JP4482481B2 - Toner production method, two-component developer and image forming apparatus using the same - Google Patents

Description

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

  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 operation, and the like. Therefore, use 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 fixing oil to prevent offset during fixing. Oilless fixing that achieves both a clear color image having high glossiness and high translucency and a non-offset property 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 by a charging charger, and then a latent image of each color is irradiated to the photoconductor as an optical signal to form an electrostatic latent image. The latent image is developed by developing with one 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 yellow toner is repeated for toners such as magenta and cyan, and a color image is formed by superimposing toner images of respective colors on a transfer member. 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 plurality of image forming stations having a charger, a photosensitive member, a developing unit, and the like are arranged side by side, an endless transfer member is brought into contact with the photosensitive member, and toners of respective colors are sequentially transferred to the transfer member sequentially. Executes the transfer process to form a multi-layer transfer color toner image on the transfer body, and then transfers the multi-layer toner image formed on the transfer body to a transfer medium such as paper or OHP at once. A tandem color process configured to execute the process, and a tandem color process for continuously transferring directly to a transfer medium of paper or an overhead projector (OHP) without using a transfer body have been proposed.

  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 transmissivity on OHP paper is increasing with the increase in color presentation opportunities.

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

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

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

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

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

  However, in the conventional pulverizing / classifying operation in the kneading and pulverizing method, the particle size that can be actually provided economically and in performance is about 8 μm even if the particle size is reduced. At present, methods for producing small-diameter toners by various methods are being studied. 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 is increased, adverse effects such as a decrease in toner fluidity, an increase in voids during transfer, and an increase in fusion to the photoreceptor occur.

  Therefore, a toner production method using various polymerization methods different from the kneading and pulverization method has been studied. For example, when a toner is prepared by a suspension polymerization method, even if an attempt is made to control the particle size distribution of the toner, it cannot leave the range of the kneading and pulverization method, and in many cases, further classification operation is required. Further, since the toner obtained by these methods has a substantially spherical shape, there is a problem that the toner remaining on the photosensitive member or the like is very poorly cleaned and the image quality reliability is impaired.

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

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

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

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

However, if the dispersibility is deteriorated by adding a release agent, color turbidity tends to occur in the toner image melted at the time of fixing. At the same time, the dispersibility of the pigment also deteriorates, and the color developability of the toner becomes insufficient. In addition, when the resin fine particles are further adhered and fused on the surface of the aggregate in the next step, the dispersion of the release agent or the like makes the adhesion of the resin fine particles unstable. Moreover, the release agent once aggregated with the resin is separated and released into the aqueous system. The dispersion of the release agent has a great influence on the agglomeration during mixing and agglomeration due to the polarity and melting point of the wax used. Furthermore, in order to realize oil-less fixing without using oil at the time of fixing, a specific wax is added in a large amount. 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.
Japanese Patent No. 2801507 JP 2002-23429 A JP-A-10-198070 JP-A-10-301332

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

  The toner production method of the present invention includes at least a resin particle dispersion in which resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a wax particle dispersion in which wax particles are dispersed in an aqueous medium. And a toner manufacturing method in which toner is produced in an aqueous system by coagulation heating, wherein at least a resin particle dispersion in which the resin particles are dispersed, a colorant particle dispersion in which the colorant particles are dispersed, and A step of preparing a mixed dispersion of the wax particle dispersion in which the wax particles are dispersed, adjusting the pH of the mixed dispersion to a range of 9.5 to 12.2, adding a water-soluble inorganic salt, and heating; The resin particles, the colorant particles and the wax particles are processed to form aggregated particles in which at least a part is melted, and the pH when the aggregated particles are formed is 7.0 to 9.5. A step ranges, then pH was adjusted to a range of 2.2 to 6.8, and a step of heat treatment.

  In another toner production method of the present invention, at least a resin particle dispersion in which resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and wax particles are dispersed in an aqueous medium. A toner manufacturing method of mixing a wax particle dispersion and preparing a toner in an aqueous system by heat aggregation, comprising at least a resin particle dispersion in which the resin particles are dispersed, and a colorant in which the colorant particles are dispersed A step of preparing a mixed dispersion of a particle dispersion and a wax particle dispersion in which the wax particles are dispersed; and adjusting the pH of the mixed dispersion to a range of 9.5 to 12.2, Addition and heat treatment to form aggregated particles in which at least a part of the resin particles, the colorant particles and the wax particles aggregated is melted, and the pH when the aggregated particles are formed is 7. A step in which the core particles are dispersed, a step in which the core particles are dispersed, a step in which the core particles are dispersed, a step in which the core particles are dispersed, A step of adding a second resin particle dispersion in which second resin particles are further dispersed, a step of adjusting the pH to a range of 5.2 to 8.8, and a glass transition of the second resin particles. A heat treatment at a temperature equal to or higher than the point temperature, a step of adjusting the pH to a range of 2.2 to 6.8, and a heat treatment at a temperature equal to or higher than the glass transition temperature of the second resin particles. Fusing the second resin particles to the core particles.

  Still another toner production method of the present invention includes a first resin particle dispersion in which at least first resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a wax in an aqueous medium. A toner manufacturing method for producing a toner in an aqueous system by mixing with a wax particle dispersion liquid in which particles are dispersed, and at least a first resin particle dispersion liquid in which at least the first resin particles are dispersed A step of preparing a mixed dispersion of the colorant particle dispersion in which the colorant particles are dispersed and the wax particle dispersion in which the wax particles are dispersed; and the pH of the mixed dispersion is 9.5 to 12.2. The water-soluble inorganic salt is added, and heat treatment is performed to form agglomerated particles in which the first resin particles, the colorant particles, and the wax particles are agglomerated to form agglomerated particles. grain A step in which the pH is in the range of 7.0 to 9.5, a step of adjusting the pH to a range of 2.2 to 6.8, and then heat-treating to form core particles; When the pH value of the core particle dispersion in which the core particles are dispersed is HS, the second resin particle dispersion in which the second resin particles in which the pH value of the dispersion is adjusted to the range of HS + 2 to HS-5 is dispersed. And adding to a core particle dispersion in which the core particles are dispersed.

  In the two-component developer of the present invention, 1 to 6 parts by weight of inorganic fine powder having an average particle diameter in the range of 6 nm to 200 nm is added to 100 parts by weight of the toner base particles. Magnetic particles comprising a toner added in the range of, a cured binder resin and magnetic fine particles, the content of the magnetic fine particles is 80 to 99 wt%, the number average particle size is 10 to 60 μm, And the surface of the said magnetic particle contains the carrier containing the magnetic particle coat | covered with the fluorine-modified silicone resin containing an aminosilane coupling agent, It is characterized by the above-mentioned.

  The image forming apparatus of the present invention has 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 is formed on the image carrier. The electrostatic latent image is visualized by the two-component developer, and the transfer process is performed in which the toner image that has been visualized by the electrostatic latent image is sequentially transferred onto a transfer medium. A transfer system, wherein the transfer process is a distance from the first transfer position to the second transfer position, or a distance from the second transfer position to the third transfer position, or from the third transfer position to the second transfer position. When the distance to the transfer position 4 is d1 (mm) and the peripheral speed of the photosensitive member is v (mm / s), the condition of d1 / v ≦ 0.65 (sec) is satisfied.

  According to the present invention, a toner having a small particle size having a sharp particle size distribution can be produced without a classification step.

  In the method of the present invention, a resin particle dispersion in which resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a wax particle dispersion in which wax is dispersed are mixed and aggregated in an aqueous system and heated. The toner base produced in this way eliminates the presence of floating wax particles that are not involved in agglomeration in the aqueous system, and the pigment also eliminates the presence of floating pigments. Thus, a toner having a small particle diameter can be prepared without a classification step.

  Further, the present invention can prevent the offset property without requiring the application of oil and can be fixed at a low temperature. Furthermore, a durable two-component developer that does not deteriorate due to spent even when used in combination with a toner containing a release agent such as wax can be realized.

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

  The present invention is an oilless fixing that has high glossiness and high translucency, suitable charging characteristics, environmental dependency, cleaning properties, transferability, and a small particle size static particle 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.

(1) Polymerization method The resin particle dispersion is prepared by subjecting the vinyl monomer to emulsion polymerization or seed polymerization in an ionic surfactant, thereby producing a vinyl monomer homopolymer or copolymer ( A dispersion is prepared by dispersing resin particles of vinyl resin) 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, azo-based or diazo-based polymerization initiators such as azobisisobutyronitrile, persulfates (potassium persulfate, ammonium persulfate, etc.), azo-based Examples thereof include compounds (4,4′-azobis-4-cyanovaleric acid and its salts, 2,2′-azobis (2-amidinopropane) salts, etc.), peroxide compounds and the like.

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

  The toner according to the exemplary embodiment is obtained by mixing and aggregating 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 in an aqueous system. Heat to produce toner base particles.

  A preferred first production method of the present invention comprises mixing 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. Aggregated particles (sometimes referred to as core particles) having a certain particle size are produced by adding a water-soluble inorganic salt to the dispersion and heating to a temperature equal to or higher than the glass transition temperature (Tg) of the resin.

  At this time, it is preferable to adjust the pH of the mixed dispersion to a range of 9.5 to 12.2 before adding the water-soluble inorganic salt and before heating. The pH can be adjusted by adding 1N NaOH. Particles with small particle size and narrow particle size distribution by adjusting pH and promoting aggregation of resin, colorant and wax particles from the relationship with water-soluble inorganic salt to be added, and suppressing excessive aggregation This is to enable formation. When the pH is less than 9.5, the formed particles tend to be coarse. On the other hand, if the pH exceeds 12.2, aggregation of the resin, the colorant and the wax particles does not proceed, and the amount of the released wax particles and colorant particles increases, making it difficult to encapsulate the wax uniformly.

  After pH adjustment, a water-soluble inorganic salt is added, and heat treatment is performed to form aggregated particles having a predetermined volume average particle size (for example, 3 to 6 μm) in which at least resin particles, colorant particles, and wax particles are aggregated. By maintaining the pH of the liquid when the aggregated particles having the predetermined volume average particle diameter are formed in the range of 7.0 to 9.5, the release of the colorant and the wax is small and the wax is included and narrow. Agglomerated particles having a particle size distribution can be formed. The amount of NaOH to be added, the type and amount of flocculant, the pH of the emulsion polymerization resin dispersion, the pH of the colorant dispersion, the pH of the wax dispersion, the heating temperature, and the time are appropriately selected.

  By heat-treating the mixed dispersion, melting of the wax having sharp melt properties starts and aggregation of the melted waxes begins. Although the glass transition point (Tg) of the resin is 30 to 70 ° 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, resin and pigment fine particles aggregate so as to surround the melted wax, and the aggregated resin is also melted and fused by heat. And the state in which the low melting point wax is encapsulated by the resin is formed.

  If the pH of the liquid when the aggregated particles are formed is less than 7.0, the aggregated particles tend to be coarse. When the pH exceeds 9.5, the colorant and wax are likely to be liberated due to poor aggregation.

  Thereafter, it is preferable to further adjust the pH to a range of 2.2 to 6.8 and heat treatment to produce toner base particles that are aggregated particles. By adjusting the heat treatment within this range, the secondary agglomeration between the agglomerated particles can be suppressed, the spheroidization of the particle shape can be promoted, and the particle size distribution can be narrowed down more sharply. The toner base particles produced by such a method are washed and dried, and then subjected to an external addition treatment to produce a toner. If the pH is less than 2.2, the effect of the surfactant is lost. When the pH exceeds 6.8, secondary aggregation of the aggregated particles occurs due to heating, and the particle diameter increases and the particle size distribution also becomes broad.

  Further, a mixed dispersion in which the pH of the mixed dispersion obtained by mixing the resin particle dispersion in which the resin particles are dispersed, the colorant particle dispersion in which the colorant particles are dispersed, and the wax particle dispersion is 6.0 or less is used. It is preferable to create When a persulfate such as potassium persulfate is used as a polymerization initiator when polymerizing an emulsion polymerization resin, the residue may be decomposed by the heat during the heat aggregation process to lower the pH. is there. After emulsion polymerization of the resin, it is preferable to carry out a heat treatment at a certain temperature or higher (preferably 80 ° C. or higher in order to sufficiently decompose the residue) for a certain time (preferably about 1 to 5 hours). At this time, the pH of the dispersion of the emulsion polymerization resin is preferably 4 or less, more preferably 1.8 or less. When the pH of the mixed dispersion is over 6.0, when the colored resin particles are formed by heating, the residual content of the polymerization initiator persulfate is decomposed and the pH in the liquid varies. The (pH reduction phenomenon) increases, and the particles obtained by heat aggregation tend to be coarse.

