JP2007292833A - Toner, method for manufacturing toner, and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner or two-component developer with which the toner of a small grain size having a sharp grain size distribution can be created without the need for a classifying step, a longer lifetime can be achieved, and voids and scattering in transfer can be prevented. <P>SOLUTION: The toner includes the particles obtained by fusing second resin particles to the core particles created by aggregating first resin particles, colorant particles and wax particles. A second resin particle dispersion liquid is obtained by subjecting a monomer to emulsion polymerization using a polymerization initiator in an aqueous medium. The polymerization initiator is persulfates of ≥4g in its solubility and an amount of addition thereof is 0.5 to 2.0 parts by weight with respect to the monomer 100 parts by weight. A vinyl component having an acid group is compounded in a specified amount with the monomer. The wax includes the wax of 50 to 120°C in an endothermic peak temperature by a DSC (differential scanning calorimetry). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

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

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

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

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

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

  Various configurations have been proposed for toners. 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 powder classified to complete toner base particles. There is also a method in which toner base particles are prepared by a chemical polymerization method. Thereafter, an external additive such as hydrophobic silica is added to the toner base particles to complete the toner. In one-component development, the toner is composed only of toner, but a two-component developer can be obtained by mixing with toner and a carrier composed of magnetic particles.

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

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

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

  In Patent Document 1 below, a toner comprising particles formed by polymerization and a coating layer made of fine particles formed by emulsion polymerization on the surface of the particles, and a water-soluble inorganic salt is added to the surface of the particles. The structure which produces | generates the coating layer by particle | grains and the structure which produces | generates the coating layer by microparticles on the particle | grain surface by changing the pH of a solution are disclosed.

  In the following Patent Document 2, at least 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 are mixed. A liquid mixture preparation step for preparing a liquid mixture, and by making the polarity of the dispersant contained in the liquid mixture the same polarity, a highly reliable electrostatic image developing toner excellent in chargeability and color development It is disclosed that it can be easily and conveniently manufactured.

  In the following Patent Document 3, 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 have a molecular weight. It is disclosed that by including at least two different types of resin particles, it is excellent in fixing property, coloring property, transparency, color mixing property and the like.

  In Patent Document 4 below, toner particles in which a resin layer (shell) formed by fusing resin particles by a salting-out / fusing method is formed on the surface of colored particles (core particles) containing a resin and a colorant. Disclosed, the amount of colorant present on the particle surface is small, and changes in image density, fog, and color due to changes in chargeability and developability even when subjected to long-term image formation in a high humidity environment The effect which does not generate | occur | produce is described.

In Patent Document 5 below, in an electrostatic charge image developing toner including toner particles containing at least a resin and a colorant, the toner particles include a core containing resin A and at least one layer of resin B covering the core. A toner having a shell containing the toner and having a film thickness of 50 nm to 500 nm on the outermost surface layer of the shell is disclosed, and the effect of the toner for developing an electrostatic charge image having excellent offset resistance and good storage stability Is described.
Japanese Unexamined Patent Publication No. 57-45558 JP-A-10-198070 JP-A-10-301332 JP 2002-116574 A JP 2004-191618 A

  In a toner produced by agglomerating resin particles and wax particles, if the dispersibility of the wax in the core particles deteriorates, the high temperature offset property may be affected, and the non-offset temperature range may become narrow. Further, when the dispersibility of the wax added for realizing the low-temperature fixing is deteriorated, the unevenly distributed wax contaminates the photoconductor and causes photoconductor filming. Further, when the dispersibility of the wax is deteriorated, the dispersibility of the resin particles and the pigment aggregated together with the wax particles is also deteriorated, so that the color developability of the toner becomes insufficient.

  In addition, when a particle is formed by agglomeration reaction in a system in which a certain amount of wax is blended, the particle size becomes coarser with the heat treatment time, and it tends to be difficult to produce small particle size particles with a narrow particle size distribution. .

  By using wax, it is possible to achieve oil-less fixing, but on the contrary, uniform mixing and aggregation with resin particles and pigment particles in the aqueous system during production is hindered, causing aggregation in the aqueous system. There are cases where the floating wax particles do not matter, the core particles become coarse, the particle size distribution becomes broad, or the surface properties of the toner particles fluctuate.

  In addition, in the method in which a salting-out agent is added to a dispersion in which resin particles and colorant particles are dispersed and the temperature of the dispersion is increased to a temperature equal to or higher than the glass transition temperature of the resin particles, aggregation is caused. Since it occurs slowly with the temperature raising time, it may be difficult to produce particles having a small particle size and a narrow particle size distribution. Further, the aggregation state of the non-aggregated particles is likely to fluctuate, and the particle size distribution of the particles obtained by fusing becomes broad, or the surface properties of the finally obtained toner particles fluctuate.

  In addition, when the resin particles are further adhered and fused (fused) to the surface of the core particles, the dispersion of the wax is non-uniform, and if the wax is unevenly distributed on the surface of the core particles, the fusion of the resin particles cannot proceed sufficiently, There are cases where some of the shell resin particles do not adhere to the surface of the core particles, do not contribute to shell formation, and there are particles that remain floating in the aqueous system.

  As a method of fusing the resin particles to the surface of the core particles, resin particles and a flocculant such as magnesium chloride are added to the dispersion of colored particles obtained in the above step, and the temperature is higher than the glass transition temperature. At this time, the resin particles are not fused to the surface of the colored particles (core particles) and are aggregated only with the resin particles, or the particles aggregated only with the resin particles are further colored particles (core The surface properties of the toner particles finally obtained may vary by adhering to the surface of the particles.

  Furthermore, the resin particles remain present in the water regardless of agglomeration, and a long processing time is required for fusing, resulting in coarsening due to secondary aggregation of the core particles and broadening of the particle size distribution. As a result, it was difficult to produce particles having a small particle size and a narrow particle size distribution.

  An object of the present invention is to produce a toner having a small particle size having a narrow particle size distribution without a classification step.

  In oilless fixing without using oil in the fixing roller, wax is used in the toner for low temperature fixing, high temperature non-offset, separation of the paper from the fixing roller, etc. and storage stability during storage at high temperature. The goal is to achieve both.

  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.

In the toner of the present invention, at least a first resin particle dispersion in which first resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and wax particles are dispersed in an aqueous medium. Add the second resin particle dispersion in which the second resin particles are dispersed to the core particle dispersion containing the core particles produced by mixing and aggregating the wax particle dispersion, and mixing and heating. And a toner containing resin fused core particles obtained by fusing the second resin particles to the core particles, wherein the second resin particle dispersion is a polymerization initiator and a polymerization chain in an aqueous medium. It is obtained by emulsion polymerization of a monomer using a transfer agent, and is 0.5 to 2.0 parts by weight with respect to 100 parts by weight of the monomer of the polymerization initiator, and the polymerization start The agent has a solubility of 4 g or more in 100 g of water at a water temperature of 20 ° C. And the monomer contains a styrene monomer, a (meth) acrylic acid ester monomer, and a vinyl monomer having an acid group, and the acid group The amount of the vinyl compound to be contained is 0.1 to 5.0% by weight in the monomer, and the wax is a wax having an endothermic peak temperature by DSC (Differential Scanning Calorimetry) method of 50 to 120 ° C. The toner is characterized in that it contains a toner.

  The toner manufacturing method according to the present invention includes 0.1 to 5.0% by weight of the styrene monomer, the (meth) acrylate monomer, and the total monomer in the aqueous medium. A monomer containing a vinyl compound having an acid group is a persulfate having a solubility in 100 g of water at a water temperature of 20 ° C. of 4 g or more, and 0.5 to 2.0 parts by weight is added to 100 parts by weight of the monomer. In the emulsion polymerization using a polymerization initiator to produce a second resin particle dispersion in which the second resin particles are dispersed, and in the aqueous medium, at least the first resin particles dispersed A resin particle dispersion, a colorant particle dispersion in which colorant particles are dispersed, and a wax particle dispersion in which wax particles having an endothermic peak temperature of 50 to 120 ° C. by DSC (differential scanning calorimeter) method are mixed, Aggregates to produce core particles A step of adding a second resin particle dispersion in which the second resin particles are dispersed to a core particle dispersion containing the core particles, and fusing the second resin particles to the core particles. And a toner production method comprising:

  The second resin particles to be fused to the core particles (sometimes called agglomerated particles) are produced by emulsion polymerization of monomers using a polymerization initiator in an aqueous medium. It has been found that the additive amount of the agent, the polymerization initiator, and the monomer composition affect the particle size, particle size distribution and surface properties of the finally obtained toner particles.

  By controlling the above configuration to a constant value, when the second resin particles are fused to the core particles, the generation of floating particles of the second resin particles that are not involved in aggregation can be suppressed, and the processing time is shortened when fusing. it can. Further, toner base particles having a small particle size and a sharp particle size distribution can be generated while suppressing the coarsening of the core particles. Moreover, generation | occurrence | production of a particle | grain can be suppressed only for the resin particle produced by aggregation of 2nd resin particles.

  Moreover, durability and electrification stabilization can be improved by fusing the second resin particles. Moreover, high temperature non-offset property and storage stability can be improved.

  In addition, image formation stations with multiple photoconductors and development units are arranged side by side, and in the tandem color process, in which the toner of each color is successively transferred to the transfer body, it is possible to prevent voids and reverse transfer during transfer. In addition, high transfer efficiency can be obtained.

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

  The resin particle dispersion is prepared by emulsion polymerization or seed polymerization of a vinyl monomer in a surfactant to obtain a resin particle of a vinyl monomer homopolymer or copolymer (vinyl resin). A dispersion is prepared by dispersing in a 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, Dissolve the resin in the oily solvent, disperse the fine particles in water together with a surfactant and polymer electrolyte using a disperser such as a homogenizer, and then heat or reduce pressure to evaporate the oily solvent. Thus, a dispersion liquid in which resin particles other than the vinyl resin are dispersed in the surfactant is prepared.

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

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

  The toner is required to have low-temperature fixing, high-temperature non-offset property in oilless fixing, separation property between paper and fixing roller, and storage stability under a certain high temperature, and these must be satisfied at the same time.

  The first constitution of the toner of the present invention is that, in an aqueous medium, at least a first resin particle dispersion in which first resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and wax particles. The second resin particle dispersion in which the second resin particles are dispersed is added to and mixed with the core particle dispersion containing the core particles produced by mixing the wax particle dispersion in which the particles are dispersed. A toner containing resin fused core particles obtained by heating and fusing the second resin particles to the core particles, wherein the second resin particle dispersion is a polymerization initiator in an aqueous medium. Is obtained by emulsion polymerization of the monomer, 0.5 to 2.0 parts by weight with respect to 100 parts by weight of the monomer of the polymerization initiator, and the polymerization initiator is And a solubility of 4 g or more in 100 g of water at a water temperature of 20 ° C. Vinyl compounds having acid groups, which are acid salts and the monomers include a styrene monomer, a (meth) acrylic acid ester monomer, and a vinyl monomer having an acid group In the monomer, and the wax contains a wax having an endothermic peak temperature of 50 to 120 ° C. according to a DSC (differential scanning calorimeter) method. is there.

  By blending a wax having an endothermic peak temperature of 50 to 120 ° C. according to the DSC method, high temperature offset property at the time of fixing can be satisfied. When the temperature is lower than 50 ° C., storage stability at a high temperature is deteriorated, and melting starts at a low temperature during the aggregation reaction, and it is difficult to reduce the core particle size to be generated. When the temperature is higher than 120 ° C., the melting temperature increases, and the productivity tends to deteriorate in the aggregation reaction of the core particles. The low-temperature fixability tends to be unsatisfactory.

  About the addition amount of a polymerization initiator, it exists in the tendency which influences the cohesion of a 2nd resin particle and a core particle by the amount of hydrophilic groups derived from a polymerization initiator. That is, when the amount of the polymerization initiator added is large, the fusion between the second resin particles and the core particles tends to proceed slowly, and when the amount of the polymerization initiator added is small, the aggregation reaction tends to proceed rapidly. . An appropriate amount of the polymerization initiator to be added when generating the second resin particles is 0.5 to 2.0 parts by weight per 100 parts by weight of the monomer. Preferably, it is 0.6-1.5 weight part, More preferably, it is 0.7-1.0 weight part. This is a range in which the second resin particles are properly fused with the core particles.

  If the amount is less than 0.5 parts by weight, the agglomeration property of the second resin particles is accelerated, and coarse particles of the resin in which the second resin particles are agglomerated alone before the core particles are fused. It tends to end up.

  When the amount is more than 2.0 parts by weight, the fusion of the second resin particles to the surface of the core particles tends to be delayed, and time is required for productivity. Further, floating particles of the second resin particles that do not participate in the fusion remain. Furthermore, the core particles tend to aggregate and become coarse.

  As the polymerization initiator, it is essential to use persulfates having a solubility in 100 g of water having a water temperature of 20 ° C. of 4 g or more. Adhesion between the second resin particles and the core particles can be made appropriate by optimizing the amount of hydrophilic groups derived from the polymerization initiator. When the solubility is low, it takes time to dissolve the persulfates during the emulsion polymerization reaction, and the productivity becomes slow. Moreover, the dispersion state of persulfates during emulsification tends to change, and the fusion may become unstable.

  It is essential that the compounding amount of the vinyl compound having an acid group is 0.1 to 5.0% by weight in the monomer. Preferably, it is 0.2 to 4.5% by weight, more preferably 0.5 to 2.0% by weight. This is a range in which the second resin particles can be properly fused.

  If the amount is less than 0.1% by weight, the number of adhering portions to the reactor increases when the second resin particles are obtained by emulsion polymerization, and the yield deteriorates. Further, the cohesiveness of the second resin particles becomes faster, and it becomes easier to generate coarse particles of the resin in which the second resin particles are aggregated alone.

  If the amount is more than 5.0% by weight, the fusion of the second resin particles to the surface of the core particles tends to be delayed, and this is because the fusion proceeds slowly due to the presence of hydrophilic groups derived from acid groups. Therefore, it takes time for productivity. Further, floating particles of the second resin particles that do not participate in the fusion remain. Furthermore, the core particles tend to aggregate and become coarse. Further, the environmental dependency of the finally obtained toner is deteriorated.

  In the first constitution of the toner of the present invention, the first resin particle dispersion used for producing the core particle dispersion is emulsion-polymerized using a polymerization initiator in an aqueous medium. The polymerization initiator is 1.0 to 2.5 parts by weight with respect to 100 parts by weight of the monomer of the polymerization initiator, and the polymerization initiator has a solubility of 4 g or more in 100 g of water at a water temperature of 20 ° C. And the monomer contains a styrene monomer, a (meth) acrylic acid ester monomer, and a vinyl monomer having an acid group, and the acid group A configuration in which the compounding amount of the vinyl compound is 0.1 to 5.0% by weight in the monomer is also preferable.

  About the addition amount of a polymerization initiator, it exists in the tendency which influences the cohesiveness of a 1st resin particle, a colorant particle, and a wax particle by the abundance of the hydrophilic group derived from a polymerization initiator. That is, when the amount of polymerization initiator added is large, the agglomeration reaction tends to proceed slowly, and when the amount of polymerization initiator added is small, the agglomeration reaction tends to proceed quickly, and the appropriate amount of polymerization initiator added is appropriate. , 0.5 to 2.5 parts by weight per 100 parts by weight of the monomer. Preferably, it is 0.7-2.0 weight part, More preferably, it is 1.0-1.5 weight part. This is a range in which the cohesiveness of the first resin particles, the colorant particles, and the wax particles is appropriate.

