtained by melting the release agent at a release agent concentration of 40 wt% or less in a medium to which a dispersing agent maintained at a temperature equal to or higher than the melting point of the release agent is added. In the volume particle size cumulative distribution when the volume particle size distribution is integrated from the small particle size side by emulsifying and dispersing the particles by a high shearing force generated by a rotating body rotating at a high speed through a fixed gap. Dispersing release agent particles having a% diameter (PR16) of 20 to 200 nm, a 50% diameter (PR50) of 40 to 300 nm, an 84% diameter (PR84) of 400 nm or less, and PR84 / PR16 of 1.2 to 2.0 This is a method for producing a toner for producing a caulking release agent particle dispersion.

  Further, the constitution of the present invention is such that, in an aqueous medium, at least a resin particle dispersion in which resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a volume particle size distribution from the small particle size side. 16% diameter (PR16) is 20-200 nm, 50% diameter (PR50) is 40-300 nm, 84% diameter (PR84) is 400 nm or less, and PR84 / PR16 is 1.2- An inorganic fine powder having an average particle diameter of 6 nm to 20 nm on a toner base produced by mixing and aggregating a release agent particle dispersion liquid in which release agent particles of 2.0 are dispersed and mixed in an aqueous system and heating. 0.5 to 2.5 parts by weight based on 100 parts by weight of the toner base, and 1.0 to 3.5 parts by weight of inorganic fine powder having an average particle size of 20 nm to 200 nm based on 100 parts by weight of the toner base. Process Toner and a two-component developer comprising a carrier containing magnetic particles is an average particle diameter of which is coated with a fluorine-modified silicone resin comprising at least the surface of the core material is an amino silane coupling agent is 20 to 60 [mu] m.

  Further, the constitution of the present invention is such that, in an aqueous medium, at least a resin particle dispersion in which resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a volume particle size distribution from the small particle size side. 16% diameter (PR16) is 20-200 nm, 50% diameter (PR50) is 40-300 nm, 84% diameter (PR84) is 400 nm or less, and PR84 / PR16 is 1.2- A release agent particle dispersion having 2.0 release agent particles dispersed therein, in the presence of a water-soluble inorganic salt, the pH of the aqueous medium is 8 or more, and the temperature of the aqueous medium is the melting point of the release agent, An inorganic fine powder having an average particle size of 6 nm to 20 nm is applied to a toner base having a volume average particle size of 3 to 8 μm and a coefficient of variation of 25 or less obtained by heating to a temperature above the glass transition point of the resin fine particles and aggregating and associating. G -0.5 to 2.5 parts by weight based on 100 parts by weight of the base and 1.0 to 3.5 parts by weight of inorganic fine powder having an average particle size of 20 to 200 nm based on 100 parts by weight of the toner base. And a carrier containing magnetic particles having an average particle diameter of 20 to 60 μm and at least the surface of the core material is coated with a fluorine-modified silicone resin containing an aminosilane coupling agent.

  Further, the constitution of the present invention is such that, in an aqueous medium, at least a resin particle dispersion in which resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a volume particle size distribution from the small particle size side. 16% diameter (PR16) is 20-200 nm, 50% diameter (PR50) is 40-300 nm, 84% diameter (PR84) is 400 nm or less, and PR84 / PR16 is 1.2- A release agent particle dispersion having 2.0 release agent particles dispersed therein, in the presence of a water-soluble inorganic salt, the pH of the aqueous medium is 8 or more, and the temperature of the aqueous medium is the melting point of the release agent, The resin fine particles are heated to a temperature equal to or higher than the glass transition point of the resin fine particles to cause aggregation and association, and further, the dispersion in which the aggregation and association particles thus aggregated are dispersed are mixed with the resin particle dispersion in which the resin particles are dispersed. Agglomeration The inorganic fine powder having an average particle diameter of 6 nm to 20 nm is added to 100 parts by weight of the toner base with a toner base having a volume average particle diameter of 3 to 8 μm and a coefficient of variation of 25 or less. 0.5 to 2.5 parts by weight, 1.0 to 3.5 parts by weight of an inorganic fine powder having an average particle diameter of 20 nm to 200 nm and 100 parts by weight of the toner base, and at least the core material A two-component developer comprising a carrier containing magnetic particles having an average particle diameter of 20 to 60 μm and having a surface coated with a fluorine-modified silicone resin containing an aminosilane coupling agent.

  In addition, the configuration of the present invention includes, in an aqueous medium, at least a resin particle dispersion in which resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a dispersant in the resin particle dispersion. A release agent particle dispersion in which release agent particles are dispersed with a dispersant having an opposite polarity and a dispersant having the same polarity as that of the release agent particle dispersion are blended, mixed and agglomerated, and heated for a certain time. In this case, the toner is externally added to the toner base produced by aggregation and aggregation, and the release agent particles have a 16% diameter in the volume particle size integration when the volume particle size distribution is integrated from the small particle size side. (PR16) is 20 to 200 nm, 50% diameter (PR50) is 40 to 300 nm, 84% diameter (PR84) is 400 nm or less, and PR84 / PR16 is 1.2 to 2.0. 3-8 μm, variation In the external addition treatment, the inorganic fine powder having an average particle diameter of 6 nm to 20 nm is 0.5 to 2.5 parts by weight with respect to 100 parts by weight of the toner base, and the average particle diameter is 20 nm to 200 nm. An average particle size obtained by coating an inorganic fine powder with 1.0 to 3.5 parts by weight of externally added toner with respect to 100 parts by weight of the toner base, and at least the surface of the core material with a fluorine-modified silicone resin containing an aminosilane coupling agent Is a two-component developer comprising a carrier containing magnetic particles having a particle size of 20 to 60 μm.

  In addition, the configuration of the present invention includes, in an aqueous medium, at least a resin particle dispersion in which resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a dispersant in the resin particle dispersion. A release agent particle dispersion in which release agent particles are dispersed with a dispersant having an opposite polarity and a dispersant having the same polarity as that of the release agent particle dispersion are blended, mixed and agglomerated, and heated for a certain time. Then, a dispersion liquid in which the aggregated and aggregated aggregated particles are dispersed and a resin particle dispersion in which resin particles are dispersed are mixed to adhere and fuse the resin particles to the surface of the aggregated aggregated particles. The toner obtained by externally adding to the toner base material has a 16% diameter (PR16) of 20 to 200 nm in the volume particle size integration when the release agent particles are integrated from the small particle size side in the volume particle size distribution. 50% diameter (PR5 ) Is 40 to 300 nm, 84% diameter (PR84) is 400 nm or less, PR84 / PR16 is 1.2 to 2.0, the volume average particle diameter of the toner is 3 to 8 μm, and the coefficient of variation is 25 or less. In the external addition treatment, the inorganic fine powder having an average particle size of 6 nm to 20 nm is 0.5 to 2.5 parts by weight with respect to 100 parts by weight of the toner base, and the inorganic fine powder having an average particle size of 20 nm to 200 nm is used as the toner base. An average particle diameter of 20 to 60 μm, in which 1.0 to 3.5 parts by weight of externally added toner with respect to 100 parts by weight and at least the surface of the core material is coated with a fluorine-modified silicone resin containing an aminosilane coupling agent. A two-component developer comprising a carrier containing magnetic particles.

  The resin particle dispersion in which the resin particles are dispersed, the colorant particle dispersion in which the colorant particles are dispersed, and the volume particle size distribution when the volume particle size distribution is integrated from the small particle size side, the 16% diameter (PR16 ) Is 20 to 200 nm, 50% diameter (PR50) is 40 to 300 nm, 84% diameter (PR84) is 400 nm or less, and release agent particles in which PR84 / PR16 is 1.2 to 2.0 are dispersed. The presence of a floating release agent that does not cause aggregation in the aqueous system due to the composition in which the toner base is formed by mixing and aggregating with the agent particle dispersion in the aqueous system and then processing the toner base produced by heating. Oil that eliminates floating pigments, achieves a small particle size, a uniform and sharp particle size distribution in a narrow range, and prevents offsetting while maintaining high OHP translucency without applying oil. A two-component developer combined with a carrier that is coated with a fluorine-modified silicone resin containing an aminosilane coupling agent can extend the life without spending toner components on the carrier. Can do. In addition, it is possible to prevent voids and scattering during transfer and to obtain high transfer efficiency.

  The present invention is an oil-less fixing, has high glossiness and high translucency, has excellent charging characteristics, environmental dependency, cleaning properties, transferability, and a small particle size static having a sharp particle size distribution. The present inventors have earnestly studied to provide a toner for developing a charge image and a two-component developer, and to provide an image formation capable of forming a high-quality and reliable color image free from toner scattering and fogging.

(Polymerization method)
The resin particle dispersion is prepared by homopolymerizing or copolymerizing a vinyl monomer (vinyl resin) by emulsion polymerization or seed polymerization of the vinyl monomer in an ionic surfactant. A dispersion is prepared by dispersing resin particles in an ionic surfactant. 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, The resin is dissolved in the oily solvent, and the solution is finely dispersed in water together with an ionic surfactant and a polymer electrolyte using a disperser such as a homogenizer, and then heated or reduced in pressure to evaporate the oily solvent. As a result, a dispersion is prepared by dispersing resin particles made of resin other than vinyl resin in an ionic surfactant.

  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 can be used.

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

  In the toner of this embodiment, a wax is added as a release agent. In the toner of this embodiment, a resin particle dispersion in which resin particles are dispersed in an aqueous medium, a colorant particle dispersion in which colorant particles are dispersed, and a wax particle dispersion as a release agent are mixed in an aqueous system. Aggregates and heats to form a toner matrix.

  At this time, after mixing and aggregating in the aqueous medium, the temperature of the aqueous medium is heated to a temperature equal to or higher than the melting point of the release agent. As a result, the melting of the wax having sharp melt properties starts and the association between the melted waxes begins. Although the glass transition point (Tg) of the resin is 40 to 60 ° C., even when the aqueous medium is at a temperature higher than the Tg of the resin, the resin does not start to melt sharply like wax, and the surface gradually melts. . Then, fine particles of resin and pigment are aggregated so as to surround the melted wax, and the aggregated resin is also melted and associated by heat. And the state where the low melting point wax is encapsulated by the resin is formed.

  In order for the low melting point wax to be uniformly encapsulated in the resin without being desorbed and suspended at the time of mixing and agglomeration, factors of the particle size distribution of the wax dispersion and the melting property of the wax are large.

  The release agent particle dispersion is prepared by heating a release agent in ion-exchanged water in an aqueous medium to which a polar surfactant is added, and melting and dispersing the release agent.

  At this time, the dispersion particle diameter of the release agent is 16% diameter (PR16) 20 to 200 nm, 50% diameter (PR50) 40 to 300 nm, 84% diameter in the cumulative volume particle size distribution from the small particle diameter side. (PR84) is emulsified and dispersed to a size of 400 nm or less and PR84 / PR16 is 1.2 to 2.0. It is preferable that particles of 200 nm or less are 65 volume% or more and particles exceeding 500 nm are 10 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 aggregated particles are formed by mixing and aggregating the resin particle dispersion, the colorant particle dispersion, and the release agent particle dispersion, the 16% diameter (PR16) is 20 to 200 nm, so that the separation is achieved. The mold agent can be easily taken up between the resin particles, and aggregation between the mold release agents themselves 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.

  Furthermore, when the aggregate particles are heated in an aqueous system to obtain molten aggregate particles, the molten resin particles include molten wax particles due to surface tension, and the release agent is easily included in the resin. Become.

PR16 is greater than 200 nm , 50% diameter (PR50) is greater than 300 nm, PR84 is greater than 400 nm, PR84 / PR16 is greater than 2.0, particles less than 200 nm are less than 65% by volume, less than 500 nm If the amount of particles exceeds 10% by volume, the release agent is difficult to be taken in between the resin particles, and aggregation occurs only between the release agents themselves. There is a tendency that particles that are not taken into the resin particles and float in water increase. When the aggregate particles are heated in an aqueous system to obtain molten aggregate particles, the molten resin particles are unlikely to include the molten release agent particles, and the release agent is less likely to be included in the resin. In addition, when the resin is adhered and fused, the amount of the release agent exposed and released on the surface of the toner base increases, filming on the photoreceptor, increased spent on the carrier, handling properties during development, and development memory are reduced. It tends to occur.

  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 re-aggregation of the release agent occurs when left standing, The standing stability of the particle size distribution is not good. In addition, the load increases during dispersion, heat generation increases, and productivity decreases.

  Further, a resin having a 50% diameter (PR50) in the volume particle size integration when the release agent particles dispersed in the release agent particle dispersion are integrated from the small particle size side forms the melt aggregate particles. By making it smaller than the 50% diameter (PR50) of the particles, the release agent can easily be taken in between the resin particles, and aggregation between the release agents themselves 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 molten resin particles include the molten release agent particles because of the surface tension, and the release agent is included in the resin. It becomes easy. More preferably, it is 20% or more smaller than the 50% diameter (PR50) of the resin particles.

  A release agent melt obtained by melting the release agent at a release agent concentration of 40 wt% or less in a medium to which a dispersant maintained at a temperature equal to or higher than the melting point of the release agent is added to a fixed body and a fixed gap. The release agent particles can be finely dispersed by emulsifying and dispersing by the action of a high shearing force generated by a rotating body that rotates at high speed via.

  By providing a gap of about 0.1 mm to 10 mm on the tank wall in the tank of a constant capacity shown in FIG. 3 and rotating the rotating body at a high speed of 30 m / s or more, preferably 40 m / s or more, A strong shear force acts to obtain an emulsified dispersion having a fine particle size. The dispersion can be formed by a treatment time of about 30 seconds to 5 minutes.