  As a preferred second production method of the present invention, the second resin particles are dispersed in an aggregated particle dispersion in which aggregated particles (also referred to as core particles) produced by the first production method are dispersed. The resin particle dispersion is mixed and heat-fused to form a resin surface layer. As a result, the durability and offset property of the toner can be improved.

  When the second resin is attached to the surface of the core particle and heated to Tg or more of the second resin to form the resin surface fusion layer, the second resin particle is not released, and It is necessary to prevent the secondary agglomeration of the core particles and to uniformly adhere to the surface of the core particles.

  Add the second resin particle dispersion in which the second resin particles are dispersed to the core particle dispersion in which the core particles are dispersed, and adjust the pH of the core particle dispersion to which the second resin particle dispersion is added. It is preferable to adjust to the range of 5.2 to 8.8 and then heat-treat at a temperature equal to or higher than the glass transition temperature of the second resin particles for 0.5 to 2 hours. The purpose of pH adjustment is to promote adhesion of the second resin particles having a particle size different by two digits on the surface of the core particles and to prevent aggregation of the second resin particles or the core particles. The repulsive force between particles and the cohesive force can be adjusted by adjusting the pH.

  By this step, the second resin particles can be uniformly adhered to the surface of the core particles while suppressing suspended particles. When the pH is less than 5.2, adhesion of the second resin particles hardly occurs and the free resin particles tend to increase. If the pH exceeds 8.8, secondary aggregation between the core particles tends to occur. When the treatment time is increased by 2 hours or more, the coarsening of the particles and the particle size distribution tend to be broad.

  Thereafter, the pH is further adjusted to a range of 3.2 to 6.8, and then heat treatment is performed at a temperature equal to or higher than the glass transition temperature of the second resin particles for 2 to 6 hours. It is preferable to fuse the resin particles.

  The core particle dispersion to which the second resin particle dispersion is added has at least two stages of adjusting the liquid pH, and in this process, the pH of the liquid adjusted for the first time is adjusted for the second time. Adjust to a value less than the value. If the heat treatment is advanced with the pH value as it is, aggregation of the core particles proceeds and the particle size becomes coarse. However, if the heat treatment is not advanced, the fusion of the second resin particles adhering to the surface of the core particles will not proceed, and the surface will remain uneven, leaving problems in development and transferability. The purpose of adjusting the pH of the first time to the range of 5.2 to 8.8 is to promote the adhesion of the second resin particles to the core particles, and therefore the pH value of the liquid is neutral. It is effective to shift to the vicinity.

  Further, the purpose of adjusting the pH again in the range of 3.2 to 6.8 is to prevent the core particles to which the second resin particles are adhered from from each other causing secondary aggregation and coarsening of the particles. This makes it possible to produce particles with a narrow particle size distribution by fusing the second resin particles to the core particles without causing secondary aggregation.

  By this step, particles having a narrow particle size distribution can be obtained by fusing the second resin particles to the core particles without causing secondary aggregation between the core particles or the second resin particles. If the pH is less than 3.2, the resin particles once adhered may be released. When the pH exceeds 6.8, secondary aggregation of the core particles tends to occur.

  The difference in volume average particle diameter between the core particles and the particles in which the second resin particles are adhered and fused to the core particles is preferably 0.5 to 2 μm. If the thickness is less than 0.5 μm, the adhesion state of the second resin is poor, and the influence of moisture and the strength of the second resin itself are insufficient. If it exceeds 2 μm, the fixing property and glossiness are lowered.

  As a preferred third production method of the present invention, the second resin particle dispersion in which the second resin particles are dispersed is added to and mixed with the core particle dispersion in which the core particles are dispersed. The toner base particles are produced by forming a resin fusion layer for fusing the second resin particles to the core particles by heat treatment at a temperature equal to or higher than the glass transition temperature of the particles, When adding the second resin particle dispersion to the produced core particle dispersion, assuming that the pH value of the core particle dispersion in which the core particles are dispersed is HS, the second resin particles are dispersed in the second resin particle dispersion. In this configuration, the pH of the resin particle dispersion is adjusted to the range of HS + 2 to HS-5.

  If a highly acidic second resin particle dispersion or the like is added to the core particle dispersion, the effect of the water-soluble inorganic salt as an aggregating agent is weakened, and adhesion between the core particles and the resin particles is hindered. Further, when a resin particle dispersion having a pH value separated from the core particle dispersion is added, the pH balance of the liquid is suddenly disturbed, so that the resin particles do not adhere to the core particles. As a result, secondary aggregation occurs. In order to suppress such a phenomenon, it is effective to adjust the pH of the second resin particle dispersion.

  With this configuration, the generation of floating particles of the second resin particles is reduced, and the second resin particles can be uniformly attached to the surface of the core particles. Further, the adhesion to the core particles is promoted, the adhesion melting treatment time is shortened, and the productivity can be improved. In addition, when the second resin particles are adhered and melted to the core particles, rapid coarsening of the particles can be prevented, and a sharp particle size distribution can be formed with a small particle size. When it is larger than HS + 2, the particles become coarse and the particle size distribution tends to be broad. If it is smaller than HS-5, the adhesion of the second resin particles to the agglomerated particles will not proceed, and not only will the treatment take a long time, but the second resin particles will remain suspended in the aqueous system and remain cloudy. There is a tendency not to progress.

  In the configuration of the preferred third production method of the present invention, the pH value of the second resin particle dispersion in which the second resin particles added to the produced core particle dispersion are dispersed is the core in which the core particles are dispersed. Regardless of the pH value of the particle dispersion, a configuration in which the particle dispersion is adjusted and added in the range of 3.5 to 10.5 is preferable.

  When the pH is less than 3.5, the adhesion of the second resin particles to the surface of the core particles does not proceed, the second resin particles remain floating in the aqueous system, and the liquid remains cloudy. When the pH is higher than 10.5, the generated particles tend to coarsen rapidly.

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

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

(2) Wax A first preferred configuration as the wax in the toner of the present embodiment is a configuration using a wax having a iodine value of 25 or less and a saponification value of 30 to 300. As a result, oilless fixing having high glossiness and translucency can be realized by preventing low offset and fixing at low temperature without applying oil. Further, the repulsion due to the charge action of the toner during the multilayer toner transfer is alleviated, and it is possible to suppress the transfer efficiency from being lowered, the character missing during the transfer, and the reverse transfer. Further, the use in combination with the 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, suspended matters in the aqueous system increase, and uniform adhesion to the surface of the aggregated particles decreases. If this remains in the toner, filming of the photoreceptor or the like is caused. The repulsion due to the charge effect of the toner is difficult to be mitigated during the multi-layer transfer of the toner in the primary transfer. 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. If the saponification value is less than 30, the presence of unsaponifiable matter and hydrocarbons increases, causing photoreceptor filming and toner chargeability deterioration. It causes a decrease in chargeability during filming and continuous use. If it exceeds 300, suspended matter in the aqueous system increases, and the uniform adhesion to the surface of the aggregated particles decreases. 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 of the generated toner 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 of the generated toner becomes broad.

The number average molecular weight is greater than 5000, the weight average molecular weight is greater than 10,000, the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is greater than 8, and the ratio of the Z average molecular weight to the number average molecular weight (Z When the average molecular weight / number average molecular weight) is larger than 10 and the molecular weight maximum peak is located in a range larger than the region of 1 × 10 ⁴ , the releasing 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 of wax are generated.

  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. Uniform adhesion to the surface of the aggregated particles is reduced.

  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 2 to 90 parts by weight with respect to 100 parts by weight of the binder resin. Preferably, 5 to 80 parts by weight, more preferably 10 to 50 parts by weight, and still more preferably 15 to 20 parts by weight is added to 100 parts by weight of the binder resin. If it is 2 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, the storage stability is difficult.

  As the wax, materials such as meadow foam oil derivatives, carnauba wax derivatives, jojoba oil derivatives, wood wax, beeswax, ozokerite, carnauba wax, canderia wax, ceresin wax, rice wax and the like are also preferable, and these derivatives are also suitable. Used for. One type or a combination of two or more types can be used.

  Meadowfoam oil derivatives include Meadowfoam oil fatty acid, metal salt of Meadowfoam oil fatty acid, Meadowfoam oil fatty acid ester, hydrogenated Meadowfoam oil, Meadowfoam oil amide, Homo Meadowfoam oil amide, Meadowfoam oil triester, Epoxy A maleic acid derivative of a halogenated meadowfoam oil, an isocyanate polymer of a meadowfoam oil fatty acid polyhydric alcohol ester, and a halogenated modified meadowfoam oil can also be preferably used. An emulsified dispersion having a small particle size and a uniform particle size distribution can be prepared. Uniform adhesion to the surface of the aggregated particles can be obtained.

  It is a preferable material that is effective for oilless fixing, prolonging the developer life, and improving transferability. These can be used alone or in combination of two or more.

  The meadow foam oil fatty acid obtained by saponification and decomposition of meadow foam oil is preferably composed of a fatty acid having 4 to 30 carbon atoms. As the metal salt, metal salts such as sodium, potassium, calcium, magnesium, barium, zinc, lead, manganese, iron, nickel, cobalt, and aluminum can be used. Good offset resistance at high temperatures.

  Meadow foam oil fatty acid esters include, for example, esters such as methyl, ethyl, butyl, glycerin, pentaerythritol, polypropylene glycol, and trimethylolpropane, and in particular, meadow foam oil fatty acid pentaerythritol monoester and meadowfoam oil fatty acid pentaerythritol triester. Ester, meadow foam oil fatty acid trimethylolpropane ester and the like are preferable. Good cold offset resistance as well as offset resistance at high temperatures.

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

  Hydrogenated Meadowfoam oil is obtained by hydrogenating Meadowfoam oil to make unsaturated bonds saturated bonds. Glossiness and translucency can be improved along with offset resistance.

  Meadowfoam oil amide is obtained by hydrolyzing meadowfoam oil and esterifying it into fatty acid methyl ester, and then reacting with a mixture of concentrated aqueous ammonia and ammonium chloride. Furthermore, it becomes possible to adjust melting | fusing point by hydrogenating this. It is also possible to hydrogenate before hydrolysis. A product having a melting point of 75 to 120 ° C. is obtained. Homomeadofoam oil amide is obtained through nitrile after hydrolyzing and reducing it to an alcohol. Glossiness and translucency can be improved along with offset resistance.

  Jojoba oil derivatives include jojoba oil fatty acid, metal salt of jojoba oil fatty acid, jojoba oil fatty acid ester, hydrogenated jojoba oil, jojoba oil amide, homo jojoba oil amide, jojoba oil triester, maleic acid derivative of epoxidized jojoba oil, jojoba An isocyanate polymer of an oil fatty acid polyhydric alcohol ester and a halogenated modified jojoba oil can also be preferably used. An emulsified dispersion having a small particle size and a uniform particle size distribution can be prepared. Uniform adhesion to the surface of the aggregated particles can be obtained. In addition, it is easy to uniformly mix and disperse the resin and wax. It is a preferable material that is effective for oilless fixing, prolonging the developer life, and improving transferability. These can be used alone or in combination of two or more.

  Jojoba oil fatty acid obtained by saponifying and decomposing jojoba oil consists of fatty acids having 4 to 30 carbon atoms. As the metal salt, metal salts such as sodium, potassium, calcium, magnesium, barium, zinc, lead, manganese, iron, nickel, cobalt, and aluminum can be used. Good offset resistance at high temperatures.

  Examples of jojoba oil fatty acid esters include methyl, ethyl, butyl, glycerin, pentaerythritol, polypropylene glycol, trimethylolpropane and the like, and in particular, jojoba oil fatty acid pentaerythritol monoester, jojoba oil fatty acid pentaerythritol triester, jojoba Oil fatty acid trimethylolpropane ester and the like are preferable. Good cold offset resistance as well as offset resistance at high temperatures.

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

  Hydrogenated jojoba oil is obtained by hydrogenating jojoba oil to make unsaturated bonds saturated bonds. Glossiness and translucency can be improved along with offset resistance.

  Jojoba oil amide is obtained by hydrolyzing jojoba oil and then esterifying it into fatty acid methyl ester, and then reacting with a mixture of concentrated aqueous ammonia and ammonium chloride. Furthermore, it becomes possible to adjust melting | fusing point by hydrogenating this. It is also possible to hydrogenate before hydrolysis. A product having a melting point of 75 to 120 ° C. is obtained. Homo jojoba oil amide is obtained through hydrolysis of jojoba oil and then reducing it to alcohol, followed by nitrile. Glossiness and translucency can be improved along with offset resistance.

