JP2007264315A - Colorant dispersion material, method for manufacturing colorant dispersion material and method for manufacturing toner for electrostatic charge image development - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a wet colorant dispersion material suitable for an aqueous medium toner, excellent in transparency and coloring property and free from problems of degradation in a dispersion liquid due to reaggregation or the like. <P>SOLUTION: The colorant dispersion material comprises at least a wet dispersion medium and colorant particles and is characterized in that: the volume cumulative average diameter Dv50 (μm) of the colorant particles in the colorant dispersion material measured by a dynamic light scattering method satisfies formula (1):0.10<Dv50<0.30; and a volume particle size distribution width index SD of the colorant particles in the colorant dispersion material satisfies formula (2):0.030<SD<0.090. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colorant dispersion for image formation, and preferably coloring for toners having good coloring power and transparency by being precisely controlled and dispersed in an electrophotographic method or electrostatic printing method. The present invention relates to an agent dispersion, a method for producing the same, and a method for producing a toner using the same.

  As an electrophotographic method, Patent Document 1 and Patent Document 2 describe various methods. In general, a photosensitive member using a photoconductive material is uniformly charged, an electric latent image is formed by means such as image exposure, and then the latent image is developed with toner to form a visible image, which is necessary. Accordingly, after transferring the toner image onto a transfer material such as paper, the toner image is fixed on the transfer material by heat, pressure or the like to obtain a copy or printed matter.

In the production of toner, a so-called pulverization method, which is performed through mixing, kneading, pulverization, classification, external addition, and sieving steps of toner raw materials such as resins and colorants, has been widely performed in the past. In response to the demand for higher functionality and higher image quality, so-called polymerized toners that form toner particles in an aqueous medium have also been proposed. As the polymerization toner, Patent Document 1 proposes a suspension polymerization method, and Patent Document 2 proposes an emulsion polymerization aggregation method. In any case, the colorant particles are dispersed in the wet dispersion medium, but in the suspension polymerization method, the colorant particles are dispersed and polymerized in the monomer layer (therefore, the colorant dispersion medium is a monomer). In the emulsion polymerization aggregation method, an aqueous dispersion of polymer primary particles and an aqueous dispersion of a colorant (and thus the colorant dispersion medium is water) undergo a coagulation / fusion process to form resin-colored fine particles, respectively. Is done.
JP 09-265206 A JP 2001-27821 A

  In the polymerization toner, the dispersion state of the colorant particles greatly affects the performance of the finally obtained toner particles. That is, since the size of the dispersed particle diameter of the colorant particles affects the transparency and colorability of the toner, it affects the image density and hue of the toner. In addition, if the colorant particles are excessively exposed on the surface of the toner, or if there are a large amount of free coarse colorant particles, they also affect the chargeability, so the durability as a toner And environmental properties are also adversely affected.

Non-Patent Document 1 below describes a factor that disturbs the stability of a dispersion, that is, the theory of sedimentation and recombination (reaggregation) of dispersed fine particles. Both the sedimentation phenomenon and the recombination phenomenon are not preferable in the sense of dispersion stability and should be suppressed as much as possible. First, regarding the sedimentation of dispersed particles, the particle sedimentation velocity u can be expressed by the following formula (A) if Stokes' law is used with the particles being spherical.
Formula (A) u = [2r ² (ρ ₂ −ρ ₁ )] g / 9η
(Where r is the particle radius, ρ ₂ is the particle density, ρ ₁ is the dispersion medium density, g is the acceleration of gravity, and η is the viscosity of the dispersion medium)
Therefore, in order to reduce the sedimentation rate of the dispersed particles, it is necessary to reduce the particle radius, to reduce the difference in density between the particles and the dispersion medium (ρ ₂ −ρ ₁ ), and to increase the viscosity η of the dispersion medium. It can be seen that the particle size plays a more important role than the density. It is also necessary that the particle size does not increase during storage.
Next, regarding recombination (reaggregation) of particles after dispersion, the following formula (B) is derived assuming that the recombination velocity v between particles follows Fick's law of diffusion.
Formula (B) v≈kγL ₀ / ηr ²
(Where k is a constant, γ is the surface tension of the dispersion medium, L ₀ is the solubility of the particles, η is the viscosity of the dispersion medium, and r is the radius of the particles)
Therefore, in order to reduce the reaggregation of the dispersed particles and keep the dispersion state stable, it is necessary that the solubility L ₀ is small and the dispersion medium viscosity η is large, and therefore the temperature is desirably low. In addition, it is desirable that the particle radius is not so small and that the particle shape is close to a sphere and the particle sizes are uniform.
Regarding the stability of particles in an actual dispersion system, there are other complex physical and chemical agents, so they vary depending on the type of colorant, and the above theory cannot explain everything. When it is viewed as a function of particle size as a function of particle size, sedimentation and re-aggregation are opposite behaviors, and the optimal particle size management method that can achieve both of these is not always clear at this time. Absent.
"Surface condition and colloidal condition" 1968 1st edition, Masayuki Nakagaki, Tokyo Kagaku Doujin

From this point of view, Patent Document 3 proposes a yellow toner in which the dispersion average particle diameter of the colorant in the toner is 100 nm or less and the content of coarse particles of 400 nm or more is 5% by number or less. In the examples, such a colorant dispersion is used. The use of such an ultrafine colorant dispersion improves the transparency and suppresses a decrease in chargeability in a high humidity environment. Certainly, if the dispersed particle size is 100 nm or less, the problem of sedimentation seems to be small. However, simply reducing the dispersed particle size increases the surface area and facilitates reaggregation due to increased cohesive force, as described above, and therefore deteriorates the temporal stability of the dispersion of the colorant particles. There's a problem. In addition, the presence of such fine particles increases the probability of exposure of the colorant particles to the toner surface, so it is presumed that there is a problem in terms of durability such as toner chargeability change.
JP 2001-228653 A

On the other hand, various wet mills have been proposed as a method for dispersing colorant particles in a wet dispersion medium. Examples of this type include a ball mill, an attritor, a sand mill, and a bead mill. The outline of each method is as follows.
Ball mill: A method in which a wet dispersion medium, a material to be pulverized, and media beads of about 10 to 30 mm are placed in a drum-like container, and the drum is rotated to grind the material to be crushed between the beads and the beads and the drum.
Attritor: A method in which a wet dispersion medium and an object to be crushed are placed in a tank, media beads of about 3 to 15 mm are placed, and the mixture is forcibly stirred and ground with an agitator arm such as alumina.
・ Sand mill is a system in which media beads of about 1 to 5 mm are added to a premixed wet dispersion medium and the material to be ground, and then a sand disk is immersed and rotated and moved at a specified speed.
・ Bead mill (annular type): Filling media beads of about 1 to 3 mm between the rotor and stator of the container, and rotating the rotor at a high speed to give a flow rate difference between the beads, shear stress and shearing force A method of grinding and dispersing by friction.

Among these, the bead mill shown in Patent Document 4 is a wet mill that can efficiently separate the colorant dispersion and the dispersion medium with a separator, and is considered to be efficient for producing the colorant dispersion. However, for toner applications, there is no proposal to obtain an optimal colorant dispersion, and it does not disclose what properties the toner colorant dispersion should have.
International Publication Number WO96 / 39251

  Generally, strong crushing energy is not required for crushing / dispersing soft primary particles or loosely bonded agglomerates, and the processed material that aggregates in the submicron region is subject to surface damage due to particle breakage when subjected to a strong impact force. A strong crushing force is not always desirable due to increased energy. On the other hand, strong crushing energy is required for crushing hard primary particles or strongly bonded aggregates. As an example of a colorant, the former includes carbon black for black, and the latter includes quinacridone pigments for magenta color.

In particular, quinacridone pigments are optimal as a colorant for magenta toner because they exhibit clear color, excellent heat resistance, and light resistance. However, as described in Patent Document 5, quinacridone pigments are known to be harder than common colorants such as azo pigments. Therefore, it is not easy to make fine particles dispersed in the toner. Patent Document 5 proposes to reduce the dispersion diameter (major axis diameter) of the quinacridone pigment to 0.4 μm or less by using a specific master batch method in order to obtain a suitable full-color image. However, this proposal does not suggest that the proposal is applied to the polymerization method toner because it is substantially limited to the pulverization method, and also relates to the adverse effects when the dispersed particle size is excessively reduced as described above. There is no mention of countermeasures.
Japanese Patent Laid-Open No. 9-80817

  As described above, the colorant dispersion having a suitable particle size used for the polymerized toner, the production method thereof, and the toner using the colorant dispersion have not been sufficiently studied. No proposal has been made at present. In particular, in the case of an aqueous medium toner that is expected to have high image quality and high durability, in particular, an emulsion aggregation toner, the absence of such a proposal is an impediment to performance improvement, and expectations for the improvement are increasing.

  An object of the present invention is to provide a colorant dispersion that solves the above-described problems, a method for producing the same, and a toner producing method using the same.

  A detailed object of the present invention is to provide a wet colorant dispersion that is suitable for an aqueous medium toner, is excellent in transparency and colorability, and does not cause a problem of deterioration of the dispersion due to reaggregation.

  Another detailed object of the present invention is to provide a method for producing a colorant dispersion which is excellent in transparency and colorability, has no problem of deterioration over time such as re-aggregation of the dispersion, and is excellent in productivity. .

  Another detailed object of the present invention is an electrostatic image having excellent image characteristics such as a clear hue, high transparency and image density, little charge change in a high humidity environment, and high durability even in repeated use. It is to provide a method for producing a developing toner.

As a result of intensive studies on a suitable particle size distribution of a colorant dispersion that can be applied particularly to an aqueous medium toner, the present inventors have not necessarily stated that the colorant dispersion diameter is necessarily finer. In order to solve the problem comprehensively, unlike the conventional idea, it was learned that an appropriate particle size distribution state of the colorant particles is necessary, and the present invention has been achieved.
That is, the present invention has the following characteristics.
A colorant dispersion comprising at least a wet dispersion medium and colorant particles, and a volume cumulative average diameter Dv50 (μm) of the colorant particles in the colorant dispersion measured by a dynamic light scattering method is represented by the following formula (1). And the volume particle size distribution width index SD of the colorant particles in the colorant dispersion satisfies the following formula (2).
Formula (1) 0.10 <Dv50 <0.30
Formula (2) 0.030 <SD <0.090
(However, Dv50 represents the particle size (μm) at which the volume particle size distribution cumulative curve of the colorant particles is 50%, and SD is the particle size at which the volume particle size distribution cumulative curve of the colorant particles is 84%. (Μ
When m) is Dv84 and the particle size (μm) at the point of 16% is Dv16, SD = (Dv84−Dv16) / 2, and the volume cumulative distribution is from the small particle size side of the volume particle size distribution. To be cumulative)
This is the first invention of the present invention.

A colorant dispersion comprising at least a wet dispersion medium and colorant particles, and a volume particle size distribution of the colorant particles in the colorant dispersion measured by a dynamic light scattering method is represented by the following formulas (5) and (6: ) And (7).
Formula (5) 0.10 <Dv50 <0.30
Formula (6) 1.0 <(Dv50 / Dv10) / (Dv90 / Dv50) <1.3
Formula (7) 0 <Pv <2
(However, Dv50 represents the volume cumulative distribution 50% diameter (μm) of the colorant particles, Dv10 represents the volume cumulative distribution 10% diameter (μm) of the colorant particles, and Dv90 represents the volume cumulative distribution 90% of the colorant particles. (Pv represents a ratio (%) of the particle size of 0.972 μm or more in the volume distribution of the colorant particles, and the volume cumulative distribution is accumulated from the small particle size side of the volume particle size distribution)
This is the second invention of the present invention.

A method for producing a colorant dispersion comprising at least a wet dispersion medium and colorant particles, a cylindrical stator, a colorant dispersion supply port provided at one end of the stator, and a colorant dispersion discharge port, A rotor that stirs and mixes the medium filled in the stator and the colorant dispersion supplied from the supply port, and is connected to a discharge path inlet that communicates with the discharge port and rotates integrally with the rotor, or Using a wet mill consisting of a separator that rotates independently and separates into a medium and a colorant dispersion by the action of centrifugal force and a screen structure, and discharges the colorant dispersion from the discharge port. A method for producing a colorant dispersion, wherein the diameter Dm is less than 100 μm.
This is the third aspect of the present invention.

An aggregating step in which at least one resin particle dispersion, at least one colorant dispersion, and an aggregating agent are mixed and added to form aggregated particles, and the glass particles are heated to a temperature higher than the glass transition point. And a fusion process of fusing the aggregated particles to form toner particles, wherein the colored body dispersion comprises at least a wet dispersion medium and colorant particles, and dynamic light. The volume cumulative average diameter Dv50 (μm) of the colorant particles in the colorant dispersion measured by the scattering method satisfies the following formula (22), and the volume particle size distribution width of the colorant particles in the colorant dispersion: A method for producing a toner for developing an electrostatic charge image, wherein the index SD satisfies the following formula (23).
Formula (22) 0.10 <Dv50 <0.30
Formula (23) 0.030 <SD <0.090
(However, Dv50 represents the particle size (μm) at which the volume particle size distribution cumulative curve of the colorant particles is 50%, and SD is the particle size at which the volume particle size distribution cumulative curve of the colorant particles is 84%. When (μm) is Dv84 and the particle size (μm) at the point of 16% is Dv16, SD = (Dv84−Dv16) / 2, and the volume cumulative distribution is the smaller particle size side of the volume particle size distribution. To be accumulated)
This is the fourth aspect of the present invention.

An agglomeration step in which at least one resin particle dispersion, at least one colorant dispersion, and an aggregating agent are mixed and added to form aggregated particles; And a fusion process of fusing the aggregated particles to form toner particles, wherein the colored body dispersion comprises at least a wet dispersion medium and colorant particles, and dynamic light. Production of an electrostatic charge image developing toner, wherein the volume particle size distribution of the colorant particles in the colorant dispersion measured by a scattering method satisfies the following formulas (26), (27) and (28): Method.
Formula (26) 0.10 <Dv50 <0.30
Formula (27) 1.0 <(Dv50 / Dv10) / (Dv90 / Dv50) <1.3
Formula (28) 0 <Pv <3
(However, Dv50 represents the volume cumulative distribution 50% diameter (μm) of the colorant particles, Dv10 represents the volume cumulative distribution 10% diameter (μm) of the colorant particles, and Dv90 represents the volume cumulative distribution 90% of the colorant particles. (Pv represents a ratio (%) of the particle size of 0.972 μm or more in the volume distribution of the colorant particles, and the volume cumulative distribution is accumulated from the small particle size side of the volume particle size distribution)
This is the fifth aspect of the present invention.

  A colorant dispersion excellent in transparency and coloring power can be obtained stably and with high efficiency, and by using the colorant dispersion, a high-quality image having a stable and clear hue, high transparency and image density. In addition, since the toner has a sufficient charge amount even in a high humidity environment, a method for producing a toner for developing an electrostatic image having high durability even in repeated use can be obtained.

  Hereinafter, the first to fifth inventions of the present invention will be sequentially described.