  Further, by applying a strong shearing force action to a fixed body as shown in FIG. 4 with a rotating body rotating at 30 m / s or more, preferably 40 m / s or more with a gap of about 1 to 100 μm. A fine dispersion can be created.

  Compared with a high-pressure disperser such as a high-pressure homogenizer, the particle size distribution of fine particles can be made narrower and sharper. 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 release agent is high, a molten liquid is prepared by heating in a high pressure state. Moreover, a mold release agent is dissolved in an oily solvent. This solution can also be obtained by dispersing fine particles in water together with a surfactant and a polymer electrolyte using a disperser shown in FIGS. 3 and 4, and then evaporating the oily solvent by heating or decompressing.

  The toner base is prepared by dispersing a resin particle dispersion in which the above-described resin particles are dispersed, a colorant particle dispersion in which the colorant particles are dispersed, and a release agent in which the above-described release agent particles are dispersed in an aqueous medium. Mixing with the agent particle dispersion, adjusting the pH of the aqueous medium under a certain condition, and heating the temperature of the aqueous medium above the melting point of the release agent or above the glass transition point of the resin particles in the presence of an inorganic salt. Then, the toner base is formed by aggregation and aggregation.

  Furthermore, the treatment is divided into two stages, and the dispersion is mixed. In the first step, the pH of the aqueous medium is adjusted to a certain condition, and the temperature of the aqueous medium is adjusted in the presence of the inorganic salt. In the second step, the pH of the aqueous medium was adjusted again to a certain condition, and the aqueous medium was further heated to further narrow the particle size distribution. An aggregated and associated toner base can be formed.

  Specifically, assuming that the temperature of the aqueous medium is the melting point Tmw of the release agent and the glass transition point of the resin particles is Tg, the dispersion is mixed, the aqueous medium is adjusted to a pH of 8 or more with 1N NaOH, an inorganic salt In the presence of the toner, a toner base can be produced by heating the aqueous medium at Tmw (° C.) to Tmw + 20 ° C. and / or Tg + 15 (° C.) to Tg + 35 ° C. for 1 to 5 hours to cause aggregation. Preferably, PH is 10 or more, more preferably 11.5 or more.

  When the temperature of the aqueous medium is lower than the melting point Tmw of the release agent, aggregation does not proceed uniformly and particle formation does not proceed. The wax cannot be uniformly encapsulated. If the temperature of the aqueous medium is higher than the melting point Tmw + 20 ° C. of the release agent, condensing proceeds excessively and particles become enormous. The purpose of mixing and agglomerating the PH in the aqueous system at that time under a condition of 8 or more is to promote the agglomeration more uniformly, to make the agglomerated particles have a small particle size and a sharp particle size distribution. When the pH is 8 or less, the agglomeration proceeds excessively, the aggregated particles become large, and the particle size distribution becomes broad. When the pH is 13 or more, the aggregation hardly proceeds. In addition, when the temperature of the aqueous medium is lower than Tg + 15 (° C.), aggregation does not proceed uniformly and particle formation does not proceed. If the temperature of the aqueous medium is higher than Tg + 35 ° C., on the contrary, the aggregation progresses too much and the particles become enormous.

  In the two-stage treatment, the dispersion is mixed, the aqueous medium is adjusted to a pH of 8 or more with 1N NaOH, and the temperature of the aqueous medium is Tmw (° C.) to Tmw + 20 ° C. or Tg + 15 (° C.) in the presence of an inorganic salt. After heating at Tg + 35 ° C. for 1 to 3 hours, in the second step, the aqueous medium is further adjusted to 1 or less again with 1N HCl, and the aqueous medium is adjusted to Tmw (° C.) + 5 ° C. to Tmw + 30 ° C. and / or Tg + 20. By further heating from (° C.) to Tg + 40 ° C. for 1 to 5 hours, an aggregated and aggregated toner base with a sharper particle size distribution can be produced. The PH of the second step is preferably 5 or less, more preferably 4.5 or less.

  If the temperature of the aqueous medium in the second step is lower than Tmw + 5 ° C. with respect to the melting point of the release agent, aggregation does not proceed uniformly and particle formation does not proceed. When the temperature of the aqueous medium is higher than the melting point Tmw + 30 ° C. of the release agent, the aggregation and melting proceed too much and the particles become enormous. When the pH of the aqueous medium is higher than 6, aggregation aggregation does not proceed and the particle size distribution becomes broad.

  Further, a dispersion liquid in which the aggregated and aggregated particles dispersed is mixed with a resin particle dispersion in which resin particles are dispersed, and the resin particles are adhered and fused to the surface of the aggregated and aggregated particles to form a toner base. It is also preferable. The toner base obtained at this time has a volume average particle size of 3 to 8 μm and a coefficient of variation of 25 or less.

  Specific conditions at this time include adjusting the pH of the dispersion in which the aggregated aggregated particles are dispersed to 1 or less with 1N HCl, and then adding and mixing the resin particle dispersion in which the resin particles are dispersed. Thereafter, a certain amount of inorganic salt is added, and the temperature of the aqueous medium is heated at 80 ° C. or higher, preferably 90 ° C. or higher for about 1 to 8 hours, and the resin particles are fused on the surface of the aggregated aggregated particles. It is filtered, washed and dried to produce a toner matrix.

  Further, after the pH of the dispersion in which the aggregated aggregated particles are dispersed is set to about 7 to 10, a resin particle dispersion in which resin particles are dispersed is added and mixed. Thereafter, a certain amount of inorganic salt is added, and the temperature of the aqueous medium is heated for about 0.5 to 2 hours under the condition of 70 to 90 ° C. to adhere the resin particles to the surface of the aggregated and associated particles. Further, a method is also preferred in which the pH is lowered to 6 or less with 1N HCl and the fusion treatment is performed for 1 to 8 hours under the condition that the temperature of the aqueous medium is 80 ° C. or higher, preferably 90 ° C. or higher. After the resin particles are uniformly attached to the surface of the aggregated aggregated particles, the pH can be lowered to perform a fusion process while preventing secondary aggregation, and it becomes possible to create small particle size particles having a more uniform particle size distribution. .

  Examples of 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.

  Particles can also be generated by the following ionization aggregation.

  In an aqueous medium, a resin particle dispersion in which resin particles are dispersed with a dispersant, a colorant particle dispersion in which colorant particles are dispersed with a dispersant having the same polarity as the dispersant of the resin particle dispersion A, and A release agent particle dispersion in which release agent particles are dispersed by a dispersant having a polarity opposite to that of the dispersant of the resin particle dispersion A, and a dispersant having the same polarity as the dispersant of the release agent particle dispersion; The agglomerate particles are formed by mixing and agglomerating, and the aqueous medium is heated to a temperature equal to or higher than the glass transition temperature of the resin to produce melt agglomerate particles, which are filtered, washed and dried to produce a toner base. This is the preferred method.

  In the step of mixing and aggregating these dispersions, aggregated particles of resin fine particles, colorant fine particles, and release agent fine particles are formed in water. At this time, the polarity of the dispersant contained in the resin particle dispersion and the polarity of the dispersant contained in the colorant particle dispersion include a dispersant having the same polarity, and in the release agent fine particle dispersion A dispersant having a polarity opposite to that of the dispersant used for the resin and the colorant is used. Furthermore, a dispersant having a polarity opposite to that of the dispersant used for the resin and the colorant is additionally used alone.

  When using wax having polarity such as acid value, long-chain alkyl group, iodine value, etc. as release agent, it can be uniformly mixed and agglomerated with resin and colorant having polar group having certain acid value, In addition, it is possible to reduce the amount of wax and colorant that do not contribute to aggregation and to float, and aggregate particles having a sharp particle size distribution can be formed.

  Further, the addition of the dispersant to be additionally used alone is carried out at a temperature below the glass transition point of the resin and below the melting point of the release agent wax because the resin particles are added in a state where the resin particles are dispersed in the colorant dispersion. Is preferred. When mixing is performed under this temperature condition, aggregation proceeds in a stable state. Mixing can be performed using, for example, a known mixing device, a homogenizer, a mixer and the like.

  The volume average particle diameter of the aggregated particles formed here is controlled to be the same as or slightly smaller than the volume average particle diameter of the toner to be obtained as the final product. The particle size to be set / changed can be controlled by the amount of the dispersant added, the stirring speed, the treatment, and the temperature.

  Further, a fine particle dispersion obtained by further dispersing resin fine particles in the above-described aggregated particle dispersion is added and mixed in the aggregated particle dispersion to adhere the resin fine particles to the aggregated particles. At this time, the polarity of the resin fine particle dispersant is the same as that of the resin dispersion used when the aggregated particles are generated.

  At this time, by adding an inorganic metal salt as an aggregating agent, resin fine particles can be attached at an early stage, and the production rate can be increased.

  When water is used as the solvent in the aggregation process, for example, when the resin fine particles obtained by the emulsion polymerization method and the colorant are dispersed in water to form aggregated particles and fused, the pH of the dispersion system is 2.0 to 14 By adjusting between the two, the electric attractive force and repulsive force of the fine particles are controlled, so that the progress of aggregation can be stopped and the dispersion system can be stabilized. In this case, in general, the surface potential can be stabilized at a lower pH if the surface potential is a cation type, and can be stabilized at a higher pH if the surface potential is an anionic type. From the viewpoint of chemical decomposition stability such as decomposition, and transient stability, it is a problem from the viewpoint of leading to destruction of the aggregated particles themselves.

  Thereafter, the toner 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 the dispersant having polarity include an aqueous medium containing a polar surfactant. 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.

  Examples of polar surfactants include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap, and cationic surfactants such as amine salt type and quaternary ammonium salt type. Can be mentioned.

  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.

  In the present invention, these polar surfactants and nonpolar surfactants can be used in combination. Examples of the nonpolar surfactant include nonionic surfactants such as polyethylene glycol, alkylphenol ethylene oxide adducts, and polyhydric alcohols.

  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.

(wax)
An ester wax is preferably used as a release agent to be added to the toner of this embodiment.

  The wax is preferably a wax having an iodine value of 25 or less and a saponification value of 30 to 300. The repulsion due to the charge effect of the toner during the multi-layer transfer of toner can be alleviated, so that the transfer efficiency can be reduced, the character dropout during transfer and reverse transfer can be suppressed. In addition, the use in combination with a carrier described later can suppress the occurrence of spent on the carrier and can extend the life of the developer. Further, the handling property in the developing device is improved, and the uniformity of the image is improved on the rear side and the front side of the development. Further, development memory generation can be reduced.

  When the iodine value is larger than 25, the mixing and cohesion in the aqueous system is deteriorated, the uniform dispersibility is lowered, and the color turbidity is generated. If the suspended matter increases and remains in the toner, filming of the photoreceptor or the like occurs. 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. The environmental dependency is large, and the change in the charging property of the material becomes large during long-term continuous use, which hinders the stability of the image. Development memory is also likely to occur. When the saponification value is less than 30, the presence of unsaponifiable matter and hydrocarbons increases, and photoconductor filming and chargeability are deteriorated. It causes a decrease in chargeability during filming and continuous use. If it exceeds 300, the wax dispersibility with the resin at the time of mixing and aggregation deteriorates. The repulsion due to the charge action of the toner is less likely to be alleviated. In addition, fog and toner scattering increase.

  The heat loss of the wax at 220 ° C. is preferably 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 at the time of generating emulsified dispersed particles during the action of high shear force due to high-speed rotation becomes broad.

Molecular weight characteristics in gel permeation chromatography (GPC), 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 1.01. 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 and has at least one molecular weight maximum peak. Preferably it is. 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 at the time of generating emulsified dispersed particles during the action of high shear force due to high-speed rotation 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 function is weakened, and fixing functions such as fixing property and offset resistance are provided. Decreases. It becomes difficult to reduce the particle size of the generated particles when the emulsified dispersed particles are generated when a high shearing force is applied by high-speed rotation. It becomes difficult to uniformly encapsulate the wax in the resin.

  An endothermic peak temperature (melting point Tmw) by DSC method is preferably 50 to 100 ° C. Preferably it is 55-95 degreeC, More preferably, it is 65-85 degreeC. When the temperature is lower than 50 ° C., the storage stability of the toner is deteriorated. When the temperature is higher than 100 ° C., it is difficult to reduce the particle diameter of the generated particles when the emulsified dispersed particles are generated. It becomes difficult to uniformly encapsulate the wax in the resin.

  Furthermore, the material whose volume increase rate at the time of 10 degreeC change at the temperature more than melting | fusing point is 2 to 30% 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.

  The addition amount is preferably 5 to 90 parts by weight with respect to 100 parts by weight of the binder resin. The addition is preferably 7 to 80 parts by weight, more preferably 10 to 70 parts by weight, and still more preferably 50 to 70 parts by weight with respect to 100 parts by weight of the binder resin. If it is 5 parts by weight or less, the effect of improving the fixing property cannot be obtained, and if it is 90 parts by weight or more, there is a problem in storage stability.

  As the wax, materials such as meadow foam oil, carnauba wax derivatives, jojoba oil, wood wax, beeswax, ozokerite, carnauba wax, canderia wax, ceresin wax, rice wax, etc. are preferable, and these derivatives are also preferably used. Is done. One type or a combination of two or more types can be used. In particular, carnauba wax having a melting point of 76 to 90 ° C by DSC method, candelilla wax having 66 to 80 ° C, hydrogenated jojoba oil having 64 to 78 ° C, hydrogenated meadowfoam oil having 74 to 78 ° C, or 74 At least one or two or more kinds of waxes selected from the group consisting of rice waxes having a temperature of ˜90 ° C. are more preferable.