  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 glacial acetic acid solution to chloroform or carbon tetrachloride solution of the sample, and titrate the remaining iodine without reacting with sodium thiosulfate standard solution to absorb iodine Calculate the amount.

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

  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, the second preferred structure as the wax used in the toner of the present embodiment is preferably a wax obtained by a reaction with a long-chain alkyl alcohol, an unsaturated polyvalent carboxylic acid or an anhydride thereof, and a synthetic hydrocarbon wax. A long chain alkyl group having 4 to 30 carbon atoms is preferable, and a wax having an acid value of 10 to 80 mgKOH / g is used.

  This wax is preferably a wax obtained by a reaction of a long-chain alkyl alcohol having 4 to 30 carbon atoms with an unsaturated polycarboxylic acid or an anhydride thereof and an unsaturated hydrocarbon wax.

  Further, a wax obtained by reacting a long chain alkylamine with an unsaturated polyvalent carboxylic acid or an anhydride thereof and an unsaturated hydrocarbon wax, or a long chain fluoroalkyl alcohol and an unsaturated polyvalent carboxylic acid or an anhydride thereof, and A wax obtained by reaction with an unsaturated hydrocarbon wax can also be suitably used. The effects include the enhancement of the releasing action by the long chain alkyl group, the improvement of the dispersion phase with the resin by the ester group, and the improvement of durability and offset property by the vinyl group.

In the molecular weight distribution in GPC of this 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 10 to 80 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) is at least one molecular weight maximum peak in the region of 1.5 to 4.5 and 1 × 10 ³ to 1 × 10 ⁴ , and the acid value is 10 to 50 mgKOH. / G, melting point 60-110 ° C. is preferable,
More preferably, the weight average molecular weight is 1000 to 2500, the Z average molecular weight is 1900 to 3000, the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is 1.2 to 1.8, and the Z average molecular weight is The number average molecular weight ratio (Z average molecular weight / number average molecular weight) is in the region of 1.7 to 2.5, 1 × 10 ^{3 to} 3 × 10 ³ , and has at least one molecular weight maximum peak, and an acid value of 35 to 50 mgKOH / G, melting point 65-95 ° C.

  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, it is possible to produce particles having a small particle size that are uniformly emulsified and dispersed in a polar dispersant, and it is possible to uniformly agglomerate with the resin pigment by mixing and agglomeration, thereby eliminating the presence of suspended matters and suppressing color turbidity. Further, uniform adhesion to the surface of the aggregated particles can be obtained. As a result, oilless fixing having high glossiness and translucency can be realized by preventing low offset and fixing at low temperature without applying oil.

  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 lowered. When the carbon number of the long-chain alkyl is larger than 30, the mixed aggregation property with the resin is deteriorated and the dispersibility is lowered. When the acid value is smaller than 10 mgKOH / g, the charge amount during long-term use of the toner is reduced. When the acid value is greater than 80 mgKOH / g, the moisture resistance decreases, and the fogging under high humidity increases. If it is high, it is difficult to reduce the particle size of the produced particles when the emulsified dispersed particles are produced. Uniform adhesion to the surface of the aggregated particles is reduced.

  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.

  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.

Alcohols include octanol (C ₈ H ₁₇ OH), dodecanol (C ₁₂ H ₂₅ OH), stearyl alcohol (C ₁₈ H ₃₇ OH), nonacosanol (C ₂₉ H ₅₉ OH), pentadecanol (C ₁₅ H ₃₁ OH) Those having an alkyl chain having 4 to 30 carbon atoms, such as, 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 synthetic hydrocarbon wax, polyethylene, polypropylene, Fischer Toro push wax, 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.

  In addition, the third configuration preferable as the wax used in the toner of the present embodiment is preferably a material such as a hydroxy stearic acid derivative, a glycerin fatty acid ester, a glycol fatty acid ester, or a sorbitan fatty acid ester, and one kind or a combination of two or more kinds. The use of is also effective. It enables creation of small particles with uniform emulsification and dispersion, uniform adhesion to the surface of aggregated particles, and prevention of offset without applying oil, low temperature fixing, high glossiness, transparency Oilless fixing with light properties can be realized. In addition to the 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 be suppressed.

  Preferred derivatives of hydroxystearic acid include methyl 12-hydroxystearate, butyl 12-hydroxystearate, propylene glycol mono12-hydroxystearate, glycerin mono12-hydroxystearate, ethylene glycol mono12-hydroxystearate, etc. Material. It has the effect of preventing paper wrapping in oilless fixing and the effect of preventing filming.

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

  As the glycol fatty acid ester, propylene glycol fatty acid esters such as propylene glycol monopalmitate and propylene glycol monostearate, and ethylene glycol fatty acid esters such as ethylene glycol monostearate and ethylene glycol monopalmitate are suitable materials. Along with oil-less fixability, it has the effect of preventing slippage during development and preventing carrier spent.

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

  In addition, as a fourth configuration preferable as the wax used in the toner of the exemplary embodiment, it is also preferable to use an aliphatic amide wax. It enables creation of small particles with uniform emulsification and dispersion, uniform adhesion to the surface of aggregated particles, and prevention of offset without applying oil, low temperature fixing, high glossiness, transparency Oilless fixing with light properties can be realized. In addition to the 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 be suppressed.

  The translucency in a color image can be improved. In particular, it is possible to promote the smoothness of the surface of the fixed image and obtain a high-quality color image. Furthermore, it is possible to prevent the copy paper from being wound around the fixing roller at the time of fixing, and it is possible to achieve both the light-transmitting property and the offset resistance and to prevent omission during transfer.

  Examples of the aliphatic amide wax include 4 to 4 carbon atoms such as palmitic acid amide, palmitoleic acid amide, stearic acid amide, oleic acid amide, arachidic acid amide, eicosenoic acid amide, behenic acid amide, erucic acid amide, and ligrinoseric acid amide. A saturated or monovalent unsaturated aliphatic amide having a melting point of 50 to 120 ° C. More preferably, it is 70-100 degreeC, More preferably, it is 75-95 degreeC. When the melting point is lower than 50 ° C., the storage stability of the toner is deteriorated. Filming on the photoreceptor is likely to occur. When the melting point is higher than 120 ° C., it is difficult to reduce the particle size of the generated particles when the emulsified dispersed particles are generated. Uniform adhesion to the surface of the aggregated particles is reduced. The smoothness of the surface of the fixed image is lowered and the translucency is deteriorated.

  The addition amount is preferably 2 to 90 parts by weight with respect to 100 parts by weight of the binder resin. Preferably, 5 to 50 parts by weight, more preferably 10 to 30 parts by weight, and still more preferably 15 to 20 parts by weight is added to 100 parts by weight of the binder resin. If it is 1 part 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.

  Furthermore, methylene bis stearic acid amide, ethylene bis stearic acid amide, propylene bis stearic acid amide, butylene bis stearic acid amide, methylene bis oleic acid amide, ethylene bis oleic acid amide, propylene bis oleic acid amide, butylene bis oleic acid amide, Methylene bis lauric acid amide, ethylene bis lauric acid amide, propylene bis lauric acid amide, butylene bis lauric acid amide, methylene bis myristic acid amide, ethylene bis myristic acid amide, propylene bis myristic acid amide, butylene bis myristic acid amide, methylene bis Palmitic acid amide, ethylene bis palmitic acid amide, propylene bis palmitic acid amide, butylene bis palmitic acid amide, methylene bis palmitic tray Acid amide, ethylene bispalmitoleic acid amide, propylene bispalmitoleic acid amide, butylene bispalmitoleic acid amide, methylene bisarachidic acid amide, ethylene bisarachidic acid amide, propylene bisarachidic acid amide, butylene bisarachidic acid amide, methylene Biseicosenoic acid amide, ethylene biseicosenoic acid amide, propylene biseicosenoic acid amide, butylene biseicosenoic acid amide, methylene bisbehenic acid amide, ethylene bisbehenic acid amide, propylene bisbehenic acid amide Alkylene bis-saturated or divalent unsaturated fatty acids such as butylene bisbehenic acid amide, methylene biserucic acid amide, ethylene biserucic acid amide, propylene biserucic acid amide, butylene biserucic acid amide Wax fatty acid amide is preferable.

  The melting point is preferably 50 to 120 ° C. More preferably, it is 70-100 degreeC, More preferably, it is 75-95 degreeC. When the melting point is lower than 50 ° C., the storage stability of the toner is deteriorated. Filming on the photoreceptor is likely to occur. When the melting point is higher than 120 ° C., it is difficult to reduce the particle size of the generated particles when the emulsified dispersed particles are generated. Uniform adhesion to the surface of the aggregated particles is reduced. The smoothness of the surface of the fixed image is lowered and the translucency is deteriorated.

  The addition amount is preferably 2 to 90 parts by weight with respect to 100 parts by weight of the binder resin. Preferably, 5 to 50 parts by weight, more preferably 10 to 30 parts by weight, and still more preferably 15 to 20 parts by weight is added to 100 parts by weight of the binder resin. If it is 1 part 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.

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

  When using styrene acrylic copolymers as resin particles, the use of ester waxes with a certain acid value and iodine value rather than vinyl waxes such as polypropylene and polyethylene makes it possible to desorb and float during mixing and aggregation. Without entrapment, it can be encapsulated in the form of being uniformly collected in one place in the resin. It is possible to eliminate the influence of free wax, to prevent filming and carrier spent on OPC and transfer belt, and to effectively prevent omission and reverse transfer during transfer.

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

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

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

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

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

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

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

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

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

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

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

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

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

  The particle size can be measured using a Horiba laser diffraction particle size measuring device (LA920), a Shimadzu laser diffraction particle size measuring device (SALD2100), or the like.

(3) Resin Examples of the resin fine particles of the toner of the present embodiment include a thermoplastic binder resin. Specifically, styrenes such as styrene, parachlorostyrene, 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 monomers include vinyl polymer acids and vinyl polymer bases such as acrylic acid, methacrylic acid, maleic acid, cinnamic acid, fumaric acid, vinyl sulfonic acid, ethyleneimine, vinyl pyridine, and vinyl amine. 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 acid or fumaric acid as a dissociating group is particularly preferred in terms 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 of the wax was 5 ° C / min using a differential scanning calorimeter (Shimadzu DSC-50), heated to 200 ° C, rapidly cooled to 10 ° C for 5 minutes, then allowed to stand for 15 minutes. The temperature was raised at ° C./min, and the endothermic (melting) peak was obtained. The amount of sample put into the cell was 10 mg ± 2 mg.

(4) Charge Control Agent The charge control agent is preferably an acrylic sulfonic acid polymer, and a vinyl copolymer of a styrene monomer and an acrylic acid monomer having a sulfonic acid group as a polar group. In particular, a copolymer with acrylamido-2-methylpropanesulfonic acid can exhibit preferable characteristics. By using it in combination with a carrier to be described later, the handling property in the developing device is improved and the uniformity of the toner density is improved. Further, development memory can be suppressed. As a preferable material, a metal salt of a salicylic acid derivative is used. With this configuration, it is possible to prevent image disturbance due to charging during fixing. This seems to be the effect of the functional group having the acid value of the wax and the charging polarity of the metal salt. In addition, it is possible to prevent a decrease in charge amount during continuous use.

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

  The addition amount is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the resin. More preferably, it is 0.1-2 weight part, More preferably, it is 0.5-1.5 weight part. When the amount is less than 0.1 parts by weight, the charging effect is lost. If it exceeds 5 parts, the dispersion will not be uniform. Color turbidity in color images is noticeable.

(5) Pigment As the colorant (pigment) used in the present embodiment, carbon black, iron black, graphite, nigrosine, and an azo dye metal complex can be preferably used as the black pigment.

  Examples of yellow pigments include C.I. I. Acetoacetic acid arylamide monoazo yellow pigments such as C.I. Pigment Yellow 1, 3, 74, 97 or 98; I. Acetoacetic acid arylamide disazo yellow pigments such as C.I. Pigment Yellow 12, 13, 14, and 17; I. Solven Yellow 19, 77, 79 or C.I. I. Disperse Yellow 164 is blended, and C.I. I. Benzimidazolone pigments of CI Pigment Yellow 93, 180 and 185 are preferred.

  Examples of magenta pigments include C.I. I. Red pigments such as CI Pigment Red 48, 49: 1, 53: 1, 57, 57: 1, 81, 122, 5; I. Red dyes such as Solvent Red 49, 52, 58 and 8 can be preferably used.

