JP2007218961A - Toner, method for manufacturing toner and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To make a small-particle-diameter toner having a sharp particle size distribution without requiring a classification step, and to provide such a toner or a two-component developer, which extends a life and prevents occurrence of voids and spattering in transfer. <P>SOLUTION: The toner contains a core particle formed by mixing in an aqueous medium at least: a resin particle dispersion prepared by dispersing resin particles; a carbon black particle dispersion prepared by dispersing carbon black particles; a cyan pigment particle dispersion prepared by dispersing cyan pigment particles; and a wax particle dispersion prepared by dispersing wax particles, and then carrying out aggregation. <P>COPYRIGHT: (C)2007,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 for realizing miniaturization, high speed, high image quality, and colorization. Therefore, a tandem color process that enables high-speed output of color images, and a clear color image with high glossiness and high translucency and non-offset properties without using fixing oil for preventing offset during fixing. Oilless fixing 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. Also, it is required to realize oilless fixing without using silicone oil or the like at the time of fixing. 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.

  The toner is generally composed of a resin component, which is a binder resin, a pigment, a charge control agent, and, if necessary, additional components such as a release agent. The toner is premixed at an appropriate ratio, and heated and kneaded by heat melting. Then, it is finely pulverized by an airflow type collision plate method and classified into fine powders 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 externally 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.

  In the conventional pulverization / classification operation in the kneading and pulverization method, there is a limit to the particle size that can be actually provided economically and in performance even if the particle size is reduced.

  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. In addition, since the toner obtained by these methods has a substantially spherical shape, there is a problem in that the toner remaining on the photosensitive member or the like is poorly cleaned and the image quality reliability is impaired.

  In 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, a step of forming aggregated particles in a dispersion obtained by dispersing at least resin particles to prepare an aggregated particle dispersion, a resin fine particle dispersion in which resin fine particles are dispersed in the aggregated particle dispersion And a method for forming the adhering particles by adhering the resin particles to the agglomerated particles, and a process for heating and fusing the adhering particles. It is disclosed that it may be performed gradually and continuously, or may be performed stepwise by dividing into a plurality of times. And the effect which was excellent in the charging performance which suppressed generation | occurrence | production of a fine particle and the particle size distribution was sharp by adding and mixing the said resin fine particle (additional particle) is described.

  In Patent Document 3 below, the content of the surfactant in the toner particles is 3% by weight or less, and the inorganic metal salt having a charge of 2 or more, for example, zinc chloride is contained at 10 ppm or more and 1% by weight or less, and ion crosslinking. The structure which improves the moisture absorption resistance by forming is disclosed. After the resin fine particle dispersion and the colorant dispersion are mixed and the aggregate dispersion is adjusted using an inorganic metal salt, the toner is formed by heating above the glass transition point of the resin and fusing the aggregate. ing. Small toner particles having excellent charging characteristics, environmental dependency, cleaning properties, transferability, and sharp particle size distribution are described.

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 is a configuration in which a dispersion of resin particles is added to a dispersion of colored particles to maintain a temperature above the glass transition temperature in succession to the salting-out / fusion process for obtaining colored particles. The amount of colorant present on the surface is small, and even if it is used for long-term image formation in a high-humidity environment, it does not cause changes in image density, fogging, and color due to changes in chargeability and developability. Is described.
Patent Document 5 listed below discloses a black toner including toner particles containing at least a binder resin and carbon black having a DBP oil absorption of 70 to 120 ml / 100 g. Since carbon black is finely dispersed and its dispersed particle size distribution is sharp, a desired image density can be achieved even with a relatively low adhesion amount, and further, it can be easily charged to a predetermined charge amount. For this reason, it is possible to sufficiently prevent the problem of void as an electrical transfer failure due to the reversely charged toner. Moreover, the effect which is excellent also in charging environment stability and stress resistance is described.

If the DBP oil absorption amount of the carbon black is too small, the carbon black will not easily get entangled with the binder resin, and the carbon black will easily migrate to the toner surface layer in the toner particles and will not be finely dispersed. The amount is not achieved. On the other hand, if the DBP oil absorption amount of carbon black is too large, there is a problem of a decrease in circularity due to a deterioration in shape controllability during production of toner particles. On the other hand, if the DBP oil absorption value is too large, the carbon black becomes difficult to wet with water, so that the dispersion stability of the carbon black aqueous dispersion is lowered. When a toner is produced using such a carbon black having low dispersion stability, aggregation is likely to occur and particle growth cannot be controlled well, and the dispersibility of carbon black in the toner deteriorates. Deteriorating effects are described.
JP-A-57-045558 Japanese Patent Laid-Open No. 10-073955 Japanese Patent Laid-Open No. 11-311877 JP 2002-116574 A Japanese Patent Laying-Open No. 2005-221836

  A method of adding a certain amount or more of a low melting point wax to improve fixability such as realization of oilless fixing is disclosed, but the wax is aggregated in an aqueous medium and aggregated with resin particles to give colored particles. When the particles are produced, the particle diameter becomes coarse with the heat treatment time, and it becomes difficult to produce small-sized particles having a narrow particle size distribution.

  In addition, in order to avoid the coarsening of the particle diameter, the method of changing the aqueous temperature and the stirring speed conversely prevents uniform mixing and aggregation with the colorant particles such as resin particles and pigments in the aqueous system. Thus, floating wax and pigment particles that are not taken into the core particles and are not involved in aggregation are likely to remain. This tendency is particularly noticeable when carbon black is used as the pigment. Conversely, if the residual carbon black particles are reduced and forced to be taken into the core particles, the particle size tends to increase or the particle size distribution tends to expand.

  If the floating wax particles or carbon black particles remain, the charge amount decreases, the toner adheres to the non-image area, and filming on the photosensitive member or transfer member occurs. Further, when the dispersibility of wax or pigment particles, particularly carbon black, in the colored particles is deteriorated, color turbidity is likely to occur in the toner image melted at the time of fixing, and the color developability of the toner becomes insufficient.

  In order to cause salting-out and fusion at the same time, after adding a salting-out agent to a dispersion in which resin particles and colorant particles are dispersed, the temperature of the dispersion becomes a glass transition of the resin particles. In the method of raising the temperature to a temperature equal to or higher than the temperature, aggregation occurs slowly with the temperature raising time, so that it is difficult to produce particles having a small particle size and a narrow particle size distribution. Further, the aggregation state of the non-fused particles tends 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, a core-shell configuration is disclosed in which toner resin particles are obtained by fusing shell resin particles to the surface of colored particles (core particles). A shell resin dispersion in which shell resin particles are dispersed is mixed with a dispersion of core particles. In the method of shelling by heating, when the shell resin particles are fused to the core particles blended with the wax described above, the presence of the wax makes the adhesion of the shell resin particles unstable, and the adhesion progresses easily. In some cases, once the shell resin particles adhere to the core particles, if the wax melts in the subsequent heat treatment step, the shell resin particles may be detached from the core particles due to the releasing action of the wax.

  SUMMARY OF THE INVENTION An object of the present invention is to provide a toner that can produce a toner having a small particle size having a sharp particle size distribution without a classification step, and a method for producing the toner. It is another object of the present invention to provide a toner that can prevent voids and splashes during transfer and can achieve high transfer efficiency.

  The toner according to the present invention includes at least a resin particle dispersion in which resin particles are dispersed, a carbon black particle dispersion in which carbon black particles are dispersed, and a cyan pigment particle dispersion in which cyan pigment particles are dispersed in an aqueous medium. And a core particle produced by mixing and aggregating a wax particle dispersion in which wax particles are dispersed.