  Saponification value refers to the number of milligrams of potassium hydroxide KOH 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. This is the number of grams of iodine absorbed by 100 g of fat, 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 chloride glacial acetic acid solution to chloroform or carbon tetrachloride solution of sample and titrate the remaining iodine without reaction 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), and 10 to 15 mg of the sample is put in this, and then 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. .

Thereby, it is possible to improve the translucency in the color image and to improve the resistance to offset to the roller. Further, it is possible to suppress the occurrence of spent on the carrier and to extend the life of the developer.

Further, a wax represented by (Chemical Formula 1) obtained by reacting a long-chain alkyl alcohol having 4 to 30 carbon atoms with an unsaturated polyvalent carboxylic acid or an anhydride thereof and an unsaturated hydrocarbon wax, or a long-chain alkylamine Wax obtained by reaction of unsaturated polyvalent carboxylic acid or its anhydride and unsaturated hydrocarbon wax, or long-chain fluoroalkyl alcohol with unsaturated polycarboxylic acid or its anhydride and unsaturated hydrocarbon wax A wax obtained by the reaction with can also be suitably used.

  In the formula, R represents hydrogen, an ethylene group or a propylene group, m and k are each an integer of 1 or more, m <k, and n is 4 to 30, preferably 6 to 20.

In the molecular weight distribution in GPC of this 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 Z-average molecular weight to number-average molecular weight (Z-average molecular weight / number-average molecular weight) has at least one molecular weight maximum peak in the region of 1.5 to 6.5, 1 × 10 ^{3 to} 3 × 10 ⁴ The penetration value at an acid value of 5 to 50 mgKOH / g, a melting point of 50 to 120 ° C. and 25 ° C. is preferably 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) preferably has at least one molecular weight maximum peak in a region of 1.5 to 4.5, 1 × 10 ³ to 1 × 10 ⁴ , more preferably. Weight average molecular weight is 1000 to 2500, Z average molecular weight is 1900 to 3000, Ratio of weight average molecular weight to number average molecular weight (weight average molecular weight / number average molecular weight) is 1.2 to 1.8, Z average molecular weight and number average molecular weight the ratio of (Z average molecular weight / number average molecular weight) is to have at least one molecular weight maximum peak in the region of ^{1.7~2.5,1 × 10 3 ~3 × 10 3} .

  Non-offset property and high glossiness in oilless fixing, and high translucency of OHP can be expressed, and high temperature storage stability is not deteriorated. In an image in which three layers of color toner are formed on thin paper, this is particularly effective for improving the paper separation from the fixing roller and belt.

  Further, uniform dispersion with a resin pigment is possible by dispersion and mixed aggregation in a specific polar dispersant described later, and the presence of suspended solids is eliminated, thereby suppressing color turbidity. Further, when the subsequent resin is further adhered and fused, the release of the wax is difficult to occur.

  Further, even if a fluorine-based or silicone-based member is used for the fixing roller, the offset of the halftone image can be prevented.

  By using it in combination with the carrier described later, the generation of spent can be suppressed together with oilless fixing, the life of the developer can be extended, the uniformity in the developing device can be maintained, and the occurrence of development memory can also be suppressed. Furthermore, charging stability during continuous use can be obtained, and both fixing property and development stability can be achieved.

  Here, if the carbon number of the long-chain alkyl of the 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. If the acid value is less than 5 mgKOH / g, the charge amount during long-term use of the toner is reduced. When the acid value is larger than 50 mgKOH / g, the moisture resistance is lowered, and the fogging under high humidity is increased. If it is high, it is difficult to reduce the particle size of the produced particles when the emulsified dispersed particles are produced. It becomes difficult to uniformly encapsulate the wax in the resin.

  When the melting point is less than 50 ° C., the storage stability of the toner is lowered. When the melting point is higher than 120 ° C., the releasing action is weakened and the non-offset temperature range is narrowed. If it is high, it is difficult to reduce the particle size of the produced particles when the emulsified dispersed particles are produced. It becomes difficult to uniformly encapsulate the wax in the resin.

  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. Also, development memory is likely to occur. The particle size distribution of the produced particles at the time of producing the emulsified dispersed particles at the time of the action of a high shearing force by high-speed rotation 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 If the peak is located in a range larger than the region of 3 × 10 ⁴ , the releasing action is weakened and the fixing offset property is lowered. It becomes difficult to reduce the particle size of the generated particles when the emulsified dispersed particles are generated when a high shearing force is applied by high-speed rotation. It becomes difficult to uniformly encapsulate the wax in the resin.

  As the alcohol, those having a long alkyl chain such as octanol, dodecanol, stearyl alcohol, nonacosanol, pentadecanol and the like 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 and the like can be preferably used. As the unsaturated polyvalent carboxylic acid or anhydride thereof, one or more of maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and the like can be used. 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.

  The addition amount is preferably 5 to 90 parts by weight with respect to 100 parts by weight of the binder resin. The addition is preferably 7 to 80 parts by weight, more preferably 10 to 70 parts by weight, and still more preferably 50 to 70 parts by weight with respect to 100 parts by weight of the binder resin. If it is 5 parts by weight or less, the effect of improving the fixing property cannot be obtained, and if it is 90 parts by weight or more, there is a problem in storage stability.

(resin)
An example of the resin fine particles of the toner of the present embodiment is a thermoplastic binder resin. Specifically, styrenes such as styrene, parachlorostyrene, and α-methylstyrene; acrylic monomers such as methyl acrylate, ethyl acrylate, n-propyl acrylate, lauryl acrylate, and 2-ethylhexyl acrylate; Methacrylic monomers such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate; and ethylenically unsaturated acids such as acrylic acid, methacrylic acid, sodium styrenesulfonate Vinyl nitriles such as acrylonitrile and methacrylonitrile; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; ethylene, Homopolymers such as monomers such as olefins such as lopyrene and butadiene, copolymers obtained by combining two or more of these monomers, or mixtures thereof, and epoxy resins, polyester resins, polyurethane resins, Polyamide resins, cellulose resins, polyether resins, etc., non-vinyl condensation resins, or mixtures of these with vinyl resins, graft polymers obtained by polymerizing vinyl monomers in the presence of these resins, etc. Can be mentioned.

  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. In the present invention, the resin particles preferably contain the vinyl monomer as a monomer component. In the present invention, among these vinyl monomers, vinyl polymer acids are more preferable from the viewpoint of ease of formation reaction of vinyl resins, and specifically, acrylic acid, methacrylic acid, maleic acid, cinnamon. A dissociable vinyl monomer having a carboxyl group such as an acid or fumaric acid as a dissociating group is particularly preferred from the viewpoint of controlling the degree of polymerization and the glass transition point.

  The content of the resin particles in the resin particle dispersion is usually 5 to 50% by weight, preferably 10 to 30% by weight.

  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 HPLC 8120 series manufactured by Tosoh Corporation, the column is TSKgel superHM-H H4000 / H3000 / H2000 (7.8 mm diameter, 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., pretreatment for measurement is to measure a resin component obtained by dissolving a sample in THF and filtering through a 0.45 μm filter to remove additives such as silica. 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.

  In addition, the measurement of the wax obtained by the reaction with a long chain alkyl alcohol having 4 to 30 carbon atoms, an unsaturated polyvalent carboxylic acid or its anhydride, and an unsaturated hydrocarbon wax was performed using a GPC-150C manufactured by WATERS. 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 The measurement temperature was 130 ° C., and the pre-measurement treatment was performed by filtering the sample with a 0.5 μm sintered metal filter after dissolving the sample in a solvent. 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 type capillary rheometer flow tester (CFT500) manufactured by Shimadzu Corporation. Applying a load of × 10 ⁵ N / m ² , pushing out from a die with a diameter of 1 mm and a length of 1 mm, the piston stroke starts 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 was determined by using a differential scanning calorimeter (Shimadzu DSC-50). The temperature was raised to 200 ° C. at 5 ° C./min, rapidly cooled to 10 ° C. for 5 minutes, then allowed to stand for 15 minutes, then 5 ° C. / The temperature was raised in min, and the endothermic (melting) peak was obtained. The amount of sample put into the cell was 10 mg ± 2 mg.

(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. When used 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. Further, as a preferable material, a metal salt of a salicylic acid derivative shown in (Chemical Formula 2) 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 at the time of emulsion polymerization (for example, a styrene monomer is suitable), and the monomer is subjected to emulsion polymerization, whereby a resin fine particle dispersion to which CCA is added can be prepared.

  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.

(Pigment)
Examples of the colorant used in this embodiment include carbon black, iron black, graphite, nigrosine, azo dye metal complexes, C.I. I. Acetoacetic acid arylamide monoazo yellow pigments such as CI Pigment Yellow 1,3,74,97,98; I. Acetoacetic acid arylamide disazo yellow pigments such as C.I. Pigment Yellow 12, 13, 14, and 17; I. Solvent Yellow 19, 77, 79, C.I. I. Disperse Yellow 164 is blended, and C.I. I. Pigment yellow 93, 180, and 185 benzimidazolone systems are preferred.

  C. 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, 8; I. One or two or more kinds of blue dyed pigments of phthalocyanine and derivatives thereof such as Pigment Blue 15: 3 are blended. 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).

(External additive)
Further, in this embodiment, as external additives, fine metal oxide powders such as silica, alumina, titanium oxide, zirconia, magnesia, ferrite and magnetite, titanates such as barium titanate, calcium titanate and strontium titanate, zirconic acid Zirconates such as barium, calcium zirconate, strontium zirconate, or mixtures thereof are used. The external additive is hydrophobized as necessary.

  As the silicone oil-based material treated with silica, those shown in (Chemical Formula 3) 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 Silica 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. For example, SH200, SH510, SF230, SH203, BY16-823, BY16-855B, etc. manufactured by Toray Dow Corning Silicone may be mentioned. For the treatment, a method of mixing inorganic fine powder and a material such as silicone oil with a mixer such as a Henschel mixer, a method of spraying a silicone oil-based material onto silica, or a solution in which a silicone oil-based material is dissolved or dispersed in a solvent Then, after mixing with silica fine powder, there is a method of removing the solvent to prepare. It is preferable that 1 to 20 parts by weight of the silicone oil-based material is blended with respect to 100 parts by weight of the inorganic fine powder.

  As silane coupling agents, dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, hexamethyldisilazane, allylphenyldichlorosilane, benzylmethylchlorosilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, There are vinyltriacetoxysilane, divinylchlorosilane, dimethylvinylchlorosilane, and the like. The silane coupling agent treatment is a dry treatment in which the vaporized silane coupling agent is reacted with a fine powder made into a cloud by stirring or the like, or a wet treatment in which a silane coupling agent in which the fine powder is dispersed in a solvent is dropped. Processed by law.

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

  The inorganic fine powder having positive electrode chargeability is treated with aminosilane, amino-modified silicone oil or epoxy-modified silicone oil represented by (Chemical Formula 4).

  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.

  It is also preferable to treat the surface of the inorganic fine powder with a fatty acid ester, a fatty acid amide, or a fatty acid metal salt. Silica or titanium oxide fine powder obtained by surface-treating any one kind or two or more kinds is more preferred.

  Examples of fatty acids and fatty acid metal salts include caprylic acid, capric acid, undecyl 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 14 to 20 carbon atoms are preferred.

Examples of the metal constituting the fatty acid metal salt include aluminum, zinc, calcium, magnesium, lithium, sodium, lead, and barium. Of these, aluminum, zinc, and sodium are preferable. Particularly preferably, 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. Moreover, it is thought that the processability with inorganic fine powders, such as a silica, improves at the time of a process.

  In addition, the handling property of the toner having a small particle diameter can be improved, and both high image quality and improved transferability can be achieved in development and transfer. In development, the latent image can be reproduced more faithfully. Transfer can be performed without deteriorating the transfer rate of the toner particles during transfer. Further, in tandem transfer, retransfer can be prevented, and occurrence of voids can be suppressed. Furthermore, a high image density can be obtained even if the development amount is reduced. In addition, use in combination with a carrier, which will be described later, can further improve spent resistance, improve handling in the developing device, and increase toner density uniformity. Moreover, development memory generation can be suppressed.

  A configuration in which an inorganic fine powder having an average particle diameter of 6 nm to 200 nm is externally added to 1.5 to 6 parts by weight with respect to 100 parts by weight of toner base particles is preferable. If the average particle diameter is smaller than 6 nm, silica floating or filming on the photoreceptor is 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 1.5 parts by weight, the fluidity of the toner is deteriorated. The occurrence of reverse transcription during transcription cannot be suppressed. If the amount is more than 6 parts by weight, silica floating and filming on the photoreceptor are likely to occur. High temperature offset is deteriorated.

  Further, the inorganic fine powder having an average particle diameter of 6 nm to 20 nm is 0.5 to 2.5 parts by weight with respect to 100 parts by weight of the toner base particles, and the inorganic fine powder having an average particle diameter of 20 nm to 200 nm is 100 parts by weight of the toner base particles. In contrast, a configuration in which 1.0 to 3.5 parts by weight is at least externally added is preferable. By using the silica whose function is separated by this configuration, it is possible to obtain a margin for handling property in development, reverse transfer at the time of transfer, dropout, and scattering. In addition, the spent on the carrier can be prevented.

  Furthermore, the ignition loss of the inorganic fine powder having an average particle diameter of 6 nm to 20 nm is preferably 1.5 to 25 wt%, and the ignition loss of the average particle diameter of 20 nm to 200 nm is preferably 0.5 to 23 wt%.