  Examples of cyan pigments include C.I. I. A blue dyed pigment of phthalocyanine and its derivatives such as Pigment Blue 15: 3 can be preferably used. The addition amount is preferably 3 to 8 parts by weight with respect to 100 parts by weight of the binder resin.

  The median diameter of each particle is usually 1 μm or less, preferably 0.01 to 1 μm. When the median diameter exceeds 1 μm, the particle size distribution of the finally obtained toner for developing an electrostatic charge image is broadened, or free particles are generated, which easily deteriorates performance and reliability. On the other hand, when the median diameter is within the above range, there are no disadvantages, and the uneven distribution among the toners is reduced, the dispersion in the toner is improved, and the variation in performance and reliability is advantageous. The median diameter can be measured using, for example, a Horiba laser diffraction particle size measuring instrument (LA920).

(6) External additive In this embodiment, as an external additive, metal oxide fine powders such as silica, alumina, titanium oxide, zirconia, magnesia, ferrite, and magnetite, barium titanate, calcium titanate, strontium titanate, etc. A zirconate such as titanate, barium zirconate, calcium zirconate, strontium zirconate or a mixture thereof is used. The external additive is hydrophobized as necessary.

  As the silicone oil-based material to be treated with the external additive, those shown in (Chemical Formula 3) are preferable.

(However, R ² is an alkyl group having 1 to ³ carbon atoms, R ³ is an alkyl group having 1 to ³ carbon atoms, a halogen-modified alkyl group, a phenyl group, or a substituted phenyl group, and R ¹ is an alkyl group having 1 to 3 carbon atoms. Group, or an alkoxy group having 1 to 3 carbon atoms, m and n represent an integer of 1 to 100.)
For example, dimethyl silicone oil, methyl hydrogen silicone oil, methyl phenyl silicone oil, cyclic dimethyl silicone oil, epoxy modified silicone oil, carboxyl modified silicone oil, carbinol modified silicone oil, methacryl modified silicone oil, mercapto modified silicone oil, polyether modified An external additive treated with at least one of silicone oil, methylstyryl-modified silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, amino-modified silicone oil, and chlorophenyl-modified silicone oil is preferably used. 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 the external additive and a material such as silicone oil with a mixer such as a Henschel mixer, a method of spraying a silicone oil-based material on the external additive, or dissolving or dispersing the silicone oil-based material in a solvent And after mixing with an external additive, the solvent is removed 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 external additive 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 the cloud of the external additive powder by stirring or the like, or a silane coupling in which the external additive powder is dispersed in a solvent. It is processed by a wet method in which an agent is dropped.

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

  The external additive having positive electrode chargeability is treated with aminosilane, amino-modified silicone oil or epoxy-modified silicone oil represented by the following formula (Formula 4).

(However, R ¹ and R ⁶ are hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkoxy group, or an aryl group, R ² is an alkylene group having 1 to 3 carbon atoms, or a phenylene group, and R 3 includes a nitrogen heterocycle. Organic group, R4 and R5 are hydrogen, an alkyl group having 1 to 3 carbon atoms, or an aryl group, m is a number of 1 or more, n and q are positive integers including 0, and n + 1 is a positive number of 1 or more .)
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 preferred are aluminum distearate (Al (OH) (C ₁₇ H ₃₅ COO) ₂ ) or aluminum monostearate (Al (OH) ₂ (C ₁₇ H ₃₅ COO)), etc. Is preferred. Having an OH group can prevent overcharging and suppress poor transfer. 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.

  As the external additive, a configuration in which 1 to 6 parts by weight of an inorganic fine powder having an average particle diameter of 6 nm to 200 nm is externally added to 100 parts by weight of the toner base particles is preferable. 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. On the other hand, a configuration in which 0.5 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. At this time, 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 carrier and wax described above can improve the spent resistance, improve the handling property in the developing device, and increase the uniformity of the toner density. 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 externally added in an amount of 0.2 to 1.5 parts by weight based on 100 parts by weight of the toner base particles. A configuration for processing 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 0.2 parts by weight, it is difficult to obtain the effect. If it exceeds 1.5 parts by weight, fogging during development increases. The ignition loss is preferably 1.5 to 20 wt%, more preferably 5 to 19 wt%.

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

Loss on drying (%) = [Loss on drying (g) / Sample amount (g)] × 100
For ignition loss, about 1 g of a sample is placed in a magnetic crucible that has been dried, allowed to cool, and precisely weighed in advance, and weighed accurately. Ignite for 2 hours in an electric furnace set to 500 ° C. After standing to cool in a desiccator for 1 hour, its weight is precisely weighed and calculated from the following formula.

Loss on ignition (%) = [Loss on ignition (g) / Sample amount (g)] × 100
Moreover, it is preferable that the moisture adsorption amount of the processed inorganic fine powder is 1 wt% or less. More preferably, it is 0.5 wt% or less, More preferably, it is 0.1 wt% or less, Most 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 (%)
(7) Toner powder physical properties In this embodiment, toner base particles containing a binder resin, a colorant and a wax have a volume average particle diameter of 3 to 7 μm and a toner particle diameter of 2.52 to 4 μm in the number distribution. Toner having a mother particle content of 10 to 75% by number, a toner particle size of 25 to 75% by volume in a volume distribution of 4 to 6.06 μm, and a toner particle size of 8 μm or more in a volume distribution Toner containing 5% by volume or less of mother particles and having a particle size of 4 to 6.06 μm in the volume distribution, V46 being the volume percent of the mother particles having a particle size of 4 to 6.06 μm in the number distribution When the number% of the base particles is P46, P46 / V46 is in the range of 0.5 to 1.5, the variation coefficient in the volume average particle size is 10 to 25%, and the variation coefficient in the number particle size distribution is 10 to 10. 28% Is preferred.

  Preferably, the toner base particles have a volume average particle size of 3 to 6.5 μm, the content of toner base particles having a particle size of 2.52 to 4 μm in the number distribution is 20 to 75% by number, and 4 to 6 in the volume distribution. Toner base particles having a particle size of 0.06 μm are 35 to 75% by volume, toner base particles having a particle size of 8 μm or more in the volume distribution are contained in 3% by volume or less, and 4 to 6. When the volume% of toner base particles having a particle size of 06 μm is V46 and the number% of toner base particles having a particle size of 4 to 6.06 μm in the number distribution is P46, P46 / V46 is 0.5. It is preferable that the coefficient of variation in the volume average particle diameter is 10 to 20% and the coefficient of variation of the number particle size distribution is 10 to 23%.

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

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

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

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

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

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

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

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

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

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

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

  Further, the degree of compression is calculated from the static bulk density and the dynamic bulk density, which is one of the indicators of toner fluidity. The fluidity of the toner is affected by the particle size distribution of the toner, the toner particle shape, the external additive, and the type and amount of the wax. When the toner particle size distribution is narrow and the amount of fine powder is small, the toner surface has few irregularities and the shape is nearly spherical, the amount of external additive added is large, or the particle size of the external additive is small, the degree of compression is small. The fluidity of the toner becomes higher. The degree of compression is preferably 5 to 40%. More preferably, it is 10 to 30%. It is possible to achieve both oilless fixing and tandem multi-layer transfer. If it is less than 5%, the fixability is lowered, and the translucency is particularly likely to deteriorate. Toner scattering tends to increase from the developing roller. Transferability greater than 40% is lowered, and tandem-type deficiency occurs and transfer failure occurs.

(8) Carrier The carrier of this embodiment is a composite magnetic particle having at least magnetic particles and a binder resin, and the surface of the magnetic particle is coated with a resin made of a fluorine-modified silicone resin containing an aminosilane coupling agent. The carrier used is preferably used.

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

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

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

  Further, the above-described toner has a shape close to a sphere, and the specific surface area value also approaches the carrier. Therefore, the mixing property with the toner can be more uniformly mixed. When toner is replenished, it has good charge rise characteristics, and even if the toner / carrier density ratio is controlled over a wider range, image quality is unlikely to deteriorate, and both image density, fog and toner scattering are reduced. I can plan.

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

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

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

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

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

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

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

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

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

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

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

  The polyorganosiloxane preferably exhibits at least one repeating unit selected from the following formulas (Chemical Formula 5) and (Chemical Formula 6).

(However, R ¹ and R ² are hydrogen atoms, halogen atoms, hydroxy groups, methoxy groups, alkyl groups having 1 to 4 carbon atoms or phenyl groups, and R ³ and R ⁴ are alkyl groups having 1 to ⁴ carbon atoms or phenyl groups. M represents an average degree of polymerization and represents a positive integer (preferably in the range of 2 to 500, more preferably in the range of 5 to 200).

(However, R ¹ and R ² are each a hydrogen atom, a halogen atom, a hydroxy group, a methoxy group, an alkyl group having 1 to 4 carbon atoms, a phenyl group, R ³ , R ⁴ , R ⁵ and R ⁶ are each having 1 to 1 carbon atoms. 4 represents an alkyl group or a phenyl group, and n represents an average degree of polymerization and represents a positive integer (preferably in the range of 2 to 500, more preferably in the range of 5 to 200).
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.

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

  Therefore, by using such an aminosilane coupling agent and a fluorine-modified silicone resin in combination, negative chargeability can be imparted to the toner while ensuring a sharp charge amount distribution, and the toner is replenished. The toner has a quick charge rising property and can reduce the toner consumption. Furthermore, the aminosilane coupling agent expresses an effect like a crosslinking agent, improves the degree of crosslinking of the fluorine-modified silicone resin layer as the base resin, further improves the coating resin hardness, Separation and the like can be reduced, the spent resistance is improved, the decrease in charge imparting ability is suppressed, the charge is stabilized, and the durability is improved.

  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 slow is assumed, and the uniformity of fog and the whole surface of the solid image is deteriorated. By using the carrier in combination, the above problems are improved, the handling property in the developing device is improved, and the 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 inhibited. However, it causes a decrease in adhesion and hardness. Further, the excessive content of the conductive fine particles in the full color developer causes the color stain of the toner transferred and fixed on the paper surface.

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

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

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

  Thus, after coating the fluorine-modified silicone resin containing an aminosilane coupling agent on the surface of the composite magnetic particles, it is preferable to perform a baking treatment. The means for performing the baking process is not particularly limited, and may be either an external heating system or an internal heating system, for example, a fixed or fluid electric furnace, a rotary kiln electric furnace, or a burner furnace. Or it may be baked by microwave. However, with regard to the temperature of the baking treatment, in order to efficiently express the effect of the fluorine silicone that improves the spent resistance of the resin coating layer, the treatment is preferably performed at a high temperature of 200 to 350 ° C., more preferably 220-280 ° C. The treatment time is preferably 1.5 to 2.5 hours. When the treatment temperature is low, the hardness of the coating resin itself is lowered. If the processing temperature is too high, charge reduction occurs.

(9) Two-component development In the development process, an AC bias is applied between the photosensitive member and the developing roller together with a DC bias. The frequency at that time is 1 to 10 kHz, the AC bias is 1.0 to 2.5 kV (pp), and the peripheral speed ratio between the photoconductor and the developing roller is 1: 1.2 to 1: 2. It is preferable. More preferably, the frequency is 3.5 to 8 kHz, the AC bias is 1.2 to 2.0 kV (pp), and the peripheral speed ratio between the photosensitive member and the developing roller is 1: 1.5 to 1: 1. .8. More preferably, the frequency is 5.5 to 7 kHz, the AC bias is 1.5 to 2.0 kV (pp), and the peripheral speed ratio between the photosensitive member and the developing roller is 1: 1.6 to 1: 1. .8.

  With this development process configuration and the use of the toner or the two-component developer of the present embodiment, dots can be faithfully reproduced, and the original density and the density of the output image are proportional (also referred to as a characteristic that repels development γ characteristics). it can. 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.

  Even if the toner surface is almost resin-based, the combined use of this carrier composition and AC bias can reduce adhesion to the carrier, maintain image density, reduce fog, and reproduce dots faithfully. Seem.

  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 photosensitive member, and has the effect of slightly releasing the toner from the carrier. Good reproducibility and halftone reproducibility are achieved, and a high image density can be obtained.

  When the AC bias is smaller than 1.0 kV (pp), the effect of suppressing charge-up cannot be obtained, and when the AC bias is larger than 2.5 kV (pp), the fog increases. If the peripheral speed ratio between the photoconductor and the developing roller is smaller than 1: 1.2 (the developing roller becomes slow), it is difficult to obtain image density. When the peripheral speed ratio between the photosensitive member and the developing roller is larger than 1: 2 (the developing roller speed is increased), toner scattering increases.