  Further, the toner production method according to the present invention includes at least a first resin particle dispersion in which first resin particles are dispersed, a carbon black particle dispersion in which carbon black particles are dispersed, cyan, in an aqueous medium. A step of mixing a cyan pigment particle dispersion liquid in which pigment particles are dispersed and a wax particle dispersion liquid in which wax particles are dispersed to form a mixed liquid; and the first resin particles and the coloring in the presence of a flocculant A step of aggregating and fusing the agent particles and the wax particles to produce core particles; and a second resin particle dispersion in which the second resin particles are dispersed in the core particle dispersion containing the core particles. Adding and heating to fuse the second resin particles to the core particles.

  The present invention relates to a toner composition including core particles produced by mixing and agglomerating each particle dispersion in which resin particles and wax particles are dispersed, and the composition including carbon black particles and cyan pigment particles in an aqueous system. This eliminates the problem of remaining floating wax particles and carbon black particles that are not taken into the core particles and are not involved in agglomeration, and enables generation of small particle size particles with a narrow particle size distribution.

  In addition, by adopting a configuration in which the second resin particles are fused to the core particles, an effect can be obtained in terms of durability, charge stabilization, high temperature non-offset property and storage stability.

  Further, for example, when an image forming station having a plurality of photosensitive members and a developing unit is arranged side by side and applied to a tandem color process in which toner of each color is sequentially executed on a transfer member, Prevents hollowing out and reverse transfer, and high transfer efficiency can be obtained.

(1) Polymerization and agglomeration step The resin particle dispersion is prepared by subjecting the vinyl monomer to emulsion polymerization or seed polymerization in a surfactant to give a vinyl monomer homopolymer or copolymer ( A dispersion obtained by dispersing resin particles of a vinyl resin) in a surfactant is prepared. 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.

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

  A first configuration of the toner of the present invention is a resin particle dispersion in which at least first resin particles (resin particles used as core particles are referred to as first resin particles) are dispersed in an aqueous medium, carbon This is a configuration in which a carbon black particle dispersion in which black particles are dispersed, a cyan pigment particle dispersion in which cyan pigment particles are dispersed, and a wax particle dispersion in which wax particles are dispersed are mixed and aggregated to produce core particles. .

  When carbon black particles are used, the agglomeration reaction for generating the core particles proceeds rapidly, and the particle formation time tends to be shorter than other cyan, magenta and the like. For this reason, the processing time is shortened, and the shape is less likely to be spherical. In addition, carbon black particles that do not participate in aggregation tend to remain. Further, even if the processing time is increased, the shape does not easily progress to a spherical shape.

  On the contrary, when a cyan pigment is used, the agglomeration reaction for generating the core particles proceeds slowly, and the particle formation time tends to be longer than that of the black toner using carbon black. Even if the processing time is short, the shape tends to be spherical.

  Therefore, by including a cyan pigment in the carbon black, the progress of the agglomeration reaction for generating the core particles is delayed, the time for particle formation becomes slow, and the shape of the black toner using carbon black is reduced. It tends to be spherical. In addition, there is an effect of suppressing the remaining carbon black particles that do not participate in aggregation.

  At this time, the weight ratio of the carbon black particles to the cyan pigment particles is preferably (carbon black particles: cyan pigment particles), 98: 2 to 70:30. Preferably it is 95: 5-75: 25, More preferably, it is 95: 5-80: 20, More preferably, it is 95: 5-85: 15. By including cyan pigment particles in 98: 2 or more, the above-described effect appears. When more cyan pigment particles are contained than 70:30, bluishness becomes strong and black reproducibility deteriorates.

  In the first constitution of the toner of the present invention or the first constitution of the toner production method described later, the carbon black contains carbon black having a DBP oil absorption (ml / 100 g) of 45 to 70, and the cyan pigment is copper phthalocyanine. A configuration using a pigment is preferable.

  As cyan pigments, for example, phthalocyanine pigments such as Hostalm B2G (Pigment Blue 15: 3), Dainippon Ink KETBLUE111, Sanyo Pigment SANDYESUPERBLUE 1809, etc. can be preferably used. The reason is unknown, but phthalocyanine pigments are more compatible with carbon black than azo yellow pigments and quinacridone magenta pigments, and are effective in suppressing carbon black agglomeration defects and forming small core particles. Guess the material.

  In addition, by using carbon black particles with a low DBP oil absorption, 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. Thus, it has been found that the effect of suppressing the remaining carbon black particles not participating in aggregation in the core particle dispersion can be obtained. Although the reason is not clearly understood, it is presumed that carbon black larger than 70 tends to agglomerate carbon black quickly and the carbon black particles are not easily taken into the core particles. And by using together with the above-mentioned cyan pigment, it becomes an effective configuration by suppressing aggregation failure that occurs when carbon black is not taken into the core particles and by forming core particles with a small particle size.

  In the first constitution of the toner of the present invention or the first constitution of the toner production method described later, the main component of the surfactant used when preparing the first resin particle dispersion is a nonionic surfactant. It is preferable that the main component of the surfactant used in the colorant particle and wax particle dispersion is a nonionic surfactant.

The interface used for the first resin particle dispersion, carbon black particle dispersion, cyan pigment particle dispersion, and wax particle dispersion in the first configuration of the toner of the present invention or the first configuration of the toner production method described later. The surfactant is a mixture of a nonionic surfactant and an ionic surfactant, and among the surfactants used in the dispersion liquid of each particle, the blending ratio of the ionic surfactant to the entire surfactant is
A configuration in which the number of wax particles <carbon black particles ≦ cyan pigment particles <first resin particles increases in order is preferable.

  First, the first resin particles that use anionic surfactant, which is an ionic surfactant in a large proportion, start agglomeration to form nuclei, and then there are more anionic surfactants than wax particles The colorant particles used in proportion start to aggregate around the core of the resin particles.

  At this time, it is preferable that the carbon black particles and the cyan pigment particles have the same or a larger proportion of the ionic surfactant in the cyan pigment particles. Since the aggregation of the cyan pigment particles starts first, the aggregation of carbon black is delayed, which delays the progress of the aggregation reaction that generates the core particles, slows the particle formation time, and the carbon black The black toner using the toner tends to be spherical. Also, it seems that the presence of carbon black particles that do not participate in aggregation can be suppressed.

  Finally, it is presumed that the wax particles using the most nonionic surfactant are aggregated and aggregated so as to wrap the colorant particles together with the resin particles to form core particles. First, the first resin particles start to aggregate to form nuclei, and the timing of aggregation of the cyan pigment particles and carbon black causes the carbon black particles to be aggregated in the core particle dispersion without being incorporated into the core particles. This is considered to be a point that avoids the phenomenon that carbon black particles not added remain.

  Of the surfactants used in the first resin particle dispersion, it is preferable that the nonionic surfactant has 50 to 95 wt% with respect to the total surfactant. More preferably, it is 55-90 wt%, More preferably, it is 60-85 wt%. Moreover, it is preferable that nonionic surfactant has 50-100 wt% with respect to the whole surfactant among surfactant used for a colorant particle dispersion and a wax particle dispersion. More preferably, it is preferable to have 60-100 wt%, and still more preferably 60-90 wt%.

  In the first constitution of the toner of the present invention or the first constitution of the toner production method described later, the surfactant used in the first resin particle dispersion is a mixture of a nonionic surfactant and an ionic surfactant. In addition, a configuration in which the main component of the surfactant used in the wax particle dispersion and the colorant particle dispersion is only a nonionic surfactant is preferable.

