JP2007121473A - Toner for electrostatic image development, method for manufacturing the same, electrostatic image developer and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner for electrostatic image development capable of maintaining charging characteristics even under high temperature, high humidity and longtime stress conditions while developing an exact secondary color or tertiary color. <P>SOLUTION: In the toner for electrostatic image development comprising a core layer containing a binder resin, a colorant and a release agent and a shell layer covering the surface of the core layer, the colorant contains at least two of yellow, cyan and magenta colorants and the proportion of the colorant present in a region within 200 nm from the outermost surface of the toner is confined to ≤10%, whereby the objective toner for electrostatic image development can be provided which is so excellent in long-life performance that it can maintain charging characteristics even under high temperature, high humidity and longtime stress conditions while developing an exact secondary color or tertiary color. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an electrostatic charge image developing toner used when developing an electrostatic latent image formed by an electrophotographic method, an electrostatic recording method or the like, a manufacturing method thereof, an electrostatic charge image developer, and an image forming method.

  A method of visualizing image information through an electrostatic charge image such as electrophotography is currently used in various fields. In electrophotography, an electrostatic charge image is formed on a photoreceptor by charging and exposure processes, and the electrostatic charge image is developed with a developer containing an electrostatic charge image developing toner (hereinafter sometimes referred to as “toner”). Then, the electrostatic image is visualized through the transfer and fixing processes.

  As the developer used here, a two-component developer composed of a toner and a carrier and a one-component developer using a magnetic toner or a non-magnetic toner alone are known. A kneading and pulverizing method is used in which a thermoplastic resin is melt-kneaded together with a release agent such as a pigment, a charge control agent, and a wax, cooled, finely pulverized, and classified. In these toners, if necessary, inorganic and organic fine particles for improving fluidity and cleaning properties may be added to the surface of the toner particles. This method can produce a very good toner. However, the toner shape is irregularly shaped, fine powder is easily generated, and the release agent is easily exposed on the surface. This causes problems such as deterioration in image quality, image quality deterioration, and contamination of other members.

  Therefore, as a means for intentionally controlling the toner shape and the surface structure of the toner, a toner production method by an emulsion polymerization aggregation method (aggregation / fusion coalescence method) has been proposed (for example, Patent Document 1, 2). In these methods, a resin fine particle dispersion is generally prepared by emulsion polymerization or the like, and a colorant dispersion in which a colorant is dispersed in a solvent and a release agent dispersion in which a release agent is dispersed in a solvent are prepared. This is a manufacturing method in which agglomerated particles corresponding to the toner particle size are mixed to form a toner by heating and fusing and coalescing.

  On the other hand, carbon black is generally used as a colorant used for black toner. However, when a small amount of carbon black is used as a colorant, an image having a strong tea taste and an accurate black color cannot be obtained. As an improvement measure, by increasing the amount of carbon black and decreasing the brightness, an accurate black can be expressed, but carbon black with high conductivity is exposed on the toner surface, resulting in a decrease in chargeability. Therefore, it has been difficult to obtain a toner having good chargeability and accurate black expression using carbon black as a colorant.

  In addition, when a black toner is prepared by using the emulsion polymerization aggregation method, carbon black having high conductivity used as a colorant can be included to some extent, the toner shape can be controlled to some extent, and chargeability and durability can be improved. However, as the coalescence progresses, the colorant is pushed out to the binder resin, and the uneven distribution of the colorant and the release agent and the diffusion of the colorant and the release agent occur at the same time. The colorant and the release agent are partly unevenly distributed to the toner, and the colorant and the release agent are exposed on the toner surface, so that the toner is charged under high-temperature and high-humidity stress conditions compared to the initial charge of the toner. There was a problem that the performance decreased.

  In order to enhance the inclusion of the colorant and the release agent composed of carbon black, for example, as in Patent Document 3, after forming the core part by an emulsion polymerization aggregation method, the surface of the core part is different from the core part. There has been proposed a toner having a core-shell structure obtained by adhering fine resin particles to form a shell layer and licking the surface of the shell layer with a sample mill.

  Further, Patent Document 4 proposes that a long-life property under high temperature and high humidity can be improved by using a charge control agent for the inorganic fine particles coated on the toner particle surface. However, in the method of Patent Document 4, the inorganic fine particles are embedded and rejected under high-temperature and high-humidity stress conditions for a long time. Not improved.

  In addition, a process black toner has been put into practical use in which the color tone is adjusted by using a colorant mixed with three types of magenta, cyan, and yellow by the subtractive color mixing method without using carbon black, and the black color is expressed. .

Japanese Patent Laid-Open No. 63-282275 JP-A-6-250439 JP 2003-295195 A JP 2004-271850 A

  However, the use of the core-shell structure toner as disclosed in Patent Document 3 improves the long-life property under the condition of high temperature and high humidity for a long time by improving the coverage of the core part by the shell layer. The charge maintenance property used as the charge image developing toner is not sufficient. Further, in the method of Patent Document 4, the inorganic fine particles are embedded and rejected under high-temperature and high-humidity stress conditions for a long time, and do not function as an original charge control agent. Not improved.

  On the other hand, in the process black toner, in the kneading and pulverizing method, the dispersibility of each of the colorants of magenta, cyan, and yellow is slightly different, and it is difficult to accurately produce black, and the chargeability is slightly different for each colorant. Therefore, there arises a problem that the chargeability is not uniform. Further, in the process black toner produced by the emulsion polymerization aggregation method, the colorant is exposed to the toner surface under a high temperature and high humidity and a long-time stress condition, and there is a problem that the charge maintenance property is lowered. Furthermore, since a plurality of colorants are not mixed uniformly, the degree of exposure to the toner surface is different, and the chargeability is slightly different for each colorant, resulting in a problem that the chargeability is not uniform. Similar problems also occur in secondary color toners that use a colorant that is a mixture of two of magenta, cyan, and yellow.

  Thus, in the electrophotographic process, in order to maintain accurate performance even under stress conditions at high temperature and high humidity and for a long time while expressing an accurate secondary color or a tertiary color such as black. Although it is important to coat the shell layer uniformly and suppress the surface exposure of the colorant and release agent, it is possible to develop an accurate secondary or tertiary color in conventional toners by emulsion polymerization aggregation. In addition, even when running for a long time under high temperature and high humidity stress conditions, it has been difficult to obtain a toner having a long life that does not decrease charging.

  The present invention relates to a toner for developing an electrostatic charge image capable of maintaining a charging characteristic even under stress conditions of high temperature and high humidity and for a long time while expressing an accurate secondary color or tertiary color, and a method for producing the same, An electrostatic image developer and an image forming method are provided.

  The present invention is an electrostatic charge image developing toner comprising a core layer containing a binder resin, a colorant and a release agent, and a shell layer covering the surface of the core layer, wherein the colorant comprises a yellow layer Including at least two of a colorant, a cyan colorant, and a magenta colorant, the ratio of the colorant present in the region within 200 nm from the outermost surface of the toner is 10% or less.

  Further, the present invention is an electrostatic charge image developing toner comprising a core layer containing a binder resin, a colorant and a release agent, and a shell layer covering the surface of the core layer, wherein the colorant is , A yellow colorant, a cyan colorant, and a magenta colorant, and the ratio of the colorant present in the region within 200 nm from the outermost surface of the toner is 10% or less.

  The present invention also provides a method for producing a toner for developing an electrostatic charge image, comprising: a core layer containing a binder resin, a colorant, and a release agent; and a shell layer covering the surface of the core layer. Composite fine particles having a volume average particle diameter of 0.6 μm or less, including 1 binder resin, at least two of a yellow colorant, a cyan colorant, and a magenta colorant, and a release agent are dispersed. An aggregating step of adding a flocculant to the composite fine particle dispersion and heating to form core particles; and a first resin fine particle having a volume average particle size of 0.6 μm or less, including a second binder resin Adding a first resin fine particle dispersion in which the first resin fine particles are dispersed to adhere the first resin fine particles to the surface of the core particles to form first adhered resin agglomerated particles; A second tree containing a resin and having a volume average particle size of 0.6 μm or less Adding a second resin fine particle dispersion in which fine particles are dispersed, and attaching the second resin fine particles to the surface of the first adhering resin agglomerated particles to form second adhering resin agglomerated particles; And a fusion step of heating and fusing the second adhered resin agglomerated particles.

  The present invention also provides an electrostatic image developer containing the electrostatic image developing toner.

  Furthermore, the present invention uses a latent image forming step for forming an electrostatic latent image on the surface of the latent image holding member and a developer carried on the developer carrying member, and the electrostatic image formed on the surface of the latent image holding member. A developing step of developing a latent image to form a toner image, a transferring step of transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target, and a toner image transferred to the surface of the transfer target A fixing step of fixing the toner, wherein the developer is the electrostatic charge image developer.

  In the present invention, in the electrostatic image developing toner comprising a core layer containing a binder resin, a colorant, and a release agent, and a shell layer covering the surface of the core layer, the colorant is a yellow colorant, By containing at least two of the cyan colorant and the magenta colorant and making the ratio of the colorant present in the region within 200 nm from the outermost surface of the toner 10% or less, an accurate secondary color or tertiary A toner for developing an electrostatic image having excellent long-life characteristics that can maintain charging characteristics even under high-temperature, high-humidity and long-time stress conditions, a method for producing the same, an electrostatic image developer, and An image forming method can be provided.

  Embodiments of the present invention will be described below.

<Toner for electrostatic image development>
In an emulsion polymerization aggregation method toner made with a simple core-shell structure using a conventional colorant dispersion of carbon black and a release agent dispersion, the colorant and the release agent are used as the coalescence of the coalescence process proceeds. Since the mold agent is extruded into the binder resin, the uneven distribution of the colorant and the release agent and the diffusion of the colorant and the release agent occur at the same time, so the uneven distribution of the colorant and the release agent near the toner surface There were some. In addition, when a colorant composed of carbon black is used, an accurate black color cannot be produced if the amount of the colorant is small, and if the amount of the colorant is large, the carbon black is exposed to the toner surface under high temperature and high humidity stress conditions. However, there is a problem that the charge maintenance is low.

  The inventors of the present invention have developed an unevenness in the shell layer in the toner of the core-shell structure due to the rejection by the external additive having a large particle size under the stress condition for a long time at high temperature and high humidity, and the coloring contained in the shell layer It has been found that the exposure of the toner and the release agent to the toner surface is the cause of the decrease in the charge retention rate.

  Therefore, in the present embodiment, a core layer including a binder resin, a colorant including at least two of a yellow colorant, a cyan colorant, and a magenta colorant, and a release agent, and a surface of the core layer In the toner for developing an electrostatic charge image having a shell layer covering the toner, the ratio of the colorant present in the region within 200 nm from the outermost surface of the toner is 10% or less. When the ratio of the colorant present in the region within 200 nm from the outermost surface of the toner is 10% or more, rejection of a large particle size external additive having a radius of 200 nm or more, for example, under a stress condition due to high temperature and high humidity for a long time As a result, the colorant is exposed on the surface, so that the charge is lowered and the long life property is lowered. However, by forming a toner structure in which the ratio of the colorant present in the region within 200 nm from the outermost surface of the toner is 10% or less, the colorant and the release agent are completely covered, so that the large particle size external additive Even when the irregularities resulting from the rejection of the large particle size external additive occur on the surface of the shell layer, the amount of the colorant exposed to the shell layer is small, and the charge retention rate is low under the above conditions. A high and long-life toner can be obtained.

  In the toner according to the exemplary embodiment, the ratio of the colorant in the region within 200 nm from the toner surface is 10% or less on the cut surface of the toner. The cut surface is desirably a portion where the area (cross-sectional area) of the cut surface of the toner is the largest.

  Further, the inventors further phase-inverted and emulsified a binder resin, a colorant containing at least two of a yellow colorant, a cyan colorant and a magenta colorant, and a release agent at the same time, Using composite fine particles containing the binder resin, the colorant, and the release agent improves the dispersibility of the colorant in the core of the toner so that an accurate secondary color or tertiary color can be expressed. I found out that it was effective.

  In particular, the binder resin, the colorant containing the yellow colorant, the cyan colorant and the magenta colorant, and the release agent are simultaneously phase-inverted and emulsified, and the binder resin, the colorant and the release agent are simultaneously emulsified. The use of composite fine particles encapsulating the agent improves the dispersibility of the colorant in the toner core and is effective for accurate black expression.

  In this embodiment, for example, first, a colorant obtained by mixing a quinacridone magenta colorant, a phthalocyanine cyan colorant, and an azo yellow colorant, a release agent, and a binder resin are phase-inverted and emulsified, and the colorant is obtained. And the composite fine particles encapsulating the release agent and the solubility parameter of the binder resin of the core layer and the shell layer are specified, so that the mixed black colorant and the release agent are not dispersed in the shell layer and It is possible to obtain a toner that can be uniformly dispersed in the layer and in which the colorant and the release agent are completely coated on the toner core. Therefore, in the present embodiment, since a colorant made of carbon black having high conductivity is not used, the amount of the colorant can be increased, and accurate black can be expressed by reducing the lightness. Further, since the toner encapsulates the colorant and the release agent in the composite particles, even when the shell layer is uneven due to deterioration due to rejection by a large particle size external additive, Exposure of the mixed black colorant and the release agent can be suppressed. In other words, even when the image of the deteriorated developer is imaged for a long time under high temperature and high humidity, the charge does not decrease, the charge retention rate is maintained, the long life is excellent, and the black color is expressed accurately. It has been found that an electrostatic charge image developing toner and a method for producing the same can be easily obtained.

  Here, a specific method for calculating the ratio of the colorant present in the region within 200 nm from the outermost surface of the toner is shown below.

  After 7 g of bisphenol A type liquid epoxy resin (Asahi Kasei Chemical Co., Ltd.) and 3 g of ZENAMID250 (Henkel Japan Co., Ltd.) as a curing agent are gently mixed and prepared, 1 g of toner is mixed and left for 24 hours to obtain a cured product. A cutting sample in which the cured product was embedded at −100 ° C. using a cutting apparatus LEICA ultramicrotome (model ULTRACT UCT manufactured by Hitachi High-Technologies) equipped with a diamond knife (manufactured by Type Cryo DIATOM). Cut to make a sample for observation. The sample for observation is left in a desiccator under an atmosphere of ruthenium tetroxide (manufactured by Soekawa Rikagaku) and dyed (determination of the dyeing condition is judged from the dyeing condition of the tape left unattended). From a stained observation sample, a cross-sectional view of the toner dyed with a Hitachi high-resolution field emission scanning electron microscope (S-4800 manufactured by Hitachi High-Technologies) equipped with a transmission electron detector is 10,000 to 100,000 times larger. Observe at magnification. From the observed TEM image, the cut surface of 50 toners is observed, the area of the colorant portion of the toner is obtained, and the average value can be obtained. Further, the dispersibility of the pigment can be evaluated from the same TEM image by a method of confirming the proportion of pigments having a pigment particle size of 250 nm or less in each of the total number of pigments for 50 toners. When the ratio of the pigment having a pigment particle diameter of 250 nm or less to the whole pigment is 90% by number or more, the pigment dispersion is good and good color development is obtained, and more preferably 95% by number or more. When the ratio of the pigment having a pigment particle diameter of 250 nm or less to the whole pigment is less than 90% by number, it indicates that there are a large number of pigment aggregates and the pigment dispersibility is low, and the target color may not be obtained.

  In the cut surface of the toner in the present embodiment, the ratio of the colorant existing in the region within 200 nm from the toner surface is 10% or less. This means that the area of the colorant portion observed on the cut surface of the toner is That is, the proportion of the region 200 nm from the surface is 10% or less.

FIG. 1 shows a case where the ratio of the colorant in the region within 200 nm from the toner surface is 10% or less. FIG. 1 is a schematic diagram of an image when a flaky sample of toner cured with an epoxy resin is observed with a TEM. A toner 1 shown in FIG. 1 is present in an epoxy resin 2, and a colorant 3 is dispersed in a matrix portion 4 whose main component is a binder resin. The matrix portion 4 whose main component is a binder resin is colored with a dye. In Figure 1, S ₁ represents an area of 200nm from the toner surface (region surrounded by the outer periphery and solid toner).

  Note that the ratio of the colorant present on the cut surface of the toner may be obtained by other methods. For example, when the toner colorant is a yellow pigment (colorant), the contrast between the matrix resin in the toner and the colorant is difficult to distinguish. In such a case, the toner is detected by detecting a specific constituent element contained in the colorant in the cut surface of the toner using XMA or EPMA (X-ray micro analyzer, Electron Probe (X-ray) Micro Analyzer). The ratio of the colorant in the region within 200 nm from the surface can be determined. For example, in a toner containing a yellow colorant (PY74), a specific constituent element of the colorant by EPMA (in the case of PY74, for example, Ca derived from rosin calcium added to the PY74 pigment, K derived from rosin potassium, etc.) Detection is performed at 5 points in a region within 200 nm from the toner surface and 5 points in a region inside the region, and coloring of a region within 200 nm from the toner surface is performed based on the ratio of the average value of the five points in each region. The proportion of the agent present can be determined.

  In the electrostatic image developing toner according to the exemplary embodiment, an accurate 2 is obtained by mixing at least two of a yellow colorant, a cyan colorant, and a magenta colorant in a certain amount by an extinction color mixing method. A secondary or tertiary color can be developed. Further, by mixing a yellow colorant, a cyan colorant, and a magenta colorant in a certain amount, an accurate black color can be expressed without using carbon black.

  Destructive color mixing refers to color mixing such as pigments and printing inks, color mixing that occurs when color filters and color celluloid plates, etc. are superimposed and transmitted light.The three primary colors of destructive color mixing are usually cyan, magenta, and yellow. Three colors are used. Color printing and color photography are examples of applying this principle. In this embodiment, a secondary colorant or a tertiary color is obtained by mixing at least two of a yellow colorant, a cyan colorant, and a magenta colorant in a certain amount by using subtractive color mixing. A colorant can be obtained. Further, there is an advantage that an accurate secondary color or tertiary color can be easily expressed by changing the ratio of the amount of each color material. Furthermore, in this embodiment, instead of using a colorant made of carbon black, a process is performed by mixing a certain amount of a yellow colorant, a cyan colorant, and a magenta colorant using subtractive color mixing. A black colorant can be obtained. This method has an advantage that accurate black can be expressed easily by changing the ratio of the amount of each color material even when the blackness is shifted.

  The toner for developing an electrostatic charge image according to the exemplary embodiment contains a binder resin, a colorant, and a release agent, and mainly covers a core particle portion that imparts a low-temperature fixing property and a core particle, and is mainly stored in heat. And a so-called function-separated core-shell toner having a shell portion that imparts properties and filming resistance.

(Core particles)
The core particles included in the electrostatic image developing toner according to the exemplary embodiment include a binder resin including at least one of a crystalline resin and an amorphous resin, a colorant, and a release agent. Contains other ingredients.

  The binder resin used for the core particles in the present embodiment includes at least one of a crystalline resin and an amorphous resin, but the crystalline resin may be used alone as the first binder resin. A blend system of a crystalline resin as the first binder resin and an amorphous resin as the second binder resin may be used, or the crystalline resin and the second binder resin may be used as the first binder resin. A blend system with a crystalline resin different from the first binder resin may be used. Alternatively, an amorphous resin may be used alone as the second binder resin without using the first binder resin (crystalline resin).

  In this embodiment, “crystalline” of “crystalline resin” means a clear endothermic peak, not a step-like endothermic change in differential scanning calorimetry (DSC) of resin, core particles, or toner. It means having. Specifically, in differential scanning calorimetry (DSC) using a differential scanning calorimeter (equipment name: DSC-60 type) manufactured by Shimadzu Corporation equipped with an automatic tangential processing system, a rate of temperature increase of 10 ° C./min. A “clear” endothermic peak is assumed when the temperature from the onset point to the top of the endothermic peak when the temperature is raised at 10 ° C. is within 10 ° C. Further, from the viewpoint of sharp melt, the temperature from the onset point to the peak top of the endothermic peak is preferably within 10 ° C, and more preferably within 6 ° C. Specify any point on the flat part of the baseline in the DSC curve and any point on the flat part of the falling part from the baseline, and the intersection of the tangents of the flat part between the two points is automatically set as the “onset point”. Obtained automatically by the tangent processing system. Further, the endothermic peak may show a peak having a width of 40 to 50 ° C. when the toner is used.

  In addition, “amorphous resin” means that when the temperature from the onset point to the peak top of the endothermic peak exceeds 10 ° C. in the differential scanning calorimetry (DSC) of the resin, core particles or toner, or a clear endothermic It indicates that the resin does not have a peak. Specifically, in differential scanning calorimetry (DSC) using a differential scanning calorimeter (equipment name: DSC-60 type) manufactured by Shimadzu Corporation equipped with an automatic tangential processing system, a rate of temperature increase of 10 ° C./min. When the temperature from the onset point to the top of the endothermic peak when the temperature is raised at 10 ° C. exceeds 10 ° C., or when no clear endothermic peak is observed, it is assumed to be “amorphous”. Further, the temperature from the onset point to the peak top of the endothermic peak preferably exceeds 12 ° C., and more preferably no clear endothermic peak is observed. The method for obtaining the “onset point” in the DSC curve is the same as in the case of the “crystalline resin”.

  In this embodiment, the crystalline resin has a lower viscosity than the amorphous resin, so that the colorant and the release agent are retained at the time of fusion, and dispersed in a mesh shape at the core of the toner. From the viewpoint of improving the dispersibility of the colorant and the release agent, it is preferable to use a crystalline resin as the first binder resin and an amorphous resin as the second binder resin. When there is only one type of binder resin for the core particles, the colorant tends to be present at the core-shell interface, the adhesion between the core particles and the shell layer is reduced, the shell becomes brittle, and the toner becomes a short-life toner. There is.

  Furthermore, it is preferable that melting | fusing point of the crystalline resin used for this embodiment is the range of 50 to 100 degreeC. When the melting point of the crystalline resin is in the range of 50 ° C. to 100 ° C., the crystalline resin is dispersed in the core part together with the colorant and the release agent at an appropriate viscosity at the time of fusion, and the uneven distribution in the core part is reduced, thereby coloring In order to reduce the toner surface exposure of the agent and the release agent, it is preferable. When the melting point of the crystalline resin exceeds 100 ° C., the viscosity of the crystalline resin is high, the colorant and the release agent cannot move at once, and the colorant and the release agent are unevenly distributed in the vicinity of the toner surface, Rejection of the external additive under high-temperature and high-humidity stress conditions for a long time may expose the colorant and the release agent, resulting in a decrease in charge retention. Further, if the melting point of the crystalline resin is less than 50 ° C., the crystalline resin may be deteriorated due to stress conditions for a long time under high temperature and high humidity, and the charge retention may be lowered.

  When a crystalline resin and an amorphous resin are used in combination, when the binder resin is 100% by weight, the amorphous resin is used in an amount of 70 to 98% by weight, and the crystalline resin is used in an amount of 30 to 2% by weight. Is preferred.

  When the amorphous resin is less than 70% by weight, since the ratio of the crystalline resin is high, the compatibility between the crystalline resin and the amorphous resin does not proceed in the core portion, and voids are formed in the core portion. Under high humidity, the moisture content tends to increase with long-term stress conditions, and long-term charging may decrease. When the amorphous resin exceeds 98% by weight, the compatibility between the crystalline resin and the amorphous resin proceeds excessively in the core part, and the colorant and the release agent are pushed out to the core part surface, The colorant and the release agent are easily exposed on the toner surface.

  In this embodiment, the melting point of the crystalline resin is measured by using a differential scanning calorimeter (DSC: DSC-60 type, manufactured by Shimadzu Corporation) at a heating rate of 10 ° C. per minute from room temperature to 150 ° C. It can be determined as the melting peak temperature of the input compensation differential scanning calorimetry shown in JIS K-7121: 87 when the measurement is performed. Further, the crystalline resin may show a plurality of melting peaks, and the maximum peak is regarded as the melting point.

  For the measurement of the main maximum peak, DSC-7 manufactured by PerkinElmer is used. The temperature correction of the detection part of the apparatus uses the melting points of indium and zinc, and the correction of heat quantity uses the heat of fusion of indium. As the sample, an aluminum pan is used, an empty pan is set as a control, and the measurement is performed at a heating rate of 10 ° C./min.