  By specifying the loss on ignition of silica, more margin can be taken against reverse transfer, dropout and scattering during transfer. Further, the use in combination with the above-described carrier and wax can improve the spent resistance, improve the handling property in the developing device, and increase the toner density uniformity. Moreover, development memory generation can be suppressed.

  If the loss on ignition with an average particle size of 6 nm to 20 nm is less than 1.5 wt%, the transfer margin for reverse transfer and voids becomes narrow. If it exceeds 25 wt%, the surface treatment becomes uneven, resulting in uneven charging. The ignition loss is preferably 1.5 to 20 wt%, more preferably 5 to 19 wt%.

  If the loss on ignition with an average particle diameter of 20 nm to 200 nm is less than 0.5 wt%, the transfer margin for reverse transfer and hollow out becomes narrow. If it exceeds 23 wt%, the surface treatment becomes uneven, resulting in uneven charging. The ignition loss is preferably 1.5 to 18 wt%, more preferably 5 to 16 wt%.

  Further, a positively chargeable inorganic fine powder having an average particle diameter of 6 nm to 200 nm and an ignition loss of 0.5 to 25 wt% is further added to at least 0.5 to 1.5 parts by weight with respect to 100 parts by weight of the toner base particles. A configuration in which external addition processing is performed is also preferable.

  The effect of adding the positively chargeable inorganic fine powder suppresses the toner from being overcharged during long-term continuous use, and can further extend 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 0.5 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 moisture adsorption amount of the processed inorganic fine powder 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 invaded in the liquid until the total amount of the inorganic fine powder 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.

Hydrophobic degree = (a / (50 + a)) × 100 (%)
(Toner powder properties)
In this embodiment, the toner base particles containing at least a binder resin, a colorant and a wax containing a binder resin, a colorant and a wax have a volume average particle size of 3 to 8 μm, preferably 3 to 6.5 μm, more preferably 3 The content of toner base particles having a particle size of 2.52 to 4 μm in the number distribution is 5 to 65% by number, and the particle size is 6.35 to 10.1 μm in the volume distribution. The toner particle size distribution is 5 to 35% by volume. The coefficient of variation in the volume average particle size is 25 or less.

  More preferably, toner base particles having a particle size of 2.52 to 4 μm in the number distribution are contained in an amount of 15 to 65% by number, and toner base particles having a particle size of 6.35 to 10.1 μm in the volume distribution. Is a particle size distribution containing from 5 to 25% by volume. The coefficient of variation in the volume average particle size is 20 or less.

  More preferably, toner base particles having a particle size of 2.52 to 4 μm in the number distribution are contained in an amount of 25 to 65% by number, and toner base particles having a particle size of 6.35 to 10.1 μm in the volume distribution. Is a particle size distribution containing 5 to 15% by volume. The coefficient of variation in volume average particle size is 18 or less.

  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.

  If the volume average particle size is larger than 8 μm, it is impossible to achieve both image quality and transfer. When the volume average particle size is smaller than 3 μm, it becomes difficult to handle the toner particles during development. If the content of toner base particles having a particle size of 2.52 to 4 μm in the number distribution is less than 5% by number, it is impossible to achieve both image quality and transfer. When the content is more than 65% by number, it becomes difficult to handle the toner base particles during development. When toner mother particles having a particle size of 6.35 to 10.1 μm are contained in an amount of more than 35% by volume, it is impossible to achieve both image quality and transfer. If it is less than 5% by volume, the toner productivity is lowered and the cost is increased.

  It is preferable that the variation coefficient of the volume particle size distribution of the toner base particles is 15 to 25% and the variation coefficient of the number particle size distribution is 15 to 28%. More preferably, the variation coefficient of the volume particle size distribution is 15 to 20%, the variation coefficient of the number particle size distribution is 15 to 23%, and more preferably, the variation coefficient of the volume particle size distribution is 15 to 18%, The variation coefficient of distribution is 15 to 20%.

  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 refers to the degree of spread of the particle size distribution, and if the coefficient of variation of the volume particle size distribution is less than 15% or the coefficient of variation of the number particle size distribution is less than 15%, it is difficult to produce, This will increase costs. If the coefficient of variation in volume particle size distribution is greater than 25% or the coefficient of variation in number particle size distribution is greater than 28%, the toner becomes more cohesive when the particle size distribution becomes broader, and filming and transfer to a photoreceptor. It is difficult to collect residual toner in a defective and cleaner-less process.

  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 release agent such as wax for realizing oil-less fixing, the amount of fine powder affects compatibility with tandem transferability.

  When the amount of fine powder is excessive, that is, when the content of toner base particles having a particle diameter of 2.52 to 4 μm is more than 65% by number, the wax that cannot be dispersed increases the exposure of the toner surface, and the photoreceptor and development Filming on the roller and the transfer member occurs. 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. On the other hand, if the amount of fine powder decreases, the image quality deteriorates and an appropriate range is required.

  The particle size distribution is measured using a Coulter Counter TA-II type (Coulter Counter Co., Ltd.) by 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.

(Career)
As the resin-coated carrier of this embodiment, a carrier having a coating resin layer made of a fluorine-modified silicone resin containing an aminosilane coupling agent as a carrier core material is preferably used.

  Examples of the carrier core material include an iron powder carrier core material, a ferrite carrier core material, a magnetite carrier core material, and a resin-dispersed carrier core material in which a magnetic material is dispersed in a resin.

  Here, as an example of the ferrite carrier core material, it is generally represented by the following formula.

(MO) _X (Fe ₂ O ₃ ) _Y
In the formula, M contains at least one selected from Cu, Zn, Fe, Mg, Mn, Ca, Li, Ti, Ni, Sn, Sr, Al, Ba, Co, Mo and the like. X and Y represent the molar ratio by weight and satisfy the condition X + Y = 100.

Ferrite carrier core material is Fe ₂ O ₃ as a main raw material, M is from Cu, Zn, Fe, Mg, Mn, Ca, Li, Ti, Ni, Sn, Sr, Al, Ba, Co, Mo, etc. At least one selected oxide is mixed and used as a raw material.

  As an example of a method for producing a ferrite-based carrier core material, first, an appropriate amount of raw materials such as the above oxides are blended, pulverized, mixed and dried for 10 hours by a wet ball mill, and then held at 950 ° C. for 4 hours. This is pulverized with a wet ball mill for 24 hours, and further added with polyvinyl alcohol, an antifoaming agent, a dispersing agent or the like as a binder to form a slurry having a raw material particle size of 5 μm or less. This slurry is granulated and dried to obtain a granulated product, which is kept at 1300 ° C. for 6 hours while controlling the oxygen concentration, and then pulverized and further classified into a desired particle size distribution.

  As the resin used in the resin coating layer of the present invention, a fluorine-modified silicone resin is effective. As the fluorine-modified silicone resin, a curable cross-linked fluorine-modified silicone resin obtained by hydrolyzing the following (Chemical Formula 5) and / or (Chemical Formula 6) with an organic silicon compound containing a perfluoroalkyl group is essential. preferable.

(Wherein R ₁ , R ₂ and R ₃ represent a hydrogen atom, a halogen atom, a hydroxy group, a methoxy group, an alkyl group having 1 to 4 carbon atoms, and a phenyl group.)
Examples of perfluoroalkyl group-containing organosilicon compounds 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 , and 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.

  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 (SH6020, SZ6023, AY43-021: from Toray Dow Corning Silicone Co., Ltd.), KBM602, KBM603, KBE903, KBM573 (Shin-Etsu Silicone Co., Ltd.), etc. 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 when the humidity is high. 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.

  Further, in the toner configuration described above, the surface of the toner to which a certain amount or more of the low melting point wax is added is substantially resin, so that the chargeability is somewhat unstable. For example, a case where the charging property is weak and the charging start-up property is delayed is assumed, and the uniformity of the fog and the whole surface of the solid image is deteriorated. By using these in combination, the above-mentioned problems are improved, the handling property in the developing device is improved, and the density uniformity on the back side and the near side of the development on the image is improved. In addition, 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. It may cause the occurrence.

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 preferred. 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 adversely affected. 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 average particle size of the carrier of this embodiment is preferably 20 to 70 μm. When the average particle diameter of the carrier is less than 20 μm, the abundance ratio of the fine particles is increased 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 70 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.

  The method for forming the coating layer on the carrier core material is not particularly limited. For example, a known coating method, for example, a dipping method in which powder as a carrier core material is immersed in a solution for forming a coating layer, or for forming a coating layer. Spray method for spraying the solution onto the surface of the carrier core material, Fluidized bed method for spraying the solution for forming the coating layer in a state where the carrier core material is suspended by the fluidized air, Solution for forming the carrier core material and the coating layer in a kneader coater In addition to wet coating methods such as the kneader coater method that removes the solvent, the powdered resin and the carrier core material are mixed at high speed, and the frictional heat is used to melt the resin powder onto the surface of the carrier core material. Examples thereof include dry coating methods for applying and coating, and any of them can be applied, but the wet coating method 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 amount of the resin coating 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, based on the carrier core material. 7 to 3% by weight. When the coating amount of the resin is less than 0.2% by weight, a uniform coating cannot be formed on the surface of the carrier, and it is greatly affected by the characteristics of the carrier core material, and the fluorine-modified silicone resin of the present invention The effect of the aminosilane coupling agent cannot be exhibited sufficiently. If it exceeds 6.0% by weight, the coating layer becomes too thick, and granulation of carrier particles occurs, and uniform carrier particles tend not to be obtained.

  After coating the resin, 120 to 280 ° C. and 0.5 to 2.5 hours are appropriate as the conditions for the curing treatment. 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.

(Two-component development)
An AC bias is applied between the photoconductor 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 the present embodiment, dots can be faithfully reproduced and development γ characteristics can be obtained. Both high-quality images and oilless fixability can be achieved. Further, even a high-resistance carrier can prevent charge-up under low humidity, and a high image density can be obtained even in continuous use. This is a toner that can exhibit high chargeability. By combining the carrier structure and AC bias, the adhesion to the carrier can be reduced, image density can be maintained, fog can be reduced, and dots can be reproduced faithfully. .

  If the frequency is smaller than 1 kHz, dot reproducibility is deteriorated and halftone reproducibility is deteriorated. 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 photoreceptor, 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.

(Tandem color process)
In addition, in order to form a color image at high speed, this embodiment has a plurality of toner image forming stations including a photosensitive member, a charging unit, and a toner carrier, and develops an electrostatic latent image formed on the image carrier. A primary transfer process in which an imaged toner image is transferred to the transfer body by bringing an endless transfer body into contact with the image carrier is sequentially performed, and a multilayer transfer toner image is formed on the transfer body. In the transfer process configured to execute a secondary transfer process in which a multi-layer toner image formed and then formed on the transfer body is collectively transferred to a transfer medium such as paper or OHP, the first primary When the distance from the transfer position to the second primary transfer position is d1 (mm) and the peripheral speed of the photoreceptor is v (mm / s), the transfer position configuration is d1 / v ≦ 0.65. , Both machine miniaturization and printing speed Is shall. In order to realize a reduction in size that can process 16 sheets per minute (A4) or more and the machine can be used for SOHO applications, 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 this configuration is adopted, 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. When the magenta toner is transferred onto the yellow toner, the magenta toner is repelled by the charge action of the yellow toner, resulting in a problem that the transfer efficiency is lowered and characters are lost during transfer. Further, during the primary transfer of the cyan toner of the third color, the cyan toner scatters, transfer failure, and transfer loss 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 this embodiment, the charge distribution is stabilized, the toner is 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.

(Cleanerless process)
Further, in this embodiment, an electrophotography having a basic structure of a cleanerless process in which the following charging, exposure, and development processes are performed without having a cleaning process step of recovering toner remaining on the photoreceptor after the transfer process by cleaning. It is preferably used for an apparatus.

  By using the toner or the two-component developer of this embodiment, toner aggregation is suppressed, overcharging is prevented, charging property is stabilized, and high transfer efficiency can be obtained. Further, the improvement in uniform dispersibility in the resin, good chargeability, and the releasability of the material make it possible to recover the toner remaining in the non-image area during development. For this reason, there is no development memory in which the image pattern in front of the non-image portion remains.

(Oil-less color fixing)
In this embodiment, it is suitably used for an electrophotographic apparatus having a fixing process of an oil-less fixing configuration in which oil is not used as a means for fixing toner. 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, 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, silicone rubber, fluororubber, or fluororesin is used as the surface layer.

  In these fixing processes, release oil has been applied so far 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 when 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 1)
Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to this.

(1) Carrier production example 1
120 g of a cross-linked fluorine-modified silicone resin containing 15 mol% of SiO having a trifluoropropyl group and 6 g of γ- (2-aminoethyl) aminopropyltrimethoxysilane were dissolved in 300 cc of a toluene solvent in terms of solid content. This was coated on 10 kg of ferrite particles having an average particle diameter of 50 μm and a saturation magnetization of 65 emu / g when the applied magnetic field was 3000 oerste using an immersion drying type coating apparatus, and then at 230 ° C. for 1.5 hours. Baking was performed to obtain carrier A1.

(2) Carrier production example 2
A core material is produced in the same process as in Production Example 1 except that the coating resin is changed to a crosslinked fluorine-modified silicone resin containing 15 mol% of C ₈ F ₁₇ CH ₂ CH ₂ Si (OCH ₃ ) _3. And carrier A2 was obtained.

(3) Carrier production example 3
The core material is manufactured and coated in the same process as in Manufacturing Example 1 except that conductive carbon (EC made by Ketjen Black International Co., Ltd.) is dispersed in a pearl mill at 5 wt% based on the resin solid content. A3 was obtained.

