JP2013214086A - Toner for electrostatic charge image development, image forming device, and toner cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that is capable of suppressing toner consumption to improve image quality, prevents poor cleaning, solves the problem of fogging after a long-term use even when used in a high-speed printer, and has excellent image stability; an image forming apparatus; and a toner cartridge.SOLUTION: A toner contains a charge control agent, and satisfies all of the following conditions (1) to (3): (1) the volume median diameter of the toner (Dv50) is 4.0 μm or more and 7.5 μm or less; (2) a relationship between the volume median diameter of the toner (Dv50) and the number% of a toner having a particle diameter range of 2.00 μm or more and 3.56 μm or less (Dns) satisfies Dns≤0.233EXP(17.3/Dv50); and (3) the average dispersion diameter of the charge control agent contained in the toner is 500 nm or less.

Description

  The present invention relates to an electrostatic charge image developing toner, an image forming apparatus, and a toner cartridge used for electrophotography, electrostatic photography and the like.

  In recent years, the use of image forming apparatuses such as electrophotographic copying machines has been expanded, and the market demand for image quality has been increasing. In particular, in office documents, in addition to the development of mapping technology and latent image forming technology for input, the types of character hieroglyphics are more abundant and finer at the time of output. Due to the spread and development, the reproducibility of a latent image with extremely high image quality that has few defects and unclearness in printed images is required. In particular, as a developer used in the case where the electrostatic latent image on the latent image carrier constituting the image forming apparatus is a line image of 100 μm or less (approximately 300 dpi or more), a conventional toner having a large particle diameter has fine line reproducibility. In general, the line image is not clear enough.

  In particular, in an image forming apparatus such as an electrophotographic printer using a digital image signal, a latent image is formed by gathering a certain number of dot units, and the solid portion, the halftone portion, and the light portion have different dot densities. It is expressed by However, if the toner is not arranged faithfully in the dot unit and the mismatch between the position of the dot unit and the position of the actually placed toner occurs, this corresponds to the ratio of the dot density of the black portion and the white portion of the digital latent image. There is a problem that the gradation of the toner image cannot be obtained. Furthermore, when the resolution is improved by reducing the dot size in order to improve the image quality, a phenomenon faithful to the latent image formed from the minute dots becomes more difficult, and the resolution is high and the gradation is poor. There is no denying the tendency for images to lack sharpness.

  In view of this, there has been proposed a device intended to improve the image quality by improving the reproducibility of minute dots by regulating the particle size distribution of the developer. Patent Document 1 proposes a toner having an average particle size of 6 to 8 μm, and attempts to form a latent image of fine dots with high reproducibility by reducing the particle size. Patent Document 2 discloses a toner base particle containing a toner having a weight average particle diameter of 4 to 8 μm and further containing 17 to 60% by weight of toner base particles having a particle diameter of 5 μm or less. Patent Document 3 discloses a magnetic toner containing 17 to 60% by number of magnetic toner base particles having a particle size of 5 μm or less. Patent Document 4 discloses toner base particles in which the content of toner base particles having a particle size of 2.0 to 4.0 μm is 15 to 40% by number in the toner particle size distribution. Further, Patent Document 5 describes a toner in which particles of 5 μm or less are about 15 to 65% by number. Further, Patent Documents 6 and 7 disclose similar toners. Further, Patent Document 8 contains 17 to 60% by number of toner base particles having a particle size of 5 μm or less, 1 to 30% by number of toner base particles having a particle size of 8 to 12.7 μm, and 16 μm or more. A toner having a specific particle size distribution in a toner having a volume average particle diameter of 4 to 10 μm and a toner having a specific particle size distribution is described. Further, in Patent Document 9, in the toner particles having a 50% volume particle diameter of 2 to 8 μm, the number of toner particles having a particle diameter of “0.7 × 50% number particle diameter” or less is 10 number% or less. Is described.

However, all of these toners contain a large number of particles having a particle size of 3.56 μm or less exceeding the upper limit of the right side in (2) of the present invention. The relative relationship is that the toner has a relatively large proportion of fine powder remaining in the toner having a predetermined particle size. In such a toner, since the ratio of fine powder is still large, particles that are not sufficiently charged are developed in a developing method that requires a toner having a fast charge rising, such as a non-magnetic one-component developing method that is charged instantly with friction. Occurs, the toner drops from the developing roller, the toner blows out, the printing history of the first round after the second round of the developing roller, and the afterimage (ghost) in which the image density selectively rises and falls, the drum cleaning failure, the development Problems remain such as contamination of the printed image due to poor toner layer formation on the roller.

  In recent years, life expectancy and high-speed printing have been demanded along with market demand for image quality. However, these required characteristics have not been sufficiently satisfied with the conventional toner. If there is a lot of fine powder like conventional toner, the fine powder will contaminate the member with continuous printing, the charge imparting ability to the toner will be reduced and the image will be distorted, and if it is introduced into a high speed printer, toner scattering will be noticeable There were also challenges.

  Also, in order to provide high image printing, the toner particle size distribution needs to be sharp. This is because when the coarse particles are contained, the toner charge amount distribution becomes broad and a phenomenon called “selective development” occurs. “Selective development” is a phenomenon in which, when the toner charge amount distribution is broad, only toner having a charge amount necessary for development is developed and consumed during copying. Therefore, a good image can be obtained at the beginning of copying, but the density gradually decreases as copying continues, or the toner particle size increases and the image becomes gritty.

  This phenomenon is said to be inferior in selective developability. Furthermore, the coarse powder having a low charge amount tends to significantly reduce the guaranteed life number. Patent Document 10 discloses a toner having a large number of coarse powders having a number variation coefficient of 24.2%. Such a toner is not suitable for stably providing a high-resolution image. Further, Patent Document 11 does not indicate that the particle size distribution is sharp.

  Furthermore, it is necessary to pay attention to toner transfer characteristics in order to provide high-quality printing. The toner having high transfer characteristics refers to toner in which toner particles latently imaged on the photoreceptor have high transfer efficiency from the intermediate transfer drum or paper, or from the intermediate transfer drum to paper. Patent Documents 12 to 14 disclose pulverized toner that does not have a high average circularity from the viewpoint of the manufacturing process, which is insufficient to provide high-quality printing.

JP-A-2-284158 JP-A-5-119530 JP-A-1-221755 JP-A-6-289648 JP 2001-134005 A Japanese Patent Laid-Open No. 11-147331 Japanese Patent Laid-Open No. 2001-175024 JP-A-2-000877 JP 2004-045948 A JP 2003-255567 A WO2004-088431 JP-A-7-98521 JP 2006-91175 A JP 2006-119616 A

  In addition, in order to stably supply a high-resolution image, it is necessary to have excellent charging characteristics, and a technique for incorporating a charge control agent into the toner is known. It was difficult to incorporate the technology.

  The present invention has been made in view of the above-described background art, and its problem is to suppress stains, afterimages (ghosts), blurring (solid followability), etc. of the white background of the image due to the presence of fine powder having a specific particle size or less. However, it is to provide a toner that can improve image quality, has good cleaning properties, improves problems such as dirt during long-term use, and has excellent image stability even when a high-speed printer is used. .

  Another object of the present invention is to provide a toner that can prevent “selective development” and stably form a high-resolution image. Furthermore, another object is to provide an image forming apparatus using the toner and a toner cartridge.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved when a specific relational expression is satisfied with respect to the toner particle diameter, and the present invention has been completed.
That is, the present invention is as follows.
(1) A toner for developing an electrostatic charge image, which contains a charge control agent and satisfies all of the following (a) to (c):
(A) The volume median diameter (Dv50) is 4.0 μm or more and 7.5 μm or less.
(B) The relationship between the volume median diameter (Dv50) of toner and the number% (Dns) of toner having a particle diameter of 2.00 μm to 3.56 μm satisfies Dns ≦ 0.233EXP (17.3 / Dv50).
(C) The average dispersion diameter of the contained charge control agent is 500 nm or less.
(2) A toner for developing an electrostatic charge image, which contains a charge control agent and satisfies all of the following (d) to (f).
(D) The volume median diameter (Dv50) is 4.0 μm or more and 7.5 μm or less.
(E) The relationship between the volume median diameter (Dv50) of toner and the number% (Dns) of toner having a particle size of 2.00 μm to 3.56 μm satisfies Dns ≦ 0.233EXP (17.3 / Dv50).
(F) The average diameter of the recess when the charge control agent on the toner surface is removed is 500 nm or less.
(3) The relationship between the volume median diameter (Dv50) of toner and the number% (Dns) of toner having a particle diameter of 2.00 μm to 3.56 μm satisfies Dns ≦ 0.11EXP (19.9 / Dv50). The toner for developing an electrostatic image according to (1) or (2) above, wherein
(4) The relationship between the volume median diameter (Dv50) of the toner and the number% (Dns) of the toner having a particle diameter of 2.00 μm to 3.56 μm satisfies 0.0517EXP (22.4 / Dv50) ≦ Dns. The toner for developing an electrostatic image according to (1) or (2) above, wherein
(5) The toner for developing an electrostatic charge image according to any one of (1) to (3), wherein the volume median diameter (Dv50) of the toner is 5.0 μm or more.
(6) The static as described in any one of (1) to (4) above, wherein the number% (Dns) of toner having a particle size of 2.00 μm to 3.56 μm is 6% or less. Toner for charge image development.
(7) The toner for developing an electrostatic charge image according to any one of (1) to (5), wherein the toner has an average circularity of 0.93 or more.
(8) The toner for developing an electrostatic charge image according to any one of (1) to (6), wherein the number variation coefficient of the toner is 24.0% or less.
(9) The electrostatic image developing toner according to any one of (1) to (7), wherein the charge control agent is present near the surface.
(10) In the above (1) to (8), the charge control agent exists in a range of ± R centering on the toner surface, where R is the average diameter of the dent when the charge control agent is removed. The toner for developing an electrostatic charge image according to any one of the above items.
(11) The toner for developing an electrostatic charge image according to any one of (1) to (9), wherein the toner is obtained by forming particles in an aqueous medium.
(11) The toner for developing an electrostatic charge image according to any one of (1) to (10), wherein the toner is produced by an emulsion polymerization aggregation method.
(12) The toner for developing an electrostatic charge image according to any one of (1) to (11), wherein the toner is obtained by fixing or adhering resin fine particles to core particles.
(13) The core particles are composed of at least polymer primary particles, and the ratio of the total amount of polar monomers in 100% by mass of all polymerizable monomers constituting the binder resin as the resin fine particles is the core particles. The electrostatic charge image development as described in (11) above, which is smaller than the ratio of the total amount of polar monomers in 100% by mass of all polymerizable monomers constituting the binder resin as the polymer primary particles constituting Toner.
(14) The electrostatic image according to any one of (1) to (13), wherein the wax is contained in an amount of 4 to 20 parts by weight with respect to 100 parts by weight of the electrostatic image developing toner. Development toner.
(15) The electrostatic charge image developing device as described in any one of (1) to (14) above, which is used in an image forming apparatus having a developing process speed of 100 mm / second or more on a latent image carrier. toner.
(16) The electrostatic image developing toner according to any one of (1) to (15), which is used in an image forming apparatus that satisfies the following formula (g).
(G) Guaranteed lifetime number of sheets (sheets) x printing rate ≧ 400 (sheets) of a developer filled with developer
(16) The electrostatic image developing toner according to any one of (1) to (15), which is used in an image forming apparatus having a resolution of 600 dpi or more on a latent image carrier.
(17) The toner according to any one of (1) to (16), which is obtained without a step of removing particles having a volume median diameter (Dv50) or less of the toner. Toner for developing electrostatic images.
(18) An image forming apparatus comprising a toner containing a charge control agent and satisfying all of the following (a) to (c):
(A) The volume median diameter (Dv50) is 4.0 μm or more and 7.5 μm or less.
(B) The relationship between the volume median diameter (Dv50) of toner and the number% (Dns) of toner having a particle diameter of 2.00 μm to 3.56 μm satisfies Dns ≦ 0.233EXP (17.3 / Dv50).
(C) The average dispersion diameter of the contained charge control agent is 500 nm or less.
(19) An image forming apparatus comprising a toner containing a charge control agent and satisfying all of the following (d) to (f):
(D) The volume median diameter (Dv50) is 4.0 μm or more and 7.5 μm or less.
(E) The relationship between the volume median diameter (Dv50) of toner and the number% (Dns) of toner having a particle size of 2.00 μm to 3.56 μm satisfies Dns ≦ 0.233EXP (17.3 / Dv50).
(F) The average diameter of the recess when the charge control agent on the toner surface is removed is 500 nm or less.
(20) A toner cartridge comprising a toner containing a charge control agent and satisfying all of the following (a) to (c):
(A) The volume median diameter (Dv50) is 4.0 μm or more and 7.5 μm or less.
(B) The relationship between the volume median diameter (Dv50) of toner and the number% (Dns) of toner having a particle diameter of 2.00 μm to 3.56 μm satisfies Dns ≦ 0.233EXP (17.3 / Dv50).
(C) The average dispersion diameter of the contained charge control agent is 500 nm or less.
(21) A toner cartridge comprising a toner containing a charge control agent and satisfying all of the following (d) to (f):
(D) The volume median diameter (Dv50) is 4.0 μm or more and 7.5 μm or less.
(E) The relationship between the volume median diameter (Dv50) of toner and the number% (Dns) of toner having a particle size of 2.00 μm to 3.56 μm satisfies Dns ≦ 0.233EXP (17.3 / Dv50).
(F) The average diameter of the recess when the charge control agent on the toner surface is removed is 500 nm or less.

  According to the present invention, the toner is excellent in the rising of charge, suppresses the occurrence of stains and afterimages (ghosts) on the white background of the image, hardly causes the above problems even during long-term use, and supplies toner with excellent image stability. can do. In addition, even during image formation by a high-speed printing method that has been developed in recent years, the toner particle size distribution is narrow, and even if the toner particle size is reduced, the amount of fine powder is small, so the toner powder filling rate, that is, the bulk density is improved. To do. Along with this, the air content intervening in the gap between the toner base particles is reduced, so that the heat insulation effect by the air is reduced, so that the heat conduction is improved and the fixing property by heating is improved. Guessed.

  Further, “selective development” can be prevented, and a high-resolution image can be stably provided even in long-term printing. In addition, it has excellent transfer characteristics, and it is possible to prevent in-machine contamination.

FIG. 2 is a schematic diagram illustrating an example of a non-magnetic one-component toner developing device using the toner of the present invention. FIG. 2 is a schematic diagram illustrating an example of an image forming apparatus that employs a tandem method, a belt conveyance method, and a direct transfer method using the toner of the present invention.