[Amorphous resin]
The amorphous resin in the present embodiment is not particularly limited as long as it is an amorphous resin as defined above, and specific examples include polyester resins, vinyl resins, etc. Polyester resins are preferred because they are versatile, such as soluble in organic solvents, have many carboxyl groups, and have good chargeability.

  Specific examples of the amorphous resin include conventionally known thermoplastic binder resins, homopolymers or copolymers of styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, Ethyl acrylate, n-propyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, etc. Homopolymers or copolymers of esters having a vinyl group; Homopolymers or copolymers of vinyl nitriles such as acrylonitrile and methacrylonitrile (vinyl resins); Vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether Homopolymers or copolymers (vinyl Homopolymers or copolymers of vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketones (vinyl resins); Homopolymers or copolymers of olefins such as ethylene, propylene, butadiene, and isoprene (Olefin resin); and the like. Further, a silicone resin containing methyl silicone, methyl phenyl silicone, or the like, a polyester containing bisphenol, glycol, or the like, an epoxy resin, a polyurethane resin, a polyamide resin, a cellulose resin, a polyether resin, a polycarbonate resin, or the like may be used. These resins may be used alone or in combination of two or more.

  Specifically, among the polymerizable monomers, styrenes such as styrene, parachlorostyrene, and α-methylstyrene; short-chain alkyl acrylates such as methyl acrylate and methyl methacrylate; and acrylic acid n It is preferable to use a copolymer obtained by combining -propyl, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, or the like.

  In the present embodiment, it is preferable to use a polyester resin as the amorphous resin. After producing the polyester, it can be dispersed together with a dispersion stabilizer under high temperature and high pressure conditions to produce a resin fine particle dispersion.

  In this embodiment, a crosslinking agent can be used in the polymerization of the amorphous resin. Specific examples of the amorphous resin crosslinking agent used include aromatic polyvinyl compounds such as divinylbenzene and divinylnaphthalene; Polyvinyl esters of aromatic polycarboxylic acids such as divinyl acid, divinyl isophthalate, divinyl terephthalate, divinyl homophthalate, divinyl trimesate / trivinyl, divinyl naphthalenedicarboxylate, divinyl biphenylcarboxylate; divinyl pyridinedicarboxylate, etc. Divinyl esters of nitrogen-containing aromatic compounds; vinyl esters of unsaturated heterocyclic carboxylic acids such as vinyl pyromutinate, vinyl furan carboxylate, vinyl pyrrole-2-carboxylate, vinyl thiophene carboxylate; butanediol methacrylate, hexanedi (Meth) acrylic acid esters of linear polyhydric alcohols such as acrylate acrylate, octanediol methacrylate, decanediol acrylate, dodecanediol methacrylate, and the like; neopentyl glycol dimethacrylate, 2-hydroxy-1,3-diacryloxypropane, etc. Branched, substituted polyhydric alcohol (meth) acrylates; polyethylene glycol di (meth) acrylate, polypropylene polyethylene glycol di (meth) acrylates; divinyl succinate, divinyl fumarate, vinyl / divinyl maleate, diglycolic acid Divinyl, vinyl itaconate / divinyl, divinyl acetone dicarboxylate, divinyl glutarate, divinyl 3,3′-thiodipropionate, trans-divinyl aconitate / trivinyl, Adipic acid divinyl, pimelic acid divinyl, divinyl suberate, azelate, divinyl sebacate, divinyl dodecanedioate divinyl, the polyvinyl esters of polycarboxylic acids such as oxalic acid, divinyl; and the like.

  In this embodiment, these crosslinking agents may be used alone or in combination of two or more. Among the crosslinking agents, as the crosslinking agent in the present embodiment, since it is required that the polymerization is slower than a normal polymerizable monomer, butanediol methacrylate, hexanediol acrylate, octanediol methacrylate, (Meth) acrylic acid esters of linear polyhydric alcohols such as decanediol acrylate and dodecanediol methacrylate; Branched, substituted polyhydric alcohols such as neopentyl glycol dimethacrylate and 2-hydroxy-1,3-diacryloxypropane (Meth) acrylic acid esters of polyethylene glycol di (meth) acrylate, polypropylene polyethylene glycol di (meth) acrylate, etc. are preferably used.

  The content of the crosslinking agent is preferably in the range of 0.05 to 5% by weight, more preferably in the range of 0.1 to 1.0% by weight, based on the total amount of polymerizable monomers.

  Examples of the polymerization initiator when the amorphous resin used for the toner in the present embodiment is produced by radical polymerization of a polymerizable monomer include the following.

  There is no restriction | limiting in particular as an initiator for radical polymerization used here. Specifically, hydrogen peroxide, acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propionyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, lauroyl peroxide Ammonium persulfate, sodium persulfate, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, tert-butyl hydroperoxide pertriphenyl acetate, tert-butyl formate, Peroxides such as tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl permethoxyacetate, tert-butyl perN- (3-toluyl) carbamate, 2,2 '-Azobispro Bread, 2,2′-dichloro-2,2′-azobispropane, 1,1′-azo (methylethyl) diacetate, 2,2′-azobis (2-amidinopropane) hydrochloride, 2,2 ′ -Azobis (2-amidinopropane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutyramide, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2- Methyl methylpropionate, 2,2′-dichloro-2,2′-azobisbutane, 2,2′-azobis-2-methylbutyronitrile, dimethyl 2,2′-azobisisobutyrate, 1,1′-azobis (1 -Methylbutyronitrile-3-sodium sulfonate), 2- (4-methylphenylazo) -2-methylmalonodinitrile, 4,4'-azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenyl Zo-2-methylmalonodinitrile, 2- (4-bromophenylazo) -2-allylmalonodinitrile, 2,2'-azobis-2-methylvaleronitrile, 4,4'-azobis-4-cyanoyoshi Dimethyl herbate, 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobiscyclohexanenitrile, 2,2′-azobis-2-propylbutyronitrile, 1,1′-azobis-1 -Chlorophenylethane, 1,1'-azobis-1-cyclohexanecarbonitrile, 1,1'-azobis-1-cycloheptanenitrile, 1,1'-azobis-1-phenylethane, 1,1'-azobiscumene, 4-Nitrophenylazobenzylcyanoacetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrophenylazotrif Nylmethane, 1,1′-azobis-1,2-diphenylethane, poly (bisphenol A-4,4′-azobis-4-cyanopentanoate), poly (tetraethylene glycol-2,2′-azobisiso) Azo compounds such as butyrate), 1,4-bis (pentaethylene) -2-tetrazene, 1,4-dimethoxycarbonyl-1,4-diphenyl-2-tetrazene and the like.

  Among these, preferred are water-soluble compounds, specifically hydrogen peroxide, acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propionyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, peroxide. Examples thereof include dichlorobenzoyl, bromomethylbenzoyl peroxide, lauroyl peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, and diisopropyl peroxycarbonate.

(Crystalline resin)
The crystalline resin in the present embodiment is not particularly limited as long as it is a resin having crystallinity as defined above, and specific examples include crystalline polyester resins, crystalline vinyl trees, and the like. A crystalline polyester resin is preferable from the viewpoint of adhesion to paper at the time, chargeability, and adjustment of the melting point within a preferable range. An aliphatic crystalline polyester resin having an appropriate melting point is more preferable.

  Crystalline vinyl resins include amyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, Undecyl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, oleyl (meth) acrylate, behenyl (meth) acrylate, etc. Examples thereof include vinyl resins using long-chain alkyl or alkenyl (meth) acrylic acid esters. In the present specification, the description “(meth) acryl” means to include both “acryl” and “methacryl”.

  The crystalline polyester resin includes an acid (dicarboxylic acid) component (hereinafter sometimes referred to as “acid-derived constituent component”) and an alcohol (diol) component (hereinafter sometimes referred to as “alcohol-derived constituent component”). Is synthesized from Hereinafter, the acid-derived constituent component and the alcohol-derived constituent component will be described in more detail. In the present embodiment, a copolymer obtained by copolymerizing other components at a ratio of 50% by weight or less with respect to the crystalline polyester main chain is also referred to as crystalline polyester.

"Acid-derived components"
The acid-derived constituent component is preferably an aliphatic dicarboxylic acid, and particularly preferably a linear carboxylic acid. For example, succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid Acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, etc., or lower alkyl esters thereof, Acid anhydrides can be mentioned but are not limited to these.

  As the acid-derived constituent component, in addition to the above-mentioned aliphatic dicarboxylic acid-derived constituent component, a constituent component such as a dicarboxylic acid-derived constituent component having a double bond, a dicarboxylic acid-derived constituent component having a sulfonic acid group, or the like is included. Is preferred. The component derived from a dicarboxylic acid having a double bond is derived from a lower alkyl ester or acid anhydride of a dicarboxylic acid having a double bond, in addition to a component derived from a dicarboxylic acid having a double bond. Components are also included. The dicarboxylic acid-derived component having a sulfonic acid group is derived from a lower alkyl ester or acid anhydride of a dicarboxylic acid having a sulfonic acid group, in addition to a component derived from a dicarboxylic acid having a sulfonic acid group. Components are also included.

  A dicarboxylic acid having a double bond can be suitably used to prevent hot offset at the time of fixing because the entire resin can be crosslinked using the double bond. Examples of such dicarboxylic acids include, but are not limited to, fumaric acid, maleic acid, 3-hexenedioic acid, and 3-octenedioic acid. Moreover, these lower alkyl esters, acid anhydrides, etc. are also mentioned. Among these, fumaric acid, maleic acid and the like are preferable in terms of cost.

  A dicarboxylic acid having a sulfonic acid group is effective in that it can favorably disperse a coloring material such as a pigment. Further, if a sulfonic acid group is present when the entire resin is emulsified or suspended in water to produce fine particles, it can be emulsified or suspended without using a surfactant, as will be described later. Examples of the dicarboxylic acid having a sulfonic acid group include, but are not limited to, 2-sulfoterephthalic acid sodium salt, 5-sulfoisophthalic acid sodium salt, and sulfosuccinic acid sodium salt. Moreover, these lower alkyl esters, acid anhydrides, etc. are also mentioned. Among these, 5-sulfoisophthalic acid sodium salt is preferable in terms of cost.

  The content of acid-derived components other than these aliphatic dicarboxylic acid-derived components (dicarboxylic acid-derived component having a double bond and / or dicarboxylic acid-derived component having a sulfonic acid group) in the acid-derived component Is preferably 1 to 20 mol%, more preferably 2 to 10 mol%.

  When the content is less than 1 component mol%, pigment dispersion may not be good, the emulsified particle diameter may be large, and adjustment of the toner diameter by aggregation may be difficult. On the other hand, if it exceeds 20 component mol%, the crystallinity of the polyester resin is lowered, the melting point is lowered, the image storage stability is deteriorated, or the emulsion particle size is too small to dissolve in water, and no latex is produced. There is a case. In the present embodiment, “constituent mol%” refers to a percentage when each constituent component (acid-derived constituent component, alcohol-derived constituent component) in the polyester resin is 1 unit (mol).

"Alcohol-derived components"
The alcohol component is preferably an aliphatic diol, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol and the like are exemplified, but not limited thereto.

  The alcohol-derived constituent component preferably has an aliphatic diol-derived constituent component content of 80 constituent mol% or more, and includes other components as necessary. As the alcohol-derived constituent component, the content of the aliphatic diol-derived constituent component is more preferably 90 constituent mol% or more.

  When the content is less than 80 mol%, the crystallinity of the polyester resin is lowered and the melting point is lowered, so that toner blocking resistance, image storage stability and low-temperature fixability may be deteriorated. On the other hand, examples of other components included as necessary include components such as a diol-derived component having a double bond and a diol-derived component having a sulfonic acid group.

  Examples of the diol having a double bond include 2-butene-1,4-diol, 3-butene-1,6-diol, 4-butene-1,8-diol and the like. On the other hand, as the diol having a sulfonic acid group, 1,4-dihydroxy-2-sulfonic acid benzene sodium salt, 1,3-dihydroxymethyl-5-sulfonic acid benzene sodium salt, 2-sulfo-1,4-butane Examples include diol sodium salt.

  Alcohol-derived components in the case of adding alcohol-derived components other than these linear aliphatic diol-derived components (diol-derived component having a double bond and / or diol-derived component having a sulfonic acid group) As content in a component, 1-20 structural mol% is preferable and 2-10 structural mol% is more preferable. When the content is less than 1 constituent mol%, pigment dispersion may be poor, the emulsified particle diameter may be large, and adjustment of the toner diameter by aggregation may be difficult. On the other hand, if it exceeds 20 component mol%, the crystallinity of the polyester resin is lowered, the melting point is lowered, the image storage stability is deteriorated, or the emulsion particle size is too small to dissolve in water, and no latex is produced. There is a case.

Furthermore, the crystalline polyester resin is preferably a crystalline polyester resin having an ester concentration M defined by the following formula (1) of 0.01 or more and 0.2 or less.
M = K / A (1)
(In the formula, M represents the ester concentration, K represents the number of ester groups in the polymer, and A represents the number of atoms constituting the polymer chain of the polymer.)

  Here, “ester concentration M” is one index indicating the content ratio of ester groups in the polymer of the crystalline polyester resin. The “number of ester groups in the polymer” represented by K in the formula (1) refers to the number of ester bonds contained in the whole polymer.

  The “number of atoms constituting the polymer polymer chain” represented by A in the formula (1) is the total number of atoms constituting the polymer polymer chain, and includes all the atoms involved in the ester bond. In addition, the number of atoms of branched parts in other constituent parts is not included. That is, carbon atoms and oxygen atoms derived from carboxyl groups and alcohol groups involved in ester bonds (two oxygen atoms in one ester bond) and the six carbons constituting the polymer chain, for example, in the aromatic ring, Although included in the calculation of the number of atoms, for example, a hydrogen atom in an aromatic ring or an alkyl group, or an atom or atomic group of a substituent thereof constituting the polymer chain is not included in the calculation of the number of atoms.

  For example, among the total of 10 atoms of 6 carbon atoms and 4 hydrogen atoms in the arylene group constituting the polymer chain, the above-mentioned “number of atoms A constituting the polymer chain of the polymer” Included are only six carbon atoms, and even if the hydrogen is replaced by any substituent, the atoms constituting the substituent are the number of atoms constituting the polymer chain of the polymer. A ”is not included.

The crystalline polyester resin has one repeating unit (for example, when the polymer is represented by H— [OCOR ₁ COOR ₂ O—] _n —H, the one repeating unit is represented in []). In the case of a single polymer consisting of only two ester bonds in one repeating unit (that is, the number of ester groups K ′ = 2 in the repeating unit), the ester concentration M is expressed by the following formula: (1-1).
M = 2 / A ′ (1-1)
(In the formula, M represents the ester concentration, and A ′ represents the number of atoms constituting the polymer chain in one repeating unit.)

Further, when the crystalline polyester resin is a copolymer composed of a plurality of copolymerized units, the number of ester groups KX and the number of atoms AX constituting the polymer chain are obtained for each copolymerized unit, and the copolymerization ratio is calculated for these. Can be obtained by summing each of them and substituting them into the equation (1). For example, a compound [(Xa) a (Xb) b (Xc)] having three copolymerized units of Xa, Xb and Xc and a copolymerization ratio of a: b: c (where a + b + c = 1) The ester concentration M for c] can be determined by the following equation (1-2).
M = {KXa * a + KXb * b + KXc * c} / {AXa * a + AXb * b + AXc * c} (1-2)
(In the formula, M represents an ester concentration, KXa represents a copolymer unit Xa, KXb represents a copolymer unit Xb, KXc represents the number of each ester group in the copolymer unit Xc, AXa represents a copolymer unit Xa, and AXb represents a copolymer. Units Xb and AXc represent the number of atoms constituting each polymer chain in copolymer unit Xc.)

  As the toner in the present exemplary embodiment, the ester concentration M defined by the above formula (1) in the crystalline polyester resin used as the binder resin is 0.01 or more and 0.2 or less. It is preferable for increasing the ratio.

  The method for producing the crystalline polyester resin is not particularly limited and can be produced by a general polyester polymerization method in which an acid component and an alcohol component are reacted. Examples thereof include direct polycondensation and transesterification. Depending on the type of monomer, it is manufactured separately. The molar ratio (acid component / alcohol component) when the acid component reacts with the alcohol component varies depending on the reaction conditions and the like, and cannot be generally stated, but is usually about 1/1.

  The production of the crystalline polyester resin can be carried out at a polymerization temperature of 180 to 230 ° C., and the reaction is carried out while reducing the pressure in the reaction system as necessary to remove water and alcohol generated during condensation. When the monomer is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point may be added as a solubilizer and dissolved. In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. When a monomer having poor compatibility exists in the copolymerization reaction, the monomer having poor compatibility is preliminarily condensed with the acid or alcohol to be polycondensed and then polycondensed together with the main component.

  Catalysts that can be used in the production of the polyester resin include alkali metal compounds such as sodium and lithium; alkaline earth metal compounds such as magnesium and calcium; metal compounds such as zinc, manganese, antimony, titanium, tin, zirconium, and germanium; A phosphorous acid compound, a phosphoric acid compound, an amine compound, etc. are mentioned, Specifically, the following compounds are mentioned.

  For example, sodium acetate, sodium carbonate, lithium acetate, lithium carbonate, calcium acetate, calcium stearate, magnesium acetate, zinc acetate, zinc stearate, zinc naphthenate, zinc chloride, manganese acetate, manganese naphthenate, titanium tetraethoxide, titanium Tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide, antimony trioxide, triphenylantimony, tributylantimony, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide, zirconium tetrabutoxide, naphthene Zirconate, zirconyl carbonate, zirconyl acetate, zirconyl stearate, zirconyl octylate, germanium oxide, triphenyl Phosphite, tris (2,4-di -t- butyl-phenyl) phosphite, ethyltriphenylphosphonium bromide, triethylamine, compounds such as triphenyl amine.

  In addition to the polymerizable monomer described above, a compound having a shorter chain alkyl group, alkenyl group, aromatic ring or the like may be used for the purpose of adjusting the melting point, molecular weight, etc. of the crystalline resin in the present embodiment. it can. Specific examples include dicarboxylic acids, alkyl dicarboxylic acids such as succinic acid, malonic acid, and oxalic acid, and phthalic acid, isophthalic acid, terephthalic acid, homophthalic acid, 4,4′-bibenzoic acid, 2,6- Aromatic dicarboxylic acids such as naphthalenedicarboxylic acid and 1,4-naphthalenedicarboxylic acid, nitrogen-containing aromatic dicarboxylic acids such as dipicolinic acid, dinicotinic acid, quinolinic acid and 2,3-pyrazinedicarboxylic acid, and the like. In this case, short-chain alkyl diols such as succinic acid, malonic acid, acetone dicarboxylic acid, diglycolic acid, etc., and in the case of short-chain alkyl vinyl polymerizable monomers, methyl (meth) acrylate, (meth Short chain alkyls such as ethyl acrylate, propyl (meth) acrylate, butyl (meth) acrylate, alkenyl (meth) ) Acrylic esters, vinyl nitriles such as acrylonitrile and methacrylonitrile, vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether, vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketones, ethylene, propylene, butadiene, isoprene Olefins and the like. These polymerizable monomers may be used individually by 1 type, and may use 2 or more types together.

  In the present embodiment, a compound having a hydrophilic polar group can be used as long as it is copolymerizable as a resin for an electrostatic charge image developing toner. As a specific example, when the resin used is a polyester, a dicarboxylic acid compound in which an aromatic ring such as sulfonyl-terephthalic acid sodium salt or 3-sulfonylisophthalic acid sodium salt is directly substituted with a sulfonyl group can be cited. In the case of vinyl resins, unsaturated aliphatic carboxylic acids such as (meth) acrylic acid and itaconic acid, glycerin mono (meth) acrylate, fatty acid-modified glycidyl (meth) acrylate, zinc mono (meth) acrylate, zinc di (meth) acrylate , Esters of (meth) acrylic acid and alcohols such as 2-hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate, sulfonyl at any of the ortho, meta, and para positions Have group That derivatives of styrene, sulfonyl group-substituted aromatic vinyl such as sulfonyl group-containing vinyl naphthalene.

(Shell layer)
In the toner according to the exemplary embodiment, the shell layer covering the core particle includes at least one of a crystalline resin and an amorphous resin as a binder resin, and mainly imparts heat storage properties and filming resistance. Therefore, it is preferable to include an amorphous resin.

  If inorganic metal fine particles or the like are used in the shell layer for the purpose of imparting heat storage properties, the hardness of the toner surface is excessively increased and the wear of the photoreceptor is likely to be promoted. Furthermore, it is preferable to use an amorphous resin from the viewpoint of selecting a resin that does not impair charging characteristics.

  As the amorphous resin used for the shell layer, a resin similar to the amorphous resin used for core particle production can be suitably used (see the above-mentioned item of amorphous resin), among which polyester-based, Styrenic and acrylic are preferred, and polyester is more preferred. In addition, the amorphous resin is preferably used in the state of a fine particle dispersion because the shell layer is formed in the liquid.

  Since the amorphous resin used for forming the shell layer is excellent in hardness, strength, heat resistance, and solvent resistance, the glass transition temperature is preferably 55 ° C. or higher, more preferably higher than 60 ° C. When the glass transition temperature of the amorphous resin constituting the amorphous resin fine particles is less than 55 ° C., sufficient heat storage properties cannot be obtained, causing blocking in the developing machine and filming to the photoreceptor. In the development process, white spot defects are likely to occur.

  In the present embodiment, when the crystalline resin as the first binder resin and the amorphous resin as the second binder resin are used in combination with the binder resin of the core particles, the second binder resin as the shell layer is used. It is preferable to use an amorphous resin as a non-crystalline resin and a third binder resin. Further, when an amorphous resin is used as the second binder resin without using the first binder resin (crystalline resin) as the binder resin of the core particles, the second binder is used as the shell layer. It is preferable to use an amorphous resin as the adhesive resin and an amorphous resin as the third binder resin.

At this time, it is preferable that the solubility parameter SPp1 of the first binder resin, the solubility parameter SPp2 of the second binder resin, and the solubility parameter SPp3 of the third binder resin satisfy the following expressions.
SPp3>SPp2> SPp1

More preferably, the solubility parameter SPp1 of the first binder resin, the solubility parameter SPp2 of the second binder resin, and the solubility parameter SPp3 of the third binder resin satisfy the following expression.
SPp3-SPp2> 0.7, 0.3>SPp2-SPp1> 0.1

When the first binder resin (crystalline resin) is not used, it is preferable that the solubility parameter SPp2 of the second binder resin and the solubility parameter SPp3 of the third binder resin satisfy the following expression. .
SPp3-SPp2> 0.7

Here, the solubility parameter (SP) is represented by the square root of the cohesive energy density (CED).
SP = (CED) ^1/2

The solubility parameter (SP) value of each resin was determined by the method of Fedors using the additivity of atomic groups [Polym. Eng. Sci. , 14 (2) 147 (1974)]. When the SP value is close, the enthalpy change of mixing becomes small, so that the free energy of mixing is reduced and the mixture becomes well compatible.
SP value = (ΣΔei / ΣΔvi) ^1/2
(In the formula, Δei: evaporation energy of atoms or atomic groups, Δvi: molar volume of atoms or atomic groups)

  When SPp3-SPp2> 0.7, the first binder resin (crystalline resin) and the second binder resin (amorphous resin) of the core particles and the third binder resin (amorphous) of the shell layer SP value is sufficiently distant from the second binder resin, and the second binder resin and the third binder resin are hardly compatible with each other. Therefore, the first binder resin and the second binder resin of the core particles The colorant contained in the toner hardly precipitates and moves to the vicinity of the surface, and the ratio of the colorant existing in the region within 200 nm from the outermost surface of the toner tends to be 10% or less. On the other hand, in the case of SPp3-SPp2 ≦ 0.7, the colorant is dispersed in the shell part when the toner is made to have a glass transition point or more at the time of toner preparation, and the colorant present in a region within 200 nm from the outermost surface of the toner. The amount exceeds 10%, and the chargeability after a long time under high temperature and high humidity tends to decrease.

