JP4449810B2 - Toner production method - Google Patents

Description

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

  In recent years, the electrophotographic apparatus is shifting from the purpose of office use to personal use, and there is a demand for technology that realizes miniaturization, high speed, high image quality, maintenance-free, and the like. Therefore, a cleaner-less process that collects waste toner during development without cleaning waste toner remaining after transfer, a tandem color process that enables high-speed output of color images, and no fixing oil to prevent offset during fixing In both cases, oilless fixing that achieves both a clear color image having high glossiness and high translucency and non-offset properties is required along with conditions such as good maintenance and low ozone exhaust. These functions need to be compatible at the same time, and not only the process but also the improvement in toner characteristics is an important factor.

  In a color printer, an image carrier (hereinafter referred to as a photoconductor) is charged by corona discharge using a charging charger, and then a latent image of each color is irradiated onto the photoconductor as an optical signal to form an electrostatic latent image. The latent image is developed by developing with color, for example, yellow toner. Thereafter, a transfer member charged with a polarity opposite to that of the yellow toner is brought into contact with the photosensitive member to transfer the yellow toner image formed on the photosensitive member. The photosensitive member is neutralized after cleaning the toner remaining at the time of transfer, and the development and transfer of the first color toner are completed. Thereafter, the same operation as that of the yellow toner is repeated for toners such as magenta and cyan, and a color image is formed by superimposing the toner images of the respective colors on the transfer body. A four-pass color process in which these superimposed toner images are transferred onto paper charged to a polarity opposite to that of the toner has been put into practical use.

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

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

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

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

  For the purpose of providing a long-life coat carrier, (Patent Document 1) and (Patent Document 2) aim to improve the durability of the developer by preventing a decrease in toner charge amount in a high humidity atmosphere. In addition, a carrier coated with a silicone resin containing an aminosilane coupling agent in combination with a toner having limited components has been proposed, but it is not sufficient for preventing toner spent. There wasn't.

  (Patent Document 3) 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, in (Patent Document 4), a coating carrier containing a conductive carbon and a cross-linked fluorine-modified silicone resin is described as a high development capability in a high-speed process, which does not deteriorate over a long period of time. Proposed. Taking advantage of the excellent charging characteristics of silicone resin, the fluorine-substituted alkyl group provides slipperiness, peelability, water repellency, etc., and prevents wear, peeling, cracks, etc. However, wear, delamination, cracks, etc. are not satisfactory, and a positively charged toner can provide an appropriate charge amount, but a negatively charged toner is used. The charge amount was too low, and a large amount of reversely charged toner (toner having positive chargeability) was generated, resulting in deterioration such as fogging and toner scattering, and was not durable.

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

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

  In the pulverization / classification in the conventional kneading and pulverization method, the particle size that can be actually provided economically and in performance is about 8 μm even if the particle size is reduced. At present, methods for producing small-diameter toners by various methods are being studied.

  Also, a method for realizing oil-less fixing by blending a release agent such as wax in a resin having a low softening point when the toner is melt-kneaded has been studied. However, there is a limit to the amount of wax that can be blended, and as the amount added increases, the fluidity of the toner decreases, the void in the transfer increases, the fuser fuses to the photoreceptor, and the toner component spent on conventional carriers increases. Such evils will occur.

  Therefore, a toner production method using various polymerization methods different from the kneading and pulverization method has been studied. For example, toner preparation methods by suspension polymerization are described in (Patent Document 5), (Patent Document 6), and the like. However, when toners are prepared using these methods, even if it is attempted to control the particle size distribution of the toner, it is not possible to leave the area of the kneading and pulverization method, and in many cases, further classification operation is required. In addition, since the toner obtained by these methods has a substantially spherical shape, there is a problem in that the toner remaining on the photosensitive member or the like is poorly cleaned and the image quality reliability is impaired.

  In addition, a toner preparation method using an emulsion aggregation method is a method in which an aqueous medium is prepared by mixing a dispersion obtained by dispersing resin particles obtained by emulsion polymerization and a colorant particle dispersion in which colorant particles are dispersed. Is heated to form aggregated particles, which are then washed and dried to produce toner.

  In (Patent Document 7), a required amount of a colorant powder, a fixability improver, and a charge control agent are added to and mixed uniformly with an emulsion of a polymer having an acidic polar group or basic group obtained by emulsion polymerization. As a result, the primary particles of the polymer, the colorant particles, and the fixing agent particles aggregate to grow into secondary particles. It is disclosed that when this dispersion is further stirred, the secondary particles aggregate and grow to associated particles having an average particle diameter of 5 to 25 μm.

  Further, in (Patent Document 8), a particle structure composed of an inner layer, which is an associated particle formed by associating secondary particles containing polymer fine particles and a colorant, and an outer layer mainly composed of a polymer, has a low temperature. It has been disclosed that it has excellent fixing properties and blocking properties, has a narrow particle size distribution, can cope with charging characteristics and high image quality, and has excellent cleaning properties.

  Further, in (Patent Document 9), a second step of forming an adhering particle by adding and mixing a fine particle dispersion in which fine particles are dispersed in an agglomerated particle dispersion to adhere the fine particles to the agglomerated particles, and A toner manufacturing method including a third step of heating and fusing the attached particles is disclosed.

    Further, in (Patent Document 10), a resin particle dispersion in which resin particles are dispersed in a polar dispersant, and a colorant particle dispersion in which colorant particles are dispersed in a polar dispersant. A mixed liquid preparation step for preparing a liquid mixture by mixing at least, and by making the polarity of the dispersant contained in the liquid mixture the same polarity, the electrostatic image development with high chargeability and color developability and high reliability It is disclosed that the toner can be easily and simply produced.

  In (Patent Document 11), 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. However, 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.

  In (Patent Document 12), a toner for developing an electrostatic charge image in which a release agent is disposed in a toner as a release agent layer along the toner surface, a resin fine particle dispersion, and a colorant dispersion are mixed. Then, agglomerated particles are formed, and then a dispersion of release agent fine particles is added and mixed to attach the release agent fine particles to the surface of the agglomerated particles, and further a dispersion of resin fine particles is added and mixed. Then, after the resin fine particles are attached to the surface of the release agent layer of the aggregated particles, the release particles are removed from the toner by heating to a temperature equal to or higher than the glass transition point of the resin fine particles to fuse and coalesce to form toner particles. Is excellent in fixability, chargeability, and powder characteristics, and has various characteristics such as chargeability, developability, transferability, fixability, and cleanability, especially in image smoothness and transparency. It is disclosed that it has excellent properties, color mixing and color development .

  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, when the dispersibility is deteriorated by adding wax, color turbidity tends to occur easily 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. Further, when the resin fine particles are further adhered and fused on the surface of the aggregate in the next step, the decrease in the dispersibility of the wax makes the adhesion of the resin fine particles unstable. Also, the wax once aggregated with the resin is separated and released into the aqueous system. The dispersion of the wax has a great influence on the agglomeration at the time of mixing and agglomeration by the heat characteristics such as the polarity and melting point of the wax used.

  Further, in order to realize oilless fixing without using oil at the time of fixing, a specific wax is added in a large amount. And when it mixes with resin from which melting | fusing point, a softening point, and viscoelasticity differ and it aggregates by heating, it will become difficult to aggregate while maintaining a uniform state.

  In particular, by using a release agent having a certain acid value and functional group, it is possible to achieve both oilless fixing, fog reduction during development, and transfer efficiency. By having an acid value and a functional group, uniform mixing and aggregation with resin fine particles and pigment fine particles in water are affected, and they exist in the water regardless of agglomeration or conversely. May progress too much and the particles themselves become coarse, and it may be difficult to control particle formation.

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

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

  An object of the present invention is to achieve both low temperature fixing, high temperature offset property and storage stability by using a release agent such as wax in the toner in oilless fixing without using oil in the fixing roller.

  An object of the present invention 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.

  It is an object of the present invention to provide an image forming apparatus that can prevent high-efficiency by preventing omission and scattering during transfer.

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

In view of the above problems, the configuration of the present invention comprises mixing , in an aqueous medium, at least a first resin particle dispersion in which a first resin is dispersed and a colorant particle dispersion in which colorant particles are dispersed . Adjusting the pH of the mixed liquid in which the first resin particle dispersion in which one resin particle is dispersed and the colorant particle dispersion in which the colorant particles are dispersed to 9.5 to 12.2 and heating A step of generating aggregated particles in which at least the first resin particles and the colorant particles are aggregated, and a second resin in which a second resin is dispersed in an aggregated particle dispersion in which the aggregated particles are dispersed A step of adding a particle dispersion and a wax particle dispersion in which wax is dispersed, adjusting the pH to a range of 5.2 to 8.8, and heating at a temperature equal to or higher than the glass transition temperature of the second resin particles Adjusting the pH to the range of 3.2 to 6.8. Extent and, furthermore, it is a method for producing a toner and a step of fusing the wax and the second resin is heated at the second glass transition temperature or higher of the resin particles to the aggregated particles.

  In addition, in the configuration of the present invention, in the aqueous medium, at least the first resin particle dispersion in which the first resin particles are dispersed and the colorant particle dispersion in which the colorant particles are dispersed are mixed, and heat treatment is performed. A step of generating aggregated particles in which at least the first resin particles and the colorant particles are aggregated; and a second resin particle in which a second resin is dispersed in an aggregated particle dispersion in which the aggregated particles are dispersed. A method of producing a toner, comprising: adding a dispersion and a wax particle dispersion in which wax is dispersed, mixing, heating, and fusing the second resin particles and the wax particles to the aggregated particles. When the pH of the aggregated particle dispersion in which the aggregated particles are dispersed is HS, the second resin particle dispersion in which the second resin particles are dispersed and / or the wax particle dispersion in which the wax is dispersed The pH of the liquid A method for producing a toner to be added is adjusted to a range of S + 2~HS-5.

  In addition, according to the present invention, in the toner production method according to claim 17, the second resin particle dispersion in which the second resin particles are dispersed and / or the wax particle dispersion in which the wax is dispersed. This is a method for producing a toner having a pH in the range of 3.5 to 10.5.

Further, the configuration of the present invention includes a first resin particle dispersion in which at least a first resin is dispersed in an aqueous medium, a colorant particle dispersion in which colorant particles are dispersed, and an endothermic peak temperature by DSC method. The step of mixing the first wax particle dispersion in which the first wax having a melting point (referred to as the melting point) of 50 to 95 ° C. is mixed, and the pH is adjusted to 9.5 before addition of the water-soluble inorganic salt and before heating. A step of adjusting to the range of 12.2 and then adding a water-soluble inorganic salt and heat-treating to form aggregated particles in which at least the first resin particles, the colorant particles and the first wax particles are aggregated. A process,
When the aggregated particles are formed, the pH is in the range of 7.0 to 9.5, and the aggregated particle dispersion in which the aggregated particles are dispersed has a melting point higher than the melting point of the first wax. And a second wax particle dispersion in which a second wax having a melting point of 80 to 120 ° C. is dispersed and a second resin particle dispersion in which a second resin is dispersed are added to adjust the pH to 5. A step of adjusting to a range of 2 to 8.8, a step of heat treatment at a temperature equal to or higher than the glass transition temperature of the second resin particles, a step of adjusting pH to a range of 3.2 to 6.8, and And a step of fusing the second wax and the second resin particles to the aggregated particles by heat treatment at a temperature equal to or higher than the glass transition temperature of the second resin particles.