  When the resin particles, the colorant particles, and the wax particles having such a structure are used and an aggregating agent is allowed to act in an aqueous medium, the resin particles first start to aggregate to form nuclei. Next, the colorant particles begin to aggregate around the cores of the resin particles. Finally, the wax particles are aggregated, and the colorant particles are encapsulated with the resin 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 by this mechanism, the presence of floating colorant particles and wax particles that are not involved in aggregation in an aqueous system is eliminated, and core particles having a small particle size, a uniform and sharp particle size distribution can be formed. .

  In the configuration in which the mixed system of the nonionic surfactant and the ionic surfactant is used, the surfactant in the first resin particle dispersion further includes 50 to 50% of the nonionic surfactant relative to the entire surfactant. It is preferable to have 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.

In the first configuration of the toner of the present invention or the first configuration of the toner production method described later, the resin particle dispersion is dispersed with a mixed surfactant of 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 nonionic interface in which the carbon black particles, cyan pigment particles and wax particles are dispersed. The average ethylene oxide addition mole number of the activator is
Cyan pigment particles ≦ carbon black particles <the wax particles,
The structure which enlarges in this order is preferable. This is because the nonionic surfactant having a smaller average number of moles of added ethylene oxide tends to have higher cohesiveness with respect 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.

  If the average ethylene oxide addition mole number of the nonionic surfactant is smaller than 18, the cohesiveness of the pigment particles with respect to the coagulant becomes too high, and grows into large particles before being surrounded by the resin, and is incorporated into the toner particles. It will not be. 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 carbon black fine particles do not agglomerate and exist as fine particles in the reaction solution. The toner particles are not taken into the toner particles.

  A configuration in which the nonionic surfactant used for dispersing the pigment 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 dripped into an aggregating agent aqueous solution of various concentrations (for example, magnesium sulfate aqueous solution) and the particles aggregate 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 an aggregating agent is allowed to act in a solution using the resin particles having such a configuration, the colorant particles and the wax particles, the resin particles using the anionic surfactant start to agglomerate and the nuclei are formed. it can. Next, cyan pigment particles and carbon black particles using a nonionic surfactant having a small average number of moles of added ethylene oxide begin to aggregate around the cores of the resin particles. Finally, it is presumed that wax particles using a nonionic surfactant having a large average mole number of ethylene oxide added aggregate to form core particles by aggregating the colorant particles together with the resin particles.

  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 relative to the pigment particles is preferably 10 to 20 parts by weight with respect to 100 parts by weight of carbon black in terms of dispersion stability.

  The first configuration of the toner production method of the present invention is the first resin particle dispersion in which the first resin particles are dispersed in the aqueous medium, the carbon black particle dispersion in which the carbon black particles are dispersed, and cyan. A step of mixing a cyan pigment particle dispersion in which pigment particles are dispersed and a wax particle dispersion in which wax particles are dispersed to produce a mixed dispersion; and in the presence of a flocculant, the first resin particles, A step of agglomerating and fusing the colorant particles and the wax particles to produce core particles; and a second resin particle dispersion in which a second resin particle is dispersed in a core particle dispersion containing the core particles. And a step of adding a liquid and heating to fuse the second resin particles to the core particles.

  A glass-lined SUS kettle as a reaction kettle used for preferred mixing, agglomeration, and fusion, and there is no particular limitation on the stirring blade for stirring the dispersion, but the blade shape is wide in the depth direction ( A flat blade is effective. As the flat plate wing, a Max Blend wing manufactured by Sumitomo Heavy Industries, Ltd., a full zone wing manufactured by Shin Steel Pantech Co., 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 first resin particles are added. By heating the aqueous medium above the glass transition temperature (Tg) and / or above the melting point of the wax, the first resin particles, carbon black particles, cyan pigment particles and wax particles at least partially melted aggregated. Core particles can be generated.

  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 core having a predetermined volume average particle diameter in which at least a part of the at least first resin particles, colorant particles, and wax particles are melted and aggregated by adding a water-soluble inorganic salt and heat-treating. Particles are formed. 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 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 ( Heat treatment at a certain temperature or higher (preferably 80 ° C. or higher in order to sufficiently disperse the residue) for a certain time (preferably about 1 to 5 hours) after emulsion polymerization. It is preferable to apply. Preferably it is 4 or less, More preferably, it is 1.8 or less.

  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 carbon black particle dispersion, the cyan pigment particle dispersion, and the wax in an aqueous medium. A mixed dispersion is produced by mixing the particle 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, there can be considered a method in which the mixed liquid and the flocculant described above are mixed in advance, and then the mixed dispersion is heated and heated to a temperature higher than the glass transition point of the first resin. In the method, since the agglomeration reaction occurs slowly with the temperature rising time, it is 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 distribution and a narrow particle size distribution in which wax and colorant are uniformly encapsulated.

  The flocculant to be added uses an aqueous solution containing a water-soluble inorganic salt having a constant water concentration. After adjusting the pH value of the aqueous solution containing the water-soluble inorganic salt, at least the first resin particles are added. The dispersed first resin particle dispersion, carbon black particle dispersion in which carbon black particles are dispersed, cyan pigment particle dispersion in which cyan pigment particles are dispersed, and wax particle dispersion in which wax particles are dispersed are mixed. It is also preferable to take a configuration of adding to the mixed dispersion.

  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 aggregated 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 having a different pH value is added to the mixed dispersion, the pH balance of the liquid is abruptly disturbed, so that the agglomeration reaction is difficult to proceed with delay, and the aggregated particles tend to be coarse. 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 aggregated particles become coarse or the particle size distribution becomes broad.

  In the first configuration of the toner production method of the present invention, the timing of adding the flocculant is the mixing of the first resin particle dispersion, the carbon black particle dispersion, the cyan pigment particle dispersion, and the wax particle dispersion. A configuration in which the flocculant is added after the temperature of the mixed dispersion obtained reaches or exceeds the melting point of the wax measured by the DSC method described later. 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 particles proceeds by adding a flocculant, and then 0.5 to 5 hours, preferably 0.5 to 3 hours, more preferably 1 Heat treatment for ˜2 hours produces core particles with 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.

  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.

  A configuration in which 1 to 100 parts by weight of the flocculant is dropped with respect to 100 parts by weight of the total of the first resin particles, carbon black particles, cyan pigment particles, and wax particles is preferable. Preferably it is 1-50 weight part, More preferably, it is 15-30 weight part, More preferably, it is 10-20 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.

  In addition to the first resin particle dispersion, the carbon black particle dispersion, the cyan pigment particle dispersion, and the wax particle dispersion, the mixed dispersion may be added with ion exchange water in order to adjust the solid concentration in the liquid. It doesn't matter. The solid concentration in the liquid is preferably 5 to 40 wt%.

  Further, as the flocculant, it is also preferable to use a water-soluble inorganic salt adjusted to a constant concentration with ion exchange water or the like. The concentration of the flocculant aqueous solution is preferably 5 to 50 wt%.

  In the first configuration of the toner of the present invention or the first configuration of the toner production method, the second resin particle dispersion in which the second resin particles are dispersed is added to the core particle dispersion in which the core particles are dispersed. A configuration is also preferred in which toner base particles are produced by mixing and heat-treating the resin particles to the core particles and then fusing the second resin particles to the core particles (hereinafter sometimes referred to as shelling).

  In the toner of the present invention, carbon black particles, cyan pigment particles, and wax particles are incorporated in the toner, but a trace amount of pigment and wax may be present on the outermost surface. When accumulated in the electrophotographic apparatus, the image quality is adversely affected. Therefore, in order to prevent such a problem in advance, the second resin particles are also bonded to the core particles as a fusion layer (also referred to as a shell layer). It is desirable to form In addition, from the viewpoint of improving 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 high temperatures, high-molecular weight emulsified resin fine particles are used. From the viewpoint of charging stability, it is desirable to form resin particles containing a charge adjusting agent as a shell layer.