  In the case of 0.3> SPp2-SPp1> 0.1, the first binder resin holding the colorant when the toner is made to have a glass transition point or higher at the time of toner preparation has a lower SP value than the second binder resin. Therefore, the colorant is encapsulated by the toner core particles, and the colorant and the release agent in the vicinity of the toner surface are less exposed, and the chargeability after a long time under high temperature and high humidity is easily maintained. On the other hand, in the case of SPp2-SPp1 ≧ 0.3, it is difficult for the first binder resin 1 and the second binder resin to proceed with each other, voids are generated in the core portion, and after a long time under high temperature and high humidity. The chargeability of the is liable to decrease. In the case of SPp2−SPp1 ≦ 0.1, since the compatibility between the first binder resin and the second binder resin proceeds excessively, the colorant is pushed out at the same time during toner preparation and exposed to the surface of the core particles. The chargeability after a long time under high temperature and high humidity tends to decrease.

  The solubility parameter of the binder resin used in the toner of the present embodiment is preferably in the range of 9.5 to 12.5. If the solubility parameter is less than 9.5, the cohesive energy is small, so that the film strength of the fixed image is weakened, and the image surface may be cracked or image defects may occur due to bending or the like. When the solubility parameter is larger than 12.5, when it is desired to obtain a toner having a small particle diameter, the pulverizability is remarkably deteriorated and the production efficiency may be lowered.

  In addition, the second binder resin is an amorphous resin, the acid value of the binder resin by neutralization titration is in the range of 5 to 15 mgKOH / g, and the third binder resin is an amorphous resin. It is preferable that the acid value of the binder resin determined by neutralization titration is 5 to 12 mgKOH / g. When the acid value of the second binder resin is less than 5 mgKOH / g, the chargeability of the core portion is low, and the chargeability of the deteriorated developer under high-temperature and high-humidity and long-time stress conditions may be low. Absent. When the acid value of the second binder resin exceeds 15 mgKOH / g, the developer that has deteriorated under high-temperature and high-humidity stress conditions for a long time may become high, which is not preferable. When the acid value of the third binder resin is less than 5 mgKOH / g, the chargeability may be lowered, which is not preferable. When the acid value of the third binder resin exceeds 12 mgKOH / g, the hygroscopicity at high temperature and high humidity may be increased, which is not preferable from the viewpoint of chargeability.

  Here, as for the acid value of the binder resin, 2 g of the resin was weighed and dissolved in 160 mL of tetrahydrofuran, or if it was insufficiently soluble, it was possible to dissolve, and the acid value was determined according to JIS K0070 using this sample. taking measurement.

  The total amount of binder resin used for the shell layer is in the range of 10 to 40% by weight with respect to the toner weight (the weight of the toner obtained is 100 to 40 weight resin in the shell layer). Are preferred). When the amount of the binder resin in the shell layer is less than 10% by weight, the entire toner surface cannot be coated, and the colorant is not exposed on the toner surface, which may reduce the charge maintenance property under high temperature and high humidity. In addition, when the amount of the binder resin in the shell layer exceeds 40% by weight, a large amount of fine particles of 3 μm or less that are likely to deteriorate due to stress conditions due to high temperature and high humidity are generated due to adhesion with only the resin used in the shell layer during toner preparation. It becomes easy.

  In order to prevent the colorant and the release agent from being exposed to the toner surface under high-temperature and high-humidity stress conditions and to improve the charge maintenance, the coverage of the core particles with the amorphous resin fine particles is 90%. It is preferably in the range of -100%, and more preferably in the range of 97% -100%. This coverage can be obtained by averaging the shortest distance between the core and the shell layer with 50 toners from the contrast difference using an X-ray photoelectron spectrometer manufactured by JEOL.

  Moreover, it is preferable that the average film thickness of a shell layer is the range of 0.3-0.9 micrometer. When the average film thickness of the shell layer is less than 0.3 μm, it is difficult to coat the colorant and the release agent, and the effect of the shell is not exhibited, so that a long life of the toner may not be realized. When the average film thickness is larger than 0.9 μm, the shell layer is too thick and the coloring property and releasability of the colorant are deteriorated. The average thickness of the shell layer is measured by observing the toner cross-sectional view with a transmission electron microscope. Take a cross-sectional view of the toner at a magnification of 10,000 times, measure the shell thickness of the toner on the photo, average the thickness of the shell of 100 toner particles, and use that value as the average shell thickness.

[Colorant]
The colorant used in the present embodiment is not particularly limited as long as it is selected in consideration of hue angle, saturation, lightness, weather resistance, and dispersibility in the toner. At least two of the system colorants are used. In the case of process black, a yellow colorant, a cyan colorant, and a magenta colorant are mixed and used. Moreover, these mixtures may be used, and also it can be used in the state of a solid solution.

  Examples of yellow colorants include insoluble azo pigments such as condensed azo pigments and azo chelate pigments in addition to monoazo yellow, disazo yellow, and benzimidazolone pigments.

  As the magenta colorant, the following known ones can be used. The colorant is C.I. I. I wrote it by name. C. of the colorant I. The name is 57 according to Red, which is based on Color Index, which is published in a co-edition of SDC (the society of dyers and coulists) and AATCC (The American Association of Textiles and Colorists). : 1, CIPigment Red 48: 1, as insoluble azo, CIPigment Red 21 (β-naphthol type), CIPigment Red 3 (β-naphthol type), CIPigment Red 1 (β-naphthol type), CIPigment Red 4 (β-naphthol series), CIPigment Red 6 (β-naphthol series), CIPigment Red 37 (virazolone series bisazo), CIPigment Red 38 (virazolone series bisazo), CIPigment Red 41 (virazolone series bisazo), CI Pigment Red 42 (virazolone bisazo) CIPigment Red 122 (quinacridone), CIPigment Red 202 (quinacridone), CIPigment Red 179 (perylene), CIPigment Red 178 (perylene), CI Pigment Red 149 (perylene) , CIPigment Red 123 (perylene), CIPigment Red 194 (perylene), CIPigment Red 168 (slen), CIPigment Red 177 (slen), CIPigment Red254 (diketopyrrolopyrrole), CIPigment Red 255 (Diketopyrrolopyrrole), CIPigment Red 2, CIPigment Red 5, CIPigment Red 7, CIPigment Red 23, CIPigment Red 48: 2, CIPigment Red 48: 3, CIPigment Red 48: 4, CIPigment Red 81: 1, CIPigment Red 144, CIPigment Red 146, CIPigment Red 169, CIPigment Red 177, CIPigment Red 184, CIPigment Red 185, CIPigment Red 206, CIPigment Red 220 , CIPigment Red 221, CIPigment Red 238, etc. No.

  As the cyan colorant, known ones such as phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green can be used.

  When a yellow colorant and a magenta colorant are mixed to make red, the ratio of the yellow colorant and the magenta colorant is 40 to 90 in order to maintain a bright red color. It is preferable that it is weight%. When the amount of the yellow colorant is less than 40% by weight, it is impossible to develop a vivid red color, and when it is more than 90% by weight, the red density is not sufficient and the color becomes light red. At this time, it is preferable to use an azo pigment as the yellow colorant and a quinacridone pigment as the magenta colorant. Moreover, it is preferable that the addition amount of a coloring agent is 4-10 weight part with respect to 100 weight part of binder resin of a core particle.

  When a magenta colorant and a cyan colorant are mixed to obtain a blue color, the amount of the magenta colorant is 50 to 80 in order to maintain a vivid blue ratio of the magenta colorant and the cyan colorant. It is preferable that it is weight%. When the amount of the magenta colorant is less than 50% by weight, it is impossible to develop a vivid blue color, and when it is more than 80% by weight, the blue density becomes insufficient and the color becomes light blue. At this time, it is preferable to use a quinacridone pigment as the magenta colorant and a phthalocyanine blue pigment as the cyan colorant. Moreover, it is preferable that the addition amount of a coloring agent is 4-10 weight part with respect to 100 weight part of binder resin of a core particle.

  When the yellow colorant and the cyan colorant are mixed to obtain a green color, the amount of the yellow colorant is 50 to 90 in order to maintain the vivid green ratio of the yellow colorant and the cyan colorant. It is preferable that it is weight%. When the amount of the yellow colorant is less than 50% by weight, it is impossible to develop a vivid green color, and when it is more than 90% by weight, the green density becomes insufficient and the color becomes light green. At this time, it is preferable to use an azo pigment as the yellow colorant and a phthalocyanine blue pigment as the cyan colorant. Moreover, it is preferable that the addition amount of a coloring agent is 4-10 weight part with respect to 100 weight part of binder resin of a core particle.

  When mixing a yellow colorant, a cyan colorant and a magenta colorant to make a process black, an azo pigment as a yellow colorant, a phthalocyanine pigment as a cyan colorant, and a magenta colorant It is preferable to use a quinacridone pigment or a mixed pigment of a quinacridone pigment and an azo pigment. More preferably, the azo yellow colorant is monoazo yellow or disazo yellow, and the quinacridone magenta colorant is dimethylquinacridone. Specifically, CIPigment Yellow 74, CIPigment Yellow 93, etc. as azo pigments, CIPigment Blue 15: 3, etc. as phthalocyanine pigments, CIPigment Red 122, CIPigment Red 202, etc. as quinacridone pigments are mentioned. be able to. The combination of the above pigments is excellent in applicability to the wet manufacturing method of the toner of the present embodiment, and has high black reproducibility because the coloring power can be easily controlled by the dispersion diameter of the pigment in the toner.

  When the weight of the quinacridone magenta colorant is A and the weight of the phthalocyanine cyan colorant is B, the ratio B / A is 0.8 to 1.2, and the weight of the azo yellow colorant is C. When the ratio C / A is 1.0 to 1.2, the ratio C / B is 0.8 to 1.5, and the three kinds of the above-mentioned three kinds of the binder resin are 100 parts by weight of the core particles used. The total amount of the color material is preferably 5 to 15 parts by weight. When the ratio B / A is less than 0.8, the redness of the fixed image becomes strong, which is not preferable. When the ratio B / A exceeds 1.2, the black bluishness of the fixed image becomes strong, which is not preferable. When the ratio C / A is less than 1.0, the redness of the fixed image becomes strong, which is not preferable. When the ratio C / A exceeds 1.2, the color tone is shifted in the Green direction, and sufficient blackness cannot be obtained. When the ratio C / B is less than 1.0, the color tone is shifted in the Blue direction, and sufficient blackness cannot be obtained. When the ratio C / B exceeds 1.2, the color tone is shifted in the Green direction, and sufficient blackness cannot be obtained. Further, when the total amount of the colorant added is less than 5 parts by weight, sufficient blackness cannot be obtained, and when it exceeds 15 parts by weight, the controllability of the toner shape is lowered and the colorant segregates near the toner surface. This is undesirable because it adversely affects the chargeability.

  Further, when the weight of the magenta colorant, which is a mixed pigment of the quinacridone pigment and the azo pigment, is D and the weight of the phthalocyanine cyan colorant is B, the ratio B / D is 0.5 to 1.0. When the weight of the azo yellow colorant is C, the ratio C / D is 0.9 to 1.7, the ratio C / B is 0.9 to 1.8, and the core particles used The total amount of the three color materials is preferably 4 to 15 parts by weight with respect to 100 parts by weight of the resin.

  In this embodiment, it is preferable that the acid value by the neutralization titration method of a yellow colorant, a cyan colorant, and a magenta colorant is 5.0 mgKOH / g or less, respectively. When the acid value of the colorant exceeds 5.0 mg KOH / g, the hydrophilicity of the colorant is increased, so that the colorant cannot be included at the time of phase inversion emulsification between the colorant, the binder resin, and the release agent. Since the agent is unevenly distributed on the surface of the composite fine particles, it is difficult to accurately produce a secondary color or a tertiary color.

〔Release agent〕
Although there is no restriction | limiting in particular as a mold release agent used in this embodiment, As specific examples, low molecular weight polyolefins, such as polyethylene, a polypropylene, polybutene; Silicones which have a softening point; Oleic acid amide, erucic acid amide, ricinoleic acid Fatty acid amides such as amide and stearamide; plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax and jojoba oil; animal waxes such as beeswax; montan wax, ozokerite, ceresin, paraffin wax , Mineral and petroleum waxes such as microcrystalline wax and Fischer-Tropsch wax; ester waxes of higher alcohols and higher alcohols such as stearyl stearate and behenyl behenate; butyl stearate and oleic acid pro Ester waxes of higher fatty acids such as monostearic glyceride, distearic glyceride, pentaerythritol tetrabehenate and unitary or polyhydric lower alcohols; diethylene glycol monostearate, dipropylene glycol distearate, distearic diglyceride, Ester waxes composed of higher fatty acids such as tetrastearic acid triglycerides and multimers of polyhydric alcohols; sorbitan higher fatty acid ester waxes such as sorbitan monostearate; cholesterol higher fatty acid ester waxes such as cholesteryl stearate Ester waxes are preferred, especially ester waxes of higher fatty acids such as stearyl stearate and behenyl behenate and higher alcohols; , Ester waxes of higher fatty acids such as propyl oleate, glyceryl monostearate, glyceryl distearate, pentaerythritol tetrabehenate and unitary or polyhydric lower alcohols; diethylene glycol monostearate, dipropylene glycol distearate, distearin Ester waxes composed of higher fatty acids such as acid diglycerides and tetrastearic acid triglycerides and multimers of polyhydric alcohols; sorbitan higher fatty acid ester waxes such as sorbitan monostearate; cholesterol higher fatty acid ester waxes such as cholesteryl stearate More preferred. These release agents may be used alone or in combination of two or more.

  In this embodiment, the mold release agent is an ester wax, preferably has a melting point of 60 to 90 ° C., and the ratio of the mold release agent having a weight average molecular weight (Mw) of 1800 or less is 30% or less.

  When the melting point of the release agent exceeds 90 ° C., the viscosity of the release agent is high, the first binder resin and the release agent cannot move at the same time, and uneven distribution near the surface of the release agent occurs. In some cases, the external additive rejection under high-temperature and high-humidity stress conditions exposes the release agent and lowers the charge retention. In addition, when the melting point of the release agent is less than 60 ° C., the release agent is severely deteriorated due to stress conditions for a long time under high temperature and high humidity, and the charge retention may be lowered.

  On the other hand, when the ratio of the weight average molecular weight (Mw) of 1800 or less of the release agent exceeds 30%, the release agent offset may occur during low-temperature fixing, and the fixed image may become rough.

  For the measurement of the melting point of the release agent, when a differential scanning calorimeter (DSC: DSC-60 manufactured by Shimadzu Corporation) was used, the temperature was measured from room temperature to 150 ° C. at a heating rate of 10 ° C. per minute. The melting peak temperature of the input compensated differential scanning calorimetry shown in JIS K-7121: 87. The release agent may show a plurality of melting peaks, and the maximum peak is regarded as the melting point.

  For the measurement of the main maximum peak, DSC-7 manufactured by PerkinElmer is used. The temperature correction of the detection part of the apparatus uses the melting points of indium and zinc, and the correction of heat quantity uses the heat of fusion of indium. As the sample, an aluminum pan is used, an empty pan is set as a control, and the measurement is performed at a heating rate of 10 ° C./min.

  It can be confirmed by GPC analysis that the ratio of the weight average molecular weight of 1800 or less of the release agent is 30% or less. Measurement is performed under the following conditions using GPC (gel permeation chromatography). First, “HLC-8120GPC, SC-8020 (manufactured by Tosoh Corporation)” is used as a measuring apparatus, and “TSKgeL, SuperHM-H (6.0 mm ID × 15 cm, manufactured by Tosoh Corporation)” is used as a column. Two are used and THF (tetrahydrofuran) is used as an eluent. The measurement conditions are set to a sample concentration of 0.5%, a flow rate of 0.6 mL / min, a sample injection amount of 10 μL, a measurement temperature of 40 ° C., and an IR detector is used. The calibration curve is “polystylen standard sample TSK standard” manufactured by Tosoh Corporation: “A-500”, “F-1”, “F-10”, “F-80”, “F-380”, “A-2500”. ”,“ F-4 ”,“ F-40 ”,“ F-128 ”, and“ F-700 ”.

  As the release agent, pentaerythritol behenate wax having a melting point of 60 ° C. to 90 ° C. is particularly preferable. More preferably, the release agent is pentaerythritol behenate wax, and the ratio of disubstituted compounds or less is 30% or less. When the mold release agent is pentaerythritol behenate wax and the ratio of disubstituted compounds is 30% or less, it is compatible with the first binder resin, so that the mold release agent is repelled during the fusing process during toner production. And can be included in the core. When the ratio of diastereomers or less in pentaerythritol behenate wax exceeds 30%, the compatibility between the release agent and the first binder resin does not progress, and the release agent becomes the binder resin during the fusion process. Since it is pushed out and moves to the vicinity of the surface and unevenly distributed in the vicinity of the toner surface, the charge maintaining property may deteriorate.

[Other additives]
Various components such as an internal additive, a charge control agent, inorganic powder (inorganic fine particles), and organic fine particles can be further added to the toner according to the exemplary embodiment as necessary.

  Examples of the internal additive include metals such as ferrite, magnetite, reduced iron, cobalt, nickel, and manganese, alloys, and magnetic materials such as compounds containing these metals.

  Examples of the charge control agent include quaternary ammonium salt compounds, nigrosine compounds, dyes composed of complexes of aluminum, iron, chromium, triphenylmethane pigments, salicylic acid metal salts, metal-containing azo compounds, and the like.

  The inorganic powder is added mainly for the purpose of adjusting the viscoelasticity of the toner. For example, silica, alumina, titania, calcium carbonate, magnesium carbonate, calcium phosphate, cerium oxide, etc. Examples thereof include all inorganic fine particles used as an external additive on the toner surface.

  Examples of the external additive other than the amorphous resin fine particles added to the toner surface include the following inorganic fine particles and organic fine particles.

  Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, cerium chloride, Examples include Bengala, chromium oxide, cerium oxide, antimony trioxide, magnesium oxide, zirconium oxide, silicon carbide, and silicon nitride. Among them, silica fine particles and titanium oxide fine particles are preferable, and hydrophobized fine particles are particularly preferable.

  Inorganic fine particles are generally used for the purpose of improving fluidity. The primary particle diameter of the inorganic fine particles is preferably in the range of 1 to 200 nm, and the addition amount is preferably in the range of 0.01 to 20 parts by weight with respect to 100 parts by weight of the toner.

  Organic fine particles are generally used for the purpose of improving cleaning properties and transfer properties, and specific examples include polystyrene, polymethyl methacrylate, polyvinylidene fluoride, and the like.

<Method for producing toner for developing electrostatic image>
As a method for producing an electrostatic charge image developing toner according to the exemplary embodiment, a conventional kneading and pulverizing method, a colorant, a release agent, and the like are suspended together with a polymerizable monomer, and the polymerizable monomer is polymerized. Suspension polymerization method, dissolution suspension method in which toner constituent materials such as resin, colorant, release agent, etc. are dissolved in an organic solvent and dispersed in an aqueous solvent in a suspended state, and then the organic solvent is removed, and the resin is emulsified There are wet production methods such as emulsion polymerization aggregation method, which are prepared by polymerization, heteroaggregated with a dispersion of colorant, release agent, etc., and then fused and coalesced. There is no particular limitation as long as the production method can be unevenly distributed. Among these, a wet production method such as a suspension polymerization method, a dissolution suspension method, and an emulsion polymerization agglomeration method is preferable, and the toner particle size controllability, narrow particle size distribution, shape controllability, narrow shape distribution, and internal dispersion controllability. Therefore, the emulsion polymerization aggregation method is optimal.

  In general, the emulsion polymerization aggregation method involves mixing a resin fine particle dispersion in which resin fine particles having a particle size of 1 μm or less are dispersed, a colorant dispersion in which a colorant is dispersed, a release agent dispersion in which a release agent is dispersed, and the like. A step of agglomerating the resin fine particles, the colorant, and the release agent to a toner particle size (hereinafter sometimes referred to as “aggregation step”), heating to a temperature higher than the glass transition point of the resin fine particles, and fusing the agglomerates to the toner A step of forming particles (hereinafter sometimes referred to as a “fusion step”).

  In the present embodiment, in the method for producing a toner for developing an electrostatic charge image comprising a core layer containing a binder resin, a colorant, and a release agent, and a shell layer covering the surface of the core layer, the first binder is used. A composite fine particle dispersion in which composite fine particles having a volume average particle size of 0.6 μm or less are dispersed, which contains a resin, at least two of a yellow colorant, a cyan colorant and a magenta colorant, and a release agent In addition, a flocculant is added and heated to form a core particle, and a second binder resin is included, and the first resin fine particles having a volume average particle size of 0.6 μm or less are dispersed. A first adhesion step of adding 1 resin fine particle dispersion to adhere the first resin fine particles to the surface of the core particles to form first adhering resin agglomerated particles, and a third binder resin; Disperse second resin fine particles having an average particle size of 0.6 μm or less A second adhering step in which the second resin fine particle dispersion is added to cause the second resin fine particles to adhere to the surface of the first adhering resin agglomerated particles to form the second adhering resin agglomerated particles; A fusing step of fusing the aggregated particles by heating.

  In the present embodiment, in the method for producing an electrostatic charge image developing toner comprising a core layer containing a binder resin, a colorant, and a release agent, and a shell layer covering the surface of the core layer, A volume average particle size of 0.6 μm or less, comprising a binder resin, a second binder resin, at least two of a yellow colorant, a cyan colorant, and a magenta colorant, and a release agent; An aggregating step of forming a core particle by adding an aggregating agent to a composite fine particle dispersion in which a composite fine particle is dispersed and heating, and a second binder resin, and the volume average particle size is 0.6 μm or less Adding a first resin fine particle dispersion in which certain first resin fine particles are dispersed, and attaching the first resin fine particles to the surface of the core particles to form first adhered resin aggregated particles; and Including a third binder resin and having a volume average particle size of 0.6 μm or less The second resin fine particle dispersion in which the second resin fine particles are dispersed is added, and the second resin fine particles are adhered to the surface of the first adhering resin agglomerated particles to form the second adhering resin agglomerated particles. An adhesion step and a fusion step in which the second adhesion resin agglomerated particles are heated and fused.

  In the present embodiment, in the method for producing an electrostatic charge image developing toner comprising a core layer containing a binder resin, a colorant, and a release agent, and a shell layer covering the surface of the core layer, A volume average particle size of 0.6 μm or less, comprising a binder resin, a second binder resin, at least two of a yellow colorant, a cyan colorant, and a magenta colorant, and a release agent; An agglomeration step in which a core particle is formed by adding a flocculant to a composite fine particle dispersion in which a composite fine particle is dispersed and heating, a second binder resin and a third binder resin, and a volume average particle A first resin fine particle dispersion in which first resin fine particles having a diameter of 0.6 μm or less are dispersed is added, and the first resin fine particles are adhered to the surface of the core particles to form first adhered resin aggregated particles. Including a first adhesion step, a third binder resin, and a volume average particle size The second resin fine particle dispersion liquid in which the second resin fine particles having a particle size of 0.6 μm or less are added, and the second resin fine particles are adhered to the surface of the first adhered resin agglomerated particles, thereby causing the second adhered resin agglomerates. A second adhering step for forming particles, and a fusing step for heating and fusing the second adhering resin aggregated particles.

  By such a method, the first binder resin, at least two of the yellow colorant, the cyan colorant and the magenta colorant, and the release agent, and the volume average particle diameter is 0.6 μm or less. Since the composite fine particles include the colorant and the release agent in the composite fine particles, when the obtained toner is used, the coloring on the toner surface is performed even under high-temperature, high-humidity and long-time stress conditions. Exposure of the agent and the release agent can be suppressed.