(10) Tandem color process In order to form a color image at high speed, this embodiment has a plurality of toner image forming stations including a photoconductor, a charging means, and a toner carrier, and a static image formed on the image carrier. A primary transfer process in which a toner image obtained by developing an electrostatic latent image is transferred to the transfer member by bringing an endless transfer member into contact with the image carrier is sequentially executed, and a multilayer image is formed on the transfer member. A transfer process configured to execute a secondary transfer process in which a multi-layer toner image formed on the transfer body is then collectively transferred to a transfer medium such as paper or OHP. When the distance from the first primary transfer position to the second primary transfer position is d1 (mm) and the peripheral speed of the photosensitive member is v (mm / s), the transfer position satisfies d1 / v ≦ 0.65. In the configuration that takes the configuration, This is intended to achieve both downsizing of the printer and printing speed. In order to realize a reduction in size that can process 20 sheets per minute (A4) or more and the machine can be used for SOHO, it is essential to have a configuration in which a plurality of toner image forming stations are short and the process speed is increased. is there. In order to achieve both a reduction in size and a printing speed, a configuration in which the above value is 0.65 or less is considered a minimum.

  However, when the configuration between the toner image forming stations is short, for example, the time from the primary transfer of the yellow toner of the first color to the primary transfer of the next magenta toner of the second color is extremely short. There is almost no charge relaxation or charge relaxation of the transferred toner, and when transferring the magenta toner onto the yellow toner, the magenta toner is repelled by the charge action of the yellow toner, the transfer efficiency decreases, The problem of hollowing out occurs. Further, during the primary transfer of the cyan toner of the third color, the cyan toner 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 the present embodiment, the charge distribution is stabilized, the toner can be prevented from being overcharged, and the fluidity fluctuation can be suppressed. For this reason, it is possible to prevent transfer efficiency from being lowered, character dropout during transfer, and reverse transfer without sacrificing fixing characteristics.

(11) Cleanerless process In this embodiment, a cleanerless process that performs the following charging, exposure, and development processes without using a cleaning process that collects toner remaining on the photoreceptor after cleaning by cleaning is basically used. It is also suitably used for the electrophotographic apparatus having the configuration.

  By using the toner or the two-component developer of the present 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.

(12) Oilless Color Fixation In this embodiment, the present invention is suitably used for an electrophotographic apparatus having a fixing process having an oilless fixing configuration in which oil is not used as a toner fixing unit. As the heating means, electromagnetic induction heating is a preferable configuration from the viewpoint of shortening the warm-up time and saving energy. A heating and pressurizing unit having at least a magnetic field generating unit, a rotary heating member having at least a heat generation layer and a release layer generated by electromagnetic induction, and a rotary pressurizing member forming a fixed nip with the rotary heating member; In this configuration, a transfer medium such as copy paper on which toner is transferred is passed between the rotary heating member and the rotary pressure member, and is fixed. As a feature thereof, the warm-up time of the rotary heating member is very fast compared to the case where a conventional halogen lamp is used. For this reason, since the copying operation is started in a state where the temperature of the rotary pressure member is not sufficiently raised, low temperature fixing and a wide range of offset resistance are required.

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

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

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

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

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

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

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

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

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

As a comparative example, a core material d of ferrite particles having an average particle size of 80 μm and a saturation magnetization of 65 Am ² / kg when the applied magnetic field is 238.74 kA / m (3000 oersted) was used.

(Carrier production example 1)
Next, R ₁ and R ₂ represented by the following formula (Chemical Formula 7) are methyl groups, that is, 15.4 mol% of (CH ₃ ) ₂ SiO _2/2 units, and R ₃ represented by the following formula (Chemical Formula 8) is A fluorine-modified silicone resin was obtained by reacting 250 g of a polyorganosiloxane having a methyl group, that is, 84.6 mol% of CH ₃ SiO _3/2 unit, and 21 g of CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ . Further, 100 g of the fluorine-modified silicone resin in terms of solid content and 10 g of aminosilane coupling agent (γ-aminopropyltriethoxysilane) were weighed and dissolved in 300 cc of toluene solvent.

(However, R ¹ , R ² , R ³ , R ⁴ are methyl groups, m is the average degree of polymerization and is 100.)

(However, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are methyl groups, and n is the average degree of polymerization and is 80.)
The carrier core material A10 kg was coated by using the immersion drying type coating apparatus and stirring the coating resin solution for 20 minutes. Thereafter, baking was performed at 260 ° C. for 1 hour to obtain carrier A1.

The carrier A1 is a spherical particle having a spherical magnetite particle content of 80.4% by mass, an average particle diameter of 30 μm, a specific gravity of 3.05, a magnetization value of 61 Am ² / kg, and a volume resistivity of 3 × 10 ⁹ Ωcm, specific surface area was 0.098 m ² / g.

(Carrier production example 2)
Production Example 1 is the same as Production Example 1 except that the carrier core material B is used and CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) _{3 is changed} to C ₈ F ₁₇ CH ₂ CH ₂ Si (OCH ₃ ) _3. Carrier B1 was obtained in the same process.

The carrier B1 is a spherical particle having a spherical magnetite particle content of 88.4% by mass, an average particle diameter of 45 μm, a specific gravity of 3.56, a magnetization value of 65 Am ² / kg, and a volume resistivity of 8 × 10 ¹⁰ Ωcm and specific surface area 0.057 m ² / g.

(Carrier production example 3)
In Production Example 1, the same procedure as in Production Example 1 was conducted except that carrier core material C was used and conductive carbon (EC made by Ketjen Black International Co., Ltd.) was dispersed in a ball mill in an amount of 5 wt% based on the resin solid content. Carrier C1 was manufactured in the process.

The carrier C1 is a spherical particle having a spherical magnetite particle content of 92.5% by mass, an average particle diameter of 48 μm, a specific gravity of 3.98, a magnetization value of 69 Am ² / kg, and a volume resistivity of 2 × 10 ⁷ Ωcm and specific surface area 0.043 m ² / g.

(Carrier Production Example 4)
In Production Example 1, Carrier A2 was produced in the same process as Production Example 1 except that the amount of aminosilane coupling agent added was changed to 30 g.

The carrier A2 is a spherical particle having a spherical magnetite particle content of 80.4% by mass, an average particle diameter of 30 μm, a specific gravity of 3.05, a magnetization value of 61 Am ² / kg, and a volume resistivity of 2 × 10 ¹⁰ Ωcm and specific surface area 0.01 m ² / g.

(Carrier Production Example 5)
Except having changed the addition amount of the aminosilane coupling agent into 50g, the core material was manufactured in the process similar to the manufacture example 1, it coated, and carrier a1 was obtained.

(Carrier Production Example 6)
100 g of straight silicone (SR-2411 manufactured by Toray Dow Corning Co., Ltd.) as a solid content was weighed as a coating resin and dissolved in 300 cc of a toluene solvent. Coating was performed on the ferrite particles d10 kg by using an immersion drying type coating apparatus and stirring the coating resin solution for 20 minutes. Thereafter, baking was performed at 210 ° C. for 1 hour to obtain a carrier d2. The average particle diameter was 80 μm, the specific gravity was 6, the magnetization value was 75 Am ² / kg, the volume resistivity was 2 × 10 ¹² Ωcm, and the specific surface area was 0.024 m ² / g.

(Carrier Production Example 7)
100 g of an acrylic modified silicone resin (KR-9706, manufactured by Shin-Etsu Chemical Co., Ltd.) as a solid content was weighed and dissolved in a 300 cc toluene solvent. Coating was performed on the ferrite particles d10 kg by using an immersion drying type coating apparatus and stirring the coating resin solution for 20 minutes. Thereafter, baking was performed at 210 ° C. for 1 hour to obtain a carrier d3. The average particle diameter was 80 μm, the specific gravity was 6, the magnetization value was 75 Am ² / kg, the volume resistivity was 2 × 10 ¹¹ Ωcm, and the specific surface area was 0.022 m ² / g.

(Example 1)
Next, examples of the toner of the present invention will be described, but the present invention is not limited to these examples.

[Creation of resin dispersion]
Table 1 shows the characteristics of the resin used. Mn is a number average molecular weight, Mw is a weight average molecular weight, Mz is a Z average molecular weight, Mp is a molecular weight peak value, Tm (° C.) is a softening point, and Tg (° C.) is a glass transition point. Styrene, n-butyl acrylate, and acrylic acid indicate the amount (g).

(1) Preparation of resin particle dispersion RL1 A monomer liquid 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. (Product: Neogen RK) 3 g, dodecanethiol 6 g, carbon tetrabromide 1.2 g was dispersed, potassium persulfate 1.2 g was added thereto, and emulsion polymerization was performed at 70 ° C. for 6 hours. Thereafter, aging treatment is further performed at 90 ° C. for 3 hours, and resin particles having Mn of 3900, Mw of 10900, Mz of 37800, Mp of 8100, Tm of 115 ° C., Tg of 43 ° C., and median diameter of 0.12 μm are dispersed. A resin particle dispersion RL1 was prepared.
(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. (Product: Neogen RK) 6 g, dodecanethiol 6 g, carbon tetrabromide 1.2 g was dispersed, potassium persulfate 1.2 g was added thereto, and emulsion polymerization was performed at 70 ° C. for 5 hours. Thereafter, aging treatment is further performed at 90 ° C. for 5 hours, and resin particles having Mn of 6600, Mw of 60300, Mz of 259000, Mp of 8100, Tm of 128 ° C., Tg of 55 ° C., and median diameter of 0.18 μm are dispersed. A resin particle dispersion RL2 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. (Product: Neogen RK) 6 g, dodecanethiol 12 g, and carbon tetrabromide 2.4 g were dispersed, and potassium persulfate 1.2 g was added thereto, followed by emulsion polymerization at 70 ° C. for 5 hours. Thereafter, aging treatment is further performed at 90 ° C. for 2 hours, and resin particles having Mn of 2600, Mw of 18300, Mz of 96200, Mp of 2700, Tm of 109 ° C., Tg of 45 ° C., and median diameter of 0.18 μm are dispersed. A resin particle dispersion RL3 was prepared.
(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. Resin in which resin particles are subjected to emulsion polymerization at 70 ° C. for 5 hours, and Mn is 41000, Mw is 242000, Mz is 575000, Mp is 154000, Tm is 193 ° C., Tg is 76 ° C., and the median diameter is 0.22 μm. A particle dispersion RH5 was prepared.

(Example 2)
[Creation of pigment dispersion]
Table 2 shows the pigments used.

(1) Preparation of Colorant Particle Dispersion Liquid PM1 20 g of magenta pigment (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 (PY74 manufactured by Sanyo Dye), 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. A colorant particle dispersion PY1 in which colorant particles having a median diameter of 0.12 μm were dispersed was prepared by using a machine for 20 minutes at an oscillation frequency of 30 kHz.
(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 3
[Creation of wax dispersion]
Of the surfactants used in the wax dispersion, it is preferable to use a mixture of an ionic surfactant and a nonionic surfactant. It is preferable that the nonionic surfactant has 10 to 90 wt% with respect to the entire surfactant. More preferably, it is 30 to 70 wt%. With this configuration, it is possible to eliminate the presence of suspended colorant particles and wax particles that are not involved in aggregation in an aqueous system, and to form core particles having a small particle size, a uniform and sharp particle size distribution in a narrow range. Further, it is possible to reduce the floating of the second resin particles, to make the adhesion and fusion uniform on the aggregated particles, and to produce a sharp particle size distribution. The properties of the waxes used are shown in (Table 3), (Table 4), (Table 5), and (Table 6).

(1) Preparation of Wax Particle Dispersion WA1 FIG. 3 is a schematic view of a stirring and dispersing apparatus, and FIG. 4 is a view seen from above. Reference numeral 801 denotes an outer tank, in which cooling water is injected from 808 and discharged from 807. Reference numeral 802 denotes a dam plate that stops the liquid to be treated, and a hole is formed in the center portion. Reference numeral 803 denotes a rotating body that rotates at a high speed and is fixed to the shaft 806 and can rotate at a high speed. A hole of about 1 to 5 mm is formed on the side surface of the rotating body, and the liquid to be processed can be moved. The tank is 120 ml, and about half of the liquid to be treated is charged. The speed MAX of the rotating body can be up to 50 m / s. The diameter of the rotating body is 52 mm, and the inner diameter of the tank is 56 mm. Reference numeral 44 denotes a raw material inlet for continuous processing. Sealed for high-pressure processing or batch processing.