  When the amount is less than 0.5 parts by weight, the aggregation property of the first resin particles is accelerated, and the core particles that are aggregated with the wax and the pigment are not produced. Will be generated.

  When the amount is more than 2.5 parts by weight, the aggregation rate of core particle generation tends to be slow, and it takes time for productivity. Further, the high temperature non-offset property deteriorates, resulting in a narrow fixing temperature range. This is thought to affect the dispersibility of the wax because the agglutination reaction proceeds slowly due to the amount of hydrophilic groups derived from the polymerization initiator, but the details are not fully understood.

  As the polymerization initiator, persulfates having a solubility of 4 g or more in 100 g of water having a water temperature of 20 ° C. are used. The cohesiveness and fixability of the core particles can be made appropriate by optimizing the amount of hydrophilic groups derived from the polymerization initiator. If the solubility is low, it takes time to dissolve the persulfates during the emulsion polymerization reaction, and the productivity is slowed down. The dispersion state of persulfates during emulsification tends to change, and the agglomeration during the agglomeration reaction may become unstable.

  The compounding quantity of the vinyl compound which has an acid group is 0.1-5.0 weight% in a monomer, Preferably, it is 0.2-4.5 weight%, More preferably, it is 0.5-2. 0% by weight. This is a range in which the cohesiveness of the first resin particles, colorant particles and wax particles can be made appropriate.

  If the amount is less than 0.1% by weight, the aggregation of the first resin particles is accelerated, and the core particles aggregated with the wax and the pigment are not generated, and the generation of resin aggregates in which the first resin particles alone are aggregated or The core particles tend to be coarse.

  If the amount is more than 5.0% by weight, the aggregation rate of core particle generation tends to be slow. This is because the aggregation reaction proceeds slowly due to the amount of hydrophilic groups derived from acid groups, and the first resin particles. It affects the cohesiveness of the wax, which causes the dispersion state of the wax to fluctuate, resulting in deterioration of the high temperature non-offset property and narrowing the fixable temperature range, but the details have been grasped. Absent.

  In the first constitution of the toner of the present invention, the addition amount of the polymerization initiator added when the first resin particles are produced by emulsion polymerization is PS1, and is added when the second resin particles are produced by emulsion polymerization. When the addition amount of the polymerization initiator is PS2, a configuration in which PS1 / PS2 is 0.25 to 5.0 is preferable. Preferably it is 1.0-4.0, More preferably, it is 1.0-2.5.

  It has been found that the ratio of the addition amount of the polymerization initiator used in the polymerization of the first resin particles and the second resin particles has an influence on the high temperature non-offset property in the fixing characteristics. By controlling the above configuration to a constant value, the wax dispersion state becomes uniform when forming the core particles, so that the effect of maintaining the high temperature non-offset property can be obtained. Moreover, since the dispersion state of the wax is uniform, the core particle surface also prevents the secondary aggregation of the core particles when the second resin particles are fused to the core particles by the action that the dispersion state of the wax is uniform. The effect is obtained, and further, the effect that the second resin fine particles can be adhered to the surface of the core particle in a short time can be obtained.

  When PS1 / PS2 is smaller than 0.25, the agglomeration property of the second resin particles becomes smaller than the agglomeration property of the core particles, the core particles agglomerate, and coarse particles are easily generated.

  When PS1 / PS2 is larger than 5.0, the agglomeration property of the second resin particles becomes larger than the agglomeration property of the core particles, and it becomes easy to produce coarse particles of the resin in which the second resin particles alone are agglomerated.

  The first configuration of the toner production method of the present invention is to produce a first resin particle dispersion in which the first resin particles are dispersed by emulsion polymerization of a monomer using a polymerization initiator in an aqueous medium. And at least a first resin particle dispersion in which first resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a wax particle dispersion in which wax particles are dispersed in an aqueous medium. Mixing and agglomerating to produce core particles, and adding the second resin particle dispersion in which the second resin particles are dispersed to the core particle dispersion containing the core particles, A method for producing a toner comprising the step of fusing a polymer to a core particle, wherein the addition amount of the polymerization initiator, the polymerization initiator, and the vinyl compound having an acid group shown in the first constitution of the toner of the present invention Including wax with a quantity and constant endothermic peak temperature It is formed.

  In the first configuration of the toner production method of the present invention, the colorant or wax particles are incorporated in the toner, but a trace amount of pigment and wax may be present on the outermost surface. If the wax accumulates in the electrophotographic apparatus, it adversely affects the image quality, so that problems such as a fused layer of second resin particles (sometimes referred to as a shell layer) are formed on the core particle surface. Can be prevented. Furthermore, from the viewpoint of enhancing the storage stability of the toner at a high temperature, resin particles having a high glass transition point (Tg (° C.)) are used, and from the viewpoint of ensuring offset resistance at a high temperature, high molecular weight emulsified resin fine particles. From the viewpoint of charging stability, resin particles containing a charge adjusting agent may be formed as a shell layer.

  As a preferred reaction vessel used for emulsion polymerization, mixing, and agglomeration, a glass-lined SUS vessel is not particularly limited as a stirring blade for stirring the dispersion, but a blade shape having a wide width in the depth direction ( A flat blade is effective. As the flat plate wing, Max Blend wing manufactured by Sumitomo Heavy Industries, Ltd., full zone wing manufactured by Shinko Pantech Co., Ltd., etc. are effective.

  FIG. 7 is a schematic diagram showing the configuration of the Max Blend wing, and FIG. 8 is a plan view seen from above. Moreover, the structure of a full zone blade | wing is shown in the schematic in FIG. 9, and the top view seen from the top in FIG. A shaft 301 is connected to a stirring motor (not shown). 302 is a stirring tank, 303 is a water surface of the liquid, 304 is a flat max blend blade, and 305 holes are provided in the blade to adjust the stirring strength of the liquid. Reference numeral 306 denotes a flat rectangular blade, and a stirring blade 307 is provided below the flat rectangular blade. The tip is bent about 130 degrees. Reference numeral 308 denotes the length of the stirring blade.

  The rotational speed of the stirring blade varies depending on the particle concentration in the dispersion and the target particle size, but is preferably 0.5 to 2.0 m / s. More preferably, it is 0.7-1.8 m / s, More preferably, it is 1.0-1.6 m / s. If the speed is too low, the particle size of the generated particles tends to be large and the particle size distribution tends to be widened. If the speed is too high, the aggregation of particles is hindered, the shape tends to be indefinite, and the generation of particles becomes difficult.

  In the first configuration of the toner production method of the present invention, as a preferable configuration for generating the core particles, the pH of the mixed dispersion is adjusted under a certain condition, a water-soluble inorganic salt is added, and the glass transition of the resin particles By heating the aqueous medium above the point temperature (Tg) and / or above the melting point of the wax, core particles in which at least a part of the first resin particles, colorant particles, and wax particles are aggregated can be generated. it can.

  It is preferable to adjust the pH of the mixed dispersion described above to a range of 9.5 to 12.2. Preferably, the pH is adjusted to 10.5 to 12.2, and more preferably the pH is adjusted to the range of 11.2 to 12.2. The pH can be adjusted by adding 1N NaOH. By setting the pH value to 9.5 or more, there is an effect of suppressing the phenomenon that the formed core particles become coarse. By setting the pH value to 12.2 or less, there is an effect of suppressing generation of free wax particles and colorant particles and facilitating uniform encapsulation of wax and colorant.

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

  When a resin particle dispersion uses a persulfate such as potassium persulfate as a polymerization initiator when polymerizing an emulsion polymerization resin, the residue is decomposed by the heat during the heat aggregation process to change the pH ( Therefore, after emulsion polymerization, heat treatment is performed for a certain time (preferably about 1 to 5 hours) at a certain temperature or more (preferably 80 ° C. or more in order to decompose the residue). It is preferable. The pH of the resin particle dispersion is preferably 4 or less, more preferably 1.8 or less.

  For the measurement of pH (hydrogen ion concentration), 10 ml of a sample to be measured is collected from the liquid tank using a pipette and placed in a beaker having the same volume. This beaker is immersed in cold water, and the sample is cooled to room temperature (30 ° C. or lower). Using a pH meter (Seven Multi: manufactured by METTLER TOLEDO), immerse the measurement probe in the sample cooled to room temperature. When the meter display is stable, read the value and use it as the pH value.

  After adjusting the pH of the mixed dispersion, the temperature of the mixed dispersion is raised while stirring the liquid. The temperature rising rate is preferably 0.1 to 10 ° C./min. Slow productivity decreases. If it is too early, the shape tends to advance too spherically before the particle surface becomes smooth.

  In the first configuration of the toner production method of the present invention, as a more preferable embodiment of core particle generation, the first resin particle dispersion, the colorant particle dispersion, and the wax particle dispersion are mixed in an aqueous medium. To produce a mixed dispersion. The mixed dispersion is heated, and after the liquid temperature of the mixed dispersion reaches a certain temperature, it is preferable to add a water-soluble inorganic salt as a flocculant to the mixed dispersion.

  As a method for generating the core particles, a method of preliminarily mixing the liquid mixture and the flocculant as described above, heating the mixed dispersion liquid at a temperature higher than the glass transition point of the resin, can be considered, Since the agglomeration reaction occurs slowly with the temperature rise time, it becomes difficult to produce particles having a small particle size and a narrow particle size distribution. Further, the aggregation state of the non-aggregated particles is likely to fluctuate, and the particle size distribution of the particles obtained by agglomeration and fusion becomes broad, or the surface properties of the finally obtained toner particles fluctuate. In particular, the particle size distribution and surface properties tend to be affected by the wax and colorant used.

  Furthermore, when using in combination with waxes having different melting points as will be described later, since the low melting point wax starts to melt first in the process of raising the temperature, aggregation of the low melting point waxes begins. When the temperature rises further, the melting of the high melting point wax starts and the aggregation starts, so that the low melting point wax particles and the aggregates of the high melting point waxes are easily generated. It tends to be in a dispersed state in which wax is unevenly distributed. Moreover, the particle size distribution of the core particles becomes wide and the shape tends to be non-uniform.

  Therefore, by adding the flocculant in a state where the temperature of the mixed dispersion reaches a certain level or more, the phenomenon in which the agglomeration slowly occurs with the temperature rising time is avoided, and the agglomeration reaction proceeds at once with the addition of the flocculant, and the short time. Core particles can be generated in time. Further, it is possible to form core particles having a small particle size and a narrow particle size distribution in which wax and colorant are uniformly dispersed.

  It is a more effective agglomeration condition for optimizing the polymerization initiator and the addition amount or the compounding amount of the vinyl compound having an acid group to express the optimum aggregability.

  In the first configuration of the method for producing a toner of the present invention, as a more preferable embodiment of core particle generation, a first resin particle dispersion liquid and colorant particles in which the first resin particles are dispersed in an aqueous medium are used. Mixing and aggregating the dispersed colorant particle dispersion to agglomerate resin particles and colorant particles to produce core particles, and dispersing the first resin particles in the core particle dispersion in which the core particles are dispersed It is also preferable to mix the first resin particle dispersion liquid and the wax particle dispersion liquid in which the wax particles are dispersed, and agglomerate the core particles, the first resin particles, and the wax particles to generate core 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 are mixed to produce a mixed liquid. Then, this mixed liquid is heated, and after the liquid temperature of the mixed liquid reaches a certain temperature, a water-soluble inorganic salt is added as a flocculant to the mixed dispersion, and the first resin particles and the colorant particles are aggregated. To produce nuclear particles. Thereafter, in a heated state, the first resin particle dispersion and the wax particle dispersion are added to the core particle dispersion in which the core particles are generated, and the core particles, the first resin particles, and the wax are aggregated. In this configuration, core particles are generated. This is a more effective agglomeration method for optimizing the polymerization initiator and the addition amount or the compounding amount of the vinyl compound having an acid group to express the optimum aggregability.

  By adding the flocculant when the temperature of the mixed solution reaches a certain level or more, the phenomenon in which the agglomeration occurs slowly with the temperature rise time is avoided, and the agglomeration reaction proceeds at once with the addition of the flocculant, and in a short time Core particles can be generated.

  Further, the contact between the wax particles and the colorant particles is performed via the first resin particles, so that the aggregation reaction is caused between the first resin particles and the colorant particles, and the reaction between the first resin particles and the wax particles. Because priority is given, it is likely that colorant particles and wax particles are easily incorporated uniformly into the core particles, and it is possible to form core particles with a small particle size and a narrow particle size distribution in which wax and colorant are uniformly encapsulated. It is.

  In addition, the core particle has a configuration in which a core particle portion in which the first resin particles and the colorant particles are aggregated, and a mixed particle of the first resin particles and the wax particles is fused to the surface of the core particles. It is preferable that By preventing the colorant particles from being exposed on the surface of the toner particles, the influence on the charging property can be minimized. By bringing the wax particles closer to the toner particle surface layer, the fixing property (non-offset temperature range) can be expanded. Further, it is also preferable to fuse the second resin particles to the surface of the core particles.

  In the first toner production method of the present invention, the flocculant to be added uses an aqueous solution containing a water-soluble inorganic salt having a constant water concentration, and the pH value of the aqueous solution containing the water-soluble inorganic salt is adjusted. After that, a mixed dispersion in which at least the first resin particle dispersion in which the first resin particles are dispersed, the colorant particle dispersion in which the colorant particles are dispersed, and the wax particle dispersion in which the wax particles are dispersed are mixed. It is also preferable to take the structure added in.

  It is considered that the aggregating action of the particles as the aggregating agent can be further enhanced by adjusting the pH value of the aqueous solution containing the aggregating agent to a constant value. It is preferable to have a certain relationship with the pH value of the mixed dispersion, and adding an aqueous flocculant solution with a different pH value to the mixed dispersion suddenly disturbs the pH balance of the liquid, so the core particles are coarse. Or wax dispersion tends to be non-uniform. In order to suppress such a phenomenon, it is effective to adjust the pH of the flocculant aqueous solution.

  When the mixed dispersion obtained by mixing the first resin particle dispersion, the colorant particle dispersion, and the wax particle dispersion is heat-treated, and the pH value of the mixed dispersion before the addition of the aqueous solution containing the flocculant is HG, aggregation occurs. The pH value of the aqueous solution containing the agent is preferably adjusted and added in the range of HG + 2 to HG-4. The range is preferably HG + 2 to HG-3, more preferably HG + 1.5 to HG-2, and still more preferably HG + 1 to HG-2.

  When an aqueous flocculant solution with a different pH value is added to the mixed dispersion, the pH balance of the liquid is abruptly disturbed, making the agglomeration reaction difficult to proceed with delay and the core or core particles becoming coarser. Cheap. In order to suppress such a phenomenon, it is effective to adjust the pH of the flocculant aqueous solution. Although the cause is unknown, a configuration in which the pH value of the aqueous solution containing the flocculant is lower than the pH value of the mixed dispersion is more preferable.

  By setting it as HG-4 or more, the aggregating action of the particles as the aggregating agent can be further enhanced, and the agglutination reaction can be accelerated. By setting it to HG + 2 or less, there is an effect of suppressing the phenomenon that the core or core particles become coarse or the particle size distribution becomes broad.