(Emulsification process)
The composite fine particles containing the first binder resin, the colorant and the release agent are preferably prepared by a phase inversion emulsification method. The colorant and the release agent are more hydrophobic than the binder resin. Due to its high property, composite fine particles encapsulated in a binder resin are obtained in an aqueous solution. Therefore, since the colorant and the release agent are easily included in the binder resin even when the toner is produced, this is an important condition. When composite fine particles are produced only with the first binder resin and the colorant, the release agent added later is pushed out in the vicinity of the shell layer at the time of fusing, and is applied to the toner surface under high-temperature, high-humidity and long-time stress conditions. Since it is exposed, it is difficult to achieve the improvement as in the present embodiment. Further, when the composite fine particles are produced only with the first binder resin and the release agent, the colorant added later is pushed out to the binder resin as the coalescence progresses, and is unevenly distributed in the vicinity of the toner surface. Under the high humidity and long time stress conditions, the toner surface is exposed, so that it is difficult to achieve the improvement as in this embodiment. In addition, after preparing a resin fine particle dispersion, a colorant dispersion, and a release agent dispersion as in the past, and mixing them, the resin fine particles, the colorant particles, and the release agent particles are aggregated, It is difficult to achieve the improvement as in the present embodiment.

  In the present embodiment, the same effect can be obtained even when composite fine particles including a first binder resin, a colorant, a release agent, and a different second binder resin are used.

  In this embodiment, the volume average particle size of the composite fine particles containing the first binder resin, the colorant, and the release agent is 0.6 μm or less, preferably 0.05 μm to 0.6 μm, more preferably 0.1 μm to 0.3 μm. When the volume average particle diameter of the composite fine particles is 0.6 μm or less, the first resin fine particles containing the second binder resin to be added later, the core particles are densely aggregated, and there are few irregularities on the surface of the aggregates, This is because the second resin fine particles including the third binder resin are uniformly attached, and the shell layer can be formed uniformly. When the volume average particle size of the composite fine particles exceeds 0.6 μm, the particle size distribution of the toner is widened, the uniformity of the chargeability is lowered, and it is difficult to ensure stable chargeability.

  In this embodiment, the volume average particle size of the first resin fine particles containing the second binder resin and the second resin fine particles containing the third binder resin is 0.6 μm or less, preferably 0.05 μm to It is 0.6 μm, more preferably 0.1 μm to 0.3 μm. When the volume average particle size of each resin fine particle is 0.6 μm or less, the resin fine particles are uniformly attached to the core particles, and the shell layer is easily and uniformly covered. In addition, a highly durable toner with little exposure of the release agent can be obtained. When the volume average particle diameter of each resin fine particle exceeds 0.6 μm, when the first resin fine particles and the second resin fine particles are adhered to the surface of the core particles, the resin fine particles are difficult to uniformly adhere, The release agent is likely to be exposed in the vicinity of the surface, and it is difficult to maintain chargeability under a long-term stress of high temperature and high humidity.

  The composite fine particle dispersion includes a first binder resin and / or a second binder resin, a colorant containing at least two of a yellow colorant, a cyan colorant, and a magenta colorant, and a release agent. The dispersion containing the agent and the water-insoluble organic solvent is emulsified and dispersed in water at 50 to 80 ° C. to form an O / W (Oil / Water) type emulsion, and then the water-insoluble organic solvent is removed. It is preferable that it is produced. By using the dispersion liquid containing the first binder resin and / or the second binder resin, the colorant, and the release agent, the colorant and the release agent can be included in the core particles.

  The emulsification dispersion temperature for carrying out the phase inversion emulsification method in this embodiment is preferably in the range of 50 ° C to 80 ° C. Since release agents such as ester wax contain impurities, the melting peak distribution is wide, and the release agent can be emulsified at a temperature lower by about 10 ° C. than the melting point, so the emulsification dispersion temperature is 50 ° C. to 80 ° C. It is possible with a range. When the emulsification dispersion temperature is less than 50 ° C., the release agent such as ester wax is not dissolved in the organic solvent, so that emulsification becomes difficult. When the emulsification dispersion temperature exceeds 80 ° C., most of the water-insoluble organic solvents to be used have a boiling point of 80 ° C. or less, which is difficult to handle and is not preferable.

  The first resin fine particles containing the second binder resin and the second resin fine particles containing the third binder resin can be produced by a method such as emulsion polymerization. For example, emulsion polymerization involves adding several types of polymerizable monomers that are not soluble in a solvent, such as water, together with a dispersion stabilizer such as a surfactant, into the dispersion medium. A micelle is formed, and further polymerization is initiated by a water-soluble polymerization initiator to produce resin fine particles. At this time, the polymerizable monomer in the micelle stabilizes the inside of the micelle by being more hydrophilic or highly polar on the surface of the micelle, in other words, on the contact surface with the solvent. The polymerization is initiated by the polymerization initiator, and at this time, the polymerization tends to start from a polymerizable monomer having a low polarity. The reason for this is considered to be that the polymerizable monomer with high polarity is deteriorated because π electrons in the polymerizable monomer having a polymerizable property are attracted by the electron attracting property of the polar group. By utilizing this property, a highly polar polymerizable monomer in the micelle can be provided in the vicinity of the surface of the resin fine particles, and furthermore, by using this highly polar polymerizable monomer having crosslinkability. It is possible to obtain resin fine particles having a high effect of the present embodiment.

  Examples of the water-insoluble organic solvent include ethyl acetate, toluene, and the like, and can be appropriately selected and used according to the type and structure of the binder resin.

  The amount of the organic solvent used is preferably in the range of 50 to 5000 parts by weight and in the range of 120 to 1000 parts by weight with respect to 100 parts by weight of the total amount of the binder resin, the colorant, and the release agent. It is more preferable.

  Examples of the dispersion medium in the composite fine particle dispersion, the resin fine particle dispersion, and other components in the present embodiment include an aqueous medium. Examples of the aqueous medium include water such as distilled water and ion exchange water, alcohol, and the like. These may be used individually by 1 type and may use 2 or more types together.

  In the production of the electrostatic image developing toner according to the exemplary embodiment, a surfactant can be used for the purpose of stabilizing the dispersion of the composite fine particle dispersion, the resin fine particle dispersion and the like in the emulsion polymerization aggregation method.

  Examples of surfactants include anionic surfactants such as sulfate, sulfonate, phosphate, and soap; cationic surfactants such as amine salts and quaternary ammonium salts; polyethylene Nonionic surfactants such as glycol, alkylphenol ethylene oxide adducts, polyhydric alcohols, and the like. Among these, an ionic surfactant is preferable, and an anionic surfactant and a cationic surfactant are more preferable.

  In this embodiment, in general, an anionic surfactant has a strong dispersion power and is excellent in dispersion of composite fine particles, resin fine particles and the like. The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant. Surfactant may be used individually by 1 type and may be used in combination of 2 or more type.

  Specific examples of anionic surfactants include fatty acid soaps such as potassium laurate, sodium oleate, and castor oil sodium; sulfates such as octyl sulfate, lauryl sulfate, lauryl ether sulfate, and nonyl phenyl ether sulfate; lauryl sulfonate , Sodium alkylnaphthalene sulfonate such as dodecylbenzene sulfonate, triisopropyl naphthalene sulfonate, dibutyl naphthalene sulfonate; sulfone such as naphthalene sulfonate formalin condensate, monooctyl sulfosuccinate, dioctyl sulfosuccinate, lauric acid amide sulfonate, oleic acid amide sulfonate Acid salts; lauryl phosphate, isopropyl phosphate, nonylphenyl ether Phosphoric acid esters such as Sufeto; dialkyl sulfosuccinate salts such as sodium dioctyl sulfosuccinate; sulfosuccinate salts such as sulfosuccinate lauryl disodium; and the like.

  Specific examples of the cationic surfactant include laurylamine hydrochloride, stearylamine hydrochloride, oleylamine acetate, stearylamine acetate, stearylaminopropylamine acetate, and other amine salts; lauryltrimethylammonium chloride, dilauryldimethylammonium Chloride, distearyldimethylammonium chloride, distearyldimethylammonium chloride, lauryldihydroxyethylmethylammonium chloride, oleylbispolyoxyethylenemethylammonium chloride, lauroylaminopropyldimethylethylammonium ethosulphate, lauroylaminopropyldimethylhydroxyethylammonium perchlorate, alkylbenzene Trimethylammonium chloride, Quaternary ammonium salts such as quilts trimethyl ammonium chloride; and the like.

  Specific examples of the nonionic surfactant include alkyl ethers such as polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxy Alkyl phenyl ethers such as ethylene nonyl phenyl ether; alkyl esters such as polyoxyethylene laurate, polyoxyethylene stearate, polyoxyethylene oleate; polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether, polyoxyethylene Alkylamines such as oleyl amino ether, polyoxyethylene soybean amino ether, polyoxyethylene beef tallow amino ether; Alkyl amides such as ethylene lauric acid amide, polyoxyethylene stearic acid amide, polyoxyethylene oleic acid amide; vegetable oil ethers such as polyoxyethylene castor oil ether and polyoxyethylene rapeseed oil ether; lauric acid diethanolamide, stearic acid Alkanolamides such as diethanolamide and oleic acid diethanolamide; sorbitan ester ethers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate And so on.

  The content of the surfactant in each dispersion may be a level that does not inhibit the effect of the present embodiment, and is generally a small amount, specifically in the range of about 0.01 to 10% by weight. More preferably, it is the range of 0.05-5 weight%, More preferably, it is the range of about 0.1-2 weight%. When the content is less than 0.01% by weight, each dispersion liquid such as the composite fine particle dispersion and the resin fine particle dispersion becomes unstable, and therefore, aggregation occurs or the stability between the particles differs during aggregation. Therefore, there are problems such as the release of specific particles, and if it exceeds 10% by weight, it is not preferable because the particle size distribution of the particles becomes wide and the control of the particle size becomes difficult.

  As the surfactant, a room-temperature solid aqueous polymer or the like can also be used. Specifically, cellulose compounds such as carboxymethyl cellulose and hydroxypropyl cellulose, polyvinyl alcohol, gelatin, starch, gum arabic and the like can be used.

  Examples of the emulsifier used when forming the emulsified particles such as composite fine particles and resin fine particles include a homogenizer, a homomixer, a pressure kneader, an extruder, and a media disperser.

  The volume average particle size of the particles contained in the composite fine particle dispersion, resin fine particles and the like can be measured with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.).

(Aggregation process)
In the aggregation step, the obtained composite fine particle dispersion is heated to 30 to 60 ° C. to aggregate to form an aggregate. The heating time may be performed so that the aggregation is sufficiently performed, and for example, it may be performed for about 0.5 hours to 10 hours.

  Formation of the aggregate of the emulsified particles is performed by acidifying the pH of the emulsion under stirring. As the said pH, the range of 2-6 is preferable, The range of 2.5-5 is more preferable, The range of 2.5-4 is further more preferable. At this time, an aggregating agent may be added in order to stabilize the aggregation of the particles, to quickly perform the aggregation, or to obtain aggregated particles having a narrower particle size distribution.

  As the flocculant, a compound having a monovalent or higher charge is preferable. Specific examples of the compound include water-soluble surfactants such as the above-mentioned ionic surfactants and nonionic surfactants, hydrochloric acid, sulfuric acid, and the like. Acids such as nitric acid, acetic acid, oxalic acid, magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, ammonium sulfate, aluminum nitrate, silver nitrate, copper sulfate, sodium carbonate, inorganic acid metal salts, sodium acetate, potassium formate, sulphate Fatty acids such as aliphatic acids such as sodium acid, sodium phthalate, potassium salicylate, metal salts of aromatic acids, metal salts of phenols such as sodium phenolate, metal salts of amino acids, triethanolamine hydrochloride, aniline hydrochloride And inorganic acid salts of aromatic and aromatic amines.

  In consideration of the stability of the aggregated particles, the stability of the aggregating agent with respect to heat and time, and the removal during washing, a metal salt of an inorganic acid is preferable as the aggregating agent. Specific examples include metal salts of inorganic acids such as magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, ammonium sulfate, aluminum nitrate, silver nitrate, copper sulfate, and sodium carbonate.

  The amount of these flocculants added varies depending on the valence of the charge, but they are all small, in the case of monovalent, about 3% by weight or less, in the case of divalent, about 1% by weight, in the case of trivalent Is about 0.5% by weight or less. Since the amount of the flocculant is preferably small, it is preferable to use a compound having a large valence.

(Adhesion process)
Next, the first resin fine particle dispersion in which the first resin fine particles including the second binder resin are dispersed is added to the liquid in which the aggregated particles are dispersed, and the first core is dispersed on the surface of the aggregated core particles. The first resin resin aggregated particles are formed by attaching the resin fine particles (first adhesion step). Thereafter, the second resin fine particle dispersion in which the second resin fine particles containing the third binder resin are dispersed is added, and the second resin fine particles are adhered to the surface of the first adhering resin agglomerated particles. Adhesive resin aggregated particles are formed (second adhesion step) to form a shell layer. Further, after adding the first resin fine particle dispersion in which the first resin fine particles containing the second binder resin are dispersed to the dispersion of the aggregated particles, the second resin fine particles containing the third binder resin are dispersed. The resin fine particle dispersion obtained by mixing the second resin fine particle dispersion may be added to the aggregated particle dispersion. That is, first and second resin fine particles are adhered to the surface of the agglomerated core particles to form first adhered resin aggregated particles (first adhesion step), and then the second resin fine particle dispersion is further added. The shell layer may be formed by adding the second resin fine particles to the surface of the first adhered resin aggregated particles to form the second adhered resin aggregated particles (second adhesion step). The formation of the shell layer is preferably performed in water from the viewpoint of productivity.

  In the formation of the shell layer, the slurry liquid may be heated for the purpose of obtaining a strong shell layer after adding the resin fine particle dispersion to the slurry liquid after the core particle granulation. At this time, it is important to heat at or below the melting point or glass transition temperature of the first binder resin of the core particles. When the heating temperature is too high, not only coarse powder is generated, but also the core component is eluted on the surface of the shell layer, which may deteriorate charging characteristics and heat storage properties.

  In the formation of the shell layer, a flocculant may be used for the purpose of promoting the coating of the amorphous resin fine particles. As the flocculant, the above-mentioned flocculant species are preferably used. Further, the timing of adding the flocculant may be before or after the addition of the resin fine particles.

  In the preparation of the toner shell layer of the present embodiment, the amount of the first resin fine particles added is preferably in the range of 5 to 70% by weight, and in the range of 10 to 15% by weight with respect to the weight of the core particles. It is more preferable. When the addition amount is less than 5% by weight, the amount of resin is small and it may be difficult to completely cover the surface of the core particles. When the added amount exceeds 70% by weight, the pigment dispersibility is lowered, and an accurate color may not be reproduced. The amount of the second resin fine particles added is preferably in the range of 10 to 70% by weight and more preferably in the range of 20 to 50% by weight with respect to the weight of the core particles. When the addition amount is less than 20% by weight, the core particle portion is likely to be exposed on the surface, and stable chargeability may not be obtained under stressed conditions. When the added amount exceeds 70% by weight, the pigment dispersibility is lowered, and an accurate color may not be reproduced.

[Fusion process]
In the fusion step, under the same stirring as in the aggregation step, the aggregation suspension is stopped by setting the pH of the aggregate suspension to a range of 3 to 10, and the temperature is equal to or higher than the melting point of the first binder resin. The aggregates are fused by heating at.

  The heating time may be performed to such an extent that the fusion is sufficiently performed, for example, about 0.5 to 10 hours.

  In the fusion step, a crosslinking reaction may be performed when the crystalline resin is heated to the melting point or higher, or after the fusion is completed. Moreover, a crosslinking reaction can also be performed simultaneously with aggregation. When the crosslinking reaction is performed, for example, an unsaturated sulfonated crystalline polyester resin obtained by copolymerizing a double bond component as a binder resin is used, and a radical reaction is caused to the resin to introduce a crosslinked structure. . At this time, the following polymerization initiator can be used.

  Examples of the polymerization initiator include t-butyl peroxy-2-ethylhexanoate, cumyl perpivalate, t-butyl peroxylaurate, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, di-t. -Butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane 1,1-bis (t-butylperoxy) cyclohexane, 1,4-bis (t-butylperoxycal) Nyl) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane, , 3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylper) Oxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di-t-butyldiperoxyisophthalate, 2,2-bis (4,4-di-t-butylperoxy) (Cyclohexyl) propane, di-t-butylperoxy α-methylsuccinate, di-t-butylperoxydimethylglutarate, di-t-butylperoxyhexahydroterephthalate Rate, di-t-butylperoxyazelate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, diethylene glycol-bis (t-butylperoxycarbonate), di-t-butylper Oxytrimethyl adipate, tris (t-butylperoxy) triazine, vinyltris (t-butylperoxy) silane, 2,2'-azobis (2-methylpropionamidine dihydrochloride), 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine], 4,4′-azobis (4-cyanovaleric acid) and the like.

  These polymerization initiators can be used alone or in combination of two or more. The amount and type of the polymerization initiator are selected depending on the amount of unsaturated sites in the polymer and the type and amount of the coexisting colorant.

  The polymerization initiator may be mixed in advance before the emulsification step, or may be incorporated into the aggregate in the aggregation step. Further, it may be introduced after the fusion step or after the fusion step. In the case of introduction after the aggregation step, the fusion step, or the fusion step, a solution in which the polymerization initiator is dissolved or emulsified is added to a particle dispersion (resin particle dispersion or the like). These polymerization initiators may be added with known crosslinking agents, chain transfer agents, polymerization inhibitors and the like for the purpose of controlling the degree of polymerization.

(Washing and drying process)
The fused particles obtained by fusing can be made into toner particles through a solid-liquid separation process such as filtration and, if necessary, a washing process and a drying process. In this case, in order to ensure sufficient charging characteristics and reliability as a toner, it is preferable to sufficiently wash with ion exchange water or the like in the washing step.

  In the drying step, an arbitrary method such as a normal vibration type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method, or the like can be adopted. It is desirable to adjust the moisture content after drying of the toner to 1.0% by weight or less, preferably 0.5% by weight or less.

<Physical properties of toner for developing electrostatic image>
The volume average particle diameter D50v of the toner for developing an electrostatic charge image according to the exemplary embodiment is preferably in the range of 3 μm to 8 μm, more preferably in the range of 5 μm to 7 μm, and the number average particle diameter D50p is 3 μm to 7 μm. The range of 4 μm to 6 μm is more preferable. If the volume average particle diameter D50v is less than 3 μm, the chargeability is insufficient and scattering to the surroundings occurs, causing image fogging, which is not preferable. On the other hand, if it exceeds 8 μm, the resolution of the image is lowered and it is difficult to achieve high image quality.

  The volume average particle diameter and the number average particle diameter can be measured by measuring at a 50 μm aperture diameter using a Coulter Counter [TA-II] type (manufactured by Beckman-Coulter). At this time, the measurement is performed after the toner is dispersed in an electrolyte aqueous solution (Isoton-II: manufactured by Beckman-Coulter) and dispersed by ultrasonic waves for 30 seconds or more.

  The volume average particle size distribution index GSDv of the electrostatic image developing toner according to this embodiment is 1.27 or less, preferably 1.25 or less. When GSDv exceeds 1.27, the particle size distribution is not sharp, resolution is deteriorated, and image defects such as toner scattering and fogging are caused.

The volume average particle diameter D50v and the volume average particle size distribution index GSDv can be obtained as follows. For example, the particle size range (channel) divided based on the particle size distribution of toner measured by a measuring instrument such as Coulter Counter TA-II (manufactured by Beckman-Coulter) or Multisizer II (manufactured by Beckman-Coulter) On the other hand, a cumulative distribution is drawn from the smaller diameter side for each volume and number. The diameter is defined as volume D84v and number D84p. At this time, D50v represents the volume average particle diameter, and the volume average particle size distribution index (GSDv) is determined as (D84v / D16v) ^1/2 . In addition, (D84p / D16p) ^1/2 represents a number average particle size distribution index (GSDp).

In addition, the shape factor SF1 represented by the following formula of the toner for developing an electrostatic charge image according to the exemplary embodiment is in the range of 110 to 140, and preferably in the range of 115 to 130.
SF1 = (ML ² / A) × (π / 4) × 100
[In the above formula, ML represents the maximum toner length (μm), and A represents the projected area (μm ² ) of the toner. ]
When the toner shape factor SF1 is smaller than 110 or exceeds 140, it is impossible to obtain excellent chargeability, cleaning property, and transferability over a long period of time.

In addition, shape factor SF1 was measured as follows using a Luzex image analyzer (manufactured by Nireco Corporation, FT). First, an optical microscopic image of toner spread on a slide glass is taken into a Luzex image analyzer through a video camera, and the maximum length (ML) and projection area (A) of 50 toners are measured. ML ² / A) × (π / 4) × 100 was calculated, and a value obtained by averaging the values was determined as the shape factor SF1.

  The charge amount of the electrostatic image developing toner according to the exemplary embodiment is preferably in the range of 20 to 55 μC / g in absolute value, and more preferably in the range of 25 to 45 μC / g. If the charge amount is less than 20 μC / g, background stains (fogging) are likely to occur, and if it exceeds 55 μC / g, the image density tends to decrease.

  The charge amount of the toner was measured by weighing 1.5 parts by weight of the electrostatic image developing toner and 30 parts by weight of ferrite particles (average particle diameter 35 μm) coated with styrene / methyl methacrylate resin in a glass bottle with a lid. The sample is allowed to stand for 24 hours under humidity (temperature 28 ° C., humidity 85%) and low temperature and low humidity (temperature 10 ° C., humidity 15%), and then stirred and shaken with a turbula mixer for 5 minutes. The charge amount (μC / g) of the toner in both environments can be measured with a blow-off charge amount measuring device (Toshiba Chemical Co., Ltd .: TB-200).

The surface area of the electrostatic image developing toner according to the exemplary embodiment is not particularly limited, and any toner can be used as long as it can be used for a normal toner. Specifically, when the BET method is used, a range of 0.5 to 10 m ² / g is preferable, preferably a range of 1.0 to 7 m ² / g, more preferably a range of 1.2 to ⁵ m ² / g. Especially preferably, it is the range of 1.2-3 m < ² > / g.

<Electrostatic image developer>
In the present embodiment, the electrostatic image developer is not particularly limited except that it contains the toner for developing an electrostatic image, and can have an appropriate component composition depending on the purpose. The electrostatic charge image developer may be a one-component electrostatic charge image developer using an electrostatic charge image developing toner alone, or may be used in combination with a carrier as a two-component electrostatic charge image developer. Also good.

  For example, in the case of using a carrier, the carrier is not particularly limited, and examples thereof include known carriers. For example, resins described in JP-A Nos. 62-39879 and 56-11461 are disclosed. Known carriers such as a coated carrier can be used.

  Specific examples of the carrier include the following resin-coated carriers. Examples of the core particle of the carrier include normal iron powder, ferrite, magnetite molding, and the like, and the volume average particle size is in the range of about 30 to 200 μm.

  Examples of the coating resin for the resin-coated carrier include styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, lauryl acrylate, acrylic acid 2 -Α-methylene fatty acid monocarboxylic acids such as ethylhexyl, methyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate; nitrogen-containing acrylics such as dimethylaminoethyl methacrylate; acrylonitrile, methacrylonitrile, etc. Vinyl nitriles; vinyl pyridines such as 2-vinyl pyridine and 4-vinyl pyridine; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl Homopolymers such as vinyl ketones such as ketones; olefins such as ethylene and propylene; vinyl-based fluorine-containing monomers such as vinylidene fluoride, tetrafluoroethylene and hexafluoroethylene; and copolymers composed of two or more types of monomers Furthermore, silicone resins containing methylsilicone, methylphenylsilicone, etc., polyesters containing bisphenol, glycol, etc., epoxy resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, polycarbonate resins and the like can be mentioned. These resins may be used alone or in combination of two or more. The coating amount of the coating resin is preferably in the range of about 0.1 to 10 parts by weight and more preferably in the range of 0.5 to 3.0 parts by weight with respect to 100 parts by weight of the core particles.

  For manufacturing the carrier, a heating kneader, a heating Henschel mixer, a UM mixer, or the like can be used. Depending on the amount of the coating resin, a heating fluidized rolling bed, a heating kiln, or the like can be used. .

  The mixing ratio of the electrostatic image developing toner and carrier in the electrostatic image developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, toner: carrier = 1: 100 to 30: 100 The range of about 3: 100 to 20: 100 is more preferable.