Hereinafter, the present invention will be described. However, the present invention is not limited to the following embodiments, and can be arbitrarily modified and implemented.
The toner for developing an electrostatic image of the present invention (hereinafter sometimes abbreviated as “toner”) is a toner containing a charge control agent and satisfies all of the following (1) to (3).
(1) The volume median diameter (Dv50) is 4.0 μm or more and 7.5 μm or less.
(2) The relationship between the volume median diameter (Dv50) of toner and the number% (Dns) of toner having a particle diameter of 2.00 μm to 3.56 μm satisfies Dns ≦ 0.233EXP (17.3 / Dv50).
(3) The average dispersion diameter of the contained charge control agent is 500 nm or less.

The electrostatic image developing toner of the present invention (hereinafter sometimes abbreviated as “toner”) is a toner containing a charge control agent and satisfies all of the following (4) to (6). .
(4) The volume median diameter (Dv50) is 4.0 μm or more and 7.5 μm or less.
(5) The relationship between the volume median diameter (Dv50) of toner and the number% (Dns) of toner having a particle diameter of 2.00 μm to 3.56 μm satisfies Dns ≦ 0.233EXP (17.3 / Dv50).
(6) The average diameter of the dent when the charge control agent on the toner surface is removed is 500 nm or less.

About (1) and (4) The volume median diameter (Dv50) of the toner is measured by the method described in the Examples and is defined as that measured. When the toner of the present invention has an external additive fixed or adhered to the surface of the toner base particles, it is measured as a measurement sample. Similarly, the average circularity, the number% (Dns) of toner having a particle size of 2.00 μm to 3.56 μm, and the number variation coefficient, which will be described later, are similarly fixed or adhered to the surface of the toner base particles. If it is a sample, measure it as a measurement sample.

  The Dv50 of the toner of the present invention is 4.0 μm or more and 7.5 μm or less. Within this range, a high-quality image can be sufficiently provided. In order to give a high-quality image, the effect is more remarkable when it is 7.0 μm or less, and it is more preferably 6.8 μm or less. Moreover, it is preferable that it is 4.5 micrometers or more from a viewpoint of reducing the generation amount of a fine powder, It is still more preferable that it is 5.0 micrometers or more, It is especially more preferable that it is 5.3 micrometers or more.

Regarding (2) and (5) The number% (Dns) of the toner having a particle diameter of 2.00 μm or more and 3.56 μm or less of the toner is measured by the method described in the examples, and is defined as that measured. The In the toner of the present invention, the relationship between the volume median diameter (Dv50) of toner and the number% (Dns) of toner having a particle diameter of 2.00 μm to 3.56 μm is Dns ≦ 0.233EXP (17.3 / Dv50). ) In the present invention, “EXP” indicates “Exponential”. That is, the base of the natural logarithm, and the right side is the exponent.

  The purpose of this relational expression is that the amount of fine powder increases as the volume median diameter (Dv) of the toner decreases, and when the Dv is 4.5 μm or less, the value of Dv becomes the particle size. In order to approach the region of 2.00 μm or more and 3.56 μm or less, the value of Dns increases exponentially. Such an area of 2.00 μm or more and 3.56 μm or less is an area expressed by a specified channel of Multisizer III manufactured by Coulter Counter.

  In the present invention, the particles included in the particle diameter range of 2.00 μm to 3.56 μm is a particle size region that should be specifically excluded in the region of the volume median diameter of toner particles of 4.0 to 7.5 μm. The basis for this follows experimental results. The toner of the present invention satisfying the condition (3) of the particle size distribution provides high image quality, and is less contaminated even when a high-speed printer is used, and afterimage (ghost) and blur (solid followability). And has excellent cleaning properties. In addition, since the charge amount distribution is very sharp because the particle size distribution is sharp, particles with a small charge amount do not cause the white background portion of the image to be smeared or scattered to stain the inside of the apparatus, Particles having a large charge amount do not develop and do not adhere to members such as a layer regulating blade or a roller and cause image defects such as streaks and blurring.

That is, the amount of fine powder affects the image with the above relational expression as a boundary. When the value of Dns exceeds the right side, the fine powder causes a defect in the image.
Since the image forming apparatus is designed to transfer particles having a specific charge amount, first, the particles having the specific charge amount are preferentially transferred to the OPC during electrostatic development. The particles exceeding the specific charge amount adhere to a member or the like and are contaminated or fluidity is deteriorated. On the other hand, particles that do not satisfy a specific charge amount accumulate in the cartridge and contaminate members and the like.

  Here, the toner charge amount correlates with the particle size of the toner when the toner composition is the same. Generally, the smaller the particle size, the higher the charge amount per unit weight, and the larger the charge amount, the smaller the charge amount per unit weight. Become. That is, if there is a large amount of toner having a small particle size, the charge amount becomes too high, and this causes adhesion to a member or the like and deterioration of toner fluidity. In the present invention, this toner is specified to be 3.56 μm or less. This 3.56 μm is a value defined for the channel of the measuring apparatus. On the other hand, the lower limit value was set to 2.00 μm because of the measurement limit of the measuring apparatus.

In addition, a toner in which the relationship between Dv50 and Dns satisfies Dns ≦ 0.110EXP (19.9 / Dv50) is preferable. On the other hand, from the viewpoint of producing with high yield, Dv50
And Dns preferably satisfy the relationship 0.0517EXP (22.4 / Dv50) ≦ Dns.
Further, a toner having a Dns of 6% by number or less is preferable in that it provides a higher quality image and hardly contaminates the image forming apparatus. Further, it is more preferable that the above-mentioned preferable particle diameter range of Dv50, for example, the conditions “Dv50 is 4.5 μm or more” and “Dns is 6% by number or less” are satisfied in combination. Within this range, it is possible to provide a high-quality image or to provide a toner that hardly contaminates the image forming apparatus without reducing the yield from the viewpoint of production.

(3) The toner of the present invention is a toner containing a charge control agent. The average dispersion diameter of the charge control agent contained in the toner is, for example, in the case of a pulverized toner obtained by mixing the charge control agent with a resin and pulverizing to obtain a toner, according to a TEM photograph of the finally obtained toner. It can be obtained from image analysis.
In addition, toner obtained by forming particles in an aqueous medium, for example, a polymerized toner, is contained in a dispersion of a charge control agent that is added before, during, or after polymerization of constituent monomers. The average dispersion diameter of the charge control agent may be regarded as the average dispersion diameter of the charge control agent contained in the toner.

(6) In the toner of the present invention containing a charge control agent, the charge control agent is preferably present in the vicinity of the toner surface.
The depression when the charge control agent on the toner surface is removed can be obtained, for example, by removing the charge control agent on the toner surface and analyzing the surface by image analysis using an SEM photograph.

  As the charge control agent contained in the toner of the present invention, conventionally known compounds are used. 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. In the case where the toner is obtained by forming particles in an aqueous medium, it is preferable that the toner does not dissolve in the aqueous medium. This is because when the toner into which water is dissolved is used in a high-humidity environment, the charge control agent dissolves in water condensed on the toner surface and peels off from the surface, thereby hindering the effect of improving toner charging. . For example, as an insoluble in an aqueous medium, E-81, 84, 88, 108, S-28, 34 manufactured by Orient Chemical Industries, TN-105, T-77 manufactured by Hodogaya Chemical Co., Ltd., and Clariant Japan N4P, N5P, etc. are mentioned. In addition, a charge control resin whose main component is formed of a resin is known as a known charge control agent. Examples of the resin include a styrene acrylic polymer and a condensation polymer. These resins have a high affinity with the binder resin forming the toner, and the probability of being distributed inside the toner is increased. As a result, exposure to the toner surface is reduced. That is, there is a high possibility that the charge control agent cannot be contributed to the charge as compared with the charge control agent described above. Therefore, the charge control agent is preferably used rather than the charge control resin for charging the toner.

The content of the charge control agent is preferably in the range of 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, and still more preferably 0.2 to 1 part by weight with respect to 100 parts by weight of the resin. . When the content is within the above range, the rising of charging is excellent, and it becomes possible to control image defects such as image contamination and afterimage.
In the toner of the present invention, the average dispersion diameter of the charge control agent contained is 500 nm or less. When the amount exceeds the above range, the amount to be contained in the toner is limited, and improvement in charging characteristics by the charge control agent is not expected. Furthermore, since the surface area per unit volume is small, the influence on charging is small, which is not preferable. In particular, the above-described influence becomes large in a toner having a small particle diameter. Further, the upper limit value of the average dispersion diameter of the contained charge control agent is preferably 400 nm or less, more preferably 300 nm or less, and most preferably 200 nm or less. On the other hand, the lower limit is preferably 50 nm or more from an industrial standpoint.

By the way, in the case where the charge control agent is to be contained in the toner by a normal method, for example, when the toner is obtained by a pulverization method, it is difficult to finely disperse the charge control agent due to the characteristics of the manufacturing process, and usually 500 nm. That's it.
In addition, when a toner is obtained by a method of forming particles in an aqueous medium, it is necessary to add an essential additive to the toner such as a colorant, but it is also possible to include a charge control agent. This is not usually done because it complicates the process and makes it difficult to control the particle size of the toner. In particular, in the toner satisfying the above (1) and (2) or (4) and (5), the charge control agent is not actively included in order to reduce the fine powder as much as possible. .

In the toner of the present invention, the charge control agent is present near the toner surface. When the charge control agent on the toner surface is removed, the size of the depression on the toner surface where the charge control agent is present depends on the diameter of the charge control agent contained, but is preferably 500 nm or less. When the amount exceeds the above range, the amount to be contained in the toner is limited, and improvement in charging characteristics by the charge control agent is not expected.
It can be considered that the depression after the charge control agent is removed from the toner surface directly reflects the average diameter of the charge control agent fixed on the toner surface. That is, if only the charge control agent is dissolved and the charge control agent is removed using a solvent that is not compatible with the resin and hardly swells, the indentation diameter is considered to be close to the introduced average diameter of the charge control agent. It is done. This average diameter is not necessarily the same as the dispersion diameter of the charge control agent in the dispersion medium. This is because the dispersed charge control agent may aggregate and be introduced into the toner as it is under the conditions such as the stirring state, salt concentration, and temperature at the time of introduction into the toner. However, when the aggregation becomes intense, the adhesion to the toner surface is suppressed, the amount to be contained in the toner is limited, and the improvement of the charging characteristics by the charge control agent is not expected. Furthermore, since the surface area per unit volume is small, the influence on charging is small, which is not preferable. In particular, the above-described influence becomes large in a toner having a small particle diameter.

  It is essential that the toner of the present invention satisfies all of the above (1) to (3) or (4) to (6). Conventional toners do not satisfy any of (1) to (3) or (4) to (6). The reason is that it is difficult to reduce the amount of fine powder as much as possible (satisfy (2) and (5)) as the toner particles become smaller (satisfy (1) and (4)). In addition, it is more difficult to contain the charge control agent. The present invention is a toner that satisfies (1), (4), (2), and (5), and that effectively contains a charge control agent. This is made possible by setting the average diameter of the dents to 500 nm or less when dispersed or when the charge control agent on the toner surface is removed.

  The toner of the present invention can obtain high image quality, and even when a high-speed printing machine is used, there is little contamination and it is possible to suppress an afterimage (ghost). In addition, since the charge amount distribution becomes very sharp because the particle size distribution is sharp, particles with a small charge amount do not cause the white background portion of the image to be smeared or scattered to contaminate the inside of the apparatus, Particles having a large charge amount do not develop and do not adhere to members such as a layer regulating blade or a roller and cause image defects such as streaks and blurring.

The toner of the present invention has a very sharp charge amount distribution as compared with conventional toners. The charge amount distribution has a correlation with the particle size distribution of the toner. When the toner has a broad particle size distribution like a conventional toner, the charge amount distribution is also broad. When the charge amount distribution becomes broad, the ratio of particles with low charge or particles with high charge that cannot be controlled by the developing conditions of the toner device increases, causing various image defects. For example, particles with a small charge amount cause stains on the white background of the image or scatter in the apparatus, and particles with a large charge amount are not developed and are layer regulating blades in the developing tank. And accumulated in members such as rollers and cause image defects such as streaks and fading due to fusion.

  In the development process design in the image forming apparatus, the development process conditions are set so as to conform to the average value of the toner charge amount. The apparatus causes image defects such as scattering, streaks, and fading, and the matching with the apparatus is not good. On the other hand, if the charge amount distribution is sharp as in the present invention, the developability can be controlled by bias adjustment or the like, and a clear image can be given without contaminating the members of the image forming apparatus. is there.

  In the present invention, the charge control agent is preferably present in the vicinity of the surface. This is because the charging characteristics of the toner are affected by the composition and shape of the surface. As a method for causing the charge control agent to be present in the vicinity of the surface, a method in which the charge control agent is applied and fixed to the surface of the toner particles may be used. However, the aqueous medium is advantageous in that the charge control agent can be uniformly present in the vicinity of the surface. Among them, it is preferable to fix the toner particles on the surface. In particular, the emulsion polymerization agglomeration method is a preferable method in the toner production method of the present invention because it easily exists in the vicinity of the surface uniformly due to the characteristics of the production process.

  Furthermore, in the present invention, it is preferable that the charge control agent is present in a range of ± R centering on the toner surface, where R is the average diameter of the dent when the charge control agent is removed. When the charge control agent is exposed on the toner surface, the function of the charge control agent is expressed. As the toner charging mechanism, an electron movement model, an ion movement model, a water bridge model, and the like have been proposed, and these are publicly known. The former two are known to be electrons and mass transfer phenomenon due to contact between the toner and other substances, and the latter is known to be a phenomenon involving water on the toner surface. For this reason, it is extremely important to distribute and expose the charge control agent on the toner surface, and the present toner production method in which the charge control agent is actually distributed in the vicinity of the surface is more advantageous than other methods.

That is, when the charge control agent is present on the toner surface from the toner surface to the inside of the toner, it means that the charge control agent is not exposed on the toner surface and the contribution to the toner charge control is lost. It is not preferable.
The average circularity of the toner is measured by the method described in Examples and is defined as the value measured as such. The average circularity of the toner of the present invention is preferably 0.93 or more, and more preferably 0.94 or more. In general, toner with a high degree of circularity has good transfer efficiency. Spherical toner having a high degree of circularity is less likely to get caught between toners or various members, so that the mechanical share of the charging roller is small, and the shape change of the surface is slight. Further, since the fluidity of the toner base itself is high, even if the amount of the externally added inorganic powder changes, the fluidity hardly changes greatly. As described above, the spherical toner has a form factor with less toner deterioration. Furthermore, since the release property from the photosensitive drum is excellent, the transfer efficiency is excellent, so that a sufficient image density can be ensured and the transfer residual toner can be reduced. For these reasons, it is desirable to use toner having a high degree of circularity as the toner used in the high-speed printer.