  The timing of adding the flocculant is such that the temperature of the mixed dispersion obtained by mixing the resin particle dispersion, the colorant particle dispersion, and the wax particle dispersion is equal to or higher than the melting point of the wax measured by the DSC method described later. A configuration in which an aggregating agent is added after reaching is preferable. By adding a flocculant in the state where the wax has started to melt, the agglomeration of the wax particles to be melted, the resin particles and the colorant particles proceeds all at once. It seems that melting progresses and particles are formed.

  At this time, even when the flocculant is added when the temperature of the mixed dispersion reaches the glass transition point of the first resin particles, the particles hardly aggregate and no particles are formed. When the temperature of the mixed dispersion reaches the specific temperature of the wax, the aggregation of the core particles proceeds by adding a flocculant, and then 0.5 to 5 hours, preferably 0.5 to 3 hours, more preferably Heat treatment for 1 to 2 hours generates core particles having a predetermined particle size distribution. The heat treatment may be performed while keeping the specific temperature of the wax, but it is preferably 80 to 95 ° C, more preferably 90 to 95 ° C. Aggregation reaction can be accelerated, leading to reduction of processing time.

  Furthermore, as described later, when two or more kinds of wax are included, it is preferable to adjust the specific temperature of the wax having the lower melting point. More preferably, the specific temperature of the wax having the higher melting point is adjusted. It is effective to add the flocculant in a temperature state where the melting of the wax particles is started.

  In addition, the first resin particle dispersion and the wax particle dispersion are added to the core particle dispersion in which the core particles obtained by aggregating the first resin particles and the colorant particles are added to the core particles and the first resin particles. In the configuration in which the core particles are produced by agglomerating the wax, the temperature of the mixed dispersion obtained by mixing the first resin particle dispersion and the colorant particle dispersion is described later as the timing of adding the aggregating agent. The flocculant is preferably added after reaching the melting point of the wax measured by the DSC method.

  This is to increase the temperature of the aqueous medium above the melting point of the wax in order to promote the adhesion of the first resin particles and wax particles subsequently dropped after the formation of the core particles to the core particles without changing the temperature of the aqueous medium. When the wax is dripped, melting of the wax is started, aggregation of the melting wax particles, the first resin particles, and the core particles proceeds at a stretch, and the heat treatment is continued to further increase the core particles. The formation of core particles in which the wax particles and the first resin particles are agglomerated progresses quickly, and it is possible to form particles having a small particle size and a narrow particle size distribution.

  Further, as described later, when two or more kinds of wax are included, it is preferable to adjust the specific temperature of the wax having the lower melting point. More preferably, the specific temperature of the wax having the higher melting point is adjusted.

  After the formation of core particles in which the first resin particles and the colorant particles are aggregated by adding the flocculant, the first resin particle dispersion in which the first resin particles are dispersed and the wax in which the wax particles are dispersed The particle dispersion is dropped, and the core particles are generated by aggregating the core particles, the first resin particles, and the wax particles. It is preferable to continue the temperature of the aqueous medium at this time without changing.

  The first resin particles used for the core particles and the first resin particles used when the core particles are subsequently added together with the wax particles may be resins having different compositions and thermal characteristics, but they are the same. The resin particles are preferred.

  When the total amount of resin particles contained in the core particles is 100, the resin particles used for the core particles preferably have a weight ratio of 30 to 80. By setting it to 30 or more, it is possible to generate core particles having a small particle size and a narrow particle size distribution due to aggregation of resin particles and colorant particles. If it is less than 30, resin particles or colorant particles that do not participate in aggregation tend to float.

  When the ratio of the resin particles at the time of core particle generation is 20 parts by weight or more, the resin particles and the wax particles are easily aggregated into the core particles, and the suspended resin particles and wax particles that do not participate in the core particle aggregation. Can be suppressed.

  The dropping of the resin particles and the wax particles is preferably a method of dropping separately, or a configuration in which a dispersion previously mixed at a constant rate is dropped at a constant dropping rate. If the total amount is added in a large amount, the temperature of the liquid may decrease, and aggregation may not progress uniformly.

  After dripping the predetermined amount of the resin particles and the wax particle dispersion, the heat treatment is continued for a predetermined time. The time is preferably 10 minutes to 2 hours. Preferably, in 10 to 30 minutes, after mixing uniformly to some extent and keeping the temperature stable, the pH of the mixed solution in which the core particles, the first resin particles, and the wax particles are mixed is adjusted to 7 or more and 10 or less. It is preferable to do. This is for the purpose of causing the first resin particles and the wax particles to adhere to the core particles. If the pH of the mixed solution is smaller than 7 or larger than 10, it becomes difficult to cause the first resin particles and wax particles to adhere to the core particles, and the core particles become coarse or the floating particles increase. It will be.

  After the pH adjustment, the heat treatment is continued for a predetermined time until a predetermined particle size and surface smoothness are obtained, whereby core particles are generated. The shape or surface smoothness of the core particles can be controlled by the heating time.

  The heating time is 0.5 to 5 hours, preferably 0.5 to 3 hours, more preferably 1 to 2 hours, whereby core particles having a predetermined particle size distribution are produced. The heat treatment may be performed while keeping the specific temperature of the wax, but it is preferably 80 to 95 ° C, more preferably 90 to 95 ° C. Aggregation reaction can be accelerated, leading to reduction of processing time.

  The flocculant preferably has a structure in which 1 to 200 parts by weight are dropped with respect to 100 parts by weight of the core particles in which the first resin particles, the colorant particles and the wax particles are agglomerated. Preferably it is 20-150 weight part, More preferably, it is 30-100 weight part, More preferably, it is 40-80 weight part. When the amount is too small, the agglutination reaction does not proceed. When the amount is too large, the generated particles tend to be coarse. As the flocculant, it is also preferable to use a water-soluble inorganic salt adjusted to a certain concentration with ion-exchanged water or the like. The concentration of the aqueous solution is preferably 5 to 50 wt%.

  The flocculant may be added all at once, but it is also preferable to add the flocculant dropwise over a period of 1 to 120 minutes. Although it may be divided, continuous dripping is preferred. By dropping the flocculant at a constant rate into the heated mixed dispersion, the flocculant gradually and uniformly mixes with the entire mixed dispersion in the reaction kettle, and the uneven distribution makes the particle size distribution broad. It has the effect of suppressing the generation of suspended particles of wax and colorant. Moreover, the rapid fall of the liquid temperature of a mixed dispersion liquid can be suppressed. Preferably it is 5-60 min, More preferably, it is 10-40 min, More preferably, it is 15-35 min. For 1 min or longer, the shape of the core particles does not proceed to an indefinite shape, and a stable shape is obtained. By setting it to 120 min or less, the effect of suppressing the presence of particles floating alone due to poor aggregation of the colorant and wax particles can be obtained.

  In the configuration in which the second resin particles are fused to the core particles, the amount of the generated core particles is 100 parts by weight as a dropping condition of the second resin particle dispersion in the core particle dispersion in which the generated core particles are dispersed. On the other hand, a structure in which the dropping rate of the second resin particles is generated by dropping under a dropping condition of 0.14 parts by weight / min to 2 parts by weight / min is preferable.

  Preferably it is 0.15 weight part / min-1 weight part / min, More preferably, it is 0.2 weight part / min-0.8 weight part / min.

  The second resin particle dispersion is added as it is when the core particles reach a predetermined particle size. The addition is preferably performed by dropping sequentially. When the predetermined total amount is added all at once or exceeds 2 parts by weight / min, only the second resin particles tend to aggregate and the particle size distribution tends to be broad. In addition, when the input amount increases, the temperature of the liquid rapidly decreases and the agglomeration reaction stops, and a part of the second resin particles are suspended in the aqueous system without being attached to the core particles. It may remain.

  On the other hand, when the amount is less than 0.14 parts by weight / min, the amount of the second resin particles adhering to the core particles is reduced, and when the heating is continued, the core particles are aggregated. , The particles are coarse and the particle size distribution tends to be broad.

  By optimizing the dropping conditions of the second resin particle dispersion, it is possible to prevent the aggregation of the core particles and the aggregation of only the second resin particles, and to generate particles having a small particle size and a narrow particle size distribution. To do.

  A configuration in which the second resin particle dispersion is dropped is preferable so that the fluctuation of the liquid temperature of the core particle dispersion in which the produced core particles are dispersed is suppressed to within 10%.

  In the configuration in which the second resin particles are fused to the core particles, the second resin particle dispersion in which the second resin particles are dispersed is added to the core particle dispersion, and the heat treatment is performed on the core particles. When forming the resin fusion layer for fusing the second resin particles to the core particles, it is preferable to add after adjusting the pH value of the second resin particle dispersion to a certain range. In particular, it is more effective to combine with the dropping condition of the second resin particle dispersion.

  By adding the second resin particle dispersion without disturbing the pH balance of the liquid, the generation of floating second resin particles that do not participate in fusion is suppressed, and the second resin particles on the core particles are suppressed. The aim is to improve the adhesion or to suppress the occurrence of secondary aggregation between the core particles.

  As a condition of the pH value of the second resin particle dispersion, when the pH value of the core particle dispersion in which the core particles are dispersed is HS, the pH of the second resin particle dispersion in which the second resin particles are dispersed Is preferably added in the range of HS + 4 to HS-4. The range is preferably HS + 3 to HS-3, more preferably HS + 3 to HS-2, and still more preferably HS + 2 to HS-1.

  When the second resin particle dispersion having a different pH value is added to the core particle dispersion, the pH balance of the liquid is suddenly disturbed, so that the second resin particles do not adhere to the core particles. Or it will result in making a production | generation particle coarse by generation | occurrence | production of the secondary aggregation of core particles. In order to suppress such a phenomenon, it is effective to adjust the pH of the second resin particle dispersion.

  With this configuration, the generation of floating particles of the second resin particles is reduced, and the second resin particles can be uniformly attached to the surface of the core particles. Further, the adhesion to the core particles is promoted, the fusion processing time is shortened, and the productivity can be improved. In addition, when the second resin particles are fused to the core particles, rapid coarsening of the particles can be prevented, and a sharp particle size distribution can be formed with a small particle size. By setting the pH value to HS + 4 or less, it is possible to suppress the tendency of the particles to become coarse and the particle size distribution to become broad. By setting the pH value to HS-4 or higher, the adhesion of the second resin particles to the core particles is advanced, and the fusion treatment can be performed in a single time. Further, an effect of suppressing the phenomenon in which the second resin particles remain floating in the water system without being fused and the liquid remains cloudy and the reaction does not proceed can be obtained.

  In the configuration in which the second resin particles are fused to the core particles, the pH value of the second resin particle dispersion in which the second resin particles added to the core particle dispersion are dispersed is the core particles in which the core particles are dispersed. Regardless of the pH value of the dispersion, a constitution in which it is adjusted to be added in the range of 3.5 to 11.5 is preferable. Preferably it is 5.5-11.5, More preferably, it is 6.5-11, More preferably, the range of 6.5-10.5 is preferable.

  By adjusting the pH to 3.5 or more, it is possible to suppress the phenomenon that the second resin particles adhere to the aggregated particle surface, the second resin particles float in the aqueous system, and the liquid remains cloudy. By setting the pH value to 11.5 or less, it is possible to suppress the tendency of the generated particles to become coarse.

  Moreover, when the pH of the second resin particle dispersion in which the second resin particles are dispersed is adjusted to be higher in the range of HS to HS + 4, the state of occurrence of secondary aggregation between the core particles can be adjusted, It is also possible to control the shape of the toner base particles finally produced when the second resin particles are added.

  This can be realized by adjusting the pH of the second resin particle dispersion to be added to a value close to or higher than the pH of the core particle dispersion in which the core particles are dispersed. By adjusting to this range, the shape of the particles can be controlled from a spherical shape to a potato shape by partially aggregating the core particles with each other during the adhesion and melting of the second resin particles to the core particles. it can.

  This is because there is a strong tendency for the shape of the toner to be determined by matching with the development, transfer, and cleaning process, and when emphasizing the cleaning properties of the photoreceptor or transfer belt, the toner shape should be potato rather than spherical. The degree of margin spreads. When emphasizing transferability, the toner shape is made close to a sphere to increase the transfer efficiency.

  In the configuration of the toner or toner manufacturing method of the present invention, a configuration in which the dispersant for dispersing the colorant is a surfactant mainly composed of a nonionic surfactant is preferable.

  Further, a configuration in which the dispersant for dispersing the wax is a surfactant mainly composed of a nonionic surfactant is preferable.

  In addition, the main component of the surfactant used in preparing the first resin particle dispersion for forming the core particles is a nonionic surfactant, and the main component of the surfactant used in the colorant dispersion is A configuration in which the main component of the surfactant used in the wax dispersion is a nonionic surfactant is a nonionic surfactant. Of the surfactants used in the colorant dispersion and the wax dispersion, it is preferable that the nonionic surfactant has 50 to 100 wt% with respect to the entire surfactant. More preferably, it is preferable to have 60-100 wt%, and still more preferably 60-90 wt%.

  The surfactant used for the first resin particle dispersion is a mixture of a nonionic surfactant and an ionic surfactant, and the main component of the surfactant used for the wax dispersion is only a nonionic surfactant. The configuration is also preferable.

  The surfactant used in the first resin particle dispersion is a mixture of a nonionic surfactant and an ionic surfactant, and the main component of the surfactant used in the colorant dispersion is only a nonionic surfactant. Also preferred is a constitution in which the main component of the surfactant used in the wax dispersion is only a nonionic surfactant.

  With this configuration, it is possible to eliminate the presence of suspended colorant particles and wax particles that are not involved in agglomeration in an aqueous system, and to produce cores or core particles having a small particle size and a uniform and sharp particle size distribution.

  The surfactant of the resin particle dispersion in which the first resin particles are dispersed is a mixture system of a nonionic surfactant and an ionic surfactant, and the nonionic surfactant is distributed over the entire surfactant. On the other hand, it is preferable to have 50 to 95 wt%. More preferably, it is 55-90 wt%, More preferably, it is preferable to have 60-85 wt%. By setting it to 50 wt% or more, the phenomenon that the particle size distribution of the produced core particles is expanded can be suppressed. By setting it to 95 wt% or less, there is an effect of stabilizing the dispersion of the resin particles themselves in the resin particle dispersion. As the ionic surfactant, an anionic surfactant is preferable.

  Moreover, it is also preferable that the surfactant used for the second resin particle dispersion is a mixture of a nonionic surfactant and an ionic surfactant.

  With this configuration, it is possible to eliminate the presence of the suspended second resin fine particles that are not involved in aggregation in the aqueous system, and to shorten the processing time when the second resin particles are fused to the surface of the core particles. Then, the coarsening of the core particles can be suppressed, and particles having a small particle size and a sharp particle size distribution can be generated. Further, aggregation of only the resin particles can be suppressed, and particles aggregated only with the resin particles can be further prevented from adhering to the surface of the core particles, and variation in surface properties of the finally obtained toner base particles can be suppressed. .