First, the first invention of the present invention is a colorant dispersion, and a volume cumulative average diameter Dv50 (μm) of the colorant particles in the colorant dispersion measured by a dynamic light scattering method is represented by the following formula (1 And the volume particle size distribution width index SD of the colorant particles in the colorant dispersion satisfies the following formula (2).
Formula (1) 0.10 <Dv50 <0.30
Formula (2) 0.030 <SD <0.090

  That is, in the formula (1), the volume cumulative distribution 50% diameter Dv50 of the colorant particles in the colorant dispersion is preferably more than 0.10 μm and less than 0.30 μm. This is because when the volume cumulative distribution 50% diameter Dv50 is 0.10 μm or less, the surface area of the dispersed particles increases and reaggregation due to the increase in cohesive force becomes severe, and this is applied to the emulsion polymerization aggregation method. This is because uniform aggregated particles cannot be formed. In addition, when the volume cumulative distribution 50% diameter Dv50 is 0.30 μm or more, the particles dispersed during storage are likely to settle, resulting in poor stability as a colorant dispersion. This is not preferable because it causes a problem of uneven distribution of the colorant particles.

  The volume particle size distribution width index SD in the formula (2) is an index representing the extent of the distribution width of the volume cumulative distribution of the colorant particles in the dispersion, as represented by SD = (Dv84−Dv16) / 2. The smaller the SD value, the sharper the particle size distribution of the colorant particles, and the SD is desired to be as small as possible. When the SD exceeds 0.090, the particle size distribution becomes broad and the dispersion stability is difficult because the dispersed particles tend to settle during storage, and the colorant dispersion of the present invention was applied to an emulsion polymerization aggregation toner. In some cases, it tends to cause uneven distribution of colorant particles, and the resulting transparency and colorability tend to be inferior. As for the lower limit, Dv84 = Dv16 in the case of an ideal monodisperse particle, so that SD is 0 and optimal. However, in an industrial and commercial product, such a situation can be as desired. If the practical lower limit is 0.030 or more, re-aggregation of the finely divided portion does not occur and coarsen, and the formation of uniform aggregated particles is inhibited when employed in the emulsion polymerization aggregation method. There is little to do.

  In a color dispersion, if it is allowed to stand for a long time after production, it cannot be completely avoided that the colorant particles settle or reaggregate and deteriorate in performance. However, as long as the above formulas (1) and (2) of the present invention are satisfied, even after being left for a long period of time, simple re-crushing (for example, stirring with an anchor blade or the like, homogenizer, etc.) Therefore, the problems caused by the colorant dispersion are unlikely to occur. However, when the equation is not satisfied, it is not possible to return to the original state by the above-described treatment, and therefore, the problem of performance deterioration of the colorant dispersion becomes more and more obvious.

And in this invention, in order to be more effective in the volume particle size distribution of the colorant particle | grains in a colorant dispersion, it is more preferable that Formula (1) is following Formula (3).
Formula (3) 0.10 <Dv50 <0.25
Moreover, when productivity is also considered, it is more preferable that Formula (2) is following Formula (4).
Formula (4) 0.040 <SD <0.085

The second invention of the present invention is a colorant dispersion similar to the first invention of the present invention, and the volume particle size distribution of the colorant particles in the colorant dispersion measured by a dynamic light scattering method. Satisfies the following equations (5), (6) and (7).
Formula (5) 0.10 <Dv50 <0.30
Formula (6) 1.0 <(Dv50 / Dv10) / (Dv90 / Dv50) <1.3
Formula (7) 0 <Pv <2
(However, Dv50 represents the volume cumulative distribution 50% diameter (μm) of the colorant particles, Dv10 represents the volume cumulative distribution 10% diameter (μm) of the colorant particles, and Dv90 represents the volume cumulative distribution 90% of the colorant particles. (Pv represents a ratio (%) of the particle size of 0.972 μm or more in the volume distribution of the colorant particles, and the volume cumulative distribution is accumulated from the small particle size side of the volume particle size distribution)

  First, the formula (5) is the same as the formula (1) of the first invention of the present invention. In the formula (6), the volume cumulative distribution 50% diameter Dv50 of the colorant particles in the colorant dispersion is 0. It should be greater than 10 μm and less than 0.30 μm. This is because when the volume cumulative distribution 50% diameter Dv50 is 0.10 μm or less, the surface area of the dispersed particles increases and reaggregation due to the increase in cohesive force becomes severe, and this is applied to the emulsion polymerization aggregation method. Cannot form uniform aggregated particles. Furthermore, when applied to toner, the probability of exposure of the colorant particles to the toner surface increases, and the toner chargeability is lowered, so that the image density, fog, and toner consumption during repeated use increase rapidly. There is a problem in terms of durability. In addition, when the volume cumulative distribution 50% diameter Dv50 is 0.30 μm or more, the particles dispersed during storage are likely to settle, resulting in poor stability as a colorant dispersion. There is a problem that causes uneven distribution of the colorant particles. Further, when applied to a toner, good transparency and coloring power cannot be obtained.

  Formula (6) is an index (Dv50 / Dv10) indicating the extent of the particle size distribution on the small particle size side with a 50% volume cumulative distribution as a boundary in the volume cumulative distribution of the colorant particles in the colorant dispersion. When the ratio is taken with an index (Dv90 / Dv50) indicating the extent of the particle size distribution on the large particle size side, this means that the value exceeds 1.0 but is less than 1.3. In other words, it is not a so-called normal distribution, but when the dispersion of the particle size distribution on the small particle size side is slightly larger than that on the large particle size side, the stability over time and transparency after dispersion when viewed as a dispersion, coloring It was found that the balance with the performance of sex was good. Here, when (Dv50 / Dv10) / (Dv90 / Dv50) is 1.0 or less, the extent of the particle size distribution on the large particle size side is larger, so the shape of the particle size distribution of the colorant particles is large. Dispersion stability is difficult because the dispersed particles tend to settle during storage, and when the colorant dispersion of the present invention is applied to an emulsion polymerization aggregation toner, uneven distribution of the colorant particles is caused. This is not preferable because it tends to be inferior and the resulting transparency and colorability tend to be inferior. Further, when (Dv50 / Dv10) / (Dv90 / Dv50) is 1.3 or more, the extent of the particle size distribution on the small particle size side is excessively large. This is not preferable because it tends to occur and become coarse, and when formed in the emulsion polymerization aggregation method, it may inhibit the formation of uniform aggregated particles.

In the formula (7), it is required that the ratio (%) Pv of the particle size of 0.972 μm or more in the volume distribution of the colorant particles does not exceed 2%. Normally, it is a matter of course that Pv is expected to be approximately 0% as a colorant dispersion. However, in practice, it is completely unavoidable that the small particle size side particles of the particle size distribution of the colorant fine particles once dispersed repeatedly re-aggregate into particles having a particle size of 0.972 μm or more. Such coarse particles are finally not taken into the aqueous medium toner, but are present in a free state on the surface, causing problems such as deterioration of high humidity characteristics. Therefore, even if coarse particles are generated, it is necessary to suppress the above range.
In a color dispersion, if the color dispersion is left for a long time after production, it cannot be completely avoided that the colorant particles settle or reaggregate and deteriorate in performance. However, as long as the above formulas (5), (6) and (7) of the present invention are satisfied, even after leaving for a long time, simple re-crushing (for example, stirring with an anchor blade or the like) , And the like, the problem due to the colorant dispersion hardly occurs. However, when the equation is not satisfied, it is not possible to return to the original state by the above-described treatment, and therefore, the problem of performance deterioration of the colorant dispersion becomes more and more obvious.

In the present invention, as in the first invention of the present invention, in order to be more effective in the volume particle size distribution of the colorant particles in the colorant dispersion, the formula (5) is expressed by the following formula (8): Is more preferable.
Formula (8) 0.10 <Dv50 <0.25
Moreover, it is more preferable that Formula (2) is the following Formula (9).
Formula (9) 1.0 <(Dv50 / Dv10) / (Dv90 / Dv50) <1.2
Furthermore, it is more preferable that Formula (3) is the following Formula (10).
Formula (10) 0 <Pv <1

  The wet dispersion medium in the present invention is a liquid having a function of dispersing and holding colorant particles, and should be appropriately set from known materials in accordance with the application purpose of the obtained colorant dispersion. Specifically, water; alcohols such as methanol, ethanol, propanol and butanol; organic solvents such as acetone, methyl ethyl ketone, tetrahydrofuran, toluene and xylene; monomers such as styrene, butyl acrylate, 2-ethylhexyl acrylate and acrylic acid These are used alone or in combination. As an application of the aqueous medium toner, for example, in the case of suspension polymerization toner, the colorant is dispersed in the oil phase, that is, the monomer phase. Therefore, the monomers may be selected as the wet medium. Since the coagulation step in this case is carried out in an aqueous system, water may be selected as the wet dispersion medium. Among these, the particle size distribution of the colorant dispersion of the present invention is most suitable for use as a colorant dispersion added to polymer primary particles in an emulsion polymerization aggregation method toner. Accordingly, water is preferred as the wet dispersion medium. The water quality is also related to the coarsening due to re-aggregation of the colorant particles in the colorant dispersion, and if the electrical conductivity is high, the dispersion stability with time tends to deteriorate. Therefore, the electrical conductivity is preferably 10 μS / cm. In the following, it is preferable to use ion-exchanged water or distilled water that has been desalted so as to be 5 μS / cm or less. The conductivity was measured using a conductivity meter (a personal SC meter model SC72 and a detector SC72SN-11 manufactured by Yokogawa Electric Corporation).

When water is used as the wet dispersion medium, it is preferable to add a surfactant to the water in order to wet and disperse the colorant particles and keep the dispersion state stable. Examples of the surfactant that can be used include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap, cationic surfactants such as amine salts and quaternary ammonium salts, Nonionic surfactants such as polyethylene glycol, alkylphenol ethylene oxide adducts, and polyhydric alcohols can be used. Among these, anionic surfactants such as anionic surfactants and cationic surfactants are preferable. The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant. The above surfactants may be used alone or in combination of two or more.

Specific examples of the anionic surfactant include fatty acid soaps such as potassium laurate, sodium oleate and sodium castor oil; sulfates such as octyl sulfate, lauryl sulfate, lauryl ether sulfate and nonylphenyl ether sulfate; lauryl sulfonate , Dodecylsulfonate, dodecylbenzenesulfonate, triisopropylnaphthalenesulfonate, dibutylnaphthalenesulfonate, alkylnaphthalene sodium sulfonate, naphthalenesulfonate formalin condensate; monooctylsulfosuccinate, dioctylsulfosuccinate, lauric acid amidesulfonate, oleic acid amidesulfonate Sulfonates such as lauryl phosphate, isopropyl phosphate And phosphoric acid esters such as nonylphenyl ether phosphate; sodium dialkylsulfosuccinate such as sodium dioctylsulfosuccinate; disodium lauryl sulfosuccinate; and sulfosuccinates such as disodium lauryl polyoxyethylene sulfosuccinate;

  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, distearyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dihydroxyethyl methyl ammonium chloride, oleyl bispolyoxyethylene methyl ammonium chloride, lauroylaminopropyldimethylethylammonium ethosulphate, lauroylaminopropyldimethylhydroxyethylammonium perchlorate, alkylbenzene dimethyl Ammonium chloride, alkylto Quaternary ammonium salts such as ammonium chloride; and the like.

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

Among these, since the stability of the colorant particles after dispersion can be maintained for a long time, it is preferable to use one or more anionic surfactants. Even when used in combination with other surfactants, at least anionic surfactants are used. Is preferably included. The amount of the surfactant used is usually 0.1 to 15 parts by weight with respect to 100 parts by weight of water, more preferably 0.5 to 10 parts by weight, and 1 to 5 parts by weight. It is best to do. When the amount of the surfactant used is larger than the above range, it becomes difficult to make the colorant finer, and the particle size distribution of the colorant of the present invention cannot be obtained. It is not preferable because reaggregation of agent particles cannot be suppressed.

The colorant particles used in the present invention are more uniformly aggregated when the density difference from the polymer primary particles (about 1.1 to 1.3 g / cm ³ as resin particles) in the emulsion polymerization aggregation method is smaller. ,
Accordingly, since the performance of the obtained toner is improved, the true density of the pigment particles measured by the pycnometer method specified in JIS K 5101-11-1: 2004 is less than 2.0 g / cm ^3. it is preferably, more preferably from 1.2~1.9g / cm ^3, particularly preferably from 1.3~1.8g / cm ^3. When the true density is large, the sedimentation property in an aqueous medium tends to deteriorate. In addition, in consideration of problems such as storage stability and sublimation, the colorant is preferably carbon black or an organic pigment.

  Examples of the above pigments include the following yellow pigments, magenta pigments, and cyan pigments. Carbon black was used as a black pigment, or the following yellow pigment / magenta pigment / cyan pigment was mixed to black. Things are used.

  Among these, carbon black as a black pigment exists as an aggregate of very fine primary particles, and when dispersed as a pigment dispersion, coarsening of particles due to reaggregation tends to occur. According to the study by the present inventors, the degree of reagglomeration of the carbon black particles is correlated with the amount of impurities contained in the carbon black (the degree of residual undecomposed organic matter). There was a tendency for coarsening due to re-aggregation. As a quantitative evaluation of the amount of impurities, the ultraviolet absorbance of the toluene extract of carbon black measured by the following method is preferably 0.05 or less, and more preferably 0.03 or less. Generally, carbon black produced by the channel method tends to have a large amount of impurities, and therefore, carbon black produced by the furnace method is preferred as the carbon black in the present invention.

The ultraviolet absorbance (λc) of carbon black is determined by the following method. First, 3 g of carbon black was sufficiently dispersed and mixed in 30 ml of toluene. Filter using 5C filter paper. Then, the value obtained by putting the filtrate in a quartz cell having a 1 cm square light absorption part and measuring the absorbance at a wavelength of 336 nm using a commercially available ultraviolet spectrophotometer (λs), and the value obtained by measuring the absorbance of toluene alone as a reference in the same manner From (λo), the UV absorbance is λ
Obtained by c = λs−λo. Examples of commercially available spectrophotometers include an ultraviolet-visible spectrophotometer (UV-3100PC) manufactured by Shimadzu Corporation.

    As yellow pigments, compounds typified by condensed azo compounds, isoindolinone compounds and the like are used. Specifically, C.I. I. CI Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 150, 155, 168, 180, 185, etc. are preferably used. It is done.

  As the magenta pigment, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 207, 209, 220, 221, 238, 254, C.I. I. Pigment Violet 19 or the like is preferably used. Among them, C.I. I. Pigment red 122, 202, 207, 209, C.I. I. A quinacridone pigment represented by pigment violet 19 is particularly preferred. Although this quinacridone pigment was suitable as a magenta pigment due to its clear hue and high light resistance, it is very difficult to finely disperse because the pigment itself is very hard particles. However, if the dispersion is excessively fine, the dispersion due to re-aggregation is so large that the potential performance cannot be fully exploited in any case. However, the dispersion having the particle size distribution of the present invention As a result, excellent performance can be exhibited without reaggregation. Among the quinacridone pigments, C.I. I. The compound represented by CI Pigment Red 122 is particularly preferable because the above-described improvement effect is remarkable.

  As the cyan pigment, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. Specifically, C.I. I. Pigment blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 and the like; I. Pigment Green 7, 36, etc. can be used particularly preferably.

  The amount of the colorant particles used in the colorant dispersion is preferably 3 to 50 parts by weight, more preferably 5 to 40 parts by weight, and more preferably 10 to 30 parts by weight with respect to 100 parts by weight of water. Part is particularly preferred. If the added amount of the colorant exceeds the above range, the concentration of the colorant is so high that the probability of reaggregation of the particles during the dispersion is increased, and this is not preferable. This is not preferable because it is difficult to obtain the particle size distribution.