  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, if 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.

  It is preferable that the main component of the surfactant used in the second resin dispersion is a nonionic surfactant, and the surfactant used in the second resin particle dispersion is a nonionic surfactant and an ionic type. A configuration in which a surfactant is mixed is also preferable. In this configuration, the nonionic surfactant preferably has 50 to 95 wt% with respect to the total surfactant. 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, adhesion of the second resin particle fine particles to the core particles can be promoted. 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.

  After the colored particles are formed, toner base particles can be obtained through an arbitrary 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 flocculant, a water-soluble inorganic salt is selected, 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.
(2) Wax In oilless fixing without using oil in the fixing roller, low temperature fixing property, high temperature non-offset property, or improvement in separation property of the transfer medium such as copy paper on which the toner melted at the time of fixing is mounted. Therefore, it is preferable to add a wax in order to expand the margin of the fixing characteristics that contradict the low temperature fixing, high temperature offset resistance and high temperature storage stability, and to improve the functionality, A configuration in which wax is added is preferable.

  In the first constitution of the toner of the present invention or the first constitution of the toner production method, it is preferable that the wax contains at least a wax having an endothermic peak temperature of 50 to 90 ° C. in order to realize low-temperature fixing. Preferably it is 55-85 degreeC, More preferably, it is 58-85 degreeC, More preferably, it is 68-74 degreeC. When the temperature is lower than 50 ° C., the agglomeration proceeds too quickly, and the produced core particles tend to be coarse. Moreover, the storage stability in a high temperature preservation state deteriorates. When it is higher than 90 ° C., the low-temperature fixability and color glossiness are not improved.

  Using the low melting point wax having a melting point of 50 to 90 ° C., and using a plurality of waxes having different melting points, which will be described later, using carbon black as a colorant, agglomerates with resin particles to produce core particles. In some cases, the use of a wax that starts melting at a low temperature and carbon black that has high cohesiveness and quick particle growth makes the core particles coarse, making it difficult to produce particles with a small particle size and a narrow particle size distribution.

  However, if the coarse particle size is suppressed by adjusting the temperature or the stirring speed, etc., the carbon black particles grow first without carbon black being taken into the core particles. In the core particle dispersion liquid, carbon black particles that do not participate in aggregation remain, and the reaction liquid remains black and turbid and becomes difficult to become transparent. In addition, residual wax particles that did not participate in aggregation were observed, and the particle size distribution tended to widen.

  Therefore, by using the above-mentioned cyan pigment particles together with the carbon black particles, the phenomenon that the carbon black particles grow first can be suppressed, and even if the core particles are made smaller, the carbon black particles are taken into the core particles. Thus, it has been found that the effect of eliminating carbon black particles remaining in the core particle dispersion without being aggregated can be obtained.

  In the first configuration of the toner of the present invention or the first configuration of the toner production method, as a preferred embodiment of the wax, a configuration in which a plurality of waxes are added is preferable.

  As a preferred first configuration of the wax, the wax contains at least the first wax and the second wax, and the endothermic peak temperature (referred to as the melting point Tmw1 (° C.)) of the first wax by the DSC method is 50 to 50. A configuration in which the endothermic peak temperature (melting point Tmw2 (° C.)) of the second wax by the DSC method is 90 to 120 ° C. is preferable. Tmw1 is preferably 55 to 85 ° C, more preferably 58 to 85 ° C, and still more preferably 68 to 74 ° C. Tmw2 is more preferably 85 to 100 ° C, further preferably 90 to 100 ° C.

  By using waxes having different melting points, the functions of the wax are separated, so that both low temperature fixing and high temperature offset resistance can be achieved, and a wide fixing temperature range characteristic can be obtained. However, using carbon black with high cohesiveness and rapid particle growth, and using waxes with different melting points, aggregates of low-melting wax particles and high-melting particle waxes easily form in the aqueous medium. It tends to be in a dispersed state in which wax is unevenly distributed. In addition, carbon black particles and wax particles that do not participate in aggregation are likely to remain in the core particle dispersion, and the particle size distribution of the core particles is likely to be widened and the shape is likely to be non-uniform.

  Therefore, as described above, by using the above-mentioned cyan pigment particles together with the carbon black particles, the residual carbon black particles and wax particles that do not participate in the aggregation in the core particle dispersion are suppressed, and the particle size distribution is small and narrow. Generation of core particles can be enabled.

  When Tmw1 is smaller than 50 ° C., the produced core particles are likely to be coarsened. Moreover, storage stability deteriorates. When it is higher than 90 ° C., the low-temperature fixability and color glossiness are not improved. 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. The shape tends to be non-uniform.

  In an embodiment in which a plurality of waxes are used, a preferred second configuration of the wax is a configuration in which the wax includes at least the first wax and the second wax, and the first wax has 16 to 24 carbon atoms. It is preferable that the second wax contains an aliphatic hydrocarbon wax and an ester wax composed of at least one of a higher alcohol and a higher fatty acid having 16 to 24 carbon atoms.

  In an embodiment using a plurality of waxes, as a preferred third configuration of the wax, the wax contains at least a first wax and a second wax, the first wax has an iodine value of 25 or less, and a saponification value. In which the second wax contains an aliphatic hydrocarbon wax.

  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., 55 to 85 ° C., more preferably 58 to It is 85 degreeC, More preferably, it is 68-74 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, 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., more preferably 90 to 100 ° C. 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 core particles are formed together with the resin, the colorant and the aliphatic hydrocarbon wax in the aqueous system, the aliphatic hydrocarbon wax is used as a resin because of its compatibility with the resin. The agglomeration tends to hardly occur, and the presence of particles floating without the wax being taken into the core particles, or the aggregation of the core particles does not progress, 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. Since the aliphatic hydrocarbon wax does not progress in compatibilization with the resin, this wax can exhibit a function of improving the high temperature offset property and the separation property from paper. That is, the first wax has a function as a dispersion aid during the emulsification dispersion treatment of the aliphatic hydrocarbon wax, and further has a function as a low-temperature fixing aid.

  In an embodiment in which a plurality of waxes are added, when wax particles having different melting points are aggregated with the first resin particles and colorant particles in an aqueous system to form core particles, the wax is uniformly taken into the toner. In order to improve core particle formation with a small particle size and a narrow particle size distribution, the first wax and the second wax are collectively mixed and emulsified and co-dispersed in the production of a wax particle dispersion. It is preferable. 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.

  This is because when the dispersion obtained by separately emulsifying and dispersing the first wax and the second wax is mixed with the resin dispersion and the colorant dispersion and heated and aggregated, the difference in the melting rate of the wax This is presumably because the presence of particles that are not incorporated into the core particles is likely to increase, and the particle size distribution tends to be broad without agglomeration of some core particles.

  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 aggregated particles of these waxes with a resin and a colorant dispersion, core particles having a small particle size and a narrow particle size distribution can be formed without releasing the wax.

  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 functions of a plurality of waxes can be efficiently separated, and there is an effect of achieving both low-temperature fixing properties, high-temperature non-offset properties, and paper separation properties. When the temperature is lower than 5 ° C., it is difficult to achieve the effects of achieving both low-temperature fixability, high-temperature non-offset property, and paper separation failure. When the temperature is higher than 50 ° C., the first wax and the second wax are phase-separated and cannot be uniformly taken into the toner particles.