However, toner having a high average circularity tends to increase the weakly charged toner ratio WST [%] measured by the E-SPART analyzer, and toner scattering may be deteriorated. Further, when the transfer residual toner is scraped off by the cleaning blade, the cleaning blade can be easily passed through, which causes the image to become dirty. In the case of high-speed printing, the effect becomes more remarkable. Therefore, the average circularity of the toner of the present invention is preferably 0.98 or less, more preferably 0.96 or less.

In addition, toner with a small particle size and high circularity is difficult to scrape off with a cleaning blade, and the toner can easily pass through the cleaning blade. Therefore, the particle size distribution should be controlled according to the circularity. Is important.
The number variation coefficient (%) is measured by the method described in the examples and is defined as that measured. The toner of the present invention preferably has a number variation coefficient of 24.0% or less, more preferably 22%, still more preferably 20% or less, and most preferably 19% or less. When the value of the number variation coefficient is high, the distribution of the charge amount becomes broad, and an image defect is caused from a charging failure. Furthermore, contamination due to adhesion to the toner member or the like and contamination due to scattering are induced. Therefore, it is preferable that the number variation coefficient is low. On the other hand, from an industrial standpoint, the number variation coefficient is preferably 0% or more, and more preferably 5% or more.

Since the toner of the present invention has a sharp charge amount distribution, the contamination (toner scattering) in the image forming apparatus caused by poorly charged toner is very small. This effect is remarkably exhibited particularly in a high-speed type image forming apparatus in which the development process speed for the electrostatic latent image carrier is 100 mm / second or more.
Further, since the toner of the present invention has a sharp charge amount distribution, the developability is very good, and there are very few toner particles that accumulate without being developed. The effect is exhibited in the apparatus. Specifically, a toner used in an image forming apparatus that satisfies the following formula (7) is preferable in order to sufficiently exhibit the above-described effects of the present invention.
(7) Guaranteed lifetime number of sheets (sheets) x printing rate ≥ 500 (sheets) of the developer filled with developer
In equation (7), “printing rate” is represented by a value obtained by dividing the sum of the printed portion areas by the total area of the printing medium in a printed matter for determining the guaranteed number of sheets that is the performance of the image forming apparatus. The “print rate” of the print% of “5%” is “0.05”.

Furthermore, since the toner of the present invention has a very sharp particle size distribution, the latent image reproducibility is very good. Therefore, the effect of the present invention is sufficiently exerted particularly when used in an image forming apparatus having a resolution of 600 dpi or more for the electrostatic latent image carrier.
The image forming apparatus and the toner cartridge of the present invention are characterized by using toner that satisfies all of the above (1) to (3) or (4) to (6). By using such a toner, a high-resolution image can be provided.

<Configuration of toner>
The toner of the present invention is constituted by appropriately selecting a binder resin, a colorant, a wax, an external additive, and the like.
The binder resin constituting the toner of the present invention may be appropriately selected from those known to be usable for toner. For example, styrene resin, vinyl chloride resin, rosin modified maleic acid resin, phenol resin, epoxy resin, saturated or unsaturated polyester resin, polyethylene resin, polypropylene resin, ionomer resin, polyurethane resin, silicone resin, ketone resin, Ethylene-acrylate copolymer, xylene resin, polyvinyl butyral resin, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-anhydrous malein An acid copolymer etc. can be mentioned. These resins can be used alone or in combination.

The colorant constituting the toner of the present invention may be appropriately selected from those known to be usable for toner. For example, yellow pigments, magenta pigments, and cyan pigments shown below can be used. As black pigments, carbon black or a mixture of the following yellow pigments / magenta pigments / cyan pigments toned to black is 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. The degree of reagglomeration of carbon black particles correlates with the amount of impurities contained in carbon black (the degree of residual undecomposed organic matter). If there are many impurities, coarsening due to reaggregation after dispersion tends to be severe. showed that. 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. Thereafter, the filtrate was put in a quartz cell having a 1 cm square light absorption part, and the value (λs) measured for absorbance at a wavelength of 336 nm using a commercially available ultraviolet spectrophotometer, and the value obtained by measuring the absorbance of toluene alone as a reference using the same method. From (λo), the ultraviolet absorbance is obtained by λc = 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, 194, 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, 17.3, 184, 185, 202, 206, 207, 209, 220, 221, 238, 254, 269, 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. Among the quinacridone pigments, C.I. I. A compound represented by CI Pigment Red 122 is particularly preferable.

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 toner of the present invention preferably contains a wax for imparting releasability. Any wax can be used as long as it has releasability, and is not particularly limited. Specifically, olefin waxes such as low molecular weight polyethylene, low molecular weight polypropylene, and copolymer polyethylene; paraffin wax; ester waxes having a long-chain aliphatic group such as behenyl behenate, montanate ester, stearyl stearate; water Plant waxes such as soy castor oil and 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 pentaerythritol Examples include carboxylic acid esters or partial esters of polyhydric alcohols obtained from polyhydric alcohols such as polyhydric alcohols and long chain fatty acids; higher fatty acid amides such as oleic acid amides and stearic acid amides; low molecular weight polyesters and the like.

  In order to improve the fixability among these waxes, the melting point of the wax is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and particularly preferably 50 ° C. or higher. 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. Furthermore, as the wax compound species, ester waxes obtained from aliphatic carboxylic acids and mono- or polyhydric alcohols are preferred, and ester waxes having 20 to 100 carbon atoms are preferred.

  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 preferably 4 to 20 parts by weight, particularly preferably 6 to 18 parts by weight, and more preferably 8 to 15 parts by weight with respect to 100 parts by weight of the toner. In addition, when the volume median diameter (Dv50) of the toner is 7 μm or less, that is, when the toner has a small particle diameter, the exposure of the wax to the toner surface becomes extremely intense as the amount of the wax used increases. The storage stability of the toner is deteriorated. The toner of the present invention has a small particle size with a sharp particle size distribution that does not cause deterioration of the toner characteristics as compared with conventional toners even when the amount of wax used is large as in the above range. It is.

  The toner of the present invention may be one in which a known external additive is blended on the surface of the toner base particles in order to control fluidity and developability. External additives include metal oxides and hydroxides such as alumina, silica, titania, zinc oxide, zirconium oxide, cerium oxide, talc and hydrotalcite, titanium such as calcium titanate, strontium titanate and barium titanate. Examples thereof include acid metal salts, nitrides such as titanium nitride and silicon nitride, carbides such as titanium carbide and silicon carbide, and organic particles such as acrylic resins and melamine resins. Among these, silica, titania, and alumina are preferable, and those that have been surface-treated with, for example, a silane coupling agent or silicone oil are more preferable. The average primary particle diameter is preferably in the range of 1 to 500 nm, more preferably in the range of 5 to 100 nm. It is also preferable to use a combination of a small particle size and a large particle size in the particle size range. The total amount of the external additive is preferably in the range of 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the toner base particles.

<Toner production method>
The method for producing the toner of the present invention is not particularly limited. That is, the toner can be produced by a pulverization method or a polymerization method. When a toner is manufactured by a pulverization method, fine particles are generally easily generated, so that a classification step is necessary. However, since the yield is remarkably lowered by an excessive classification operation, such an operation is not performed from an industrial viewpoint. On the other hand, the toner of the present invention preferably forms particles in an aqueous medium from the viewpoint of hardly generating fine powder.

The following describes a method for producing particles by polymerization in an aqueous medium from the viewpoint that fine particles are not easily generated among methods for forming particles in an aqueous medium, and further a method for producing particles by an emulsion polymerization aggregation method. To do.
In order to obtain a toner satisfying the above formulas (2) and (5), it is preferable to employ an operation in which the aggregation speed is not high compared to the operation normally performed in the aggregation step. Examples of operations that do not cause the aggregation speed to be high include, for example, cooling the dispersion to be used in advance, adding the dispersion over time, adopting an electrolyte that does not have a large aggregating action, continuously using the electrolyte, or There are methods such as intermittent addition, slowing the rate of temperature rise, and long aggregation time. In the aging step, it is preferable to adopt an operation in which the aggregated particles are difficult to redisperse. Examples of the operation in which the agglomerated particles are difficult to finely disperse include, for example, a method in which the number of revolutions for stirring is decreased, a dispersion stabilizer is added continuously or intermittently, and a dispersion stabilizer and water are mixed in advance. In addition, the above formulas (2) and (5
The toner satisfying the above) is preferably obtained without the step of removing particles having a volume median diameter (Dv50) or less from the finally obtained toner or toner base particles by an operation such as classification. .

  As a production method for obtaining a toner in an aqueous medium, a method in which radical polymerization is carried out in an aqueous medium such as a suspension polymerization method or an emulsion polymerization aggregation method (hereinafter abbreviated as “polymerization method”), the obtained toner is “polymerized”. (Abbreviated as “toner”), a chemical pulverization method typified by a melt suspension method, and the like can be preferably used. There is no particular limitation on the method for making the toner have a particle size in the specific range of the present invention. For example, in the production process of the polymerized toner, in the case of the suspension polymerization method, a method in which a high shearing force is applied in the process in which polymerizable monomer droplets are generated, or a dispersion stabilizer or the like is increased.

  As a method for obtaining a toner having a particle size in a specific range of the present invention, any of the above-described polymerization methods such as the suspension polymerization method and the emulsion polymerization aggregation method, and the chemical pulverization method represented by the melt suspension method can be used. However, in the “suspension polymerization method” and the “chemical pulverization method represented by the melt suspension method”, in order to adjust the size from a size larger than the particle size of the toner to a smaller size. When trying to reduce the average particle size, the particle size ratio on the small particle side tends to increase, and an excessive burden is imposed in the classification step and the like. In contrast, the emulsion polymerization agglomeration method has a relatively sharp particle size distribution and is adjusted from a size smaller than the particle size of the toner to a larger size. A toner having a distribution is obtained. Therefore, for the above reasons, it is particularly preferable to produce a toner contained in the toner of the present invention by an 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, an aging 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, a charge control agent, and wax, and the primary particles in the dispersion liquid are aggregated to form core particles. Then, if necessary, the toner base particles can be obtained by washing and drying the particles obtained by fusing and adhering the resin fine particles or the like as necessary.

  As the binder resin constituting the polymer primary particles 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 polymerizable monomer having an acidic group” (hereinafter sometimes simply referred to as “acidic monomer”), “a polymerizable monomer having a basic group” (hereinafter simply referred to as “basic monomer”). "Polymerizable monomer having a polar group" (hereinafter sometimes referred to simply as "polar monomer") and "polymerizability having neither an acidic group nor a basic group" It is preferable to use “monomer” (hereinafter sometimes referred to as “other monomer”) as a raw material polymerizable monomer. At this time, each polymerizable monomer may be added separately, or a plurality of polymerizable monomers may be mixed in advance and added simultaneously. Furthermore, it is also possible to change the polymerizable monomer composition during the addition of the polymerizable monomer. Further, the polymerizable monomer may be added as it is, or may be added as an emulsion prepared by mixing with water or an emulsifier in advance.

  Examples of the “acidic monomer” include polymerizable monomers having a carboxyl group such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and cinnamic acid, polymerizable monomers having a sulfonic acid group such as sulfonated styrene, vinyl Examples thereof include polymerizable monomers having a sulfonamide group such as benzenesulfonamide. Examples of the “basic monomer” include aromatic vinyl compounds having an amino group such as aminostyrene, and nitrogen-containing heterocyclic ring-containing polymerizable monomers such as vinylpyridine and vinylpyrrolidone.

These polar 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, and (meth) acrylic acid is more preferable. The proportion of the total amount of polar monomers in 100% by mass of all polymerizable monomers constituting the binder resin as the polymer primary particles is preferably 0.05% by mass or more, more preferably 0.3% by mass or more, and particularly Preferably it is 0.5 mass% or more, More preferably, it is 1 mass% or more. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 2% by mass or less.
When it is in the above range, the dispersion stability of the obtained polymer primary particles is improved, and the particle shape and particle diameter can be easily adjusted in the aggregation step.

  “Other monomers” include styrenes such as styrene, methylstyrene, chlorostyrene, dichlorostyrene, p-tert-butylstyrene, pn-butylstyrene, pn-nonylstyrene, methyl acrylate, acrylic acid Acrylic esters such as ethyl, propyl acrylate, n-butyl acrylate, isobutyl acrylate, hydroxyethyl acrylate, ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methacryl Methacrylates such as isobutyl acid, hydroxyethyl methacrylate, ethylhexyl methacrylate, acrylamide, N-propylacrylamide, N, N-dimethylacrylamide, N, N-dipropylacrylamide, N N- dibutyl acrylamide, acrylic acid amide and the like. A polymerizable monomer may be used independently and may be used in combination of multiple.

  In the present invention, among the above-mentioned polymerizable monomers used in combination, as a preferred embodiment, an acidic monomer and other monomers may be used in combination. More preferably, (meth) acrylic acid is used as the acidic monomer, and a polymerizable monomer selected from styrenes and (meth) acrylic acid esters is used as the other monomer. It is preferable to use (meth) acrylic acid as the monomer, and use a combination of styrene and (meth) acrylic acid esters as the other monomer, and particularly preferably use (meth) acrylic acid as the acidic monomer and other monomers. As a combination of styrene and n-butyl acrylate.

  Furthermore, it is also preferable to use a crosslinked resin as the binder resin constituting the polymer primary particles. In that case, a polyfunctional monomer having radical polymerizability is used as a crosslinking agent shared with the above polymerizable monomer. Examples of the multifunctional monomer include divinylbenzene, hexanediol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol acrylate, diallyl phthalate, and the like. Is mentioned. In addition, a polymerizable monomer having a reactive group in a pendant group such as glycidyl methacrylate, methylol acrylamide, acrolein or the like can be used as a crosslinking agent. Among them, radically polymerizable bifunctional monomers are preferable, and divinylbenzene and hexanediol diacrylate are particularly preferable.

  These crosslinking agents such as 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 crosslinking agent such as a polyfunctional monomer in the total polymerizable monomer constituting the resin is preferably 0.005% by mass or more, More preferably, it is 0.1 mass% or more, More preferably, it is 0.3 mass% or more, Preferably it is 5 mass% or less, More preferably, it is 3 mass% or less, More preferably, it is 1 mass% or less. desirable.

Known emulsifiers can be used for the emulsion polymerization, but one or more emulsifiers selected from cationic surfactants, anionic surfactants and nonionic surfactants are used in combination. be able to.
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 the like.