In the present invention, the volume particle size distribution of the pigment particles in the pigment dispersion is measured by a dynamic light scattering method. This method obtains the particle size distribution by detecting the speed of Brownian motion of finely dispersed particles, irradiating the particles with laser light, and detecting light scattering (Doppler shift) with different phases according to the speed. It is. The value of the volume particle size of these colorant particles is a value when the colorant particles are stably dispersed in the aqueous system, and means the particle size of the colorant and wet cake as a powder before dispersion. Absent. In actual measurement, the above volume particle size was measured using the following settings using an ultrafine particle size distribution measuring apparatus (Nikkiso Co., Ltd., UPA-EX150, hereinafter abbreviated as UPA) using a dynamic light scattering method. went.
Measurement upper limit: 6.54 μm
Measurement lower limit: 0.0008 μm
Number of channels: 52
Measurement time: 100 sec.
Particle permeability: Absorption Particle refractive index: N / A (not applicable)
Particle shape: non-spherical density (g / cm ³ ): 1
Dispersion medium type: WATER
Dispersion medium refractive index: 1.333
At the time of measurement, the colorant dispersion was diluted with pure water so that the sample concentration index was in the range of 0.01 to 0.1, and measured with a sample subjected to dispersion treatment with an ultrasonic cleaner.

  Dv50, Dv84 and Dv16 according to the present invention are measured by accumulating the above volume particle size distribution results from the small particle size side to obtain a volume cumulative distribution, and the volume particle size distribution width index SD is calculated from Dv84 and Dv16. .

Next, the third invention of the present invention will be described. A third invention of the present invention is a method for producing a colorant dispersion comprising at least a wet dispersion medium and colorant particles, a cylindrical stator, a colorant dispersion supply port provided at one end of the stator, and coloring It is connected to the discharge port of the agent dispersion, the rotor filled with the medium filled in the stator and the colorant dispersion supplied from the supply port, and the discharge passage inlet communicating with the discharge port, and is integrated with the rotor. Or a separator that rotates independently from the rotor, separates into a medium and a colorant dispersion by the action of centrifugal force and a screen structure, and discharges the colorant dispersion from the discharge port. A method for producing a colorant dispersion, wherein a wet mill is used and the diameter Dm of the media is less than 100 μm. Further, it is preferable that the wet mill has a hollow discharge passage that communicates with the discharge port around the shaft of the shaft that rotationally drives the separator.
By this method for producing a colorant dispersion, the particle size distribution of the pigment dispersions of the first and second inventions can be achieved.

  The wet mill according to the present invention is a so-called bead mill, which is composed of a hermetic stator having a cylindrical shape, and a pin, a disk, or an annular type rotor that is arranged on the axis of the stator and is driven to rotate by a motor. In the state filled with media beads, a colorant dispersion comprising a wet dispersion medium and colorant particles is supplied, and the rotor is driven to rotate, and the media and the colorant dispersion are agitated and mixed to pulverize the colorant dispersion. Is what you do.

An example of the method for producing the colorant dispersion will be described with reference to FIGS.
FIG. 1 is a longitudinal sectional view showing an example of a wet mill (bead mill) according to the present invention. The wet mill in FIG. 1 has a vertical or horizontal cylindrical shape. Here, the horizontal type will be described. The cylindrical portion includes a stator 7 provided with a jacket 6 through which cooling water for cooling the mill is passed, and a bearing that is positioned at the shaft center of the stator 7 so as to be rotatable at a mounting portion (base portion) of the stator. And a shaft 5 provided with a mechanical seal in the bearing portion and having a hollow discharge passage 8 around the axis of the root portion, and a pin or disk projecting radially from the shaft root to the end portion Rotor 9, a separator 4 fixed by a rotary centrifugal screen for media separation, and a colorant dispersion premix product supply port 10 provided on the side of the shaft 5 at the base of the stator. It consists of an inlet 11. The separator 4 rotates the shaft 5 together with the medium and applies a centrifugal force to the medium and the dispersion. The separator 4 disperses the medium radially outward due to the difference in specific gravity. It is made to discharge through the discharge path 8.

  This separator 4 applies centrifugal force to the media and the dispersion, and repels the heavy media by the difference in specific gravity between the media and the slurry, and further separates the media completely by filtering through a screen. The dispersion is discharged from the discharge passage around the shaft. Since it is a screen system, beads are not ejected from the stator, and micro media can be used. Since the flow rate and throughput can be increased and there is no change in separation performance over time, it can be operated stably over a long period of time, and since fine media can be used, it has the advantage that fine grinding is possible. Yes.

  FIG. 2 is a schematic diagram illustrating an example of a one-pass treatment cycle of a colorant dispersion by a wet mill according to the present invention. In FIG. 2, the colorant dispersion slurry extracted by the raw material pump 2 from the raw material tank 1 storing the premixed product such as the wet dispersion medium and the colorant particles is supplied to the horizontal wet mill 3. After being pulverized by being stirred together with the medium, the medium is separated by the separator, discharged through the shaft axis, and collected in the product tank 30. This one-pass cycle is suitable for pulverizing and dispersing soft primary particles and loosely bonded agglomerates, and is applied to the dispersion of carbon black particles.

FIG. 3 is a schematic view showing an example of a circulation dispersion treatment cycle of a colorant dispersion by a wet mill according to the present invention. In FIG. 3, the colorant dispersion slurry extracted by the raw material pump 2 from the raw material tank 1 storing the premixed product such as the wet dispersion medium and the colorant particles is supplied to the horizontal wet mill 3. After being pulverized by being stirred together with the medium, the medium is separated by the separator 4 and discharged through the axis of the shaft 5, followed by a path returned to the tank 1, and circulated and pulverized. . The circulating dispersion treatment is used for crushing hard primary particles and strongly bonded aggregates (aggregates), and is essential for dispersing organic pigments, particularly quinacridone pigments.

  Next, a method for producing a pigment dispersion will be described with reference to FIGS. The medium in the stator 7 of the mill 3 is filled with 80 to 90% of the internal volume of the stator, the valves 12 and 13 are closed, and the valves 14 and 15 are opened. 2 is driven. The rotor 9 and the separator 4 are driven to rotate by the former motor driving, while the pigment dispersion premix slurry in the raw material tank 1 is sent to the introduction port 11 of the supply port 10 by a certain amount by driving the latter raw material pump 2. Are fed into the mill. The dispersion slurry and media in the mill are agitated and mixed by the rotation of the rotor 9 and the dispersion is pulverized. The rotation of the separator 4 separates the media and the dispersion due to the difference in specific gravity. Whereas the dispersion having a low specific gravity is filtered through a screen, it is completely separated from the media and discharged through a discharge passage 8 formed around the shaft 5. The ratio of the feed rate of the raw material slurry to the mill and the effective internal volume of the stator is preferably in the range described below.

  FIG. 3 is a schematic view showing an example of a circulation dispersion treatment cycle of a colorant dispersion by a wet mill according to the present invention. In FIG. 3, the colorant dispersion slurry extracted by the raw material pump 2 from the raw material tank 1 storing the premixed product such as the wet dispersion medium and the colorant particles is supplied to the horizontal wet mill 3. After being pulverized by being stirred together with the medium, the medium is separated by the separator 4 and discharged through the axis of the shaft 5, followed by a path returned to the tank 1, and circulated and pulverized. . The circulating dispersion treatment is used for crushing hard primary particles and strongly bonded aggregates (aggregates), and is essential for dispersing organic pigments, particularly quinacridone pigments.

  Here, the raw material pump 2 is preferably a non-pulsating pump. In ordinary metering pumps, the rotational motion of the circular eccentric cam is changed to reciprocating motion, so pulsation occurs on the discharge side, and an accurate flow rate cannot be obtained. In some cases, a share is added, and a disadvantage of accelerating reaggregation of the colorant in the colorant dispersion is likely to occur. The non-pulsating metering pump employs a constant velocity cam mechanism, etc., so that an accurate flow rate can be ensured even with a small amount, and the dispersion is hardly damaged, so that reaggregation of the colorant can be avoided. Specific examples of the non-pulsating metering pump include a non-pulsating metering pump type PLSXMA2 (hydraulic diaphragm type), PLSXDA2 (direct acting diaphragm type) manufactured by Takumina Corporation.

  In the present invention, the wet dispersion medium for forming the pigment dispersion is preferably water containing a surfactant, and the details thereof are as described above. In addition, the true density of the colorant particles and the kind of the desired colorant are preferably as described above.

  In the present invention, the selection of media beads is important. In particular, in order to achieve the particle size distribution of the pigment particles according to the first invention of the present application, the diameter of the media needs to be less than 100 μm, more preferably 10 to 90 μm, and particularly preferably 30 to 70 μm. In the case of beads exceeding the above range, since the destructive force by collision is generally high, there is a tendency to increase the ultrafine particle portion of the pigment particles. And since these ultrafine particle portions actually reagglomerate and coarsen immediately, eventually, the particle size distribution of the first invention of the present invention cannot be achieved, and these large particle size beads are pigments. As the pulverization of the particles progresses, the pulverization efficiency decreases, and the contact point (action point) of the media beads decreases, which is not preferable because the particle size distribution of the first invention of the present invention cannot be achieved. The media beads are monodisperse spherical particles, and variations in their diameters can be almost ignored.

A known material can be used for the media beads. For example, the following can be mentioned.
・ Zirconia (ZrO2), true density 6.0 g / cm ³
Silica, true density 2.6 g / cm ³
・ Glass, true density 2.5g / cm ³
・ Titanium oxide, true density 4.3 g / cm ³
Copper sphere, true density 8.9g / cm ³
Silicic acid zirconia (ZrSiO ₄ ), true density 3.8 g / cm ³
Among these, in order to smoothly separate the media and the colorant particles, it is preferable that the two have a certain density difference. Therefore, the true density of the media is preferably 5 or more. More preferably, the difference in density between the media and the colorant particles (less than 2.0 g / cm ³ ) is 3 or more. Among the above-mentioned media, zirconia (ZrO ₂ ) is preferable because it has high wear resistance and impact resistance and is difficult to be crushed in the manufacturing process. Further, the filling rate of the media is greatly related to the crushing ability, and is preferably 65 to 95% with respect to the stator effective internal volume (the crushing chamber volume excluding the volume occupied by the separator and the rotor from the total internal volume of the stator). More preferably, it is -90%.

  The colorant dispersion premix is prepared by predispersing water, a surfactant, and a pigment in advance with a stirrer, a homomixer, a homogenizer or the like equipped with a propeller blade, an anchor blade, etc. can get. The particle diameter of the colorant in the premix product is preferably measured by the Coulter method, laser diffraction method, or the like, and the volume cumulative distribution is 50% in diameter and is 100 μm or less because a suitable particle size distribution can be easily obtained later.

The colorant particles in the dispersion obtained by the method for producing a colorant dispersion of the present invention have a volume cumulative average diameter Dv50 (μm) satisfying the following formula (11) when measured by a dynamic light scattering method, and It is preferable that the volume particle size distribution width index SD of the colorant particles in the colorant dispersion satisfies the following formula (12).
Formula (11) 0.10 <Dv50 <0.30
Formula (12) 0.030 <SD <0.090

And as a range which has the effect of the present invention still more, it is more preferred that formula (11) is the following formula (13).
Formula (13) 0.10 <Dv50 <0.25
Moreover, when productivity is considered, it is more preferable that Formula (12) is following Formula (14).
Formula (14) 0.040 <SD <0.085

Further, the colorant particles in the dispersion obtained by the method for producing a pigment dispersion of the present invention have the following formulas (15), (16) and (16) in the volume particle size distribution when measured by a dynamic light scattering method. It is also preferable to satisfy 17). The symbols in the formula are as described above.
Formula (15) 0.10 <Dv50 <0.30
Formula (16) 1.0 <(Dv50 / Dv10) / (Dv90 / Dv50) <1.3
Formula (17) 0 <Pv <3

And in order to be more effective, it is more preferable that Formula (15) is following Formula (18).
Formula (18) 0.10 <Dv50 <0.25
Moreover, it is more preferable that Formula (16) is the following Formula (19).
Formula (19) 1.0 <(Dv50 / Dv10) / (Dv90 / Dv50) <1.2
Furthermore, it is more preferable that Formula (17) is the following Formula (20).
Formula (20) 0 <Pv <2

In addition, the supply rate at the time of performing one-pass or cyclic pulverization of the colorant dispersion slurry in the wet mill is also important in achieving a suitable particle size distribution. In the present invention, it is preferable to determine the supply speed in relation to the stator effective internal volume. Specifically, it is preferable to satisfy the following formula (21).
Formula (21) 10 ≦ V / M ≦ 200
(Where V represents the supply rate (liter / hr) of the colorant dispersion, and M represents the effective internal volume (liter) of the stator of the wet mill)
In particular, the case of 20 ≦ V / M ≦ 80 is optimal.
The stator effective internal volume is preferably 0.15 to 10 liters.
In the present invention, it is desirable to satisfy the above formula by satisfying the preferred ranges in the configuration of the wet mill, media size / material, density, filling rate, slurry supply speed, slurry premix particle size, and the like described above. Outside the range of the above formula, it is not preferred because there are inconveniences such as excessive pulverization of the colorant particles to increase the re-aggregation property of the particles and mixing of coarse particles.

According to a fourth aspect of the present invention, there is provided an agglomeration step in which at least one resin particle dispersion, at least one colorant dispersion, and an aggregating agent are mixed and added to form aggregated particles; And a fusion step of fusing the aggregated particles to form toner particles by heating to a glass transition point or higher, wherein the colored dispersion includes at least a wet dispersion medium and a colored The volume cumulative average diameter Dv50 (μm) of the colorant particles in the colorant dispersion measured by the dynamic light scattering method satisfies the following formula (22) and is measured in the colorant dispersion. A method for producing a toner for developing an electrostatic charge image, wherein the volume particle size distribution width index SD of the colorant particles satisfies the following formula (23).
Formula (22) 0.10 <Dv50 <0.30
Formula (23) 0.030 <SD <0.090
(However, Dv50 represents the particle size (μm) at which the volume particle size distribution cumulative curve of the colorant particles is 50%, and SD is the particle size at which the volume particle size distribution cumulative curve of the colorant particles is 84%. When (μm) is Dv84 and the particle size (μm) at the point of 16% is Dv16, SD = (Dv84−Dv16) / 2, and the volume cumulative distribution is the smaller particle size side of the volume particle size distribution. To be accumulated)

  That is, in the formula (22), the volume cumulative distribution 50% diameter Dv50 of the colorant particles in the colorant dispersion is preferably more than 0.10 μm and less than 0.30 μm. This is because when the volume cumulative distribution 50% diameter Dv50 is 0.10 μm or less, uniform aggregated particles cannot be formed when employed in the emulsion polymerization aggregation method. Furthermore, when applied to toner, the probability of exposure of the colorant particles to the toner surface increases, and the toner chargeability is lowered, so that the image density, fog, and toner consumption during repeated use increase rapidly. This is because there is a problem in terms of durability. Further, when the volume cumulative distribution 50% diameter Dv50 is 0.30 μm or more, there is a problem that uneven distribution of colorant particles occurs when employed in the emulsion polymerization aggregation method, and it is good when applied to toner. This is because transparency and coloring power cannot be obtained.

  The volume particle size distribution width index SD in the formula (23) is an index representing the extent of the distribution width of the volume cumulative distribution of the colorant particles in the dispersion, as represented by SD = (Dv84−Dv16) / 2. The smaller the SD value, the sharper the particle size distribution of the colorant particles. Therefore, when the SD exceeds 0.090, the particle size distribution becomes broad, and the dispersion stability is difficult because the dispersed particles are likely to settle during storage, and the colorant dispersion of the present invention is applied to the emulsion polymerization aggregation method toner. When applied, it tends to cause uneven distribution of colorant particles, and the resulting transparency and colorability tend to be inferior. As for the lower limit, Dv84 = Dv16 in the case of an ideal monodisperse particle, so that SD is 0 and optimal. However, in an industrial and commercial product, such a situation can be as desired. If the practical lower limit is 0.030 or more, re-aggregation of the finely divided portion does not occur and coarsen, and the formation of uniform aggregated particles is inhibited when employed in the emulsion polymerization aggregation method. There is nothing to do.