<Image forming method>
The image forming method according to the present embodiment uses a latent image forming step of forming an electrostatic latent image on the surface of the latent image carrier and a developer carried on the developer carrier, and is formed on the surface of the latent image carrier. A development process for developing the electrostatic latent image to form a toner image, a transfer process for transferring the toner image formed on the surface of the latent image holding body to the surface of the transfer target, and a toner transferred to the surface of the transfer target In the image forming method including the fixing step of fixing the image, the electrostatic image developer containing the electrostatic image developing toner of the present embodiment is used as the developer.

  The developer may be either a one-component system or a two-component system. As each of the above steps, a known step in the image forming method can be used. The image forming method according to the present embodiment may include steps other than the steps described above.

  As the latent image holding member, for example, an electrophotographic photosensitive member and a dielectric recording member can be used. In the case of an electrophotographic photosensitive member, the surface of the electrophotographic photosensitive member is uniformly charged by a corotron charger, a contact charger or the like and then exposed to form an electrostatic latent image (latent image forming step). Next, the toner particles are attached to the electrostatic latent image by contacting or approaching a developing roll having a developer layer formed on the surface, thereby forming a toner image on the electrophotographic photosensitive member (developing step). The formed toner image is transferred onto the surface of a transfer medium such as paper using a corotron charger or the like (transfer process). Further, the toner image transferred to the surface of the transfer target is heat-fixed by a fixing machine (fixing step) to form a final toner image.

  In the case of heat fixing by a fixing device, a release agent is usually supplied to a fixing member in the fixing device in order to prevent offset and the like.

The release agent is preferably not used from the viewpoint of eliminating the adhesion of oil to the transfer target and image after fixing. However, when the supply amount of the release agent is 0 mg / cm ² , the fixing member and the paper are fixed during fixing. The amount of wear of the fixing member increases and the durability of the fixing member may decrease when it comes into contact with a transfer medium such as the like. If necessary, the amount of release agent used is 8.0. It is preferable that a small amount is supplied to the fixing member in a range of × 10 ⁻³ mg / cm ² or less.

When the supply amount of the release agent exceeds 8.0 × 10 ⁻³ mg / cm ² , the image quality deteriorates due to the release agent adhering to the image surface after fixing, and in particular, transmitted light such as OHP is used. In such a case, such a phenomenon may appear remarkably. Further, the adhesion of the release agent to the transfer target becomes remarkable, and stickiness may occur. Further, the larger the supply amount of the release agent, the larger the capacity of the tank for storing the release agent, which causes an increase in the size of the fixing device itself.

  Although there is no restriction | limiting in particular as a mold release agent, For example, liquid mold release agents, such as modified oils, such as a dimethyl silicone oil, a fluorine oil, a fluoro silicone oil, and an amino modified silicone oil, are mentioned. Among these, modified oils such as amino-modified silicone oils are preferable because they are adsorbed on the surface of the fixing member and can form a uniform release agent layer, because they have excellent wettability to the fixing member. Further, from the viewpoint of forming a homogeneous release agent layer, fluorine oil and fluorosilicone oil are preferable.

  Fluorine oil or fluorosilicone oil is used as the release agent in the conventional image forming method that does not use the electrostatic image developing toner according to this embodiment, and the supply amount of the release agent itself can be reduced. However, in the case of using the electrostatic image developing toner according to the present embodiment, since the supply amount of the release agent can be drastically reduced, there is no practical problem in terms of cost.

  The method for supplying the release agent to the surface of the roller or belt that is a fixing member used for the heat fixing is not particularly limited. For example, a pad method using a pad impregnated with a liquid release agent, a web method, a roller Examples thereof include a non-contact type shower method (spray method), and a web method and a roller method are particularly preferable. These methods are advantageous in that the release agent can be supplied uniformly and the supply amount can be easily controlled. In order to supply the release agent uniformly to the entire fixing member by the shower method, it is necessary to use a separate blade or the like.

  The supply amount of the release agent can be measured as follows. That is, when a normal paper (typically, a copy paper manufactured by Fuji Xerox Co., Ltd., trade name J paper) used in a general copying machine is passed through a fixing member supplied with a release agent on its surface. The release agent adheres to the plain paper. Then, the attached release agent is extracted using a Soxhlet extractor. Here, hexane is used as the solvent.

  By quantifying the amount of the release agent contained in hexane with an atomic absorption analyzer, the amount of the release agent adhering to the plain paper can be quantified. This amount is defined as the amount of release agent supplied to the fixing member.

  Examples of the transfer target (recording material) to which the toner image is transferred include plain paper, OHP sheet, and the like used for electrophotographic copying machines and printers. In order to further improve the smoothness of the image surface after fixing, it is preferable that the surface of the transfer object is as smooth as possible. For example, coated paper in which the surface of plain paper is coated with a resin or the like, art paper for printing Etc. can be used suitably.

  The image forming method according to the present embodiment uses the electrostatic charge image developer (the toner according to the present embodiment), so that an accurate secondary color or tertiary color is expressed, and high temperature, high humidity, and long time. The charging characteristics can be maintained even under the stress conditions.

  Hereinafter, although an example and a comparative example are given and the present invention is explained more concretely in detail, the present invention is not limited to the following examples.

  The toner in the embodiment of the present invention can be obtained by the following method. That is, a first binder resin and / or a second binder resin, a colorant containing at least two of a yellow colorant, a cyan colorant, and a magenta colorant, and a release agent are included. , One or more metal salt flocculants containing polyaluminum chloride are added to a composite fine particle dispersion having a volume average particle size of 0.6 μm or less, and agglomerated at a temperature of 30 to 60 ° C. (aggregation step), Next, a first resin fine particle dispersion liquid in which first resin fine particles containing a second binder resin and having a volume average particle diameter of 0.6 μm or less are dispersed is added to the surface of the core particles. First resin-aggregated particles are formed by adhering resin fine particles (first adhesion step), and second resin fine particles containing a third binder resin and having a volume average particle size of 0.6 μm or less are formed. Add the dispersed second resin fine particle dispersion to agglomerate the first adhered resin On the surface of the child, depositing a second resin fine particle (second attachment step) to form a shell layer. Thereafter, the pH is maintained at 9 to 10, the growth of the particles is stopped, this is heated to the melting point of the first binder resin or a temperature of Tg or higher, fused and united, and then cooled to 40 ° C. or lower. Get toner. Further, this stepwise operation of aggregation may be repeated a plurality of times. Then, a desired toner is obtained by a method of washing and drying as appropriate.

  The production examples of the method for adjusting each material and the method for producing aggregated particles are described below.

<Adjustment of crystalline polyester resin (A)>
A heat-dried three-necked flask was charged with 98 mol% dimethyl sebacate, 2 mol% dimethyl-5-sulfonate sodium, 100 mol% ethylene glycol, and 0.3 parts by weight of dibutyltin oxide as a catalyst. The air in the container was brought into an inert atmosphere with nitrogen gas, and the mixture was stirred and refluxed at 180 ° C. for 5 hours with mechanical stirring. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure, and the mixture was stirred for 2 hours. When it became a viscous state, it was air-cooled, the reaction was stopped, and the crystalline polyester resin (A) (SP value 9.52) Was synthesized. The weight average molecular weight (Mw) of the obtained crystalline polyester resin (A) was 9700 by molecular weight measurement (polystyrene conversion) by gel permeation chromatography. Further, when the melting point (Tm) of the crystalline polyester resin (A) was measured by a differential scanning calorimeter (DSC: DSC-60 type, manufactured by Shimadzu Corporation) by the above-described measuring method, a clear endothermic peak was obtained. The endothermic peak temperature was 76.1 ° C. Table 1 shows the properties of the resin.

<Adjustment of crystalline polyester resin (B)>
After adding 98 mol% dimethyl sebacate, 2 mol% dimethyl-5-sulfonate sodium, 100 mol% 1,6-hexanediol, and 0.3 parts by weight of dibutyltin oxide as a catalyst in a heat-dried three-necked flask Then, the air in the container was brought into an inert atmosphere with nitrogen gas by depressurization, and the mixture was stirred and refluxed at 180 ° C. for 5 hours with mechanical stirring. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure, and the mixture was stirred for 4 hours. When it became viscous, it was air-cooled to stop the reaction, and the crystalline polyester resin (B) (SP value 9.52) Was synthesized. The weight average molecular weight (Mw) of the obtained crystalline polyester resin (B) was 30000 by molecular weight measurement (polystyrene conversion) by gel permeation chromatography. Further, when the melting point (Tm) of the crystalline polyester resin (B) was measured by the above-described measurement method using a differential scanning calorimeter (DSC), it showed a clear endothermic peak, and the endothermic peak temperature was 51 ° C. there were. Table 1 shows the properties of the resin.

<Adjustment of crystalline polyester resin (C)>
After putting 95 mol% of dimethyl terephthalate, 5 mol% of sodium dimethyl-5-sulfonate, 100 mol% of 1,9-nonanediol, and 0.3 parts by weight of dibutyltin oxide as a catalyst into a heat-dried three-necked flask Then, the air in the container was brought into an inert atmosphere with nitrogen gas by depressurization, and the mixture was stirred and refluxed at 180 ° C. for 5 hours with mechanical stirring. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure, and the mixture was stirred for 2 hours. When it became viscous, it was air-cooled to stop the reaction, and the crystalline polyester resin (C) (SP value 9.68) Was synthesized. The weight average molecular weight (Mw) of the obtained crystalline polyester resin (C) was 4000 by molecular weight measurement (polystyrene conversion) by gel permeation chromatography. Further, when the melting point (Tm) of the crystalline polyester resin (C) was measured using a differential scanning calorimeter (DSC) by the above-described measurement method, it showed a clear endothermic peak, and the endothermic peak temperature was 94 ° C. there were. Table 1 shows the properties of the resin.

<Adjustment of amorphous polyester resin (G)>
Bisphenol A propylene oxide adduct 80mol%
Cyclohexanedimethanol 20 mol%
Dodecenyl succinic acid 15mol%
Terephthalic acid 60mol%
Dodecanoic acid 25 mol%
The above monomer is charged into a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying column, and the temperature is raised to 190 ° C. over 1 hour, and the reaction system is uniformly stirred. After confirming the above, 1.2 parts by weight of dibutyltin oxide was added. Further, while distilling off the generated water, the temperature was increased to 240 ° C. over 6 hours from the same temperature, and the dehydration condensation reaction was continued at 240 ° C. for another 3 hours. The acid value was 9.0 mgKOH / g, and the weight average molecular weight. Amorphous polyester resin (G) (SP value 9.76) of 9700 was obtained. Table 1 shows the properties of the resin.

<Adjustment of amorphous polyester resin (H)>
Terephthalic acid 100mol%
Bisphenol A ethylene oxide 2 mol adduct 100 mol%
The above monomer is charged into a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying column, and the temperature is raised to 190 ° C. over 1 hour, and the reaction system is uniformly stirred. After confirming the above, 1.2 parts by weight of dibutyltin oxide was added. Further, while distilling off generated water, the temperature was increased to 240 ° C. over 6 hours from the same temperature, and the dehydration condensation reaction was continued at 240 ° C. for another 3 hours. An amorphous polyester resin (H) of 9,000 (SP value 10.5) was obtained. Table 1 shows the properties of the resin.

<Adjustment of amorphous polyester resin (I)>
Bisphenol A propylene oxide adduct 80mol%
Cyclohexanedimethanol 20 mol%
Dodecenyl succinic acid 15mol%
Terephthalic acid 37mol%
Dodecanoic acid 48mol%
The above monomer is charged into a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying column, and the temperature is raised to 190 ° C. over 1 hour, and the reaction system is uniformly stirred. After confirming the above, 1.2 parts by weight of dibutyltin oxide was added. Further, while distilling off the water produced, it took 6 hours from the same temperature to raise the temperature to 240 ° C., and continued the dehydration condensation reaction at 240 ° C. for another 5 hours, with an acid value of 5.0 mgKOH / g, weight average molecular weight Amorphous polyester resin (I) having 8500 (SP value 9.61) was obtained. Table 1 shows the properties of the resin.

<Adjustment of amorphous polyester resin (J)>
Terephthalic acid 99mol%
Bisphenol A ethylene oxide 2 mol adduct 90 mol%
Hexanediol 10mol%
The above monomer is charged into a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying column, and the temperature is raised to 190 ° C. over 1 hour, and the reaction system is uniformly stirred. After confirming the above, 1.2 parts by weight of dibutyltin oxide was added. Further, while distilling off the generated water, the temperature was increased to 240 ° C. over 6 hours from the same temperature, and the dehydration condensation reaction was continued at 240 ° C. for another 3 hours. An amorphous polyester resin (J) (SP value 10.5) of 9000 was obtained. Table 1 shows the properties of the resin.

<Adjustment of amorphous polyester resin (K)>
Bisphenol A propylene oxide adduct 80mol%
Cyclohexanedimethanol 20 mol%
Dodecenyl succinic acid 15mol%
Terephthalic acid 63mol%
Dodecanoic acid 22mol%
The above monomer is charged into a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying column, and the temperature is raised to 190 ° C. over 1 hour, and the reaction system is uniformly stirred. After confirming the above, 1.2 parts by weight of dibutyltin oxide was added. Further, while distilling off the water produced, it took 6 hours from the same temperature to raise the temperature to 240 ° C., and continued the dehydration condensation reaction at 240 ° C. for another 5 hours. An amorphous polyester resin (K) of 30000 (SP value 9.79) was obtained. Table 1 shows the properties of the resin.

<Adjustment of amorphous polyester resin (O)>
Terephthalic acid 99mol%
Bisphenol A ethylene oxide 2 mol adduct 30 mol%
Bisphenol A ethylene oxide 2 mol adduct 60 mol%
The above monomer is charged into a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying column, and the temperature is raised to 190 ° C. over 1 hour, and the reaction system is uniformly stirred. After confirming the above, 1.2 parts by weight of dibutyltin oxide was added. Further, while distilling off the generated water, it took 6 hours from the same temperature to increase the temperature to 240 ° C., and continued the dehydration condensation reaction at 240 ° C. for another 3 hours, with an acid value of 3.0 mgKOH / g, weight average molecular weight An amorphous polyester resin (O) (SP value 10.5) of 9000 was obtained. Table 1 shows the properties of the resin.

<Preparation of composite fine particle dispersion (1)>
A resin fine particle dispersion was prepared using a crystalline polyester resin (A), an amorphous resin (G), a colorant and a release agent.
Crystalline resin (A) 33 parts by weight Amorphous resin (G) 60 parts by weight Cyan pigment (copper phthalocyanine CI Pigment Blue 15: 3, hereinafter sometimes simply referred to as PB15: 3: manufactured by Dainichi Seika, 11 parts by weight of yellow pigment (CI Pigment Yellow 74, hereinafter sometimes simply referred to as PY74: manufactured by Clariant, acid value of 4.2 mg KOH / g) 11 parts by weight Magenta pigment (C.I.) I. Pigment Red 122, hereinafter may be simply referred to as PR122: manufactured by Dainichi Seika Co., Ltd., acid value 4.0 mg KOH / g) 11 parts by weight ester wax (WEP5: pentaerythritol behenic acid wax: manufactured by NOF Corporation) 33 parts by weight acetic acid Isopropyl 233 parts by weight 0.3N NaOH aqueous solution 0.1 parts by weight Placed in a 00mL separable flask, heated to 70 ° C., and stirred with a Three-One Motor to prepare a homogeneous solution. Further, 373 parts by weight of ion-exchanged water is added with stirring to perform phase inversion and remove the solvent to obtain a composite fine particle dispersion (1) of crystalline resin (A), amorphous resin (G), wax, and colorant. ) Was obtained at a volume average particle size of 200 nm and a solid content of 30 parts by weight. Table 2 shows the properties of the dispersion.

<Preparation of composite fine particle dispersion (2)>
A resin fine particle dispersion was prepared using the crystalline polyester resin (B), the amorphous resin (I), the colorant and the release agent.
Crystalline resin (B) 33 parts by weight Amorphous resin (I) 60 parts by weight Cyan pigment (copper phthalocyanine PB15: 3: manufactured by Dainichi Seika, acid value 3.0 mgKOH / g) 9.9 parts by weight Yellow pigment (PY74 : Made by Clariant, acid value 4.2 mgKOH / g) 11.6 parts by weight Magenta pigment (PR122: Made by Dainichi Seika, acid value 4.0 mgKOH / g) 11.6 parts by weight Ester wax (WEP5: Pentaerythritol behenic acid wax 33 parts by weight Isopropyl acetate 233 parts by weight 0.3 N NaOH aqueous solution 0.1 part by weight The above materials are placed in a 500 mL separable flask, heated to 75 ° C., and stirred with a three-one motor to produce a uniform solution. did. Further, 373 parts by weight of ion-exchanged water is added with stirring, phase is changed, and the solvent is removed to obtain a dispersion (2) of the crystalline resin (B), the amorphous resin (I), the wax, and the colorant. The volume average particle size was 590 nm and the solid content was 30 parts by weight. Table 2 shows the properties of the dispersion.

<Preparation of composite fine particle dispersion (3)>
A resin fine particle dispersion was prepared using a crystalline polyester resin (C), an amorphous resin (K), a colorant and a release agent.
Crystalline resin (C) 33 parts by weight Amorphous resin (K) 60 parts by weight Cyan pigment (copper phthalocyanine PB15: 3: manufactured by Dainichi Seika, acid value 3.0 mgKOH / g) 9 parts by weight Yellow pigment (PY74: Clariant Manufactured, acid value 4.2 mg KOH / g) 13.2 parts by weight Magenta pigment (PR122: manufactured by Dainichi Seisaku Co., Ltd., acid value 4.0 mg KOH / g) 10.9 parts by weight ester wax (WEP5: pentaerythritol behenic acid wax: Japan 33 parts by weight Isopropyl acetate 233 parts by weight 0.3 N NaOH aqueous solution 0.1 part by weight The above materials were placed in a 500 mL separable flask, heated to 75 ° C., and stirred with a three-one motor to prepare a uniform solution. Further, 373 parts by weight of ion-exchanged water is added with stirring to perform phase inversion and remove the solvent to obtain a dispersion (3) of the crystalline resin (C), the amorphous resin (K), the wax, and the colorant. The volume average particle size was 590 nm and the solid content was 30 parts by weight. Table 2 shows the properties of the dispersion.

<Preparation of composite fine particle dispersion (4)>
A resin fine particle dispersion was prepared using an amorphous resin (G), a colorant and a release agent.
Amorphous resin (G) 93 parts by weight Cyan pigment (copper phthalocyanine PB15: 3: manufactured by Dainichi Seika, acid value 3.0 mgKOH / g) 11 parts by weight Yellow pigment (PY74: manufactured by Clariant, acid value 4.2 mgKOH / g) ) 11 parts by weight Magenta pigment (PR122: manufactured by Dainichi Seika Co., Ltd., acid value: 4.0 mg KOH / g) 11 parts by weight Ester wax (WEP5: pentaerythritol behenic acid wax: manufactured by Nippon Oil & Fats) 33 parts by weight Isopropyl acetate 233 parts by weight 3N NaOH aqueous solution 0.1 part by weight The above materials were put into a 500 mL separable flask, heated to 70 ° C., and stirred with a three-one motor to prepare a uniform solution. Further, 257 parts by weight of ion-exchanged water is added with stirring to perform phase inversion, and the solvent is removed, whereby the dispersion (4) of the amorphous resin (G), the wax, and the colorant has a volume average particle size of 200 nm, solids An amount of 30 parts by weight was obtained. Table 2 shows the properties of the dispersion.

<Preparation of composite fine particle dispersion (5)>
A resin fine particle dispersion was prepared using a crystalline polyester resin (A), an amorphous resin (G), and a release agent.
Crystalline resin (A) 33 parts by weight Amorphous resin (G) 60 parts by weight Ester wax (WEP5: pentaerythritol behenate wax: manufactured by NOF Corporation) 33 parts by weight Isopropyl acetate 233 parts by weight 0.3 N NaOH aqueous solution 0.1 part by weight Part The above materials were put into a 500 mL separable flask, heated to 70 ° C., and stirred with a three-one motor to prepare a uniform solution. Further, 333 parts by weight of ion-exchanged water is added with stirring to perform phase inversion and remove the solvent, whereby the volume average particle diameter of the crystalline resin (A), the amorphous resin (G), and the wax dispersion (5) is reduced. Obtained at 200 nm and a solid content of 30 parts by weight. Table 2 shows the properties of the dispersion.

<Preparation of composite fine particle dispersion (6)>
A resin fine particle dispersion was prepared using a crystalline polyester resin (A), an amorphous resin (G), and a colorant.
Crystalline resin (A) 33 parts by weight Amorphous resin (G) 60 parts by weight Cyan pigment (copper phthalocyanine PB15: 3: manufactured by Dainichi Seika, acid value 3.0 mgKOH / g) 11 parts by weight Yellow pigment (PY74: Clariant 11 parts by weight of magenta pigment (PR122: manufactured by Dainichi Seika, acid value of 4.0 mg KOH / g) 11 parts by weight Isopropyl acetate 233 parts by weight 0.3 N NaOH aqueous solution 0.1 parts by weight The material was placed in a 500 mL separable flask, heated to 70 ° C., and stirred with a three-one motor to prepare a uniform solution. Further, 296 parts by weight of ion-exchanged water was added with stirring to perform phase inversion and remove the solvent, whereby the volume average of the crystalline resin (A), the amorphous resin (G), and the colorant dispersion (6) was obtained. The particle size was 200 nm and the solid content was 30 parts by weight. Table 2 shows the properties of the dispersion.

<Preparation of composite fine particle dispersion (7)>
A resin fine particle dispersion was prepared using a crystalline polyester resin (A), an amorphous resin (G), a colorant and a release agent.
Crystalline resin (A) 50 parts by weight Amorphous resin (G) 60 parts by weight Cyan pigment (copper phthalocyanine PB15: 3: manufactured by Dainichi Seika, acid value 3.0 mgKOH / g) 11 parts by weight Yellow pigment (PY74: Clariant 11 parts by weight of magenta pigment (PR122: manufactured by Dainichi Seisaku Co., Ltd., acid value of 4.0 mgKOH / g) 11 parts by weight of ester wax (WEP5: pentaerythritol behenic acid wax: manufactured by NOF Corporation) 33 Part by weight Isopropyl acetate 233 parts by weight 0.3 N NaOH aqueous solution 0.1 part by weight The above materials were put into a 500 mL separable flask, heated to 80 ° C., and stirred by a three-one motor to prepare a uniform solution. Further, 373 parts by weight of ion-exchanged water is added to the mixture while stirring to remove the solvent, thereby removing the crystalline resin (A), the amorphous resin (G), the wax, and the colorant (7) by volume average. The particle diameter was 700 nm and the solid content was 30 parts by weight. Table 2 shows the properties of the dispersion.

<Preparation of resin fine particle dispersion (8)>
The amorphous polyester resin (G) was melted and transferred to Cavitron CD1010 (Eurotech Co., Ltd.) at a rate of 100 g / min. Separately prepared aqueous medium tank is filled with 0.37 wt% diluted ammonia water diluted with ion-exchanged water with reagent-exchanged water, and heated at 120 ° C with a heat exchanger at a rate of 0.1 liter per minute. The amorphous polyester resin (G) melt was transferred to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.). The Cavitron was operated under conditions of a rotor rotation speed of 60 Hz and a pressure of 5 kg / cm ² , and an amorphous polyester resin (G) (SP value 9.76) having a volume average particle size of 0.2 μm and a solid content of 30 parts by weight. Amorphous polyester resin dispersion (8) was obtained. Table 2 shows the properties of the dispersion.

<Preparation of resin fine particle dispersion (9)>
The amorphous polyester resin (H) was melted and transferred to Cavitron CD1010 (Eurotech Co., Ltd.) at a rate of 100 g / min. Separately prepared aqueous medium tank is filled with 0.37% by weight diluted ammonia water diluted with ion exchange water and heated at 120 ° C by a heat exchanger at a rate of 0.1 liter per minute. The amorphous polyester resin (H) melt was transferred to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.). The Cavitron was operated under conditions of a rotor rotation speed of 60 Hz and a pressure of 5 kg / cm ² , and an amorphous polyester resin (H) having a volume average particle size of 0.2 μm and a solid content of 30 parts by weight (SP value of 9.76). Amorphous polyester resin dispersion (9) was obtained. Table 2 shows the properties of the dispersion.