Examples of the anionic surfactant include fatty acid soaps such as sodium stearate and sodium dodecanoate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, and sodium lauryl sulfate.
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 emulsifier is usually 1 to 10 parts by weight with respect to 100 parts by weight of the polymerizable monomer, and these emulsifiers include, for example, partially or completely saponified polyvinyl alcohol such as saponified polyvinyl alcohol, hydroxy One type or two or more types of cellulose derivatives such as ethyl cellulose can be used in combination as a protective colloid.
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; Azo compounds such as 2′-azobis (2,4-dimethylvaleronitrile); redox initiators and the like are used. One or more of them are usually used in an amount of about 0.1 to 3 parts by weight with respect to 100 parts by weight of the polymerizable monomer. Among them, it is preferable that at least part or all of the initiator is hydrogen peroxide or organic peroxides.

Any of the polymerization initiators may be added to the polymerization system before, simultaneously with, or after the addition of the polymerizable monomer, and these addition methods may be combined as necessary.
In the emulsion polymerization, a known chain transfer agent may 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 a range of 5% by mass or less based on the total polymerizable monomer. Moreover, a pH adjuster, a polymerization degree adjuster, an antifoaming agent, etc. can be further mix | blended with a reaction system suitably.

In the emulsion polymerization, the polymerizable monomer is 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 diameter (Mv) of the polymer primary particles obtained by emulsion polymerization is usually 0.02 μm or more, preferably 0.05 μm or more, more preferably 0.1 μm or more, and usually 3 μm or less, preferably 2 μm or less. More preferably, the thickness is 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 method of the binder resin as the polymer primary particles in the present invention is preferably 40 to 80 ° C, more preferably 55 to 65 ° C. Within this range, the storage stability is good and, in addition, the cohesiveness is not impaired. When Tg is too high, the cohesiveness is poor, and an aggregating agent must be added excessively or the aggregation temperature must be excessively increased. As a result, fine powder may be easily generated. Here, when the Tg of the binder resin overlaps with the caloric change based on other components, for example, the melting peak of polylactone or wax, the toner was prepared in a state in which such other components were excluded. The Tg at the time is meant.

In the present invention, 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 lower limit of the solid content concentration of the polymer primary particles in the “polymer primary particle dispersion” used in the present invention is preferably 14% by mass or more, and more preferably 21% by mass or more. On the other hand, the upper limit is preferably 30% by mass or less, and more preferably 25% by mass or less. When it is within the above range, it is easy to adjust the aggregation speed of the polymer primary particles empirically in the aggregation process, and as a result, the particle diameter, particle shape, and particle size distribution of the core particles can be easily adjusted to an arbitrary range. It becomes.

In the present invention, a dispersion liquid containing polymer primary particles obtained by emulsion polymerization is mixed with a dispersion liquid such as a colorant, a charge control agent, and wax, and the primary particles in the dispersion liquid are aggregated to form core particles. The toner base particles are preferably obtained by washing and drying the particles obtained by fixing or adhering resin fine particles or the like and then fusing them.
The resin fine particles may be produced by the same method as the above polymer primary particles, and the structure thereof is not particularly limited, but the polar monomer occupying in 100% by mass of all polymerizable monomers constituting the binder resin as the resin fine particles The ratio of the total amount is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.2% by mass or more. The upper limit is preferably 3% by mass or less, more preferably 1.5% by mass or less. When it is in the above range, the dispersion stability of the obtained resin fine particles is improved, and it becomes easy to adjust the particle shape and particle diameter in the aggregation process.

  Further, the proportion of the total amount of polar monomers in 100% by mass of the total polymerizable monomer constituting the binder resin as the resin fine particles is in 100% by mass of the total polymerizable monomer constituting the binder resin as the polymer primary particle. It is preferable that the ratio is smaller than the ratio of the total amount of polar monomers in view of easy adjustment of the particle shape and particle diameter in the aggregation process, generation of fine powder can be suppressed, and excellent charging characteristics.

In addition, the Tg of the binder resin as the resin fine particles is preferably higher than the Tg of the binder resin as the polymer primary particles from the viewpoint of storage stability and the like.
The colorant is not particularly limited as long as it is a commonly used colorant. Examples thereof include the pigments described above, carbon black such as furnace black and lamp black, and magnetic colorants. The content of the colorant may be an amount sufficient for the obtained toner to form a visible image by development. For example, the content is preferably in the range of 1 to 25 parts by weight, more preferably 1 to 15 parts by weight, particularly preferably 3 to 12 parts by weight.

The colorant may have magnetism, and examples of the magnetic colorant include a ferromagnetic material that exhibits ferrimagnetism or ferromagnetism in the vicinity of 0 to 60 ° C., which is a use environment temperature of a printer, a copying machine, and the like. Is, for example, magnetite (Fe ₃ O ₄ ), maghemite (γ-Fe ₂ O ₃ ), an intermediate or mixture of magnetite and maghemite, M _x Fe _3-x O ₄ , where M is Mg, Spinel ferrite such as Mn, Fe, Co, Ni, Cu, Zn, Cd, hexagonal ferrite such as BaO.6Fe ₂ O ₃ , SrO.6Fe ₂ O ₃ , Y ₃ Fe ₅ O ₁₂ , Sm ₃ Fe ₅ O garnet-type oxides such as _12, shown rutile oxides such as CrO _2, and, Cr, Mn, Fe, Co, the magnetic near 0 to 60 ° C. of such metal or their ferromagnetic alloys such as Ni Ones, and among them, magnetite, maghemite, or magnetite and maghemite intermediates are preferred.

When it is contained from the viewpoint of scattering prevention, charge control, etc. while having the characteristics as a non-magnetic toner, the content of the magnetic powder in the toner is 0.2 to 10% by mass, preferably 0.5 to 0.5%. It is 8 mass%, More preferably, it is 1-5 mass%. When used as a magnetic toner, the content of the magnetic powder in the toner is usually 15% by mass or more, preferably 20% by mass or more, and usually 70% by mass or less, preferably 60% by mass or less. It is desirable. If the content of the magnetic powder is less than the above range, the magnetic force required for the magnetic toner may not be obtained, and if it exceeds the above range, it may cause poor fixing properties.

  As a blending method of 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. The colorant is preferably used in the state of being emulsified in water by a mechanical means such as a sand mill or a bead mill in the presence of an emulsifier. 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 emulsifier with respect to 100 parts by weight of water. The particle diameter of the colorant in the dispersion is monitored while being dispersed, and the volume average diameter (Mv) is finally adjusted to 0.01 to 3 μm, more preferably 0.05 to It is preferable to control within the range of 0.5 μm. The blend of the colorant dispersion at the time of emulsion aggregation is calculated and used so as to be 2 to 10% by mass in the finished toner base particles after aggregation.

The wax may be contained in the polymer primary particles or in the resin fine particles. However, in general, as the amount of wax used increases, aggregation control tends to deteriorate and the particle size distribution tends to become broader.
Therefore, as a method of blending the wax in the emulsion polymerization aggregation method, a wax dispersion that has been previously emulsified and dispersed in water at a volume average diameter (Mv) of 0.01 to 2.0 μm, more preferably 0.01 to 0.5 μm, is emulsified. It is preferable to add at the time of superposition | polymerization or to add at the aggregation process. 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 wax content in the polymer primary particles is preferably 4 to 30% by mass, more preferably 5 to 20% by mass, and particularly preferably 7 to 15% by mass.

  Also, wax may be contained in the resin fine particles, and in this case as well, it is preferable to add wax as a seed during emulsion polymerization, as in the case of obtaining polymer primary particles. The content ratio of the wax in the entire resin fine particles is preferably smaller than the content ratio of the wax in the entire polymer primary particles. Generally, when wax is contained in resin fine particles, the fixability is improved, but on the other hand, the generation amount of fine powder tends to increase. The reason for this is that the fixability is improved because the speed of movement of the wax to the toner surface is increased when heat is applied, but the inclusion of the wax in the resin fine particles broadens the particle size distribution of the resin fine particles. It is considered that the aggregation control becomes difficult, and as a result, an increase in fine powder is caused.

  When a charge control agent is contained in the toner in the emulsion polymerization aggregation method, the charge control agent is blended with a polymerizable monomer or the like at the time of emulsion polymerization, or is blended in the aggregation process with the polymer primary particles and the colorant. The blended primary particles, the colorant, and the like can be blended by a method such as blending after agglomeration to obtain an appropriate particle size as a toner. Of these, the charge control agent is preferably emulsified and dispersed in water using an emulsifier, and used as an emulsified dispersion having a volume average diameter (Mv) of 0.01 μm to 3 μm. The blending of the charge control agent dispersion at the time of emulsion aggregation is preferably calculated and used so as to be 0.1 to 5% by mass in the finished toner base particles after aggregation.

As a method for producing an emulsion dispersion of the charge control agent, various wet dispersion mills can be used in addition to a homomixer and a disper capable of high-speed stirring and mixing, a homogenizer capable of high-pressure emulsification, an ultrasonic irradiation machine, and the like. For example, a ball mill, an attritor, a sand mill, a bead mill and the like. While these add energy to the object to be crushed by point contact between beads, a roll type mill that applies energy by line contact between rotating rollers, and rotating plate type beadless dispersion that applies energy by surface contact between flat plates A machine can also be used.

  The emulsification dispersion medium in the present invention is a liquid having a function of dispersing and holding the charge control agent particles, and should be appropriately set from known materials in accordance with the application purpose of the obtained charge control agent 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. For example, in the case of a suspension polymerization toner, the colorant is dispersed in an oil phase, that is, a monomer phase. Therefore, it is sufficient to select monomers as the emulsion dispersion medium. In this case, the aggregating step is carried out in an aqueous system, so water may be selected as the emulsifying dispersion medium. Among them, since the charge control agent dispersion of the present invention is used in an emulsion polymerization aggregation method toner, it is preferable that the emulsification dispersion medium is water. The water quality is also related to the coarsening due to reaggregation of the charge control agent particles in the charge control agent dispersion, and if the conductivity is high, the dispersion stability with time tends to deteriorate, so the conductivity is preferably 10 μS. It is preferable to use ion-exchanged water or distilled water that has been desalted so as to be not more than / cm, more preferably not more than 5 μS / cm. 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 emulsifying dispersion medium, it is preferable to add a surfactant to the water for the purpose of wetting and dispersing the colorant particles and keeping the dispersion state stable. Examples of surfactants 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.

The volume average diameter (Mv) of polymer primary particles, resin fine particles, colorant particles, wax particles, charge control agent particles, etc. in the above dispersion is measured using a nanotrack by the method described in the examples. , Defined as its measured value.
In the aggregation step in the emulsion polymerization aggregation method, the above-described primary polymer particles, resin fine particles, colorant particles, and charge components such as a charge control agent and wax are mixed at the same time or sequentially. It is possible to prepare a dispersion of the above components, that is, a polymer primary particle dispersion, a resin fine particle dispersion, a colorant particle dispersion, a charge control agent dispersion, and a wax fine particle dispersion. It is preferable from the viewpoint of uniformity.

  In addition, when mixing these different types of dispersions, the components contained in each dispersion have different agglomeration speeds. Therefore, in order to perform agglomeration uniformly, it is added over a certain period of time continuously or intermittently. It is preferable to mix them. Since the suitable time required for the addition varies depending on the amount of the dispersion to be mixed, the solid concentration, and the like, it is preferable to adjust appropriately. For example, when the colorant particle dispersion is mixed with the polymer primary particle dispersion, it is preferably added over 3 minutes or more. Also, when mixing the resin fine particle dispersion with the core particles, it is preferable to add over 3 minutes.

  The agglomeration treatment includes a heating method, a method of adding an electrolyte, a method of reducing the concentration of an emulsifier in the system, a method of combining these, and the like. When primary particles are agglomerated under stirring to obtain particle agglomerates that are approximately the size of the toner, the particle size of the particle agglomerates is controlled from the balance between the agglomeration force between the particles and the shearing force due to agitation. However, the cohesive force can be increased by the above method.

As an electrolyte in the case of performing aggregation by adding an electrolyte, 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 may be used. Inorganic salts having a monovalent metal cation such as CH ₃ COONa, C ₆ H ₅ SO ₃ Na; inorganic salts having a divalent metal cation such as MgCl ₂ , CaCl ₂ , MgSO ₄ , CaSO ₄ , ZnSO ₄ ; Examples thereof include inorganic salts having a trivalent metal cation such as Al ₂ (SO ₄ ) ₃ and Fe ₂ (SO ₄ ) ₃ . Among these, when an inorganic salt having a divalent or higher polyvalent metal cation is used, it is preferable in terms of productivity because the agglomeration speed is increased. On the other hand, the amount of polymer primary particles and the like that are not incorporated into the core particle is small. As a result, fine powder that does not reach the desired toner particle size is likely to be generated. Therefore, it is preferable to use an inorganic salt having a monovalent metal cation that does not have a strong aggregating action in terms of suppressing the amount of fine powder generated.

  The amount of the electrolyte used varies depending on the type of electrolyte, target particle size, etc., but is usually 0.05 to 25 parts by weight, preferably 0.1 to 15 parts per 100 parts by weight of the solid component of the mixed dispersion. Part by weight, more preferably 0.1 to 10 parts by weight. When the amount used 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. In the case of exceeding the above range, it tends to cause rapid agglomeration, making it difficult to control the particle diameter, and may cause problems such as inclusion of coarse powder or amorphous particles in the obtained core particles. is there.

  In addition, it is preferable that the electrolyte is added not intermittently but intermittently or continuously over a certain period of time. The addition time varies depending on the amount used, but is preferably added over 0.5 minutes. Usually, when an electrolyte is added, abrupt aggregation starts as soon as the electrolyte is added, so that there is a tendency that a large amount of polymer primary particles, colorant particles, aggregates, and the like left behind in the aggregation remain. These are considered to be one of the sources of fine powder. According to the above operation, uniform agglomeration can be performed without abrupt agglomeration, so that generation of fine powder can be prevented.

  Moreover, 20-70 degreeC is preferable and, as for the final temperature of the aggregation process in the case of performing aggregation by adding electrolyte, 30-60 degreeC is more preferable. Here, controlling the temperature before the aggregation step is one of the methods for controlling the particle size within a specific range of the present invention. Some colorants added to the aggregating step induce aggregation, such as the above-described electrolyte, and sometimes agglomerate without adding an electrolyte. Therefore, the aggregation can be prevented by cooling the temperature of the polymer primary particle dispersion in advance when mixing the colorant dispersion. This aggregation causes fine powder to be generated. In the present invention, the polymer primary particles are preferably cooled in advance in a range of preferably 0 to 15 ° C, more preferably 0 to 12 ° C, and still more preferably 2 to 10 ° C. Note that this method is not effective only when the electrolyte is added to perform aggregation, and the aggregation is performed without adding an electrolyte, such as a method of controlling the pH or adding a polar organic solvent such as alcohol to perform the aggregation method. The method is also used, and is not particularly limited to the aggregation method.