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

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

  Further, the preferred first wax composition includes a wax having an iodine value of 25 or less and a saponification value of 30 to 300. By using 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 emulsion 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 emulsion 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, Q100 type (genuine electric refrigerator is used for cooling) , Set the measurement mode to “standard”, purge gas (N2) flow rate 50 ml / min, power on, set the temperature in the measurement cell to 30 ° C., leave it in that state for 1 hour, and 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 is prevented, and core particles having a small particle size and a narrow particle size distribution can be generated.

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

  As the second wax, a fatty acid hydrocarbon wax such as polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax, microcrystalline wax, paraffin wax, or Fischer-to-push wax can be preferably used.

  Further, in order to uniformly encapsulate the wax in the resin without desorbing and floating during the mixing and aggregation, the dispersion particle size distribution of the wax, the composition of the wax, and the melting characteristics of the wax are also affected.

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

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

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

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

  Furthermore, when obtaining aggregated particles obtained by heating the core particles in an aqueous system, the molten resin particles surround and include the molten wax particles because of the surface tension, and the release agent is included in the resin. It becomes easy.

  PR16 is greater than 200 nm, 50% diameter (PR50) is greater than 300 nm, PR84 is greater than 400 nm, PR84 / PR16 is greater than 2.0, particles of 200 nm or less are less than 65% by volume, and particles greater than 500 nm When the amount exceeds 10% by volume, the wax is less likely to be taken in between the resin particles, and aggregation tends to occur frequently only between the waxes themselves. In addition, particles that are not taken into the core particles and float in water tend to increase. When the core particles are obtained by heating the core particles in an aqueous system to obtain molten core particles, the molten resin particles are unlikely 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 treatment liquid can be formed by a treatment for 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 prepared.

  The particle size distribution of fine particles can be made narrower and sharper than a disperser such as a homogenizer. Further, even if the particles are left for a long time, the fine particles forming the dispersion liquid do not re-aggregate and can maintain a stable dispersion state, and the storage 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. Alternatively, the wax is dissolved in an oily solvent. This solution is obtained by dispersing fine particles in water together with a surfactant and a polymer electrolyte using the disperser shown in FIGS. 3, 4, 5, and 6, and then evaporating the oily solvent by heating or decompressing. .

The particle size can be measured using a Horiba laser diffraction particle size measuring device (LA920), a Shimadzu laser diffraction particle size measuring device (SALD2100), or the like.
(3) Resin Examples of the resin fine particles of the toner of the present embodiment include a thermoplastic binder resin. Specifically, styrenes such as styrene, parachlorostyrene and α-methylstyrene, acrylic monomers such as methyl acrylate, ethyl acrylate, n-propyl acrylate, lauryl acrylate and 2-ethylhexyl acrylate , Methacrylic monomers such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, and other carboxyl groups such as acrylic acid, methacrylic acid, maleic acid and fumaric acid Homopolymers such as unsaturated polyvalent carboxylic acid-based monomers possessed as, copolymers obtained by combining two or more of these monomers, or mixtures thereof.

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

  The content of the resin particles in the resin particle dispersion is usually 5 to 50% by weight, preferably 10 to 40% by weight.

The first resin constituting the core particles in order to eliminate the presence of floating particles in the formation of aggregated particles (sometimes referred to as core particles) by agglutination reaction with wax and colorant, and to form particles with a sharp particle size distribution The glass transition point of the particles is preferably 45 ° C to 60 ° C and the softening point is 90 ° C to 140 ° C. More preferably, the glass transition point is 45 ° C to 55 ° C, the softening point is 90 ° C to 135 ° C, and still more preferably, the glass transition point is 45 ° C to 52 ° C, and the softening point is 90 ° C to 130 ° C. preferable.
Moreover, as a preferable structure of the first resin particles, the weight average molecular weight (Mw) is 10,000 to 60,000, and the ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.5 to 6. Some configurations are preferred. It is preferable that the weight average molecular weight (Mw) is 10,000 to 50,000 and the ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.5 to 3.9. More preferably, the weight average molecular weight (Mw) is 10,000 to 30,000, and the ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.5 to 3.

  With the configuration including the first resin particles and the wax, it is possible to prevent the core particles from becoming coarse and 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.

  A configuration in which the second resin particles are fused to the core particles to form a resin fusion layer is also preferable, and the resin has a glass transition point of 55 ° C to 75 ° C and a softening point of 140 ° C. ˜180 ° C., weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is 50,000 to 500,000, ratio Mw / Mn of weight average molecular weight (Mw) to number average molecular weight (Mn) is 2 to 10 The structure which is is preferable. More preferably, the glass transition point is 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.

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

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

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

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

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

The glass transition point of the resin was raised to 100 ° C. using a differential scanning calorimeter (Shimadzu DSC-50), allowed to stand at that temperature for 3 minutes, and then cooled to room temperature at a cooling rate of 10 ° C./min. When the sample was heated at a heating rate of 10 ° C / min and the thermal history was measured, the maximum slope between the base line extension below the glass transition point and the peak rising portion to the peak apex was obtained. Says the temperature of the intersection with the indicated tangent.
(4) Pigment Carbon black is used as the black pigment of the colorant (pigment) used in the present embodiment. 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.

  When a core particle is formed by agglomerating together with resin particles using a wax having a low melting point of 50 to 90 ° C. and carbon black, a wax that starts melting from a low temperature and a carbon black that has high cohesiveness and rapid particle growth With the use, the core particles are coarsened, and it tends to be difficult to produce particles having a small particle size and a narrow particle size distribution.

  Therefore, by using carbon black particles having a low 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. Thus, it has been found that an effect of eliminating carbon black particles remaining in the core particle dispersion without being aggregated can be obtained. Although the reason is not clearly understood, it is presumed that carbon black larger than 70 tends to agglomerate carbon black quickly and the carbon black particles are not easily taken into the 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.

  Examples of cyan pigments include C.I. I. Blue dyes and pigments of phthalocyanine and its derivatives such as Pigment Blue 15: 3 can be preferably used. Phthalocyanine pigments such as SANDYESUPERBLUE 1809 manufactured by the company can be preferably used.

  Examples of pigments used as color toners include yellow pigments, 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.

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).
(5) 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 the silane coupling agent, dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, hexamethyldisilazane, allylphenyldichlorosilane, vinyltriethoxysilane, divinylchlorosilane or dimethylvinylchlorosilane can be suitably 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 by the present invention is smooth and homogenized, and the surface is composed only of a resin. Although advantageous, the compatibility with the external additive used with respect to charge imparting property or charge retention property 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 (%).
(6) Toner powder physical properties In this embodiment, toner base particles containing a binder resin, a colorant and a wax have a volume average particle size of 3 to 7 μm and a toner particle size of 2.52 to 4 μm in the number distribution. Toner having a mother particle content of 10 to 75% by number, a toner particle size of 25 to 75% by volume in a volume distribution of 4 to 6.06 μm, and a toner particle size of 8 μm or more in a volume distribution Toner containing 5% by volume or less of mother particles and having a particle size of 4 to 6.06 μm in the volume distribution, V46 being the volume percent of the mother particles having a particle size of 4 to 6.06 μm in the number distribution When the number% of the base particles is P46, P46 / V46 is in the range of 0.5 to 1.5, the variation coefficient in the volume average particle size is 10 to 25%, and the variation coefficient in the number particle size distribution is 10 to 10. 28% Is preferred.

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

  More preferably, the toner base particles have a volume average particle size of 3 to 5 μm, the content of toner base particles having a particle size of 2.52 to 4 μm in the number distribution is 40 to 75% by number, and 4 to 6 in the volume distribution. The toner base particles having a particle size of 0.06 μm are 45 to 75% by volume, the toner base particles having a particle size of 8 μm or more in the volume distribution are contained at 1% by volume or less, and P46 / V46 is 0.5 It is preferable that the variation coefficient in the volume average particle size is 10 to 15% and the variation coefficient of the number particle size distribution is 10 to 18%.