  Moreover, the structure of this invention is a two-component developer which consists of the carrier containing the magnetic particle by which the surface of the core material was coat | covered with the fluorine-modified silicone resin containing an aminosilane coupling agent.

  A toner produced by mixing and aggregating 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 in an aqueous system. Small particle size with a small particle size, uniform and sharp particle size distribution, with the presence of floating wax particles that are not involved in agglomeration in water and the presence of suspended pigments in the pigment. This toner can be prepared without a classification step.

  Even without applying oil, oil-free fixing can be realized by preventing low offset and fixing at low temperature.

  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 oil-less fixing, has high glossiness and high translucency, has excellent charging characteristics, environmental dependency, cleaning properties, transferability, and a small particle size static having a sharp particle size distribution. The present inventors have earnestly studied to provide a toner for developing a charge image and a two-component developer, and to provide an image formation capable of forming a high-quality and reliable color image free from toner scattering and fogging.
(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, azobisisobutyronitrile and other azo or diazo polymerization initiators, persulfates (potassium persulfate, ammonium persulfate, etc.), azo compounds (4,4′-azobis-4-cyanovaleric acid and its salt, 2,2′-azobis (2-amidinopropane) salt, etc.), peroxide compounds and the like.

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

  As a preferred first configuration of the present invention, a first resin particle dispersion in which first resin particles are dispersed in an aqueous medium, and a colorant particle dispersion in which colorant particles are dispersed in an aqueous system. Aggregate and heat to form aggregated particles. The second resin particle dispersion in which the second resin particles are dispersed and the wax particle dispersion in which the wax is dispersed are added to and mixed with the aggregated particle dispersion in which the generated aggregated particles are dispersed, and the second resin is mixed. In this configuration, the toner base material is formed by forming a second resin and wax layer on the surface of the aggregated particles by heat-sealing to a Tg or higher.

Compared to a configuration in which wax is included in aggregated particles (sometimes expressed as core particles or core particles), this configuration can be easily melted using a resin composition having a low softening point to fix the toner at a low temperature. The offset resistance, the peelability between the paper and the fixing roller, and the separation can be improved .
In a preferred first configuration of the present invention, the second resin particle dispersion in which the second resin particles are dispersed and the wax particle dispersion in which the wax is dispersed are added to the aggregated particle dispersion in which the aggregated particles are dispersed. PH is adjusted to the range of 5.2 to 8.8, and then heat treatment is performed at a temperature equal to or higher than the glass transition temperature of the second resin particles for 0.5 to 2 hours, and then the pH is set to 3.2. After adjusting to the range of ˜6.8, the second resin particles are further heat-treated at a temperature equal to or higher than the glass transition temperature of the second resin particles for 0.5 to 5 hours to fuse the second resin particles and wax to the aggregated particles. It is preferable to produce by a method of wearing .
The aim of the method of this, when the wax has a polar, by adjusting the pH of the aqueous, starts preferentially deposited wax on the surface of the aggregated particles, begin melting of the wax having a sharp melting property, the surface of the aggregated particles Wax melts and adheres. 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. . And it becomes easy to become the laminated structure to which resin adheres and fuse | melts in the form which covers the surface of the wax previously melt | fused to the aggregated particle surface. It is possible to save the trouble of performing the two-stage process of separately laminating and mixing the wax dispersion and the resin dispersion.

  The purpose of the heat treatment for 0.5 to 2 hours at a temperature equal to or higher than the glass transition temperature of the second resin particles after adjusting the pH to the range of 5.2 to 8.8 is preferential to the surface of the aggregated particles. Then, the second resin particles are uniformly adhered to the surface of the melted wax, and then the pH is adjusted to the range of 3.2 to 6.8, and then the glass of the second resin particles is further added. By heat treatment at a temperature higher than the transition temperature, particles with a narrow particle size distribution are produced by suppressing the release of wax particles without causing secondary aggregation, and fusing the wax and second resin particles to the aggregated particles. Can be obtained.

  When the pH when the second resin particle dispersion and the wax particle dispersion are added is smaller than 5.2, adhesion of the wax particles and the second resin particles to the aggregated particles hardly occurs, and the free resin particles To increase. When it is larger than 8.8, secondary aggregation of the aggregated particles tends to occur. In addition, separate aggregation of the second resin particles and the wax alone is likely to occur.

  If the pH after the heat treatment for 0.5 to 2 hours is less than 3.2, the resin particles once adhered may be released. When it is larger than 6.8, secondary aggregation of the aggregated particles tends to occur.

  The difference in volume average particle diameter between the aggregated particles and the particles in which the second resin particles and wax particles are adhered and fused to the aggregated particles is preferably 0.5 to 2 μm. If it is smaller than 0.5 μm, the adhesion state of the second resin particles and the wax particles 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.

  A preferred second configuration of the present invention includes a first resin particle dispersion in which first resin particles are dispersed in an aqueous medium, a colorant particle dispersion in which colorant particles are dispersed, and a first The first wax particle dispersion in which the wax is dispersed is mixed and agglomerated and heated to form agglomerated particles. Then, the second resin particle dispersion in which the second resin particles are dispersed and the second wax particle dispersion in which the second wax is dispersed are added and mixed in the aggregated particle dispersion in which the generated aggregated particles are dispersed. In this configuration, the toner base is formed by forming a layer of the second resin and the second wax on the surface of the aggregated particles by heat-sealing to Tg or more of the second resin.

  With this configuration, the wax is included in the agglomerated particles, so that both low-temperature fixing property, offset resistance, releasability between the paper and the fixing roller, and separation property can be improved.

In a preferred second configuration of the present invention, the second wax preferably has a melting point higher than that of the first wax, and the melting point is preferably 80 to 120 ° C. At this time, the melting point of the first wax is preferably 50 to 95 ° C. As a result, the second high-melting wax retains the functions of offset resistance, peelability between the paper and the fixing roller, and separability, while the low-melting first wax has a low-temperature fixing function. Coexistence of fixing property and offset resistance can be enhanced .
When the melting point of the second wax is lower than 80 ° C., the storage stability is weakened. When the melting point of the second wax exceeds 120 ° C., the cohesiveness of the second resin particles and the second wax decreases, and free particles that do not aggregate in the aqueous system increase. When the melting point of the first wax is lower than 50 ° C., the storage stability is deteriorated. When the melting point of the first wax is higher than 95 ° C., the low-temperature fixability deteriorates.

  The aggregated particles preferably have a configuration in which the first wax has a mean particle size of 1 μm or less and is dispersed and formed in a mixed state with the first resin.

  By making the agglomerated particles co-dispersed with resin and wax, the softening point is lowered, and even if the amount of wax is reduced, cold offset is prevented at low temperatures, and fixing properties such as fixing strength are improved. In particular, there is an effect. In addition, the storage stability may be improved.

  By making the capsule structure with an average particle size larger than 1 μm and wax gathering, it is possible to bring out the effect of preventing offset, but a large amount of wax is required. Even if melting occurs and a hard resin layer is provided on the outer shell, it tends to harden due to thermal aggregation. Also, unless the pressing force of the fixing machine is increased, the internal wax tends to be difficult to ooze out.

In a preferred second configuration of the present invention, the aggregated particles include particles having a capsule structure in which a wax in which the first wax is aggregated larger than an average particle diameter of 1 μm is encapsulated in the resin; A configuration including one resin and particles in which the first wax is mixed and dispersed is also preferable. Of these, the number of particles in a state where wax is mixed and dispersed may be 50% by number or more .
Figure 7,8,9,10,11 shows a cross-sectional image by TEM (transmission electron microscope) of the toner particles. TEM was Hitachi, H-800, acceleration voltage 100 kv, and the sample was stained with ruthenic acid (0.2% aqueous solution) for the purpose of clarifying the phase separation structure inside the sample (5 minutes), then room temperature The sample was embedded in a curable epoxy resin, and the sample cross section was observed with a TEM by an ultra-thin cutting method.

  7 and 8 are enlarged views of the toner particles. The black thin film 301 that appears in the outermost shell is a dyeing process for making the interface easy to see during TEM observation, and is not related to the toner. A state 302 in which a hazy resin, wax, and colorant are mixed and dispersed can be seen in the central portion (hereinafter also referred to as a mixed dispersion state). In addition, a state in which the shell resin 303 is fused is observed.

  In FIG. 9, particles 304 encapsulated are seen in the lower right, but most other particles are in a mixed and dispersed state. In FIG. 10, the encapsulated particles 305 are seen around the middle left, but about 60% of the particles are in a mixed dispersion state. FIG. 9 is an enlarged view of a part of FIG.

  As a comparative example, FIG. 11 shows a capsule structure in which wax 401 is gathered in white at the center, a resin / pigment layer 402 on the outside, and a shell resin 403 on the outside. Observed. The configuration in which the wax 401 gathers in the center in FIG. 11 is clearly agglomerated from the mixed dispersion state 302 in which the resin, the wax, and the colorant are mixed and dispersed as seen in the center in FIG. It can be seen that the state of particle dispersion is different.

  The existence ratio was specified by selecting 100 particles having a size of ± 1 μm of the volume average particle diameter of the toner in the TEM observation image.

  If it is less than 50% by number, it becomes difficult to obtain the effect of improving the low-temperature fixability and the effect of improving the storage stability.

  When the size of the encapsulated wax is aggregated to 1 μm or more, the storage stability tends to deteriorate. An effect of improving low-temperature fixability and an effect of improving storage stability can be obtained by being in a mixed dispersion state with a size of 1 μm or less, preferably 0.5 μm or less.

  It is preferable that the outer shell of the aggregated particles is covered with a second resin particle having a thickness of 0.1 μm or more. This improves the durability of the toner. The effect of improving the high temperature offset property is obtained.

As a preferred third configuration of the present invention, the second resin particle dispersion and the wax (or second wax) particle dispersion in which the second resin particles are dispersed in the aggregated particle dispersion in which the aggregated particles are dispersed. The wax (or second wax) particle dispersion in which is dispersed is added and mixed, and heat-treated at a temperature equal to or higher than the glass transition temperature of the second resin particles to give the second resin particles and wax ( Or a second wax) is formed on the aggregated particles to form toner base particles, and the generated aggregated particle dispersion includes the second resin particle dispersion and When adding the wax (or second wax) particle dispersion in which the wax (or the second wax) is dispersed, when the pH of the aggregated particle dispersion in which the aggregated particles are dispersed is HS, the second resin particles Second resin particles with dispersed In this configuration, the pH of the wax (or second wax) particle dispersion in which the child dispersion and / or the wax (or the second wax) is dispersed is adjusted within the range of HS + 2 to HS-5. (Corresponding to claims 3 and 18)
When the strongly acidic second resin particle dispersion or the like is added to the aggregated particle dispersion, the effect of the water-soluble inorganic salt as an aggregating agent is weakened, and adhesion between the aggregated particles and the resin particles is hindered. In addition, adding a resin particle dispersion having a pH value apart from the aggregated particle dispersion suddenly disturbs the pH balance of the liquid, so that the resin particles do not adhere to the aggregated 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 or wax particle dispersion.