The final temperature of the agglomeration step in the case of agglomeration by heating is usually a temperature range of (Tg-20 ° C) to Tg of the polymer primary particles, and a range of (Tg-10 ° C) to (Tg-5 ° C). It is preferable that
In addition, as a method for preventing sudden agglomeration in order to prevent generation of fine powder, there is a method of adding demineralized water or the like. The method of adding demineralized water or the like is not a method that is actively employed in terms of production efficiency because the coagulation action is not so strong compared to the method of adding electrolyte, but rather, a large amount of filtrate is used in the subsequent filtration step, etc. Since it will be obtained, it may be unpreferable. However, it is very effective when fine aggregation control is required as in the present invention. Moreover, in this invention, it is preferable to employ | adopt in combination with the method of adding the said heating method, the method of adding electrolyte, etc. At this time, the method of adding demineralized water after adding the electrolyte is particularly preferable in that the aggregation is easily controlled.

  The time required for agglomeration is optimized by the shape of the apparatus and the processing scale. In order to reach the target particle size of the toner base particles, the temperature at which the aggregation process is completed, for example, the emulsifier It is preferable that the time from the temperature 8 ° C. lower than the temperature at the time of operation to stop the growth of the core particles by addition, pH control, etc. (hereinafter referred to as the aggregation final temperature) to 30 minutes or more is 1 hour. More preferably, the above is used. The polymer core particles, colorant particles, or aggregates thereof remaining by extending the time are not left behind, but are taken into the target core particles or agglomerate with each other, so that the target core is obtained. Become a particle.

  In the present invention, toner mother particles can be formed by coating (adhering or fixing) resin fine particles on the surface of the core particles as necessary. The volume average diameter (Mv) of the resin fine particles is preferably 0.02 μm to 3 μm, more preferably 0.05 μm to 1.5 μm. Generally, the use of the resin fine particles promotes the generation of fine powder that does not reach a predetermined toner particle size. Therefore, the amount of fine powder less than the predetermined toner particle size is increased in the conventional toner coated with resin fine particles.

In the present invention, when the amount of the wax is increased, the high temperature fixability is improved, but the wax tends to be exposed on the toner surface, so that the chargeability and heat resistance may be deteriorated. The deterioration of performance can be prevented by coating with resin fine particles not containing.
However, when the resin fine particles contain wax for the purpose of improving the high-temperature fixability, the resin fine particles once attached to the surface of the core particles are easily peeled off. This is because the particle size distribution of the resin fine particles described above becomes wide, and there are large particle size resin fine particles with weak adhesion. Therefore, in order to reduce the peeling off, it is preferable to raise the temperature while adding an aqueous solution in which a dispersion stabilizer and water are mixed in advance in a liquid in which particles having resin fine particles attached to the surface are dispersed. .

  When adopting the conventional method “step of starting the temperature rise after the addition of the emulsifier”, that is, when the aging step is performed after abruptly reducing the cohesive force, once the cohesive force is drastically reduced. The adhered resin fine particles may be easily detached. Therefore, it is preferable to fuse the resin fine particles after adhering them without significantly reducing the cohesive force and suppressing the particle diameter growth.

In the emulsion polymerization aggregation method, in order to increase the stability of the particle aggregate obtained by aggregation, an emulsifier and a pH adjuster are added as a dispersion stabilizer to reduce the aggregation force between the particles and grow the toner base particles. It is preferable to add an aging step for causing fusion between the agglomerated particles after stopping.
The amount of the emulsifier is not limited, but is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, and further preferably 3 parts by weight or more with respect to 100 parts by weight of the solid component of the mixed dispersion. Moreover, it is 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 aging process, by adding an emulsifier or increasing the pH value of the aggregation liquid, it is possible to suppress aggregation of the particle aggregates aggregated in the aggregation process. The generation of coarse particles in the toner can be suppressed.

Here, as a method of controlling the particle size within a specific range, which means that the particle size distribution of the small particle toner of the present invention is sharp, the stirring rotational speed is reduced before the step of adding an emulsifier or a pH adjuster. That is, there is a method of reducing the shearing force by stirring. This method is preferably employed when a system having a weak aggregating action, such as an emulsifier or a pH adjuster, is added at a time to rapidly shift to a stable (dispersed) system. As described above, if a method of raising the temperature while adding an aqueous solution in which a dispersion stabilizer and water are mixed in advance is adopted, the system tends to be too inclined to agglomerate when the stirring rotation speed is lowered. May lead to enlargement.

As an example, the toner having a specific particle size distribution according to the present invention can be obtained by the above-described method. More specifically, the content of fine powder particles can be adjusted by the degree to which the rotational speed is reduced. For example, when the stirring rotational speed is decreased from 250 rpm to 150 rpm, a toner having a small particle size with a sharper particle size distribution than that of a known toner can be provided, and the toner having a specific particle size distribution of the present invention can be obtained. However, this value is naturally
(A) The diameter of the stirring vessel (as a so-called general cylindrical shape) and the maximum diameter of the stirring blade (and its relative ratio)
(B) Height of stirring container
(C) Peripheral speed of the tip of the stirring blade
(D) Shape of stirring blade
(E) Position of the blades in the stirring vessel
It depends on the conditions. About special (c), 1.0-2.5 m / sec is preferable, 1.2-2.3 m / sec is more preferable, 1.5-2.2 m / sec is especially preferable. This is because, within the above range, a suitable shear rate that does not peel off and does not enlarge is given to the particles.

  The temperature of the aging step is preferably not less than Tg of the binder resin as the polymer primary particles, more preferably not less than 5 ° C higher than the Tg, and preferably not more than 80 ° C higher than the Tg, more preferably The temperature is 50 ° C. or higher than the Tg. The time required for the aging step varies depending on the shape of the target toner, but after reaching the glass transition temperature of the polymer constituting the polymer primary particles, usually 0.1 to 5 hours, preferably 1 to It is desirable to hold for 3 hours.

  By such a heat treatment, the polymer primary particles in the aggregate are fused and integrated, and the shape of the toner base particles as the aggregate becomes close to a spherical shape. The particle aggregate before the aging step is considered to be an aggregate due to electrostatic or physical aggregation of the polymer primary particles, but after the aging step, the polymer primary particles constituting the particle aggregate are fused to each other. In addition, the shape of the toner base particles can be made nearly spherical. According to such an aging process, by controlling the temperature and time of the aging process, the shape of the polymer primary particles is agglomerated, a potato type with advanced fusion, a spherical form with further fusion For example, various shapes of toner can be manufactured according to the purpose.

The particle aggregate obtained through each of the above steps is subjected to solid / liquid separation according to a known method, the particle aggregate is recovered, then washed as necessary, and then dried. Toner mother particles can be obtained.
Further, an outer layer mainly composed of a polymer is further formed on the surface of the particles obtained by the emulsion polymerization aggregation method by, for example, a spray drying method, an in-situ method, or a submerged particle coating method. It is also possible to obtain encapsulated toner base particles by forming them with a thickness of preferably 0.01 to 0.5 μm.

Further, in the emulsion polymerization aggregation method toner, the average circularity measured using a flow type particle image analyzer FPIA-2100 is preferably 0.90 or more, more preferably 0.92 or more, and further preferably 0.94 or more. It is. It is considered that the closer to a sphere, the less the charge amount is localized in the particles, and the developability tends to be uniform. However, making a perfect spherical toner deteriorates the cleaning property, so the average circularity Is preferably 0.98 or less, more preferably 0.97 or less.

  Further, at least one of the peak molecular weights in the gel permeation chromatography (hereinafter sometimes abbreviated as “GPC”) of the tetrahydrofuran (THF) soluble part of the toner is preferably 30,000 or more, more preferably 40,000 or more. More preferably, it is 50,000 or more, preferably 200,000 or less, more preferably 150,000 or less, and still more preferably 100,000 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 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 charge control agent, selection and blending amount of the external additive, and the like.
As a blending method of the charge control agent in the emulsion polymerization aggregation method, the polymer primary particle dispersion and the colorant dispersion are mixed to obtain a mixed dispersion as described above, and then this is agglomerated for particle aggregation. The particle size of the aggregation and growth process at this time is monitored on the way, and when the predetermined particle size is reached, an emulsified dispersion of the charge control agent is added, and then the aging step is started. Before entering the ripening step, there is a case where the interior and the surface of the toner are inclined to improve the toner fixing property and storage stability, and the toner particles are coated with the resin fine particles as described above. When the resin fine particle dispersion is added, the charge control agent emulsified dispersion may be added before, after, or at the same time.

  Regarding the addition rate of the charge control agent emulsified dispersion, if this dispersion is added all at once within a short period of time, the dispersion of the charge control agent becomes unstable and the dispersions aggregate to form a charge control agent in the toner. Not only is this not introduced, but this leads to the formation of fine powder of toner, making it difficult to control the particle size of the toner. For this reason, it is desirable to add over a period of about 0.02 to 0.5 hours, preferably about 0.03 to 0.3 hours.

  In order to obtain a toner satisfying the above formulas (2) and (5), it is preferable to employ an operation in which the aggregation speed is not high compared to the operation normally performed in the aggregation step. Examples of operations that do not cause the aggregation speed to be high include, for example, cooling the dispersion to be used in advance, adding the dispersion over time, adopting an electrolyte that does not have a large aggregating action, continuously using the electrolyte, or There are methods such as intermittent addition, slowing the rate of temperature rise, and long aggregation time. In the aging step, it is preferable to adopt an operation in which the aggregated particles are difficult to redisperse. Examples of the operation in which the agglomerated particles are difficult to finely disperse include, for example, a method in which the number of revolutions for stirring is decreased, a dispersion stabilizer is added continuously or intermittently, and a dispersion stabilizer and water are mixed in advance. The toner satisfying the above formulas (2) and (5) removes particles having a volume median diameter (Dv50) or less from the finally obtained toner or toner base particles by an operation such as classification. It is preferable to be obtained without going through the steps.

  The toner for developing an electrostatic image of the present invention is a magnetic two-component developer in which a carrier for conveying the toner to the electrostatic latent image portion by a magnetic force coexists, or a magnetic toner containing a magnetic powder in the toner. Although it may be used for either a component developer or a non-magnetic one-component developer that does not use magnetic powder as a developer, in order to exhibit the effects of the present invention remarkably, a non-magnetic one-component development is particularly preferred. It is preferably used as a developer for the system.

When used as the magnetic two-component developer, the carrier that is mixed with the toner to form the developer is a known magnetic substance such as an iron powder type, ferrite type, or magnetite type carrier, or a resin coating on the surface thereof. Or a magnetic resin carrier can be used. As the carrier coating resin, generally known styrene resins, acrylic resins, styrene acrylic copolymer resins, silicone resins, modified silicone resins, fluorine resins, and the like can be used, but are not limited thereto. It is not a thing. The average particle size of the carrier is not particularly limited, but preferably has an average particle size of 10 to 200 μm. These carriers are preferably used in an amount of 5 to 100 parts by weight with respect to 1 part by weight of the toner.

  The image forming method of the present invention will be described in more detail with reference to the drawings. FIG. 1 is an explanatory diagram showing an example of a developing device using a non-magnetic one-component toner that can be used for performing an image forming method using the toner of the present invention. In FIG. 1, the toner 6 of the present invention built in the toner hopper 7 is forcibly brought to a roller-like sponge roller (toner supply auxiliary member) 4 by the stirring blade 5, and the toner is supplied to the sponge roller 4. The The toner taken into the sponge roller 4 is carried to the toner conveying member 2 by the sponge roller 4 rotating in the direction of the arrow, and is rubbed and electrostatically or physically adsorbed. It rotates strongly in the direction of the arrow, and a uniform thin toner layer is formed by a steel elastic blade (toner layer thickness regulating member) 3 and is frictionally charged. Thereafter, the toner is conveyed to the surface of the electrostatic latent image carrier 1 that is in contact with the toner conveying member 2, and the latent image is developed. The electrostatic latent image is obtained, for example, by subjecting an organic photoreceptor to DC charging of 500 V and then exposure.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the following examples, “parts” means “parts by weight”.

<Volume Average Diameter (Mv), Measurement Method and Definition of Average Dispersion Diameter of Charge Control Agent>
The volume average diameter (Mv) of particles having a volume average diameter (Mv) of less than 1 μm is handled by using Nitraso Co., Ltd., model: Microtrac Nanotrac 150 (hereinafter abbreviated as “Nanotrack”). In accordance with the instructions, using the company's analysis software Microtrac Particle Analyzer Ver10.1.2.-019EE, using ion-exchanged water with an electric conductivity of 0.5 μS / cm as the dispersion medium, enter the following conditions or the following conditions respectively: And measured by the method described in the instruction manual.

For wax dispersion and polymer primary particle dispersion,
Solvent refractive index: 1.333
・ Measurement time: 100 seconds
・ Number of measurements: 1 time
-Particle refractive index: 1.59
・ Transparency: Transmission
・ Shape: Spherical shape
Density: 1.04

For pigment premix liquid and colorant dispersion,
Solvent refractive index: 1.333
・ Measurement time: 100 seconds
・ Number of measurements: 1 time
-Particle refractive index: 1.59
・ Permeability: Absorption
・ Shape: Non-spherical
・ Density: 1.00

For the charge control agent dispersion,
Solvent refractive index: 1.333
・ Measurement time: 100 seconds
・ Number of measurements: 1 time
-Particle refractive index: 1.59
・ Permeability: Absorption
・ Shape: Non-spherical
・ Density: 1.00

<Measurement method and definition of volume median diameter (Dv50)>
As a pre-measurement treatment of the toner finally obtained through the external addition process, it was performed as follows. In a cylindrical polyethylene (PE) beaker having an inner diameter of 47 mm and a height of 51 mm, 0.100 g of toner using a spatula and 20% by weight DBS aqueous solution using a dropper (Daiichi Kogyo Seiyaku Co., Ltd., Neogen S-20A) 0.15 g was added. At this time, toner and a 20% DBS aqueous solution were added only to the bottom of the beaker so that the toner would not scatter on the edge of the beaker. Next, the mixture was stirred for 3 minutes using a spatula until the toner and 20% DBS aqueous solution became a paste.

At this time, the toner was prevented from being scattered on the edge of the beaker.
Subsequently, 30 g of dispersion medium Isoton II was added, and the mixture was stirred for 2 minutes using a spatula to obtain a uniform solution as a whole. Next, a fluororesin-coated rotor having a length of 31 mm and a diameter of 6 mm was placed in a beaker and dispersed using a stirrer at 400 rpm for 20 minutes. At this time, using a spatula at a rate of once every 3 minutes, macroscopic particles visually observed at the gas-liquid interface and the edge of the beaker were dropped into the beaker so as to form a uniform dispersion. Subsequently, this was filtered through a mesh having an opening of 63 μm, and the obtained filtrate was designated as “toner dispersion”.