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

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

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

  If toner base particles having a particle size of 4 to 6.06 μm in the volume distribution exceed 75% by volume, it is impossible to achieve both image quality and transfer. When it is less than 25% by volume, the image quality is deteriorated.

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

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

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

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

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

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

Further, the degree of compression is calculated from the static bulk density and the dynamic bulk density, which is one of the indicators of toner fluidity. The fluidity of the toner is affected by the particle size distribution of the toner, the toner particle shape, the external additive, and the type and amount of the wax. When the toner particle size distribution is narrow and the amount of fine powder is small, the toner surface has few irregularities and the shape is nearly spherical, the amount of external additive added is large, or the particle size of the external additive is small, the degree of compression is small. The fluidity of the toner becomes higher. The degree of compression is preferably 5 to 40%. More preferably, it is 10 to 30%. It is possible to achieve both oilless fixing and tandem multi-layer transfer. If it is less than 5%, the fixability is lowered, and the translucency is particularly likely to deteriorate. Toner scattering tends to increase from the developing roller. Transferability greater than 40% is lowered, and tandem-type deficiency occurs and transfer failure occurs.
(7) Oilless Color Fixation In this embodiment, the present invention is suitably used for an electrophotographic apparatus having a fixing process of an oilless fixing configuration in which oil is not used as a toner fixing means. 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.
(8) 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 photosensitive member, a charging means, and a toner carrier, and a static image formed on the image carrier. A primary transfer process in which a toner image obtained by developing an electrostatic latent image is transferred to the transfer member by bringing an endless transfer member into contact with the image carrier is sequentially executed, and a multilayer image is formed on the transfer member. A transfer process configured to execute a secondary transfer process in which a multi-layer toner image formed on the transfer body is then collectively transferred to a transfer medium such as paper or OHP. When the distance from the first primary transfer position to the second primary transfer position is d1 (mm) and the peripheral speed of the photosensitive member is v (mm / s), the transfer position satisfies d1 / v ≦ 0.65. Take the configuration in the machine The size of the printer and the printing speed are both compatible. 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.

(1) Carrier production example
39.7Mol% create MnO Conversion (a) a carrier CA1, 9.9 mol% in terms of MgO, in 0.8 mol% wet ball mill 49.6Mol% and SrO terms in terms _{of Fe} 2 _{O 3,} and ground for 10 hours, After mixing and drying, pre-baking was performed by holding at 950 ° C. for 4 hours. 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 Next, examples of the toner of the present invention will be described, but the present invention is not limited to these examples.
(Table 1) shows the binders obtained in the resin particle dispersions (RL1, RL2, RL3, RH1, RH2, rl4, rl5, rh3, rh4) according to the present invention, which were prepared as preparation examples of the resin particle dispersion. The characteristic of resin is shown. “Mn” is the number average molecular weight, “Mw” is the weight average molecular weight, “Mz” is the Z average molecular weight, and “Mw / Mn” is the ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn). , “Mz / Mn” is the ratio Mz / Mn of the Z average molecular weight (Mz) to the number average molecular weight (Mn), “Mp” is the peak value of molecular weight, Tg (° C.) is the glass transition point, and Ts (° C.) is softened. Represents a 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 RL1 A monomer liquid composed of 240.1 g of styrene, 59.9 g of n-butyl acrylate, and 4.5 g of acrylic acid was added to 440 g of ion-exchanged water, and a nonionic surfactant. (Sanyo Kasei Co., Ltd .: Nonipol 400) 7.2 g, anionic surfactant (Daiichi Kogyo Seiyaku, Neogen S20-F (20% concentration)) 24 g (substantial anion amount 4.8 g), dodecanethiol 6 g were used. 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 2 hours, and resin particles having Mn of 7200, Mw of 13800, Mz of 20500, Mp of 10800, Ts of 98 ° C., Tg of 52 ° C., and a median diameter of 0.14 μm are dispersed. A resin particle dispersion RL1 was prepared. The pH of the resin dispersion at this time was 1.8.

  (Table 3) shows monomers used for each resin particle dispersion based on the preparation of the resin particle dispersion RL1 in the emulsion polymerization of each resin particle dispersion RL2, RL3, RH1, RH2, rl4, rl5, rh3, rh4. The blending amount of etc. is shown.

(3) Preparation of Pigment Dispersion (Table 4) The black pigment and cyan pigment used in Table 5 and the surfactant used are shown.

(a) Preparation of pigment particle dispersion CBS1 In a 1 L beaker, 308 g of ion exchange 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 CBS-1. 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, based on the adjustment conditions of the pigment particle dispersion CBS-1, the conditions of each black pigment dispersion, the black pigment used for each cyan pigment dispersion, the cyan pigment, the surfactant used, and the black pigment dispersion ( Table 6) shows.

(4) Preparation of Wax Dispersion (Table 7), (Table 8) and (Table 9) were respectively used in the preparation of the wax particle dispersion according to the present example formed as a preparation example 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, (Table 10) shows the wax used for each wax particle dispersion wax particle dispersion (WA1 to WA4, wa5 to wa6, WA7 to WA12) based on the adjustment conditions of the wax particle dispersion WA1, and the interface used. Indicates the type and properties of the active agent. “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. Moreover, when using wax W13, W14, W15, the inside of the tank is pressurized to 0.4 MPa.
(5) Preparation of toner base
(a) Preparation of toner base M1 In a cylindrical 2 L glass container equipped with a thermometer, a cooling tube, a pH meter, and a stirring blade, 204 g of the first resin particle dispersion RL1 and 56 g of the carbon black particle dispersion CBS1 are used. Then, 6 g of cyan pigment particle dispersion PCS1 and 80 g of wax particle dispersion WA7 were added, 200 ml of ion-exchanged water was added, and the mixture was mixed for 10 min using a homogenizer (IKA Corporation: Ultra Turrax T25). Was prepared.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11.5 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. (the pH value of the mixed particle dispersion was 10.1), the pH value of the aqueous solution was adjusted to 9.0. 950 g of magnesium sulfate aqueous solution was continuously added dropwise for a required time of 30 min and heat-treated for 1 hour, and then heated to 90 ° C. and heat-treated for 3 hours to obtain core particles. The obtained core particle dispersion had a pH of 8.2.

  Thereafter, 145 g of the second resin particle dispersion RH1 having a pH adjusted to 8.5 was added in a state where the water temperature was 92 ° C., and heat treatment was performed for 1.5 hours after completion of the dropwise addition to melt the second resin particles. The attached particles were obtained.

  After cooling, the product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid dryer, and the volume average particle diameter was 3.7 μm and the coefficient of variation was 15.9.

For toner bases M2, M3, M4, M6, M7, M8, and M11, the cohesiveness of the core particles was observed by changing the carbon black particle dispersion and the wax particle dispersion based on the condition of M1.
(b) Preparation of toner base M5 In a cylindrical 2 L glass container equipped with a thermometer, a cooling tube, a pH meter, and a stirring blade, 204 g of the first resin particle dispersion RL1 and 58 g of the carbon black particle dispersion CBS12 are obtained. Then, 4 g of the cyan pigment particle dispersion PCS1 and 80 g of the wax particle dispersion WA1 were added, 150 ml of ion exchange water was added, and the mixture was mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T25). Prepared.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 11.5, and then 900 g of a 23% strength magnesium sulfate aqueous solution was added and stirred for 10 minutes. Thereafter, the temperature was raised from 20 ° C. to 90 ° C. at a rate of 1 ° C./min, followed by heat treatment for 3 hours to obtain core particles. The obtained core particle dispersion had a pH of 9.1.