  When the surfactant of the resin particle dispersion in which the second resin particles are dispersed is a mixed system of a nonionic surfactant and an ionic surfactant, the nonionic surfactant is distributed over the entire surfactant. On the other hand, it is preferable to have 50 to 95 wt%. More preferably, it is 55-90 wt%, More preferably, it is preferable to have 60-85 wt%. By setting it to 50 wt% or more, aggregation of only the resin particles can be suppressed, and particles aggregated with only the resin particles can be further prevented from adhering to the surface of the core particles, thereby suppressing variations in the surface properties of the toner particles. can do. By setting it to 95 wt% or less, there is an effect of stabilizing the dispersion of the resin particles themselves in the resin particle dispersion. As the ionic surfactant, an anionic surfactant is preferable.

  When the first resin particles, colorant particles, wax particles, and second resin particles having such a configuration are used and an aggregating agent is allowed to act in an aqueous medium, the first first fat particles start to aggregate. To make a nucleus. Next, the colorant particles start to aggregate around the cores of the resin particles to produce resin particles and colorant particle particles. The particles are wrapped in such a manner that the wax particles aggregate and the colorant particles are sandwiched with the resin particles. The first resin particles are usually added several times or more in weight concentration as compared to the colorant particles and wax particles. Therefore, the nuclei of only the resin particles also aggregate on the wax particles, and the outermost surface is covered with the resin. It is estimated that broken core particles are formed.

  If the surface of the core particle is covered with the first resin, when the second resin particle is further added and the second resin fusion layer is formed on the surface of the core particle, whether the resin is compatible with each other is short. It is estimated that the second resin particles can be attached to the surface of the core particles over time. By such a mechanism, the presence of floating colorant particles and wax particles that are not involved in aggregation in an aqueous system can be eliminated, and core particles having a small particle size and a uniform and sharp particle size distribution can be formed. Further, it is considered that the second resin particles can be prevented from floating and the second resin particles can be uniformly fused in a short time to form a toner having a small particle size and a narrow particle size distribution.

  In the configuration of the toner or toner manufacturing method of the present invention, the resin particle dispersion is dispersed with a surfactant mixed with a nonionic surfactant and an anionic surfactant, and the colorant particles and the wax particle dispersion are dispersed. The nonionic surfactant is preferably dispersed with a nonionic surfactant, and the average number of moles of ethylene oxide added to the nonionic surfactant used for dispersing the wax particles is the nonionic surfactant used for dispersing the colorant particles. The structure which is larger than the average ethylene oxide addition mole number is preferable. This is because the nonionic surfactant having a smaller average number of moles of ethylene oxide added tends to increase the cohesiveness to the coagulant.

  The average number of moles of ethylene oxide added to the nonionic surfactant used for dispersing the colorant particles is preferably 18 to 33. More preferably, it is 20-30, More preferably, it is 20-26.

  When the average ethylene oxide addition mole number of the nonionic surfactant is smaller than 18, the coagulability of the colorant particles with respect to the aggregating agent becomes too high, and grows into large particles before being surrounded by the resin. It will not be captured. On the other hand, when the average ethylene oxide addition mole number of the nonionic surfactant is larger than 33, the aggregation with respect to the aggregating agent becomes too low, and the colorant particles do not agglomerate and exist in the reaction solution as fine particles. The toner particles are not taken into the toner particles.

  A configuration in which the nonionic surfactant used for dispersing the colorant particles or wax particles contains a plurality of nonionic surfactants is also preferable. By itself, even if the average ethylene oxide addition mole number of the nonionic surfactant is not in the range of 20 to 30, the weight average ethylene oxide addition mole number of the plurality of nonionic surfactants may be in the range of 20 to 30. That's fine.

Here, the aggregating property of each particle with respect to the aggregating agent is evaluated by the concentration of the aggregating agent when the particle dispersion is dropped into an aggregating agent aqueous solution of various concentrations (for example, magnesium sulfate aqueous solution) and the particles are aggregated to a certain size. The higher the cohesiveness of the particles to the flocculant, the more the particles will aggregate at a lower flocculant concentration.
When the aggregating agent is allowed to act in the solution using the resin particles and the colorant particles having such a configuration, first, the resin particles using the anionic surfactant start aggregating to form nuclei. Next, colorant particles using a nonionic surfactant having a small average number of moles of added ethylene oxide begin to aggregate around the nuclei of the resin particles to form the core particles of resin particles and colorant particles.

  Finally, it is presumed that wax particles using a nonionic surfactant having a large average number of moles of added ethylene oxide flocculate so as to enclose the core particles together with the resin particles to form core particles.

  Resin particles are usually added several times or more in weight concentration as compared with colorant particles and wax particles, so that the core of the resin particles only aggregates on the wax particles and the outermost surface is covered with resin. Is estimated to be formed. It is considered that the phenomenon in which the colorant particles and the wax particles that are not taken into the core particles and are not added to the aggregation in the core particle dispersion liquid can be avoided.

  The amount of the nonionic surfactant with respect to the colorant particles is desirably 10 to 20 parts by weight with respect to 100 parts by weight of the colorant particles in terms of weight stability from the viewpoint of dispersion stability.

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

  As the polymerization initiator, persulfates such as potassium persulfate, ammonium persulfate, sodium persulfate and the like are preferable materials.

  A water-soluble inorganic salt is selected as the flocculant, and examples thereof 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. It is also preferable to use it after adjusting to a constant concentration with ion-exchanged water or the like.

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

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

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

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

Specific examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate and the like.
Specific examples of the cationic surfactant include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like. These may be used individually by 1 type and may use 2 or more types together.

[resin]
Examples of the resin particles of the present invention include thermoplastic binder resins. 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 and 2-ethylhexyl methacrylate, carboxyl groups of acid groups such as acrylic acid, methacrylic acid, maleic acid and fumaric acid Homopolymers such as unsaturated polyvalent carboxylic acid monomers having a dissociation group, copolymers obtained by combining two or more of these monomers, or mixtures thereof.

The solid content of the resin particles in the resin particle dispersion is usually 5 to 50% by weight, preferably 10 to 40% by weight.
[First resin]
The glass transition point of the first resin particles constituting the core particles is 45 ° C. to 60 ° C. in order to eliminate the presence of floating particles in the formation of the core particles by the agglomeration reaction with the wax and the colorant and to form particles with a narrow particle size distribution. A structure having a softening point of 90 ° C. to 140 ° C. is preferable. More preferably, the glass transition point is 45 ° C to 55 ° C, the softening point is 90 ° C to 135 ° C, and still more preferably, the glass transition point is 45 ° C to 52 ° C, and the softening point is 90 ° C to 130 ° C. preferable.

  Moreover, as a preferable structure of the first resin particles, the weight average molecular weight (Mw) is 10,000 to 60,000, and the ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.5 to 6. Some configurations are preferred. It is preferable that the weight average molecular weight (Mw) is 10,000 to 50,000 and the ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.5 to 3.9. More preferably, the weight average molecular weight (Mw) is 10,000 to 30,000, and the ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.5 to 3. The resin particles are preferably 60 wt% or more, more preferably 70 wt% or more, and still more preferably 80 wt% or more based on the total toner resin.

  With the configuration including the first resin particles and the wax particles described later, it is possible to prevent the core particles from becoming coarse and to efficiently generate particles having a narrow particle size distribution. In addition, low-temperature fixability is possible, and further, there is an effect that the image gloss can be made constant by reducing the change of the image gloss to the fixing temperature. Normally, since the glossiness of an image increases as the fixing temperature rises, the glossiness of the image fluctuates due to fluctuations in the fixing temperature, and it is necessary to control the fixing temperature severely. However, with this configuration, the effect of little fluctuation in image gloss can be obtained even when the fixing temperature varies.

When the glass transition point of the first resin particles is lower than 45 ° C., the core particles are coarsened. Storage stability and heat resistance are reduced. When it is higher than 60 ° C., the low-temperature fixability deteriorates. When Mw is smaller than 10,000, the core particles are coarsened. Storage stability and heat resistance are reduced. If it exceeds 60,000, the low-temperature fixability deteriorates. When Mw / Mn is larger than 6, the shape of the core particles is not stable, tends to be indefinite, and irregularities remain on the particle surface, resulting in poor surface smoothness.
[Second resin]
As the constitution of the second resin particles, the glass transition point is 55 ° C to 75 ° C, the softening point is 140 ° C to 180 ° C, and the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is 50,000 to 50. It is preferable that the ratio Mw / Mn of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is 2 to 10. More preferably, the glass transition point is 60 ° C to 70 ° C, the softening point is 145 ° C to 180 ° C, the Mw is 80,000 to 500,000, and the Mw / Mn is 2 to 7. More preferably, the glass transition point is 65 ° C to 70 ° C, the softening point is 150 ° C to 180 ° C, Mw is 120,000 to 500,000, and Mw / Mn is 2 to 5.

The aim is to improve the durability, high-temperature offset resistance, and separability by promoting thermal fusion of the core particle surfaces and increasing the softening point. If the glass transition point of the second resin particles is lower than 55 ° C., secondary aggregation tends to occur. Moreover, storage stability deteriorates. If it is higher than 75 ° C., the heat fusion property to the surface of the core particles is deteriorated and the uniform adhesion is lowered. When the softening point of the second resin particles is lower than 140 ° C., durability, high-temperature offset resistance and separability are deteriorated. When it is higher than 180 ° C., glossiness and translucency are lowered. By making Mw / Mn small and making the molecular weight distribution close to monodisperse, it is possible to uniformly heat-bond the second resin particles to the surface of the core particles. When the Mw of the second resin particles is smaller than 50,000, durability, high temperature non-offset property, and paper separation property are deteriorated. If it exceeds 500,000, the low-temperature fixability, glossiness, and translucency are lowered.
[GPC]
The molecular weights of the resin, wax, and toner are values measured by gel permeation chromatography (GPC) using several types of monodisperse polystyrene as standard samples. The apparatus is HLC8120GPC series manufactured by Tosoh Corporation, the column is TSKgel super HM-H H4000 / H3000 / H2000 (6.0 mm ID-150 mm × 3), eluent THF (tetrahydrofuran), flow rate 0.6 mL / min, sample concentration 0 .1%, injection volume 20 μL, detector RI, measurement temperature 40 ° C., pre-measurement treatment was performed by dissolving the sample in THF and leaving it to stand overnight, followed by filtration with a 0.45 μm membrane filter. The resin component from which the additive has been removed is measured. The measurement conditions are conditions in which the molecular weight distribution of the target sample is included in a range in which the logarithm of the molecular weight and the count number are linear in a calibration curve obtained with several types of monodisperse polystyrene standard samples.
[Flow tester]
The softening point of the binder resin was about 9.8 × 10 with a plunger while heating a sample of 1 cm ^{3 at} a heating rate of 6 ° C./min with a constant-load extrusion type capillary rheometer flow tester (CFT500) manufactured by Shimadzu Corporation. Applying a load of ⁵ N / m ² and extruding from a die with a diameter of 1 mm and a length of 1 mm, the temperature at which the piston stroke begins to rise is determined from the relationship between the temperature rise characteristic of the plunger stroke and temperature. The flow starting temperature (Tfb), 1/2 of the difference between the lowest value of the piston stroke characteristic curve and the flow ending point, is obtained, and the temperature at the point where the lowest value of the curve is added is the melting temperature in the 1/2 method ( Softening point Ts ° C.).
[DSC]
The glass transition point of the resin was measured 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 measuring the thermal history by raising the temperature at a heating rate of 10 ° C./min, the tangent line indicating the maximum slope between the base line extension below the glass transition point and the peak rising portion to the peak apex. Says the temperature of the intersection with.
[wax]
Low temperature fixing property, high temperature non-offset property, or improvement of the separation property of the transfer medium such as copy paper on which the toner melted at the time of fixing is heated, etc. It is also preferable to add a plurality of waxes in order to expand the margin of the fixing characteristics that contradict the storage stability of the toner and to improve its functionality.

  In addition to optimizing the addition amount of the polymerization initiator and the compounding amount of the vinyl compound having an acid group, the fixing characteristics can be optimally expressed by the configuration of the specific wax composition.

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

  In the configuration of the toner or the toner production method of the present invention, as the first configuration preferable as the wax, the wax includes at least the first wax and the second wax, and the endothermic peak temperature of the first wax by the DSC method. A configuration in which the melting point Tmw1 (° C.) is 50 to 90 ° C. and the endothermic peak temperature (melting point Tmw2 (° C.)) of the second wax by the DSC method is preferably 80 to 120 ° C. Tmw1 is preferably 55 to 85 ° C, more preferably 60 to 85 ° C, and still more preferably 65 to 75 ° C. When Tmw1 is smaller than 50 ° C., the storage stability is deteriorated. When it is higher than 90 ° C., the low-temperature fixability and color glossiness are not improved. Tmw2 is more preferably 85 to 100 ° C, further preferably 90 to 100 ° C. When Tmw2 is smaller than 80 ° C., the high temperature non-offset property and the paper separation property are weakened. When it exceeds 120 ° C., the cohesiveness of the wax decreases, and free particles that do not aggregate in the aqueous system increase.

  In the first configuration preferable as the wax, when the toner particles are formed by aggregating the waxes having different melting points with the resin and the colorant in the aqueous system, the first wax and the second wax are separately emulsified and dispersed. When the dispersion is mixed with the resin dispersion and the colorant dispersion and heated and agglomerated, due to the difference in the melting rate of the wax, the presence of particles floating without the wax being taken into the core particles or the aggregation of the core particles In some cases, the particle size distribution tends to become broad without progressing, the wax is uniformly taken into the toner, and it becomes difficult to form particles having a small particle size and a narrow particle size distribution. In addition, the problem that the generated particles rapidly become coarse during the shell formation in which the second resin is melted and adhered to the core particles cannot be sufficiently solved.

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

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

  As a third configuration preferable as a wax, the wax contains at least a first wax and a second wax, and the first wax contains a wax having an iodine value of 25 or less and a saponification value of 30 to 300, A configuration in which the second wax includes an aliphatic hydrocarbon wax is preferable.

  In the second configuration and the third configuration preferable as the wax, the endothermic peak temperature (melting point Tmw1 (° C.)) of the first wax by DSC method is 50 to 90 ° C., preferably 55 to 85 ° C., more preferably 60-85 degreeC, More preferably, it is 65-75 degreeC. When the temperature is lower than 50 ° C., the storage stability and heat resistance of the toner deteriorate. When it exceeds 90 ° C., the cohesiveness of the wax decreases, and free particles that do not aggregate in the aqueous system increase. Also, low temperature fixability and glossiness are not improved.

  Further, in the second configuration and the third configuration preferable as the wax, the endothermic peak temperature (melting point Tmw2 (° C.)) of the second wax by DSC method is 80 to 120 ° C., preferably 85 to 100 ° C. Preferably it is 90-100 degreeC. When the temperature is lower than 80 ° C., the storage stability is deteriorated, and the high temperature non-offset property and the paper separation property are weakened. When it exceeds 120 ° C., the cohesiveness of the wax decreases, and free particles that do not aggregate in the aqueous system increase. In addition, low-temperature fixability and color translucency are hindered.

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

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

  Therefore, by using a wax composed of the second wax containing the specific aliphatic hydrocarbon wax and the first wax containing the specific wax as the wax, the aliphatic hydrocarbon wax becomes the core. The presence of particles floating without being taken into the particles can be suppressed, the particle size distribution of the core particles can be prevented from becoming broad, and the phenomenon that the core particles can be rapidly coarsened when shelled can be suppressed. .