  With this configuration, the generation of floating particles of the wax (or second wax) particles and the second resin particles is reduced, and the wax (or second wax) particles and the second resin particles are uniformly distributed on the surface of the aggregated particles. Can be attached. Further, the adhesion to the aggregated particles is promoted, the treatment time for adhesion melting is shortened, and the productivity can be improved. In addition, when the wax (or second wax) particles and the second resin particles are adhered and melted to the aggregated particles, rapid coarsening of the particles can be prevented, and a sharp particle size distribution is formed with a small particle size. be able to. 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 wax (or the second wax) particles or the second resin particles do not adhere to the aggregated particles, and not only the processing takes a long time but also the wax (or the second wax). ) The particles or the second resin particles remain floating in the water system and tend not to proceed while becoming cloudy.

In a preferred third configuration of the present invention, the second resin particle dispersion and / or the wax (or second wax) in which the second resin particles to be added to the produced aggregated particle dispersion are dispersed are dispersed. Regardless of the pH value of the aggregated particle dispersion in which the aggregated particles are dispersed, the pH value of the wax (or second wax) particle dispersion is adjusted to the range of 3.5 to 10.5 and added. Is preferred .
When pH is smaller than 3.5, the adhesion of the wax particles, the second wax particles, or the second resin particles to the surface of the aggregated particles does not proceed, and the wax particles, the second wax particles, or the second resin particles. Remains floating in the water system and the liquid remains cloudy. When the pH is higher than 10.5, the generated particles tend to coarsen rapidly.

  In a preferred first, second or third configuration of the present invention, the aggregated particles are prepared by dispersing the first resin particle dispersion in which the first resin particles are dispersed and the colorant particles in an aqueous medium. The first resin particle dispersion in which the first resin particles are dispersed and the colorant particle dispersion in which the colorant particles are dispersed and the first wax are dispersed. After mixing with the first wax dispersion, the pH of the aqueous medium is adjusted to a certain condition, and heated to the glass transition temperature (Tg) or higher of the first resin of the aqueous medium in the presence of an inorganic salt. Aggregated particles can be produced by agglomeration.

  Specifically, in an aqueous medium, at least the first resin particle dispersion in which the first resin particles are dispersed and the colorant particle dispersion in which the colorant particles are dispersed are mixed, or the first The first resin particle dispersion in which the resin particles are dispersed, the colorant particle dispersion in which the colorant particles are dispersed, and the first wax dispersion in which the first wax is dispersed are mixed, and the pH is adjusted to 6. It is preferable to prepare a mixed dispersion liquid having 0 or less. For example, when potassium persulfate is used when polymerizing an emulsion polymerization resin, the residue may be decomposed by the heat at the time of heat aggregation to lower the pH. The pH can be lowered by applying an acid or by shifting to acidity with hydrochloric acid or the like.

  Thereafter, a water-soluble inorganic salt is added and heated to a temperature not lower than the glass transition temperature (Tg) of the first resin, and the mixed dispersion pH is adjusted to 9. before the addition and heating of the water-soluble inorganic salt. It is preferable to adjust to the range of 5 to 12.2. The pH can be adjusted by adding 1N NaOH.

  Thereafter, a predetermined volume average particle in which water-soluble inorganic salt is added and heat-treated to aggregate at least the first resin particles and the colorant particles, or the first resin particles, the colorant particles, and the first wax particles are aggregated. Aggregated particles having a diameter (3 to 6 μm) are formed. By setting the pH of the liquid when the agglomerated particles having a predetermined volume average particle size to be in the range of 7.0 to 9.5, the release of the wax is small, and the resin and wax are mixed with a narrow particle size distribution. Aggregated particles in a dispersed state can be easily 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 can be adjusted.

  When the pH at the time of preparing the mixed dispersion becomes higher than 6.0, when heated to form aggregated particles, the pH fluctuation (decrease phenomenon) in the liquid becomes large, and the particles become coarse.

  When adjusting the pH of the mixed dispersion before addition of the water-soluble inorganic salt and before heating, if it is smaller than 9.5, the formed aggregated particles are coarsened, and the resin and wax tend not to be mixed and dispersed. . If it is greater than 12.2, the amount of free wax will increase, making it difficult to encapsulate the wax uniformly.

  If the pH of the liquid when the aggregated particles are formed is less than 7.0, the aggregated particles are coarsened. When it is larger than 9.5, the free wax increases due to poor aggregation.

  In the preferred first, second or third configuration of the present invention, toner base particles can be obtained through an optional 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 laurylamine hydrochloride or stearic acid amine hydrochloride, 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 preferred first or third configuration of the present invention is that a second resin particle dispersion in which a second resin is dispersed in a dispersion in which aggregated particles are dispersed, and wax particles in which wax is dispersed. The dispersion is mixed, heat-treated, and the wax and the second resin are fused to the aggregated particles to form a toner base. As a preferred wax to be used, an iodine value of 25 or less, saponification A wax having a constitution of 30 to 300 is preferable.

  The repulsion due to the charge effect of the toner during the multi-layer transfer of toner can be alleviated, so that the transfer efficiency can be reduced, the character dropout during transfer and reverse transfer can be suppressed. 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. It becomes difficult to uniformly encapsulate the wax in the resin.

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

  Furthermore, the material whose volume increase rate at the time of 10 degreeC change at the temperature more than melting | fusing point is 2 to 30% is preferable. When it changes from solid to liquid when it melts with heat during fixing, the adhesion between the toners is further strengthened, the fixing property is further improved, and the releasability from the fixing roller is also improved. Offset property is also improved.

  The addition amount is preferably 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 a meadow foam oil derivative, carnauba wax derivative, jojoba oil derivative, wood wax, beeswax, ozokerite, carnauba wax, canderia wax, ceresin wax and rice wax are preferable, and these derivatives are also suitable. Used for. One type or a combination of two or more types can be used. In particular, carnauba wax having a melting point of 76-90 ° C., candelilla wax having 66-80 ° C., hydrogenated jojoba oil having 64-78 ° C., hydrogenated meadowfoam oil having 74-78 ° C. or 74 At least one or two or more kinds of waxes selected from the group consisting of rice waxes having a temperature of ˜90 ° C. are more preferable.

  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. 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.

  Meadowfoam oil fatty acids obtained by saponification and decomposition of meadowfoam oil are preferably composed 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.

  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, esterification reaction products of jojoba oil fatty acid and polyhydric alcohols 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 chloride glacial acetic acid solution to chloroform or carbon tetrachloride solution of sample and titrate the remaining iodine without reaction with sodium thiosulfate standard solution to absorb iodine Calculate the amount.

  For the measurement of weight loss by 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 weighed precisely to 0.1 mg (W2 mg). The sample cell is set on a differential thermobalance, 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 Co., Ltd., 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, as the wax used in the preferred first or third constitution of the present invention, a wax having an acid value of 10 to 80 mg KOH / g having at least a long-chain alkyl group having 4 to 30 carbon atoms, an ester group and a vinyl group is preferably used. it can.

  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) is 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, 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 ratio of the number average molecular weight (Z average molecular weight / number average molecular weight) is at least one molecular weight maximum peak in the region of 1.7 to 2.5, 1 × 10 ^{3 to} 3 × 10 ³ , and the acid value is 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.

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

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

  Here, if the carbon number of the long-chain alkyl of the wax is smaller than 4, the releasing action is weakened, and the separation property and the high temperature non-offset property are 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. It becomes difficult to uniformly encapsulate the wax in the resin.

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

  When the penetration at 25 ° C. is larger than 4, the toughness is lowered and the photoreceptor filming occurs during long-term use.

Weight average molecular weight smaller than 1000, Z average molecular weight smaller than 1500, Weight average molecular weight / number average molecular weight smaller than 1.1, Z average molecular weight / number average molecular weight smaller than 1.5, molecular weight maximum peak Is located in a range smaller than 1 × 10 ³ , the storage stability of the toner is lowered, and filming occurs on the photosensitive member and the intermediate transfer member. Further, the handling property in the developing device is lowered, and the uniformity of the toner density is lowered. Also, development memory is likely to occur. The particle size distribution of the produced particles at the time of producing the emulsified dispersed particles at the time of the action of a high shearing force by high-speed rotation becomes a load.

The weight average molecular weight is greater than 6000, the Z average molecular weight is greater than 9000, the weight average molecular weight / number average molecular weight is greater than 3.8, the Z average molecular weight / number average molecular weight is greater than 6.5, and the molecular weight maximum If the peak is located in a range larger than the region of 3 × 10 ⁴ , the releasing action is weakened and the fixing offset property is lowered. It becomes difficult to reduce the particle size of the generated particles when the emulsified dispersed particles are generated. It becomes difficult to uniformly encapsulate the wax in the resin.

  As the alcohol, those having a long alkyl chain such as octanol, dodecanol, stearyl alcohol, nonacosanol, pentadecanol and the like can be used. Moreover, N-methylhexylamine, nonylamine, stearylamine, nonadecylamine, etc. can be used conveniently as amines. As the fluoroalkyl alcohol, 1-methoxy- (perfluoro-2-methyl-1-propene), hexafluoroacetone, 3-perfluorooctyl-1,2-epoxypropane and the like can be preferably used. As the unsaturated polyvalent carboxylic acid or anhydride thereof, one or more of maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and the like can be used. Of these, maleic acid and maleic anhydride are more preferable. As the unsaturated hydrocarbon wax, ethylene, propylene, α-olefin and the like can be suitably used.

  Unsaturated polyhydric carboxylic acid or its anhydride is polymerized with alcohol or amine, and this is then added to synthetic hydrocarbon wax in the presence of dicrummi peroxide or tertiary butyl peroxyisopropyl monocarbonate. Can be obtained.

  In addition, as the wax used in the preferred first or third constitution of the present invention, a material such as a hydroxy stearic acid derivative, a glycerin fatty acid ester, a glycol fatty acid ester, a sorbitan fatty acid ester or the like is also preferable, and one kind or two or more kinds are combined The use of is also effective. Uniform emulsification-dispersed small particle size particles can be produced, and mixed aggregation allows uniform aggregation with the resin pigment, eliminating the presence of suspended solids and suppressing color turbidity. Further, uniform adhesion to the surface of the aggregated particles can be obtained.

  With 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 the wax used in the preferred first or third constitution of the present invention, it is also preferred to use an aliphatic amide wax. Uniform emulsification-dispersed small particle size particles can be produced, and mixed aggregation allows uniform aggregation with the resin pigment, eliminating the presence of suspended solids and suppressing color turbidity. Further, uniform adhesion to the surface of the aggregated particles can be obtained.

  With 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-based wax include carbonic acid amides 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. It becomes difficult to uniformly encapsulate the wax in the resin. 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 of saturated or divalent unsaturated fatty acid such as butylene bisbehenic acid amide, methylene biserucic acid amide, ethylene biserucic acid amide, propylene biserucic acid amide, butylene biserucic acid amide Scan fatty acid amide wax are 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 aggregated particles are generated. The uniform adhesion of the wax or second resin particles to the surface of the aggregated particles is reduced. It becomes difficult to uniformly encapsulate the wax in the resin. 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.

  Moreover, in the preferable 2nd or 3rd structure of this invention, it is preferable that the 2nd wax has melting | fusing point higher than melting | fusing point of 1st wax, and its melting | fusing point is 80-120 degreeC. When the melting point is lower than 80 ° C., high temperature offset resistance and storage stability are deteriorated. When the temperature is higher than 120 ° C., the adhesion to the surface of the aggregated particles is lowered, and unevenness remains in the surface state after adhesion and melting, and the charge amount of the toner tends to be easily changed.