70 g of ion-exchanged water, 0.8 g of an anionic surfactant (SCF manufactured by Sanyo Chemical Industries, Ltd.), 1.2 g of a nonionic surfactant (New Coal 565C manufactured by Nippon Emulsifier Co., Ltd.), and 28 g of wax (W-1) are charged. The speed of the rotating body was 20 m / s for 5 min, and then the rotating speed was increased to 50 m / s for 2 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 wax particle dispersion WA2
Under the same conditions as in (1), 70 g of ion-exchanged water, 0.5 g of an anionic surfactant (SCF manufactured by Sanyo Chemical Industries, Ltd.), 1.5 g of a nonionic surfactant (Newcol 565C manufactured by Nippon Emulsifier Co., Ltd.), wax ( W-2) 28 g was charged, the speed of the rotating body was 3 m at 20 m / s, and then the rotating speed was increased to 45 m / s, followed by 2 min to form a wax particle dispersion WA2.
(3) Preparation of wax particle dispersion WA3
Under the same conditions as in (1), 70 g of ion-exchanged water, 1 g of an anionic surfactant (SCF manufactured by Sanyo Kasei Kogyo Co., Ltd.), nonionic surfactant (Nippon Emulsifier Co., Ltd.) with the inside pressurized to 0.4 MPa (New Coal 565C) 1 g and 28 g of wax (W-3) were charged, the speed of the rotating body was 3 min at 20 m / s, and then the rotating speed was increased to 50 m / s, followed by 2 min processing to form a wax particle dispersion WA3. It was.
(4) Preparation of wax particle dispersion WA4
Under the same conditions as in (1), 70 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-4) 28 g was charged, the speed of the rotating body was 3 minutes at 20 m / s, and then the rotational speed was increased to 50 m / s, followed by treatment for 1 minute to form a wax particle dispersion WA4.
(5) Preparation of wax particle dispersion WA5
Under the same conditions as (3), 70 g of ion-exchanged water, 1 g of an anionic surfactant (SCF manufactured by Sanyo Kasei Kogyo Co., Ltd.), 1 g of nonionic surfactant (New Coal 565C manufactured by Nippon Emulsifier Co., Ltd.), wax (W-5) 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 45 m / s for 4 minutes to form a wax particle dispersion WA5.
(6) Preparation of wax particle dispersion WA6
Under the same conditions as (3), 70 g 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.), wax (W-6) 28 g was charged, the speed of the rotating body was 3 minutes at 20 m / s, and then the rotational speed was increased to 45 m / s, followed by treatment for 4 minutes to form a wax particle dispersion WA6.
(7) Preparation of wax particle dispersion WA7
Under the same conditions as (3), 70 g 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.), wax (W-7) 28 g was charged, and the speed of the rotating body was 20 m / s for 3 min, and then the rotating speed was increased to 45 m / s for 4 min to form a wax particle dispersion WA7.
(8) Preparation of Wax Particle Dispersion WA8 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 rotating body 853 and the pushing force of the rotating body 853. Reference numeral 854 denotes a shaft connected to a motor (not shown). The raw material charged from 850 receives a strong shearing force between the gap between the stationary body and the rotating body and is dispersed into fine particles in the liquid. The processed raw material liquid is discharged from 856. FIG. 6 shows a view from above. The discharged raw material liquid 855 is blown radially and collected in a sealed container. The outer diameter of the rotating body is 100 mm.

  The raw material liquid is pre-dispersed with a wax and a surfactant in an aqueous medium that has been heated under pressure in advance, and is introduced into the inlet 80 to be instantly refined. The supply amount was 1 kg / h, and the rotating body was rotated at a maximum speed of 100 m / s.

70 g of ion exchange 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-8) were charged, and the speed of the rotating body Was processed at 100 m / s and the supply rate was 1 kg / h, and a wax particle dispersion WA8 was formed.
(10) Preparation of Wax Particle Dispersion Wa10 70 g of ion-exchanged water, 1 g of anionic surfactant (SCF manufactured by Sanyo Kasei Kogyo Co., Ltd.), 1 g of nonionic surfactant (New Coal 565C manufactured by Nippon Emulsifier Co., Ltd.), paraffin wax (Nippon Seiki) HNP-10 (manufactured by Sakai Co., Ltd., melting point: 75 ° C.) (28 g) was charged and treated with a homogenizer for 30 minutes to form a wax particle dispersion wa10.
(11) Preparation of Wax Particle Dispersion Wa11 70 g 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.) FT0070 (manufactured by Nippon Seisaku Co., Ltd., melting point: 72 ° C.) (28 g) was charged and treated with a homogenizer for 30 minutes to form a wax particle dispersion wa11.
(12) Preparation of Wax Particle Dispersion Wa12 70 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.), a hydrocarbon wax ( 28 g of LUVAX 2191 manufactured by Nippon Seiki Co., Ltd., melting point 83 ° C.) was charged and treated with a homogenizer for 30 min to form a wax particle dispersion wa12.

Example 4
[Create toner base]
The composition of the produced toner is shown in (Table 7).
d50 (μm) is the volume average particle diameter of the toner base particles, P2 is the number% content of toner base particles having a particle diameter of 2.52 to 4 μm in the number distribution, and V46 is 4 to 6.06 μm in the volume distribution. The volume% content P46 of toner base particles having a particle size is the content% content of toner base particles having a particle size of 4 to 6.06 μm in the number distribution, and P8 is the particle size of 8 μm or more in the volume distribution. The content volume% amount of toner mother particles having

(1) Preparation of toner base M1 A 2000 ml four-necked flask equipped with a thermometer, a cooling tube, a stirrer, and a pH meter was charged with 204 g of the first resin particle dispersion RL2 and 20 g of the colorant particle dispersion PM1 and wax. 50 g of particle dispersion WA1 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. The pH of the obtained mixed dispersion was 5.8.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11.9, and then 260 g of a 23% strength magnesium sulfate aqueous solution was added and stirred for 10 min. Thereafter, the temperature was raised from 22 ° C. to 70 ° C. at a rate of 5 ° C./min, and then heated at 70 ° C. for 2 hours. Thereafter, the temperature was raised to 85 ° C., and heat treatment was performed for 3 hours. The obtained aggregated particle dispersion had a pH of 9.3. When observed with a Coulter counter (manufactured by Coulter Inc .: Multisizer 2), the volume average particle diameter was 4.0 μm and the coefficient of variation was 19.7.

  Thereafter, the pH was further adjusted to 6.6, and heat treatment was performed at 90 ° C. for 2 hours to obtain aggregated particles.

  After cooling, the reaction product (toner matrix) was filtered and washed three times with ion exchange water. The toner base thus obtained was dried at 40 ° C. for 6 hours with a fluid dryer to obtain toner base M1. The volume average particle size was 4.3 μm, and the coefficient of variation was 18.1.

  At this time, if the pH at the time of preparing the mixed dispersion is higher than 6.0, when the colored resin particles are formed by heating, the pH fluctuation (decrease phenomenon) in the liquid becomes large and the particles become coarse. End up.

  When adjusting the pH of the mixed dispersion before addition of the water-soluble inorganic salt and before heating, if it is lower than 9.5, the formed colored resin particles become coarse. When the pH was 12.5, the amount of free wax increased, making it difficult to encapsulate the wax uniformly. If the pH of the liquid when the aggregated particles are formed is higher than 9.5, the aggregation is poor and free wax increases.

The temperature was raised from 22 ° C. to 70 ° C. at a rate of 5 ° C./min, and then heated at 70 ° C. for 2 hours. Thereafter, the temperature is raised to 85 ° C. and heat-treated for 3 hours, and then the particles tend to be coarsened if the heat treatment is carried out without adjusting the pH, or even when the pH is higher than 6.8. It is in. When the pH is lowered to less than 2.2, the effect of the surfactant tends to disappear and the particle diameter tends to become coarse.
(2) Preparation of toner base M2 In a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod and a pH meter, 2000 ml, 204 g of the first resin particle dispersion RL2 and 20 g of the colorant particle dispersion PM1 are waxed. 50 g of particle dispersion WA2 and 200 ml of ion-exchanged water were added, and mixed for 10 min using a homogenizer (manufactured by IKA: Ultra Tarrax T50) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 2.8.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 9.7, and then 260 g of a 23% strength magnesium sulfate aqueous solution was added and stirred for 10 min. Thereafter, the temperature was raised from 22 ° C. to 70 ° C. at a rate of 5 ° C./min, and then heated at 70 ° C. for 2 hours. Thereafter, the temperature was raised to 85 ° C. and treated for 5 hours to obtain aggregated particles. The obtained aggregated particle dispersion had a pH of 7.2. The volume average particle size was 5.7 μm, and the coefficient of variation was 18.9.

  Thereafter, the pH was further adjusted to 2.5, and heat treatment was performed at 90 ° C. for 2 hours to obtain aggregated particles.

After cooling, the reaction product (toner matrix) was filtered and washed three times with ion exchange water. The toner base thus obtained was dried at 40 ° C. for 6 hours with a fluid-type dryer to obtain a toner base M2. The volume average particle size was 6.0 μm, and the coefficient of variation was 16.9.
(3) Preparation of toner base M3 In a 4-ml flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter, 204 g of the first resin particle dispersion RL2 and 20 g of the colorant particle dispersion PM1 and wax 50 g of particle dispersion WA3 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. The pH of the obtained mixed dispersion was 4.2.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11.2, and then 260 g of a 23% strength magnesium sulfate aqueous solution was added and stirred for 10 min. Thereafter, the temperature was raised from 22 ° C. to 70 ° C. at a rate of 5 ° C./min, and then heated at 70 ° C. for 2 hours. Thereafter, the temperature was raised to 85 ° C. and treated for 5 hours to obtain aggregated particles. The obtained aggregated particle dispersion had a pH of 8.5. The volume average particle size was 4.7 μm, and the coefficient of variation was 19.9.

  Thereafter, the pH was further adjusted to 4.5, and heat treatment was performed at 90 ° C. for 2 hours to obtain aggregated particles.

After cooling, the reaction product (toner matrix) was filtered and washed three times with ion exchange water. The toner base thus obtained was dried at 40 ° C. for 6 hours with a fluid-type dryer to obtain a toner base M3. The volume average particle size was 4.9 μm and the coefficient of variation was 18.1.
(4) Preparation of toner matrix M4 In a four-necked flask equipped with a thermometer, cooling tube, stirring rod, and pH meter, 2000 ml, 204 g of the first resin particle dispersion RL1, 24 g of the colorant particle dispersion PM1, and wax 50 g of particle dispersion WA4 and 250 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. The pH of the obtained mixed dispersion was 5.8.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11.9, and then 264 g of a 23% strength magnesium sulfate aqueous solution was added and stirred for 10 min. Thereafter, the temperature was raised from 22 ° C. to 70 ° C. at a rate of 5 ° C./min, and then heated at 70 ° C. for 2 hours. Thereafter, the temperature was raised to 85 ° C. and treated for 5 hours. The pH of the dispersion at that time was 9.3. The produced particles had a volume average particle size of 3.7 μm and a coefficient of variation of 21.4.

  Thereafter, the pH was further adjusted to 6.6, and heat treatment was performed at 90 ° C. for 2 hours to obtain core particles. The volume average particle size was 3.9 μm, and the coefficient of variation was 19.8.

  Thereafter, the water temperature was 60 ° C., 43 g of the second shell resin particle dispersion RH4 was added, 1N NaOH was added, and the pH was adjusted to 8.6.

  The water temperature was heated at 80 ° C. for 0.5 hour, and then 1N HCl was added to adjust the pH to 6.6.

  Thereafter, the mixture was further heated at 90 ° C. for 2 hours.

  After cooling, the reaction product (toner matrix) was filtered and washed three times with ion exchange water. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid dryer, thereby obtaining a toner base M4 having a volume average particle size of 4.8 μm and a coefficient of variation of 20.1.

  When the pH when the second resin particle dispersion (RH4 in this example) was added was 5.0, adhesion of the second resin particles hardly occurred and free resin particles increased. Moreover, when pH was set to 9.0, secondary aggregation of core particles occurred, and the particles became coarse.

When the pH after the heat treatment was 3.0, some of the resin particles once adhered were released and fine particles were generated. When 7.0, secondary aggregation of the core particles occurred and the particles became coarse.
(5) Preparation of toner base M5 In a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod and a pH meter, 2000 ml, 204 g of the first resin particle dispersion RL3, 24 g of the colorant particle dispersion PM1, and wax 50 g of particle dispersion WA5 and 250 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. The pH of the obtained mixed dispersion was 2.2.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 9.7, and then 264 g of a 23% strength magnesium sulfate aqueous solution was added, followed by stirring 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 70 ° C. for 2 hours. Thereafter, the temperature was raised to 85 ° C. and treated for 5 hours. The pH of the obtained dispersion was 7.2. The produced particles had a volume average particle size of 4.7 μm and a coefficient of variation of 17.4.