<Preparation of resin fine particle dispersion (10)>
The amorphous polyester resin (I) was melted and transferred to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) at a rate of 100 g / min. Separately prepared aqueous medium tank is filled with 0.37 wt% diluted ammonia water diluted with ion-exchanged water with reagent-exchanged water, and heated at 120 ° C with a heat exchanger at a rate of 0.1 liter per minute. The amorphous polyester resin (I) melt was transferred to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.). The Cavitron was operated under conditions of a rotor rotation speed of 60 Hz and a pressure of 4 kg / cm ² , and amorphous polyester resin (I) (SP value 9.61) having an average particle size of 0.59 μm and a solid content of 30 parts by weight was obtained. An amorphous polyester resin dispersion (10) containing was obtained. Table 2 shows the properties of the dispersion.

<Preparation of resin fine particle dispersion (11)>
The amorphous polyester resin (J) was melted and transferred to Cavitron CD1010 (Eurotech Co., Ltd.) at a rate of 100 g / min. Separately prepared aqueous medium tank is filled with 0.37% by weight diluted ammonia water diluted with ion exchange water and heated at 120 ° C by a heat exchanger at a rate of 0.1 liter per minute. The amorphous polyester resin (J) melt was transferred to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.). The Cavitron was operated under conditions of a rotor rotation speed of 60 Hz and a pressure of 4 kg / cm ² , and an amorphous polyester resin (J) (SP value 10.5) having an average particle size of 0.59 μm and a solid content of 30 parts by weight was obtained. An amorphous polyester resin dispersion (11) containing was obtained. Table 2 shows the properties of the dispersion.

<Preparation of resin fine particle dispersion (12)>
The amorphous polyester resin (K) was melted and transferred to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) at a rate of 100 g / min. Separately prepared aqueous medium tank is filled with 0.37% by weight diluted ammonia water diluted with ion exchange water and heated at 120 ° C by a heat exchanger at a rate of 0.1 liter per minute. The amorphous polyester resin (K) melt was transferred to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.). The Cavitron was operated under conditions of a rotor rotation speed of 60 Hz and a pressure of 4 kg / cm ² , and an amorphous polyester resin (K) (SP value 9.79) having an average particle size of 0.59 μm and a solid content of 30 parts by weight. An amorphous polyester resin dispersion (12) containing was obtained. Table 2 shows the properties of the dispersion.

<Preparation of resin fine particle dispersion (13)>
The amorphous polyester resin (O) was melted and transferred to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) at a rate of 100 g / min. Separately prepared aqueous medium tank is filled with 0.37% by weight diluted ammonia water diluted with ion exchange water and heated at 120 ° C by a heat exchanger at a rate of 0.1 liter per minute. The amorphous polyester resin (O) melt was transferred to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.). The Cavitron was operated under the conditions of a rotor rotation speed of 60 Hz and a pressure of 4 kg / cm ^2. An amorphous polyester resin (O) (SP value 10.5) having an average particle size of 0.59 μm and a solid content of 30 parts by weight was obtained. An amorphous polyester resin dispersion (13) containing was obtained. Table 2 shows the properties of the dispersion.

<Preparation of resin fine particle dispersion (14)>
The amorphous polyester resin (G) was melted and transferred to Cavitron CD1010 (Eurotech Co., Ltd.) at a rate of 100 g / min. Separately prepared aqueous medium tank is filled with 0.37 wt% diluted ammonia water diluted with ion-exchanged water with reagent-exchanged water, and heated at 120 ° C with a heat exchanger at a rate of 0.1 liter per minute. The amorphous polyester resin (G) melt was transferred to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.). The Cavitron was operated under the conditions of a rotor rotation speed of 60 Hz and a pressure of 3 kg / cm ² , and an amorphous polyester resin (G) (SP value 9.76) having an average particle size of 0.7 μm and a solid content of 30 parts by weight. An amorphous polyester resin dispersion (14) containing was obtained. Table 2 shows the properties of the dispersion.

<Preparation of resin fine particle dispersion (15)>
The amorphous polyester resin (H) was melted and transferred to Cavitron CD1010 (Eurotech Co., Ltd.) at a rate of 100 g / min. Separately prepared aqueous medium tank is filled with 0.37% by weight diluted ammonia water diluted with ion exchange water and heated at 120 ° C by a heat exchanger at a rate of 0.1 liter per minute. The amorphous polyester resin (H) melt was transferred to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.). The Cavitron was operated under conditions of a rotor rotation speed of 60 Hz and a pressure of 3 kg / cm ² , and an amorphous polyester resin (H) (SP value 10.5) having an average particle size of 0.7 μm and a solid content of 30 parts by weight was used. An amorphous polyester resin dispersion (15) containing was obtained. Table 2 shows the properties of the dispersion.

<Preparation of composite fine particle dispersion (16)>
A resin fine particle dispersion was prepared using a crystalline polyester resin (A), an amorphous resin (G), a colorant and a release agent.
Crystalline resin (A) 33 parts by weight Amorphous resin (G) 60 parts by weight Carbon black (R330, manufactured by CABOT) 33 parts by weight Ester wax (WEP5: Pentaerythritol behenic acid wax: manufactured by NOF Corporation) 33 parts by weight Acetic acid Isopropyl 233 parts by weight 0.3 N NaOH aqueous solution 0.1 part by weight The above materials were put into a 500 mL separable flask, heated to 70 ° C., and stirred by a three-one motor to prepare a uniform solution. Further, 373 parts by weight of ion-exchanged water is added with stirring to perform phase inversion and remove the solvent to obtain a dispersion (16) of the crystalline resin (A), the amorphous resin (G), the wax, and the colorant. The volume average particle size was 200 nm, and the solid content was 30 parts by weight. Table 2 shows the properties of the dispersion.

<Preparation of cyan colorant dispersion>
Cyan pigment (copper phthalocyanine B15: 3: manufactured by Dainichi Seika) 81 parts by weight Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku) 5 parts by weight Ion-exchanged water 200 parts by weight For 10 minutes to obtain a cyan colorant dispersion having a center particle size of 168 nm and a solid content of 30 parts by weight.

<Preparation of Yellow Colorant Dispersion (1)>
Yellow pigment (PY74: Clariant) 81 parts by weight Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts by weight Ion-exchanged water 200 parts by weight The above components are mixed and dissolved, and then homogenizer (IKA Ultra Tarrax) for 10 minutes. Dispersion gave a yellow colorant dispersion (1) having a center particle size of 168 nm and a solid content of 30 parts by weight.

<Preparation of yellow colorant dispersion (2)>
Yellow pigment (PY180: Hoechst) 81 parts by weight Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts by weight Ion-exchanged water 200 parts by weight The above components are mixed and dissolved. Dispersion was carried out for minutes to obtain a yellow colorant dispersion (2) having a central particle size of 150 nm and a solid content of 30 parts by weight.

<Preparation of magenta colorant dispersion>
Magenta pigment (R122: manufactured by Dainichi Seika) 81 parts by weight Ionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku) 5 parts by weight Ion-exchanged water 200 parts by weight The above components are mixed and dissolved. Dispersion for 10 minutes gave a magenta colorant dispersion having a center particle size of 168 nm and a solid content of 30 parts by weight.

<Preparation of black colorant dispersion>
Black pigment (R330: carbon black, manufactured by CABOT) 81 parts by weight Ionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku) 5 parts by weight Ion-exchanged water 200 parts by weight ) For 10 minutes to obtain a black colorant dispersion having a center particle size of 168 nm and a solid content of 30 parts by weight.

<Preparation of process black colorant dispersion>
Cyan colorant dispersion 11 parts by weight Yellow colorant dispersion (1) 11 parts by weight Magenta colorant dispersion 11 parts by weight Obtained.

<Preparation of blue colorant dispersion>
Cyan colorant dispersion 10 parts by weight Magenta colorant dispersion 20 parts by weight The above was mixed to obtain a blue colorant dispersion having a center particle size of 168 nm and a solid content of 30 parts by weight.

<Preparation of red colorant dispersion>
Yellow colorant dispersion (2) 25 parts by weight Magenta colorant dispersion 5 parts by weight The above was mixed to obtain a blue colorant dispersion having a center particle size of 168 nm and a solid content of 30 parts by weight.

<Preparation of green colorant dispersion>
Yellow colorant dispersion (2) 25 parts by weight Cyan colorant dispersion 5 parts by weight The above was mixed to obtain a green colorant dispersion having a center particle size of 168 nm and a solid content of 30 parts by weight.

<Preparation of release agent dispersion>
Ester wax (WEP5: manufactured by NOF Corporation, melting point: 84.5 ° C, ratio of Mw 1700 or less: 24%) 50 parts by weight Cationic surfactant Neogen RK (Daiichi Kogyo Seiyaku) 5 parts by weight Ion-exchanged water 111 parts by weight The mixture was heated to 95 ° C. and sufficiently dispersed with IKA Ultra Turrax T50, and then dispersed with a pressure discharge type gorin homogenizer to obtain a wax dispersion having a center diameter of 220 nm and a solid content of 30%. In addition, it is confirmed from the peak area that the ratio of the weight average molecular weight of 1800 or less in the ester wax (WEP5: manufactured by NOF Corporation, melting point: 84.5 ° C., ratio of 2 or less: 24%) is 24% in GPC analysis. did.

Example 1
<Preparation of toner base particles (1)>
Composite Particulate Dispersion (1) 160 parts by weight The above was sufficiently mixed and dispersed in a round stainless steel flask with Ultra Turrax T50. Next, 0.20 part by weight of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, a dispersion obtained by mixing 57 parts by weight of the resin fine particle dispersion (8) and 57 parts by weight of the resin fine particle dispersion (9) was gradually added thereto. Further 20 minutes later, 60 parts by weight of the resin fine particle dispersion (9) was gradually added. Thereafter, the pH of the system was adjusted to 9.0 with a 0.5 mol / L sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained. After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Next, vacuum drying was continued for 12 hours to obtain toner mother particles (1) with SPp3-SPp2 = 0.74 and SPp2-SPp1 = 0.24.

  When the volume average particle size at this time was measured with a Coulter counter, D50v was 5.9 μm, and the particle size distribution coefficient GSDv was 1.26. The particle size distribution coefficient GSDp was 1.28. The toner base particles (1) were observed with a transmission electron microscope (TEM), and it was confirmed that the ratio of the colorant present in the region within 200 nm from the outermost surface of the toner was 4%. The toner base particles (1) were observed with a transmission electron microscope (TEM), and it was confirmed that the percentage of wax existing within 200 nm from the outermost surface of the toner was 5%. Further, the dispersibility of each colorant of yellow, cyan and magenta was confirmed by TEM. Of the number of pigments in the toner, the proportion of each pigment having a pigment particle size of 250 nm or less was confirmed for 50 toners. As a result, 95% by number of pigments having a particle size of 250 nm or less were confirmed to be uniformly dispersed. .

<Preparation of Externally Added Toner (1)>
Next, an external toner was prepared. Toner base particles (1) 100 parts by weight, rutile type titanium oxide (volume average particle size 20 nm, n-decyltrimethoxysilane treatment) 1.0 part by weight, silica (produced by vapor phase oxidation method, volume average particle size 40 nm) , Silicone oil treatment) 2.0 parts by weight, 0.5 parts by weight of a higher alcohol pulverized product (volume average particle size 200 nm) was added, and blended for 15 minutes at a peripheral speed of 30 m / s using a 5-liter Henschel mixer. Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to prepare an externally added toner (1). Further, this was weighed so that the toner concentration was 5% by weight with respect to a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% by weight of polymethyl methacrylate resin (Mw: 75000, manufactured by Soken Chemical Co., Ltd.), and 5% by a ball mill. The developer (1) was prepared by stirring and mixing for a minute.

<Evaluation>
Further, the developer (1) is loaded into a remodeled machine of the color copying machine DocuCentreColor 400 (manufactured by Fuji Xerox Co., Ltd.) and the developer (1) after being idled for 2 minutes in an environment of a temperature of 28 ° C. and a humidity of 85%. The charge amount (μC / g) of the toner was measured with a blow-off charge amount measuring device and found to be 60 μC / g. Furthermore, in the above environment, a live-action test was performed in which 200,000 sheets of color originals with a toner loading of 13.0 g / m ² were continuously printed, and a fine image was obtained without fogging on the 200,000th sheet. . The toner charge amount (μC / g) in the developer (1) at the end of the test was measured with a blow-off charge amount measuring device. As a result, it was 55 μC / g and the charge retention rate was 92%. Furthermore, the fixed image of the 200,000th sheet was observed, and it was confirmed by visual observation that the blackness of black was not shifted. The results are shown in Table 3.

The charge retention rate was ranked as follows.
◎: Charge retention ratio is 91% or more ○: Charge retention ratio is in the range of 86 to 90% △: Charge retention ratio is in the range of 80 to 85% ×: Charge retention ratio is in the range of 79% or less

(Example 2)
<Preparation of toner mother particles (2)>
Composite fine particle dispersion (2) 160 parts by weight The above was sufficiently mixed and dispersed in a round stainless steel flask with Ultra Turrax T50. Next, 0.20 part by weight of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, a dispersion obtained by mixing 57 parts by weight of the resin fine particle dispersion (10) and 57 parts by weight of the resin fine particle dispersion (11) was gradually added thereto. Further 20 minutes later, 60 parts by weight of the resin fine particle dispersion (11) was gradually added. Thereafter, the pH of the system was adjusted to 9.0 with a 0.5 mol / L sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained. After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Next, vacuum drying was continued for 12 hours to obtain toner mother particles (2) having SPp3-SPp2 = 0.89 and SPp2-SPp1 = 0.09.

  When the volume average particle diameter of the toner was measured with a Coulter counter, D50v was 5.9 μm, and the particle size distribution coefficient GSDv was 1.24. The particle size distribution coefficient was GSDp 1.28. The toner base particles (2) were observed with a transmission electron microscope (TEM), and it was confirmed that the ratio of the colorant present in the region within 200 nm from the outermost surface of the toner was 9%. The toner base particles (2) were observed with a transmission electron microscope (TEM), and it was confirmed that the percentage of wax existing within 200 nm from the outermost surface of the toner was 9%. Further, the dispersibility of each colorant of yellow, cyan and magenta was confirmed by TEM. Of the number of pigments in the toner, the proportion of each pigment having a pigment particle size of 250 nm or less was confirmed for 50 toners. As a result, 91% by number of pigments having a particle size of 250 nm or less were confirmed to be uniformly dispersed. .

<Preparation of Externally Added Toner (2)>
Next, the toner base particles (2) were treated in the same manner as the externally added toner (1) to produce an externally added toner (2). Further, this was weighed so that the toner concentration was 5% by weight with respect to a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% by weight of polymethyl methacrylate resin (Mw: 75000, manufactured by Soken Chemical Co., Ltd.), and 5% by a ball mill. The developer (2) was prepared by stirring and mixing for a minute.

<Evaluation>
Further, the developer (2) is loaded into a remodeled machine of the color copying machine DocuCentreColor 400 (manufactured by Fuji Xerox Co., Ltd.), and after being idle for 2 minutes in an environment of a temperature of 28 ° C. and a humidity of 85%, the developer (2) The toner charge amount (μC / g) was measured by a blow-off charge amount measuring device and found to be 58 μC / g. Furthermore, in the above environment, a live-action test was performed in which 200,000 sheets of color originals with a toner loading of 13.0 g / m ² were continuously printed, and a fine image was obtained without fogging on the 200,000th sheet. . When the charge amount (μC / g) of the toner in the developer (2) at the end of the test was measured with a blow-off charge amount measuring device, it was 51 μC / g and the charge retention rate was 88%. Furthermore, the fixed image of the 200,000th sheet was observed, and it was confirmed by visual observation that the blackness of black was not shifted. The results are shown in Table 3.

(Example 3)
<Preparation of toner mother particles (3)>
Composite Fine Particle Dispersion (3) Dispersion 160 parts by weight The above was sufficiently mixed and dispersed in a round stainless steel flask with Ultra Turrax T50. Next, 0.20 part by weight of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, a dispersion obtained by mixing 60 parts by weight of the resin fine particle dispersion (12) and 60 parts by weight of the resin fine particle dispersion (13) was gradually added thereto. Further 20 minutes later, 60 parts by weight of the resin fine particle dispersion (13) was gradually added. Thereafter, the pH of the system was adjusted to 9.0 with a 0.5 mol / L sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained. After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Next, vacuum drying was continued for 12 hours to obtain toner mother particles (3) with SPp3-SPp2 = 0.71 and SPp2-SPp1 = 0.11.

  When the volume average particle size of the toner was measured with a Coulter counter, D50v was 5.9 μm, and the particle size distribution coefficient GSDv was 1.27. The toner base particles (3) were observed with a transmission electron microscope (TEM), and it was confirmed that the ratio of the colorant present in the region within 200 nm from the outermost surface of the toner was 8%. The particle size distribution coefficient was GSDp 1.29. The toner base particles (3) were observed with a transmission electron microscope (TEM), and it was confirmed that the proportion of wax present in the region within 200 nm from the outermost surface of the toner was 8%. Further, the dispersibility of each colorant of yellow, cyan and magenta was confirmed by TEM. Of the number of pigments in the toner, the proportion of each pigment having a pigment particle size of 250 nm or less was confirmed for 50 toners. As a result, 90% by number of pigments having a particle size of 250 nm or less were confirmed to be uniformly dispersed. .

<Preparation of externally added toner (3)>
Next, the toner base particles (3) were treated in the same manner as the externally added toner (1) to produce an externally added toner (3). Further, this was weighed so that the toner concentration was 5% by weight with respect to a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% by weight of polymethyl methacrylate resin (Mw: 75000, manufactured by Soken Chemical Co., Ltd.), and 5% by a ball mill. The developer (3) was prepared by stirring and mixing for a minute.

<Evaluation>
Further, the developer (3) is loaded into a remodeled machine of the color copier DocuCentreColor 400 (manufactured by Fuji Xerox), and the developer (3) after being idled for 2 minutes in an environment of a temperature of 28 ° C. and a humidity of 85% is used. The toner charge amount (μC / g) was measured by a blow-off charge amount measuring device and found to be 56 μC / g. Furthermore, in the above environment, a live-action test was performed in which 200,000 sheets of color originals with a toner loading of 13.0 g / m ² were continuously printed. It was. The toner charge amount (μC / g) in Developer 1 at the end of the test was measured with a blow-off charge amount measuring device. As a result, it was 48 μC / g and the charge retention rate was 85%. Furthermore, the fixed image of the 200,000th sheet was observed, and it was confirmed by visual observation that the blackness of black was not shifted. The results are shown in Table 3.

Example 4
<Preparation of toner mother particles (4)>
Composite Fine Particle Dispersion (1) Dispersion 160 parts by weight The above was sufficiently mixed and dispersed in a round stainless steel flask with Ultra Turrax T50. Next, 0.20 part by weight of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, a dispersion obtained by mixing 60 parts by weight of the resin fine particle dispersion (8) was slowly added thereto. Further 20 minutes later, 120 parts by weight of the resin fine particle dispersion (9) was gradually added. Thereafter, the pH of the system was adjusted to 9.0 with a 0.5 mol / L sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained. After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Next, vacuum drying was continued for 12 hours to obtain toner mother particles (4) with SPp3-SPp2 = 0.74 and SPp2-SPp1 = 0.24.

  When the volume average particle size of the toner was measured with a Coulter counter, D50v was 5.9 μm, and the particle size distribution coefficient GSDv was 1.27. The particle size distribution coefficient was GSDp 1.29. The toner base particles (4) were observed with a transmission electron microscope (TEM), and it was confirmed that the ratio of the colorant present in the region within 200 nm from the outermost surface of the toner was 9%. The toner base particles (4) were observed with a transmission electron microscope (TEM), and it was confirmed that the proportion of wax present in the region within 200 nm from the outermost surface of the toner was 8%. Further, the dispersibility of each colorant of yellow, cyan and magenta was confirmed by TEM. Of the number of pigments in the toner, the proportion of each pigment having a pigment particle size of 250 nm or less was confirmed for 50 toners. As a result, 90% by number of pigments having a particle size of 250 nm or less were confirmed to be uniformly dispersed. .

<Preparation of Externally Added Toner (4)>
Next, the toner base particles (4) were treated in the same manner as the externally added toner (1) to produce an externally added toner (4). Further, this was weighed so that the toner concentration became 5% by weight with respect to a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% by weight of polymethyl methacrylate resin (Mw: 75000, manufactured by Soken Chemical Co., Ltd.), and 5% by a ball mill. The developer (4) was prepared by stirring and mixing for a minute.

<Evaluation>
Further, developer (4) is loaded into a color copier DocuCentreColor400 (Fuji Xerox Co., Ltd.) remodeled machine, and the toner in developer 4 after being idled for 2 minutes in an environment of temperature 28 ° C. and humidity 85% When the charge amount (μC / g) was measured with a blow-off charge amount measuring device, it was 57 μC / g. Furthermore, in the above environment, a live-action test was performed in which 200,000 sheets of color originals with a toner loading of 13.0 g / m ² were continuously printed. It was. The toner charge amount (μC / g) in the developer 1 at the end of the test was measured with a blow-off charge amount measuring device. As a result, it was 49 μC / g and the charge retention rate was 86%. Furthermore, the fixed image of the 200,000th sheet was observed, and it was confirmed by visual observation that the blackness of black was not shifted. The results are shown in Table 3.

(Example 5)
<Preparation of toner mother particles (5)>
Composite Fine Particle Dispersion (4) Dispersion 160 parts by weight The above was sufficiently mixed and dispersed in a round stainless steel flask with Ultra Turrax T50. Next, 0.20 part by weight of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, a dispersion obtained by mixing 60 parts by weight of the resin fine particle dispersion (8) and 60 parts by weight of the resin fine particle dispersion (9) was gradually added thereto. Further 20 minutes later, 60 parts by weight of the resin fine particle dispersion (9) was gradually added. Thereafter, the pH of the system was adjusted to 9.0 with a 0.5 mol / L sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained. After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Next, vacuum drying was continued for 12 hours to obtain toner mother particles (5) with SPp3-SPp2 = 0.74.

  When the volume average particle size of the toner was measured with a Coulter counter, D50v was 5.9 μm, and the particle size distribution coefficient GSDv was 1.27. The particle size distribution coefficient was GSDp 1.28. The toner base particles (5) were observed with a transmission electron microscope (TEM), and it was confirmed that the ratio of the colorant present in the region within 200 nm from the outermost surface of the toner was 9%. The toner base particles (5) were observed with a transmission electron microscope (TEM), and it was confirmed that the ratio of the wax existing in the region within 200 nm from the outermost surface of the toner was 8%. Further, the dispersibility of each colorant of yellow, cyan and magenta was confirmed by TEM. Of the number of pigments in the toner, the proportion of each pigment having a pigment particle size of 250 nm or less was confirmed for 50 toners. As a result, 91% by number of pigments having a particle size of 250 nm or less was confirmed to be uniformly dispersed. .

<Preparation of Externally Added Toner (5)>
Next, the toner base particles (5) were treated in the same manner as the externally added toner (1) to produce an externally added toner (5). Further, this was weighed so that the toner concentration became 5% by weight with respect to a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% by weight of polymethyl methacrylate resin (Mw: 75000, manufactured by Soken Chemical Co., Ltd.), and 5% by a ball mill. A developer (5) was prepared by stirring and mixing for minutes.