Regarding the measurement of the particle diameter during the production process of the toner base particles, the filtrate obtained by filtering the agglomerated slurry with a 63 μm mesh was used as the “slurry liquid”.
The volume median diameter (Dv50) of the particles is Bocman Coulter's Multisizer III (aperture diameter 100 μm) (hereinafter abbreviated as “Multisizer”), the dispersion medium is Isoton II, and the above-mentioned “ "Toner dispersion" or "slurry" is diluted to a dispersoid concentration of 0.03% by mass, and K
The D value was measured as 118.5. The measurement particle diameter range is from 2.00 to 64.00 μm, and this range is discretized into 256 divisions so as to be equidistant on a logarithmic scale, and the volume calculated based on the statistical values on the basis of the volume is the volume. The median diameter (Dv50) was used.

<Measurement Method and Definition of Number% (Dns) of Toner with Particle Size of 2.00 μm to 3.56 μm>
As a pre-measurement process for the toner after the external addition step, the following procedure was performed. In a cylindrical polyethylene (PE) beaker having an inner diameter of 47 mm and a height of 51 mm, 0.100 g of toner using a spatula and 20% by weight DBS aqueous solution using a dropper (Daiichi Kogyo Seiyaku Co., Ltd., Neogen S-20A) 0.15 g was added. At this time, toner and a 20% DBS aqueous solution were added only to the bottom of the beaker so that the toner would not scatter on the edge of the beaker. Next, the mixture was stirred for 3 minutes using a spatula until the toner and 20% DBS aqueous solution became a paste. At this time, the toner was prevented from being scattered on the edge of the beaker.

Subsequently, 30 g of dispersion medium Isoton II was added, and the mixture was stirred for 2 minutes using a spatula. Next, a fluororesin-coated rotor having a length of 31 mm and a diameter of 6 mm was placed in a beaker and dispersed using a stirrer at 400 rpm for 20 minutes. At this time, macroscopic particles visually observed at the gas-liquid interface and the edge of the beaker were dropped into the beaker at a rate of once every 3 minutes to make a uniform dispersion. continue,
This was filtered through a mesh having an opening of 63 μm, and the obtained filtrate was used as a toner dispersion.

For the number% (Dns) of toner having a particle size of 2.00 μm or more and 3.56 μm or less, a multisizer (aperture diameter 100 μm) is used, and Isoton II made by the same company is used as a dispersion medium. The “slurry liquid” was diluted to a dispersoid concentration of 0.03% by mass and measured with Multisizer III analysis software with a KD value of 118.5.
The lower limit particle size of 2.00 μm is the detection limit of the measuring device multisizer, and the upper limit particle size of 3.56 μm is a prescribed channel value in the measuring device multisizer. In the present invention, an area having a particle size of 2.00 μm or more and 3.56 μm or less is recognized as a fine powder area.

  The measurement particle size range is from 2.00 to 64.00 μm, and this range is discretized into 256 divisions so as to be equidistant on a logarithmic scale, and based on the statistical value on the basis of the number, 2.00 To 3.56 μm, the ratio of the particle size component was calculated on the basis of the number and was defined as “Dns”.

<Measurement method and definition of dent of charge control agent on toner surface>
The “dent” in the present invention is measured as follows and is defined as follows.
1 g of toner powder base particles were put into 10 g of alcohol (ethanol) and stirred for 1 hour with a magnetic stirrer. Thereafter, the toner and the solution were separated by suction filtration. After the toner remaining on the filter paper was dried at room temperature, the surface was observed with an SEM, and an image was taken. From the obtained image, image analysis was performed on the indentation where the charge control agent was dissolved on the toner surface, and the circular equivalent diameter was calculated. This circular phase equal diameter is defined as the diameter of the circle, this value is measured at 10 points, and the average value is defined as the “average diameter of the recess” in the present invention.

<Measuring method and definition of average circularity>
The “average circularity” in the present invention is measured as follows and is defined as follows. That is, the toner base particles are dispersed in a dispersion medium (Isoton II, manufactured by Beckman Coulter, Inc.) so as to be in the range of 5720-7140 particles / μL, and a flow type particle image analyzer (Sysmex Corporation (formerly Toa Medical Electronics)). (Manufactured by FPIA 2100), measurement is performed under the following apparatus conditions, and the value is defined as “average circularity”. In the present invention, the same measurement is performed three times, and an arithmetic average value of three “average circularity” is adopted as the “average circularity”.
・ Mode: HPF
-HPF analysis amount: 0.35 μL
-HPF detection number: 2000-2500
The following is measured by the above device and automatically calculated and displayed in the above device, and “circularity” is defined by the following formula.

[Circularity] = [circumference of a circle having the same area as the particle projection area] / [periphery of the particle projection image] Then, 2000 to 2500 HPF detection numbers were measured, and the circularity of each particle was measured. The arithmetic mean (arithmetic mean) is displayed on the device as “average circularity”.

<Measurement method and definition of number variation coefficient>
The number variation coefficient is represented by standard deviation of number-based particle distribution × 100 / number average particle diameter. The particle size distribution of the present invention was measured as follows.
The particle number coefficient of variation is Beckman Coulter's Multisizer III (aperture diameter 100 μm) (hereinafter abbreviated as “Multisizer”), the dispersion medium is Isoton II, and the above “toner dispersion” Alternatively, the “slurry liquid” is diluted to a dispersoid concentration of 0.03% by mass, and the KD value is 1 with Multisizer III analysis software (V3.51).
It was measured as 18.5. The measurement particle size range is from 2.00 to 64.00 μm, and this range is discretized into 256 divisions at equal intervals on a logarithmic scale, and the number calculated based on the statistical value on the basis of the number is used. The coefficient of variation was used.

<Method of measuring electrical conductivity>
The electrical conductivity was measured using a conductivity meter (a personal SC meter model SC72 and a detector SC72SN-11 manufactured by Yokogawa Electric Corporation) according to an ordinary method according to the instruction manual.

<Measuring method of melting point peak temperature, melting peak half width, crystallization temperature, crystallization peak half width>

From the endothermic curve when the temperature was raised from 10 ° C. to 110 ° C. at a rate of 10 ° C./min by the method described in the company's instruction manual using Seiko Instruments Inc., model: SSC5200, the melting point peak temperature The half-width of the melting peak was measured, and then the crystallization temperature and the half-width of the crystallization peak were measured from the exothermic curve when the temperature was lowered from 110 ° C. to 10 ° C. at a rate of 10 ° C./min.

<Measurement method of solid content concentration>
Using a solid content concentration measuring instrument INFRARED MOISTURE DETERMINATION BALANCE Model FD-100 manufactured by Kett Science Laboratory, a sample containing 1.00 g containing the solid content is precisely weighed on a balance, and the heater temperature is 300 ° C. and the heating time is 90 minutes. The solid content concentration was measured.

<Charging rise evaluation method>
A sample in which 0.4 g of toner was mixed with 9.6 g of a magnetic carrier (ferrite carrier F150 manufactured by Powdertech) was placed in a glass sample bottle and shaken using a reciprocating shaker (NR-1 manufactured by Taitec). One minute after the start of shaking, 0.1 g of the sample was weighed from the sample bottle and placed in a mesh case. The mesh case was fitted into a predetermined position inside a blow-off powder charge measuring device (TYPE TB-200 manufactured by Toshiba Chemical Corporation), and the charge amount of the toner was measured. From the sample shaking value of 1 minute, the charge rising of the toner was evaluated.

<Method of live-action evaluation>
Real photograph evaluation 100g of toner is a non-magnetic one component (using organic photoreceptor), roller charging, rubber development roller contact development system, development speed 164mm / second, belt transfer system, blade drum cleaning system, guarantee at 5% printing rate It was loaded into a cartridge of a 600 dpi machine with a lifespan of 30,000 sheets, and 50 charts with a 1% printing rate were continuously printed.

<Dirt>
In the actual image evaluation, the smear of the image after printing 50 sheets was visually observed and judged according to the following criteria.
A: No dirt at all
○: Slightly dirty but usable level
Δ: Partially dirty
X: Dirt can be clearly confirmed partially or entirely.

<Afterimage (Ghost)>
In the above-mentioned actual image evaluation, a solid image was printed, and the image density of the tip portion and the image density of the portion printed after two rotations of the developing roller were measured with X-rite 938 (manufactured by X-Rite), respectively. The ratio (%) of the image density after two rounds to the tip portion was obtained.
A: No problem at all (98% or more)
○: Level that can be used although there is a slight difference in image density (95% or more and less than 98%)
Δ: Level at which it can be recognized that there is a slight difference in image density (85% or more and less than 95%)
X: Level with a clear difference in image density (less than 85%)

Example 1
<Preparation of charge control agent dispersion α>
10 parts of a powder of charge control agent E-81 (manufactured by Orient Chemical Industries), 10 parts of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen S-20A) in a 1 L stainless beaker with a stirring blade set, 80 parts of ion-exchanged water having an electric conductivity of 2 μS / cm was added and well mixed by stirring, and a charge control agent premix solution was obtained by preliminary dispersion.

  The premix solution was dispersed as a raw material slurry using a wet bead mill (a batch type tabletop sand mill manufactured by Kansai Paint Co., Ltd.). As dispersion media, zirconia beads having a diameter of 300 μm (true density 6.0 g / cm 3) were used and mixed with the raw material slurry 1 at a weight ratio of 5 to a total amount of 1200 g. A stainless steel disc-shaped stirring blade with a diameter of 7 cm and a thickness of 0.6 cm is fixed along the rotation center axis of the bead mill, and the premix solution is placed so that the blade is sufficiently immersed in the mixture of raw material slurry and beads. I set a beaker. This beaker was immersed in a constant temperature water bath, and 10 ° C. cooling water was circulated by a constant temperature cooler during the bead mill operation. The number of revolutions of the stirring blade was made constant at 1490 rpm, and the mixture was stirred for about 1 hour to obtain a dispersion when the particle size reached a predetermined level.

  The beads and filtrate were completely separated with a 100 mesh stainless steel sieve to obtain a charge control agent dispersion. This dispersion was diluted with UPA (manufactured by Nikkiso Co., Ltd., UPA-150) to an appropriate concentration in water in which several μL of the above anionic surfactant was dropped, and the particle size distribution of the particles was measured in a measurement time of 100 seconds. did. The volume particle size distribution median diameter of the obtained particles was 200 nm.

<Preparation of wax / long-chain polymerizable monomer dispersion A1>
Paraffin wax (Nihon Seiki Co., Ltd. HNP-9, surface tension 23.5 mN / m, thermal characteristics: melting point peak temperature 82 ° C., melting heat 220 J / g, melting peak half width 8.2 ° C., crystallization temperature 66 ° C., Crystallization peak half-value width 13.0 ° C.) 27 parts (540 g), stearyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.8 parts, 20 mass% sodium dodecylbenzenesulfonate aqueous solution (Daiichi Kogyo Seiyaku Co., Ltd., Neogen S20A) ( (Hereinafter abbreviated as “20% DBS aqueous solution”) 1.9 parts and 68.3 parts of demineralized water are heated to 90 ° C. and used for 10 minutes using a homomixer (Mark II f model manufactured by Tokushu Kika Kogyo Co., Ltd.) Stir.

  Next, this dispersion was heated to 90 ° C., and circulation emulsification was started under a pressure condition of 25 MPa using a homogenizer (manufactured by Gorin, 15-M-8PA type). Dispersion was carried out until (Mv) reached 250 nm to prepare a wax / long-chain polymerizable monomer dispersion A1 (emulsion solid content concentration = 30.2 mass%).

<Preparation of polymer primary particle dispersion A1>
In a reactor (inner volume 21 L, inner diameter 250 mm, height 420 mm) equipped with a stirrer (three blades), a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device, the wax / long-chain polymerizable unit The monomer dispersion A1 (35.6 parts, 712.12 g) and 259 parts of demineralized water were charged, and the temperature was raised to 90 ° C. under a nitrogen stream while stirring.

  Thereafter, the mixture of the following “polymerizable monomers and the like” and “emulsifier aqueous solution” was added to the solution over 5 hours while continuing to stir the liquid. The time at which this mixture was started to be dropped was designated as “polymerization start”, and the following “initiator aqueous solution” was added over 4.5 hours from 30 minutes after the start of polymerization. The agent aqueous solution ”was added over 2 hours, and the internal temperature was maintained at 90 ° C. for 1 hour while continuing stirring.

[Polymerizable monomers, etc.]
Styrene 76.8 parts (1535.0 g)
23.2 parts butyl acrylate
Acrylic acid 1.5 parts
Hexanediol diacrylate 0.7 parts
1.0 part of trichlorobromomethane
[Emulsifier aqueous solution]
20% DBS aqueous solution 1.0 part
67.1 parts of demineralized water
[Initiator aqueous solution]
15.5 parts of 8% by weight aqueous hydrogen peroxide solution
15.5 parts of 8 mass% L (+)-ascorbic acid aqueous solution
[Additional initiator aqueous solution]
8 mass% L (+)-ascorbic acid aqueous solution 14.2 parts
After the completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer primary particle dispersion A1. The volume average diameter (Mv) measured using Nanotrac was 280 nm, and the solid content concentration was 21.1% by mass.

<Preparation of polymer primary particle dispersion A2>
In a reactor (inner volume 21 L, inner diameter 250 mm, height 420 mm) equipped with a stirrer (three blades), a heating / cooling device, a concentrating device, and each raw material / auxiliary charging device, 1.0 part of a 20 mass% DBS aqueous solution Then, 312 parts of demineralized water was added, the temperature was raised to 90 ° C. under a nitrogen stream, and 3.2 parts of an 8% by mass hydrogen peroxide aqueous solution and 3.2 parts of an 8% by mass L (+)-ascorbic acid aqueous solution were stirred. Added all at once. The time point 5 minutes after the batch addition of these is defined as “polymerization start”.

  A mixture of the following “polymerizable monomers etc.” and “emulsifier aqueous solution” was added over 5 hours from the start of polymerization, and the following “initiator aqueous solution” was added over 6 hours from the start of polymerization. While stirring, the internal temperature was maintained at 90 ° C. for 1 hour.

[Polymerizable monomers, etc.]
92.5 parts of styrene (1850.0 g)
7.5 parts butyl acrylate
Acrylic acid 0.5 part
0.5 parts of trichlorobromomethane
[Emulsifier aqueous solution]
1.5 parts of 20% DBS aqueous solution
66.0 parts of demineralized water
[Initiator aqueous solution]
18.9 parts of 8% hydrogen peroxide solution
8% by mass L (+)-ascorbic acid aqueous solution 18.9 parts
After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer primary particle dispersion A2. The volume average diameter (Mv) measured using Nanotrac was 290 nm, and the solid content concentration was 19.0% by mass.