  At this time, the melting point of the first wax is preferably 50 to 95 ° C. When the melting point is lower than 50 ° C., the storage stability of the toner is deteriorated. When it is higher than 95 ° C., it is difficult to reduce the particle size of the generated particles when the aggregated particles are generated. The smoothness of the surface of the agglomerated particles tends to be lowered and unevenness tends to remain, and the uniform adhesion of the wax or the second resin particles is lowered.

  With this configuration, the high melting point second wax retains the functions of offset resistance, peelability between the paper and the fixing roller, and separation property, and the low melting point first wax has the function of low temperature fixability. Thus, it is possible to reinforce both low-temperature fixability and offset resistance.

  As the first wax, a wax having an iodine value of 25 or less and a saponification value of 30 to 300, a derivative of hydroxystearic acid, a glycerin fatty acid ester, a glycol fatty acid ester or a sorbitan fatty acid ester is preferable. It is highly compatible with the binder resin and has the effect of facilitating the formation of aggregated particles having the above-described configuration. In addition, the smoothness of the surface of the generated aggregated particles is increased, and unevenness does not remain on the surface, and uniform adhesion and meltability of the second wax or the second resin particles can be obtained.

  As the second wax, the wax having an acid value of 10 to 80 mg KOH / g having a long-chain alkyl group having at least 4 to 30 carbon atoms, an ester group and a vinyl group as described above can be preferably used. In addition, Fischer Tropus wax can be preferably used as the aliphatic hydrocarbon wax.

  In order for the low melting point wax 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 copolymer for resin particles, ester wax is used rather than vinyl wax such as polypropylene and polyethylene, so that the resin particles are not loosely separated and suspended during mixing and agglomeration. Can be encapsulated in a single location. 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.

  The wax particle dispersion is prepared by heating, melting, and dispersing wax in ion-exchanged water in an aqueous medium to which a polar 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 and PR84 / PR16 is emulsified and dispersed to a size of 1.2 to 2.0. It is preferable that particles of 200 nm or less are 65 volume% or more and particles exceeding 500 nm are 10 volume% or less.

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

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

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

  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 agglomeration occurs only between the waxes. There is a tendency that particles that are not taken into the resin particles and float in water increase. 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. The standing stability of is not good. In addition, the load increases during dispersion, heat generation increases, and productivity decreases.

  Further, 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 50% of the resin particles when forming the melt aggregate particles. By making the diameter smaller than the diameter (PR50), the wax is easily taken in 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 obtaining aggregated particles obtained by heating and melting aggregate particles in an aqueous system, it is easy to achieve a mixed dispersion state. 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 in the tank wall in the tank of a certain 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. You can also

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

  The content of the resin particles in the resin particle dispersion is usually 5 to 50% by weight, preferably 10 to 30% by weight. The molecular weights of the resin, wax, and toner are values measured by gel permeation chromatography (GPC) using several types of monodisperse polystyrene as standard samples.

  The apparatus is HPLC 8120 series manufactured by Tosoh Corporation, the column is TSKgel superHM-H H4000 / H3000 / H2000 (7.8 mm diameter, 150 mm × 3), eluent THF (tetrahydrofuran), flow rate 0.6 ml / min, sample concentration 0.1 %, Injection amount 20 μL, detector RI, measurement temperature 40 ° C., pretreatment for measurement is to measure a resin component obtained by dissolving a sample in THF and filtering through a 0.45 μm filter to remove additives such as silica. The measurement conditions are conditions in which the molecular weight distribution of the target sample is included in a range in which the logarithm of the molecular weight and the count number are linear in a calibration curve obtained with several types of monodisperse polystyrene standard samples.

  In addition, the measurement of the wax obtained by the reaction with a long chain alkyl alcohol having 4 to 30 carbon atoms, an unsaturated polyvalent carboxylic acid or its anhydride, and an unsaturated hydrocarbon wax was performed using a GPC-150C manufactured by WATERS. Shodex HT-806M (8.0 mm ID-30 cm × 2), eluent is o-dichlorobenzene, flow rate is 1.0 mL / min, sample concentration is 0.3%, injection volume is 200 μL, detector is RI The measurement temperature was 130 ° C., and the pre-measurement treatment was performed by filtering the sample with a 0.5 μm sintered metal filter after dissolving the sample in a solvent. The measurement conditions are conditions in which the molecular weight distribution of the target sample is included in a range in which the logarithm of the molecular weight and the count number are linear in a calibration curve obtained with several types of monodisperse polystyrene standard samples.

The softening point of the binder resin was about 9.8 with a plunger while heating a 1 cm ³ sample at a heating rate of 6 ° C./min with a constant-load extrusion capillary rheometer flow tester (CFT500) manufactured by Shimadzu Corporation. Applying a load of × 10 ⁵ N / m ² and extruding from a die with a diameter of 1 mm and a length of 1 mm, the piston stroke begins to rise from the relationship between the temperature rise characteristic of the plunger stroke and temperature. The temperature is the outflow start temperature (Tfb), 1/2 of the difference between the lowest value of the curve and the end point of the outflow, and the temperature at the point where the minimum value of the curve is added is the melting temperature (softening point) 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 of DSC by DSC was raised to 200 ° C. at 5 ° C./min using a differential scanning calorimeter (Shimadzu Corporation DSC-50), rapidly cooled to 10 ° C. for 5 minutes, and then left 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.
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 at the time of emulsion polymerization (for example, a styrene monomer is suitable), and the monomer is subjected to emulsion polymerization, whereby a resin fine particle dispersion to which CCA is added can be prepared.

The addition amount is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the resin. More preferably, it is 0.1-2 weight part, More preferably, it is 0.5-1.5 weight part. When the amount is less than 0.1 parts by weight, the charging effect is lost. If it exceeds 5 parts, the dispersion will not be uniform. Color turbidity in color images is noticeable.
Pigment The colorant used in this embodiment includes carbon black, iron black, graphite, nigrosine, metal complexes of azo dyes, C.I. I. Acetoacetic acid arylamide monoazo yellow pigments such as CI Pigment Yellow 1,3,74,97,98; I. Acetoacetic acid arylamide disazo yellow pigments such as C.I. Pigment Yellow 12, 13, 14, and 17; I. Solvent Yellow 19, 77, 79, C.I. I. Disperse Yellow 164 is blended, and C.I. I. Benzimidazolone pigments of CI Pigment Yellow 93, 180 and 185 are preferred.

  C. I. Red pigments such as CI Pigment Red 48, 49: 1, 53: 1, 57, 57: 1, 81, 122, 5; I. Red dyes such as Solvent Red 49, 52, 58, 8; I. One or two or more kinds of blue dyed pigments of phthalocyanine and derivatives thereof such as Pigment Blue 15: 3 are blended. The addition amount is preferably 3 to 8 parts by weight with respect to 100 parts by weight of the binder resin.

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

  As the silicone oil-based material treated with silica, those shown in (Chemical Formula 1) are preferable.

  For example, dimethyl silicone oil, methyl hydrogen silicone oil, methyl phenyl silicone oil, cyclic dimethyl silicone oil, epoxy modified silicone oil, carboxyl modified silicone oil, carbinol modified silicone oil, methacryl modified silicone oil, mercapto modified silicone oil, polyether modified Silica treated with at least one of silicone oil, methylstyryl-modified silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, amino-modified silicone oil, and chlorophenyl-modified silicone oil is preferably used. For example, SH200, SH510, SF230, SH203, BY16-823, BY16-855B, etc. manufactured by Toray Dow Corning Silicone may be mentioned. For the treatment, a method of mixing inorganic fine powder and a material such as silicone oil with a mixer such as a Henschel mixer, a method of spraying a silicone oil-based material onto silica, or a solution in which a silicone oil-based material is dissolved or dispersed in a solvent Then, after mixing with silica fine powder, there is a method of removing the solvent to prepare. It is preferable that 1 to 20 parts by weight of the silicone oil-based material is blended with respect to 100 parts by weight of the inorganic fine powder.

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

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

  The inorganic fine powder having positive electrode chargeability is treated with aminosilane, amino-modified silicone oil or epoxy-modified silicone oil shown in (Chemical Formula 2).

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

  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 such as aluminum distearate (Al (OH) (C ₁₇ H ₃₅ COO) ₂ ) or aluminum monostearate (Al (OH) ₂ (C ₁₇ H ₃₅ COO)), and mono fatty acid aluminum. Is preferred. Having an OH group can prevent overcharging and suppress poor transfer. Moreover, it is thought that the processability with inorganic fine powders, such as a silica, improves at the time of a process.

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

  A configuration in which 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 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 in a toner base prepared by a wet method, it is possible to obtain a margin for handling in development, reverse transfer during transfer, voids, 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 spent resistance of the wax to the carrier can be improved, the handling property in the developing device can be improved, and the uniformity of the toner density can be increased. 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. Preferably it is 0.5 wt% or less, More preferably, it is 0.1 wt% or less, More preferably, it is 0.05 wt% or less. When the content is more than 1 wt%, chargeability is deteriorated and filming on the photoconductor during durability is caused. The water adsorption amount was measured with a continuous vapor adsorption device (BELSORP18: Nippon Bell Co., Ltd.) for the water adsorption device.

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

Hydrophobic degree = (a / (50 + a)) × 100 (%)
Toner powder physical properties In this embodiment, the toner base particles containing at least a binder resin, a colorant and a wax containing a binder resin, a colorant and a wax have a volume average particle diameter of 3 to 7 μm, preferably 3 to 6.5 μm. More preferably, the content of toner base particles having a particle size of 2.52 to 4 μm in the number distribution is from 5 to 65% by number, and from 6.35 to 10.1 μm in the volume distribution. The toner base particle having a particle size of 5 to 35% by volume contains a particle size distribution. The coefficient of variation in the volume average particle size is 25 or less.

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

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

  It is possible to prevent high-resolution image quality, and also prevent reverse transfer and dropout in tandem transfer, and achieve both oil-less fixing.

  If the volume average particle size is larger than 7 μm, it is impossible to achieve both image quality and transfer. When the volume average particle size is smaller than 3 μm, it becomes difficult to handle the toner particles during development. If the content of toner base particles having a particle size of 2.52 to 4 μm in the number distribution is less than 5% by number, it is impossible to achieve both image quality and transfer. When the content is more than 65% by number, it becomes difficult to handle the toner base particles during development. When toner mother particles having a particle size of 6.35 to 10.1 μm are contained in an amount of more than 35% by volume, it is impossible to achieve both image quality and transfer. If it is less than 5% by volume, the toner productivity is lowered and the cost is increased.

  It is preferable that the variation coefficient of the volume particle size distribution of the toner base particles is 10 to 25% and the variation coefficient of the number particle size distribution is 10 to 28%. More preferably, the variation coefficient of the volume particle size distribution is 10 to 20%, the variation coefficient of the number particle size distribution is 10 to 23%, and more preferably, the variation coefficient of the volume particle size distribution is 10 to 15%, The coefficient of variation of the distribution is 10 to 18%.

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

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

  The fine powder in the toner affects toner fluidity, image quality, storage stability, filming on the photosensitive member, developing roller, and transfer member, aging characteristics, transferability, particularly multi-layer transfer in the tandem system. Furthermore, it affects the non-offset property, glossiness and translucency in oilless fixing. In a toner containing a wax for realizing oil-less fixing, the amount of fine powder affects the compatibility with tandem transferability.