And in order to be more effective, it is more preferable that Formula (22) is following Formula (24).
Formula (24) 0.10 <Dv50 <0.25

Moreover, when productivity is also considered, it is more preferable that Formula (23) is following Formula (25).
Formula (25) 0.040 <SD <0.085

The fourth invention of the present invention is a method for producing a toner for developing an electrostatic charge image as in the third invention of the present invention, wherein at least one resin particle dispersion and at least one colorant dispersion are used. And an aggregating step of mixing and adding an aggregating agent to form aggregated particles, and a fusing step of heating above the glass transition point of the resin particles to fuse the aggregated particles to form toner particles. In the method for producing an electrostatic image developing toner, the volume particle size distribution of the colorant particles in the colorant dispersion measured by a dynamic light scattering method is expressed by the following equations (26), (27), and (28). A method for producing a toner for developing an electrostatic charge image, wherein
Formula (26) 0.10 <Dv50 <0.30
Formula (27) 1.0 <(Dv50 / Dv10) / (Dv90 / Dv50) <1.3
Formula (28) 0 <Pv <3
(However, Dv50 represents the volume cumulative distribution 50% diameter (μm) of the colorant particles, Dv10 represents the volume cumulative distribution 10% diameter (μm) of the colorant particles, and Dv90 represents the volume cumulative distribution 90% of the colorant particles. (Pv represents a ratio (%) of the particle size of 0.972 μm or more in the volume distribution of the colorant particles, and the volume cumulative distribution is accumulated from the small particle size side of the volume particle size distribution)

  That is, in the formula (26), the volume cumulative distribution 50% diameter Dv50 of the colorant particles in the colorant dispersion is preferably more than 0.10 μm and less than 0.30 μm. When the volume cumulative distribution 50% diameter Dv50 is 0.10 μm or less, uniform aggregated particles cannot be formed when employed in the emulsion polymerization aggregation method. Furthermore, when applied to toner, the probability of exposure of the colorant particles to the toner surface increases, and the toner chargeability is lowered, so that the image density, fog, and toner consumption during repeated use increase rapidly. There is a problem in terms of durability. Further, when the volume cumulative distribution 50% diameter Dv50 is 0.30 μm or more, there is a problem in that the colorant particles are unevenly distributed when employed in the emulsion polymerization aggregation method. Further, when applied to a toner, good transparency and coloring power cannot be obtained.

  Formula (27) is an index (Dv50 / Dv10) indicating the extent of the particle size distribution on the small particle diameter side of the volume cumulative distribution of the colorant particles in the colorant dispersion, with the 50% volume cumulative distribution as a boundary. When the ratio is taken with an index (Dv90 / Dv50) indicating the extent of the particle size distribution on the large particle size side, this means that the value exceeds 1.0 but does not exceed 1.3. That is, rather than a so-called normal distribution, when the dispersion of the particle size distribution on the small particle size side is slightly larger than that on the large particle size side, stability over time and transparency after dispersion when viewed as a dispersion, It was found that the color balance performance was well balanced. Here, when (Dv50 / Dv10) / (Dv90 / Dv50) is 1.0 or less, the degree of spread of the large particle size side particle size distribution is larger. When the agent dispersion is applied, it tends to cause uneven distribution of the colorant particles, and the obtained transparency and colorability tend to be inferior. Further, when (Dv50 / Dv10) / (Dv90 / Dv50) is 1.3 or more, the extent of the particle size distribution on the small particle size side is excessively large. Is undesirable because it may inhibit the formation of uniform aggregated particles.

  In the formula (28), it is required that the ratio (%) Pv of the particle size of 0.972 μm or more in the volume distribution of the colorant particles does not exceed 3%. Normally, it is natural that the colorant dispersion is expected to have a Pv of approximately 0%. However, in practice, it is completely unavoidable that the small particle size side particles of the particle size distribution of the colorant fine particles once dispersed repeatedly reaggregate to become particles having a particle size of 0.972 μm or more. Such coarse particles are finally not taken into the aqueous medium toner, but are present in a free state on the surface, causing problems such as deterioration of high humidity characteristics. Therefore, even if coarse particles are generated, it is necessary to suppress the above range.

And in order to produce the effect of this invention still more, it is more preferable that Formula (26) is the following formula | equation (29).
Formula (29) 0.10 <Dv50 <0.25
Moreover, it is more preferable that Formula (27) is the following Formula (30).
Formula (30) 1.0 <(Dv50 / Dv10) / (Dv90 / Dv50) <1.2
Furthermore, the formula (28) is more preferably the following formula (31).
Formula (31) 0 <Pv <2

  Due to the recent demand for low energy fixing, toner particles produced with an aqueous medium are adopted because they can easily contain a large amount of a low melting point wax, and a method for obtaining toner in an aqueous medium is as follows. A polymerization method such as a combination method or an emulsion polymerization aggregation method, a chemical pulverization method, or the like is preferably used. As the toner production method of the third invention of the present invention, the range of setting of the shape of the obtained particles is wide, the sharpness of the particle size distribution, etc., and thereby toner particles having stable chargeability can be obtained over a long period of time. From the emulsion polymerization aggregation method.

Hereinafter, the toner produced by the emulsion polymerization aggregation method will be described in more detail.
When a toner is produced by an emulsion polymerization aggregation method, it usually has a polymerization process, a mixing process, an aggregation process, a fusion process, and a washing / drying process. That is, generally, a dispersion liquid containing primary polymer particles obtained by emulsion polymerization is mixed with a dispersion liquid such as a colorant, wax, charge control agent, etc. Aggregation is performed to form particle aggregates, and an operation of attaching fine particles or the like is performed as necessary, and then the particles obtained by fusing are washed and dried to obtain mother particles.

  As the binder resin constituting the polymer primary particles of the resin dispersion used in the emulsion polymerization aggregation method, one or more polymerizable monomers that can be polymerized by the emulsion polymerization method may be appropriately used. Examples of the polymerizable monomer include a monomer having a Bronsted acidic group (hereinafter sometimes simply referred to as an acidic monomer) or a monomer having a Bronsted basic group (hereinafter sometimes simply referred to as a basic monomer), It is preferable to use, as a raw material monomer, a monomer that does not have any of a Sted acid group or a Bronsted basic group (hereinafter, may be referred to as another monomer). At this time, each monomer may be added separately, or a plurality of monomers may be mixed in advance and added simultaneously. Furthermore, it is possible to change the monomer composition during the monomer addition. The monomer may be added as it is, or may be added as an emulsion mixed and adjusted in advance with water or a surfactant.

  Examples of acidic monomers include monomers having a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and cinnamic acid, monomers having a sulfonic acid group such as sulfonated styrene, and sulfonamide groups such as vinylbenzenesulfonamide. And the like. In addition, as the basic monomer, an aromatic vinyl compound having an amino group such as aminostyrene, a nitrogen-containing heterocyclic ring-containing monomer such as vinylpyridine or vinylpyrrolidone, or an amino group such as dimethylaminoethyl acrylate or diethylaminoethyl methacrylate ( And (meth) acrylic acid esters.

  These acidic monomers and basic monomers may be used alone or in combination, and may exist as a salt with a counter ion. Among these, it is preferable to use an acidic monomer, more preferably acrylic acid and / or methacrylic acid. The total amount of acidic monomer and basic monomer in 100% by weight of all monomers constituting the binder resin as the polymer primary particles is preferably 0.05% by weight or more, more preferably 0.5% by weight or more, further It is preferably 1% by weight or more, preferably 10% by weight or less, and more preferably 5% by weight or less.

  Examples of other monomers include styrenes such as styrene, methylstyrene, chlorostyrene, dichlorostyrene, p-tert-butylstyrene, pn-butylstyrene, and pn-nonylstyrene, methyl acrylate, ethyl acrylate, Acrylic esters such as propyl acrylate, n-butyl acrylate, isobutyl acrylate, hydroxyethyl acrylate, ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate , Methacrylate esters such as hydroxyethyl methacrylate, ethylhexyl methacrylate, acrylamide, N-propylacrylamide, N, N-dimethylacrylamide, N, N-dipropylacrylamide, N, N Dibutyl acrylamide, acrylic acid amide and the like, monomers may be used alone, or may be used in combination.

  In the present invention, among the above-described monomers used in combination, as a preferred embodiment, an acidic monomer and other monomers may be used in combination. More preferably, acrylic acid and / or methacrylic acid is used as the acidic monomer, and a monomer selected from styrenes, acrylic esters, and methacrylic esters is used as the other monomer, and more preferably acidic monomer is used. It is preferable to use acrylic acid and / or methacrylic acid as a monomer and a combination of styrene and acrylic acid esters and / or methacrylic acid esters as other monomers, and particularly preferably acrylic acid and / or methacrylic acid as an acidic monomer. The acid is preferably a combination of styrene and n-butyl acrylate as the other monomer.

  Further, when a crosslinked resin is used as the binder resin constituting the polymer primary particles, a polyfunctional monomer having radical polymerization is used as the crosslinking agent shared with the above-mentioned monomers, for example, divinylbenzene, hexanediol diene. Examples include acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol acrylate, and diallyl phthalate. It is also possible to use a monomer having a reactive group in a pendant group, such as glycidyl methacrylate, methylol acrylamide, acrolein and the like. Among these, radical polymerizable bifunctional monomers are preferable, and divinylbenzene and hexanediol diacrylate are particularly preferable.

  These polyfunctional monomers may be used alone or in combination. When a crosslinked resin is used as the binder resin constituting the polymer primary particles, the blending ratio of the polyfunctional monomer in the total monomers constituting the resin is preferably 0.005% by weight or more, more preferably 0.1%. It is desirable that the content is not less than wt%, more preferably not less than 0.3 wt%, preferably not more than 5 wt%, more preferably not more than 3 wt%, still more preferably not more than 1 wt%.

Known surfactants can be used for the emulsion polymerization, and one or more surfactants selected from cationic surfactants, anionic surfactants, and nonionic surfactants are used. It can be used in combination.
Examples of the cationic surfactant include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl ammonium bromide, and examples of the anionic surfactant include And fatty acid soap such as sodium stearate and sodium dodecanoate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate and the like. Nonionic surfactants include, for example, polyoxyethylene dodecyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monooleate ether, monodecanoyl sucrose, etc. Is mentioned.

  The amount of the surfactant used is usually 1 to 10 parts by weight with respect to 100 parts by weight of the polymerizable monomer, and these surfactants include, for example, polyvinyl alcohol such as partially or completely saponified polyvinyl alcohol. One kind or two or more kinds of alcohols and cellulose derivatives such as hydroxyethyl cellulose can be used in combination as protective colloids.

  Examples of the polymerization initiator include hydrogen peroxide; persulfates such as potassium persulfate; organic peroxides such as benzoyl peroxide and lauroyl peroxide; 2,2′-azobisisobutyronitrile; One or two or more azo compounds such as 2′-azobis (2,4-dimethylvaleronitrile); and a redox initiator are usually added in an amount of 0.1 to 100 parts by weight of the polymerizable monomer. Used in an amount of about 3 parts by weight. Among them, it is preferable that at least a part or all of the initiator is hydrogen peroxide or organic peroxides.

In addition, one or two or more suspension stabilizers such as calcium phosphate, magnesium phosphate, calcium hydroxide, and magnesium hydroxide are usually used in an amount of 1 to 10 parts by weight with respect to 100 parts by weight of the polymerizable monomer. May be.
Any of the polymerization initiator and the suspension stabilizer may be added to the polymerization system at any time before, simultaneously with, or after the addition of the monomers, and these addition methods may be combined as necessary. good.

  In the emulsion polymerization, a known chain transfer agent can be used as necessary. Specific examples of such a chain transfer agent include t-dodecyl mercaptan, 2-mercaptoethanol, diisopropyl xanthogen, four Examples thereof include carbon chloride and trichlorobromomethane. The chain transfer agent may be used alone or in combination of two or more, and is usually used in the range of 5% by weight or less based on the total monomers. Further, a pH adjuster, a polymerization degree adjuster, an antifoaming agent, and the like can be appropriately added to the reaction system.

In the emulsion polymerization, the above monomers are polymerized in the presence of a polymerization initiator, and the polymerization temperature is usually 50 to 120 ° C, preferably 60 to 100 ° C, and more preferably 70 to 90 ° C.
The volume average particle diameter (volume-based arithmetic average diameter) of the polymer primary particles of the resin dispersion obtained by emulsion polymerization is usually 0.02 μm or more, preferably 0.05 μm or more, more preferably 0.1 μm or more. It is usually 3 μm or less, preferably 2 μm or less, more preferably 1 μm or less. When the particle size is less than the above range, it may be difficult to control the aggregation rate. When the particle size exceeds the above range, the particle size of the toner obtained by aggregation tends to be large, and a toner having a target particle size can be obtained. It can be difficult.

  Tg by the DSC (Differential Scanning Calorimetry) method of the binder resin constituting the polymer primary particles is preferably 40 to 80 ° C. Here, when the Tg of the binder resin overlaps with the heat amount change based on other components, for example, the melting peak of the wax and cannot be clearly determined, when the toner is prepared in a state in which such other components are excluded. Of Tg.

  The acid value of the binder resin constituting the polymer primary particles is preferably 3 to 50 mgKOH / g, more preferably 5 to 30 mgKOH / g as a value measured by the method of JISK-0070.

  The colorant dispersion used in the present invention is a dispersion of a colorant in a wet dispersion medium, preferably a dispersion of a colorant in water containing a surfactant. These are the first invention of the present invention. Each of those described in the second invention is preferable. And as a manufacturing method of the coloring agent dispersion, what was demonstrated by the 3rd invention of this invention is suitable.

  As a method for blending the colorant in the emulsion polymerization aggregation method, usually, a polymer primary particle dispersion and a colorant dispersion are mixed to form a mixed dispersion, and then aggregated to obtain a particle aggregate. At this time, the colorant dispersion is preferably added with 10 to 30 parts by weight of the colorant and 1 to 15 parts by weight of the surfactant with respect to 100 parts by weight of water. The addition of the colorant dispersion at the time of emulsion aggregation is calculated and used so as to be 2 to 10% by weight in the finished mother particles after aggregation.

  It is preferable to add wax to the toner in order to impart release formation. Any wax can be used as long as it has release formation, and is not particularly limited. Specifically, olefin waxes such as low molecular weight polyethylene, low molecular weight polypropylene and copolymer polyethylene; paraffin wax; esters having long chain aliphatic groups such as behenyl behenate, montanate ester, stearyl stearate Plant waxes such as hydrogenated castor oil carnauba wax; ketones having long chain alkyl groups such as distearyl ketone; silicones having alkyl groups; higher fatty acids such as stearic acid; long chain aliphatic alcohols such as eicosanol; glycerin And carboxylic acid ester or partial ester of polyhydric alcohol obtained from polyhydric alcohol such as pentaerythritol and long chain fatty acid; higher fatty acid amide such as oleic acid amide and stearic acid amide; low molecular weight polyester and the like.