<Preparation of Colorant Dispersion (Quinacridone)>
In a container with an internal volume of 300 L equipped with a stirrer (propeller blade), 20 parts (40 kg) of quinacridone (manufactured by Clariant Japan, Hosterperm Pin E-WD), 1 part of 20% DBS aqueous solution, nonionic surfactant (manufactured by Kao Corporation) 4 parts of Emulgen 120) and 75 parts of ion-exchanged water having an electric conductivity of 2 μS / cm were added and predispersed to obtain a pigment premix solution. The volume average diameter (Mv) of quinacridone in the dispersion after pigment premixing measured with Nanotrac was about 90 μm.

The pigment premix solution was supplied as a raw material slurry to a wet bead mill and circulated and dispersed. The inner diameter of the stator was φ75 mm, the separator diameter was φ60 mm, the distance between the separator and the disk was 15 mm, and zirconia beads having a diameter of 50 μm (true density 6.0 g / cm ³ ) were used as the dispersing medium. Since the effective internal volume of the stator is 0.5 L and the filling volume of the media is 0.35 L, the media filling rate is 70% by mass. The pigment premix liquid is continuously supplied from the supply port at a supply speed of 50 L / hr by a non-pulsating metering pump, and the rotor rotation speed is constant (peripheral speed at the rotor tip is 11 m / sec), and continuously from the discharge port. The colorant dispersion (quinacridone) was obtained when it reached a predetermined particle size by being repeatedly circulated. The volume average diameter (Mv) of the colorant dispersion (quinacridone) measured with Nanotrac was 243 nm, and the solid content concentration was 24.2% by mass.

<Manufacture of toner mother particles K>
Using the following components, toner base particles K were produced by carrying out the following aggregation processes (core material aggregation process / shell coating process), circularization process, washing process, and drying process.
Polymer primary particle dispersion A1 95 parts as solid content (998.2 g as solid content)
Polymer primary particle dispersion A2 5 parts as solid content
Colorant dispersion (quinacridone) 9 parts as colorant solids
20% DBS aqueous solution In the core material agglomeration process, the solid content is 0.2 parts.
20% DBS aqueous solution In the rounding process, 6 parts as solid content

○ Core material aggregation process
Polymer primary particle dispersion A1 and 20% in a mixer (volume 12 L, inner diameter 208 mm, height 355 mm) equipped with a stirring device (double helical blade), heating / cooling device, concentrating device, and each raw material / auxiliary charging device A DBS aqueous solution was charged and mixed uniformly at an internal temperature of 7 ° C. for 5 minutes. Subsequently, while maintaining the internal temperature at 7 ° C. and continuing stirring at 250 rpm, 0.52 part of 5 mass% aqueous solution of ferrous sulfate was added as FeSO ₄ · 7H ₂ O over 5 minutes, and then the colorant The dispersion was added over 5 minutes, mixed uniformly at an internal temperature of 7 ° C., and a 0.5% by mass aqueous solution of aluminum sulfate was added dropwise over 8 minutes with the same conditions (solid to resin solids). Min is 0.10 parts). Thereafter, the internal temperature was raised to 55.0 ° C. while maintaining the rotational speed of 250 rpm, the volume median diameter (Dv50) was measured using a multisizer, and grown to 7.11 μm.

○ Shell coating process
Thereafter, a liquid obtained by mixing 0.3 part of the polymer primary particle dispersion A2 and the charge control agent dispersion α was added over 3 minutes while maintaining the internal temperature at 55.0 ° C. and the rotation speed of 250 rpm, and the mixture was held as it was for 60 minutes. .
○ Circularization process
Subsequently, the rotational speed was reduced to 150 rpm (a peripheral speed of 1.56 m / sec at the tip of the stirring blade, a stirring speed reduced by 40% with respect to the rotational speed of the aggregation process), and then a 20% DBS aqueous solution (6 parts as solid content) was added. The mixture was added over 10 minutes, then heated to 84 ° C. over 30 minutes, and heating and stirring were continued until the average circularity reached 0.943. Thereafter, it was cooled to 30 ° C. over 20 minutes to obtain a slurry.

○ Cleaning process
The obtained slurry was extracted and subjected to suction filtration with an aspirator using filter paper of type 5 C (No5C manufactured by Toyo Roshi Kaisha, Ltd.). The cake remaining on the filter paper is transferred to a stainless steel container having an internal volume of 10 L equipped with a stirrer (propeller blade), and 8 kg of ion exchange water having an electric conductivity of 1 μS / cm is added and stirred uniformly at 50 rpm. Thereafter, stirring was continued for 30 minutes.

Thereafter, the filter paper was suction filtered with an aspirator again using Type 5 C (Toyo Filter Paper No. 5C) filter paper, and the solid matter remaining on the filter paper was again equipped with a stirrer (propeller blade) and had an electrical conductivity of 1 μS / cm. It was transferred to a container with an internal volume of 10 L containing 8 kg of ion-exchanged water, and uniformly dispersed by stirring at 50 rpm and kept stirring for 30 minutes. When this process was repeated 5 times, the electrical conductivity of the filtrate was 2 μS / cm.

○ Drying process
The solid matter obtained here was spread on a stainless steel bat so as to have a height of 20 mm, and dried in a blow dryer set at 40 ° C. for 48 hours, whereby toner base particles K were obtained.

<Manufacture of toner K>
○ External process
To the obtained toner base particles K250 g, 1.41 g of H2000 silica manufactured by Clariant Co. and 0.56 g of SMT150IB titania fine powder manufactured by Teica Co., Ltd. were mixed as external additives, and 1 sample at 6000 rpm with a sample mill (manufactured by Kyoritsu Riko Co., Ltd.). The resulting mixture was mixed for 1 minute and sieved with 150 mesh to obtain toner K.

○ Analysis process
The volume median diameter (Dv50) measured using a multisizer of toner K obtained here is 7.11 μm, and “number% (Dns) of toner having a particle size of 2.00 μm to 3.56 μm” is The average circularity was 0.943 and the number variation coefficient was 19.2%.
Further, the depression of the charge control agent on the toner surface was 400 nm, and the charge control agent was present within ± R with respect to the toner surface.

Example 2
<Manufacture of toner mother particles L>
The component of the toner base particle K is 9.0 parts of the colorant dispersion quinacridone, and the agglomeration process (core material agglomeration process / shell coating process), circularization process, washing process, and drying process of “manufacturing the toner base particle K” 1 except that the “core material agglomeration step”, “shell coating step” and “circularization step” were changed as described below in the same manner as in “Production of toner mother particles K” in Example 1. Particles L were obtained.

○ Core material aggregation process
Polymer primary particle dispersion A1 and 20% in a mixer (volume 12 L, inner diameter 208 mm, height 355 mm) equipped with a stirring device (double helical blade), heating / cooling device, concentrating device, and each raw material / auxiliary charging device A DBS aqueous solution was charged and mixed uniformly at an internal temperature of 7 ° C. for 5 minutes. Subsequently, while maintaining the internal temperature at 7 ° C. and continuing stirring at 250 rpm, 0.52 part of 5 mass% aqueous solution of ferrous sulfate was added as FeSO ₄ · 7H ₂ O over 5 minutes, and then the colorant The dispersion was added over 5 minutes, mixed uniformly at an internal temperature of 7 ° C., and a 0.5% by mass aqueous solution of aluminum sulfate was added dropwise over 8 minutes with the same conditions (solid to resin solids). Min is 0.10 parts). Thereafter, the internal temperature was raised to 55.0 ° C. while maintaining the rotational speed of 250 rpm, the volume median diameter (Dv50) was measured using a multisizer, and grown to 7.02 μm.

○ Shell coating process
Thereafter, with an internal temperature of 55.0 ° C. and a rotational speed of 250 rpm, a liquid in which 1.0 part of the polymer primary particle dispersion A2 and the charge control agent dispersion α were mixed was added over 3 minutes and held for 60 minutes. .
○ Circularization process
Subsequently, the rotational speed was reduced to 150 rpm (a peripheral speed of 1.56 m / sec at the tip of the stirring blade, a stirring speed reduced by 40% with respect to the rotational speed of the aggregation process), and then a 20% DBS aqueous solution (6 parts as solid content) was added. The mixture was added over 10 minutes, then heated to 84 ° C. over 30 minutes, and heating and stirring were continued until the average circularity reached 0.951. Thereafter, it was cooled to 30 ° C. over 20 minutes to obtain a slurry.

<Manufacture of toner L>
Thereafter, the toner L was changed by the same external addition process as in “Production of Toner K” except that the amount of H2000 silica as an external additive was changed to 1.41 g and the amount of SMT150IB titania fine powder was changed to 0.56 g. Got.
○ Analysis process
The volume median diameter (Dv50) measured using a multisizer of the toner L obtained here is 7.02 μm, and “the number% (Dns) of toner having a particle size of 2.00 μm to 3.56 μm” is The average circularity was 0.951 and the number variation coefficient was 21.4%.
Further, the depression of the charge control agent on the toner surface was 400 nm, and the charge control agent was present within ± R with respect to the toner surface.

Example 3
<Preparation of Charge Control Agent Dispersion β>
10 parts of powder of charge control agent TN-105 (Hodogaya Chemical Co., Ltd.), 10 parts of anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen S-20A) in a 1 L stainless beaker with a stirring blade set Then, 80 parts of ion-exchanged water having an electric conductivity of 2 μS / cm was added and mixed well with stirring, and a charge control agent premix solution was obtained by preliminary dispersion.

  The premix solution was dispersed as a raw material slurry using a wet bead mill (a batch type tabletop sand mill manufactured by Kansai Paint Co., Ltd.). As dispersion media, zirconia beads having a diameter of 300 μm (true density 6.0 g / cm 3) were used and mixed with the raw material slurry 1 at a weight ratio of 5 to a total amount of 1200 g. A stainless steel disc-shaped stirring blade with a diameter of 7 cm and a thickness of 0.6 cm is fixed along the rotation center axis of the bead mill, and the premix solution is placed so that the blade is sufficiently immersed in the mixture of raw material slurry and beads. I set a beaker. This beaker was immersed in a constant temperature water bath, and 10 ° C. cooling water was circulated by a constant temperature cooler during the bead mill operation. The number of revolutions of the stirring blade was made constant at 1490 rpm, and the mixture was stirred for about 1 hour to obtain a dispersion when the particle size reached a predetermined level.

  The beads and filtrate were completely separated with a 100 mesh stainless steel sieve to obtain a charge control agent dispersion. This dispersion was diluted with UPA (manufactured by Nikkiso Co., Ltd., UPA-150) to an appropriate concentration in water in which several μL of the above anionic surfactant was dropped, and the particle size distribution of the particles was measured in a measurement time of 100 seconds. did. The volume particle size distribution median diameter of the obtained particles was 160 nm.

<Manufacture of toner mother particles M>
The component of the toner base particle K is 9.0 parts of the colorant dispersion quinacridone, and the agglomeration process (core material agglomeration process / shell coating process), circularization process, washing process, and drying process of “manufacturing the toner base particle K” 1 except that the “core material agglomeration step”, “shell coating step” and “circularization step” were changed as described below in the same manner as in “Production of toner mother particles K” in Example 1. Particle M was obtained.

○ Core material aggregation process
Polymer primary particle dispersion A1 and 20% in a mixer (volume 12 L, inner diameter 208 mm, height 355 mm) equipped with a stirring device (double helical blade), heating / cooling device, concentrating device, and each raw material / auxiliary charging device A DBS aqueous solution was charged and mixed uniformly at an internal temperature of 7 ° C. for 5 minutes. Subsequently, while maintaining the internal temperature at 7 ° C. and continuing stirring at 250 rpm, 0.52 part of 5 mass% aqueous solution of ferrous sulfate was added as FeSO ₄ · 7H ₂ O over 5 minutes, and then the colorant The dispersion was added over 5 minutes, mixed uniformly at an internal temperature of 7 ° C., and a 0.5% by mass aqueous solution of aluminum sulfate was added dropwise over 8 minutes with the same conditions (solid to resin solids). Min is 0.10 parts). Thereafter, the internal temperature was raised to 55.0 ° C. while maintaining the rotational speed of 250 rpm, the volume median diameter (Dv50) was measured using a multisizer, and grown to 7.25 μm.

○ Shell coating process
Thereafter, a liquid obtained by mixing 0.3 part of the polymer primary particle dispersion A2 and the charge control agent dispersion β was added over 3 minutes while maintaining the internal temperature at 55.0 ° C. and the rotation speed of 250 rpm, and held as it was for 60 minutes. .
○ Circularization process
Subsequently, the rotational speed was reduced to 150 rpm (a peripheral speed of 1.56 m / sec at the tip of the stirring blade, a stirring speed reduced by 40% with respect to the rotational speed of the aggregation process), and then a 20% DBS aqueous solution (6 parts as solid content) was added. The mixture was added over 10 minutes, then heated to 84 ° C. over 30 minutes, and heating and stirring were continued until the average circularity reached 0.944. Thereafter, it was cooled to 30 ° C. over 20 minutes to obtain a slurry.

<Manufacture of toner M>
Thereafter, the toner M was prepared in the same manner as in “Production of Toner K” except that the amount of H2000 silica as an external additive was changed to 1.41 g and the amount of SMT150IB titania fine powder was changed to 0.56 g. Got.
○ Analysis process
The volume median diameter (Dv50) measured using a multisizer of the toner M obtained here is 7.25 μm, and “number% (Dns) of toner having a particle diameter of 2.00 μm to 3.56 μm” is The average circularity was 0.944 and the number variation coefficient was 18.9%.
Further, the depression of the charge control agent on the toner surface was 350 nm, and the charge control agent was present within ± R with respect to the toner surface.

Example 4
<Manufacture of toner mother particles N>
The component of the toner base particle K is 9.0 parts of the colorant dispersion quinacridone, and the agglomeration process (core material agglomeration process / shell coating process), circularization process, washing process, and drying process of “manufacturing the toner base particle K” 1 except that the “core material agglomeration step”, “shell coating step” and “circularization step” were changed as described below in the same manner as in “Production of toner mother particles K” in Example 1. Particle N was obtained.