  When the amount of fine powder is excessive, that is, when the content of toner base particles having a particle diameter of 2.52 to 4 μm is more than 65% by number, filming on the photosensitive member, the developing roller, and the transfer member occurs. Furthermore, fine powder tends to be offset because of its high adhesion to the heat roller. Further, in the tandem system, toner aggregation tends to be strong, and transfer failure of the second color is likely to occur during multilayer transfer. On the other hand, if the amount of fine powder decreases, the image quality deteriorates and an appropriate range is required.

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

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

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

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

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

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

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

  As the resin used for the resin coating layer of the present 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.

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

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

  In this embodiment, an aminosilane coupling agent is contained in the coating resin layer. As this aminosilane coupling agent, known ones may be used. For example, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, octadecylmethyl [3- (trimethoxy Cyril) propyl] ammonium chloride (SH6020, SZ6023, AY43-021: from Toray Dow Corning Silicone Co., Ltd.), KBM602, KBM603, KBE903, KBM573 (Shin-Etsu Silicone Co., Ltd.), etc. Amines are preferred. A secondary or tertiary amine substituted with a methyl group, ethyl group, phenyl group or the like is weak in polarity and has little effect on the charge rising characteristics with the toner. When the amino group is an aminomethyl group, aminoethyl group, or aminophenyl group, the most advanced silane coupling agent is a primary amine, but the amino group in a linear organic group extending from the silane. Does not contribute to the charge start-up characteristics with the toner and, conversely, is affected by moisture 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 uniformity of density on the back side and the near side of the development on the image is improved. In addition, so-called development memory in which a history remains after collecting a solid image can be reduced.

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

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

  The average particle size of the carrier used in the present invention is preferably 20 to 70 μm. When the average particle diameter of the carrier is less than 20 μm, the abundance ratio of the fine particles is increased in the carrier particle distribution, and the carrier particles have a low magnetization per carrier particle, so that the carrier is easily developed on the photoreceptor. On the other hand, when the average particle of the carrier exceeds 70 μm, the specific surface area of the carrier particle becomes small and the toner holding force becomes weak, so that toner scattering occurs. In addition, a full color with many solid portions is not preferable because the reproduction of the solid portions is particularly poor.

  The method for forming the coating layer on the carrier core material is not particularly limited. For example, a known coating method, for example, a dipping method in which powder as a carrier core material is immersed in a solution for forming a coating layer, or for forming a coating layer. Spray method for spraying the solution onto the surface of the carrier core material, Fluidized bed method for spraying the solution for forming the coating layer in a state where the carrier core material is suspended by the fluidized air, Solution for forming the carrier core material and the coating layer in a kneader coater In addition to wet coating methods such as the kneader coater method that removes the solvent, the powdered resin and the carrier core material are mixed at high speed, and the frictional heat is used to melt the resin powder onto the surface of the carrier core material. 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 amount of the resin coating is preferably 0.2 to 6.0% by weight, more preferably 0.5 to 5.0% by weight, still more preferably 0.6 to 4.0% by weight, based on the carrier core material. 7 to 3% by weight. When the coating amount of the resin is less than 0.2% by weight, a uniform coating cannot be formed on the surface of the carrier, and it is greatly affected by the characteristics of the carrier core material, and the fluorine-modified silicone resin of the present invention The effect of the aminosilane coupling agent cannot be exhibited sufficiently. If it exceeds 6.0% by weight, the coating layer becomes too thick, and granulation of carrier particles occurs, and uniform carrier particles tend not to be obtained.

Thus, after coating the fluorine-modified silicone resin containing an aminosilane coupling agent on the surface of the carrier core material, 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.
Two-component development An AC bias is applied together with a DC bias between the photoconductor and the developing roller.
The frequency at that time is 1 to 10 kHz, the AC bias is 1.0 to 2.5 kV (pp), and the peripheral speed ratio between the photoconductor and the developing roller is 1: 1.2 to 1: 2. It is preferable.

  More preferably, the frequency is 3.5 to 8 kHz, the AC bias is 1.2 to 2.0 kV (pp), and the peripheral speed ratio between the photosensitive member and the developing roller is 1: 1.5 to 1: 1. .8.

  More preferably, the frequency is 5.5 to 7 kHz, the AC bias is 1.5 to 2.0 kV (pp), and the peripheral speed ratio between the photosensitive member and the developing roller is 1: 1.6 to 1: 1. .8.

  With this development process configuration and the use of the toner or the two-component developer of the present embodiment, dots can be faithfully reproduced and development γ characteristics can be obtained. Both high-quality images and oilless fixability can be achieved. Further, even a high-resistance carrier can prevent charge-up under low humidity, and a high image density can be obtained even in continuous use.

  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.
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 unit, and a toner carrier, and an electrostatic latent image formed on the image carrier. A primary transfer process in which an endless transfer member is brought into contact with the image bearing member and transferred to the transfer member is successively performed in succession, and a multi-layer transfer is performed on the transfer member. In a transfer process configured to execute a secondary transfer process in which a toner image is formed and then a multi-layer toner image formed on the transfer body is 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 configuration is d1 / v ≦ 0.65. Take a small machine It is intended to achieve both mold formation 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 this embodiment, the charge distribution is stabilized, the toner is prevented from being overcharged, and the fluidity fluctuation can be suppressed. For this reason, it is possible to prevent transfer efficiency from being lowered, character dropout during transfer, and reverse transfer without sacrificing fixing characteristics.
Cleaner-less process In addition, the basic configuration of this embodiment is a cleaner-less process that performs the following charging, exposure, and development processes without having a cleaning process that collects toner remaining on the photoconductor by cleaning after the transfer process. The electrophotographic apparatus is also preferably used.

By using the toner or the two-component developer of this embodiment, toner aggregation is suppressed, overcharging is prevented, charging property is stabilized, and high transfer efficiency can be obtained. Further, the improvement in uniform dispersibility in the resin, good chargeability, and the releasability of the material make it possible to recover the toner remaining in the non-image area during development. For this reason, there is no development memory in which the image pattern in front of the non-image portion remains.
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 means for fixing toner. As the heating means, electromagnetic induction heating is a preferable configuration from the viewpoint of shortening the warm-up time and saving energy. A heating and pressurizing unit having at least a magnetic field generating unit, a rotary heating member having at least a heat generation layer and a release layer generated by electromagnetic induction, and a rotary pressurizing member forming a fixed nip with the rotary heating member; In this configuration, a transfer medium such as copy paper on which toner is transferred is passed between the rotary heating member and the rotary pressure member, and is fixed.

  As a feature, the warm-up time of the rotary heating member is very fast compared to the case where a conventional halogen lamp is used. For this reason, since the copying operation is started in a state where the temperature of the rotary pressure member is not sufficiently raised, low temperature fixing and a wide range of offset resistance are required.

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

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

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

(Carrier production example 1)
39.7Mol% in terms of MnO, 9.9 mol% in terms of MgO, in 0.8 mol% wet ball mill 49.6Mol% and SrO terms in terms _{of Fe} 2 _{O 3,} and ground for 10 hours, mixed, dried , Kept at 950 ° C. for 4 hours, and pre-baked. This was pulverized with a wet ball mill for 24 hours, then granulated with a spray dryer, dried, and held in an electric furnace at 1270 ° C. for 6 hours in an atmosphere with an oxygen concentration of 2%, followed by firing. Then, it was crushed and further classified to obtain a ferrite particle core material having an average particle diameter of 50 μm and a saturation magnetization of 65 emu / g when the applied magnetic field was 3000 oersted.

Next, R ₁ and R ₂ represented by (Chemical Formula 5) are methyl groups, that is, (CH ₃ ) ₂ SiO _2/2 units are 15.4 mol%, and R ₃ represented by (Chemical Formula 6) is a methyl group, that is, 250 g of polyorganosiloxane having a CH ₃ SiO _3/2 unit of 84.6 mol% and CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ 21 g were reacted to obtain a fluorine-modified silicone resin. 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.

Coating was performed on 10 kg of the ferrite particles by stirring the coating resin solution for 20 minutes using an immersion drying type coating apparatus. Thereafter, baking was performed at 260 ° C. for 1 hour to obtain carrier A1.
(Carrier production example 2)
A core material is manufactured and coated in the same process as in Production Example 1 except that 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 A2 was obtained.
(Carrier production example 3)
The core material is manufactured and coated in the same process as in Production Example 1 except that conductive carbon (EC made by Ketjen Black International Co., Ltd.) is dispersed in a pearl mill in an amount of 5 wt% based on the resin solid content. A3 was obtained.
(4) Carrier production example 4
Except having changed the addition amount of the aminosilane coupling agent into 30g, the core material was manufactured in the process similar to the manufacture example 3, it coated, and carrier A4 was obtained.
(5) Carrier Production Example 5 Comparative Example A core material was produced in the same steps as in Production Example 3 except that the amount of aminosilane coupling agent added was changed to 50 g, and coating was performed to obtain carrier b1.
(6) Carrier Production Example 6 Comparative Example 100 g of straight silicone (Toray Dow Corning SR-2411) as a coating resin was weighed in terms of solid content and dissolved in 300 cc of toluene solvent.

Coating was performed on 10 kg of the ferrite particles by stirring the coating resin solution for 20 minutes using an immersion drying type coating apparatus. Thereafter, baking was performed at 210 ° C. for 1 hour to obtain a carrier b2.
(7) Carrier Production Example 7 Comparative Example 100 g of perfluorooctylethyl acrylate / methacrylate copolymer as a coating resin was measured in terms of solid content and dissolved in 300 cc of toluene solvent.

Coating was performed on 10 kg of the ferrite particles by stirring the coating resin solution for 20 minutes using an immersion drying type coating apparatus. Thereafter, baking was performed at 200 ° C. for 1 hour to obtain a carrier b3.
(8) Carrier Production Example 8 Comparative Example 100 g of an acrylic-modified silicone resin (KR-9706, manufactured by Shin-Etsu Chemical Co., Ltd.) was weighed in terms of solid content and dissolved in a 300 cc toluene solvent.
Coating was performed on 10 kg of the ferrite particles by stirring the coating resin solution for 20 minutes using an immersion drying type coating apparatus. Thereafter, baking was performed at 210 ° C. for 1 hour to obtain carrier b4.

(Example 2)
Next, examples of the toner of the present invention will be described, but the present invention is not limited to these examples.
Creation of resin dispersion
Table 1 shows the characteristics of the resin used. Mn is a number average molecular weight, Mw is a weight average molecular weight, Mz is a Z average molecular weight, Mp is a 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 first 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 first 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 first 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 second resin particle dispersion RH4 was prepared in which resin particles of 262000, Mz of 577000, Mp of 182000, Tm of 197 ° C., Tg of 77 ° C., and median diameter of 0.12 μm were dispersed.
(5) Preparation of resin particle dispersion RH5 A monomer liquid consisting of 102 g of styrene in which 4 g of an aluminum salicylate metal complex (Orient Chemical Co., Ltd .: E88) was melted, 18 g of n-butyl acrylate, and 1.8 g of acrylic acid was ionized. In 200 g of exchange water, 3 g of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) was dispersed using 0 g of dodecanethiol and 0 g of carbon tetrabromide, and 1.2 g of potassium persulfate was added thereto. Emulsion polymerization was performed at 70 ° C. for 5 hours, and resin particles having Mn of 41000, Mw of 242000, Mz of 575000, Mp of 154000, Tm of 193 ° C., Tg of 76 ° C., and median diameter of 0.22 μm were dispersed. A second resin particle dispersion RH5 was prepared.
Example 3
Creating pigment dispersions
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 4
Preparation of Wax Dispersion Among 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 processed, and a hole is formed in the central portion. Reference numeral 803 denotes a rotating body that rotates at a high speed and is fixed to the shaft 806 and can rotate at a high speed. A hole of about 1 to 5 mm is formed on the side surface of the rotating body, and the liquid to be processed can be moved. The tank is 120 ml, and about half of the liquid to be treated is charged. The speed of the rotating body was rotated at a maximum of 50 m / s. The diameter of the rotating body is 52 mm, and the inner diameter of the tank is 56 mm. Reference numeral 804 denotes a raw material inlet for continuous processing. Sealed when batch-type.