  Among these waxes, in order to improve the fixability, a low melting point wax is preferable. Specifically, the melting point of the wax measured by DSC is preferably 30 ° C. or higher, more preferably 40 ° C. or higher. 50 ° C. or higher is particularly preferable. Moreover, 100 degrees C or less is preferable, 90 degrees C or less is still more preferable, and 80 degrees C or less is especially preferable. If the melting point is too low, the wax tends to be exposed and sticky after fixing, and if the melting point is too high, the fixability at low temperatures is poor. Further, the wax compound species is preferably an ester wax obtained from paraffin wax or aliphatic carboxylic acid and a mono- or polyhydric alcohol, and in the case of an ester wax, those having 20 to 100 carbon atoms are preferable. Further, those having 20 to 100 carbon atoms are particularly preferred. Furthermore, silicone waxes that may be modified can also be suitably used. The wax preferably has a surface tension of preferably 35 mN / m or less, more preferably 30 mN / m or less, still more preferably 28 mN / m or less, preferably 20 mN / m or more, more preferably 24 mN / m. m or more is desirable. The half width of the melting peak of the wax is preferably 20 ° C. or less, more preferably 15 ° C. or less, and further preferably 12 ° C. or less. When the half-value width of the melting peak exceeds the above range, the wax does not melt quickly at the time of fixing, so that a sufficient fixing reinforcing effect may not be exhibited. The lower limit of the half width of the melting peak is not limited, but is usually 2 ° C. or higher, preferably 5 ° C. or higher. Here, the half width of the melting peak of the wax means the peak width (° C.) at the position of half the melting peak height. In addition, the heat of fusion of the wax is preferably 80 J / g or more, more preferably 90 J / g or more. A high heat of fusion means that a large amount of heat is required to melt at the time of fixing, but if there is a heat amount to soften the binder resin, no problem occurs in melting of the wax. On the other hand, when the heat of fusion is less than the above range, the toner may be blocked as a result of melting of the wax during storage of the toner or during standby in the cartridge. In some cases, the toner is contaminated by melting of the wax before the toner passes through the developing process and moves to the fixing process. The upper limit of the heat of fusion is not limited, but is usually 300 J / g or less, preferably 250 J / g or less. Here, the heat of fusion of the wax means a value calculated from the area of the melting peak. In the wax of the present invention, the half width of the crystallization peak is preferably 25 ° C. or less, more preferably 20 ° C. or less. If the half width of the crystallization peak is within the above range, the wax melted at the time of fixing is quickly solidified, so that filming to the fixing roller does not occur and high temperature offset property tends to be good. The lower limit of the half width of the crystallization peak is not limited, but is usually 5 ° C. or higher, preferably 10 ° C. or higher. Here, the half width of the crystallization peak of the wax means the peak width (° C.) at the position of half the peak height.

  The above waxes may be used alone or in combination. Further, the melting point of the wax compound can be appropriately selected depending on the fixing temperature for fixing the toner. The amount of the wax used is usually 1 to 40%, more preferably 2 to 35%, still more preferably 5 to 30%, and particularly preferably 5 to 15%.

  As a method of blending the wax in the emulsion polymerization aggregation method, is it possible to add a wax dispersion emulsified and dispersed in water to a volume average diameter of 0.01 to 2.0 μm, more preferably 0.01 to 0.5 μm in advance during emulsion polymerization? Alternatively, it is preferably added in the aggregation step. In order to disperse the wax with a suitable dispersed particle diameter in the toner, it is preferable to add the wax as a seed during emulsion polymerization. By adding as a seed, polymer primary particles in which wax is encapsulated can be obtained, so that a large amount of wax does not exist on the toner surface, and deterioration of chargeability and heat resistance of the toner can be suppressed. The amount of wax present in the polymer primary particles is preferably 4 to 30% by weight, more preferably 5 to 20% by weight, and particularly preferably 7 to 15% by weight.

  A charge control agent may be added to the toner used in the present invention in order to impart charge amount and charge stability. Conventionally known compounds are used as the charge control agent. Examples thereof include hydroxycarboxylic acid metal complexes, azo compound metal complexes, naphthol compounds, naphthol compound metal compounds, nigrosine dyes, quaternary ammonium salts, and mixtures thereof. The addition amount of the charge control agent is preferably in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the resin.

  When a charge control agent is contained in the toner in the emulsion polymerization aggregation method, the charge control agent is added together with the monomer during emulsion polymerization, or is added in the aggregation step together with the polymer primary particles and the colorant, or the polymer primary It can be blended by a method of adding particles after agglomerating particles, a colorant and the like to a particle size suitable for a toner. Of these, the charge control agent is preferably emulsified and dispersed in water using a surfactant and used as an emulsion having a volume average particle size of 0.01 to 3 μm. The addition of the charge control agent dispersion at the time of emulsion aggregation is calculated and used so as to be 0.1 to 5% by weight in the finished mother particles after aggregation.

The volume average particle diameter of the polymer primary particles, the colorant dispersed particles, the wax dispersed particles, the charge control agent dispersed particles, etc. in the above dispersion can be measured using, for example, UPA.
In the aggregation step in the emulsion polymerization aggregation method, the above-described blending components such as the polymer primary particles, the colorant particles, the wax, and the charge control agent are mixed simultaneously or sequentially. It is possible to prepare a polymer primary particle dispersion, a colorant particle dispersion, a wax fine particle dispersion, and a charge control agent dispersion and mix them to obtain a mixed dispersion. It is preferable from the viewpoint of uniformity.

The agglomeration treatment usually includes a method of heating in a stirring tank, a method of adding an aggregating agent such as an electrolyte, a method of combining these, and the like. The particle size is controlled, but the cohesive force can be increased by heating or adding an electrolyte. Among these, it is essential to add at least an aggregating agent when primary particles are aggregated with stirring to obtain particle aggregates approximately similar to the size of the toner.

As an aggregating agent to be added for agglomerating particles, either an organic salt or an inorganic salt may be used. Specifically, NaCl, KCl, LiCl, Na ₂ SO 4, K ₂ SO ₄ , Li ₂ SO ₄ , _{MgCl 2, CaCl 2, MgSO 4} , CaSO 4, ZnSO 4, Al 2 (SO 4) 3, Fe 2 (SO4) 3, CH 3 COONa, C 6 H 5 SO 3 Na and the like. Of these, inorganic salts having a divalent or higher polyvalent metal cation are preferred.

  The addition amount of the flocculant varies depending on the type of flocculant, the target particle size, and the like, but is usually 0.05 to 25 parts by weight, preferably 0.1 to 100 parts by weight of the solid component of the mixed dispersion. -15 parts by weight, more preferably 0.1-10 parts by weight. When the addition amount is less than the above range, the progress of the agglutination reaction is slow, and fine particles of 1 μm or less remain after the agglomeration reaction, or the average particle size of the obtained particle aggregate does not reach the target particle size. If the above range is exceeded, rapid aggregation tends to occur, making it difficult to control the particle size, and the resulting aggregated particles may contain problems such as coarse powder and irregular shapes. is there. The agglomeration temperature when aggregating is performed by adding an aggregating agent may be equal to or lower than the Tg of the resin particles (polymer primary particles), preferably 20 to 70 ° C, and more preferably 30 to 60 ° C.

  The time required for agglomeration is optimized depending on the shape of the apparatus and the processing scale, but in order to reach the target particle size, the toner particles are usually held at the predetermined temperature for at least 30 minutes. Is desirable. The temperature rise until reaching a predetermined temperature may be raised at a constant rate within the above temperature range, or may be raised stepwise.

  In the present invention, toner particles can be formed by coating (adhering or fixing) resin fine particles on the surface of the particle aggregate after the above-described aggregation treatment, if necessary. In the present invention, when the amount of the wax is increased, the low temperature fixability is improved, but the wax is likely to be exposed on the toner surface, so that the chargeability and heat resistance may be deteriorated. In some cases, the deterioration of performance can be prevented by coating with. The volume average particle size (volume-based arithmetic average diameter) of the resin fine particles is preferably 0.02 to 3 μm, more preferably 0.05 to 1.5 μm.

As the resin fine particles, those obtained by polymerizing monomers similar to those used in the above-mentioned polymer primary particles can be used, and among them, a crosslinked resin containing a polyfunctional monomer as a raw material is preferable. The resin fine particles may contain a wax.
The resin fine particles are usually used as a dispersion liquid in a liquid mainly composed of water with a surfactant. When the charge control agent is added after the aggregation treatment, a dispersion liquid containing particle aggregates is used. It is preferable to add resin fine particles after adding the charge control agent.

  In the emulsion polymerization aggregation method, a fusion step for causing fusion between the aggregated particles is added in order to increase the stability of the particle aggregate obtained by aggregation. The temperature of the fusing step is preferably not less than the Tg of the binder resin constituting the primary particles, preferably not less than 5 ° C higher than the Tg, more preferably not less than 10 ° C higher than the Tg, The temperature is preferably 80 ° C. or higher than the Tg, more preferably 50 ° C. or lower than the Tg. The time required for the fusing step varies depending on the shape of the target toner, but after reaching the glass transition temperature of the polymer constituting the primary particles, usually 0.1 to 10 hours, preferably 1 to 6 hours. It is desirable to hold.

  In the emulsion polymerization aggregation method, it is preferable to add a surfactant or raise the pH value of the aggregation liquid after the aggregation process, preferably before the fusion process or during the fusion process. As the surfactant used here, one or more kinds of surfactants that can be used when producing the polymer primary particles can be selected and used, and in particular, polymer primary particles were produced. It is preferable to use the same surfactant as that used at the time. The addition amount in the case of adding the surfactant is not limited, but is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, further preferably 3 parts by weight with respect to 100 parts by weight of the solid component of the mixed dispersion. Part or more, preferably 20 parts by weight or less, more preferably 15 parts by weight or less, and still more preferably 10 parts by weight or less. After the aggregation process, before the completion of the fusion process, by adding a surfactant or increasing the pH value of the aggregation liquid, aggregation of particle aggregates aggregated in the aggregation process can be suppressed. In some cases, the generation of coarse particles in the toner after the process can be suppressed.

  By such heat treatment, the primary particles in the aggregate are fused and integrated, and the shape of the toner particles as the aggregate is also nearly spherical. The particle aggregate before the fusion step is considered to be an aggregate due to electrostatic or physical aggregation of the primary particles, but after the fusion step, the polymer primary particles constituting the particle aggregate are fused together. In addition, the shape of the toner particles can be made nearly spherical. According to such a fusion process, by controlling the temperature and time of the fusion process, a cocoon shape in which primary particles are aggregated, a potato type with advanced fusion, a spherical shape with further fusion, etc. Various shapes of toner can be produced according to the purpose.

The particle aggregate (fused body) obtained through the above steps is solid / liquid separated according to a known method (for example, a centrifugal separation method, a filter press method, etc.), and the particle aggregate is recovered. The desired mother particles can be obtained by washing the product as necessary and then drying.
Further, on the surface of the particles obtained by the emulsion polymerization / aggregation method, an outer layer containing a polymer as a main component is further formed by a method such as a spray drying method, an in-situ method, or a submerged particle coating method. Is preferably formed to a thickness of 0.01 to 0.5 μm, whereby encapsulated mother particles can be obtained.

  Other components (particles) such as a fluidity improver, a cleaning aid, a lubricant, or an abrasive can also be externally added to the toner base particles thus obtained as external additives.

  In order to control fluidity and developability, external additives added to the toner particle surface include metal oxides such as alumina, silica, titania, zinc oxide, zirconium oxide, cerium oxide, talc, hydrotalcite, and the like. Hydroxides, metal titanates such as calcium titanate, strontium titanate and barium titanate, nitrides such as titanium nitride and silicon nitride, carbides such as titanium carbide and silicon carbide, organics such as acrylic resins and melamine resins A particle etc. are mentioned, It is possible to combine two or more. Among them, silica, titania, and alumina are preferably used alone or in combination, and more preferably those subjected to a hydrophobic surface treatment with, for example, a silane coupling agent or a silicone compound. In particular, those subjected to surface treatment with a silicone compound are preferred from the viewpoint of maintaining the charge amount. The number average primary particle diameter by the electron microscopy is preferably in the range of 1 to 500 nm, more preferably in the range of 5 to 100 nm. Further, those having a small particle diameter (number average primary particle diameter in the range of less than 1 to 30 nm) and those having a large particle diameter (number average primary particle diameter in the range of 30 to 500 nm) Are preferably used in combination so that the particle size difference is 10 nm or more, more preferably 30 nm or more. The total amount of the external additive added is preferably in the range of 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight with respect to 100 parts by weight of the toner particles.

  Examples of the lubricant include fatty acid amides such as ethylene bisstearylamide and oleic acid amide; fatty acid metal salts such as zinc stearate and calcium stearate; Examples of the abrasive include the aforementioned silica, alumina, cerium oxide, and the like. The average particle size of these particles is usually at most 1 μm (that is, 1 μm or less), preferably 0.01 to 1 μm.

  In toners, particularly aqueous medium toners such as emulsion aggregation toners, the shape is close to a sphere and the particle surface is smooth, so it is difficult to firmly attach these external additives. Therefore, as the external addition device, a high-speed fluid mixer in which a stirring blade rotates at a high speed is used, and the device itself can be controlled at 30 to 55 ° C. through a medium whose temperature is adjusted to the jacket, preferably water, around the mixer. Is preferable. As a result, the particle surface is softened in the external additive device, and adhesion of the external additive is promoted and strengthened.

  Examples of the high-speed fluid mixer include Henschel mixers FM-300 and FM-500 manufactured by Mitsui Mining Co., Ltd., and Supermixers SMB-500 and SMG-500 manufactured by Kawata Corporation.

  The chargeability of the emulsion polymerization aggregation method toner may be positively charged or negatively charged, but is preferably used as a negatively chargeable toner. Control of the chargeability of the toner can be adjusted by selection and content of the resin monomer and charge control agent, selection and addition amount of the external additive, and the like.

  The toner obtained by the toner production method of the present invention preferably has an arithmetic average particle size (Dv) determined from a volume particle size distribution of 3 to 9 μm, more preferably 4 to 8 μm, still more preferably 5 to 7.5 μm. . Further, the lower limit of the content ratio of fine powder particles having a volume particle size of 5.04 μm or less is preferably 0.1% or more, more preferably 0.5% or more, and particularly preferably 1% or more. The upper limit is preferably 10% or less, more preferably 7% or less, and particularly preferably 5% or less. The lower limit of the content ratio of the fine particles having a number particle size of 5.04 μm or less is preferably 0.5% or more, more preferably 1% or more, particularly preferably 3% or more, and the upper limit is preferably 20%. % Or less, more preferably 15% or less, and particularly preferably 10% or less. Furthermore, the content of coarse particles having a volume particle size of 12.7 μm or more is preferably 2% or less, more preferably 1% or less, and particularly preferably 0.5% or less. It is most preferable that particles having a volume particle size of 5.04 μm or less and a volume particle size of 12.7 μm or more, particularly coarse particles having a volume particle size of 12.7 μm or more are not present at all, but are difficult in actual production. In addition, since the removal process requires equipment, it is desirable to control within the above range. When the volume average particle diameter or the particle content ratio deviates from the above range, it may not be suitable for high-resolution image formation, and when it is less than the above range, handling as a powder tends to be difficult. Furthermore, the value (Dv / Dn) obtained by dividing Dv by the arithmetic average particle diameter (Dn) obtained from the number particle size distribution is preferably 1.0 to 1.25, more preferably 1.0 to 1.20, Preferably it is 1.0-1.15, and the one near 1.0 is desirable. A toner having a sharper particle size distribution tends to have a more uniform chargeability between particles. Therefore, Dv / Dn of an electrostatic charge image developing toner for achieving high image quality and high speed is in the above range. Is preferred. In order to obtain such a particle size distribution, it is desirable to employ the emulsion polymerization aggregation method of the third invention of the present invention.