(4) Carrier production example 4
Except having changed the addition amount of the aminosilane coupling agent into 30g, the core material was manufactured in the process similar to the manufacture example 3, it coated, and carrier A4 was obtained.

(5) Carrier Production Example 5 Ratio A core material was produced in the same steps as in Production Example 3 except that the amount of aminosilane coupling agent added was changed to 50 g, and coating was performed to obtain carrier b1.

(6) Carrier production example 6 ratio Except that the coating resin was changed to straight silicone (SR-2411 manufactured by Toray Dow Corning Co., Ltd.), the core material was produced in the same process as in Production Example 1, coated, and carrier b2 Got.

(7) Carrier Production Example 7 Ratio Except that the coating resin was changed to a perfluorooctylethyl acrylate / methacrylate copolymer, a core material was produced in the same steps as in Production Example 3, and coated to obtain carrier b3. .

(8) Carrier production example 8 ratio Except for changing the coating resin to an acrylic-modified silicone resin (KR-9706, manufactured by Shin-Etsu Chemical Co., Ltd.), the core material is produced and coated in the same process as carrier production example 3, and the carrier is produced. b4 was obtained.

(Example 2)
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 peak value of molecular weight, Tm is a softening point, and Tg 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 consisting of 96 g of styrene, 24 g of n-butyl acrylate, and 3.6 g of acrylic acid was added to an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd.) in 200 g of ion-exchanged water. Manufactured by: Neogen RK) 3 g, dodecanethiol 6 g, carbon tetrabromide 1.2 g, potassium persulfate 1.2 g was added thereto, and emulsion polymerization was performed at 70 ° C. for 6 hours. A resin particle dispersion RL1 was prepared in which resin particles having Mw of 10900, Mz of 37800, Mp of 8100, Tm of 115 ° C., Tg of 43 ° C., and a median diameter of 0.12 μm were dispersed.

(2) Preparation of resin particle dispersion RL2 A monomer liquid consisting of 204 g of styrene, 36 g of n-butyl acrylate, and 3.6 g of acrylic acid was added to an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd.) in 400 g of ion-exchanged water. Manufactured by Neogen RK) 6 g, dodecanethiol 6 g, carbon tetrabromide 1.2 g, potassium persulfate 1.2 g was added thereto, and emulsion polymerization was performed at 70 ° C. for 5 hours. A resin particle dispersion RL2 in which resin particles having an Mw of 60300, an Mz of 259000, an Mp of 8100, a Tm of 128 ° C., a Tg of 55 ° C., and a median diameter of 0.18 μm was prepared was prepared.

(3) Preparation of resin particle dispersion RL3 A monomer liquid consisting of 204 g of styrene, 36 g of n-butyl acrylate, and 3.6 g of acrylic acid was added to an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd.) in 400 g of ion-exchanged water. (Production: Neogen RK) 6 g, dodecanethiol 12 g, carbon tetrabromide 2.4 g, and potassium persulfate 1.2 g was added thereto, and emulsion polymerization was performed at 70 ° C. for 5 hours. A resin particle dispersion RL3 was prepared in which resin particles having an Mw of 18300, Mz of 96200, Mp of 2700, Tm of 109 ° C., Tg of 45 ° C., and a median diameter of 0.18 μm were dispersed.

(4) Preparation of resin particle dispersion RH4 A monomer liquid consisting of 102 g of styrene, 18 g of n-butyl acrylate, and 1.8 g of acrylic acid was added to an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd.) in 200 g of ion-exchanged water. Manufactured by: Neogen RK) 3 g, dodecanethiol 0 g, carbon tetrabromide 0 g, and potassium persulfate 1.2 g is added thereto, followed by emulsion polymerization at 70 ° C. for 5 hours. Mn is 43300, Mw is A resin particle dispersion RH4 was prepared in which resin particles having 262000, Mz of 577000, Mp of 182000, Tm of 197 ° C., Tg of 77 ° C., and median diameter of 0.12 μm were dispersed.

(5) Preparation of resin particle dispersion RH5 A monomer liquid consisting of 102 g of styrene in which 4 g of an aluminum salicylate metal complex (Orient Chemical Co., Ltd .: E88) was melted, 18 g of n-butyl acrylate, and 1.8 g of acrylic acid was ionized. In 200 g of exchange water, 3 g of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) was dispersed using 0 g of dodecanethiol and 0 g of carbon tetrabromide, and 1.2 g of potassium persulfate was added thereto. Emulsion polymerization was performed at 70 ° C. for 5 hours, and resin particles having Mn of 41000, Mw of 242000, Mz of 575000, Mp of 154000, Tm of 193 ° C., Tg of 76 ° C., and median diameter of 0.22 μm were dispersed. Resin particle dispersion RH5 was prepared.

Example 3
Table 2 shows the pigments used.

(1) Preparation of Colorant Particle Dispersion Liquid PM1 20 g of magenta pigment (KETRED 309 manufactured by Dainippon Ink & Co.), 2 g of anionic surfactant (Neogen R manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 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 liquid 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 & Co., Ltd.), 2 g of anionic surfactant (Neogen R manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 78 g of ion-exchanged water are mixed and ultrasonicated. Dispersion was performed for 20 minutes at an oscillation frequency of 30 kHz using a 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 (Y180 manufactured by Clariant), 2 g of anionic surfactant (Neogen R manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and 78 g of ion-exchanged water were mixed, and an ultrasonic disperser. Was used for dispersion for 20 minutes at an oscillation frequency of 30 kHz 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 Co., Ltd.), 2 g of anionic surfactant (Neogen R manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 78 g of ion-exchanged water are mixed and ultrasonically dispersed. Dispersion was performed for 20 minutes at an oscillation frequency of 30 kHz using a machine to prepare a colorant particle dispersion PB1 in which colorant particles having a median diameter of 0.12 μm were dispersed.

Example 4
Creating a release agent dispersion
(Table 3), (Table 4), (Table 5), and (Table 6) show the characteristics of the wax of the release agent used.

(1) Preparation of Release Agent 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 of the rotating body was rotated at a maximum of 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 when batch-type.

  68 g of ion exchange water, 1 g of an anionic surfactant (SCF manufactured by Sanyo Chemical Industries, Ltd.), 1 g of a nonionic surfactant (New Coal 565C manufactured by Nippon Emulsifier Co., Ltd.), and 28 g of wax (W-1) were charged, and the speed of the rotating body Was 20 min / s for 5 min, and then the rotational speed was increased to 50 m / s and treated for 5 min. The liquid temperature in the tank rose to 92 ° C. The heat melted the wax, and a fine wax particle dispersion WA1 was formed by a strong shearing force.

(2) Preparation of release agent particle dispersion WA2
Under the same conditions as in (1), 68 g of ion-exchanged water, 1 g of an anionic surfactant (SCF manufactured by Sanyo Chemical Industries, Ltd.), 1 g of a nonionic surfactant (New Coal 565C manufactured by Nippon Emulsifier Co., Ltd.), wax (W-2) 28 g was charged, and the speed of the rotating body was 3 minutes at 20 m / s, and then the rotational speed was increased to 45 m / s for 5 minutes to form a wax particle dispersion WA2.

(3) Preparation of release agent particle dispersion WA3
Under the same conditions as in (1), 68 g of ion-exchanged water, 1 g of an anionic surfactant (SCF manufactured by Sanyo Chemical Industries, Ltd.), 1 g of a nonionic surfactant (New Coal 565C manufactured by Nippon Emulsifier Co., Ltd.), wax (W-2) 28 g was charged, and the speed of the rotating body was 20 m / s for 3 minutes, and then the rotational speed was increased to 50 m / s for 4 minutes to form a wax particle dispersion WA3.

(4) Preparation of Release Agent Particle Dispersion WA4 FIG. 5 shows a schematic view of a stirring and dispersing apparatus, and FIG. 6 shows a view from above. 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 a preheated aqueous medium, which is charged through the 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 68 ml of ion-exchanged water, 1 g of an anionic surfactant (SCF manufactured by Sanyo Kasei Kogyo Co., Ltd.), 1 g of a nonionic surfactant (New Coal 565C manufactured by Nippon Emulsifier Co., Ltd.), and 28 g of wax (W-3). Was processed at 100 m / s and the supply rate was 1 kg / h to form a wax particle dispersion WA4.

(5) Preparation of release agent particle dispersion WA5
Under the same conditions as in (1), 68 g of ion-exchanged water, 1 g of an anionic surfactant (SCF manufactured by Sanyo Chemical Industries, Ltd.), 1 g of a nonionic surfactant (Newcol 565C manufactured by Nippon Emulsifier Co., Ltd.), wax (W-4) 28 g was charged, and the speed of the rotating body was 3 minutes at 20 m / s, and then the rotational speed was increased to 40 m / s for 4 minutes to form a wax particle dispersion WA5.

(6) Preparation of release agent particle dispersion WA6
Under the same conditions as in (4), the speed of the rotating body was rotated at 90 m / s, 68 g of ion-exchanged water, 1 g of an anionic surfactant (SCF manufactured by Sanyo Kasei Kogyo Co., Ltd.), nonionic surfactant (manufactured by Nippon Emulsifier Co., Ltd.) 1 g of New Coal 565C) and 28 g of wax (W-1) were charged to form a wax particle dispersion WA6.

(7) Preparation of release agent particle dispersion WA7
Under the same conditions as in (1), 68 g of ion-exchanged water, 1 g of an anionic surfactant (SCF manufactured by Sanyo Chemical Industries, Ltd.), 1 g of a nonionic surfactant (Newcol 565C manufactured by Nippon Emulsifier Co., Ltd.), wax (W-4) 28 g was charged, and the speed of the rotating body was 3 minutes at 20 m / s, and then the rotational speed was increased to 40 m / s for 4 minutes to form a wax particle dispersion WA5.

(8) Preparation of release agent particle dispersion Wk1
Under the same conditions as in (1), 68 ml of ion-exchanged water, 2 g of cationic surfactant (Sanisol B50 manufactured by Kao Corporation) and 28 g of wax (W-1) were charged, and the speed of the rotating body was 3 min at 20 m / s. Thereafter, the rotational speed was increased to 50 m / s and the treatment was performed for 2 minutes, whereby a fine wax particle dispersion Wk1 was formed.

(9) Preparation of release agent particle dispersion Wk2
Under the same conditions as in (1), 68 ml of ion-exchanged water, 2 g of cationic surfactant (Sanisol B50 manufactured by Kao Corporation) and 28 g of wax (W-3) were charged, and the speed of the rotating body was 3 min at 20 m / s. Thereafter, the rotational speed was increased to 40 m / s and the treatment was performed for 3 minutes, whereby a fine wax particle dispersion Wk2 was formed.

(10) Preparation of release agent particle dispersion wa8 68 ml of ion-exchanged water, 1 g of anionic surfactant (SCF manufactured by Sanyo Kasei Kogyo Co., Ltd.), 1 g of nonionic surfactant (Newcol 565C manufactured by Nippon Emulsifier Co., Ltd.), wax (W -1) 28 g was charged, and under the same conditions as in (1), the speed of the rotating body was 35 m / s and the treatment was performed for 5 minutes, whereby a wax particle dispersion wa8 was formed.

(11) Preparation of release agent particle dispersion wa9 68 ml of ion-exchanged water, 1 g of anionic surfactant (SCF manufactured by Sanyo Kasei Kogyo Co., Ltd.), 1 g of nonionic surfactant (Newcol 565C manufactured by Nippon Emulsifier Co., Ltd.), wax (W -2) 28 g was charged, and under the same conditions as in (1), the speed of the rotating body was 25 m / s and the treatment was performed for 5 minutes, whereby a wax particle dispersion wa9 was formed.

(12) Preparation of release agent particle dispersion wa10
Under the same conditions as in (4), the speed of the rotating body was rotated at 90 m / s, 68 ml of ion exchange water, 1 g of an anionic surfactant (SCF manufactured by Sanyo Kasei Kogyo Co., Ltd.), nonionic surfactant (manufactured by Nippon Emulsifier Co., Ltd.) 1 g of New Coal 565C) and 28 g of wax (W-3) were charged to form a wax particle dispersion wa10.

(Example 5)
Preparation of toner base The composition of the toner produced as a trial toner is shown in Table 7.

(1) Preparation of toner base M1 In a four-necked flask with 2000 ml of a thermometer and a cooling tube, 204 g of a 20 wt% concentration resin particle dispersion RL2 and 20 g of a 20 wt% colorant particle dispersion PM1 and a concentration of 30 wt% 50 g of the release agent particle dispersion WA1 and 200 ml of ion-exchanged water were added and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T50) to prepare a mixed particle dispersion.

  1N NaOH was added to the obtained mixed particle dispersion to adjust the pH to 9, and then 200 g of a 30% strength magnesium sulfate aqueous solution was added and stirred for 10 minutes. Thereafter, the temperature was raised from 22 ° C. to 72 ° C. at a rate of 5 ° C./min, and then heated at 72 ° C. for 2 hours. Thereafter, 1N HCl was added to adjust the pH to 5.8, the temperature was raised to 75 ° C., and the mixture was treated for 3 hours to obtain aggregated and associated particles. 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 to obtain toner base M1. When observed with a Coulter counter (manufactured by Coulter Inc .: Multisizer 2), the volume average particle size was 4.1 μm and the coefficient of variation was 20.

  At this time, when PH was set to a value higher than 12.5, aggregation did not proceed, resin and wax particles were left free, and particle formation did not proceed. However, if it is 12.5 or less, particles having a small particle size and a sharp particle size distribution can be obtained. A suitable PH value in combination with the release agent of the present invention is 8 to 12.5.