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 5 min. The liquid temperature in the tank rose to 92 ° C. The heat melted the wax, and a fine wax particle dispersion WA1 was formed by a strong shearing force.
(2) Preparation of 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 minutes at 20 m / s, and then the rotational speed was increased to 45 m / s, followed by treatment for 5 minutes 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 Chemical Industries, Ltd.), 1 g of a nonionic surfactant (New Coal 565C manufactured by Nippon Emulsifier Co., Ltd.), wax (W-3) 28 g was charged, and the speed of the rotating body was 20 m / s for 3 minutes, and then the rotational speed was increased to 50 m / s for 4 minutes to form a wax particle dispersion WA3.
(4) Preparation of 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 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-4) 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 4 min processing to form a wax particle dispersion WA4. It was done.

(5) Preparation of Wax Particle Dispersion WA5 FIG. 5 is a schematic view of a stirring and dispersing apparatus, and FIG. 6 is a top view. Reference numeral 850 denotes a raw material inlet, and reference numeral 852 denotes a fixed body having a floating structure. A narrow gap of about 1 μm to 10 μm is formed by the pressing force of the 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 a preheated aqueous medium, which is charged through the inlet 850 and instantly refined. The supply amount was 1 kg / h, and the rotating body was rotated at a maximum speed of 100 m / s.

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-5) were charged, and the speed of the rotating body Was processed at 100 m / s and the supply rate was 1 kg / h to form a wax particle dispersion WA5.
(6) Preparation of wax particle dispersion WA6
Under the same conditions as in (4), 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-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 in (5), the speed of the rotating body was rotated at 90 m / s, 70 g of ion-exchanged water, 1 g of an anionic surfactant (SCF manufactured by Sanyo Kasei Kogyo Co., Ltd.), nonionic surfactant (manufactured by Nippon Emulsifier Co., Ltd.) 1 g of New Coal 565C) and 28 g of wax (W-7) were charged to form a wax particle dispersion WA7.
(8) Preparation of wax particle dispersion WA8
Under the same conditions as in (4), 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-8) 28 g was charged, the speed of the rotating body was 3 min at 20 m / s, and then the rotating speed was increased to 40 m / s, followed by 4 min processing to form a wax particle dispersion WA8.
(9) Preparation of wax particle dispersion WA9
Under the same conditions as in (4), 70 g of ion-exchanged water, 0.6 g of an anionic surfactant (SCF manufactured by Sanyo Kasei Kogyo Co., Ltd.), 1.4 g of a nonionic surfactant (New Coal 565C manufactured by Nippon Emulsifier Co., Ltd.), Fischer Tro 28 g of push wax (Nippon Seiki FPN0090, melting point 90.2 ° C.) was added, the speed of the rotating body was 3 min at 20 m / s, and then the rotating speed was increased to 45 m / s and treated for 4 min. WA9 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 5)
Preparation of Toner Base The composition of the toner as a prototype toner is shown in Table 7.

(1) Preparation of toner base M1 In a 4-ml flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter, 2000 g of the first resin particle dispersion RL2 and 30 g of the colorant particle dispersion PM1 are ionized. 300 ml of exchanged water was added and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T25) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 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 30% 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 to obtain aggregated particles. The obtained aggregated particle dispersion had a pH of 9.3. The volume average particle diameter was 2.5 μm, and the coefficient of variation was 18.1.

Thereafter, the water temperature was set to 60 ° C., 43 g of second shell resin particle dispersion RH4 and 50 g of wax dispersion WA1 were obtained.
And 1N NaOH was added to bring the pH to 8.6.

  Then, the water temperature was heated at 80 ° C. for 0.5 hours, 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.

  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 M1 having a volume average particle size of 3.8 μm and a coefficient of variation of 18.9.

  If the pH when the second resin particle dispersion (RH4 in this example) and the wax dispersion (WA1 in this example) are added is 5.0, the aggregated particles of wax and tree second resin particles are obtained. The adhesion of the particles hardly occurred and the number of free particles increased. Further, when the pH was set to 9.0, secondary aggregation between the aggregated particles occurred, and the particles were coarsened to about 20 μm.

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 agglomeration of the agglomerated particles occurred, and the particles were coarsened to about 24 μm.
(2) Preparation of toner base M2 To 2000 ml of a four-necked 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 30 g of the colorant particle dispersion PM1 are ionized. 300 ml of exchanged water was added and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T25) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 2.8.

    Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 9.7, and then 260 g of a 30% strength magnesium sulfate aqueous solution was added and stirred for 10 minutes. Thereafter, the temperature was raised from 22 ° C. to 70 ° C. at a rate of 5 ° C./min, and then heated at 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 5.2 μm, and the coefficient of variation was 18.9.

  Thereafter, the water temperature was adjusted to 60 ° C., 43 g of second shell resin particle dispersion RH4 and 50 g of wax dispersion WA2 were added, and 1N NaOH was added to adjust the pH to 8.6. Then, the water temperature was heated at 80 ° C. for 0.5 hours, 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.

Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid-type dryer, resulting in a volume average particle size of 6.6 μm and a coefficient of variation of 18.8. Toner base M2 was obtained.
(3) Preparation of toner base M3 In a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter, 2000 ml, 204 g of the first resin particle dispersion RL2, 30 g of the colorant particle dispersion PM1, and ions 300 ml of exchanged water was added and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T25) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 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 30% strength magnesium sulfate aqueous solution was added and stirred for 10 minutes. Thereafter, the temperature was raised from 22 ° C. to 70 ° C. at a rate of 5 ° C./min, and then heated at 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 4.1 μm, and the coefficient of variation was 19.1.

  Thereafter, the water temperature was 60 ° C., 43 g of the second shell resin particle dispersion RH4 and 50 g of the wax dispersion WA3 were added, and 1N NaOH was added to adjust the pH to 8.6.

  Then, the water temperature was heated at 80 ° C. for 0.5 hours, 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.

Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. The toner base thus obtained was dried at 40 ° C. for 6 hours with a fluid dryer, and the volume average particle size was 5.3 μm and the coefficient of variation was 18.1. A toner base M3 was obtained.
(4) Preparation of toner base M4 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 30 g of the colorant particle dispersion PM1 are ionized. 300 ml of exchanged water was added and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T25) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 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 30% 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 to obtain aggregated particles. The obtained aggregated particle dispersion had a pH of 9.3. The volume average particle diameter was 3.2 μm, and the coefficient of variation was 18.0.

Thereafter, the water temperature was adjusted to 60 ° C., 43 g of second shell resin particle dispersion RH4 and 50 g of wax particle dispersion WA 5 were added, and 1N NaOH was added to adjust the pH to 8.6.

  Then, the water temperature was heated at 80 ° C. for 0.5 h, 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.

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 M4 having a volume average particle size of 4.5 μm and a coefficient of variation of 17.2.
(5) Preparation of toner base M5 In 2000 ml of a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter, 204 g of the first resin particle dispersion RL1 and 30 g of the colorant particle dispersion PM1 are ionized. 300 ml of exchanged water was added and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T50) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 2.2.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 9.7, and then 260 g of a 30% strength magnesium sulfate aqueous solution was added and stirred for 10 minutes. Thereafter, the temperature was raised from 22 ° C. to 70 ° C. at a rate of 5 ° C./min, and then heated at 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 5.5 μm, and the coefficient of variation was 17.8.

Thereafter, the water temperature was set to 60 ° C., 43 g of second shell resin particle dispersion RH5 and 50 g of wax particle dispersion WA 7 were added, and 1N NaOH was added to adjust the pH to 5.0.

  Then, 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.

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 M5 having a volume average particle size of 6.8 μm and a coefficient of variation of 17.9.
(6) Preparation of toner base M6 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 RL3, 30 g of the colorant particle dispersion PM1, and wax 50 g of the particle dispersion WA1 and 350 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 3.8.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11.2, and then 310 g of a 30% strength magnesium sulfate aqueous solution was added and stirred for 10 minutes. Thereafter, the temperature was raised from 22 ° C. to 70 ° C. at a rate of 5 ° C./min, and then heated at 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 4.4 μm, and the coefficient of variation was 18.6.

  Thereafter, the water temperature was set to 60 ° C., 43 g of second shell resin particle dispersion RH4 and 50 g of wax particle dispersion WA4 were added, and 1N NaOH was added to adjust the pH to 6.8.

  Then, the water temperature was heated at 80 ° C. for 1 h, 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.

  Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid drier to obtain a toner base M6 having a volume average particle size of 5.8 μm and a coefficient of variation of 19.7.

  As shown in FIGS. 7 and 8, the agglomerated wax was dispersed in a state of being mixed with the resin having a particle size of 1 μm or less.

  At this time, when the pH at the time of preparing the mixed dispersion becomes 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, the formed aggregated particles are coarsened if it is smaller than 9.5. When the pH was 9.1, the volume average particle size was 15.5 μm and the coefficient of variation was 32.5, which was coarse. When the pH was 12.5, the amount of free wax increased, making it difficult to encapsulate the wax uniformly.

Further, when the pH of the liquid when the aggregated particles are formed is higher than 9.5, the aggregation is poor and free wax increases. When the pH is less than 7.0, the particles become coarse.
(7) Preparation of toner base M7 In a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter, 2000 ml, 204 g of the first resin particle dispersion RL3, 30 g of the colorant particle dispersion PM1, and wax 50 g of particle dispersion WA2 and 350 ml of ion-exchanged water were added, and mixed for 10 min using a homogenizer (manufactured by IKA: Ultra Turrax T25) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 4.2.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11.2, and then 310 g of a 30% strength magnesium sulfate aqueous solution was added and stirred for 10 minutes. Thereafter, the temperature was raised from 22 ° C. to 70 ° C. at a rate of 5 ° C./min, and then heated at 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 4.2 μm, and the coefficient of variation was 18.2.

  Thereafter, the water temperature was adjusted to 60 ° C., 43 g of second resin particle dispersion RH4 and 50 g of wax particle dispersion WA6 were added, and 1N NaOH was added to adjust the pH to 6.8.

  Then, the water temperature was heated at 80 ° C. for 1 h, 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.