The toner particle size measuring device uses a Coulter Counter Multisizer II (manufactured by Beckman Coulter, Inc.), an interface (manufactured by Nikki) that outputs the number distribution and volume distribution, and a general personal computer. Connect and prepare 1% NaCl aqueous solution as the electrolyte using special grade or first grade sodium chloride. As a measuring method, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and measured using a Coulter counter Multisizer II type with a 100 μm aperture. The volume and number of toners are measured to calculate a volume distribution and a number distribution, and a volume average diameter Dv and a number average diameter Dn are obtained, respectively.

  The shape of the toner of the present invention, particularly the toner produced by the emulsion polymerization aggregation method, is preferably as close to spherical as possible, and the average circularity is preferably 0.900 or more, more preferably 0.920 or more, and further Preferably it is 0.930 or more. The closer to a sphere, the less the localization of the charge amount in the particles and the developability tends to be uniform, but since it is difficult to produce a perfect spherical toner, the average circularity is Preferably it is 0.995 or less, More preferably, it is 0.990 or less.

The circularity in the present invention is used as a simple method for quantitatively expressing the particle shape. In the present invention, the circularity is measured by using a flow type particle image analyzer FPIA-2100 manufactured by Sysmex Corporation. The circularity of the obtained particles is obtained by the following equation (1).
Circularity a = L0 / L (1)
[In the formula, L0 represents the circumference of a circle having the same projected area as the particle image, and L represents the particle image when image processing is performed at an image processing resolution of 512 × 512 (0.3 μm × 0.3 μm pixels). Indicates the perimeter. ]

  The circularity used in the present invention is an index of the degree of unevenness of the toner particles, and indicates 1.00 when the toner is a perfect sphere. The more complicated the surface shape, the smaller the circularity.

  Furthermore, the measurement device used in the present invention, “FPIA-2100”, has a thinner sheath flow (7 μm → 4 μm) than “FPIA1000” which has been used to calculate the shape of the toner. ) And the magnification of the processed particle image, and further improved the processing resolution of the captured image (256 × 256 → 512 × 512), so that the accuracy of toner shape measurement has been improved, thereby more reliably capturing fine particles. It is a device that has achieved. Therefore, when it is necessary to measure the shape more accurately as in the present invention, the FPIA 2100 that can obtain information on the shape more accurately is more useful.

  As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of water from which impurities in the container have been removed in advance, and a measurement sample is 0. Add about 1-0.5g. The suspension in which the sample is dispersed is irradiated with ultrasonic waves (50 kHz, 120 W) for 1 to 3 minutes, the dispersion concentration is set to 1.2 to 2 million pieces / μl, and the flow type particle image measurement apparatus is used. The circularity distribution of particles having an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm is measured.

  The outline of the measurement is as follows.

  The sample dispersion is passed through a flow path (expanded along the flow direction) of a flat and flat flow cell (thickness: about 200 μm). The strobe and the CCD camera are mounted on the flow cell so as to be opposite to each other so as to form an optical path that passes through the thickness of the flow cell. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a certain range parallel to the flow cell. Photographed as a two-dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area is calculated as the equivalent circle diameter. The circularity of each particle is calculated from the projected area of the two-dimensional image of each particle and the perimeter of the projected image using the above circularity calculation formula.

Further, the gel permeation chromatography (hereinafter referred to as GP) of the THF soluble content of the toner.
C may be abbreviated as C), and at least one of the peak molecular weights is preferably 10,000 or more, more preferably 20,000 or more, still more preferably 30,000 or more, preferably 150,000 or less, more preferably 100,000 or less. More preferably, it is desirably 70,000 or less. When the peak molecular weight is lower than the above range, the mechanical durability in the non-magnetic one-component development method may be deteriorated. When the peak molecular weight is higher than the above range, the low temperature fixability and the fixing strength are deteriorated. There is a case. The THF-insoluble content of the toner is preferably 10% or more, more preferably 20% or more, and preferably 60% or less, more preferably when measured by a gravimetric method using Celite filtration described later. It should be 50% or less. If it is not within the above range, it may be difficult to achieve both mechanical durability and low-temperature fixability.

  The peak molecular weight of the toner is measured under the following conditions using a measuring apparatus: HLC-8120GPC (manufactured by Tosoh Corporation).

  The column is stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 ml / min.

  The toner is dissolved in THF and filtered through a 0.2 μm filter, and the filtrate is used as a sample.

Measurement is performed by injecting 50 to 200 μl of a THF sample solution of a resin adjusted to a sample concentration of 0.05 to 0.6 mass%. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Ltd. Alternatively, the molecular weight of Toyo Soda Kogyo Co. is 6 × 10 ^2,
2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9
X10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ are used, and it is appropriate to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

As the column, in order to accurately measure the molecular weight region of 10 ^{3 to} 2 × 10 ⁶ , it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, μ-styragel 500, 10 ³ , manufactured by Waters, 10 ⁴ , 10 ⁵ combination or shodex KA made by Showa Denko
A combination of 801, 802, 803, 804, 805, 806, 807 is preferred.

  As a preferred embodiment of the toner of the fourth invention described above, the colorant dispersion of the first invention obtained by the method for producing the colorant dispersion of the second invention is used in the toner for developing an electrostatic image of the third invention. It may be obtained by applying to a manufacturing method. The colorant dispersion having a suitable particle size distribution according to the present invention is found to be distributed in the width of the particle size distribution almost as it is in the obtained toner, even if employed in the emulsion polymerization aggregation method, although there are differences in measurement methods. Therefore, it is presumed that the toner has suitable performance with improved conventional defects.

Specific examples of the present invention will be described below in more detail with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist.
In the following examples, “parts” means “parts by weight”. Various measurements in the present invention were measured by the following methods.
[Size distribution of colorant dispersion, wax particles and polymer primary particles]
It was measured with UPA described in the text. Unless otherwise noted, these were measured immediately after production.
[Particle sedimentation of colorant dispersion]
The sedimentation acceleration test was performed at room temperature using a centrifuge (manufactured by Hagitec Co., Ltd., CN-2060), and was ranked as follows. Desirably, it is more than ○. The sedimentation vessel was 50 ml, charged with 30 ml of the colorant dispersion, and the centrifugation conditions were 5000 rpm for 5 minutes. The evaluation value is obtained by measuring the sedimentation height from the bottom of the container when all particles settled by sufficient centrifugation in advance (100% by weight sedimentation), and the ratio of each to the measured height. This is expressed as
A: The amount of precipitated particles is less than 20% by weight (the sedimentation property is very small)
○: Amount of precipitated particles 20% by weight or more and less than 40% by weight (less sedimentation)
Δ: Amount of precipitated particles 40% by weight or more and less than 60% by weight (sedimentation is slightly high, but there is no practical problem)
X: Amount of precipitated particles 60% by weight or more (sedimentation is large and unusable)

[Re-agglomeration of colorant dispersion]
After the colorant dispersion was produced, the dispersion 1L was weighed into a plastic container and allowed to stand as it was, and after 48 hours, the container was shaken 10 times up and down, and then the ratio of the particle size of 0.972 μm or more in the volume distribution of the colorant particles Pv (%) was measured again and evaluated by taking a ratio between the value and the value immediately after production, and was ranked as follows, and Δ or more was regarded as acceptable. Desirably, it is more than ○.
A: Increase ratio is less than 1.2 times (reaggregation property is very small)
○: Increase ratio is 1.2 times or more and less than 2 times (reaggregation property is small)
Δ: Increase ratio is 2 times or more and less than 3 times.
×: Increase ratio is 3 times or more (high re-aggregation property and unbearable)

[Thermal properties of wax]
Measured by using DSC model 120 manufactured by Seiko Denshi Co., Ltd. according to JIS K7121, with a sample amount of 10 mg, raising the temperature in the range of 5 to 120 ° C. at 10 ° C./min, and then lowering (cooling) at 10 ° C./min. did. From the figure when the horizontal axis is the temperature and the vertical axis is the heat balance, the measurement was performed according to the following criteria.
(1) Melting point: Peak temperature of melting peak (° C)
(2) Half-width of melting peak: Peak width (° C) at half the position of the melting peak height
(3) Heat of fusion: calculated from the area of the melting peak (J / g)
(4) Half width of crystallization peak: Peak width (° C.) at the position of half the cooling crystallization peak height

[Surface tension of wax]
Measurement was performed by a contact angle method using Zisman-plot using four liquids of tetrachloroethane, 1-methylnaphthalene, diiodomethane, and α-bromonaphthalene. [Toner particle size distribution]
Multisizer II described in the text was measured.
[Toner insoluble in THF (THF)]
1 g of sample was added to 50 g of THF, and allowed to stand at 25 ° C. for 24 hours. The mixture was filtered with 10 g of Celite through a glass filter (11GP100 manufactured by SIBATA). The amount insoluble in THF was calculated by subtracting from the above.

[Peak molecular weight of toner solubles in THF]
It measured using HLC-8120 described in the text using the filtrate in the above-mentioned THF insoluble matter measurement.
[Glass Transition Temperature (Tg) of Toner]
It was measured by DSC7 manufactured by PerkinElmer. The temperature was raised from 30 ° C. to 100 ° C. in 7 minutes, rapidly cooled from 100 ° C. to −20 ° C., the temperature was raised from −20 ° C. to 100 ° C. in 12 minutes, and Tg observed at the second temperature rise. The value of was used.

[Softening point of toner (Sp)]
Using a flow tester (CFT-500, manufactured by Shimadzu Corporation), a sample of about 1 g was heated to a rate of temperature increase of 3 ° C./min. 30 kg / c with a 1 cm ² plunger while heating
Applying a load of m2 and extruding from a die with a hole diameter of 1 mm and length of 10 mm, this draws a plunger stroke-temperature curve, and when the height of the S-curve is h, the temperature corresponding to h / 2 is softened Points.
[Average circularity of toner]
Measured with FPIA-2100 described in the text.

[transparency]
For magenta, cyan, and yellow toners, a solid toner image (toner adhesion amount of about 0.6 mg / cm ² ) on the OHP sheet is silicone-coated using the same fixing roller as that measured for the fixing temperature range. After fixing under the conditions of no application of oil, fixing speed of 30 mm / second, and 180 ° C., a spectrophotometer (U-3210, manufactured by Hitachi, Ltd.) was used.
The transmittance is measured in the wavelength range of m, and the difference between the transmittance at the wavelength with the highest transmittance (maximum transmittance (%)) and the transmittance at the wavelength with the lowest transmittance (minimum transmittance (%)). Transparency was evaluated using (maximum transmittance−minimum transmittance) as a value. If the transmittance was 65% or more, the transparency was judged good.

[Live-action evaluation]
Using a non-magnetic one-component contact development type full-color printer (ColorPage PrestoN4 manufactured by Casio Co., Ltd.), up to 6000 sheets were repeatedly photographed, and single-color image evaluation and full-color image evaluation were performed.

[Toner charge amount]
The toner is put into a developing tank of a non-magnetic one-component developing device (ColorPagePrestoN4 developing tank manufactured by Casio Co., Ltd.). Model 210HS), the toner on the roller was sucked onto a filter paper (Whatman Grade 1), and the charge amount per unit weight of toner was determined from the displayed capacitance and the toner weight on the sucked filter paper.

[Evaluation of image density and fog]
The image density was measured with a reflection spectral densitometer (X-rite 504, manufactured by SDG Co., Ltd.) for the solid portion of the print sample obtained in the actual image evaluation. The image density is preferably within 0.15, more preferably within 0.10, during the actual shooting. If the change in image density exceeds 0.15, an uncomfortable feeling (overdeveloped or insufficient) of the image is felt, which is not preferable. For the fog, a colorimeter (ZE2000, manufactured by Nippon Denshoku Co., Ltd.) was used, and the difference in Hunter whiteness shown below was measured for the paper before and after the live action. The fog is preferably within 1.5, more preferably within 1.0 throughout the live action. If the fog exceeds 1.5, the sharpness of the image becomes inferior.
Hunter whiteness W (L * a * b *) = 100 − [(100−L *) ² + a * ² + b * ² ] ^1/2

"Method for producing toner for developing electrostatic image"
<Preparation of wax dispersion A>
Alkyl-modified silicone wax (thermal characteristics: melting point 77 ° C., heat of fusion 97 J / g, melting peak half-width 10.9 ° C., crystallization peak half-width 17.0 ° C.) 30 parts, anionic surfactant (Daiichi Kogyo Seiyaku) 0.3 parts of Neogen SC) and 70 parts of demineralized water were heated to 90 ° C. and stirred with a disperser for 10 minutes. Next, this dispersion was heated to 100 ° C., emulsification was started under a pressure condition of about 15 MPa using a homogenizer (manufactured by Gorin Co., Ltd., 15-M-8PA type), and the volume average particle diameter was measured while measuring with a particle size distribution meter. Was dispersed to about 0.2 μm to prepare a wax dispersion A.

<Preparation of wax dispersion B>
Paraffin wax (Nippon Seiki Co., Ltd. HNP-9, surface tension 23.5 mN / m, melting point 82 ° C., heat of fusion 220 J / g, melting peak half width 8.2 ° C., crystallization peak half width 13.0 ° C.) Except for the use, a wax dispersion C for test toner production was prepared by dispersing to an average particle size of 0.2 μm in the same manner as in the preparation of the wax dispersion A.

<Preparation of Colorant Dispersion A>
Carbon black produced by a furnace method in which a toluene extract has an ultraviolet absorbance of 0.02 and a true density of 1.8 g / cm ³ in a container of a stirrer equipped with a propeller blade (manufactured by Mitsubishi Chemical Corporation, Mitsubishi Carbon Black) MA100S) 20 parts, anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen S-20A) 1 part, nonionic surfactant (Kao Co., Ltd., Emulgen 120) 4 parts, ion with conductivity 2 μS / cm 75 parts of exchange water was added and predispersed to obtain a pigment premix solution. The volume cumulative 50% diameter Dv50 of carbon black in the dispersion after premixing was about 90 μm. The premix solution was supplied as a raw material slurry to a wet bead mill as shown in FIG. 1, and one-pass dispersion was performed with the configuration shown in FIG. Note that zirconia beads (true density 6.0 g / cm ³ ) having a diameter of 120 mmφ, a separator having a diameter of 60 mmφ, and a diameter of 50 μm were used as a dispersion medium. Since the effective internal volume of the stator is about 2 liters and the media filling volume is 1.4 liters, the media filling rate is 70%. When the rotational speed of the rotor is constant (the peripheral speed at the tip of the rotor is about 11 m / sec), the premix slurry is supplied from the supply port by a non-pulsating metering pump at a supply speed of about 40 liters / hr, and reaches a predetermined particle size. The product was acquired from the outlet. During operation, cooling was performed while circulating cooling water at about 10 ° C. from the jacket to obtain a black colorant dispersion A. A summary of the manufacturing conditions is shown in Table 1, and the volume particle size distribution and characteristics of the particles measured by UPA are shown in Table 2.

<Preparation of Colorant Dispersions B and C>
In the adjustment of the colorant dispersion A, black colorant dispersions B and C were obtained in the same manner as in the preparation of the colorant dispersion A, except that the media diameters used were 30 μm and 90 μm. A summary of the manufacturing conditions is shown in Table 1, and the volume particle size distribution and characteristics of the particles measured by UPA are shown in Table 2.