  Thereafter, the pH was further adjusted to 2.5, and heat treatment was performed at 90 ° C. for 2 hours to obtain core particles. The volume average particle size was 4.9 μm, and the coefficient of variation was 16.8.

  Thereafter, the water temperature was 60 ° C., 43 g of the second shell resin particle dispersion RH4 was added, 1N NaOH was added, and the pH was adjusted to 5.0.

  The water temperature was heated at 80 ° C. for 2 hours, and then 1N HCl was added to adjust the pH to 3.4. Thereafter, the mixture was further heated at 90 ° C. for 2 hours.

After cooling, the reaction product (toner matrix) was filtered and washed three times with ion exchange water. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid drier to obtain a toner base M5 having a volume average particle size of 5.9 μm and a coefficient of variation of 15.9.
(6) Preparation of toner base M6 In a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod and a pH meter, 2000 ml, 204 g of the first resin particle dispersion RL1 and 24 g of the colorant particle dispersion PM1 are waxed. 50 g of particle dispersion WA6 and 250 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. The pH of the obtained mixed dispersion was 3.8.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11.2, and then 260 g of a 23% strength magnesium sulfate aqueous solution was added and stirred for 10 min. Thereafter, the temperature was raised from 22 ° C. to 70 ° C. at a rate of 5 ° C./min, and then heated at 70 ° C. for 2 hours. Thereafter, the temperature was raised to 85 ° C. and treated for 5 hours. The pH of the obtained dispersion was 8.5. The produced particles had a volume average particle size of 4.0 μm and a coefficient of variation of 19.6.

  Thereafter, the pH was further adjusted to 4.8, and heat treatment was performed at 90 ° C. for 2 hours to obtain core particles. The volume average particle size was 4.3 μm, and the coefficient of variation was 18.1.

  Thereafter, the water temperature was 60 ° C., 43 g of the second shell resin particle dispersion RH4 was added, 1N NaOH was added, and the pH was adjusted to 6.8.

  The water temperature was heated at 80 ° C. for 1 hour, and then 1N HCl was added to adjust the pH to 5.0. Thereafter, the mixture was further heated at 90 ° C. for 5 hours.

After cooling, the reaction product (toner matrix) was filtered and washed three times with ion exchange water. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid drier to obtain a toner base M6 having a volume average particle size of 5.2 μm and a coefficient of variation of 16.8.
(7) Preparation of toner matrix M7 In a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter, 2000 ml, 204 g of the first resin particle dispersion RL3, 24 g of the colorant particle dispersion PM1, and wax 50 g of particle dispersion WA7 and 250 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. The pH of the obtained mixed dispersion was 4.2.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11.2, and then 264 g of a 23% strength magnesium sulfate aqueous solution was added and stirred for 10 min. Thereafter, the temperature was raised from 22 ° C. to 70 ° C. at a rate of 5 ° C./min, and then heated at 70 ° C. for 2 hours. Thereafter, the temperature was raised to 85 ° C. and treated for 5 hours. The pH of the obtained dispersion was 8.5. The produced particles had a volume average particle size of 4.0 μm and a coefficient of variation of 19.2.

Thereafter, the pH was further adjusted to 4.8, and heat treatment was performed at 90 ° C. for 2 hours to obtain core particles. The volume average particle diameter was 4.2 μm, and the coefficient of variation was 17.8.
Thereafter, the water temperature was set to 60 ° C., 43 g of the second shell resin particle dispersion RH5 was added, and 1N NaOH was added to adjust the pH to 6.8.

  The water temperature was heated at 80 ° C. for 1 hour, and then 1N HCl was added to adjust the pH to 5.0. Thereafter, the mixture was further heated at 90 ° C. for 5 hours.

After cooling, the reaction product (toner matrix) was filtered and washed three times with ion exchange water. The toner base thus obtained was dried at 40 ° C. for 6 hours with a fluid dryer, thereby obtaining a toner base M7 having a volume average particle size of 5.2 μm and a coefficient of variation of 17.1.
(8) Preparation of toner base M8 In a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter, 2000 ml, 204 g of the first resin particle dispersion RL3, 24 g of the colorant particle dispersion PM1, and wax 50 g of particle dispersion WA8 and 250 ml of ion-exchanged water were added, and mixed for 10 min using a homogenizer (manufactured by IKA: Ultra Tarrax T50) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 4.2.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11.2, and then 264 g of a 23% strength magnesium sulfate aqueous solution was added and stirred for 10 min. Thereafter, the temperature was raised from 22 ° C. to 70 ° C. at a rate of 5 ° C./min, and then heated at 70 ° C. for 2 hours. Thereafter, the temperature was raised to 85 ° C. and treated for 5 hours. The pH of the obtained dispersion was 8.5. The produced particles had a volume average particle size of 4.7 μm and a coefficient of variation of 21.8.

  Thereafter, the pH was further adjusted to 4.8, and heat treatment was performed at 90 ° C. for 2 hours to obtain core particles. The volume average particle size was 4.9 μm, and the coefficient of variation was 19.8.

  Thereafter, the water temperature was set to 60 ° C., 43 g of the second shell resin particle dispersion RH5 was added, and 1N NaOH was added to adjust the pH to 6.8.

  The water temperature was heated at 80 ° C. for 1 hour, and then 1N HCl was added to adjust the pH to 5.0. Thereafter, the mixture was further heated at 90 ° C. for 5 hours.

After cooling, the reaction product (toner matrix) was filtered and washed three times with ion exchange water. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid drier to obtain a toner base M8 having a volume average particle size of 6.0 μm and a coefficient of variation of 18.1.
(9) Preparation of toner base M9 In a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter, 2000 ml, 204 g of the first resin particle dispersion RL1, 24 g of the colorant particle dispersion PM1, and wax 60 g of the particle dispersion WA2 and 250 ml of ion-exchanged water were added, and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T25) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 3.8.

Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11.9, and then 273 g of a 23% strength magnesium sulfate aqueous solution was added and stirred for 10 min. Thereafter, the temperature was raised from 20 ° C. to 90 ° C. at a rate of 1 ° C./min, followed by heat treatment for 3 hours to obtain an aggregated particle dispersion having a pH of 9.3. Thereafter, the pH was further adjusted to 6.6, and heat treatment was performed at 90 ° C. for 1 hour to obtain core particles. The obtained core particle dispersion had a pH of 6.3.
Thereafter, 43 g of the second resin particle dispersion RH4 having a pH adjusted to 5.5 was added at a dropping rate of 1 g / min while the water temperature was 90 ° C., and the mixture was heated at 90 ° C. for 2 hours after the completion of the dropping. It processed and obtained the particle | grains which the 2nd resin particle fuse | melted. By the heat treatment for about 2 hours, the second resin particles were uniformly fused, and the effect of shortening the treatment time was confirmed.
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, thereby obtaining a toner base M9c having a volume average particle diameter of 4.2 μm and a coefficient of variation of 16.7.
After mixing in (Table 8), the temperature in the tank and the pH of the liquid, the volume average particle diameter (d50 (μm)) after the lapse of time in the aggregated particle generation step, the second in the second resin particle adhesion melting step After completion of the resin particle-dispersed droplets, “R: (numerical value) described in the column of the temperature inside the tank with respect to the time elapsed after the dropping, the volume average particle diameter (d50 (μm)), and the second resin particle-dispersed droplets end. ")" Indicates the pH value after adjustment of the second resin particle dispersion. M9a to j have pH values after adjustment of the second resin particle dispersion of 10.5, 9.5, 8.5, 7.5, 6.5, 5.5, 4.5, 3. 5 and 11 are shown, and the volume average particle size and shape factor at the end of dropping at 2 h are shown.

By adjusting the pH value from 8.5 to 10.5, the shape tends to shift to an irregular shape.
When the second resin particle dispersion is dropped at a pH value of 3.5, the second resin particles do not adhere to the agglomerated particles at all, and only the second resin particles agglomerate, resulting in a volume variation coefficient of 40 or more. The particle size distribution was quite broad, and the dispersion remained cloudy. When the pH value was 11, the generated particles were coarsened to a volume average particle size of 15 μm or more.
(10) Preparation of toner base m10 A 2000 ml four-necked flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter, 204 g of resin particle dispersion RL2, 20 g of colorant particle dispersion PM1, and wax particle dispersion 30 g of wa10 and 200 ml of ion-exchanged water were added and mixed for 10 min using a homogenizer (manufactured by IKA: Ultra Tarrax T50) to prepare a mixed particle dispersion.

  1N NaOH was added to the obtained mixed particle dispersion to adjust the pH to 9.2, and then 260 g of a 23% strength magnesium sulfate aqueous solution was added and stirred for 10 min. Thereafter, the temperature was raised from 22 ° C. to 70 ° C. at a rate of 5 ° C./min, and then heated at 70 ° C. for 2 hours. Thereafter, the temperature was raised to 90 ° C. and treated for 5 hours to obtain aggregated particles. The pH of the obtained aggregated particles was 6.7.

Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid drier to obtain a toner base m10 having a volume average particle size of 9.1 μm and a coefficient of variation of 31.2.
(11) Preparation of toner base m11 A 2000 ml four-necked flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter, 204 g of resin particle dispersion RL2, 20 g of colorant particle dispersion PM1, and wax particle dispersion 30 g of wa11 and 200 ml of ion-exchanged water were added and mixed for 10 min using a homogenizer (manufactured by IKA: Ultra Tarrax T50) to prepare a mixed particle dispersion.

  1N NaOH was added to the obtained mixed particle dispersion to adjust the pH to 9.3, and then 260 g of a 23% strength magnesium sulfate aqueous solution was added and stirred for 10 min. Thereafter, the temperature was raised from 22 ° C. to 70 ° C. at a rate of 5 ° C./min, and then heated at 70 ° C. for 2 hours. Thereafter, the temperature was raised to 85 ° C. and treated for 5 hours to obtain aggregated particles. The pH of the obtained aggregated particles was 6.8.

Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid drier to obtain a toner base m11 having a volume average particle size of 8.1 μm and a variation coefficient of 31.8.
(12) Preparation of toner base m12 A 2000 ml four-necked flask equipped with a thermometer, a cooling tube, a stirring rod and a pH meter, 204 g of resin particle dispersion RL2, 20 g of colorant particle dispersion PM1, and wax particle dispersion wa12. 30 g and 200 ml of ion-exchanged water were added and mixed for 10 min using a homogenizer (manufactured by IKA: Ultra Tarrax T50) to prepare a mixed particle dispersion.

  1N NaOH was added to the obtained mixed particle dispersion to adjust the pH to 9.2, and then 260 g of a 23% strength magnesium sulfate aqueous solution was added and stirred for 10 min. Thereafter, the temperature was raised from 22 ° C. to 70 ° C. at a rate of 5 ° C./min, and then heated at 70 ° C. for 2 hours. Thereafter, the temperature was raised to 85 ° C. and treated for 5 hours to obtain aggregated particles. The pH of the obtained aggregated particles was 6.7.

  Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours with a fluid dryer to obtain a toner base m12 having a volume average particle size of 7.5 μm and a coefficient of variation of 42.9.

Table 9 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 10 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 the blending amount (part 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 photoconductor is 125 mm / s.

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

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

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

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

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

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

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

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

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

  FIG. 2 shows the fixing process. A belt 203 is placed between the fixing roller 201 and the heat roller 204. A predetermined load is applied between the fixing roller 201 and the pressure roller 202, and a nip is formed between the belt 203 and the pressure roller 202. An induction heater unit 205 including a ferrite core 206 and a coil 207 is provided on the outer peripheral surface of the heat roller 204, and a temperature sensor 208 is arranged 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 a fluororesin (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 11 shows the results of image output using the electrophotographic apparatus shown in FIG. Occurrence of toner component filming on the photoreceptor, image density before and after the durability test, fogging due to toner adhesion to non-image areas, uniformity of density when a solid image is taken over the entire surface, magenta, cyan In the full-color image in which three colors of yellow toner are superimposed, scattering at the time of transfer in a character portion or a so-called hollow state where a part of the full-color image remains on the photoconductor without being transferred, after yellow or magenta toner is transferred, the next magenta The yellow or magenta toner already transferred at the time of transferring the cyan or black toner, on the contrary, adheres to the photosensitive member and returns to the reverse transfer state.

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

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

  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. Also, even in the full-color image in which the three colors overlap each other, there is no problem with reverse transfer transfer, and no paper wraps around the fixing belt during fixing.