  During the heat aggregation, the first wax is compatibilized with the resin, so that the aggregation with the aliphatic hydrocarbon wax resin is promoted and uniformly incorporated, and the generation of suspended particles can be prevented. I think that the. Furthermore, the first wax tends to be improved in low-temperature fixability due to partial progress of compatibilization with the resin. In addition, since the aliphatic hydrocarbon wax is less likely to be compatibilized with the resin, this wax can exhibit a function of improving the high temperature offset property and the separation property from paper. That is, the first wax has a function as a dispersion aid during the emulsification dispersion treatment of the aliphatic hydrocarbon wax, and further has a function as a low-temperature fixing aid.

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

  Further, in the first, second, or third configuration preferable as a wax, when the weight ratio of the first wax to 100 parts by weight of the wax in the wax particle dispersion is ES1, and the weight ratio of the second wax is FT2, FT2 / ES1 is preferably 0.2 to 10. More preferably, it is the range of 1-9. More preferably, it is the range of 1.5-5. If it is less than 0.2, that is, if the first wax weight ratio is too large, the effect of high temperature non-offset property cannot be obtained, and the storage stability deteriorates. If it is larger than 10, that is, if the weight ratio of the second wax is too large, low-temperature fixing cannot be realized, and the above-mentioned problem that the core particles tend to become coarse cannot be solved. Furthermore, when the blending ratio of FT2 is 50 wt% or more, preferably 60 wt% or more, it is a well-balanced ratio in which low-temperature fixability, high-temperature storage stability and fixing high-temperature non-offset property can be compatible.

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

  Therefore, it is preferable that the wax particle dispersion is prepared by mixing, emulsifying and dispersing the first wax and the second wax with a surfactant mainly composed of a nonionic surfactant.

  By mixing and dispersing with a surfactant mainly composed of a nonionic surfactant to prepare an emulsified dispersion, aggregation of the wax itself is suppressed and dispersion stability is improved. In the production of core particles of these waxes with a resin and a colorant dispersion, wax is not liberated and particles having a small particle size and a narrow particle size distribution can be formed.

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

  In the first, second, or third configuration preferable as the wax, a configuration in which Tmw2 is higher than Tmw1 by 5 ° C. or more and 50 ° C. or less is preferable. More preferably, the temperature is 10 ° C. or higher, 40 ° C. or lower, more preferably 15 ° C. or higher, and 35 ° C. or lower. The function of the wax can be efficiently separated, and there is an effect of satisfying both low temperature fixing property, high temperature non-offset property and paper separation property. When the temperature is lower than 5 ° C., it is difficult to achieve the effects of achieving both low-temperature fixability, high-temperature non-offset property, and paper separation failure. When the temperature is higher than 50 ° C., the first wax and the second wax are easily phase-separated and cannot be uniformly taken into the toner particles.

  The preferred first wax comprises at least one ester composed of at least one of a higher alcohol having 16 to 24 carbon atoms and a higher fatty acid having 16 to 24 carbon atoms. By using this wax, it is possible to suppress the presence of particles that are not incorporated into the core particles and the aliphatic hydrocarbon wax to float, to suppress the particle size distribution of the core particles from being broadened, and to form a shell. In addition, it is possible to alleviate the phenomenon that the core particles are coarsened rapidly. Moreover, low temperature fixing can be promoted. The combined use with the second wax prevents high-temperature non-offset property and paper separability as well as coarse particle size, and makes it possible to produce toner base particles including core particles having a small particle size and a narrow particle size distribution.

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

    Specifically, esters comprising a higher alcohol having 16 to 24 carbon atoms and a higher fatty acid having 16 to 24 carbon atoms such as stearyl stearate, palmityl palmitate, behenyl behenate or stearyl montanate, butyl stearate, behen Esters composed of a higher fatty acid having 16 to 24 carbon atoms such as isobutyl acid, propyl montanate or 2-ethylhexyl oleate and a lower monoalcohol, montanic acid monoethylene glycol ester, ethylene glycol distearate, monostearate glyceride, 1 carbon number such as monobehenic acid glyceride, tripalmitic acid glyceride, pentaerythritol monobehenate, pentaerythritol dilinoleate, pentaerythritol trioleate or pentaerythritol tetrastearate Esters comprising -24 higher fatty acids and polyhydric alcohols, or diethylene glycol monobehenate, diethylene glycol dibehenate, dipropylene glycol monostearate, distearic acid diglyceride, tetrastearic acid triglyceride, hexabehenic acid tetraglyceride or decastearin Preferable examples include esters composed of a higher fatty acid having 16 to 24 carbon atoms such as acid decaglyceride and a polyhydric alcohol multimer. These waxes may be used alone or in combination of two or more.

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

  Further, the preferred first wax composition includes a wax having an iodine value of 25 or less and a saponification value of 30 to 300. By using in combination with the second wax, coarsening of the particle size is prevented, and core particles having a small particle size and a narrow particle size distribution can be generated. By defining the iodine value, the effect of improving the dispersion stability of the wax can be obtained, the core particles can be formed uniformly with the resin and the colorant particles, and the core particles with a small particle size and a narrow particle size distribution can be formed. To do. The iodine value is preferably 20 or less, the saponification value is 30 to 200, more preferably the iodine value is 10 or less, and the saponification value is 30 to 150.

  On the other hand, if the iodine value is greater than 25, the dispersion stability is too good, the core particles cannot be formed uniformly with the resin and the colorant particles, and the floating particles of the wax tend to increase. The particle size distribution tends to be high. If the floating particles remain in the toner, filming of the photoreceptor or the like is caused. The repulsion due to the charge effect of the toner is difficult to be mitigated during the multi-layer transfer of the toner in the primary transfer. When the saponification value is less than 30, the presence of unsaponifiable matter and hydrocarbons increases, and it becomes difficult to form uniform core particles having a small particle size. The filming of the photosensitive member and the charging property of the toner are deteriorated, and the charging property during continuous use is reduced. When it becomes larger than 300, suspended matter in the water system increases. The repulsion due to the charge action of the toner is less likely to be alleviated. In addition, fog and toner scattering increase.

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

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

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

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

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

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

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

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

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

  Furthermore, an esterification reaction product of 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.

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

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

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

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

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

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

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

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

  Measurement of endothermic peak temperature (melting point ° C), onset temperature and endothermic amount by DSC method (differential scanning calorimetry measurement method) of wax, manufactured by TA Instruments Co., Ltd., Q100 type (a genuine electric refrigerator is used for cooling) , Set the measurement mode to “standard”, purge gas (N2) flow rate of 50 ml / min, power on, set the temperature in the measurement cell to 30 ° C., leave it in that state for 1 hour, then use pure aluminum The sample to be measured was placed in the pan as a sample amount of 10 mg ± 2 mg, and the aluminum pan containing the sample was put into the measuring instrument. Thereafter, the temperature was maintained at 5 ° C. for 5 minutes, and the temperature was increased to 150 ° C. at a temperature increase rate of 1 ° C./min. For the analysis, “Universal Analysis Version 4.0” attached to the apparatus was used.

  In the graph, the horizontal axis shows the temperature of an empty aluminum crimp pan, the vertical axis shows the heat flow, the temperature at which the endothermic curve starts to rise from the baseline is the onset temperature, and the endothermic curve peak value is the endothermic peak temperature. (Melting point).

  In general, when measuring by the DSC method, in order to erase the thermal history of the sample, once the temperature is raised and cooled, the temperature is raised again and the endotherm at that time is measured. Since the structure was predicted to change, the heating process and cooling process for eliminating the thermal history were omitted.

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

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

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

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

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

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

  As the second wax, fatty acid hydrocarbon waxes such as polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax, microcrystalline wax, paraffin wax, and Fischer-to-push wax can be suitably used.

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

  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% diameter (PR84) for the volume particle diameter cumulative distribution when integrated from the small particle diameter side. It is preferable that emulsified and dispersed to a size of 400 nm or less and PR84 / PR16 of 1.2 to 2.0, with particles of 200 nm or less being 65% by volume or more and particles exceeding 500 nm being 10% by volume or less.

  Preferably, the 16% diameter (PR16) is 20 to 100 nm, the 50% diameter (PR50) is 40 to 160 nm, the 84% diameter (PR84) is 260 nm or less, and 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, the 84% diameter (PR84) is 220 nm or less, and PR84 / PR16 is 1.2 to 1.8. It is preferable that particles of 130 nm or less are 65 volume% or more, and particles exceeding 300 nm are 10 volume% or less.

  When the resin particle dispersion, the colorant particle dispersion, and the wax particle dispersion are mixed and aggregated to form aggregated particles, the 50% diameter (PR50) is 40 to 300 nm, and the wax is resin particles. It is easy to be taken in between, preventing aggregation between the waxes itself, and uniform dispersion. Particles that are taken into the resin particles and float in the water can be eliminated.

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

  Particles with PR16 greater than 200 nm, 50% diameter (PR50) greater than 300 nm, PR84 greater than 400 nm, PR84 / PR16 greater than 2.0, less than 200 nm particles less than 65% by volume and greater than 500 nm When the amount exceeds 10% by volume, the wax is difficult to be taken in between the resin particles, and the agglomeration of only the waxes tends to occur frequently. In addition, particles that are not taken into the resin particles and float in water tend to increase. When the agglomerated particles are heated in an aqueous system to obtain fused agglomerated particles, the molten resin particles are less likely to include the melted wax particles, and the wax is less likely to be included in the resin. In addition, when the resin is adhered and fused, the amount of wax that is exposed and released on the surface of the toner base increases, filming on the photoconductor, increased spent on the carrier, handling characteristics during development, and development memory are generated. It becomes easy.

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

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

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

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

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

When the melting point of the wax is high, a molten liquid is prepared by heating in a high pressure state. Also, the wax is dissolved in an oily solvent. This solution is obtained by dispersing fine particles in water together with a surfactant using the disperser shown in FIGS. 3, 4, 5 and 6, and then evaporating the oily solvent by heating or decompressing.
The particle size can be measured using a Horiba laser diffraction particle size measuring device (LA920), a Shimadzu laser diffraction particle size measuring device (SALD2100), or the like.
[Pigment]
Examples of the colorant (pigment) used in the present embodiment include C.I. I. Blue dyes and pigments of phthalocyanine and derivatives thereof such as CI Pigment Blue 15: 3 can be preferably used. Phthalocyanine pigments such as SANDYESUPERBLUE 1809 manufactured by the company can be preferably used.

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

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

  Carbon black can be suitably used as the black pigment. For example, # 52, # 50, # 47, # 45, # 45L, # 44, # 40, # 33, # 32, # 25, # 260, MA100S, # 40 manufactured by Mitsubishi Chemical Corporation, MOGULL manufactured by Cabot Corporation REGAL660R, REGAL500R, REGAL400R, REGAL330R, REGAL300R, REGAL250R, etc. can be preferably used.

  More preferably, carbon black having a DBP oil absorption (ml / 100 g) of 45 to 70 is preferred. Preferably it is 45-63, More preferably, it is 45-60, More preferably, it is 45-53.

  By using carbon black particles having a predetermined DBP oil absorption amount, the phenomenon of carbon black particles growing first can be suppressed, and even if the core particles are reduced in size, the carbon black particles are taken into the core particles. In addition, an effect of eliminating carbon black particles remaining without adding to the aggregation of core particles or core particles can be obtained. Although the reason is not clearly understood, it is presumed that carbon black larger than 70 is likely to cause aggregation of carbon black quickly, and the carbon black particles are not easily taken into the core particles or core particles.

  The particle size of carbon black is preferably 20 to 40 nm. Preferably the particle size is 20-35 nm. The particle diameter is an arithmetic average diameter measured by an electron microscope. When the particle size is large, the coloring power is lowered. When the particle size is small, dispersion in the liquid becomes difficult. For example, Mitsubishi Chemical Corporation # 52 (particle size 27 nm, DBP oil absorption 63 ml / 100 g), # 50 (28 nm, 65 ml / 100 g), # 47 (23 nm, 64 ml / 100 g), # 45 (same as above) 24 nm, 53 ml / 100 g), # 45L (24 nm, 45 ml / 100 g), Cabot REGAL 250R (35 nm, 46 ml / 100 g), REGAL 330R (25 nm, 65 ml / 100 g), MOGULL (24 nm) , 60 ml / 100 g). More preferred are # 45, # 45, and LREGAL250R.

DBP oil absorption (JISK6217) was measured by putting 20 g (Ag) of sample dried at 150 ° C. ± 1 ° C. for 1 hour into a mixing chamber of an absorber meter (manufactured by Brabender, spring tension 2.68 kg / cm), After setting the limit switch to about 70% of the maximum torque in advance, the mixer is rotated. At the same time, DBP (specific gravity 1.045 to 1.050 g / cm ³ ) is added from the automatic burette at a rate of 4 ml / min. As the end point is approached, the torque increases rapidly and the limit switch is turned off. The DBP oil absorption (= Bx100 / A) (ml / 100 g) per 100 g of the sample is determined from the DBP amount (Bml) added so far and the sample weight.

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, inorganic fine powder is mixed and added as an external additive. External additives include silica, alumina, titanium oxide, zirconia, magnesia, ferrite, magnetite and other metal oxide fine powders, barium titanate, calcium titanate, titanates such as strontium titanate, barium zirconate, zircon Zirconates such as calcium acid and strontium zirconate, or mixtures thereof are used. The external additive is hydrophobized as necessary.

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

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

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

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

  The external additive having positive electrode chargeability is treated with aminosilane, amino-modified silicone oil or epoxy-modified silicone oil.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Hydrophobicity = (a / (50 + a)) × 100 (%).
[Toner powder properties]
In this embodiment, the toner base particles including the binder resin, the colorant, and the wax have a volume average particle diameter of 3 to 6 μm, a volume-based variation coefficient of 10 to 25%, and a number-based distribution of 2.0 to 3.63 μm. Of toner particles having a particle size of 10 to 85% by number, toner particles having a particle size of 3.5 to 4.53 μm in a volume-based distribution are 25 to 75% by volume, and 6.06 μm in a volume-based distribution. 2. Toner particles having the above particle diameters are contained at 5% by volume or less, and the volume% of toner particles having a particle diameter of 3.5 to 4.53 μm in the volume-based distribution is V34. When the number% of toner particles having a particle diameter of 5 to 4.53 μm is P34, P34 / V34 is preferably in the range of 0.4 to 1.5.

  Preferably, the toner base particles have a volume average particle size of 3 to 5 μm, a volume-based variation coefficient of 10 to 20%, and a content of toner particles having a particle size of 2.0 to 3.63 μm in a number-based distribution is 15 ~ 85% by number, toner particles having a particle size of 3.5 to 4.53 μm in a volume-based distribution are 30 to 65% by volume, toner particles having a particle size of 6.06 μm or more in a volume-based distribution are 2 volumes %, And P34 / V34 is preferably in the range of 0.5 to 1.3.

  More preferably, the toner base particles have a volume average particle size of 3 to 5 μm, a volume-based variation coefficient of 10 to 16%, and a content of toner particles having a particle size of 2.0 to 3.63 μm in a number-based distribution. 25 to 85% by number, toner particles having a particle size of 3.5 to 4.53 μm in the volume-based distribution are 40 to 60% by volume, toner particles having a particle size of 6.06 μm or more in the volume-based distribution are It is preferably contained at 0.5% by volume or less, and P34 / V34 is preferably in the range of 0.5 to 0.9.