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 M7 having a volume average particle size of 5.6 μm and a coefficient of variation of 17.9. As shown in FIGS. 7 and 8, the agglomerated wax was dispersed in a state of being mixed with the resin having a particle size of 1 μm or less.
(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, 30 g of the colorant particle dispersion PM1, and wax 50 g of particle dispersion WA3 and 350 ml of ion-exchanged water were added, and mixed for 10 min using a homogenizer (manufactured by IKA: Ultra Turrax T25) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 4.3.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11.6, and then 310 g of a 30% strength magnesium sulfate aqueous solution was added and stirred for 10 minutes. Thereafter, the temperature was raised from 22 ° C. to 70 ° C. at a rate of 5 ° C./min, and then heated at 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 8.7. The volume average particle diameter was 3.2 μm, and the coefficient of variation was 18.9.

  Thereafter, the water temperature was set to 60 ° C., 43 g of second shell resin particle dispersion RH5 and 50 g of wax particle dispersion WA8 were added, and 1N NaOH was added to adjust the pH to 7.0.

  Then, the water temperature was heated at 80 ° C. for 1 h, and then 1N HCl was added to adjust the pH to 5.2. Thereafter, the mixture was further heated at 90 ° C. for 5 hours.

Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours with a fluid dryer to obtain a toner base M8 having a volume average particle size of 4.8 μm and a coefficient of variation of 17.9. As shown in FIGS. 7 and 8, the agglomerated wax was dispersed in a state of being mixed with the resin having a particle size of 1 μm or less.
(9) Preparation of toner base M9 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 30 g of the colorant particle dispersion PM1 and wax 25 g of the particle dispersion WA1 and 350 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 4.3.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11.6, and then 290 g of a 30% 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 to obtain aggregated particles. The obtained aggregated particle dispersion had a pH of 8.7. The volume average particle size was 3.1 μm, and the coefficient of variation was 18.9.

  Thereafter, the water temperature was set to 60 ° C., 53 g of second shell resin particle dispersion RH4 and 50 g of wax particle dispersion WA9 were added, and 1N NaOH was added to adjust the pH to 7.0.

Then, the water temperature was heated at 80 ° C. for 1 h, and then 1N HCl was added to adjust the pH to 5.2. Thereafter, the mixture was further heated at 90 ° C. for 5 hours.
Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid dryer to obtain a toner base M9 having a volume average particle size of 4.7 μm and a coefficient of variation of 17.9. As shown in FIGS. 7 and 8, the agglomerated wax was dispersed in a state of being mixed with the resin having a particle size of 1 μm or less.
(10) Preparation of toner base M10 In a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter, 2000 ml, 204 g of the first resin particle dispersion RL2 and 30 g of the colorant particle dispersion PM1 are ionized. 300 ml of exchanged water was added and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T25) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 3.8.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11.9, and then 260 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 aggregated particles. The obtained aggregated particle dispersion had a pH of 9.3.

  Thereafter, in a state where the water temperature is 90 ° C., the second resin particle dispersion RH4 having a pH adjusted to 6.5 is 43 g at a dropping rate of 1 g / min, and the wax dispersion having a pH adjusted to 6.5. 50 g of WA1 was added at a dropping rate of 1 g / min, and after completion of the dropping, heat treatment was performed for 2 hours at 95 ° C. to obtain particles in which the second resin particles and the wax were fused.

Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid drier to obtain a toner base M10e having a volume average particle size of 4.2 μm and a coefficient of variation of 16.8.
After mixing in (Table 8), the temperature in the tank relative to the time elapsed in the aggregated particle generation process, the pH of the liquid, the volume average particle diameter (d50 (μm)), the second resin particles and the wax adhesion melting process After completion of the second resin particle dispersion and the wax particle dispersion droplet, the temperature in the tank with respect to the elapsed time after the addition, the volume average particle diameter (d50 (μm)), the second resin particle dispersion and the wax particle dispersion “R: (numerical value) W: (numerical value)” described in the column of completion of dropping indicates the pH value after adjustment of the second resin particle dispersion and wax particle dispersion. M10a to j have pH values after adjustment of the second resin particle dispersion and the wax 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 for 2 hours are shown.

  By adjusting the pH value from 8.5 to 10.5, the shape tends to shift to an irregular shape.

When the pH value is 3.5, when the second resin particle dispersion and the wax particle dispersion are dropped, the second resin particles and the wax particles do not adhere to the aggregated particles at all, and only the second resin particles or the wax particles are present. Agglomeration and the volume variation coefficient was 40 or more, and 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.
(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 was charged with 204 g of the first resin particle dispersion RL2 and 30 g of the colorant particle dispersion PM1. 25 g of one wax particle dispersion WA1 was added, 350 ml of ion-exchanged water was added, and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T50) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 2.2.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 9.7, and then 290 g of a 23% strength magnesium sulfate aqueous solution was added, followed by stirring for 10 minutes. Thereafter, the temperature was raised from 20 ° C. to 90 ° C. at a rate of 1 ° C./min, followed by heat treatment for 3 hours to obtain aggregated particles. The obtained aggregated particle dispersion had a pH of 7.

  Thereafter, in a state where the water temperature is 90 ° C., the second resin particle dispersion RH4 having a pH adjusted to 5 is 43 g at a dropping rate of 10 g / min, and the second wax dispersion WA9 having a pH adjusted to 5 is prepared. 50 g was added at a dropping rate of 10 g / min, added, and after completion of the dropping, heat treatment was performed for 1.5 hours at 90 ° C., and the second resin particles and the second wax were fused. Obtained.

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 M11e having a volume average particle size of 6.1 μm and a coefficient of variation of 17.1.
After mixing in (Table 9), the temperature in the tank and the pH of the liquid, the volume average particle diameter (d50 (μm)), the second resin particles, and the second wax adhering and melting with respect to the time elapsed in the aggregate particle generation step After completion of the second resin particle dispersion and the second wax particle dispersion droplet in the process, the temperature in the tank with respect to the time elapsed after the addition, the volume average particle diameter (d50 (μm)), the second resin particle dispersion “R: (numerical value) W: (numerical value)” described in the column below the liquid and the second wax particle dispersion droplet indicates a pH value after adjustment of the second resin particle dispersion and the wax particle dispersion. M11a-j shows the state when the pH value after adjustment of the second resin particle dispersion and wax particle dispersion is 9, 8, 7, 6, 5, 4, 2.5, 11; The volume average particle diameter at the time of completion of dropping at 1.5 hours and the shape factor are shown.

  By adjusting the pH value from 6 to 9, the shape tends to shift to an irregular shape.

When the pH value is 2.5, when the second resin particle dispersion and the wax particle dispersion are dropped, the second resin particles and the wax particles do not adhere to the aggregated particles at all, and only the second resin particles or the wax particles. Agglomeration and the volume variation coefficient was 40 or more, and 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.
(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, 30 g of colorant particle dispersion PM1, and wax particle dispersion 50 g of wa 10 and 300 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.

  1N NaOH was added to the obtained mixed particle dispersion to adjust the pH to 10.0, and then 260 g of a 30% strength magnesium sulfate aqueous solution was added and stirred for 10 min. Thereafter, the temperature was raised from 22 ° C. to 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 obtained aggregated particle dispersion had a pH of 7.5. The volume average particle diameter was 8.8 μm, and the coefficient of variation was 20.1.

  Thereafter, the water temperature was set to 60 ° C., 43 g of the second shell resin particle dispersion RH4 was added, and 1N NaOH was added to adjust the pH to 6.0.

Then, the water temperature was heated at 80 ° C. for 1 h, and then 1N HCl was added to adjust the pH to 5.5. Thereafter, it was further heated at 90 ° C. for 5 hours.
Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid drier to obtain a toner base m12 having a volume average particle diameter of 12.5 μm and a coefficient of variation of 23.5.
(13) Preparation of toner base m13 In a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter, 2000 ml, 204 g of resin particle dispersion RL2, 30 g of colorant particle dispersion PM1, and wax particle dispersion 50 g of wa 11 and 300 ml of ion-exchanged water were added, and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Tarrax T25) to prepare a mixed particle dispersion.

  1N NaOH was added to the obtained mixed particle dispersion to adjust the pH to 9.0, and then 260 g of a 30% strength aqueous magnesium sulfate solution was added and stirred for 10 min. Thereafter, the temperature was raised from 22 ° C. to 90 ° C. at a rate of 5 ° C./min, and then heat-treated at 90 ° C. for 6 hours to obtain aggregated particles. The resulting aggregated particle dispersion had a pH of 6.5. The volume average particle size was 12.5 μm, and the coefficient of variation was 32.8.

  Thereafter, the water temperature was adjusted to 60 ° C., 43 g of the second shell resin particle dispersion RH4 was added, and 1N NaOH was added to adjust the pH to 4.8.

Then, the water temperature was heated at 90 ° C. for 1 h, and then 1N HCl was added to adjust the pH to 3.0. Thereafter, it was further heated at 90 ° C. for 5 hours.
Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. The toner base thus obtained was dried at 40 ° C. for 6 hours with a fluid-type dryer to obtain toner base m13. A broad particle size distribution with a volume average particle size of 14.9 μm and a coefficient of variation of 39.9 was obtained. The wax of aggregated particles had a large proportion of aggregated particles in a dispersed state as shown in FIG.
(14) Preparation of toner base m14 In a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod and a pH meter, 2000 ml, resin particle dispersion RL2 204 g, 20 wt% concentration of colorant particle dispersion PM1 30 g, 30 wt. 50% of the wax particle dispersion wa11 having a concentration of% and 300 ml of ion-exchanged water were added, and mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T50) to prepare a mixed particle dispersion.

  1N NaOH was added to the obtained mixed particle dispersion to adjust the pH to 9.2, and then 260 g of a 30% strength aqueous magnesium sulfate solution was added and stirred for 10 min. Thereafter, the temperature was raised from 22 ° C. to 85 ° C. at a rate of 5 ° C./min, and then heat-treated at 85 ° C. for 5 hours to obtain aggregated particles. The resulting aggregated particle dispersion had a pH of 6.5. The volume average particle diameter was 18.5 μm, and the coefficient of variation was 32.1.

  Thereafter, the water temperature was adjusted to 60 ° C., 43 g of the second shell resin particle dispersion RH4 was added, and 1N NaOH was added to adjust the pH to 4.8.

Then, the water temperature was heated at 90 ° C. for 1 h, and then 1N HCl was added to adjust the pH to 3.0. Thereafter, the mixture was further heated at 90 ° C. for 5 hours.
Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. The toner base thus obtained was dried at 40 ° C. for 6 hours with a fluid-type dryer to obtain toner base m14. A broad particle size distribution with a volume average particle size of 14.8 μm and a coefficient of variation of 41.2 was obtained. The wax of aggregated particles had a large proportion of aggregated particles in a dispersed state as shown in FIG.
(15) Preparation of toner base m15 To 2000 ml of a four-necked flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter, 204 g of the first resin particle dispersion RL 1 and 30 g of the colorant particle dispersion PM1 50 g of wax particle dispersion WA2 and 350 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 4.2.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11.2, and then 310 g of a 30% strength magnesium sulfate aqueous solution was added and stirred for 10 minutes. Thereafter, the temperature was raised from 22 ° C. to 70 ° C. at a rate of 5 ° C./min, and then heated at 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.