(2) Preparation of toner base M2 In a four-necked flask with 2000 ml of a thermometer and a cooling tube, 204 g of a 20 wt% resin particle dispersion RL1 and 20 g of a 20 wt% colorant particle dispersion PM1 and 30 wt% 50 g of the release agent particle dispersion WA2 and 200 ml of ion-exchanged water were added and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T50) to prepare a mixed particle dispersion.

  1N NaOH was added to the obtained particle dispersion to adjust the pH to 9, and then 200 g of a 30% strength magnesium sulfate aqueous solution was added and stirred for 10 minutes. Thereafter, the temperature was raised from 22 ° C. to 86 ° C. at a rate of 5 ° C./min, and then heated at 86 ° C. for 2 hours. Thereafter, 1N HCl was added, the pH was adjusted to 5.8, the temperature was raised to 88 ° C., and the mixture was treated for 2 hours to obtain aggregated and associated particles.

  Thereafter, the water temperature was 60 ° C., 1N HCl was added, the pH was adjusted to 8.3, 43 g of 20 wt% concentration resin particle dispersion RH4 was added, and 43 g of 30% concentration magnesium sulfate aqueous solution was added. The water temperature was heated at 90 ° C. for 0.5 h, and further at 90 ° C. for 2 h. Thereafter, 1N HCl was added to adjust the pH to 5.0, and the mixture was heated at 90 ° C. for 5 hours. 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-type dryer to obtain a toner base M2 having a volume average particle size of 4.9 μm and a coefficient of variation of 18.

(3) Preparation of Toner Base M3 In a four-necked flask with 2000 ml of a thermometer and a cooling tube, 204 g of 20 wt% resin particle dispersion RL2 and 20 g of 20 wt% colorant particle dispersion PM1 are 30 wt%. 50 g of the release agent particle dispersion WA3 and 200 ml of ion-exchanged water were added and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T50) to prepare a mixed particle dispersion.

  1N NaOH was added to the obtained mixed particle dispersion to adjust the pH to 10, and then 200 g of a 30% strength magnesium sulfate aqueous solution was added and stirred for 10 minutes. Thereafter, the temperature was raised from 22 ° C. to 85 ° C. at a rate of 5 ° C./min, and then heated at 85 ° C. for 2 hours. Thereafter, 1N HCl was added to adjust the pH to 5.8, the temperature was raised to 88 ° C., and the mixture was treated for 3 hours to obtain aggregated and associated particles. 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-type dryer to obtain a toner base M3.

(4) Preparation of Toner Base M4 In a four-necked flask with 2000 ml of a thermometer and a cooling tube, 204 g of 20 wt% resin particle dispersion RL3, 20 g of 20 wt% colorant particle dispersion PM1, and 30 wt% concentration 50 g of the release agent particle dispersion WA4 and 200 ml of ion-exchanged water were added, and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T50) to prepare a mixed particle dispersion.

  1N NaOH was added to the obtained particle dispersion to adjust the pH to 10.5, and then 200 g of a 30% strength magnesium sulfate aqueous solution was added and stirred for 10 minutes. Thereafter, the temperature was raised from 22 ° C. to 74 ° C. at a rate of 5 ° C./min, and then heated at 74 ° C. for 2 hours. Thereafter, 1N HCl was added, the pH was adjusted to 5.8, the temperature was raised to 80 ° C., and the mixture was treated for 2 hours to obtain aggregated aggregated particles.

  Thereafter, the water temperature was 60 ° C., 1N HCl was added, the pH was adjusted to 8.3, 43 g of 20 wt% liquid resin particle dispersion RH4 was added, and 43 g of 30% strength magnesium sulfate aqueous solution was added. The water temperature was heated at 75 ° C. for 0.5 h, and further at 90 ° C. for 2 h. Thereafter, 1N HCl was added to adjust the pH to 5.0, and the mixture was heated at 90 ° C. for 5 hours. 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 to obtain toner base M4.

(5) Preparation of toner base M5 In a four-necked flask with 2000 ml of a thermometer and a cooling tube, 204 g of 20 wt% concentration of resin particle dispersion RL2 and 20 g of 20 wt% concentration of colorant particle dispersion PM1 and 30 wt% 50 g of the release agent particle dispersion WA5 and 200 ml of ion-exchanged water were added and mixed for 10 min using a homogenizer (manufactured by IKA: Ultra Turrax T50) to prepare a mixed particle dispersion.

  1N NaOH was added to the obtained mixed particle dispersion to adjust the pH to 9, and then 200 g of a 30% strength magnesium sulfate aqueous solution was added and stirred for 10 minutes. Thereafter, the temperature was raised from 22 ° C. to 93 ° C. at a rate of 5 ° C./min, and then heated at 93 ° C. for 2 hours. Thereafter, 1N HCl was added, the pH was adjusted to 5.8, the temperature was raised to 95, and the mixture was treated for 2 hours to obtain aggregated and associated particles. 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 to obtain toner base M5.

(6) Preparation of toner base M6 In a four-necked flask with 2000 ml of a thermometer and a cooling tube, 204 g of a 20 wt% resin particle dispersion RL1 and 20 g of a 20 wt% colorant particle dispersion PM1 and 30 wt% 50 g of the release agent particle dispersion WA6 and 200 ml of ion-exchanged water were added, and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T50) to prepare a mixed particle dispersion.

  1N NaOH was added to the obtained particle dispersion to adjust the pH to 10.5, and then 200 g of a 30% strength magnesium sulfate aqueous solution was added and stirred for 10 minutes. Thereafter, the temperature was raised from 22 ° C. to 70 ° C. at a rate of 5 ° C./min, and then heated at 74 ° C. for 2 hours. Thereafter, 1N HCl was added, the pH was adjusted to 5.8, the temperature was raised to 74 ° C., and the mixture was treated for 2 hours to obtain aggregated and associated particles.

  Thereafter, the water temperature was 60 ° C., 1N HCl was added, the pH was adjusted to 8.3, 43 g of 20 wt% liquid resin particle dispersion RH4 was added, and 43 g of 30% strength magnesium sulfate aqueous solution was added. The water temperature was heated at 75 ° C. for 0.5 h, and further at 90 ° C. for 2 h. Thereafter, 1N HCl was added to adjust the pH to 5.0, and the mixture was heated at 90 ° C. for 5 hours. 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 to obtain toner base M6.

(7) Preparation of toner base M7 In a four-necked flask having 2000 ml of a thermometer and a cooling tube, 204 g of 20 wt% resin particle dispersion RL3 and 20 g of 20 wt% colorant particle dispersion PM1 are 30 wt%. 50 g of the release agent particle dispersion WA7 and 200 ml of ion-exchanged water were added and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T50) to prepare a mixed particle dispersion.

  1N NaOH was added to the obtained particle dispersion to adjust the pH to 10.5, and then 200 g of a 30% strength magnesium sulfate aqueous solution was added and stirred for 10 minutes. Thereafter, the temperature was raised from 22 ° C. to 93 ° C. at a rate of 5 ° C./min, and then heated at 93 ° C. for 2 hours. Thereafter, 1N HCl was added, the pH was adjusted to 5.8, the temperature was raised to 93 ° C., and the mixture was treated for 2 hours to obtain aggregated aggregated particles.

  Thereafter, the water temperature was set to 60 ° C., 1N HCl was added, the pH was adjusted to 8.3, 43 g of 20 wt% concentration liquid resin particle dispersion RH5 was added, and 43 g of 30% concentration magnesium sulfate aqueous solution was added. The water temperature was heated at 75 ° C. for 0.5 h, and further at 95 ° C. for 2 h. Thereafter, 1N HCl was added to adjust the pH to 5.0, and the mixture was heated at 95 ° C. for 5 hours. 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 to obtain toner base M7.

(8) Preparation of toner base Mk1 204 g of resin particle dispersion RL2, 20 g of colorant particle dispersion PM1, 50 g of release agent particle dispersion Wk1, and 200 parts by weight of ion-exchanged water are homogenized in a round stainless steel flask. (IKA: Ultra Turrax T50) was mixed and dispersed to prepare a particle dispersion.

  To the obtained particle dispersion, 2.8 g of a cationic surfactant (Sanisol B50 manufactured by Kao Corporation) and 60 g of ion-exchanged water were added, and the flask was heated to 50 ° C. while stirring in an oil bath for heating. Holding for a minute, an aggregated particle dispersion was obtained. Thereafter, the temperature of the aggregated particle dispersion was further raised to 55 ° C. and held for 1 hour, and 1N NaOH was added dropwise to the resulting aggregated particle dispersion to adjust the pH to 7.0. Thereafter, the stainless steel flask was sealed, heated to 90 ° C. while continuing stirring using a magnetic seal, and held for 2 hours. After cooling, the reaction product (toner particles) was filtered and washed three times with ion exchange water. Thereafter, the obtained toner base was dried with a fluid dryer at 40 ° C. for 6 hours to obtain a toner base Mk1.

(9) Preparation of toner base Mk2 210 g of resin particle dispersion RL1, 20 g of colorant particle dispersion, 50 g of release agent particle dispersion WA1, and 110 g of ion exchange water in a round stainless steel flask (IKA) Manufactured by Ultra Turrax T50) and dispersed to prepare a particle dispersion.

  To the obtained particle dispersion, 2.8 g of a cationic surfactant (Sanisol B50 manufactured by Kao Corporation) and 60 g of ion-exchanged water were added, and the flask was heated to 50 ° C. while stirring in an oil bath for heating. Holding for a minute, an aggregated particle dispersion was obtained. Thereafter, the temperature of the aggregated particle dispersion was further increased to 55 ° C. and held for 1 hour to obtain an aggregated particle dispersion in which core material aggregated particles were formed.

  To the resulting aggregated particle dispersion, 1N NaOH was added dropwise to adjust the pH to 7.0. Thereafter, 44 g of resin particle dispersion RH4 was added, and then the stainless steel flask was sealed, heated to 90 ° C. while continuing stirring using a magnetic seal, and held for 2 hours. After cooling, the reaction product (toner particles) was filtered and washed three times with ion exchange water. Thereafter, the obtained toner base was dried with a fluid dryer at 40 ° C. for 6 hours to obtain a toner base Mk2 in which the resin was shelled.

(10) Preparation of toner base Mk3 210 g of resin particle dispersion RL1, 20 g of colorant particle dispersion, 50 g of release agent particle dispersion WA3, and 110 g of ion exchange water in a round stainless steel flask (IKA) Manufactured by Ultra Turrax T50) and dispersed to prepare a particle dispersion.

  To the obtained particle dispersion, 2.8 g of a cationic surfactant (Sanisol B50 manufactured by Kao Corporation) and 60 g of ion-exchanged water were added, and the flask was heated to 50 ° C. while stirring in an oil bath for heating. Holding for a minute, an aggregated particle dispersion was obtained. Thereafter, the temperature of the aggregated particle dispersion was further increased to 55 ° C. and held for 1 hour to obtain an aggregated particle dispersion in which core material aggregated particles were formed.

  To the resulting aggregated particle dispersion, 1N NaOH was added dropwise to adjust the pH to 7.0. Thereafter, 44 g of resin particle dispersion RH5 was added, and then the stainless steel flask was sealed, heated to 90 ° C. while continuing stirring using a magnetic seal, and held for 2 hours. After cooling, the reaction product (toner particles) was filtered and washed three times with ion exchange water. Thereafter, the obtained toner base was dried with a fluid dryer at 40 ° C. for 6 hours to obtain a toner base Mk3 in which the resin was shelled.

(11) Preparation of toner base m8 In a four-necked flask with 2000 ml of a thermometer and a cooling tube, 204 g of 20 wt% liquid resin particle dispersion RL2 and 20 g of 20 wt% colorant particle dispersion PM1 and 30 wt% concentration 50 g of the release agent particle dispersion wa8 and 200 ml of ion-exchanged water were added, and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T50) to prepare a mixed particle dispersion.

  1N NaOH was added to the obtained mixed particle dispersion to adjust the pH to 7.5, and then 200 g of a 30% strength magnesium sulfate aqueous solution was added and stirred for 10 minutes. Thereafter, the temperature was raised from 22 ° C. to 80 ° C. at a rate of 5 ° C./min, and then heat-treated at 80 ° C. for 3 hours to obtain aggregated and associated particles. 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 to obtain toner base m8. The volume average particle size was 8.5 μm, the variation coefficient was 25, and the particle size distribution was broad. In addition, there were a lot of floating release agent particles.

(12) Preparation of toner base m9 In a 4-ml flask having a thermometer and a cooling tube, 204 g of 20 wt% liquid resin particle dispersion RL2 and 20 g of 20 wt% colorant particle dispersion PM1 and 30 wt% concentration 50 g of the release agent particle dispersion wa9 and 200 ml of ion-exchanged water were added, and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T50) to prepare a mixed particle dispersion.

  1N NaOH was added to the obtained mixed particle dispersion to adjust the pH to 12.6, and then 200 g of a 30% strength magnesium sulfate aqueous solution was added and stirred for 10 min. Thereafter, the temperature was raised from 22 ° C. to 80 ° C. at a rate of 5 ° C./min, and then heat-treated at 80 ° C. for 3 hours to obtain aggregated and associated particles. 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 to obtain toner base m9. The particle size distribution was very broad with a volume average particle size of 4.5 μm and a coefficient of variation of 45. In addition, there were a lot of floating release agent particles.