  It is possible to prevent high-resolution image quality, and also prevent reverse transfer and dropout in tandem transfer, and achieve both oil-less fixing. The toner particle size distribution affects toner fluidity, image quality, storage stability, filming on a photoreceptor, a developing roller, and a transfer body, aging characteristics, transferability, and in particular, multi-layer transfer in a tandem system. In addition, it affects the high temperature non-offset property and glossiness 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 volume average particle size exceeds 6 μm, it is impossible to achieve both image quality and transfer. When the volume average particle size is less than 3 μm, it becomes difficult to handle toner particles during development.

  If the content of toner particles having a particle size of 2.0 to 3.63 μm in the number standard distribution is less than 10% by number, it is impossible to achieve both image quality and transfer. If it exceeds 85% by number, it becomes difficult to handle the toner base particles during development. Further, filming on the photosensitive member, the developing roller, and the transfer member may occur. Furthermore, fine powder tends to be offset at high temperature because of its high adhesion to the heat roller. Further, in the tandem system, toner aggregation tends to be strong, and transfer failure of the second color is likely to occur during multilayer transfer. An appropriate range is required.

  When the toner particles having a particle size of 3.5 to 4.53 μm in the volume reference distribution are less than 25% by volume, the image quality is deteriorated. If it exceeds 75% by volume, it is impossible to achieve both image quality and transfer.

  If toner particles having a particle size of 6.06 μm or more in the volume-based distribution are contained in excess of 5% by volume, the image quality is deteriorated, resulting in transfer failure.

  When P34 / V34 is smaller than 0.4, the amount of fine powder present becomes excessive, resulting in poor fluidity, poor transferability, and poor ground fog. When it is larger than 1.5, there are many large particles and the particle size distribution becomes broad, so that high image quality cannot be achieved.

  The purpose of defining P34 / V34 can be used as an index for making toner particles small and narrowing the particle size distribution.

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

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

  Further, when the shape index of the toner base particles is SC and the volume average particle diameter is d50 (μm), the product of SC and d50 (SC × d50) is preferably 3.9 to 7.4. Preferably it is 4.0-6.6, More preferably, it is 4.1-5.7. The shape index is preferably 1.31-1.49, more preferably 1.33-1.46, and still more preferably 1.35-1.42.

  By prescribing this numerical value, the cleaning performance with the rubber blade tends to deteriorate when the spheroidization of the shape proceeds when the particle shifts to a small particle size. In addition, when the particles shift to a large particle size, if the shape progresses to an irregular shape, transferability and image quality may deteriorate, and in the case of small particle size, the shape is shifted to an irregular shape to improve cleaning properties. In the case of large particles, the product of SC and d50 is set within a certain range in order to maintain the image quality by shifting the shape to a spherical shape. If it is smaller than 3.9, the cleaning property tends to deteriorate. If it is larger than 7.4, the image quality is liable to deteriorate.

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

  The shape index (KC) is obtained by the following formula using a real surface view microscope (VE7800) manufactured by Keyence Co., Ltd., taking about 100 toner base particles magnified 1000 times, measuring the perimeter and cross-sectional area. (D: circumference of toner base, A: cross-sectional area of toner base).

KC (shape factor) = d ² / (4π · A) × 100
Further, the degree of compression is calculated from the static bulk density and the dynamic bulk density, which is one of the indicators of toner fluidity. The fluidity of the toner is affected by the particle size distribution of the toner, the toner particle shape, the external additive, and the type and amount of the wax. When the toner particle size distribution is narrow and the amount of fine powder is small, the toner surface has few irregularities and the shape is nearly spherical, the amount of external additive added is large, or the particle size of the external additive is small, the degree of compression is small. The fluidity of the toner becomes higher. The degree of compression is preferably 5 to 40%. More preferably, it is 10 to 30%. It is possible to achieve both oilless fixing and tandem multi-layer transfer. If it is less than 5%, the fixability is lowered, and the translucency is particularly likely to deteriorate. Toner scattering tends to increase from the developing roller. Transferability greater than 40% is lowered, and tandem-type deficiency occurs and transfer failure occurs.
[Oil-less color fixing]
In the present embodiment, it is suitably used for an electrophotographic apparatus having a fixing process of an oil-less fixing configuration in which oil is not used as a means for fixing toner. As the heating means, electromagnetic induction heating is a preferable configuration from the viewpoint of shortening the warm-up time and saving energy. A heating and pressurizing unit having at least a magnetic field generating unit, a rotary heating member having at least a heat generation layer and a release layer generated by electromagnetic induction, and a rotary pressurizing member forming a fixed nip with the rotary heating member; In this configuration, a transfer medium such as copy paper on which toner is transferred is passed between the rotary heating member and the rotary pressure member, and is fixed. As a feature thereof, the warm-up time of the rotary heating member is very fast compared to the case where a conventional halogen lamp is used. For this reason, since the copying operation is started in a state where the temperature of the rotary pressure member is not sufficiently raised, low temperature fixing and a wide range of offset resistance are required.

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

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

Therefore, by using the toner of this embodiment, low temperature fixing and a wide range of offset resistance can be realized without using oil, and high color translucency can be obtained. Further, the toner can be prevented from being overcharged, and toner flying due to the charging action with the heating member or the fixing member can be suppressed.
[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 is visualized. A primary transfer process in which an endless transfer member is brought into contact with the image carrier and transferred to the transfer member is sequentially executed to form a multilayer transfer toner image on the transfer member. Then, in the transfer process configured to execute a secondary transfer process in which the multilayer toner images formed on the transfer body are collectively transferred to a transfer medium such as paper or OHP, the first primary transfer is performed. When the distance from the position to the second primary transfer position is d1 (mm) and the peripheral speed of the photoconductor is v (mm / s), the transfer position configuration is d1 / v ≦ 0.65. Achieving both a compact machine and printing speed It is intended. In order to realize a reduction in size that can process 20 sheets per minute (A4) or more and the machine can be used for SOHO, it is essential to have a configuration in which a plurality of toner image forming stations are short and the process speed is increased. is there. In order to achieve both a reduction in size and a printing speed, a configuration in which the above value is 0.65 or less is considered a minimum.

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

  Therefore, by using the toner or the two-component developer of the present embodiment, the charge distribution is stabilized, the toner can be prevented from being overcharged, and the fluidity fluctuation can be suppressed. For this reason, it is possible to prevent transfer efficiency from being lowered, character dropout during transfer, and reverse transfer without sacrificing fixing characteristics.

Next, examples of the toner of the present invention will be described, but the present invention is not limited to these examples.
(1) Production Example of Carrier (a) Production of Carrier CA1 39.7 mol% in terms of MnO, 9.9 mol% in terms of MgO, 49.6 mol% in terms of Fe ₂ O ₃ and 0.8 mol% in terms of SrO The mixture was pulverized for 10 hours, mixed, and dried, and then held at 950 ° C. for 4 hours to carry out calcination. 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 1) are methyl groups, that is, (CH ₃ ) ₂ SiO _2/2 units are 15.4 mol%, and R ₃ represented by (Chemical Formula 2) 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 CA1.
(2) Preparation of resin particle dispersion (Table 1) shows resin particle dispersions (RL2, RL3, RL4, RL7, RL8, RL9, RL10, RH2) according to the present invention prepared as preparation examples of resin particle dispersions. , RH3, RH4, RL7, RL8, RL9) and the properties of the binder resin obtained in the resin particle dispersions (rl1, rl5, rl6, rl11, rh1, rh5, rh6, rh10) according to comparative examples.

  “Mn” is the number average molecular weight, “Mw” is the weight average molecular weight, “Mw / Mn” is the ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn), and “Mp” is the peak of the molecular weight. The value, Tg (° C.) represents the glass transition point, and Ts (° C.) represents the softening point. Table 2 shows the nonionic amount (g), the anionic amount (g), and the ratio (wt%) of the nonionic amount to the total surfactant amount used for each resin particle dispersion.

(a) Preparation of resin particle dispersion RL2 A monomer liquid consisting of 230.1 g of styrene, 69.9 g of butyl acrylate, and 1.5 g of acrylic acid was added to 440 g of ion-exchanged water with a nonionic surfactant ( Sanyo Kasei Co., Ltd .: Nonipol 400) 7.5 g, anionic surfactant (Daiichi Kogyo Seiyaku, Neogen S20-F (20% concentration)) 22.5 g (substantial anion amount 4.5 g), dodecanethiol 6 g Then, 4.5 g of potassium persulfate was added thereto, and emulsion polymerization was performed at 75 ° C. for 4 hours. Thereafter, aging treatment is further performed at 90 ° C. for 5 hours to disperse resin particles in which Mn is 7400, Mw is 17400, Mp is 18400, Tg is 48 ° C., Ts is 108 ° C., and the median diameter is 0.18 μm. Liquid RL2 was prepared. The pH of the resin dispersion at this time was 1.9.

  (Table 3) and (Table 4) show the blending amounts of acrylic acid and potassium persulfate used for each resin particle dispersion based on the preparation of resin particle dispersion RL2 in the emulsion polymerization of each resin particle dispersion. Show.

(3) Preparation of pigment dispersion The pigment which is the colorant used in Table 5 and Table 6 and the surfactant used are shown.

(A) Preparation of pigment particle dispersion CBS1 In a 1 L beaker, 308 g of ion-exchanged water and 12 g of surfactant SA4 were weighed and stirred with a magnetic stirrer until the solid content of the surfactant was dissolved. To this surfactant aqueous solution, 80 g of carbon black CB1 was added, and subsequently stirred with a magnetic stirrer for 10 minutes. Next, the contents were transferred to a 1 L tall beaker and dispersed using a homogenizer (manufactured by IKA, T-25) at a rotational speed of 9500 rpm for 10 minutes. This dispersion was further dispersed with a disperser (TK Fillmix: 56-50 manufactured by Tokushu Kika Co., Ltd.). The produced dispersion was designated as pigment particle dispersion CBS1. The pigment concentration was 20 wt%.

  In a liquid using an anionic surfactant (Daiichi Kogyo Seiyaku, Neogen S20-F (solid content 20% concentration)), ion-exchanged water was adjusted so that the pigment concentration was about 20 wt%. The weight ratio in Table 5 shows the actual anion amount ratio.

  Hereinafter, black pigment dispersions CBS2, CBS3, cyan pigment dispersion PCS1, magenta pigment dispersion PMS1, and yellow pigment dispersion PYS1 were prepared based on the preparation conditions of pigment particle dispersion CBS1. The conditions of the black pigment, cyan pigment, magenta pigment, yellow pigment and the surfactant used in these pigment particle dispersions are shown in Table 7.

(4) Preparation of Wax Dispersion (Table 8), (Table 9) and (Table 10) were respectively used in the preparation of the wax particle dispersion according to the present example formed as an example of the preparation of the wax particle dispersion. The wax material and its properties are shown.

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

  The inside of the tank was charged with 67 g of ion-exchanged water, 3 g of a nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd .: Elminol NA400), and 30 g of wax (W-1), and the speed of the rotating body was 30 m / s for 5 min, and then the rotational speed was increased to 50 m / s for 2 min. A wax particle dispersion WA1 was formed.

  Hereinafter, based on the preparation conditions of the wax particle dispersion WA1, each wax particle dispersion (WA1 to WA12) was prepared. The types and properties of the wax used in these wax particle dispersions and the surfactant used are shown in (Table 11) and (Table 12). “First wax” and “second wax” indicate the wax material charged in the wax particle dispersion, and the value in parentheses at the end of the symbol indicating the wax is the blended weight composition amount (weight ratio) of the wax. ).

In a liquid using an anionic surfactant (Daiichi Kogyo Seiyaku, Neogen S20-F (20% concentration)), ion-exchanged water was adjusted so that the pigment concentration was about 20 wt%. The weight ratio in the table indicates the actual anion amount ratio, and the total amount is the same amount. Further, when the waxes W13 and W14 are used, the inside of the tank is pressurized to 0.4 MPa.
(5) Preparation of Toner Base (Table 13) shows toner bases (CT2, CT3, CT4, CT8, CT9, CT10, CT11, CT14, CT15, CT16, CT17) according to the present invention prepared as examples of toner bases. CT20, CT21, CT22, CT25, CT26, CT27, CT28, CT31, CT32, CT33, CT34, MT1, YT1) and a toner base for comparison (ct1, ct5, ct6, ct7, ct12, ct13, ct18, ct19, The respective compositions are shown for ct23, ct24, ct29, ct30, ct35, ct36).

(a) Preparation of toner base CT2 In a cylindrical 2 L glass container equipped with a thermometer, a cooling tube, a pH meter, and a stirring blade, a first resin particle dispersion RL3 (the resin used for the core particles is the first resin). 204 g of resin particles), 56 g of the colorant particle dispersion PCS1 and 60 g of the wax particle dispersion WA10, 400 g of ion-exchanged water are added, and the mixture is used for 10 min using a homogenizer (manufactured by IKA: Ultra Turrax T25). A mixed particle dispersion was prepared by mixing. The pH of the obtained mixed dispersion was 3.5.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11.5, and then 300 g of a 23% strength magnesium sulfate aqueous solution was added and stirred for 10 minutes. Thereafter, the temperature was raised from 20 ° C. to 90 ° C. at a rate of 1 ° C./min, followed by heat treatment for 3 hours to obtain core particles. The obtained core particle dispersion had a pH of 8.8.

  Thereafter, in the state where the water temperature was 90 ° C., the second resin particle dispersion RH2, 145 g, whose pH was adjusted to 7.5, was continuously added dropwise over a required time of 30 minutes, and 1.5 hours after the completion of the addition. Heat treatment was performed to obtain particles in which the second resin particles were fused.

  After cooling, the product (toner base material) was filtered and washed 7 times with ion-exchanged water. The toner base thus obtained was dried at 33 ° C. for 8 hours with a fluid drier to obtain toner base CT2.

  The toner base CT2 has a volume average particle size of 3.9 μm, a volume-based coefficient of variation of 16.9%, and a toner particle content of 2.0 to 3.63 μm in the number-based distribution is 55.6. %, Toner particles having a particle size of 3.5 to 4.53 μm in the volume-based distribution are 54.3% by volume, toner particles having a particle size of 6.06 μm or more in the volume-based distribution are 0.1% by volume The volume% of toner particles having a particle diameter of 3.5 to 4.53 μm in the volume-based distribution is V34, and the number% of toner particles having a particle diameter of 3.5 to 4.53 μm in the number-based distribution is When P34, P34 / V34 is 0.8.

  Toner bases CT3, CT4, CT8, CT9, CT10, CT11, CT14, CT15, CT16, CT17, CT20, CT21, CT22, CT25, CT26, CT27, CT28, CT31, CT32, CT33, CT34, MT1, YT1, ct1, ct5, ct6, ct7, ct12, ct13, ct18, ct19, ct23, ct24, ct29, ct30, ct35, ct36 are based on the conditions of CT2, changing the first resin particles and the second resin particles, The cohesiveness of the particles was observed.

  Table 14 shows the characteristics obtained in the toner base prepared. d50 (μm) indicates the volume average particle diameter of the toner base particles, and “coefficient of variation” indicates the spread of the particle size distribution on the volume basis of the toner base particles in the obtained toner base.