  Thereafter, 145 g of the second resin particle dispersion RH1 having a pH adjusted to 6.8 was added in a state where the water temperature was 92 ° C., and heat treatment was carried out for 1.5 hours after completion of the dropwise addition to obtain the second resin particles. Fused particles were obtained.

Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid dryer, and the volume average particle diameter was 4.1 m and the coefficient of variation was 15.4.
(c) Preparation of toner base m9 In a cylindrical 2 L glass container equipped with a thermometer, cooling pipe, pH meter, stirring blade, 204 g of the first resin particle dispersion RL1 and 58 g of the carbon black particle dispersion CBS15 Then, 4 g of the cyan pigment particle dispersion PCS4 and 70 g of the wax particle dispersion WA12 were added, 150 ml of ion-exchanged water was added, and the mixture was mixed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T25). Prepared.

  Thereafter, 1N NaOH was added to the obtained mixed dispersion to adjust the pH to 9.7, and then 900 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 7.1.

  Thereafter, 145 g of the second resin particle dispersion RH1 having a pH adjusted to 6.8 was added in a state where the water temperature was 92 ° C., and heat treatment was carried out for 1.5 hours after completion of the dropwise addition to obtain the second resin particles. Fused particles were obtained.

  Then, after cooling, the reaction product (toner base material) was filtered and washed with ion-exchanged water three times. Thereafter, the obtained toner base was dried at 40 ° C. for 6 hours by a fluid-type dryer, resulting in a volume average particle size of 8.9 m and a coefficient of variation of 28.9.

  The toner bases M12, m10, m11, and m13 to m18 were evaluated by trial production by changing the carbon black particle dispersion, the cyan pigment particle dispersion, and the wax particle dispersion based on the condition (b) M5.

  Table 11 shows the respective compositions of the toner bases (M1 to M8, M11 to M12) according to the present invention prepared as examples of toner bases and the toner bases (m9 to m10, m13 to m18) for comparison. And the characteristics obtained in the produced toner base. Table 12 shows the state of core particle aggregation, d50 (μm) is the volume average particle diameter of the toner base particles, and “variation coefficient” is the particle size distribution of the toner base particles in the obtained toner base on the volume basis. The characteristic which showed the breadth is shown.

  Whether carbon black particles and wax particles are surrounded by resin particles and taken into the toner in the process of agglomerating and fusing resin particles with carbon black particles, cyan pigment particles, and wax particles This confirmation can be made by taking out the reaction solution during the aggregation and fusion reaction at regular intervals and subjecting it to centrifugation. If the carbon black particles and the wax particles are taken into the toner, the reaction solution is separated into two layers of solid and liquid when centrifuged, and the supernatant becomes colorless and transparent. When the wax fine particles are not taken into the toner, the supernatant liquid becomes cloudy. When carbon black particles are not taken into the toner, the supernatant liquid is black. When both the carbon black particles and the wax particles are not taken into the toner, the supernatant liquid is grayish black.

For the core particle aggregating property, the dispersion sampled during the core particle agglutination reaction was diluted with an equal amount of ion-exchanged water, placed in a test tube, and placed in a centrifuge at 3000 min ⁻¹ for 5 minutes. It shows a state in which the turbidity of the centrifuged supernatant is visually determined.

  In M1 to M8 and M11 to M12, the supernatant liquid becomes transparent in 2 hours (h) to 4 hours (h), and particles having a small particle size and a narrow particle size distribution are obtained.

  In m15 to m16, there was a tendency to become cloudy black due to the color of the suspended carbon black particles that did not participate in poor aggregation.

  In m17 to m18, the suspended black carbon particles that do not participate in the aggregation of poor aggregation and the presence of floating particles of wax particles remain in a grayish black color.

  Although m9, m10, m13, and m14 became substantially transparent at 6 h, slightly black particles are still seen. In addition, the particle size distribution becomes slightly large, and the particle size distribution tends to widen a little. In image evaluation, the amount of fogging and transfer of characters was slightly larger than that of other toners, but practically, it seems to be at the limit of the usable range.

  By using a cyan pigment particle dispersion liquid in which cyan pigment particles are dispersed together with a carbon black particle dispersion liquid in which carbon black particles are dispersed in this manner, wax particles and resin particles are aggregated to produce core particles, By eliminating the presence of carbon black particles due to poor aggregation and floating particles that do not participate in the aggregation of wax particles, particles having a small particle size and a narrow particle size distribution can be obtained.

  Furthermore, the use of a certain amount of carbon black DBP oil absorption and the melting point of copper phthalocyanine pigment eliminates the presence of carbon black particles due to poor aggregation and floating particles that do not participate in the aggregation of wax particles. Particles with a narrow distribution are obtained.

  Further, resin particles, carbon black particles, cyan pigment particles, and wax particles dispersed with a surfactant mixed with a nonionic surfactant and an anionic surfactant, the nonionic surfactant and the anionic interface of each particle By defining the weight mixing ratio with the active agent, it is possible to eliminate the presence of floating particles that do not participate in the aggregation of the carbon black particles and the wax particles due to poor aggregation, and to obtain particles having a small particle size and a narrow particle size distribution.

Furthermore, resin particles dispersed with a surfactant mixed with a nonionic surfactant and an anionic surfactant, carbon black particles dispersed with a nonionic surfactant, cyan pigment particles, and a nonionic surfactant. When the dispersed wax particles are aggregated, the average ethylene oxide addition mole number of the nonionic surfactant for dispersing the carbon black is increased by increasing the average ethylene oxide addition mole number of the nonionic surfactant for wax dispersion. The presence of carbon black particles due to defects and floating particles that do not participate in the aggregation of wax particles can be eliminated, and particles having a small particle size and a narrow particle size distribution can be obtained.
(6) External additive Next, examples of the external additive will be described. (Table 13) 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 Composition and External Addition Processing Next, a toner composition and an example of external addition processing will be described. Table 14 shows the material composition of the toner according to the present invention prepared as a toner preparation example. Unblended indicates no addition. Note that 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.

  The other magenta toner, cyan toner, and yellow toner were each made of the same composition as that of toner M1, using PERMANENT RUBIN F6B manufactured by Clariant, KETBLUE111 manufactured by Dainippon Ink, and PY74 manufactured by Sanyo Dye.

  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 simultaneously with image formation, a YMCK toner image is formed on the transfer belt 12 by the action of the first transfer rollers 10C and 10K. 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 last K 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 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 15) shows the results of evaluating the two-component developer used in this example by conducting a 100,000 sheet running endurance test on the composition of toner and carrier as the two-component developer and A4 size paper. Show. In the table, “◯” indicates that the evaluation result is good, “Δ” indicates that there is a problem, and “×” indicates that there is a problem.

  The two-component developers DM1 to DM8 and DM11 to DM12 using the toner according to the present invention were at a level that causes no practical problem with respect to toner filming on the photoreceptor when the running durability test was performed. . In addition, toner filming on the transfer belt was at a level causing no practical problem. Further, no transfer belt cleaning failure occurred.

  As for the image density before and after the running durability test, the two-component developers DM1 to DM8 and DM11 to DM12 using the toner according to the present invention can obtain an image with a high density of 1.3 or more. It was. Even after the running durability test, 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 developers DM1 to DM8 and DM11 to DM12 according to the present invention are all toners having a high image density and no non-image area fogging. There was no splattering, and it was high resolution. Further, the uniformity when taking the entire solid image at the time of development was also good. With regard to transferability (character skipping during transfer, reverse transfer, and transfer skipping), skipping and the like were at a level that has no practical problem. In addition, no transfer failure occurred even in a full-color image in which the three colors overlapped. The transfer efficiency was 90% or more.