  At cm1, cm2, and cm3, charge increase occurred and fog was conspicuous. Further, when a solid image 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. The mixing ratio of the toner and the carrier was in the range of 5 to 8 wt%, even if the density was changed, there was little change in image quality such as image density and ground cover. When the value is large, the ground cover increases.

In Table 12, a solid image with an adhesion amount of 1.2 mg / cm ² was processed at a process speed of 125 mm / s shown in FIG. 2 and the OHP transmittance (fixing temperature: 160 ° C.) using a belt not coated with oil. , Offset property at high temperature (temperature at which high temperature offset occurs), storage stability after leaving at 60 ° C. for 5 hours, and wrapping property of the paper around the fixing belt during fixing and toner scattering during fixing The state of toner disturbance was evaluated. The OHP transmittance was measured with a spectrophotometer U-3200 (Hitachi, Ltd.) for the transmittance of 700 nm light.

  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). In the toners of tm10, tm11, and tm12, the wax was poorly dispersed, the storage stability was deteriorated, which seems to be caused by the broad particle size distribution, and the paper was wound around the fixing belt.

  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.

1 is a cross-sectional view illustrating a configuration of an image forming apparatus used in an embodiment of the present invention. FIG. 3 is a cross-sectional view illustrating a configuration of a fixing unit used in one embodiment of the present invention. 1 is a schematic view of a stirring and dispersing device used in one embodiment of the present invention. The figure seen from the stirring dispersion | distribution apparatus used in one Example of this invention. 1 is a schematic view of a stirring and dispersing device used in one embodiment of the present invention. The figure seen from the stirring dispersion | distribution apparatus used in one Example of this invention.

Explanation of symbols

1Y, 1M, 1C, 1K Photoconductors 2Y, 2M, 2C, 2K Charging rollers 3Y, 3M, 3C, 3K Laser signal light 4Y, 4M, 4C, 4K Developing rollers 5Y, 5M, 5C, 5K Blades 6Y, 6M, 6C , 6K Agitating rollers 7Y, 7M, 7C, 7K Developers 8Y, 8M, 8C, 8K Cleaners 9Y, 9M, 9C, 9K Waste toner boxes 10Y, 10M, 10C, 10K First transfer roller 11 Drive roller 12 Transfer belt 13 Drive Tension roller 14 Second transfer roller 15 Roller 16 Belt cleaner blade 17 Transfer belt unit 18B, 18C, 18M, 18Y Image forming unit 19 Transfer medium 201 Fixing roller 202 Pressure roller 203 Fixing belt 204 Heating medium roller 205 Induction heater section 206 Ferrite Core 207 Outside coil 801 802 dam 803 rotating body 806 shaft 807 cooling water discharge port 808 cooling water inlet 850 raw material inlet 852 fixed body 853 rotating member 854 shaft 856 material liquid discharged

Claims (23)

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 wax particle dispersion in which the wax particles are dispersed are mixed, and the aqueous system is obtained by aggregation heating. A toner manufacturing method for producing toner in
Creating a mixed dispersion of at least a resin particle dispersion in which the resin particles are dispersed, a colorant particle dispersion in which the colorant particles are dispersed, and a wax particle dispersion in which the wax particles are dispersed; and
At least a part of the resin particles, the colorant particles and the wax particles aggregated by adjusting the pH of the mixed dispersion to a range of 9.5 to 12.2, adding a water-soluble inorganic salt, and heat-treating. Forming molten aggregated particles, and the pH when the aggregated particles are formed is in the range of 7.0 to 9.5;
And a step of adjusting the pH to a range of 2.2 to 6.8, followed by heat treatment. In an aqueous medium, at least the first resin particle dispersion in which the first resin particles are dispersed, the colorant particle dispersion in which the colorant particles are dispersed, and the wax particle dispersion in which the wax particles are dispersed are mixed. And a toner production method for producing toner in an aqueous system by heat aggregation,
A mixed dispersion of at least a first resin particle dispersion in which the first resin particles are dispersed, a colorant particle dispersion in which the colorant particles are dispersed, and a wax particle dispersion in which the wax particles are dispersed. Creating a process;
The pH of the mixed dispersion is adjusted to a range of 9.5 to 12.2, a water-soluble inorganic salt is added, and heat treatment is performed to aggregate the first resin particles, the colorant particles, and the wax particles. Forming a core particle at least partially melted, and a step in which the pH when the core particle is formed is in a range of 7.0 to 9.5;
Thereafter, adjusting the pH to a range of 2.2 to 6.8, and heat-treating to form core particles;
Adding the second resin particle dispersion in which the second resin particles are further dispersed to the core particle dispersion in which the core particles are dispersed;
adjusting the pH to a range of 5.2 to 8.8;
Heat treatment at a temperature equal to or higher than the glass transition temperature of the second resin particles;
adjusting the pH to a range of 2.2 to 6.8;
And a step of fusing the second resin particles to the core particles by heat treatment at a temperature equal to or higher than the glass transition temperature of the second resin particles. In an aqueous medium, at least the first resin particle dispersion in which the first resin particles are dispersed, the colorant particle dispersion in which the colorant particles are dispersed, and the wax particle dispersion in which the wax particles are dispersed are mixed. And a toner production method for producing toner in an aqueous system by heat aggregation,
A mixed dispersion of at least a first resin particle dispersion in which the first resin particles are dispersed, a colorant particle dispersion in which the colorant particles are dispersed, and a wax particle dispersion in which the wax particles are dispersed. Creating a process;
The pH of the mixed dispersion is adjusted to a range of 9.5 to 12.2, a water-soluble inorganic salt is added, and heat treatment is performed to aggregate the first resin particles, the colorant particles, and the wax particles. Forming a core particle at least partially melted, and a step in which the pH when the core particle is formed is in a range of 7.0 to 9.5;
Thereafter, adjusting the pH to a range of 2.2 to 6.8, and heat-treating to form core particles;
When the pH value of the core particle dispersion in which the core particles are dispersed is HS, the second resin particle dispersion in which the second resin particles in which the pH value of the dispersion is adjusted to the range of HS + 2 to HS-5 is dispersed. And a step of adding and mixing to a core particle dispersion in which the core particles are dispersed.   The method for producing a toner according to claim 3, wherein the second resin particle dispersion in which the second resin particles are dispersed is added after adjusting the pH to a range of 3.5 to 10.5. The toner has a volume average particle size in the range of 3 to 7 μm, the content of toner base particles having a particle size of 2.52 to 4 μm in the number distribution is in the range of 10 to 75% by number, and 4 to 6.06 μm in the volume distribution. Toner mother particles having a particle size of 25 to 75% by volume, toner mother particles having a particle size of 8 μm or more in the volume distribution are contained at 5% by volume or less,
When the volume% of toner base particles having a particle diameter of 4 to 6.06 μm in the volume distribution is V46, and the number% of toner base particles having a particle diameter of 4 to 6.06 μm in the number distribution is P46, The toner production method according to claim 1, wherein P46 / V46 is in the range of 0.5 to 1.5.   The toner according to any one of claims 1 to 4, wherein the wax includes an ester wax having an iodine value of 25 or less, a saponification value of 30 to 300, and an endothermic peak temperature (melting point) by DSC method of 50 to 100 ° C. Method.   The wax according to any one of claims 1 to 4, wherein the wax contains at least a wax having an acid value of 10 to 80 mg KOH / g obtained by a reaction with a long-chain alkyl alcohol, an unsaturated polyvalent carboxylic acid or an anhydride thereof, and a synthetic hydrocarbon wax. A method for producing the toner according to the description.   The toner manufacturing method according to claim 1, wherein the wax includes one or more waxes selected from the group consisting of a hydroxy stearic acid derivative, a glycerin fatty acid ester, a glycol fatty acid ester, and a sorbitan fatty acid ester.   The toner according to claim 1, wherein the wax comprises an aliphatic amide wax having 4 to 30 carbon atoms or a saturated or divalent unsaturated alkylene bis fatty acid amide wax. Production method.   The toner according to claim 7, wherein the wax is a wax 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. Production method. The wax 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) in the molecular weight distribution in gel permeation chromatography (GPC). 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. The method for producing a toner according to any one of claims 1 to 4, comprising an ester-based wax having a peak and having a heat loss at 220 ° C of 8% by weight or less. The toner produced in any one of claims 1 to 11 is used as base particles, and an inorganic fine powder having an average particle size in the range of 6 nm to 200 nm is in the range of 1 to 6 parts by weight with respect to 100 parts by weight of the toner base particles. Add in
Magnetic particles comprising a cured binder resin and magnetic fine particles, wherein the content of the magnetic fine particles is 80 to 99 wt%, the number average particle diameter is 10 to 60 μm, and the surface of the magnetic particles is an aminosilane cup And a carrier containing magnetic particles coated with a fluorine-modified silicone resin containing a ring agent.   The two-component developer according to claim 12, wherein the magnetic particles comprise magnetic fine particles and a phenol resin cured by reacting an aldehyde with a phenol. The ^two- component developer according to claim 12, wherein the BET specific surface area of the carrier containing the magnetic particles coated on the surface is 0.03 to 0.3 m ² / g.   The two-component developer according to claim 12, wherein the magnetic particle coating resin contains 5 to 40 parts by weight of an aminosilane coupling agent in 100 parts by weight of the coating resin.   The two-component developer according to claim 12, 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.   13. The two-component developer according to claim 12, wherein the fluorine-modified silicone resin is a crosslinkable fluorine-modified silicone resin obtained from a reaction between a perfluoroalkyl group-containing organosilicon compound and polyorganosiloxane. The perfluoroalkyl group-containing organosilicon compound is CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , C ₄ F ₉ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , C ₈ F ₁₇ CH _2. Selected from CH ₂ Si (OCH ₃ ) ₃ , C ₈ F ₁₇ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ , and (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH ₂ Si (OCH ₃ ) ₃ The two-component developer according to claim 17, which is at least one selected from the group consisting of: The two-component developer according to claim 17, wherein the polyorganosiloxane is at least one selected from the following (Chemical Formula 1) and (Chemical Formula 2).

(However, R ¹ and R ² are hydrogen atoms, halogen atoms, hydroxy groups, methoxy groups, alkyl groups having 1 to 4 carbon atoms or phenyl groups, and R ³ and R ⁴ are alkyl groups having 1 to ⁴ carbon atoms or phenyl groups. M represents the average degree of polymerization and represents a positive integer.)

(However, R ¹ and R ² are each a hydrogen atom, a halogen atom, a hydroxy group, a methoxy group, an alkyl group having 1 to 4 carbon atoms, a phenyl group, R ³ , R ⁴ , R ⁵ and R ⁶ are each having 1 to 1 carbon atoms. 4 represents an alkyl group or a phenyl group, and n represents an average degree of polymerization and represents a positive integer.)   Crosslinkable fluorine-modified silicone obtained by a reaction in which the fluorine-modified silicone resin is a reaction in which the organosilicon compound containing a perfluoroalkyl group is 3 to 20 parts by weight with respect to 100 parts by weight of the polyorganosiloxane. The two-component developer according to claim 17, which is a resin.   The inorganic fine powder having an average particle diameter of 6 nm to 20 nm is 0.5 to 2.5 parts by weight based on 100 parts by weight of the toner base, and the inorganic fine powder having an average particle diameter of 20 nm to 200 nm is based on 100 parts by weight of the toner base. The two-component developer according to claim 12, wherein 0.5 to 3.5 parts by weight are externally added.   An inorganic fine powder having an average particle size of 6 nm to 20 nm and an ignition loss of 1.5 to 25 wt% is 0.5 to 2.5 parts by weight with respect to 100 parts by weight of the toner base, an average particle size of 20 nm to 200 nm, strong The two-component developer according to claim 12, wherein 0.5 to 3.5 parts by weight of an inorganic fine powder having a heat loss of 0.5 to 23 wt% is externally added to 100 parts by weight of the toner base.   And a plurality of toner image forming stations including at least an image carrier, a charging unit for forming an electrostatic latent image on the image carrier and a toner carrier, and an electrostatic latent image formed on the image carrier. The toner produced by the production method according to any one of claims 1 to 11, or the toner that has been visualized by the two-component developer according to any one of claims 12 to 22 to visualize an electrostatic latent image. A transfer system configured to execute a transfer process for sequentially transferring images onto a transfer medium, wherein the transfer process is a distance from a first transfer position to a second transfer position; When the distance from the second transfer position to the third transfer position or the distance from the third transfer position to the fourth transfer position is d1 (mm) and the peripheral speed of the photosensitive member is v (mm / s) , D1 / v ≦ 0.65 (sec) is satisfied Image forming apparatus characterized by.

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