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

Then, the water temperature was heated at 80 ° C. for 1 h, 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.
Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid drier to obtain a toner base m15 having a volume average particle size of 5.8 μm and a variation coefficient of 21.8.
(16) Preparation of toner base m16 In a 2000 ml four-necked flask equipped with a thermometer, a cooling tube, a stirring rod, and a pH meter, 204 g of the first resin particle dispersion RL 1 and 30 g of the colorant particle dispersion PM1 50 g of wax particle dispersion WA3 and 350 ml of ion exchange water were added, and mixed for 10 min using a homogenizer (manufactured by IKA: Ultra Turrax T25) to prepare a mixed particle dispersion. The pH of the obtained mixed dispersion was 4.3.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11.6, and then 310 g of a 30% strength magnesium sulfate aqueous solution was added and stirred for 10 minutes. Thereafter, the temperature was raised from 22 ° C. to 70 ° C. at a rate of 5 ° C./min, and then heated at 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 8.7.

  Thereafter, the water temperature was set to 60 ° C., 43 g of second shell resin particle dispersion RH5 and 50 g of wax particle dispersion WA8 were added, and 1N NaOH was added to adjust the pH to 7.0.

  Then, the water temperature was heated at 80 ° C. for 1 h, and then 1N HCl was added to adjust the pH to 5.2. Thereafter, the mixture was further heated at 90 ° C. for 5 hours.

Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid drier to obtain a toner base m16 having a volume average particle size of 4.9 μm and a coefficient of variation of 19.2.
Table 10 shows the external additives used in this example. The amount of charge was measured by the blow-off method of frictional charging with an uncoated ferrite carrier. In an environment of 25 ° C. and 45 RH%, 50 g of carrier and 0.1 g of silica or the like are mixed in a 100 ml polyethylene container, stirred for 5 minutes and 30 minutes at a speed of 100 min ⁻¹ by longitudinal rotation, and 0.3 g is collected. Then, nitrogen gas was blown for 1 minute with 1.96 × 10 ⁴ (Pa).

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

Table 11 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 photosensitive member is 125 mm / s.

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

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

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

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

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

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

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

The paper is transported from below the transfer unit 17 so that the paper 19 is fed by a paper feed roller (not shown) to the nip portion where the transfer belt 12 and the second transfer roller 14 are pressed. A conveyance path is formed.
The toner on the transfer belt 12 is transferred to the paper 19 by +1000 V applied to the second transfer roller 14, and includes a fixing roller 201, a pressure roller 202, a fixing belt 203, a heating medium roller 204, and an induction heater unit 205. It is conveyed to the fixing unit and fixed there.

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

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

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

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

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

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

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

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

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

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

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

  Table 12 shows the results of image output using the electrophotographic apparatus shown in FIG. Filming on the photoconductor, change in image density before and after endurance test, degree of toner adhesion on non-image area, fogging, uniformity when taking an image on the entire surface, magenta, cyan, yellow In a full-color image in which three colors of toner are superimposed, scattering at the time of transfer in a character portion or a so-called hollow state in which a part is not transferred and is not transferred, after yellow or magenta toner is transferred, the next magenta or cyan Alternatively, the yellow or magenta toner already transferred at the time of transferring the black toner is reversely attached to the photosensitive member and returned.

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 the images were taken out with DM11 to DM21, the solid black image was uniform with no horizontal line disturbance, toner scattering, character voids, etc., and the image line of 16 lines / mm was reproduced. An image was obtained, and a high density image having an image density of 1.3 or more was obtained. In addition, the ground cover of the non-image area did not occur. Further, even in the long-term durability test of 1 million 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 is little change in carrier resistance and decrease in charge amount, and fog does not occur. The charge rising property at the time of rapid toner replenishment was also good, and there was no phenomenon that fogging increased in a high humidity environment. Also, when used for a long time, a high saturation charge amount was obtained and could be maintained for a long time. Fluctuations in charge amount under low temperature and low humidity hardly occur. Also, in the transfer, the void is at a level that causes no problem in practical use, and the transfer efficiency is about 95%. Further, the filming of the toner on the photosensitive member and the transfer belt was at a level where there was no practical problem. There was no defective cleaning of the transfer belt. Also, there is almost no toner disturbance or toner skipping during fixing. In addition, in the full-color image in which the three colors overlap, no transfer failure occurred, and no paper wrapping around the fixing belt occurred during fixing.

  When the process speed is 100 mm / s and the distance between the photoconductors is 70 mm, the developer of cm1, cm2, and cm3 has acceptable levels of scattering of characters during transfer, lack of transfer characters, and reverse transferability. However, when the process speed was increased to 125 mm / s or when the distance between the photoconductors was set to 60 mm, the uniformity of the entire solid image and the scattering of characters during transfer were slightly deteriorated. With the cm1, cm3, and cm6 developers, an increase in charge occurred and the image density decreased.

  The fog was noticeable in the cm4, cm5, and cm6 developers. Further, when the entire surface was continuously taken and the toner was replenished rapidly, the charge decreased and the fog increased. The phenomenon worsened particularly in a high humidity environment.

  Table 13 shows the OHP transmittance, the minimum fixing temperature (° C.), the high temperature offset occurrence temperature, the storage stability, and the paper wrapping property around the fixing belt in fixing.

In the fixing device shown in FIG. 2 using a solid image with an adhesion amount of 1.2 mg / cm ^{2 at} a process speed of 125 mm / s and a belt not coated with oil, OHP transmittance (fixing temperature 160 ° C.), minimum fixing temperature (toner The temperature at which the cold offset that does not completely melt and remains on the fixing belt does not occur), and the offset property at a high temperature was evaluated. The OHP transmittance was measured with a spectrophotometer U-3200 (Hitachi, Ltd.) for the transmittance of 700 nm light. Storage stability shows the result after standing at 60 ° C. for 5 hours.

  With the TM1 to TM11 toners, no OHP jam occurred at the fixing nip portion. 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 belt not using oil. In addition, almost no aggregation was observed in the storage stability at 60 ° C. for 5 hours (◯ level).

  With tm12, 13, and 14 toners, the storage stability and the like that seemed to be affected by the residual toner particles on the surface of the wax were poor, and with tm15 and 16, the offset magazine was narrow.

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

Sectional drawing which shows the structure of the image forming apparatus used in the Example of this invention Sectional drawing which shows the structure of the fixing unit used in the Example of this invention Schematic of the stirring and dispersing apparatus used in the examples of the present invention View from above of the stirring and dispersing device used in the examples of the present invention Schematic of the stirring and dispersing apparatus used in the examples of the present invention View from above of the stirring and dispersing device used in the examples of the present invention Cross-sectional observation image of a toner according to an embodiment of the present invention using a transmission electron microscope Cross-sectional observation image of a toner according to an embodiment of the present invention using a transmission electron microscope Cross-sectional observation image of a toner according to an embodiment of the present invention using a transmission electron microscope Cross-sectional observation image of a toner according to an embodiment of the present invention using a transmission electron microscope Cross-sectional observation image of the toner of the comparative example of the present invention using a transmission electron microscope

Explanation of symbols

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

Claims (14)

In the aqueous medium, at least the first resin particle dispersion in which the first resin is dispersed and the colorant particle dispersion in which the colorant particles are dispersed are mixed, and the first resin particles are dispersed. At least the first resin particles are prepared by adjusting the pH of the mixed liquid obtained by mixing the resin particle dispersion liquid and the colorant particle dispersion liquid in which the colorant particles are dispersed to a range of 9.5 to 12.2. And producing agglomerated particles in which the colorant particles are agglomerated;
A second resin particle dispersion in which a second resin is dispersed and a wax particle dispersion in which a wax is dispersed are added to the aggregated particle dispersion in which the aggregated particles are dispersed, and the pH is set to 5.2 to 8. Adjusting to a range of 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 3.2 to 6.8;
And a step of fusing the wax and the second resin to the aggregated 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 and the colorant particle dispersion in which the colorant particles are dispersed are mixed and subjected to heat treatment to at least the first resin. Generating aggregated particles in which the particles and the colorant particles are aggregated;
The second resin particle dispersion in which the second resin is dispersed and the wax particle dispersion in which the wax is dispersed are added to the aggregated particle dispersion in which the aggregated particles are dispersed, mixed, heated, and heated. A method for producing a toner, comprising: fusing two resin particles and wax particles to the aggregated particles,
When the pH value of the aggregated particle dispersion in which the aggregated particles are dispersed is HS, the second resin particle dispersion in which the second resin particles are dispersed and / or the wax particle dispersion in which the wax is dispersed A method for producing a toner, wherein the pH is adjusted within the range of HS + 2 to HS-5. 3. The toner production method according to claim 2, wherein the pH of the second resin particle dispersion in which the second resin particles are dispersed and / or the wax particle dispersion in which the wax is dispersed is 3.5 to 10.3. 5. A toner production method, wherein the toner production range is 5. Claims to adjust the pH of the mixed solution in which the first resin particle dispersion in which the first resin particles are dispersed and the colorant particle dispersion in which the colorant particles are dispersed to 9.5 to 12.2. Item 4. A method for producing a toner according to Item 2 or 3 . In an aqueous medium, at least, a first resin particle dispersion, the endothermic peak temperature by colorant particles and the colorant particles are dispersed dispersion and DSC method are dispersed first resin (referred to as melting point) of 50 Mixing a first wax particle dispersion in which a first wax at ˜95 ° C. is dispersed;
Adjusting the pH to a range of 9.5 to 12.2 before adding the water-soluble inorganic salt and before heating;
Thereafter, a water-soluble inorganic salt is added, and heat treatment is performed to form aggregated particles in which at least the first resin particles, the colorant particles, and the first wax particles are aggregated, and
The pH when the aggregated particles are formed is in the range of 7.0 to 9.5,
Further, second wax particles in which the second wax having a melting point higher than the melting point of the first wax and having a melting point of 80 to 120 ° C. is dispersed in the aggregated particle dispersion in which the aggregated particles are dispersed. Adding a dispersion and a second resin particle dispersion in which a second resin is dispersed, and 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 3.2 to 6.8;
And a step of fusing the second wax and the second resin particles to the aggregated particles by heat treatment at a temperature equal to or higher than the glass transition temperature of the second resin particles. Production method. The method for producing a toner according to claim 1 , wherein the wax contains a wax having an iodine value of 25 or less and a saponification value of 30 to 300. The method for producing a toner according to any one of claims 1 to 3, wherein the wax comprises a wax having an acid value of 10 to 80 mgKOH / g having at least a long-chain alkyl group having 4 to 30 carbon atoms, an ester group and a vinyl group. The method for producing a toner according to any one of claims 1 to 3, wherein the wax contains one or more waxes selected from the group consisting of a derivative of hydroxystearic acid, a glycerin fatty acid ester, a glycol fatty acid ester, and a sorbitan fatty acid ester. The method for producing a toner according to claim 1, wherein the wax contains an aliphatic hydrocarbon wax. The method for producing a toner according to claim 5 , wherein the first wax includes a wax having an iodine value of 25 or less and a saponification value of 30 to 300. 6. The method for producing a toner according to claim 5, wherein the second wax contains a wax having an acid value of 10 to 80 mg KOH / g having at least a long-chain alkyl group having 4 to 30 carbon atoms, an ester group and a vinyl group. The toner production method according to claim 5, wherein the second wax includes an aliphatic hydrocarbon wax. In the molecular weight distribution in gel permeation chromatography (GPC), 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). 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 claim 6 , wherein the loss on heating at 220 ° C. is 8% by weight or less. The toner production according to claim 7 or 11, wherein the wax is a wax obtained by a reaction with a long-chain alkyl alcohol having 4 to 30 carbon atoms, an unsaturated polycarboxylic acid or an anhydride thereof, and an unsaturated hydrocarbon wax. Method.