<Evaluation>
Further, the developer (5) is loaded into a color copier DocuCentreColor400 (Fuji Xerox Co., Ltd.) modified machine, and the toner in the developer 5 after being idled for 2 minutes in an environment of a temperature of 28 ° C. and a humidity of 85%. When the charge amount (μC / g) was measured with a blow-off charge amount measuring device, it was 58 μC / g. Furthermore, in the above environment, a live-action test was performed in which 200,000 sheets of color originals with a toner loading of 13.0 g / m ² were continuously printed. It was. The toner charge amount (μC / g) in Developer 1 at the end of the test was measured with a blow-off charge amount measuring device, which was 50 μC / g and the charge retention rate was 87%. Furthermore, the fixed image of the 200,000th sheet was observed, and it was confirmed by visual observation that the blackness of black was not shifted. The results are shown in Table 3.

(Example 6)
<Preparation of toner mother particles (6)>
Composite Fine Particle Dispersion (4) Dispersion 160 parts by weight The above was sufficiently mixed and dispersed in a round stainless steel flask with Ultra Turrax T50. Next, 0.20 part by weight of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, 120 parts by weight of the resin fine particle dispersion (8) was gradually added thereto. Further 20 minutes later, 60 parts by weight of the resin fine particle dispersion (9) was gradually added. Thereafter, the pH of the system was adjusted to 9.0 with a 0.5 mol / L sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained. After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Next, vacuum drying was continued for 12 hours to obtain toner mother particles (6) with SPp3-SPp2 = 0.74.

  When the volume average particle size of the toner was measured with a Coulter counter, D50v was 5.9 μm, and the particle size distribution coefficient GSDv was 1.27. The particle size distribution coefficient was GSDp 1.29. The toner base particles (6) were observed with a transmission electron microscope (TEM), and it was confirmed that the ratio of the colorant present in the region within 200 nm from the outermost surface of the toner was 9%. The toner base particles (6) were observed with a transmission electron microscope (TEM), and it was confirmed that the proportion of wax present in the region within 200 nm from the outermost surface of the toner was 8%. Further, the dispersibility of each colorant of yellow, cyan and magenta was confirmed by TEM. Of the number of pigments in the toner, the proportion of each pigment having a pigment particle size of 250 nm or less was confirmed for 50 toners. As a result, 93% by number of pigments having a particle size of 250 nm or less were confirmed to be uniformly dispersed. .

<Preparation of Externally Added Toner (6)>
Next, the toner base particles (6) were treated in the same manner as the externally added toner (1) to produce an externally added toner (6). Further, this was weighed so that the toner concentration became 5% by weight with respect to a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% by weight of polymethyl methacrylate resin (Mw: 75000, manufactured by Soken Chemical Co., Ltd.), and 5% by a ball mill. The developer (6) was prepared by stirring and mixing for minutes.

<Evaluation>
Further, the developer (6) is loaded into a color copier DocuCentreColor400 (Fuji Xerox Co., Ltd.) remodeled machine, and the toner in the developer 6 after being idled for 2 minutes in an environment of a temperature of 28 ° C. and a humidity of 85%. The charge amount (μC / g) was measured with a blow-off charge amount measuring device and found to be 59 μC / g. Furthermore, in the above environment, a live-action test was performed in which 200,000 sheets of color originals with a toner loading of 13.0 g / m ² were continuously printed. It was. The toner charge amount (μC / g) in the developer 1 at the end of the test was measured with a blow-off charge amount measuring device, which was 52 μC / g and the charge retention rate was 88%. Furthermore, the fixed image of the 200,000th sheet was observed, and it was confirmed by visual observation that the blackness of black was not shifted. The results are shown in Table 3.

(Comparative Example 1)
<Preparation of toner mother particles (7)>
Composite Fine Particle Dispersion (4) Dispersion 160 parts by weight The above was sufficiently mixed and dispersed in a round stainless steel flask with Ultra Turrax T50. Next, 0.20 part by weight of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, a dispersion obtained by mixing 120 parts by weight of the resin fine particle dispersion (8) was gradually added thereto. Further 20 minutes later, 120 parts by weight of the resin fine particle dispersion (8) was gradually added. Thereafter, the pH of the system was adjusted to 9.0 with a 0.5 mol / L sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained. After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Next, vacuum drying was continued for 12 hours to obtain toner mother particles (7) with SPp3-SPp2 = 0.

  When the volume average particle diameter of the toner was measured with a Coulter counter, D50v was 5.8 μm, and the particle size distribution coefficient GSDv was 1.27. The particle size distribution coefficient was GSDp 1.28. The toner base particles (7) were observed with a transmission electron microscope (TEM), and it was confirmed that the ratio of the colorant present in the region within 200 nm from the outermost surface of the toner was 14%. The toner base particles (7) were observed with a transmission electron microscope (TEM), and it was confirmed that the proportion of wax present in the region within 200 nm from the outermost surface of the toner was 13%. Further, the dispersibility of each colorant of yellow, cyan and magenta was confirmed by TEM. Of the number of pigments in the toner, the proportion of each pigment having a pigment particle size of 250 nm or less was confirmed for 50 toners. As a result, 90% by number of pigments having a particle size of 250 nm or less were confirmed to be uniformly dispersed. .

<Preparation of Toner (7)>
Next, the toner base particles (7) were treated in the same manner as the externally added toner (1) to produce an externally added toner (7). Further, this was weighed so that the toner concentration became 5% by weight with respect to a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% by weight of polymethyl methacrylate resin (Mw: 75000, manufactured by Soken Chemical Co., Ltd.), and 5% by a ball mill. A developer (7) was prepared by stirring and mixing for a minute.

<Evaluation>
Further, the developer (7) is loaded into a modified machine of the color copying machine DocuCenterColor400 (Fuji Xerox Co., Ltd.) and the developer (7) after idling for 2 minutes in an environment of temperature 28 ° C. and humidity 85%. The toner charge amount (μC / g) was measured by a blow-off charge amount measuring device and found to be 54 μC / g. Furthermore, under the above environment, a live-action test was performed in which 200,000 sheets of color originals with a toner loading of 13.0 g / m ² were continuously printed. I couldn't. When the fixed image was observed, it was visually confirmed that the blackness of black was not shifted. The toner charge amount (μC / g) in Developer 1 at the end of the test was measured with a blow-off charge amount measuring device. As a result, it was 37 μC / g and the charge retention rate was 69%. The results are shown in Table 3.

(Comparative Example 2)
<Preparation of toner mother particles (8)>
Composite fine particle dispersion (5) Dispersion 143 parts by weight Process black colorant dispersion 17 parts by weight The above was sufficiently mixed and dispersed in a round stainless steel flask with Ultra Turrax T50. Next, 0.20 part by weight of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, a dispersion obtained by mixing 60 parts by weight of the resin fine particle dispersion (8) and 60 parts by weight of the resin fine particle dispersion (9) was gradually added thereto. Further 20 minutes later, 60 parts by weight of the resin fine particle dispersion (9) was gradually added. Thereafter, the pH of the system was adjusted to 9.0 with a 0.5 mol / L sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained. After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Next, vacuum drying was continued for 12 hours to obtain toner mother particles (8) with SPp3-SPp2 = 0.74 and SPp2-SPp1 = 0.24.

  When the volume average particle diameter of the toner was measured with a Coulter counter, D50v was 5.7 μm and the particle size distribution coefficient GSDv was 1.27. The particle size distribution coefficient was GSDp 1.28. The toner base particles (8) were observed with a transmission electron microscope (TEM), and it was confirmed that the ratio of the colorant present in the region within 200 nm from the outermost surface of the toner was 18%. The toner base particles (8) were observed with a transmission electron microscope (TEM), and it was confirmed that the proportion of wax existing in the region within 200 nm from the outermost surface of the toner was 13%. Further, the dispersibility of yellow, cyan and magenta colorants was confirmed by TEM. Of the number of pigments in the toner, the proportion of each pigment having a pigment particle size of 250 nm or less was confirmed for 50 toners. As a result, 87% by number of pigments having a particle size of 250 nm or less were present, and the colorant partially aggregated. Was observed.

<Preparation of Externally Added Toner (8)>
Next, the toner base particles (8) were treated in the same manner as the externally added toner (1) to produce an externally added toner (8). Further, this was weighed so that the toner concentration became 5% by weight with respect to a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% by weight of polymethyl methacrylate resin (Mw: 75000, manufactured by Soken Chemical Co., Ltd.), and 5% by a ball mill. A developer (8) was prepared by stirring and mixing for minutes.

<Evaluation>
Further, the developer (8) is loaded in a color copier DocuCentreColor400 (Fuji Xerox Co., Ltd.) remodeled machine, and the toner in the developer (8) after being idled for 2 minutes in an environment of a temperature of 28 ° C. and a humidity of 85%. The charge amount (μC / g) was measured with a blow-off charge amount measuring device and found to be 65 μC / g. Furthermore, under the above environment, a live-action test was performed in which 200,000 sheets of color originals with a toner loading of 13.0 g / m ² were continuously printed. I couldn't. When the fixed image was observed, it was visually confirmed that the blackness of black was not shifted. The toner charge amount (μC / g) in the developer 1 at the end of the test was measured with a blow-off charge amount measuring device. As a result, it was 49 μC / g and the charge retention rate was 76%. The results are shown in Table 3.

(Comparative Example 3)
<Preparation of toner mother particles (9)>
Composite fine particle dispersion (6) Dispersion 127 parts by weight Release agent dispersion 33 parts by weight The above was sufficiently mixed and dispersed in a round stainless steel flask with Ultra Turrax T50. Next, 0.20 part by weight of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, a dispersion obtained by mixing 60 parts by weight of the resin fine particle dispersion (8) and 60 parts by weight of the resin fine particle dispersion (9) was gradually added thereto. Further 20 minutes later, 60 parts by weight of the resin fine particle dispersion (9) was gradually added. Thereafter, the pH of the system was adjusted to 9.0 with a 0.5 mol / L sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained. After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Next, vacuum drying was continued for 12 hours to obtain toner mother particles (9) with SPp3-SPp2 = 0.74 and SPp2-SPp1 = 0.24.

  When the volume average particle diameter of the toner was measured with a Coulter counter, D50v was 5.8 μm, and the particle size distribution coefficient GSDv was 1.25. The particle size distribution coefficient was GSDp 1.28. The toner base particles (9) were observed with a transmission electron microscope (TEM), and it was confirmed that the ratio of the colorant present in the region within 200 nm from the outermost surface of the toner was 13%. The toner base particles (9) were observed with a transmission electron microscope (TEM), and it was confirmed that the proportion of wax present in the region within 200 nm from the outermost surface of the toner was 19%. Further, the dispersibility of each colorant of yellow, cyan and magenta was confirmed by TEM. Of the number of pigments in the toner, the proportion of each pigment having a pigment particle size of 250 nm or less was confirmed for 50 toners. As a result, 91% by number of pigments having a particle size of 250 nm or less was confirmed to be uniformly dispersed. .

<Preparation of Externally Added Toner (9)>
Next, the toner base particles (9) were treated in the same manner as the externally added toner (1) to produce an externally added toner (9). Further, this was weighed so that the toner concentration was 5% by weight with respect to a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% by weight of polymethyl methacrylate resin (Mw: 75000, manufactured by Soken Chemical Co., Ltd.), and 5% by a ball mill. A developer (9) was prepared by stirring and mixing for a minute.

<Evaluation>
Further, the developer (9) is loaded in a color copier DocuCentreColor400 (Fuji Xerox Co., Ltd.) remodeled machine, and the toner in the developer (9) is spun for 2 minutes in an environment of a temperature of 28 ° C. and a humidity of 85%. The charge amount (μC / g) was measured with a blow-off charge amount measuring device and found to be 54 μC / g. Furthermore, under the above environment, a live-action test was performed in which 200,000 sheets of color originals with a toner loading of 13.0 g / m ² were continuously printed. I couldn't. When the fixed image was observed, it was visually confirmed that the blackness of black was not shifted. The toner charge amount (μC / g) in Developer 1 at the end of the test was measured with a blow-off charge amount measuring device. As a result, it was 42 μC / g and the charge retention rate was 78%. The results are shown in Table 3.

(Comparative Example 4)
<Preparation of toner mother particles (10)>
Composite fine particle dispersion liquid (7) Dispersion liquid 160 parts by weight The above was sufficiently mixed and dispersed in a round stainless steel flask with an Ultra Turrax T50. Next, 0.20 part by weight of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, a dispersion obtained by mixing 60 parts by weight of the resin fine particle dispersion (8) and 60 parts by weight of the resin fine particle dispersion (9) was gradually added thereto. Further 20 minutes later, 60 parts by weight of the resin fine particle dispersion (9) was gradually added. Thereafter, the pH of the system was adjusted to 9.0 with a 0.5 mol / L sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained. After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Next, vacuum drying was continued for 12 hours to obtain toner mother particles (10) with SPp3-SPp2 = 0.74 and SPp2-SPp1 = 0.24.

  When the volume average particle size of the toner was measured with a Coulter counter, D50v was 5.9 μm, and the particle size distribution coefficient GSDv was 1.27. The particle size distribution coefficient was GSDp 1.28. The toner base particles (10) were observed with a transmission electron microscope (TEM), and it was confirmed that the ratio of the colorant present in the region within 200 nm from the outermost surface of the toner was 13%. The toner base particles (10) were observed with a transmission electron microscope (TEM), and it was confirmed that the proportion of wax present in the region within 200 nm from the outermost surface of the toner was 13%. Further, the dispersibility of each colorant of yellow, cyan and magenta was confirmed by TEM. Of the number of pigments in the toner, the proportion of each pigment having a pigment particle size of 250 nm or less was confirmed for 50 toners. As a result, 91% by number of pigments having a particle size of 250 nm or less was confirmed to be uniformly dispersed. .

<Preparation of Externally Added Toner (10)>
Next, the toner base particles (10) were treated in the same manner as the externally added toner (1) to produce an externally added toner (10). Further, this was weighed so that the toner concentration became 5% by weight with respect to a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% by weight of polymethyl methacrylate resin (Mw: 75000, manufactured by Soken Chemical Co., Ltd.), and 5% by a ball mill. The developer (10) was prepared by stirring and mixing for minutes.

<Evaluation>
Further, the developer (10) is loaded into a color copier DocuCentreColor400 (Fuji Xerox Co., Ltd.) remodeled machine, and the toner in the developer (10) after being idled for 2 minutes in an environment of a temperature of 28 ° C. and a humidity of 85%. The charge amount (μC / g) was measured with a blow-off charge amount measuring device and found to be 64 μC / g. When the fixed image was observed, it was visually confirmed that the blackness of black was not shifted. Furthermore, under the above environment, a live-action test was performed in which 200,000 sheets of color originals with a toner loading of 13.0 g / m ² were continuously printed. I couldn't. The toner charge amount (μC / g) in Developer 1 at the end of the test was measured with a blow-off charge amount measuring device, which was 50 μC / g and the charge retention rate was 78%. The results are shown in Table 3.

(Comparative Example 5)
<Preparation of toner mother particles (11)>
Composite Fine Particle Dispersion (1) Dispersion 160 parts by weight The above was sufficiently mixed and dispersed in a round stainless steel flask with Ultra Turrax T50. Next, 0.20 part by weight of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, a dispersion obtained by mixing 60 parts by weight of the resin fine particle dispersion (14) was slowly added thereto. Further 20 minutes later, 120 parts by weight of the resin fine particle dispersion (9) was gradually added. Thereafter, the pH of the system was adjusted to 9.0 with a 0.5 mol / L sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained. After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchanged water at 40 ° C. and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Next, vacuum drying was continued for 12 hours to obtain toner mother particles (11) with SPp3-SPp2 = 0.74 and SPp2-SPp1 = 0.24.

  The volume average particle size of the toner was measured with a Coulter counter. As a result, D50v was 5.8 μm and the particle size distribution coefficient GSDv was 1.26. The particle size distribution coefficient was GSDp 1.27. The toner base particles (11) were observed with a transmission electron microscope (TEM), and it was confirmed that the ratio of the colorant present in the region within 200 nm from the outermost surface of the toner was 12%. The toner base particles (11) were observed with a transmission electron microscope (TEM), and it was confirmed that the proportion of wax existing in the region within 200 nm from the outermost surface of the toner was 13%. Further, the dispersibility of each colorant of yellow, cyan and magenta was confirmed by TEM. Of the number of pigments in the toner, the proportion of each pigment having a pigment particle size of 250 nm or less was confirmed for 50 toners. As a result, 90% by number of pigments having a particle size of 250 nm or less were confirmed to be uniformly dispersed. .

<Preparation of Externally Added Toner (11)>
Next, the toner base particles (11) were treated in the same manner as the externally added toner (1) to produce an externally added toner (11). Further, this was weighed so that the toner concentration was 5% by weight with respect to a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% by weight of polymethyl methacrylate resin (Mw: 75000, manufactured by Soken Chemical Co., Ltd.), and 5% by a ball mill. The developer (11) was prepared by stirring and mixing for a minute.

Further, the developer (11) is loaded into a color copier DocuCentreColor400 (Fuji Xerox Co., Ltd.) modified machine, and the toner in the developer (11) after being idled for 2 minutes in an environment of a temperature of 28 ° C. and a humidity of 85%. The charge amount (μC / g) was measured with a blow-off charge amount measuring device and found to be 64 μC / g. Furthermore, under the above environment, a live-action test was performed in which 200,000 sheets of color originals with a toner loading of 13.0 g / m ² were continuously printed. I couldn't. When the fixed image was observed, it was visually confirmed that the blackness of black was not shifted. The toner charge amount (μC / g) in the developer 1 at the end of the test was measured with a blow-off charge amount measuring device. As a result, it was 49 μC / g and the charge retention rate was 77%. The results are shown in Table 3.

(Comparative Example 6)
<Preparation of toner mother particles (12)>
Composite Fine Particle Dispersion (1) Dispersion 160 parts by weight The above was sufficiently mixed and dispersed in a round stainless steel flask with Ultra Turrax T50. Next, 0.20 part by weight of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, a dispersion obtained by mixing 60 parts by weight of the resin fine particle dispersion (8) was slowly added thereto. Further, 20 minutes later, 120 parts by weight of the amorphous polyester resin (15) dispersion was gradually added. Thereafter, the pH of the system was adjusted to 9.0 with a 0.5 mol / L sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained. After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Next, vacuum drying was continued for 12 hours to obtain toner base particles (12) having SPp3-SPp2 = 0.74 and SPp2-SPp1 = 0.24.

  The volume average particle size of the toner was measured with a Coulter counter. As a result, D50v was 6.0 μm and the particle size distribution coefficient GSDv was 1.24. The particle size distribution coefficient was GSDp 1.28. The toner base particles (12) were observed with a transmission electron microscope (TEM), and it was confirmed that the ratio of the colorant present in the region within 200 nm from the outermost surface of the toner was 14%. The toner base particles (12) were observed with a transmission electron microscope (TEM), and it was confirmed that the proportion of wax existing in a region within 200 nm from the outermost surface of the toner was 13%. Further, the dispersibility of each colorant of yellow, cyan and magenta was confirmed by TEM. Of the number of pigments in the toner, the proportion of each pigment having a pigment particle size of 250 nm or less was confirmed for 50 toners. As a result, 91% by number of pigments having a particle size of 250 nm or less was confirmed to be uniformly dispersed. .

<Preparation of Externally Added Toner (12)>
Next, the toner base particles (12) were treated in the same manner as the externally added toner (1) to produce an externally added toner (12). Further, this was weighed so that the toner concentration became 5% by weight with respect to a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% by weight of polymethyl methacrylate resin (Mw: 75000, manufactured by Soken Chemical Co., Ltd.), and 5% by a ball mill. The developer (12) was prepared by stirring and mixing for minutes.

<Evaluation>
Further, the developer (12) is loaded in a color copier DocuCentreColor400 (Fuji Xerox Co., Ltd.) remodeled machine, and the toner in the developer (12) is spun for 2 minutes in an environment of a temperature of 28 ° C. and a humidity of 85%. The charge amount (μC / g) was measured with a blow-off charge amount measuring device and found to be 64 μC / g. Furthermore, in the above environment, a live-action test was performed in which 500,000 sheets of color originals with a toner loading of 13.0 g / m ² were continuously printed. Fog was observed on the 200,000th sheet, and a fine image was obtained. I couldn't. When the fixed image was observed, it was visually confirmed that the blackness of black was not shifted. The toner charge amount (μC / g) in Developer 1 at the end of the test was measured with a blow-off charge amount measuring device, which was 46 μC / g and the charge retention rate was 72%. The results are shown in Table 3.

(Comparative Example 7)
<Preparation of toner mother particles (13)>
Composite fine particle dispersion (16) 160 parts by weight The above was sufficiently mixed and dispersed in a round stainless steel flask with Ultra Turrax T50. Next, 0.20 part by weight of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, a dispersion obtained by mixing 60 parts by weight of the resin fine particle dispersion (8) and 60 parts by weight of the resin fine particle dispersion (9) was gradually added thereto. Furthermore, 60 parts by weight of the amorphous polyester resin (9) dispersion was gradually added 20 minutes later. Thereafter, the pH of the system was adjusted to 9.0 with a 0.5 mol / L sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained. After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Next, vacuum drying was continued for 12 hours to obtain toner mother particles (13) with SPp3-SPp2 = 0.74 and SPp2-SPp1 = 0.24.

  When the volume average particle diameter of the toner was measured with a Coulter counter, D50v was 5.9 μm and the particle size distribution coefficient GSDv was 1.25. The particle size distribution coefficient was GSDp 1.28. The toner base particles (13) were observed with a transmission electron microscope (TEM), and it was confirmed that the proportion of the colorant present in the region within 200 nm from the outermost surface of the toner was 4%. The toner base particles (13) were observed with a transmission electron microscope (TEM), and it was confirmed that the proportion of wax present in the region within 200 nm from the outermost surface of the toner was 5%.

<Preparation of externally added toner (13)>
Next, an external toner was prepared. 100 parts by weight of toner mother particles (13), 1.0 part by weight of rutile type titanium oxide (average particle diameter 20 nm, n-decyltrimethoxysilane treatment), silica (prepared by vapor phase oxidation method, volume average particle diameter 40 nm, (Silicone oil treatment) 2.0 parts by weight, 0.5 parts by weight of a higher alcohol pulverized product (volume average particle size 200 nm) was added, and blended for 15 minutes at a peripheral speed of 30 m / s using a 5-liter Henschel mixer. Coarse particles were removed using a sieve having an opening of 45 μm to prepare an externally added toner (13). Further, this was weighed so that the toner concentration was 5% by weight with respect to a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% by weight of polymethyl methacrylate resin (Mw: 75000, manufactured by Soken Chemical Co., Ltd.), and 5% by a ball mill. A developer (13) was prepared by stirring and mixing for a minute.

<Evaluation>
Further, the developer (13) is loaded into a color copier DocuCentreColor400 (Fuji Xerox Co., Ltd.) remodeled machine, and the toner is charged in the developer 13 after idling for 2 minutes in an environment of a temperature of 28 ° C. and a humidity of 85%. When the amount (μC / g) was measured by a blow-off charge amount measuring device, it was 65 μC / g. Furthermore, under the above environment, a live-action test was performed in which 200,000 sheets of color originals with a toner loading of 13.0 g / m ² were continuously printed. I couldn't. When the charge amount (μC / g) of the toner in the developer 13 at the end of the test was measured with a blow-off charge amount measuring device, it was 47 μC / g and the charge retention rate was 72%. Further, when the fixed image was observed, it was visually confirmed that the black color was brown and reddish. The results are shown in Table 3.

  As can be seen from Table 3, in Examples 1 to 6, the colorant and the release agent are completely covered inside the toner, and even when the toner deteriorates, the exposure of the colorant and the release agent to the toner surface is eliminated. When the deteriorated developer was allowed to stand for a long time under high temperature and high humidity, the charge did not decrease, and the charge retention rate of the developer increased to 86% or more, and a developing toner excellent in long life was obtained. Furthermore, the dispersibility of the colorant in the core particles was good, and an accurate black color could be expressed. On the other hand, in Comparative Examples 1 to 7, the charge retention rate was low when left for a long time under high temperature and high humidity. Further, since the toner of Comparative Example 7 uses carbon black as a colorant, it cannot express an accurate black color.