  In the ct6 toner, the aggregation of the first resin particles progressed rapidly when the core particles aggregated, and a coarse aggregate of the first resin alone was generated, and the particle size distribution was doubled. In the ct36 toner, the progress of the aggregation of the core particles is slow when the core particles are aggregated, and the liquid is not completely transparent even after 6 hours. In the ct1, ct7, ct13, ct19, ct24, and ct30 toner, coarse aggregates of the second resin alone were generated when the second resin particles were aggregated, and the particle size distribution was doubled.

  In addition, in the toners ct5, ct12, ct18, ct23, ct29, and ct35, the progress of the aggregation of the second resin particles is slow when the second resin particles are aggregated, and the liquid is not completely transparent even after 6 hours. For CT2, CT3, CT4, CT8, CT9, CT10, CT11, CT14, CT15, CT16, CT17, CT20, CT21, CT22, CT25, CT26, CT27, CT28, CT31, CT32, CT33, CT34, MT1, YT1 toner Good cohesion was exhibited.

  CT3, CT8, CT14, CT15, CT20 in which the ratio PS1 / PS2 of the initiator amount PS1 during the production of the first resin particles and the initiator amount PS2 during the production of the second resin particles is 1.0 to 4.0. , CT21, CT25, CT26, CT27, CT28, CT32, CT33, CT34, MT1, and YT1 toners had a small particle size and a narrow particle size distribution.

  (Table 15) shows the toner bases (BT2, BT3, BT4, BT5, CT37, MT2, YT2) and toner bases for comparison (bt1, bt6) prepared as examples of toner bases according to the present invention. The composition is shown.

(b) Preparation of toner base BT2 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, 56 g of the colorant particle dispersion CBS2, and wax 60 g of the particle dispersion WA11 was added, 400 ml of ion exchange water was added, and the mixture was 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 3.5.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11.8 and stirred for 10 minutes. Thereafter, when the temperature was raised from 20 ° C. at a rate of 1 ° C./min and reached 70 ° C., 300 g of a 23% strength magnesium sulfate aqueous solution was continuously added dropwise over a required time of 30 min, followed by heat treatment for 1 hour, and then 90 The temperature was raised to 0 ° C. and heat-treated for 3 hours to obtain core particles. The obtained core particle dispersion had a pH of 9.2.

  Thereafter, 145 g of the second resin particle dispersion RH7 having a pH adjusted to 8.5 with a water temperature of 92 ° C. was added at a dropping rate of 5 g / min. Thus, particles in which the second resin particles were fused were obtained.

  After cooling, the 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 BT2.

  The toner base material BT2 has a volume average particle size of 4.7 μm, a volume-based variation coefficient of 17.1%, and a toner particle content of 2.0 to 3.63 μm in the number-based distribution of 68.0 particles. %, 50.1% by volume of toner particles having a particle size of 3.5 to 4.53 μm in the volume-based distribution, and 0.1% by volume of toner particles having a particle size of 6.06 μm or more in the volume-based distribution The volume% of toner particles having a particle diameter of 3.5 to 4.53 μm in the volume-based distribution is V34, and the number% of toner particles having a particle diameter of 3.5 to 4.53 μm in the number-based distribution is When P34, P34 / V34 is 0.7.

  For toner bases BT3, BT4, BT5, BT6, CT37, MT2, YT2, bt1, and bt6, based on the conditions of BT2, change the first resin particles and the second resin particles and observe the cohesiveness of the particles did.

  Table 16 shows the characteristics obtained with the toner base prepared. d50 (μm) indicates the volume average particle diameter of the toner base particles, and “coefficient of variation” indicates the spread of the particle size distribution on the volume basis of the toner base particles in the obtained toner base.

  In the bt1 toner, when the second resin particles were aggregated, coarse aggregates of the second resin alone were generated, and the particle size distribution was doubled. In the bt6 toner, the progress of the aggregation of the second resin particles is slow when the second resin particles are aggregated, and the liquid is not completely transparent even after 6 hours.

  BT2, BT3, BT4, BT5, CT32, MT2 and YT2 toners showed good aggregation properties.

  Moreover, BT2, BT3, BT4, MT2, YT2 in which the ratio PS1 / PS2 of the initiator amount PS1 during the production of the first resin particles and the initiator amount PS2 during the production of the second resin particles is 1.0 to 4.0 The toner had a small particle size and a narrow particle size distribution.

  (Table 17) shows the toner bases (BT8, BT9, BT10, BT11, CT38, MT3, YT3) and toner bases for comparison (bt7, bt12) prepared as examples of toner bases according to the present invention. The composition is shown.

(c) Preparation of toner base BT8 In a cylindrical 2 L glass container equipped with a thermometer, a cooling tube, a pH meter, and a stirring blade, 102 g of the first resin particle dispersion RL3 and 58 g of the carbon black particle dispersion CBS3 are used. Then, 400 ml of ion-exchanged water was 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 dispersion to adjust the starting pH to 11.2 and stirred for 10 minutes. Thereafter, when the temperature was raised from 20 ° C. at a rate of 1 ° C./min and reached 80 ° C. (pH value of the mixed particle dispersion was 10.1), the magnesium sulfate having a concentration of 23 wt% adjusted to 9.0 was set. 300 g of the aqueous solution was continuously added dropwise for a required time of 30 minutes. Thereafter, the temperature was raised to 90 ° C., and heat treatment was performed for 2 hours to generate core particles. The obtained core particle dispersion had a pH of 7.8.

  Thereafter, the mixture of the wax particle dispersion WA7 (80 g) adjusted to pH 7.2 and the first resin particle dispersion RL3 (102 g) was continuously added dropwise at a required time of 30 min. And heat-treated for 30 minutes after completion of the dropping. Thereafter, 1N NaOH was added, the pH of the mixed solution was adjusted to 9.4, and the mixture was heated at 90 ° C. for 2 hours, and the wax particle dispersion and the first resin particle dispersion were aggregated on the core particles. Core particles were obtained. The obtained core particle dispersion had a pH of 8.7.

  Thereafter, 145 g of the second resin particle dispersion RH7 having a pH adjusted to 8.5 was continuously dropped at a water temperature of 92 ° C. over a required time of 30 minutes, and heated for 1.5 hours after the dropping was completed. It processed and obtained the particle | grains which the 2nd resin particle fuse | melted.

  Then, after cooling, the product (toner base material) was filtered and washed 7 times with methyl alcohol. Thereafter, toner base particles BT8 were obtained by drying the toner base thus obtained at 35 ° C. for 10 hours using a fluid dryer.

  The toner base BT8 has a volume average particle size of 4.8 μm, a volume-based coefficient of variation of 17.1%, and a toner particle content of 2.0 to 3.63 μm in the number-based distribution of 72.3 particles. 41.1% by volume of toner particles having a particle size of 3.5 to 4.53 μm in a volume-based distribution, and 0.1% by volume of toner particles having a particle size of 6.06 μm or more in a volume-based distribution. The volume% of toner particles having a particle diameter of 3.5 to 4.53 μm in the volume-based distribution is V34, and the number% of toner particles having a particle diameter of 3.5 to 4.53 μm in the number-based distribution is When P34, P34 / V34 is 0.6.

  The toner bases BT9, BT10, BT11, CT38, MT3, YT3 and the toner bases bt7, bt12 for comparison are based on the conditions of BT8 by changing the first resin particles and the second resin particles, Agglomeration was observed.

  Table 18 shows the characteristics obtained with the toner base prepared. d50 (μm) indicates the volume average particle diameter of the toner base particles, and “coefficient of variation” indicates the spread of the particle size distribution on the volume basis of the toner base particles in the obtained toner base.

  In the bt7 toner, when the second resin particles were aggregated, coarse aggregates of the second resin alone were generated, and the particle size distribution was doubled. In the bt12 toner, the progress of the aggregation of the second resin particles is slow when the second resin particles are aggregated, and the liquid is not completely transparent even after 6 hours.

  BT8, BT9, BT10, BT11, CT38, MT3, and YT3 toners showed good aggregation properties.

Moreover, BT2, BT3, BT4, MT2, YT2 in which the ratio PS1 / PS2 of the initiator amount PS1 during the production of the first resin particles and the initiator amount PS2 during the production of the second resin particles is 1.0 to 4.0 The toner had a small particle size and a narrow particle size distribution.
(6) External additive Next, examples of the external additive will be described. (Table 19) shows each material and its characteristic about the external additive (S1, S2, S3, S4, S5, S6, S7, S8, S9) used in the present Example.

In the case of processing with a plurality of types of the processing material 1 and the processing material 2, () shows the blending weight ratio of each processing material. “5-minute value” and “30-minute value” represent the charge amount ([μC / g]), which were measured by the blow-off method of frictional charge with an uncoated ferrite carrier. Specifically, in an environment of 25 ° C. and 45 RH%, after mixing 50 g of carrier and 0.1 g of silica, etc. in a 100 ml polyethylene container, stirring for 5 minutes and 30 minutes at a speed of 100 minutes- ^{1 by} longitudinal rotation. 0.3 g was collected and measured by blowing with nitrogen gas 1.96 × 10 ⁴ [Pa] for 1 minute.

For negative chargeability, the 5-minute value is preferably −100 to −800 μC / g, and the 30-minute value is preferably −50 to −600 μC / g. A high charge amount of silica can exhibit such characteristics with a small amount of addition.
(7) Toner External Addition Treatment and Composition Next, a toner composition and an external addition treatment example will be described. (Table 20) shows toners (TCT2 to TCT4, TCT8 to TCT11, TCT14 to TCT17, TCT20 to TCT22, TCT25 to TCT28, TCT31 to TCT34, TCT37 to TCT38, TMT1 to TMT3) prepared as toner preparation examples. , TYT1 to TYT3, TBT2 to TBT5, TBT8 to TBT11) and toners for comparison (tct1, tct5 to tct7, tct12 to tct13, tct18 to tct19, tct23 to tct24, tct29 to tct30, tct35 to tt, tct35 to tt Respective material compositions are shown for tbt7 and tbt12). Unblended indicates no addition. The value in parentheses at the end of the symbol indicating the external additive in the external additive column represents the blending amount (parts by weight) of the external additive with respect to 100 parts by weight of the toner base. In the external addition process (Henschel mixer FM20B, manufactured by Mitsui Mining Co., Ltd.), stirring blade Z0S0 type, rotation speed 2000 min ⁻¹ , treatment time 5 min, and input amount 1 kg were performed.

  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.

  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 to effectively prevent slack and charge accumulation due to long-term use of the transfer belt 12, and the coating of the surface with a fluororesin is effective for toner filming on the surface of the transfer belt after long-term use. This is to prevent it. If the volume resistance is less than 10 ⁷ Ω · cm, retransfer is likely to occur, and if it is greater than 10 ¹² Ω · cm, the transfer efficiency deteriorates.

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

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

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

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

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

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

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

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

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

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

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

  A fixing roller 201 as a fixing member is a silicone rubber having a rubber hardness (JIS-A) of 20 degrees according to JIS standard on the surface of an aluminum hollow roller metal core 213 having a length of 250 mm, an outer diameter of 14 mm, and a thickness of 1 mm. An elastic layer 214 having a thickness of 3 mm is provided. A silicone rubber layer 215 is formed thereon with a thickness of 3 mm and has an outer diameter of about 26 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 photoreceptor 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.
(Example of image evaluation)
Next, an example of image output evaluation for toner and two-component developer will be described. Here, an image forming apparatus is used, and several kinds of two-component developers with different mixing ratios of toner and carrier are subjected to a running durability test of 100,000 sheets each with A4 plate output to determine the charge amount and the image density. In addition to the measurement, the ground fog in the non-image area in the output sample, the uniformity in the entire solid image, the transferability (character skipping during transfer, reverse transfer, transfer omission), and toner filming were evaluated. Image density (ID) evaluation measured the black solid part using the reflection densitometer RD-914 made from Macbeth Division of Kollmorgen Instruments Corporate.

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

  (Table 21) shows the two-component developer (DCT2 to DCT4, DCT8 to DCT11, DCT14 to DCT17, DCT20 to DCT22, DCT25 to DCT28, DCT31 to DCT34, DCT37 to DCT38, used in this example. DMT1 to DMT3, DYT1 to DYT3, DBT2 to DBT5, DBT8 to DBT11) and toners for comparison (dct1, dct5 to dct7, dct12 to dct13, dct18 to dct19, dct23 to dct24, dct29 to dct30dt, dct30 to dct30dt , Dbt6, dbt7, and dbt12) show the results of evaluating the configuration of the toner and carrier as a two-component developer and conducting a 100,000 sheet running durability test on A4 size paper. In the table, “◯” indicates that the evaluation result is good, and “x” indicates that there is a problem.

  Two-component developers DCT2 to DCT4, DCT8 to DCT11, DCT14 to DCT17, DCT20 to DCT22, DCT25 to DCT28, DCT31 to DCT34, DCT37 to DCT38, DMT1 to DMT3, DYT1 to DYT3, DBT2 to DBT5, DBT8 to The DBT 11 was practically free of toner filming on the photoreceptor when the 100,000 sheet running durability test was performed on A4 size paper. In addition, toner filming on the transfer belt was at a level causing no practical problem. Further, no transfer belt cleaning failure occurred. Even in a full-color image in which the three colors overlap, no paper wrapping around the fixing belt occurred.

  Further, regarding the image density before and after the running test, the two-component developer according to the present invention obtained a high density image having an image density of 1.3 or more. Even after the endurance test of 100,000 A4 stencil sheets, the fluidity of the two-component developer was stable, and the image density showed stable characteristics with little change of 1.3 or more.

  Further, regarding the non-image area fogging and the entire surface solid image uniformity, the two-component developer according to the present invention has a high image density, no non-image area fogging, no toner scattering, and the like. It was resolution. Further, the uniformity when taking the entire solid image at the time of development was also good.

  In addition, no abnormal image of the vertical streak occurred even during continuous use. Further, the spent component of the toner component on the carrier hardly occurred. In addition, there is little change in carrier resistance and a decrease in charge amount. In addition, the rise of charge when the toner is rapidly replenished by continuing to take a solid image is good, and the phenomenon that fog increases in a high humidity environment is also observed. I couldn't. Moreover, even in long-term use, a high saturation charge amount could be maintained for a long time. Moreover, there was almost no change in the charge amount under low temperature and low humidity.

  Further, with regard to transferability (character skipping during transfer, reverse transfer, and transfer skipping), the two-component developer according to the present invention was at a level where there was no practical problem with skipping. In addition, no transfer failure occurred even in a full-color image in which the three colors overlapped. The transfer efficiency was about 95%.

  Even if the mixing ratio of the toner and the carrier is changed to 5 to 20 wt%, the two-component developer according to the present invention has little change in image quality such as image density and ground fog, and can control the toner density widely. became.

  On the other hand, the two-component developer for comparison (dct1, dct5 to dct7, dct12 to dct13, dct18 to dct19, dct23 to dct24, dct29 to dct30, dct35 to dct36, dbt1, dbt6, dbt7, dbt12) In FIG. 2, toner filming on the photoconductor occurs. Also, the image density before and after the running test was low, the image density was lowered after long-term use, or the fog in the non-image area increased. Further, when the entire surface was continuously taken and the toner was replenished rapidly, the charge decreased and the fog increased. In particular, the phenomenon worsened in a high humidity environment. The mixing ratio of the toner and the carrier is in the range of 6 to 8 wt%. Even if the density is changed, there is little change in image quality such as image density and ground cover. In addition, the ground cover increased when the value was large.