(13) Preparation of toner base m10 In a four-necked flask with 2000 ml of a thermometer and a cooling tube, 204 g of 20 wt% liquid resin particle dispersion RL2 and 20 g of 20 wt% colorant particle dispersion PM1 and 30 wt% concentration 50 g of the release agent particle dispersion wa10 and 200 ml of ion-exchanged water were added, and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T50) to prepare a mixed particle dispersion.

  1N NaOH was added to the obtained mixed particle dispersion to adjust the pH to 10, and then 200 g of a 30% strength magnesium sulfate aqueous solution was added and stirred for 10 minutes. Thereafter, the temperature was raised from 22 ° C. to 80 ° C. at a rate of 5 ° C./min, and then heat-treated at 80 ° C. for 3 hours to obtain aggregated and associated particles. 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-type dryer to obtain toner base m10. The volume average particle size was 8.1 μm, the coefficient of variation was 31, and the particle size distribution was broad. In addition, there were a lot of floating release agent particles.

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, etc. are mixed in a 100 ml polyethylene container, and stirred for 5 minutes and 30 minutes at a speed of 100 min ⁻¹ by longitudinal rotation. Then, nitrogen gas was blown with 1.96 × 10 ⁴ (Pa) for 1 minute.

  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. The external addition process was performed in FM20B with a stirring blade Z0S0 type, a rotational speed of 2000 min ⁻¹ , a processing time of 5 min, and an input amount of 1 kg.

  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 photosensitive member 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 for the purpose of effectively preventing loosening and charge accumulation due to long-term use of the transfer belt 12, and the reason that the surface is coated with fluororesin is that the toner filming on the surface of the transfer belt after long-term use. This is so that it can be effectively prevented. When the volume resistivity is less than 10 ⁷ Ω · cm, easily retransfer occurs, it is large, transfer efficiency than 10 ¹² Ω · cm to deteriorate.

The first transfer roller 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. 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 less than 10 ² Omega, easy retransfer occurs. 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 urethane foam roller having an outer diameter of 15 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 less than 10 ² Omega, easy retransfer occurs. 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 photoconductor, 3 is a pixel laser signal light, 4 is a developing roller having an outer diameter of 12 mm made of aluminum having a magnet having a magnetic force of 1200 Gauss inside, and is opposed to the photoconductor 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 source is omitted, a direct current of −500 V and an alternating 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 12 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. In Table 11, the state of transfer failure in the character portion of a full-color image in which the toners are magenta, cyan, and yellow are overlapped, and the paper wrapping property on the fixing belt in fixing is evaluated.

The charge amount is measured by the blow-off method of frictional charging with the ferrite carrier. In an environment of 25 ° C. and 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 using a developer to produce an image, the image is very high resolution with a uniform solid black image and 16 lines / mm. A high density image having an image density of 1.3 or higher was obtained. In addition, the ground cover of the non-image area did not occur. Further, even in the long-term durability test of 10,000 sheets of A4 paper, both the fluidity and the image density showed little change and stable characteristics. 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 is little change in carrier resistance and decrease in charge amount, and fog does not occur. The charge rising property at the time of rapid toner replenishment was also good, and there was no phenomenon that fogging increased in 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. 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. Also, there is almost no toner disturbance or toner skipping during fixing. In addition, 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.

  For cm1, cm2, and cm3, toner and developer have a process speed of 100 mm / s, and when the distance between the photoconductors is 70 mm, the characters are scattered during transfer, and the transferred characters are not acceptable and the reverse transferability is acceptable. However, when the process speed was increased to 125 mm / s or when the distance between the photoconductors was set to 60 mm, the uniformity of the entire solid image was slightly deteriorated.

  At cm4, cm5, cm6, and cm7, an increase in charge occurred, the image density decreased, and fog was conspicuous. In addition, when the entire surface was continuously taken with two-component development and the toner was replenished rapidly, charge reduction occurred and fogging increased. The phenomenon worsened particularly in a high humidity environment. Further, the characters were scattered at the time of transfer, the transferred characters were missing, and reverse transfer occurred, which was an unacceptable level for practical use. In addition, a lot of filming and fogging of the photoconductor occurred. In addition, there was a large amount of spent on the carrier, a large change in carrier resistance, a tendency to decrease the charge amount and increase fog. An increase in fog due to a decrease in charge amount under high temperature and high humidity and a decrease in image density due to an increase in charge amount under low temperature and low humidity were observed. The transfer efficiency decreased to about 60 to 70%, and filming of the transfer belt and poor cleaning occurred. When the entire solid image was taken at the time of development, the second half was blurred. During continuous use, the wax was fused to the developing blade, and an abnormal image of vertical stripes was generated. When the three-color image was output, the paper was wound around the fixing belt. Toner skip occurred during fixing.

Next, a solid image with a deposit amount of 1.2 mg / cm ² was evaluated for OHP transmittance (fixing temperature 160 ° C.) and offset property at high temperature using a fixing device using a belt with a process speed of 125 mm / s and no oil applied. did. 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 60 ° C. for 5 hours.

  No OHP jam occurred at the fixing nip. In the full-solid 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, the surface deterioration phenomenon of the belt is not 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 60 ° C. for 5 hours (◯ level). However, the toners of tm8, tm9, and tm10 were hardened in the storage stability test, and the high temperature offset property was deteriorated.

  The present invention is useful not only for an electrophotographic system using a photoconductor but also for a system in which toner is directly attached to paper for printing.

Sectional drawing which shows the structure of the image forming apparatus used in the Example of this invention Sectional drawing which shows the structure of the fixing unit used in the Example of this invention Schematic of the stirring and dispersing apparatus used in the examples of the present invention View from above of the stirring and dispersing device used in the examples of the present invention Schematic of the stirring and dispersing apparatus used in the examples of the present invention View from above of the stirring and dispersing device used in the examples 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 14 2nd transfer roller 13 Drive tension 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 outlet 808 Cooling water inlet 850 Raw material inlet 852 Fixed body 853 Rotation Body 854 Shaft 856 Raw material discharge

Claims (35)