<Preparation of composite fine particle dispersion (17)>
A resin fine particle dispersion was prepared using a crystalline polyester resin (A), an amorphous resin (G), a colorant and a release agent.
Crystalline resin (A) 33 parts by weight Amorphous resin (G) 60 parts by weight Cyan pigment (copper phthalocyanine B15: 3: manufactured by Dainichi Seika, acid value 3.0 mgKOH / g) 10 parts by weight Magenta pigment (R122: large Nissei Kabushiki Kaisha, acid value 4.0 mgKOH / g) 20 parts by weight Ester wax (WEP5: pentaerythritol behenic acid wax: manufactured by Nippon Oil & Fats) 33 parts by weight Isopropyl acetate 233 parts by weight 0.3 N NaOH aqueous solution 0.1 part by weight Was put in a 500 mL separable flask, heated to 70 ° C., and stirred with a three-one motor to prepare a uniform solution. Further, 373 parts by weight of ion-exchanged water is added with stirring to cause phase inversion and solvent removal, whereby a composite fine particle dispersion (17) of crystalline resin (A), amorphous resin (G), wax, and colorant is added. ) Was obtained at a volume average particle size of 200 nm and a solid content of 30 parts by weight. Table 2 shows the properties of the dispersion.

<Preparation of composite fine particle dispersion (18)>
A resin fine particle dispersion was prepared using a crystalline polyester resin (A), an amorphous resin (G), a colorant and a release agent.
Crystalline resin (A) 33 parts by weight Amorphous resin (G) 60 parts by weight Yellow pigment (CI Pigment Yellow 180: manufactured by Hoechst, acid value 4.5 mgKOH / g) 5 parts by weight Magenta pigment (PR122: large Nissei Kasei, acid value 4.0 mgKOH / g) 25 parts by weight Ester wax (WEP5: pentaerythritol behenic acid wax: manufactured by Nippon Oil & Fats) 33 parts by weight Isopropyl acetate 233 parts by weight 0.3 N NaOH aqueous solution 0.1 part by weight Was put in a 500 mL separable flask, heated to 70 ° C., and stirred with a three-one motor to prepare a uniform solution. Further, 373 parts by weight of ion-exchanged water is added to perform phase inversion with stirring, and the solvent is removed to remove a composite fine particle dispersion (18) of crystalline resin (A), amorphous resin (G), wax, and colorant. ) Was obtained at a volume average particle size of 200 nm and a solid content of 30 parts by weight. Table 2 shows the properties of the dispersion.

<Preparation of composite fine particle dispersion (19)>
A resin fine particle dispersion was prepared using a crystalline polyester resin (A), an amorphous resin (G), a colorant and a release agent.
Crystalline resin (A) 33 parts by weight Amorphous resin (G) 60 parts by weight Cyan pigment (copper phthalocyanine PB15: 3: manufactured by Dainichi Seika, acid value: 3.0 mgKOH / g) 5 parts by weight Yellow pigment (PY180: Hoechst 25 parts by weight of ester wax (WEP5: pentaerythritol behenic acid wax: manufactured by NOF Corporation) 33 parts by weight Isopropyl acetate 233 parts by weight 0.3 N NaOH aqueous solution 0.1 part by weight It put into a 500 mL separable flask, heated at 70 degreeC, and stirred with the three one motor, and produced the uniform solution. Further, 373 parts by weight of ion-exchanged water is added to perform phase inversion with stirring, and the solvent is removed, whereby a composite fine particle dispersion (19) of crystalline resin (A), amorphous resin (G), wax, and colorant is added. ) Was obtained at a volume average particle size of 200 nm and a solid content of 30 parts by weight. Table 2 shows the properties of the dispersion.

(Example 7)
<Preparation of toner mother particles (14)>
Composite fine particle dispersion (17) 160 parts by weight The above was sufficiently mixed and dispersed in a round stainless steel flask with an Ultra Turrax T50. Next, 0.20 part by weight of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, a dispersion obtained by mixing 57 parts by weight of the resin fine particle dispersion (8) and 57 parts by weight of the resin fine particle dispersion (9) was gradually added thereto. Furthermore, 60 parts by weight of the amorphous polyester resin (9) dispersion was gradually added 20 minutes later. Thereafter, the pH of the system was adjusted to 9.0 with a 0.5 mol / L sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained. After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Next, vacuum drying was continued for 12 hours to obtain toner mother particles (14) with SPp3-SPp2 = 0.74 and SPp2-SPp1 = 0.24.

  When the volume average particle size at this time was measured with a Coulter counter, D50v was 5.9 μm, and the particle size distribution coefficient GSDv was 1.26. The particle size distribution coefficient GSDp was 1.25. The toner base particles (14) were observed with a transmission electron microscope (TEM), and it was confirmed that the ratio of the colorant present in the region within 200 nm from the outermost surface of the toner was 6%. The toner base particles (14) were observed with a transmission electron microscope (TEM), and it was confirmed that the percentage of wax existing within 200 nm from the outermost surface of the toner was 7%. Further, the dispersibility of cyan and magenta colorants was confirmed by TEM. Of the number of pigments in the toner, the proportion of each pigment having a pigment particle size of 250 nm or less was confirmed for 50 toners. As a result, 90% by number of pigments having a particle size of 250 nm or less were confirmed to be uniformly dispersed. .

<Preparation of Externally Added Toner (14)>
Next, the toner base particles (14) were treated in the same manner as the externally added toner (1) to produce an externally added toner (14). Further, this was weighed so that the toner concentration became 5% by weight with respect to a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% by weight of polymethyl methacrylate resin (Mw: 75000, manufactured by Soken Chemical Co., Ltd.), and 5% by a ball mill. The developer (14) was prepared by stirring and mixing for a minute.

<Evaluation>
Furthermore, the developer (14) is loaded into a color copier DocuCentreColor400 (Fuji Xerox Co., Ltd.) remodeled machine, and the developer (14) after idling for 2 minutes in an environment of a temperature of 28 ° C. and a humidity of 85%. The toner charge amount (μC / g) was measured by a blow-off charge amount measuring device and found to be 58 μC / g. Furthermore, in the above environment, a live-action test was performed in which 200,000 sheets of color originals with a toner loading of 13.0 g / m ² were continuously printed, and a fine image was obtained without fogging on the 200,000th sheet. . When the charge amount (μC / g) of the toner in the developer (14) at the end of the test was measured with a blow-off charge amount measuring device, it was 52 μC / g and the charge retention rate was 90%. Further, the 200,000th fixed image was observed, and it was confirmed by visual observation that the blue bluish color was not shifted. The results are shown in Table 4.

(Example 8)
<Preparation of toner mother particles (15)>
Composite fine particle dispersion (18) 160 parts by weight The above was sufficiently mixed and dispersed in a round stainless steel flask with an Ultra Turrax T50. Next, 0.20 part by weight of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, a dispersion obtained by mixing 57 parts by weight of the resin fine particle dispersion (8) and 57 parts by weight of the resin fine particle dispersion (9) was gradually added thereto. Furthermore, 60 parts by weight of the amorphous polyester resin (9) dispersion was gradually added 20 minutes later. Thereafter, the pH of the system was adjusted to 9.0 with a 0.5 mol / L sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained. After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Then, vacuum drying was continued for 12 hours to obtain toner mother particles (15) with SPp3-SPp2 = 0.74 and SPp2-SPp1 = 0.24.

  When the volume average particle size at this time was measured with a Coulter counter, D50v was 5.8 μm, and the particle size distribution coefficient GSDv was 1.24. The particle size distribution coefficient GSDp was 1.29. The toner base particles (15) were observed with a transmission electron microscope (TEM), and it was confirmed that the ratio of the colorant present in the region within 200 nm from the outermost surface of the toner was 5%. The toner base particles (15) were observed with a transmission electron microscope (TEM), and it was confirmed that the percentage of wax existing in the region within 200 nm from the outermost surface of the toner was 6%. Further, the dispersibility of the yellow and magenta colorants was confirmed by TEM. Of the number of pigments in the toner, the proportion of each pigment having a pigment particle diameter of 250 nm or less was confirmed for 50 toners. As a result, 92% by number of pigments having a particle size of 250 nm or less were confirmed to be uniformly dispersed. .

<Preparation of Externally Added Toner (15)>
Next, the toner base particles (15) were treated in the same manner as the externally added toner (1) to produce an externally added toner (15). Further, this was weighed so that the toner concentration became 5% by weight with respect to a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% by weight of polymethyl methacrylate resin (Mw: 75000, manufactured by Soken Chemical Co., Ltd.), and 5% by a ball mill. A developer (15) was prepared by stirring and mixing for minutes.

<Evaluation>
Further, the developer (15) is loaded into a modified machine of a color copying machine DocuCenterColor400 (Fuji Xerox Co., Ltd.) and the developer (15) after idling for 2 minutes in an environment of a temperature of 28 ° C. and a humidity of 85%. The toner charge amount (μC / g) was measured by a blow-off charge amount measuring device and found to be 57 μC / g. Furthermore, in the above environment, a live-action test was performed in which 200,000 sheets of color originals with a toner loading of 13.0 g / m ² were continuously printed, and a fine image was obtained without fogging on the 200,000th sheet. . When the charge amount (μC / g) of the toner in the developer (15) at the end of the test was measured with a blow-off charge amount measuring device, it was 52 μC / g and the charge retention rate was 91%. Furthermore, the fixed image of the 200,000th sheet was observed, and it was confirmed by visual observation that the reddish red color was not shifted. The results are shown in Table 4.

Example 9
<Preparation of toner mother particles (16)>
Composite fine particle dispersion (19) 160 parts by weight The above was sufficiently mixed and dispersed in a round stainless steel flask with Ultra Turrax T50. Next, 0.20 part by weight of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, a dispersion obtained by mixing 57 parts by weight of the resin fine particle dispersion (8) and 57 parts by weight of the resin fine particle dispersion (9) was gradually added thereto. Furthermore, 60 parts by weight of the amorphous polyester resin (9) dispersion was gradually added 20 minutes later. Thereafter, the pH of the system was adjusted to 9.0 with a 0.5 mol / L sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained. After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Next, vacuum drying was continued for 12 hours to obtain toner mother particles (16) having SPp3-SPp2 = 0.74 and SPp2-SPp1 = 0.24.

  When the volume average particle size at this time was measured with a Coulter counter, D50v was 6.0 μm and the particle size distribution coefficient GSDv was 1.26. The particle size distribution coefficient GSDp was 1.27. The toner base particles (16) were observed with a transmission electron microscope (TEM), and it was confirmed that the ratio of the colorant present in the region within 200 nm from the outermost surface of the toner was 6%. The toner base particles (16) were observed with a transmission electron microscope (TEM), and it was confirmed that the proportion of wax present in the region within 200 nm from the outermost surface of the toner was 6%. Further, the dispersibility of the yellow and cyan colorants was confirmed by TEM. Of the number of pigments in the toner, the proportion of each pigment having a pigment particle size of 250 nm or less was confirmed for 50 toners. As a result, 93% by number of pigments having a particle size of 250 nm or less were confirmed to be uniformly dispersed. .

<Preparation of Externally Added Toner (16)>
Next, the toner base particles (16) were treated in the same manner as the externally added toner (1) to produce an externally added toner (16). Further, this was weighed so that the toner concentration became 5% by weight with respect to a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% by weight of polymethyl methacrylate resin (Mw: 75000, manufactured by Soken Chemical Co., Ltd.), and 5% by a ball mill. The developer (16) was prepared by stirring and mixing for a minute.

<Evaluation>
Further, the developer (16) is loaded into a remodeled machine of the color copying machine DocuCentreColor 400 (manufactured by Fuji Xerox Co., Ltd.), and the developer (16) after idling for 2 minutes in an environment of a temperature of 28 ° C. and a humidity of 85%. The toner charge amount (μC / g) was measured by a blow-off charge amount measuring device and found to be 58 μC / g. Furthermore, in the above environment, a live-action test was performed in which 200,000 sheets of color originals with a toner loading of 13.0 g / m ² were continuously printed, and a fine image was obtained without fogging on the 200,000th sheet. . When the charge amount (μC / g) of the toner in the developer (16) at the end of the test was measured with a blow-off charge amount measuring device, it was 53 μC / g and the charge retention rate was 91%. Furthermore, the fixed image of the 200,000th sheet was observed and it was confirmed by visual observation that the greenish green color was not shifted. The results are shown in Table 4.

(Comparative Example 8)
<Preparation of toner mother particles (17)>
Composite fine particle dispersion liquid (5) Dispersion liquid 143 parts by weight Blue colorant dispersion liquid 17 parts by weight The above was sufficiently mixed and dispersed in a round stainless steel flask with Ultra Turrax T50. Next, 0.20 part by weight of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, a dispersion obtained by mixing 57 parts by weight of the resin fine particle dispersion (8) and 57 parts by weight of the resin fine particle dispersion (9) was gradually added thereto. Furthermore, 60 parts by weight of the amorphous polyester resin (9) dispersion was gradually added 20 minutes later. Thereafter, the pH of the system was adjusted to 9.0 with a 0.5 mol / L sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained. After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Then, vacuum drying was continued for 12 hours to obtain toner mother particles (17) having SPp3-SPp2 = 0.74 and SPp2-SPp1 = 0.24.

  When the volume average particle size at this time was measured with a Coulter counter, D50v was 6.1 μm, and the particle size distribution coefficient GSDv was 1.25. The particle size distribution coefficient GSDp was 1.26. The toner base particles (17) were observed with a transmission electron microscope (TEM), and it was confirmed that the ratio of the colorant present in the region within 200 nm from the outermost surface of the toner was 12%. The toner base particles (17) were observed with a transmission electron microscope (TEM), and it was confirmed that the proportion of wax existing within 200 nm from the outermost surface of the toner was 11%. Further, dispersibility of cyan and magenta colorants was confirmed by TEM. Of the number of pigments in the toner, the proportion of each pigment having a pigment particle size of 250 nm or less was confirmed for 50 toners. As a result, 87% by number of pigments having a particle size of 250 nm or less were present, and the colorant partially aggregated. Was observed.

<Preparation of Externally Added Toner (17)>
Next, the toner base particles (17) were treated in the same manner as the externally added toner (1) to produce an externally added toner (17). Further, this was weighed so that the toner concentration was 5% by weight with respect to a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% by weight of polymethyl methacrylate resin (Mw: 75000, manufactured by Soken Chemical Co., Ltd.), and 5% by a ball mill. The developer (17) was prepared by stirring and mixing for a minute.

<Evaluation>
Further, the developer (17) is loaded into a remodeled machine of a color copier DocuCenter Color400 (manufactured by Fuji Xerox), and the developer (17) after idling for 2 minutes in an environment of a temperature of 28 ° C. and a humidity of 85% is used. The toner charge amount (μC / g) was measured by a blow-off charge amount measuring device and found to be 63 μC / g. Furthermore, in the above environment, a live-action test was performed in which 200,000 sheets of color originals with a toner loading of 13.0 g / m ² were continuously printed, and a fine image was obtained without fogging on the 200,000th sheet. . When the charge amount (μC / g) of the toner in the developer (17) at the end of the test was measured with a blow-off charge amount measuring device, it was 49 μC / g and the charge retention rate was 78%. Further, the 200,000th fixed image was observed, and it was confirmed by visual observation that the blue bluish color was shifted to magenta. The results are shown in Table 4.

(Comparative Example 9)
<Preparation of toner mother particles (18)>
Composite fine particle dispersion (5) Dispersion 143 parts by weight Red colorant dispersion 17 parts by weight The above was sufficiently mixed and dispersed in a round stainless steel flask with Ultra Turrax T50. Next, 0.20 part by weight of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, a dispersion obtained by mixing 57 parts by weight of the resin fine particle dispersion (8) and 57 parts by weight of the resin fine particle dispersion (9) was gradually added thereto. Furthermore, 60 parts by weight of the amorphous polyester resin (9) dispersion was gradually added 20 minutes later. Thereafter, the pH of the system was adjusted to 9.0 with a 0.5 mol / L sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained. After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Next, vacuum drying was continued for 12 hours to obtain toner mother particles (18) with SPp3-SPp2 = 0.74 and SPp2-SPp1 = 0.24.

  When the volume average particle size at this time was measured with a Coulter counter, D50v was 5.7 μm and the particle size distribution coefficient GSDv was 1.25. The particle size distribution coefficient GSDp was 1.28. The toner base particles (18) were observed with a transmission electron microscope (TEM), and it was confirmed that the ratio of the colorant present in the region within 200 nm from the outermost surface of the toner was 13%. The toner base particles (18) were observed with a transmission electron microscope (TEM), and it was confirmed that the ratio of the wax existing within 200 nm from the outermost surface of the toner was 12%. Further, the dispersibility of yellow and magenta colorants was confirmed by TEM. Of the number of pigments in the toner, the proportion of each pigment having a pigment particle size of 250 nm or less was confirmed for 50 toners. As a result, the number of pigments having a particle size of 250 nm or less was 84% by number, and the colorant partially aggregated. Was observed.

<Preparation of Externally Added Toner (18)>
Next, the toner base particles (18) were treated in the same manner as the externally added toner (1) to produce an externally added toner (18). Further, this was weighed so that the toner concentration became 5% by weight with respect to a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% by weight of polymethyl methacrylate resin (Mw: 75000, manufactured by Soken Chemical Co., Ltd.), and 5% by a ball mill. The developer (18) was prepared by stirring and mixing for a minute.

<Evaluation>
Furthermore, the developer (18) is loaded into a color copier DocuCenter Color400 (Fuji Xerox Co., Ltd.) remodeled machine, and the developer (18) after idling for 2 minutes in an environment of a temperature of 28 ° C. and a humidity of 85%. The toner charge amount (μC / g) was measured by a blow-off charge amount measuring device and found to be 64 μC / g. Furthermore, in the above environment, a live-action test was performed in which 200,000 sheets of color originals with a toner loading of 13.0 g / m ² were continuously printed, and a fine image was obtained without fogging on the 200,000th sheet. . When the charge amount (μC / g) of the toner in the developer (18) at the end of the test was measured with a blow-off charge amount measuring device, it was 49 μC / g and the charge retention rate was 77%. Furthermore, the fixed image of the 200,000th sheet was observed, and it was confirmed by visual observation that the reddish red color was shifted to cyan. The results are shown in Table 4.

(Comparative Example 10)
<Preparation of toner mother particles (19)>
Composite fine particle dispersion (5) Dispersion 143 parts by weight Green colorant dispersion 17 parts by weight The above was sufficiently mixed and dispersed in a round stainless steel flask with Ultra Turrax T50. Next, 0.20 part by weight of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, a dispersion obtained by mixing 57 parts by weight of the resin fine particle dispersion (8) and 57 parts by weight of the resin fine particle dispersion (9) was gradually added thereto. Furthermore, 60 parts by weight of the amorphous polyester resin (9) dispersion was gradually added 20 minutes later. Thereafter, the pH of the system was adjusted to 9.0 with a 0.5 mol / L sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained. After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Next, vacuum drying was continued for 12 hours to obtain toner mother particles (19) having SPp3-SPp2 = 0.74 and SPp2-SPp1 = 0.24.

  When the volume average particle size at this time was measured with a Coulter counter, D50v was 5.8 μm, and the particle size distribution coefficient GSDv was 1.26. The particle size distribution coefficient GSDp was 1.27. The toner base particles (20) were observed with a transmission electron microscope (TEM), and it was confirmed that the ratio of the colorant present in the region within 200 nm from the outermost surface of the toner was 13%. The toner base particles (20) were observed with a transmission electron microscope (TEM), and it was confirmed that the proportion of wax existing within 200 nm from the outermost surface of the toner was 11%. Further, the dispersibility of yellow and cyan colorants was confirmed by TEM. Of the number of pigments in the toner, the proportion of each pigment having a pigment particle diameter of 250 nm or less was confirmed for 50 toners. As a result, the number of pigments of 250 nm or less was 86% by number, and the colorant partially aggregated. Was observed.

<Preparation of Externally Added Toner (19)>
Next, the toner base particles (19) were treated in the same manner as the externally added toner (1) to produce an externally added toner (19). Further, this was weighed so that the toner concentration was 5% by weight with respect to a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% by weight of polymethyl methacrylate resin (Mw: 75000, manufactured by Soken Chemical Co., Ltd.), and 5% by a ball mill. A developer (19) was prepared by stirring and mixing for a minute.

<Evaluation>
Further, the developer (19) is loaded into a modified machine of a color copier DocuCentreColor400 (Fuji Xerox Co., Ltd.), and the developer (19) after idling for 2 minutes in an environment of a temperature of 28 ° C. and a humidity of 85%. The charge amount (μC / g) of the toner was measured with a blow-off charge amount measuring device and found to be 60 μC / g. Furthermore, in the above environment, a live-action test was performed in which 200,000 sheets of color originals with a toner loading of 13.0 g / m ² were continuously printed, and a fine image was obtained without fogging on the 200,000th sheet. . When the charge amount (μC / g) of the toner in the developer (19) at the end of the test was measured with a blow-off charge amount measuring device, it was 47 μC / g and the charge retention rate was 79%. Furthermore, the fixed image of the 200,000th sheet was observed, and it was confirmed by visual observation that the greenish green color was shifted to yellow. The results are shown in Table 4.

  As can be seen from Table 4, in Examples 7 to 9, the colorant and the release agent are completely coated inside the toner, and even when the toner deteriorates, the exposure of the colorant and the release agent to the toner surface is almost eliminated. Thus, even when the deteriorated developer was allowed to stand for a long time under high temperature and high humidity, the charge did not decrease, and the charge retention rate for the exposure increased to 86% or more, and a developing toner excellent in long life was obtained. Furthermore, the dispersibility of the colorant in the core particles was good, and an accurate secondary color could be expressed. On the other hand, in Comparative Examples 8 to 10, the charge retention rate was low when left for a long time under high temperature and high humidity. Moreover, an accurate secondary color could not be expressed.

The schematic diagram of the image at the time of observing the flaky sample of the toner which concerns on embodiment of this invention by TEM is shown.

Explanation of symbols

1 Toner, 2 Epoxy resin, 3 Colorant, 4 Binder resin (matrix part).

Claims (5)

An electrostatic charge image developing toner comprising: a core layer containing a binder resin, a colorant, and a release agent; and a shell layer covering the surface of the core layer,
The colorant includes at least two of a yellow colorant, a cyan colorant, and a magenta colorant,
A toner for developing an electrostatic image, wherein a ratio of a colorant present in a region within 200 nm from the outermost surface of the toner is 10% or less. An electrostatic charge image developing toner comprising: a core layer containing a binder resin, a colorant, and a release agent; and a shell layer covering the surface of the core layer,
The colorant includes a yellow colorant, a cyan colorant and a magenta colorant,
A toner for developing an electrostatic image, wherein a ratio of a colorant present in a region within 200 nm from the outermost surface of the toner is 10% or less. A method for producing a toner for developing an electrostatic charge image, comprising: a core layer containing a binder resin, a colorant, and a release agent; and a shell layer covering the surface of the core layer,
Dispersing composite fine particles having a volume average particle diameter of 0.6 μm or less, including a first binder resin, at least two of a yellow colorant, a cyan colorant, and a magenta colorant, and a release agent An aggregating step of adding a flocculant to the composite fine particle dispersion and heating to form core particles;
A first resin fine particle dispersion containing a second binder resin and having a volume average particle size of 0.6 μm or less dispersed therein is added, and the first resin fine particle dispersion is added to the surface of the core particle. A first attachment step of attaching resin fine particles to form first attached resin agglomerated particles;
A second resin fine particle dispersion containing a third binder resin and having a volume average particle size of 0.6 μm or less dispersed therein is added to the surface of the first adhered resin agglomerated particles, A second adhering step of forming the second adhering resin agglomerated particles by adhering the second resin fine particles;
A fusion step of heating and fusing the second adhered resin aggregated particles;
A method for producing a toner for developing an electrostatic charge image, comprising:   An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 1. A latent image forming step for forming an electrostatic latent image on the surface of the latent image holding member and a developer carried on the developer carrying member are used to develop the electrostatic latent image formed on the surface of the latent image holding member. A developing step for forming a toner image, a transfer step for transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target, and a fixing step for fixing the toner image transferred on the surface of the transfer target. An image forming method comprising:
The image forming method according to claim 4, wherein the developer is the electrostatic charge image developer according to claim 4.

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