  However, although m9, m10, m13, and m14 had a slight amount of background fog and transfer of characters more than other toners, they are practically at the limit of the usable range.

  Further, m15 to m18 had many carbon black free particles, low charge, and a sample that could withstand image evaluation was not obtained.

Next, (Table 16) shows the evaluation results for the fixing property, offset resistance, high-temperature storage stability, and paper wrapping property around the fixing belt. In the table, “◯” indicates that the evaluation result is good, “Δ” indicates that there is a problem, and “×” indicates that there is a problem. Here, the minimum fixing temperature and the temperature at which the offset phenomenon occurred at a high temperature were measured with 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. The storage stability was evaluated by the state of the toner after standing at 55 ° C. for 24 hours. The film transmittance for OHP was measured with a spectrophotometer U-3200 (Hitachi, Ltd.) for the transmittance of 700 nm light.

  The toner bases M1 to M8, M11, and M12 according to the present invention are obtained in a non-offset temperature range in a fixing roller that does not use oil in terms of fixability and offset resistance. Wide range from temperature to temperature at which high temperature offset phenomenon occurs. 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. The toners of tm9, tm10, tm13, and tm14 have a slightly weak offset.

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

Sectional drawing which shows the structure of the image forming apparatus used in one Example of this invention Sectional drawing which shows the structure of the fixing unit used in one Example of this invention. Schematic of the stirring and dispersing apparatus used in the embodiment of the present invention View from above of the stirring and dispersing apparatus used in the embodiment of the present invention Schematic of the stirring and dispersing apparatus used in the embodiment of the present invention View from above of the stirring and dispersing apparatus used in the embodiment of the present invention Schematic of the stirring and dispersing apparatus used in the embodiment of the present invention View from above of the stirring and dispersing apparatus used in the embodiment of the present invention Schematic of the stirring and dispersing apparatus used in the embodiment of the present invention View from above of the stirring and dispersing apparatus used in the embodiment of the present invention

Explanation of symbols

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

Claims (23)

In an aqueous medium, at least a resin particle dispersion in which resin particles are dispersed, a carbon black particle dispersion in which carbon black particles are dispersed, a cyan pigment particle dispersion in which cyan pigment particles are dispersed, and wax particles are dispersed. A toner comprising core particles produced by mixing and aggregating a wax particle dispersion. 2. The toner according to claim 1, wherein the carbon black contains carbon black having a DBP oil absorption (ml / 100 g) of 45 to 70, and the cyan pigment contains a copper phthalocyanine pigment. The surfactant used in the resin particle dispersion, carbon black particle dispersion, cyan pigment particle dispersion and wax particle dispersion is a mixture of a nonionic surfactant and an ionic surfactant,
Among the surfactants used in the dispersion liquid of each particle, the blending ratio of the ionic surfactant to the whole surfactant is large in the order of the wax particles <the carbon black particles ≦ the cyan pigment particles <the resin particles. The toner according to claim 1, which has the following structure. The surfactant used for the resin particle dispersion is a mixture of a nonionic surfactant and an ionic surfactant,
The toner according to claim 1, wherein the main component of the surfactant used in the carbon black particle dispersion, the cyan pigment 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
A wax particle dispersion is dispersed with a nonionic surfactant; and
The average ethylene oxide addition mole number of a nonionic surfactant for dispersing carbon black particles, cyan pigment particles, and wax particles increases in the order of the cyan pigment particles ≦ the carbon black particles <the wax particles. The toner described. The toner according to claim 1, wherein the nonionic surfactant has a mixing ratio of 50 to 95 wt% of the surfactant used in the resin particle dispersion with respect to the entire surfactant. The wax comprises at least a first wax and a second wax, the endothermic peak temperature of the first wax by DSC method (melting point Tmw1 (° C.)) is 50 to 90 ° C., and the second wax The toner according to claim 1, wherein the endothermic peak temperature (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 toner according to claim 6, wherein the melting point of the second wax is 5 to 50 ° C. higher than the melting point of the first wax. In an aqueous medium, at least a first resin particle dispersion in which first resin particles are dispersed, a carbon black particle dispersion in which carbon black particles are dispersed, a cyan pigment particle dispersion in which cyan pigment particles are dispersed, and Mixing a wax particle dispersion in which wax particles are dispersed to produce a mixed solution;
A step of aggregating the first resin particles, the carbon black particles, the cyan pigment particles, and the wax particles in the presence of an aggregating agent to produce core particles;
A step of adding a second resin particle dispersion in which the second resin particles are dispersed to the core particle dispersion containing the core particles, and heating to fuse the second resin particles to the core particles. And a method for producing a toner. Resin particle dispersion in which first resin particles are dispersed, carbon black particle dispersion in which carbon black particles are dispersed, cyan pigment particle dispersion in which cyan pigment particles are dispersed, and wax particle dispersion in which wax particles are dispersed The method for producing a toner according to claim 11, wherein the core particles are generated by a step of adding a flocculant after the heat treatment to generate a mixed liquid. Resin particle dispersion in which first resin particles are dispersed, carbon black particle dispersion in which carbon black particles are dispersed, cyan pigment particle dispersion in which cyan pigment particles are dispersed, and wax particle dispersion in which wax particles are dispersed The method for producing a toner according to claim 11, wherein the flocculant is added after the water temperature of the mixed dispersion obtained by mixing the above reaches the melting point of the wax or higher. The surfactant used in the first resin particle dispersion, carbon black particle dispersion, cyan pigment particle dispersion, and wax particle dispersion is a mixture of a nonionic surfactant and an ionic surfactant,
Among the surfactants used in the dispersion liquid of each particle, the blending ratio of the ionic surfactant to the whole surfactant is large in the order of the wax particles <the carbon black particles ≦ the cyan pigment particles <the resin particles. The method for producing a toner according to claim 11, wherein the toner has the following structure. The surfactant used in the first resin particle dispersion is a mixture of a nonionic surfactant and an ionic surfactant,
The method for producing a toner according to claim 11, wherein the main component of the surfactant used in the colorant particle dispersion and the wax particle dispersion is only a nonionic surfactant. The first 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
A wax particle dispersion is dispersed with a nonionic surfactant; and
The average ethylene oxide addition mole number of the nonionic surfactant for dispersing the carbon black particles, the cyan pigment particles and the wax particles is
14. The method for producing a toner according to claim 11, wherein the toner particle size is increased in the order of the cyan pigment particle ≦ the carbon black particle <the wax particle. The toner according to claim 11, wherein the nonionic surfactant has a mixing ratio of 50 to 95 wt% of the surfactant used in the first resin particle dispersion with respect to the total surfactant. 12. The method for producing a toner according to claim 11, wherein the carbon black includes carbon black having a DBP oil absorption (ml / 100 g) of 45 to 70, and the cyan pigment includes a copper phthalocyanine pigment. The wax comprises at least a first wax and a second wax, the endothermic peak temperature of the first wax by DSC (referred to as the melting point Tmw1 (° C.)) is 50 to 90 ° C., and the second wax The method for producing a toner according to claim 11, wherein the endothermic peak temperature (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 claim 11, 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 method for producing a toner according to claim 11, wherein the toner comprises a wax. The method for producing a toner according to claim 11, wherein the melting point of the second wax is 5 to 50 ° C. higher than the melting point of the first wax. 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. A transfer medium comprising a heating and pressurizing unit, onto which the toner according to any one of claims 1 to 10 or the toner produced by the method according to any one of claims 11 to 22 is transferred between the heating member and the pressing member. An image forming apparatus having a fixing process for fixing the toner by passing it through.

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