Next, (Table 22) shows the evaluation results for the fixing property, non-offset property, high temperature storage stability, and paper wrapping property around the fixing belt in a full-color image. In the table, “◯” indicates that the evaluation result is good, and “x” indicates that there is a problem. Here, in a fixing device using a solid image with an adhesion amount of 1.2 mg / cm ^{2 at} a process speed of 125 mm / s and a belt not coated with oil, OHP film transmittance (fixing temperature 160 ° C.) and minimum fixing temperature And the temperature at which the offset phenomenon occurred at high temperature was measured. Further, in the storage stability test at a high temperature, the state of the toner after being left at 50 ° C. for 24 hours was evaluated. The film transmittance for OHP was measured with a spectrophotometer U-3200 (Hitachi, Ltd.) for the transmittance of 700 nm light.

  Toner according to the present invention Toners according to the present invention DCT2 to DCT4, DCT8 to DCT11, DCT14 to DCT17, DCT20 to DCT22, DCT25 to DCT28, DCT31 to DCT34, DCT37 to DCT38, DMT1 to DMT3, DYT1 to DYT3, DBT2 to DBT5, DBT8 to DBT11 are all good in terms of fixability, with an OHP film transmittance of 70% or more. As for non-offset properties, a non-offset temperature range can be obtained in a wide range in a fixing roller that does not use oil, and a fixable temperature range (a range from the lowest fixing temperature to a high temperature offset phenomenon occurrence temperature) is wide. The offset phenomenon did not occur at all even with 200,000 full-color images of plain paper. Further, the surface deterioration phenomenon of the belt is not observed even if the oil is not applied with a silicone or fluorine-based fixing belt. In addition, regarding the high-temperature storage stability, almost no aggregation was observed in the storage stability at 50 ° C. for 24 hours. In addition, as for the paper wrapping property around the fixing belt, no jamming of the OHP film occurred in the fixing nip portion.

  Comparative toners dct1, dct5 to dct7, dct12 to dct13, dct18 to dct19, dct23 to dct24, dct29 to dct30, dct35 to dct36, dbt1, dbt6, dbt7 and dbt12 have low high temperature non-offset properties. The margin of the fixable area is narrow. It seems that the dispersion state of the wax is not in an appropriate state due to the influence of the hydrophilic group derived from the initiator. For comparison toners dct1, dct5 to dct7, dct12 to dct13, dct18 to dct19, dct23 to dct24, dct29 to dct30, dct35 to dct36, dbt1, dbt6, dbt7 and dbt12, the density of the wax is poor. It is difficult to produce, and high temperature non-offset property and low temperature fixability are poor. Storage stability, which is considered to be the effect of floating wax or resin particles remaining on the toner, has deteriorated.

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

Sectional drawing which shows the structure of the image forming apparatus used in 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 Schematic of the stirring and dispersing apparatus used in the examples of the present invention View from above of the stirring and dispersing device used in the examples of the present invention Schematic of the stirring and dispersing apparatus used in the examples of the present invention View from above of the stirring and dispersing device used in the examples of the present invention

Explanation of symbols

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

Claims (34)

In an aqueous medium, at least the first resin particle dispersion in which the first resin particles are dispersed, the colorant particle dispersion in which the colorant particles are dispersed, and the wax particle dispersion in which the wax particles are dispersed are mixed. The second resin particle dispersion, in which the second resin particles are dispersed, is added to the core particle dispersion containing the core particles produced by agglomeration, mixed, heated, and then the second resin particles. A toner including resin-fused core particles obtained by fusing the core particles to the core particles,
The second resin particle dispersion is obtained by emulsion polymerization of a monomer using a polymerization initiator in an aqueous medium,
0.5 to 2.0 parts by weight with respect to 100 parts by weight of the monomer of the polymerization initiator, and
The polymerization initiator is a persulfate having a solubility of 4 g or more in 100 g of water at a water temperature of 20 ° C., and
The monomer includes a styrene monomer, a (meth) acrylic acid ester monomer, and a vinyl monomer having an acid group. 0.1 to 5.0% by weight in the monomer,
The toner, wherein the wax includes a wax having an endothermic peak temperature of 50 to 120 ° C. according to a DSC (Differential Scanning Calorimeter) method. The first resin particle dispersion is obtained by emulsion polymerization of a monomer using a polymerization initiator in an aqueous medium,
0.5 to 2.5 parts by weight with respect to 100 parts by weight of the monomer of the polymerization initiator, and
The polymerization initiator is a persulfate having a solubility of 4 g or more in 100 g of water at a water temperature of 20 ° C., and
The monomer includes a styrene monomer, a (meth) acrylic acid ester monomer, and a vinyl monomer having an acid group. 2. The toner according to claim 1, wherein the toner content is 0.1 to 5.0% by weight in the toner. When the addition amount of the polymerization initiator added when producing the first resin particles by emulsion polymerization is PS1, and the addition amount of the polymerization initiator added when producing the second resin particles by emulsion polymerization is PS2,
The toner according to claim 1, wherein PS1 / PS2 is 0.25 to 5.0. The wax contains at least a first wax and a second wax, the first wax has an endothermic peak temperature (melting point Tmw1 (° C.) by DSC method) of 50 to 90 ° C., and the second wax. The toner according to any one of claims 1 to 3, wherein an endothermic peak temperature (referred to as a melting point Tmw2 (° C)) of the wax by DSC method is 80 to 120 ° C. The wax includes at least a first wax and a second wax, and the first wax includes an ester wax composed of at least one of a higher alcohol having 16 to 24 carbon atoms and a higher fatty acid having 16 to 24 carbon atoms. The toner according to claim 1, wherein the second wax contains an aliphatic hydrocarbon wax. The wax includes at least a first wax and a second wax, the first wax includes a wax having an iodine value of 25 or less and a saponification value of 30 to 300, and the second wax is an aliphatic hydrocarbon type The toner according to claim 1, wherein the toner comprises a wax. The endothermic peak temperature (melting point Tmw1 (° C.)) of the first wax by DSC method is 50 to 90 ° C., and the endothermic peak temperature (melting point Tmw2 (° C.)) of the second wax by DSC method is 80 to 120 ° C. The toner according to claim 5 or 6. The toner according to claim 4, wherein the melting point of the second wax is 5 ° C. or more and 50 ° C. or less higher than the melting point of the first wax. The toner according to claim 1, wherein the dispersant for dispersing the colorant is a surfactant mainly composed of a nonionic surfactant. The toner according to claim 1, wherein the dispersant for dispersing the wax is a surfactant mainly composed of a nonionic surfactant. The main component of the surfactant used in the resin particle dispersion in which the resin particles are dispersed or the second resin particle dispersion in which the second resin particles are dispersed is a nonionic surfactant, and
The dispersant for dispersing the colorant is a surfactant mainly composed of a nonionic surfactant,
The toner according to claim 1, wherein the dispersant for dispersing the wax is a surfactant mainly composed of a nonionic surfactant. The surfactant used in the resin particle dispersion in which the resin particles are dispersed or the second resin particle dispersion in which the second resin particles are dispersed is a mixture of a nonionic surfactant and an ionic surfactant, and the resin dispersion The toner according to claim 1 or 2, wherein the mixing ratio of the surfactant used in the liquid is such that the nonionic surfactant has 50 to 95 wt% or more of the entire surfactant. The surfactant used in the resin particle dispersion in which the resin particles are dispersed is a mixture of a nonionic surfactant and an ionic surfactant, and the mixing ratio of the surfactant used in the resin dispersion is a nonionic surfactant. Is a structure having 50 to 95 wt% or more based on the entire surfactant, and
The toner according to claim 1 or 2, wherein the main component of the surfactant used in the colorant particle dispersion and the wax particle dispersion is only a nonionic surfactant. The resin particle dispersion is dispersed with a mixed surfactant with a nonionic surfactant and an anionic surfactant, and
The colorant particle dispersion is dispersed with a nonionic surfactant, and
The wax particle dispersion is dispersed with a nonionic surfactant, and
2. The constitution is such that the average ethylene oxide addition mole number of the nonionic surfactant for dispersing the wax particles is larger than the average ethylene oxide addition mole number of the nonionic surfactant for dispersing the colorant particles. 2. The toner according to 2. In an aqueous medium, a monomer containing a styrene monomer, a (meth) acrylic acid ester monomer, and a vinyl compound having an acid group in an amount of 0.1 to 5.0% by weight in all monomers, Emulsion polymerization is performed using a polymerization initiator that is a persulfate having a solubility in 100 g of water at a water temperature of 20 ° C. of 4 g or more and is added in an amount of 0.5 to 2.0 parts by weight with respect to 100 parts by weight of the monomer. Producing a second resin particle dispersion in which the resin particles are dispersed;
In the aqueous medium, at least the first resin particle dispersion in which the first resin particles are dispersed, the colorant particle dispersion in which the colorant particles are dispersed, and the endothermic peak temperature by DSC (Differential Scanning Calorimetry) method is 50. A step of mixing and aggregating a wax particle dispersion in which wax particles having a temperature of ˜120 ° C. are dispersed to produce core particles;
Adding a second resin particle dispersion in which the second resin particles are dispersed to a core particle dispersion containing the core particles, and fusing the second resin particles to the core particles. And a method for producing the toner. The first resin particle dispersion is obtained by emulsion polymerization of a monomer using a polymerization initiator in an aqueous medium,
1.0 to 2.5 parts by weight with respect to 100 parts by weight of the monomer of the polymerization initiator, and
The polymerization initiator is a persulfate having a solubility of 4 g or more in 100 g of water at a water temperature of 20 ° C., and
The monomer includes a styrene monomer, a (meth) acrylic acid ester monomer, and a vinyl monomer having an acid group. The toner manufacturing method according to claim 15, wherein the toner content is 0.1 to 5.0% by weight in the toner. The addition amount of the polymerization initiator added when producing the first resin particles by emulsion polymerization is PS1, and the addition amount of the polymerization initiator added when producing the second resin particles by emulsion polymerization is PS2. Then
16. The toner production method according to claim 15, wherein PS1 / PS2 is 0.25 to 5.0. Producing the core particles,
At least the first resin particle dispersion in which the first resin particles are dispersed, the colorant particle dispersion in which the colorant particles are dispersed, and the wax particle dispersion in which the wax particles are dispersed are mixed to produce a mixed solution. And a step of adding a flocculant to the liquid mixture after the heat treatment of the liquid mixture to agglomerate the first resin particles, the colorant particles and the wax particles to produce core particles. The method for producing a toner according to 15 or 16. Producing the core particles,
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 to produce a mixture, and after the heat treatment of the mixture, Adding a flocculant to the mixture to produce core particles containing the first resin particles and the colorant particles;
In the core particle dispersion in which the core particles are dispersed, the first resin particle dispersion in which the first resin particles are dispersed and the wax particle dispersion in which the wax particles are dispersed are mixed, the core particles, The toner manufacturing method according to claim 15, wherein the toner particles are aggregated with the first resin particles and the wax particles to generate core particles. The method for producing a toner according to claim 17 or 19, wherein the flocculant is added after the water temperature of the liquid mixture reaches or exceeds the melting point of the wax particles. When the pH value of the core particle dispersion in which the core particles are dispersed is HS, the pH value of the second resin particle dispersion in which the second resin particles are dispersed is in the range of HS + 4 to HS-4. Item 17. A method for producing a toner according to Item 15 or 16. The toner production method according to claim 21, wherein the pH of the second resin particle dispersion in which the second resin particles are dispersed is in the range of 3.5 to 11.5. Production method. The wax contains at least a first wax and a second wax, the first wax has an endothermic peak temperature (melting point Tmw1 (° C.) by DSC method) of 50 to 90 ° C., and the second wax. The toner production method according to claim 15 or 16, wherein the endothermic peak temperature (referred to as melting point Tmw2 (° C)) of the wax by DSC method is 80 to 120 ° C. The wax includes at least a first wax and a second wax, and the first wax includes an ester wax composed of at least one of a higher alcohol having 16 to 24 carbon atoms and a higher fatty acid having 16 to 24 carbon atoms. The method for producing a toner according to any one of claims 15, 16 and 23, wherein the second wax contains an aliphatic hydrocarbon wax. The wax includes at least a first wax and a second wax, the first wax includes a wax having an iodine value of 25 or less and a saponification value of 30 to 300, and the second wax is an aliphatic hydrocarbon type 24. The method for producing a toner according to claim 15, 16 or 23, wherein the toner comprises a wax. The endothermic peak temperature (melting point Tmw1 (° C.)) of the first wax by DSC method is 50 to 90 ° C., and the endothermic peak temperature (melting point Tmw2 (° C.)) of the second wax by DSC method is 80 to 120 ° C. 27. A method for producing a toner according to claim 25 or 26. 27. The method for producing a toner according to claim 23, wherein the melting point of the second wax is higher by 5 ° C. or higher and 50 ° C. or lower than the melting point of the first wax. The method for producing a toner according to claim 15 or 16, wherein the dispersant for dispersing the colorant is a surfactant mainly composed of a nonionic surfactant. The toner manufacturing method according to claim 15 or 16, wherein the dispersant for dispersing the wax is a surfactant mainly composed of a nonionic surfactant. The main component of the surfactant used in the resin particle dispersion in which the resin particles are dispersed or the second resin particle dispersion in which the second resin particles are dispersed is a nonionic surfactant, and
The dispersant for dispersing the colorant is a surfactant mainly composed of a nonionic surfactant,
The method for producing a toner according to claim 15 or 16, wherein the dispersant for dispersing the wax is a surfactant mainly composed of a nonionic surfactant. The surfactant used in the resin particle dispersion in which the resin particles are dispersed or the second resin particle dispersion in which the second resin particles are dispersed is a mixture of a nonionic surfactant and an ionic surfactant, and the resin dispersion The method for producing a toner according to claim 15 or 16, wherein the mixing ratio of the surfactant used in the liquid is such that the nonionic surfactant has 50 to 95 wt% or more based on the entire surfactant. The surfactant used in the first resin particle dispersion in which the resin particles are dispersed is a mixture of a nonionic surfactant and an ionic surfactant, and the mixing ratio of the surfactant used in the resin dispersion is nonionic. The surfactant has a structure of 50 to 95 wt% or more based on the whole surfactant, and
The method for producing a toner according to claim 15 or 16, wherein a main component of the surfactant used in the colorant particle dispersion and the wax particle dispersion is only a nonionic surfactant. The resin particle dispersion is dispersed with a mixed surfactant with a nonionic surfactant and an anionic surfactant, and
The colorant particle dispersion is dispersed with a nonionic surfactant, and
The wax particle dispersion is dispersed with a nonionic surfactant, and
The average ethylene oxide addition mole number of the nonionic surfactant for dispersing the wax particles is larger than the average ethylene oxide addition mole number of the nonionic surfactant for dispersing the colorant particles. 16. The method for producing a toner according to 16. At least a magnetic field generating means, a heating member having a rotating action having at least a heat generating layer and a release layer that generate heat by electromagnetic induction, and a pressing member having a rotating action that forms a fixed nip with the heating member. 35. A transfer medium comprising a heating and pressing means, onto which the toner according to any one of claims 1 to 14 or the toner produced by the method according to any one of claims 15 to 33 is transferred between the heating member and the pressing member. An image forming apparatus comprising: a fixing process for passing the toner through and fixing.

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