In an aqueous medium, at least the resin particle dispersion in which the resin particles are dispersed, the colorant particle dispersion in which the colorant particles are dispersed, and the volume particle size integration when integrating from the small particle size side in the volume particle size distribution Release agent having a 16% diameter (PR16) of 20 to 200 nm, a 50% diameter (PR50) of 40 to 300 nm, an 84% diameter (PR84) of 400 nm or less, and PR84 / PR16 of 1.2 to 2.0 in the distribution. An inorganic fine powder having an average particle diameter of 6 nm to 20 nm is added to 100 parts by weight of the toner base material by mixing and aggregating the release agent particle dispersion liquid in which the particles are dispersed in an aqueous system and heating. An inorganic fine powder having an average particle diameter of 0.5 to 2.5 parts by weight and an average particle diameter of 20 nm to 200 nm is externally added in an amount of 1.0 to 3.5 parts by weight with respect to 100 parts by weight of the toner base. Over. In an aqueous medium, at least the resin particle dispersion in which the resin particles are dispersed, the colorant particle dispersion in which the colorant particles are dispersed, and the volume particle size integration when integrating from the small particle size side in the volume particle size distribution Release agent having a 16% diameter (PR16) of 20 to 200 nm, a 50% diameter (PR50) of 40 to 300 nm, an 84% diameter (PR84) of 400 nm or less, and PR84 / PR16 of 1.2 to 2.0 in the distribution. Mixing with a release agent particle dispersion in which particles are dispersed, the pH of the aqueous medium is set to 8 or more, and the temperature of the aqueous medium in the presence of the water-soluble inorganic salt is adjusted to the melting point of the release agent and / or the resin fine particles. An inorganic fine powder having an average particle diameter of 6 nm to 20 nm is added to a toner base having a volume average particle diameter of 3 to 8 μm and a coefficient of variation of 25 or less obtained by heating to a temperature not lower than the glass transition point and aggregating and assembling. An inorganic fine powder having an average particle diameter of 0.5 to 2.5 parts by weight with respect to 100 parts by weight of the base and an average particle size of 20 to 200 nm was externally added to 1.0 to 3.5 parts by weight with respect to 100 parts by weight of the toner base. Toner characterized by the above. In an aqueous medium, at least the resin particle dispersion in which the resin particles are dispersed, the colorant particle dispersion in which the colorant particles are dispersed, and the volume particle size integration when integrating from the small particle size side in the volume particle size distribution Release agent having a 16% diameter (PR16) of 20 to 200 nm, a 50% diameter (PR50) of 40 to 300 nm, an 84% diameter (PR84) of 400 nm or less, and PR84 / PR16 of 1.2 to 2.0 in the distribution. Mixing with a release agent particle dispersion in which particles are dispersed, the pH of the aqueous medium is set to 8 or more, and the temperature of the aqueous medium in the presence of the water-soluble inorganic salt is adjusted to the melting point of the release agent and / or the resin fine particles. By heating to a temperature above the glass transition point of
Further, a volume average particle obtained by mixing a dispersion liquid in which the aggregated aggregated particles are dispersed and a resin particle dispersion in which resin particles are dispersed and adhering and fusing the resin particles to the surface of the aggregated aggregated particles For a toner base having a diameter of 3-8 μm and a coefficient of variation of 25 or less,
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. A toner characterized in that 1.0 to 3.5 parts by weight are externally added. In an aqueous medium, at least a resin particle dispersion in which resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a dispersant having a polarity opposite to that of the dispersant in the resin particle dispersion. A release agent particle dispersion in which mold agent particles are dispersed and a dispersant having the same polarity as the dispersant in the release agent particle dispersion are blended, mixed and agglomerated, and heated for a certain time to be agglomerated and formed. Toner added to the toner base,
In the volume particle size cumulative distribution when the release agent particles are integrated from the small particle size side in the volume particle size distribution, the 16% diameter (PR16) is 20 to 200 nm, and the 50% diameter (PR50) is 40 to 300 nm, 84. % Diameter (PR84) is 400 nm or less, PR84 / PR16 is 1.2 to 2.0,
The toner has a volume average particle diameter of 3 to 8 μm and a coefficient of variation of 25 or less;
In the external addition treatment, the inorganic fine powder having an average particle diameter of 6 nm to 20 nm is 0.5 to 2.5 parts by weight with respect to 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 used as the toner. A toner having a treatment of 1.0 to 3.5 parts by weight with respect to 100 parts by weight of a base material. In an aqueous medium, at least a resin particle dispersion in which resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a dispersant having a polarity opposite to that of the dispersant in the resin particle dispersion. A release agent particle dispersion in which mold agent particles are dispersed, and a dispersant having the same polarity as the dispersant in the release agent particle dispersion are blended, mixed and agglomerated, and heated for a predetermined time to be aggregated and associated.
Further, a dispersion liquid in which the aggregated and aggregated particles dispersed are mixed with a resin particle dispersion in which resin particles are dispersed and externally added to a toner base in which the resin particles are adhered and fused to the surface of the aggregated aggregated particles. Processed toner,
In the volume particle size cumulative distribution when the release agent particles are integrated from the small particle size side in the volume particle size distribution, the 16% diameter (PR16) is 20 to 200 nm, and the 50% diameter (PR50) is 40 to 300 nm, 84. % Diameter (PR84) is 400 nm or less, PR84 / PR16 is 1.2 to 2.0,
The toner has a volume average particle diameter of 3 to 8 μm and a coefficient of variation of 25 or less;
In the external addition treatment, the inorganic fine powder having an average particle diameter of 6 nm to 20 nm is 0.5 to 2.5 parts by weight with respect to 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 used as the toner. A toner having a treatment of 1.0 to 3.5 parts by weight with respect to 100 parts by weight of a base material. The 16% diameter (PR16) is 20 to 100 nm and the 50% diameter (PR50) is 40 nm in the volume particle size integrated distribution when integrated from the small particle size side of the release agent particles dispersed in the release agent particle dispersion. The toner according to claim 1, wherein the toner has a diameter of ˜160 nm, an 84% diameter (PR84) of 260 nm or less, and a PR84 / PR16 of 1.2 to 1.8. 16% diameter (PR16) is 20 to 60 nm and 50% diameter (PR50) is 40 nm in the volume particle size cumulative distribution when the release agent particles dispersed in the release agent particle dispersion are integrated from the small particle size side. The toner according to claim 1, wherein the toner has a diameter of ˜120 nm, a 84% diameter (PR84) of 220 nm or less, and a PR84 / PR16 of 1.2 to 1.8. The toner according to claim 1, wherein the release agent comprises an ester wax having an iodine value of 25 or less, a saponification value of 30 to 300, and an endothermic peak temperature of 50 ° C. to 100 ° C. In the molecular weight distribution in gel permeation chromatography (GPC), the release agent has a number average molecular weight of 100 to 5000, a weight average molecular weight of 200 to 10,000, and a 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 8, the ratio of the Z average molecular weight to the number average molecular weight (Z average molecular weight / number average molecular weight) is 1.02 to 10, and the molecular weight is 5 × 10 ² to 1 × 10 ^4. An ester wax having a maximum peak, having an iodine value of 25 or less, a saponification value of 30 to 300, an endothermic peak temperature of 50 ° C to 100 ° C, and a heat loss at 220 ° C of 8% by weight or less. 5. The toner according to any one of 5 above. The release agent is an acid value of 5 to 50 mg KOH / g, melting point 50 obtained by a reaction with a long-chain alkyl alcohol having at least 4 to 30 carbon atoms, an unsaturated polycarboxylic acid or an anhydride thereof, and an unsaturated hydrocarbon wax. The toner according to claim 1, comprising a wax having a penetration of 4 or less at ˜120 ° C. and 25 ° C. 6. A release agent melt obtained by melting the release agent at a release agent concentration of 40 wt% or less in a medium to which a dispersant maintained at a temperature equal to or higher than the melting point of the release agent is added to a fixed body and a fixed gap. By emulsifying and dispersing by the action of a high shear force generated by a rotating body that rotates at a high speed through the volume particle size distribution, the 16% diameter (PR16) is 20 to 20 in the volume particle size integrated distribution when integrated from the small particle size side. Release agent particle dispersion liquid in which release agent particles having 200 nm, 50% diameter (PR50) of 40 to 300 nm, 84% diameter (PR84) of 400 nm or less, and PR84 / PR16 of 1.2 to 2.0 are dispersed. And a toner production method. The method for producing toner according to claim 11, wherein a relative speed of the rotating body rotating through the fixed body and the fixed gap is 30 mm / s or more. The 16% diameter (PR16) is 20 to 100 nm and the 50% diameter (PR50) is 40 nm in the volume particle size integration when the release agent particles dispersed in the release agent particle dispersion are integrated from the small particle size side. The method for producing a toner according to claim 11, wherein the toner has a diameter of ˜160 nm, an 84% diameter (PR84) of 260 nm or less, and PR84 / PR16 of 1.2 to 1.8. The 16% diameter (PR16) is 20 to 60 nm and the 50% diameter (PR50) is 40 nm in the volume particle size integration when the release agent particles dispersed in the release agent particle dispersion are integrated from the small particle size side. The method for producing a toner according to claim 11, wherein the toner has a diameter of ˜120 nm, an 84% diameter (PR84) of 220 nm or less, and PR84 / PR16 of 1.2 to 1.8. The method for producing a toner according to claim 11, wherein the release agent comprises an ester wax having an iodine value of 25 or less, a saponification value of 30 to 300, and an endothermic peak temperature of 50 ° C. to 100 ° C. In the molecular weight distribution in gel permeation chromatography (GPC), the release agent has a number average molecular weight of 100 to 5000, a weight average molecular weight of 200 to 10,000, and a 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 8, the ratio of the Z average molecular weight to the number average molecular weight (Z average molecular weight / number average molecular weight) is 1.02 to 10, and the molecular weight is 5 × 10 ² to 1 × 10 ^4. 12. An ester wax having a maximum peak, an iodine value of 25 or less, a saponification value of 30 to 300, an endothermic peak temperature of 50 ° C. to 100 ° C., and a loss on heating at 220 ° C. of 8% by weight or less. Toner production method. The release agent is an acid value of 5 to 50 mg KOH / g, melting point 50 obtained by a reaction with a long-chain alkyl alcohol having at least 4 to 30 carbon atoms, an unsaturated polycarboxylic acid or an anhydride thereof, and an unsaturated hydrocarbon wax. The method for producing a toner according to claim 11, comprising a wax having a penetration of 4 or less at ˜120 ° C. and 25 ° C. In an aqueous medium, at least the resin particle dispersion in which the resin particles are dispersed, the colorant particle dispersion in which the colorant particles are dispersed, and the volume particle size integration when integrating from the small particle size side in the volume particle size distribution Release agent having a 16% diameter (PR16) of 20 to 200 nm, a 50% diameter (PR50) of 40 to 300 nm, an 84% diameter (PR84) of 400 nm or less, and PR84 / PR16 of 1.2 to 2.0 An inorganic fine powder having an average particle diameter of 6 nm to 20 nm is added to 100 parts by weight of the toner base material by mixing and aggregating the release agent particle dispersion liquid in which the particles are dispersed in an aqueous system and heating. 0.5 to 2.5 parts by weight, 1.0 to 3.5 parts by weight of an externally treated toner with an inorganic fine powder having an average particle diameter of 20 to 200 nm and 100 parts by weight of the toner base, and at least Two-component developer, characterized in that comprising a carrier containing an average particle size surface of the A member is coated with a fluorine-modified silicone resin containing an aminosilane coupling agent is a magnetic particle is 20 to 60 [mu] m. In an aqueous medium, at least the resin particle dispersion in which the resin particles are dispersed, the colorant particle dispersion in which the colorant particles are dispersed, and the volume particle size integration when integrating from the small particle size side in the volume particle size distribution Release agent having a 16% diameter (PR16) of 20 to 200 nm, a 50% diameter (PR50) of 40 to 300 nm, an 84% diameter (PR84) of 400 nm or less, and PR84 / PR16 of 1.2 to 2.0 Mixing with a release agent particle dispersion in which particles are dispersed, the pH of the aqueous medium is set to 8 or more, and the temperature of the aqueous medium in the presence of the water-soluble inorganic salt is adjusted to the melting point of the release agent and / or the resin fine particles. An inorganic fine powder having an average particle size of 6 nm to 20 nm is added to a toner base having a volume average particle size of 3 to 8 μm and a coefficient of variation of 25 or less, which is obtained by heating to a temperature above the glass transition point and aggregating and assembling. An inorganic fine powder having an average particle diameter of 0.5 to 2.5 parts by weight with respect to 100 parts by weight of the toner and an average particle diameter of 20 to 200 nm was externally added to 1.0 to 3.5 parts by weight with respect to 100 parts by weight of the toner base. A two-component developer comprising: a toner; and a carrier containing magnetic particles having an average particle diameter of 20 to 60 µm and having an average particle diameter of at least a core material coated with a fluorine-modified silicone resin containing an aminosilane coupling agent. In an aqueous medium, at least the resin particle dispersion in which the resin particles are dispersed, the colorant particle dispersion in which the colorant particles are dispersed, and the volume particle size integration when integrating from the small particle size side in the volume particle size distribution Release agent having a 16% diameter (PR16) of 20 to 200 nm, a 50% diameter (PR50) of 40 to 300 nm, an 84% diameter (PR84) of 400 nm or less, and PR84 / PR16 of 1.2 to 2.0 Mixing with a release agent particle dispersion in which particles are dispersed, the pH of the aqueous medium is set to 8 or more, and the temperature of the aqueous medium in the presence of the water-soluble inorganic salt is adjusted to the melting point of the release agent and / or the resin fine particles. By heating to a temperature above the glass transition point of
Furthermore, the dispersion liquid in which the aggregated aggregated particles dispersed and the resin particle dispersion in which the resin particles are dispersed are mixed, and the volume average particle size obtained by adhering and fusing the resin particles to the surface of the aggregated aggregated particles is 3 Toner base of ˜8 μm and coefficient of variation of 25 or less,
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. 1.0 to 3.5 parts by weight of an externally added toner and magnetic particles having an average particle diameter of 20 to 60 μm, at least the surface of the core material is coated with a fluorine-modified silicone resin containing an aminosilane coupling agent A two-component developer comprising a carrier. In an aqueous medium, at least a resin particle dispersion in which resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a dispersant having a polarity opposite to that of the dispersant in the resin particle dispersion. A release agent particle dispersion in which mold agent particles are dispersed and a dispersant having the same polarity as the dispersant in the release agent particle dispersion are blended, mixed and agglomerated, and heated for a certain time to be agglomerated and formed. Toner added to the toner base,
When the release agent particles are integrated from the small particle size side in the volume particle size distribution, the 16% diameter (PR16) is 20 to 200 nm, and the 50% diameter (PR50) is 40 to 300 nm, 84. % Diameter (PR84) is 400 nm or less, PR84 / PR16 is 1.2 to 2.0,
The toner has a volume average particle diameter of 3 to 8 μm and a coefficient of variation of 25 or less;
In the external addition treatment, the inorganic fine powder having an average particle diameter of 6 nm to 20 nm is 0.5 to 2.5 parts by weight with respect to 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 used as the toner. 1.0 to 3.5 parts by weight of externally added toner with respect to 100 parts by weight of the base, and at least the surface of the core material is coated with a fluorine-modified silicone resin containing an aminosilane coupling agent. A two-component developer comprising a carrier containing magnetic particles. In an aqueous medium, at least a resin particle dispersion in which resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a dispersant having a polarity opposite to that of the dispersant in the resin particle dispersion. A release agent particle dispersion in which mold agent particles are dispersed, and a dispersant having the same polarity as the dispersant in the release agent particle dispersion are blended, mixed and agglomerated, and heated for a predetermined time to be aggregated and associated.
Further, a dispersion liquid in which the aggregated and aggregated particles dispersed therein are dispersed and a resin particle dispersion in which resin particles are dispersed are mixed and externally added to a toner base in which the resin particles are adhered and fused to the surface of the aggregated aggregated particles. Processed toner,
When the release agent particles are integrated from the small particle size side in the volume particle size distribution, the 16% diameter (PR16) is 20 to 200 nm, and the 50% diameter (PR50) is 40 to 300 nm, 84. % Diameter (PR84) is 400 nm or less, PR84 / PR16 is 1.2 to 2.0,
The toner has a volume average particle diameter of 3 to 8 μm and a coefficient of variation of 25 or less;
In the external addition treatment, the inorganic fine powder having an average particle diameter of 6 nm to 20 nm is 0.5 to 2.5 parts by weight with respect to 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 used as the toner. An average particle diameter of 20 to 60 μm, in which toner is externally added in an amount of 1.0 to 3.5 parts by weight with respect to 100 parts by weight of the base material, and at least the surface of the core material is coated with a fluorine-modified silicone resin containing an aminosilane coupling agent. A two-component developer comprising a carrier containing certain magnetic particles. The 16% diameter (PR16) is 20 to 100 nm and the 50% diameter (PR50) is 40 nm in the volume particle size integrated distribution when integrated from the small particle size side of the release agent particles dispersed in the release agent particle dispersion. The two-component developer according to any one of claims 18 to 22, wherein the developer is -160 nm, the 84% diameter (PR84) is 260 nm or less, and PR84 / PR16 is 1.2-1.8. 16% diameter (PR16) is 20 to 60 nm and 50% diameter (PR50) is 40 nm in the volume particle size cumulative distribution when the release agent particles dispersed in the release agent particle dispersion are integrated from the small particle size side. The two-component developer according to any one of claims 18 to 22, having a diameter of ~ 120 nm, an 84% diameter (PR84) of 220 nm or less, and a PR84 / PR16 of 1.2 to 1.8. The two-component developer according to any one of claims 18 to 22, wherein the release agent comprises an ester wax having an iodine value of 25 or less, a saponification value of 30 to 300, and an endothermic peak temperature of 50 ° C to 100 ° C. In the molecular weight distribution in gel permeation chromatography (GPC), the release agent has a number average molecular weight of 100 to 5000, a weight average molecular weight of 200 to 10,000, and a 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 8, the ratio of the Z average molecular weight to the number average molecular weight (Z average molecular weight / number average molecular weight) is 1.02 to 10, and the molecular weight is 5 × 10 ² to 1 × 10 ^4. 19. An ester wax having a maximum peak, an iodine value of 25 or less, a saponification value of 30 to 300, an endothermic peak temperature of 50 ° C. to 100 ° C., and a heat loss at 220 ° C. of 8% by weight or less. 22. The two-component developer according to any one of 22. The release agent is an acid value of 5 to 50 mg KOH / g, melting point 50 obtained by a reaction with a long-chain alkyl alcohol having at least 4 to 30 carbon atoms, an unsaturated polycarboxylic acid or an anhydride thereof, and an unsaturated hydrocarbon wax. The two-component developer according to any one of claims 18 to 20, comprising a wax having a penetration of 4 or less at -120 ° C and 25 ° C. The two-component developer according to any one of claims 18 to 22, 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 any one of claims 18 to 22, 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 any one of claims 18 to 22, wherein the coating resin layer contains 5 to 40 parts by weight of an aminosilane coupling agent with respect to 100 parts by weight of the coating resin. The two-component developer according to any one of claims 18 to 22, 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. 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 pressing member having a rotating action that forms a fixed nip with the heating member. An image comprising a heating and pressurizing unit and having a fixing process in which a transfer medium on which the toner according to any one of claims 1 to 10 is transferred is fixed between the heating member and the pressing member. Forming equipment. An AC bias having a frequency of 1 to 10 kHz and a bias of 1.0 to 2.5 kV (pp) is applied between the photosensitive member and the developing roller, and a peripheral speed ratio between the photosensitive member and the developing roller. An image forming apparatus comprising a developing unit having a ratio of 1: 1.2 to 1: 2, and using the toner according to claim 1. 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. A primary transfer in which the toner image is visualized with the toner according to any one of 1 to 10 and the electrostatic latent image is visualized, and an endless transfer body is brought into contact with the image carrier and transferred to the transfer body A secondary transfer process is performed in which the process is successively executed to form a multi-layer transfer toner image on the transfer body, and then the multi-layer toner image formed on the transfer body is collectively transferred to a transfer medium. A transfer system configured such that the transfer process is a distance from a first primary transfer position to a second primary transfer position, or from a second primary transfer position to a third primary transfer position. Distance or third primary transfer position When the distance from the first to the fourth primary transfer position is d1 (mm) and the peripheral speed of the photoreceptor is v (mm / s), the configuration satisfies the condition of d1 / v ≦ 0.65 (sec). An image forming apparatus. 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. 1. A transfer system configured to execute a transfer process in which the toner image visualized with the toner according to any one of 1 to 10 and the electrostatic latent image visualized is sequentially transferred to a transfer medium. The transfer process is performed by the distance from the first transfer position to the second transfer position, the distance from the second transfer position to the third transfer position, or the third transfer position to the fourth transfer position. The image formation is characterized by satisfying the condition of d1 / v ≦ 0.65 (sec) where d1 (mm) is the distance up to and the peripheral speed of the photosensitive member is v (mm / s). apparatus.

Images