<Preparation of Colorant Dispersion D (Comparison)>
In the preparation of the colorant dispersion A, a black colorant dispersion D was obtained in the same manner as the preparation of the colorant dispersion A, except that the diameter of the medium used was 120 μm. A summary of the manufacturing conditions is shown in Table 1, and the volume particle size distribution and characteristics of the particles measured by UPA are shown in Table 2.

<Preparation of Colorant Dispersion E (Comparison)>
In the preparation of the colorant dispersion A, a black colorant dispersion E was obtained in the same manner as in the preparation of the colorant dispersion A, except that the media diameter used was 300 μm. A summary of the manufacturing conditions is shown in Table 1, and the volume particle size distribution and characteristics of the particles measured by UPA are shown in Table 2.

<Preparation of Colorant Dispersion F>
In the adjustment of the colorant dispersion A, except that the conductivity of the ion-exchanged water used is adjusted to 12 μS / cm, and the volume cumulative 50% diameter Dv50 of the particles in the dispersion after premixing is about 90 μm. In the same manner as in the preparation of the colorant dispersion A, a black colorant dispersion F was obtained. A summary of the manufacturing conditions is shown in Table 1, and the volume particle size distribution and characteristics of the particles measured by UPA are shown in Table 2.

<Preparation of Colorant Dispersion G>
In the preparation of the colorant dispersion A, as the carbon black to be used, carbon black produced by a furnace method with a toluene extract having an ultraviolet absorbance of 0.08 and a true density of 1.8 g / cm ³ (manufactured by Degussa) The black colorant dispersion G was prepared in the same manner as the colorant dispersion A except that 20 parts of PrinteX 350) and the volume cumulative 50% diameter Dv50 of the particles in the dispersion after premixing were about 90 μm. Obtained. A summary of the manufacturing conditions is shown in Table 1, and the volume particle size distribution and characteristics of the particles measured by UPA are shown in Table 2.

<Preparation of Colorant Dispersion H>
In a stirrer vessel equipped with a propeller blade, a quinacridone pigment having a true density of 1.5 g / cm ³ was obtained.
I. Pigment Red 122 (Clariant Japan, Hostaperm Pink E-WD) 20 parts, Anionic surfactant (Daiichi Kogyo Seiyaku, Neogen S-20A) 1 part, Nonionic surfactant (Kao Corporation, Emulgen) 120) 4 parts and 75 parts of ion-exchanged water having a conductivity of 2 μS / cm were added and predispersed to obtain a pigment premix solution. The volume cumulative 50% diameter Dv50 of the particles in the dispersion after premixing was about 90 μm. The premix solution was supplied as a raw material slurry to a wet bead mill as shown in FIG. 1, and circulated and dispersed in the configuration shown in FIG. Note that zirconia beads (true density 6.0 g / cm ³ ) having a diameter of 120 mmφ, a separator having a diameter of 60 mmφ, and a diameter of 50 μm were used as a dispersion medium. Since the effective internal volume of the stator is about 2 liters and the media filling volume is 1.4 liters, the media filling rate is 70%. When the rotational speed of the rotor is constant (the peripheral speed at the tip of the rotor is about 11 m / sec), the premix slurry is supplied from the supply port by a non-pulsating metering pump at a supply speed of about 40 liters / hr, and reaches a predetermined particle size. The product was acquired at. During operation, cooling water at about 10 ° C. was circulated from the jacket to obtain a magenta colorant dispersion H. A summary of the manufacturing conditions is shown in Table 1, and the volume particle size distribution and characteristics of the particles measured by UPA are shown in Table 2.

<Preparation of Colorant Dispersion I>
In the preparation of the colorant dispersion H, a magenta colorant dispersion I is obtained in the same manner as the preparation of the colorant dispersion H, except that the slurry is circulated and ground using a medium having a diameter of 30 μm. It was. A summary of the manufacturing conditions is shown in Table 1, and the volume particle size distribution and characteristics of the particles measured by UPA are shown in Table 2.

<Preparation of Colorant Dispersion J (Comparison)>
In the preparation of the colorant dispersion H, a magenta colorant dispersion J is obtained in the same manner as the preparation of the colorant dispersion H, except that the slurry is circulated and ground using a medium having a diameter of 120 μm. It was. A summary of the manufacturing conditions is shown in Table 1, and the volume particle size distribution and characteristics of the particles measured by UPA are shown in Table 2.

<Preparation of Colorant Dispersion K (Comparison)>
In the preparation of the colorant dispersion H, the magenta colorant dispersion K was prepared in the same manner as the preparation of the colorant dispersion H except that the premix slurry was supplied at a supply rate of about 3 liters / hr and circulated and ground. Got. A summary of the manufacturing conditions is shown in Table 1, and the volume particle size distribution and characteristics of the particles measured by UPA are shown in Table 2.

<Preparation of Colorant Dispersion L (Comparative)>
In the preparation of the colorant dispersion H, the magenta colorant dispersion L was prepared in the same manner as the preparation of the colorant dispersion H except that the premix slurry was supplied at a supply rate of about 55 liters / hr and circulated and ground. Got. A summary of the manufacturing conditions is shown in Table 1, and the volume particle size distribution and characteristics of the particles measured by UPA are shown in Table 2.

<Preparation of Colorant Dispersion M>
Quinacridone pigments in the preparation of colorant dispersion H, C. the true density 1.6 g / cm ³ I
. Pigment Blue 15: 3 (manufactured by Clariant Japan, Hostaperm Blue B2G) and similar to the preparation of the colorant dispersion H except that the volume cumulative 50% diameter Dv50 of the particles in the dispersion after premixing is about 90 μm Thus, a cyan colorant dispersion M was obtained. A summary of the manufacturing conditions is shown in Table 1, and the volume particle size distribution and characteristics of the particles measured by UPA are shown in Table 2.

<Preparation of Colorant Dispersion N>
Quinacridone pigments in the preparation of colorant dispersion H, C. the true density 1.5 g / cm ³ I
. Pigment Yellow 93 (manufactured by Nagase Sangyo Co., Ltd., Chrophtal Yellow 3G) A yellow colorant dispersion N was obtained. A summary of the manufacturing conditions is shown in Table 1, and the volume particle size distribution and characteristics of the particles measured by UPA are shown in Table 2.

<Preparation of Colorant Dispersions O and P (Comparison)>
In the preparation of the colorant dispersion H, a homogenizer (manufactured by Ishii Rika Kikai Seisakusho Co., Ltd., Polytron homogenizer model PT2100 / DA2120 / 2) is used in place of the wet mill. The homogenizer shaft was put into a container containing 300 ml, and the rotor in the shaft was rotated at a high speed at a peripheral speed of 20 m / sec for dispersion for 10 minutes. Subsequently, using a pressure homogenizer (manufactured by SMT Co., Ltd., model LAB1000), the treatment pressure was about 49 MPa, the dispersion time was 30 minutes and 60 minutes, respectively, and magenta colorant dispersions O and P were obtained. A summary of the manufacturing conditions is shown in Table 1, and the volume particle size distribution and characteristics of the particles measured by UPA are shown in Table 2.

<Production of polymer primary particle emulsion A>
In a reactor equipped with a stirrer, a heating / cooling device, and a concentrating device, 365 parts of demineralized water and 45 parts of wax dispersion A were placed and heated to 90 ° C. While maintaining the reaction solution at 90 ° C. under a nitrogen stream, the following raw material mixture was added to the reactor over 5 hours, and emulsion copolymerization was performed using wax particles as seeds. Next, the mixture was cooled to obtain a milky polymer primary particle emulsion A (solid content of about 19% by weight) of a styrene-butyl acrylate-acrylic acid copolymer.
When the volume average particle diameter of the binder resin fine particles contained in the obtained emulsion was measured by UPA, the volume average particle diameter (arithmetic average diameter based on volume) was 0.26 μm. The emulsion polymer thus obtained had a weight-average molecular weight of about 83,000, a number-average molecular weight of 19,000, a peak molecular weight of about 43,000, and a THF-insoluble content of 26% by weight. , Sp was 114 ° C., Tg was 56 ° C., and the acid value was 9 mgKOH / g.

[Raw material mixture]
Styrene 79 parts by weight Butyl acrylate 21 parts by weight Acrylic acid 3 parts by weight 1,6-hexanediol diacrylate 0.7 parts by weight Trichlorobromomethane (chain transfer agent) 1.3 parts by weight 10% anionic surfactant (neogen) SC) Aqueous solution 12 parts by weight 8% hydrogen peroxide aqueous solution 43 parts by weight 8% ascorbic acid aqueous solution 43 parts by weight

<Production of polymer primary particle emulsion B>
In the production of the polymer primary particle emulsion A, a milky polymer primary particle emulsion B is obtained in exactly the same manner as in the production of the polymer primary particle emulsion A except that the wax dispersion used is changed to the wax dispersion B. It was.
When the volume average particle diameter of the binder resin fine particles contained in the obtained emulsion was measured by UPA, the volume average particle diameter (arithmetic average diameter based on volume) was 0.20 μm. In addition, the weight average molecular weight of the THF-soluble component of the obtained emulsion polymer is about 90,000, the number average molecular weight is 20,000, the peak molecular weight is about 41,000, and the THF-insoluble content is 25% by weight. , Sp was 116 ° C., Tg was 58 ° C., and the acid value was 9 mgKOH / g.

[Example 1]
<Manufacture of Black Toner B1>
(1) To 100 parts of the polymer primary particle emulsion A, 6 parts of the colorant dispersion A is added, and an aqueous aluminum sulfate solution (0.5 part as aluminum sulfate) is added dropwise with stirring with a disperser. The temperature was raised to 50 ° C. over 30 minutes and held for 1 hour, and further aggregated by raising the temperature to 52 ° C. with stirring. When the volume average particle size as an aggregate was about 7 μm as measured by Multisizer II, 3 parts of an anionic surfactant (Neogen SC) 10% aqueous solution was added.
(2) Subsequently, 10 styrene / butyl acrylate polymer fine particles A (Tg 80 ° C., volume average particle size 0.14 μm measured by UPA) (resin solid content 20 wt%) as encapsulated resin fine particles 10 Part was added.
(3) Subsequently, the temperature is raised to 97 ° C. over 50 minutes with stirring, and the aggregate and the encapsulated resin fine particles adhering to the surface are fused by maintaining at this temperature for 1.5 hours. Got. In addition, when the thickness of the capsule layer was measured from the cross-sectional photograph of this mother particle (cross-sectional photograph taken with a transmission electron microscope microscope Hitachi H7500 system), the average was about 0.1 μm.
0.5 parts of silica fine particles A having an average primary particle size of 50 nm hydrophobized with dimethyl silicone oil and an average primary particle size hydrophobized with dimethyl silicone oil with respect to 100 parts of the obtained black toner base particles Then, 2.0 parts of 12 nm silica fine particles B were added, warm water at 45 ° C. was passed through the outer jacket, and the mixture was stirred and mixed with a temperature-controlled Henschel mixer to obtain black toner B1. A summary of the toner composition is shown in Table 3, and a summary of various physical properties is shown in Table 4.

<Image evaluation>
After the black toner B1 is filled in the black position developer of the tandem full color printer (ColorPagePresto N4, manufactured by Casio Co., Ltd.), which is a contact type non-magnetic one-component developing method, a black single color image is continuously formed by a full-face character pattern of 5% solid part. Images were evaluated after forming about 6,000 times. The evaluation was performed at normal temperature and humidity (25 ° C., 55% RH, hereinafter referred to as NN environment).
As a result, from the initial stage up to 6,000 sheets, there was no change in image density, fogging, resolution, etc., and good image quality and a clear black color image were obtained. During this time, there was no image contamination due to photoconductor filming or internal contamination due to a decrease in toner charge, no toner fusion to the developing roller or blade, and good mechanical durability. Further, when the charge amount of the real toner was measured, the initial -16 μC / g was stable with little change to -15 μC / g even after 6,000 sheets.
After that, the above-mentioned image evaluation was performed in an environmental test room set in a high-temperature and high-humidity environment (35 ° C., 85% RH, hereinafter referred to as HH environment). Results were obtained. The toner charge amount in a high-temperature and high-humidity environment was initially -14 μC / g, and remained stable with little change at −12 μC even after 6,000 sheets. The evaluation results are summarized in Table 5.

[Examples 2 to 4]
In Example 1, except that the polymer primary particles and the colorant dispersion are changed to those shown in Table 3, toner mother particles are obtained in exactly the same manner as in Example 1, and hereinafter, the toner mother particles are obtained in exactly the same manner as in Example 1. Then, black toners B2 to B4 were obtained. Table 4 shows the measurement results of various physical properties of the toner. The evaluation was performed in exactly the same manner as in Example 1, and Table 5 shows the results of toner evaluation. As a result, from the initial stage up to 6,000 sheets, there was no change in image density, fogging, resolution, etc., and good image quality and a clear black color image were obtained. During this time, there was no image contamination due to photoconductor filming or internal contamination due to a decrease in toner charge, no toner fusion to the developing roller or blade, and good mechanical durability.

[Comparative Examples 1-2]
In Example 1, toner base particles were obtained in exactly the same manner as in Example 1 except that the polymer primary particles and the colorant dispersion were changed to those shown in Table 3. The black toners B5 and B6 were obtained respectively. Table 4 shows the measurement results of various physical properties of the toner. The evaluation was performed in exactly the same manner as in Example 1, and Table 5 shows the results of toner evaluation. As a result, image density change and fog increase were recognized in the latter half of the NN life, and the image quality was unusable. In addition, a decrease in charge amount was observed particularly with HH.

[Examples 5 to 6]
In Example 1, toner base particles were obtained in exactly the same manner as in Example 1 except that the polymer primary particles and the colorant dispersion were changed to those shown in Table 3, and the following steps were followed in exactly the same way as in Example 1. Then, black toners B7 and B8 were obtained, respectively. Table 4 shows the measurement results of various physical properties of the toner. The evaluation was performed in exactly the same manner as in Example 1, and Table 5 shows the results of toner evaluation. As a result, although within the practical range, a slight change in image density and an increase in fog were observed in the latter half of the NN life.

[Examples 7 to 8]
In Example 1, toner base particles were obtained in exactly the same manner as in Example 1 except that the polymer primary particles and the colorant dispersion were changed to those shown in Table 3, and the following steps were followed in exactly the same way as in Example 1. Addition was performed to obtain magenta toners M1 and M2, respectively. Table 4 shows the measurement results of various physical properties of the toner. The evaluation was performed in exactly the same manner as in Example 1, and Table 5 shows the results of toner evaluation. As a result, from the initial stage up to 6,000 sheets, there was no change in image density, fogging, resolution, etc., and a good magenta color image with good image quality was obtained. During this time, there was no image contamination due to photoconductor filming or internal contamination due to a decrease in toner charge, no toner fusion to the developing roller or blade, and good mechanical durability. Transparency was also good.

[Comparative Example 3]
In Example 1, except that the polymer primary particles and the colorant dispersion are changed to those shown in Table 3, toner mother particles are obtained in exactly the same manner as in Example 1, and hereinafter, the toner mother particles are obtained in exactly the same manner as in Example 1. Then, magenta toner M3 was obtained. Table 4 shows the measurement results of various physical properties of the toner. The evaluation was performed in exactly the same manner as in Example 1, and Table 5 shows the results of toner evaluation. As a result, image density change and fog increase were recognized in the latter half of the NN life, and the image quality was unusable. In addition, a decrease in charge amount was observed particularly with HH.

[Examples 9 to 10]
In Example 1, except that the polymer primary particles and the colorant dispersion are changed to those shown in Table 3, toner mother particles are obtained in exactly the same manner as in Example 1, and hereinafter, the toner mother particles are obtained in exactly the same manner as in Example 1. Addition was performed to obtain magenta toners M4 and M5, respectively. Table 4 shows the measurement results of various physical properties of the toner. The evaluation was performed in exactly the same manner as in Example 1, and Table 5 shows the results of toner evaluation. As a result, although within the practical range, a slight change in image density and an increase in fog were observed in the latter half of the NN life.

[Example 11]
In Example 1, toner base particles were obtained in exactly the same manner as in Example 1 except that the polymer primary particles and the colorant dispersion were changed to those shown in Table 3, and the following steps were followed in exactly the same way as in Example 1. Then, cyan toner C1 was obtained. Table 4 shows the measurement results of various physical properties of the toner. The evaluation was performed in exactly the same manner as in Example 1, and Table 5 shows the results of toner evaluation. As a result, from the initial stage up to 6,000 sheets, there was no change in image density, fogging, resolution, etc., and a good magenta color image with good image quality was obtained. During this time, there was no image contamination due to photoconductor filming or internal contamination due to a decrease in toner charge, no toner fusion to the developing roller or blade, and good mechanical durability. Transparency was also good.

[Example 12]
In Example 1, toner base particles were obtained in exactly the same manner as in Example 1 except that the polymer primary particles and the colorant dispersion were changed to those shown in Table 3, and the following steps were followed in exactly the same way as in Example 1. Then, yellow toner Y1 was obtained. Table 4 shows the measurement results of various physical properties of the toner. The evaluation was performed in exactly the same manner as in Example 1, and Table 5 shows the results of toner evaluation. As a result, from the initial stage up to 6,000 sheets, there was no change in image density, fogging, resolution, etc., and a good magenta color image with good image quality was obtained. During this time, there was no image contamination due to photoconductor filming or internal contamination due to a decrease in toner charge, no toner fusion to the developing roller or blade, and good mechanical durability. Transparency was also good.
The toner was not fused to the toner, and the mechanical durability was good. Transparency was also good.

[Comparative Examples 4 to 5]
In Example 1, toner base particles were obtained in exactly the same manner as in Example 1 except that the polymer primary particles and the colorant dispersion were changed to those shown in Table 3, and the following steps were followed in exactly the same way as in Example 1. Then, magenta toners M6 to M7 were obtained. Table 4 shows the measurement results of various physical properties of the toner. The evaluation was performed in exactly the same manner as in Example 1, and Table 5 shows the results of toner evaluation. As a result, image density change and fog increase were recognized in the latter half of the NN life, and the image quality was unusable. In addition, a decrease in charge amount was observed particularly with HH.

[Example 13]
In the contact type non-magnetic one-component developing tandem type full-color printer (ColorPagePresto N4 manufactured by Casio), black toner B1 is developed in the black position developing device, magenta toner M1 is developed in the magenta position developing device, and cyan toner C1 is developed in the cyan position developing device. The yellow position developing unit is filled with yellow toner Y1, and a full color image is continuously formed about 200 times by the pattern of identification number N5 defined in JIS X9201: 2001 (high definition color digital standard image). Evaluated.

  As a result, from the initial stage to 200 sheets, the image quality was good, such as good image density, fog, and resolution, and a clear full-color image was exhibited. In the meantime, there was no image contamination due to photoconductor filming or internal contamination due to a decrease in toner charge, no toner fusion to the developing roller or blade of the non-magnetic one-component developing machine, and the mechanical durability was good. The evaluation was performed at normal temperature and humidity (25 ° C., 55% RH, hereinafter referred to as NN environment).

It is a longitudinal cross-sectional view which shows an example of the wet mill (bead mill) used for this invention. It is the schematic which shows an example of the one-pass dispersion processing cycle of the coloring agent dispersion by the wet mill in connection with this invention. It is the schematic which shows an example of the circulation dispersion processing cycle of the coloring agent dispersion by the wet mill in connection with this invention.

Explanation of symbols

1 Raw material tank
2 Raw material pump
3 Wet mill (bead mill)
4 rotating screen
5 Shaft
6 Jacket 7 Stator 8 Discharge path
9 Rotor
10 Raw material slurry supply port
11 Raw material slurry inlet
12 Valve
13 Valve 14 Valve 15 Valve
16 Product tank

Claims (35)

A colorant dispersion comprising at least a wet dispersion medium and colorant particles, and a volume cumulative average diameter Dv50 (μm) of the colorant particles in the colorant dispersion measured by a dynamic light scattering method is represented by the following formula (1). And the volume particle size distribution width index SD of the colorant particles in the colorant dispersion satisfies the following formula (2).
Formula (1) 0.10 <Dv50 <0.30
Formula (2) 0.030 <SD <0.090
(However, Dv50 represents the particle size (μm) at which the volume particle size distribution cumulative curve of the colorant particles is 50%, and SD is the particle size at which the volume particle size distribution cumulative curve of the colorant particles is 84%. When (μm) is Dv84 and the particle size (μm) at the point of 16% is Dv16, SD = (Dv84−Dv16) / 2, and the volume cumulative distribution is the smaller particle size side of the volume particle size distribution. To be accumulated) 2. The colorant dispersion according to claim 1, wherein the volume particle size distribution of the colorant particles in the colorant dispersion satisfies the following formula (3).
Formula (3) 0.10 <Dv50 <0.25 3. The colorant dispersion according to claim 1, wherein the volume particle size distribution of the colorant particles in the colorant dispersion satisfies the following formula (4).
Formula (4) 0.040 <SD <0.085 A colorant dispersion comprising at least a wet dispersion medium and colorant particles, and a volume particle size distribution of the colorant particles in the colorant dispersion measured by a dynamic light scattering method is represented by the following formulas (5) and (6: ) And (7).
Formula (5) 0.10 <Dv50 <0.30
Formula (6) 1.0 <(Dv50 / Dv10) / (Dv90 / Dv50) <1.3
Formula (7) 0 <Pv <2
(However, Dv50 represents the volume cumulative distribution 50% diameter (μm) of the colorant particles, Dv10 represents the volume cumulative distribution 10% diameter (μm) of the colorant particles, and Dv90 represents the volume cumulative distribution 90% of the colorant particles. (Pv represents a ratio (%) of the particle size of 0.972 μm or more in the volume distribution of the colorant particles, and the volume cumulative distribution is accumulated from the small particle size side of the volume particle size distribution) 2. The colorant dispersion according to claim 1, wherein the volume particle size distribution of the colorant particles in the colorant dispersion satisfies the following formula (8).
Formula (8) 0.10 <Dv50 <0.25 3. The colorant dispersion according to claim 1, wherein the volume particle size distribution of the colorant particles in the colorant dispersion satisfies the following formula (9).
Formula (9) 1.0 <(Dv50 / Dv10) / (Dv90 / Dv50) <1.2 The colorant dispersion according to any one of claims 1 to 3, wherein the volume particle size distribution of the colorant particles in the colorant dispersion satisfies the following formula (10).
Formula (10) 0 <Pv <1   The colorant dispersion according to any one of claims 1 to 7, wherein the wet dispersion medium is water containing a surfactant.   The colorant dispersion according to any one of claims 1 to 8, wherein the colorant particles are quinacridone pigments.   The colorant particles are C.I. I. The colorant dispersion according to claim 9, wherein the colorant dispersion is a pigment classified into Pigment Red 122.   A method for producing a colorant dispersion comprising at least a wet dispersion medium and colorant particles, a cylindrical stator, a colorant dispersion supply port provided at one end of the stator, and a colorant dispersion discharge port, A rotor that stirs and mixes the medium filled in the stator and the colorant dispersion supplied from the supply port, and is connected to a discharge path inlet that communicates with the discharge port and rotates integrally with the rotor, or Using a wet mill consisting of a separator that rotates independently and separates into a medium and a colorant dispersion by the action of centrifugal force and a screen structure, and discharges the colorant dispersion from the discharge port. A method for producing a colorant dispersion, wherein the diameter Dm is less than 100 μm. The volume cumulative average diameter Dv50 (μm) of the colorant particles in the colorant dispersion measured by the dynamic light scattering method satisfies the following formula (11), and the volume of the colorant particles in the colorant dispersion: The method for producing a colorant dispersion according to claim 11, wherein the particle size distribution width index SD satisfies the following formula (12).
Formula (11) 0.10 <Dv50 <0.30
Formula (12) 0.030 <SD <0.090
(However, Dv50 represents the particle size (μm) at which the volume particle size distribution cumulative curve of the colorant particles is 50%, and SD is the particle size at which the volume particle size distribution cumulative curve of the colorant particles is 84%. When (μm) is Dv84 and the particle size (μm) at the point of 16% is Dv16, SD = (Dv84−Dv16) / 2, and the volume cumulative distribution is the smaller particle size side of the volume particle size distribution. To be accumulated) The method for producing a colorant dispersion according to claim 12, wherein the volume particle size distribution of the colorant particles in the colorant dispersion satisfies the following formula (13).
Formula (13) 0.10 <Dv50 <0.25 The method for producing a colorant dispersion according to any one of claims 12 and 13, wherein the volume particle size distribution of the colorant particles in the colorant dispersion satisfies the following formula (14).
Formula (14) 0.040 <SD <0.085 The volume particle size distribution of the colorant particles in the colorant dispersion measured by a dynamic light scattering method satisfies the following formulas (15), (16), and (17). A method for producing a colorant dispersion.
Formula (15) 0.10 <Dv50 <0.30
Formula (16) 1.0 <(Dv50 / Dv10) / (Dv90 / Dv50) <1.3
Formula (17) 0 <Pv <3
(However, Dv50 represents the volume cumulative distribution 50% diameter (μm) of the colorant particles, Dv10 represents the volume cumulative distribution 10% diameter (μm) of the colorant particles, and Dv90 represents the volume cumulative distribution 90% of the colorant particles. (Pv represents a ratio (%) of the particle size of 0.972 μm or more in the volume distribution of the colorant particles, and the volume cumulative distribution is accumulated from the small particle size side of the volume particle size distribution) The method for producing a colorant dispersion according to claim 15, wherein the volume particle size distribution of the colorant particles in the colorant dispersion satisfies the following formula (18).
Formula (18) 0.10 <Dv50 <0.25 The method for producing a colorant dispersion according to any one of claims 15 and 16, wherein the volume particle size distribution of the colorant particles in the colorant dispersion satisfies the following formula (19).
Formula (19) 1.0 <(Dv50 / Dv10) / (Dv90 / Dv50) <1.2 The method for producing a colorant dispersion according to any one of claims 15 to 17, wherein the volume particle size distribution of the colorant particles in the colorant dispersion satisfies the following formula (20).
Formula (20) 0 <Pv <2 The method for producing a colorant dispersion according to claim 11, wherein the following formula (21) is satisfied when the colorant dispersion is supplied to a supply port of the wet mill.
Formula (21) 10 ≦ V / M ≦ 200
(Where V represents the supply rate of the colorant dispersion (liter / hr), and M represents the effective internal volume (liter) of the stator of the wet mill)   The method for producing a colorant dispersion according to any one of claims 11 to 19, wherein the wet dispersion medium is water containing a surfactant. The method for producing a colorant dispersion according to any one of claims 11 to 20, wherein the true density of the colorant particles is less than 2.0 g / cm ³ .   The method for producing a colorant dispersion according to any one of claims 11 to 21, wherein the colorant particles are quinacridone pigments.   The colorant particles are C.I. I. The method for producing a colorant dispersion according to claim 22, wherein the pigment is classified into Pigment Red 122.   The method for producing a colorant dispersion according to any one of claims 11 to 23, wherein a diameter of the medium is 10 to 90 µm. The method for producing a colorant dispersion according to any one of claims 11 to 24, wherein the material of the medium is ZrO ₂ . An aggregating step in which at least one resin particle dispersion, at least one colorant dispersion, and an aggregating agent are mixed and added to form aggregated particles, and the glass particles are heated to a temperature higher than the glass transition point. And a fusion process of fusing the aggregated particles to form toner particles, wherein the colored body dispersion comprises at least a wet dispersion medium and colorant particles, and dynamic light. The volume cumulative average diameter Dv50 (μm) of the colorant particles in the colorant dispersion measured by the scattering method satisfies the following formula (22), and the volume particle size distribution width of the colorant particles in the colorant dispersion: A method for producing a toner for developing an electrostatic charge image, wherein the index SD satisfies the following formula (23).
Formula (22) 0.10 <Dv50 <0.30
Formula (23) 0.030 <SD <0.090
(However, Dv50 represents the particle size (μm) at which the volume particle size distribution cumulative curve of the colorant particles is 50%, and SD is the particle size at which the volume particle size distribution cumulative curve of the colorant particles is 84%. When (μm) is Dv84 and the particle size (μm) at the point of 16% is Dv16, SD = (Dv84−Dv16) / 2, and the volume cumulative distribution is the smaller particle size side of the volume particle size distribution. To be accumulated) 27. The method for producing a toner for developing an electrostatic charge image according to claim 26, wherein the volume particle size distribution of the colorant particles in the colorant dispersion satisfies the following formula (24).
Formula (24) 0.10 <Dv50 <0.25 28. The method for producing a toner for developing an electrostatic charge image according to claim 26, wherein the volume particle size distribution of the colorant particles in the colorant dispersion satisfies the following formula (25).
Formula (25) 0.040 <SD <0.085 An agglomeration step in which at least one resin particle dispersion, at least one colorant dispersion, and an aggregating agent are mixed and added to form aggregated particles; And a fusion process of fusing the aggregated particles to form toner particles, wherein the colored body dispersion comprises at least a wet dispersion medium and colorant particles, and dynamic light. Production of an electrostatic charge image developing toner, wherein the volume particle size distribution of the colorant particles in the colorant dispersion measured by a scattering method satisfies the following formulas (26), (27) and (28): Method.
Formula (26) 0.10 <Dv50 <0.30
Formula (27) 1.0 <(Dv50 / Dv10) / (Dv90 / Dv50) <1.3
Formula (28) 0 <Pv <3
(However, Dv50 represents the volume cumulative distribution 50% diameter (μm) of the colorant particles, Dv10 represents the volume cumulative distribution 10% diameter (μm) of the colorant particles, and Dv90 represents the volume cumulative distribution 90% of the colorant particles. (Pv represents a ratio (%) of the particle size of 0.972 μm or more in the volume distribution of the colorant particles, and the volume cumulative distribution is accumulated from the small particle size side of the volume particle size distribution) 30. The method for producing a toner for developing an electrostatic charge image according to claim 29, wherein the volume particle size distribution of the colorant particles in the colorant dispersion satisfies the following formula (29).
Formula (29) 0.10 <Dv50 <0.25 31. The method for producing a toner for developing an electrostatic charge image according to claim 29, wherein the volume particle size distribution of the colorant particles in the colorant dispersion satisfies the following formula (30).
Formula (30) 1.0 <(Dv50 / Dv10) / (Dv90 / Dv50) <1.2 32. The method for producing an electrostatic charge image developing toner according to claim 29, wherein the volume particle size distribution of the colorant particles in the colorant dispersion satisfies the following formula (31).
Formula (31) 0 <Pv <2   33. The method for producing a toner for developing an electrostatic charge image according to claim 26, wherein the colorant dispersion contains at least water, a surfactant, and colorant particles.   34. The method for producing a toner for developing an electrostatic charge image according to any one of claims 26 to 33, wherein the colorant particles are quinacridone pigments.   The colorant particles are C.I. I. 35. The method for producing a toner for developing an electrostatic charge image according to claim 34, wherein the pigment is a pigment classified as Pigment Red 122.

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