○ Core material aggregation process
Polymer primary particle dispersion A1 and 20% in a mixer (volume 12 L, inner diameter 208 mm, height 355 mm) equipped with a stirring device (double helical blade), heating / cooling device, concentrating device, and each raw material / auxiliary charging device A DBS aqueous solution was charged and mixed uniformly at an internal temperature of 7 ° C. for 5 minutes. Subsequently, while maintaining the internal temperature at 7 ° C. and continuing stirring at 250 rpm, 0.52 part of 5 mass% aqueous solution of ferrous sulfate was added as FeSO ₄ · 7H ₂ O over 5 minutes, and then the colorant The dispersion was added over 5 minutes, mixed uniformly at an internal temperature of 7 ° C., and a 0.5% by mass aqueous solution of aluminum sulfate was added dropwise over 8 minutes with the same conditions (solid to resin solids). Min is 0.10 parts). Thereafter, the internal temperature was raised to 55.0 ° C. while maintaining the rotational speed of 250 rpm, the volume median diameter (Dv50) was measured using a multisizer, and grown to 7.05 μm.

○ Shell coating process
Thereafter, with an internal temperature of 55.0 ° C. and a rotational speed of 250 rpm, a solution obtained by mixing 0.5 part of the polymer primary particle dispersion A2 and the charge control agent dispersion β was added over 3 minutes and held for 60 minutes. .
○ Circularization process
Subsequently, the rotational speed was reduced to 150 rpm (a peripheral speed of 1.56 m / sec at the tip of the stirring blade, a stirring speed reduced by 40% with respect to the rotational speed of the aggregation process), and then a 20% DBS aqueous solution (6 parts as solid content) was added. The mixture was added over 10 minutes, then heated to 84 ° C. over 30 minutes, and heating and stirring were continued until the average circularity reached 0.943. Thereafter, it was cooled to 30 ° C. over 20 minutes to obtain a slurry.

<Manufacture of toner N>
Thereafter, the toner N was prepared by the same external addition process as in “Production of toner K” except that the amount of H2000 silica as an external additive was changed to 1.41 g and the amount of SMT150IB titania fine powder was changed to 0.56 g. Got.
○ Analysis process
The volume median diameter (Dv50) measured using a multisizer of toner N obtained here is 7.05 μm, and “the number% (Dns) of toner having a particle size of 2.00 μm to 3.56 μm” is The average circularity was 0.943 and the number variation coefficient was 19.6%.
Further, the depression of the charge control agent on the toner surface was 350 nm, and the charge control agent was present within ± R with respect to the toner surface.

Example 5
<Manufacture of toner mother particles O>
The component of the toner base particle K is 9.0 parts of the colorant dispersion quinacridone, and the agglomeration step (core material agglomeration step / shell coating step), circularization step, washing step, drying step 1 except that the “core material agglomeration step”, “shell coating step” and “circularization step” were changed as described below in the same manner as in “Production of toner mother particles K” in Example 1. Particle O was obtained.

○ Core material aggregation process
Polymer primary particle dispersion A1 and 20% in a mixer (volume 12 L, inner diameter 208 mm, height 355 mm) equipped with a stirring device (double helical blade), heating / cooling device, concentrating device, and each raw material / auxiliary charging device A DBS aqueous solution was charged and mixed uniformly at an internal temperature of 7 ° C. for 5 minutes. Subsequently, while maintaining the internal temperature at 7 ° C. and continuing stirring at 250 rpm, 0.52 part of 5 mass% aqueous solution of ferrous sulfate was added as FeSO ₄ · 7H ₂ O over 5 minutes, and then the colorant The dispersion was added over 5 minutes, mixed uniformly at an internal temperature of 7 ° C., and a 0.5% by mass aqueous solution of aluminum sulfate was added dropwise over 8 minutes with the same conditions (solid to resin solids). Min is 0.10 parts). Thereafter, the internal temperature was raised to 55.0 ° C. while maintaining the rotational speed of 250 rpm, the volume median diameter (Dv50) was measured using a multisizer, and grown to 7.08 μm.

○ Shell coating process
Thereafter, a liquid obtained by mixing 1.0 part of the polymer primary particle dispersion A2 and the charge control agent dispersion β was added over 3 minutes while maintaining the internal temperature at 55.0 ° C. and the rotation speed of 250 rpm, and held for 60 minutes. .
○ Circularization process
Subsequently, the rotational speed was reduced to 150 rpm (a peripheral speed of 1.56 m / sec at the tip of the stirring blade, a stirring speed reduced by 40% with respect to the rotational speed of the aggregation process), and then a 20% DBS aqueous solution (6 parts as solid content) was added. The mixture was added over 10 minutes, then heated to 84 ° C. over 30 minutes, and heating and stirring were continued until the average circularity reached 0.948. Thereafter, it was cooled to 30 ° C. over 20 minutes to obtain a slurry.

<Manufacture of toner O>
Thereafter, the amount of H2000 silica as an external additive was changed to 1.41 g, and the amount of SMT150IB titania fine powder was changed to 0.56 g. Got.
○ Analysis process
The volume median diameter (Dv50) measured using a multisizer of toner O obtained here is 7.08 μm, and “number% (Dns) of toner having a particle size of 2.00 μm to 3.56 μm” is The average circularity was 0.948 and the number variation coefficient was 19.1%.
Further, the depression of the charge control agent on the toner surface was 350 nm, and the charge control agent was present within ± R with respect to the toner surface.

Example 6
<Preparation of Charge Control Agent Dispersion γ>
10 parts powder of charge control agent T-77 (made by Hodogaya Chemical Co., Ltd.), 10 parts anionic surfactant (made by Daiichi Kogyo Seiyaku Co., Ltd., Neogen S-20A) in a 1 L stainless beaker with a stirring blade set Then, 80 parts of ion-exchanged water having an electric conductivity of 2 μS / cm was added and mixed well with stirring, and a charge control agent premix solution was obtained by preliminary dispersion.

  The premix solution was dispersed as a raw material slurry using a wet bead mill (a batch type tabletop sand mill manufactured by Kansai Paint Co., Ltd.). As dispersion media, zirconia beads having a diameter of 300 μm (true density 6.0 g / cm 3) were used and mixed with the raw material slurry 1 at a weight ratio of 5 to a total amount of 1200 g. A stainless steel disc-shaped stirring blade with a diameter of 7 cm and a thickness of 0.6 cm is fixed along the rotation center axis of the bead mill, and the premix solution is placed so that the blade is sufficiently immersed in the mixture of raw material slurry and beads. I set a beaker. This beaker was immersed in a constant temperature water bath, and 10 ° C. cooling water was circulated by a constant temperature cooler during the bead mill operation. The number of revolutions of the stirring blade was made constant at 1490 rpm, and the mixture was stirred for about 1 hour to obtain a dispersion when the particle size reached a predetermined level.

  The beads and filtrate were completely separated with a 100 mesh stainless steel sieve to obtain a charge control agent dispersion. This dispersion was diluted with UPA (manufactured by Nikkiso Co., Ltd., UPA-150) to an appropriate concentration in water in which several μL of the above anionic surfactant was dropped, and the particle size distribution of the particles was measured in a measurement time of 100 seconds. did. The volume particle size distribution median diameter of the obtained particles was 180 nm.

<Manufacture of toner mother particles P>
The component of the toner base particle K is 9.0 parts of the colorant dispersion quinacridone, and the agglomeration process (core material agglomeration process / shell coating process), circularization process, washing process, and drying process of “manufacturing the toner base particle K” 1 except that the “core material agglomeration step”, “shell coating step” and “circularization step” were changed as described below in the same manner as in “Production of toner mother particles K” in Example 1. Particles P were obtained.

○ Core material aggregation process
Polymer primary particle dispersion A1 and 20% in a mixer (volume 12 L, inner diameter 208 mm, height 355 mm) equipped with a stirring device (double helical blade), heating / cooling device, concentrating device, and each raw material / auxiliary charging device A DBS aqueous solution was charged and mixed uniformly at an internal temperature of 7 ° C. for 5 minutes. Subsequently, while maintaining the internal temperature at 7 ° C. and continuing stirring at 250 rpm, 0.52 part of 5 mass% aqueous solution of ferrous sulfate was added as FeSO ₄ · 7H ₂ O over 5 minutes, and then the colorant The dispersion was added over 5 minutes, mixed uniformly at an internal temperature of 7 ° C., and a 0.5% by mass aqueous solution of aluminum sulfate was added dropwise over 8 minutes with the same conditions (solid to resin solids). Min is 0.10 parts). Thereafter, the internal temperature was raised to 55.0 ° C. while maintaining the rotational speed of 250 rpm, the volume median diameter (Dv50) was measured using a multisizer, and grown to 6.91 μm.

○ Shell coating process
Thereafter, with an internal temperature of 55.0 ° C. and a rotational speed of 250 rpm, a liquid in which 1.0 part of the polymer primary particle dispersion A2 and the charge control agent dispersion γ were mixed was added over 3 minutes, and held for 60 minutes. .
○ Circularization process
Subsequently, the rotational speed was reduced to 150 rpm (a peripheral speed of 1.56 m / sec at the tip of the stirring blade, a stirring speed reduced by 40% with respect to the rotational speed of the aggregation process), and then a 20% DBS aqueous solution (6 parts as solid content) was added. The mixture was added over 10 minutes, then heated to 84 ° C. over 30 minutes, and heating and stirring were continued until the average circularity reached 0.948. Thereafter, it was cooled to 30 ° C. over 20 minutes to obtain a slurry.

<Manufacture of toner P>
Thereafter, the toner P was prepared by the same external addition process as in “Production of Toner K” except that the amount of H2000 silica as an external additive was changed to 1.41 g and the amount of SMT150IB titania fine powder was changed to 0.56 g. Got.
○ Analysis process
The volume median diameter (Dv50) measured using a multisizer of the toner P obtained here is 6.91 μm, and “the number% (Dns) of toner having a particle size of 2.00 μm to 3.56 μm” is The average circularity was 0.948 and the number variation coefficient was 22.3%.
Further, the depression of the charge control agent on the toner surface was 400 nm, and the charge control agent was present within ± R with respect to the toner surface.

Comparative Example 1
<Manufacture of toner mother particles Q>
The component of the toner base particle K is 9.0 parts of the colorant dispersion quinacridone, and the agglomeration process (core material agglomeration process / shell coating process), circularization process, washing process, and drying process of “manufacturing the toner base particle K” 1 except that the “core material agglomeration step”, “shell coating step” and “circularization step” were changed as described below in the same manner as in “Production of toner mother particles K” in Example 1. Particle Q was obtained.

○ Core material aggregation process
Polymer primary particle dispersion A1 and 20% in a mixer (volume 12 L, inner diameter 208 mm, height 355 mm) equipped with a stirring device (double helical blade), heating / cooling device, concentrating device, and each raw material / auxiliary charging device A DBS aqueous solution was charged and mixed uniformly at an internal temperature of 7 ° C. for 5 minutes. Subsequently, while maintaining the internal temperature at 7 ° C. and continuing stirring at 250 rpm, 0.52 part of 5 mass% aqueous solution of ferrous sulfate was added as FeSO ₄ · 7H ₂ O over 5 minutes, and then the colorant The dispersion was added over 5 minutes, mixed uniformly at an internal temperature of 7 ° C., and a 0.5% by mass aqueous solution of aluminum sulfate was added dropwise over 8 minutes with the same conditions (solid to resin solids). Min is 0.10 parts). Thereafter, the internal temperature was raised to 55.0 ° C. while maintaining the rotational speed of 250 rpm, the volume median diameter (Dv50) was measured using a multisizer, and grown to 6.71 μm.

○ Shell coating step Thereafter, the polymer primary particle dispersion A2 was added over 3 minutes while maintaining the internal temperature at 55.0 ° C. and the rotation speed at 250 rpm, and held as it was for 60 minutes.
○ Circularization process
Subsequently, the rotational speed was reduced to 150 rpm (a peripheral speed of 1.56 m / second at the tip of the stirring blade, a stirring speed reduced by 40% with respect to the rotational speed of the aggregation process), and then a 20% DBS aqueous solution (6 parts as solid content) was added. The mixture was added over 10 minutes, then heated to 84 ° C. over 30 minutes, and heating and stirring were continued until the average circularity reached 0.945. Thereafter, it was cooled to 30 ° C. over 20 minutes to obtain a slurry.

<Manufacture of toner Q>
Thereafter, the amount of H2000 silica as an external additive was changed to 1.41 g, and SMT150IB
Except for changing the amount of fine titania powder to 0.56 g, Toner Q was obtained by the same operation of the external addition process as “Production of Toner K”.
○ Analysis process
The volume-median diameter (Dv50) of the toner Q obtained using the multisizer obtained here is 6.71 μm, and “the number% (Dns) of toner having a particle size of 2.00 μm to 3.56 μm” is The average circularity was 0.945 and the number variation coefficient was 20.3%.

Comparative Example 2
<Preparation of Charge Control Agent Dispersion δ>
10 parts of a powder of charge control agent E-84 (manufactured by Orient Chemical Co., Ltd.), 10 parts of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen S-20A) in a 1 L stainless beaker with a stirring blade set, 80 parts of ion-exchanged water having an electric conductivity of 2 μS / cm was added and well mixed by stirring, and a charge control agent premix solution was obtained by preliminary dispersion.

  The premix solution was dispersed as a raw material slurry using a wet bead mill (a batch type tabletop sand mill manufactured by Kansai Paint Co., Ltd.). As dispersion media, zirconia beads having a diameter of 300 μm (true density 6.0 g / cm 3) were used and mixed with the raw material slurry 1 at a weight ratio of 5 to a total amount of 1200 g. A stainless steel disc-shaped stirring blade with a diameter of 7 cm and a thickness of 0.6 cm is fixed along the rotation center axis of the bead mill, and the premix solution is placed so that the blade is sufficiently immersed in the mixture of raw material slurry and beads. I set a beaker. This beaker was immersed in a constant temperature water bath, and 10 ° C. cooling water was circulated by a constant temperature cooler during the bead mill operation. The number of revolutions of the stirring blade was kept constant at 525 rpm, and the mixture was stirred for about 0.5 hours to obtain a dispersion when the particle size reached a predetermined level.

  The beads and filtrate were completely separated with a 100 mesh stainless steel sieve to obtain a charge control agent dispersion. This dispersion was diluted with UPA (manufactured by Nikkiso Co., Ltd., UPA-150) to an appropriate concentration in water in which several μL of the above anionic surfactant was dropped, and the particle size distribution of the particles was measured in a measurement time of 100 seconds. did. The volume particle size distribution median diameter of the obtained particles was 650 nm.

<Manufacture of toner mother particle R>
The component of the toner base particle K is 9.0 parts of the colorant dispersion quinacridone, and the agglomeration process (core material agglomeration process / shell coating process), circularization process, washing process, and drying process of “manufacturing the toner base particle K” 1 except that the “core material agglomeration step”, “shell coating step” and “circularization step” were changed as described below in the same manner as in “Production of toner mother particles K” in Example 1. Particle R was obtained.

○ Core material aggregation process
Polymer primary particle dispersion A1 and 20% in a mixer (volume 12 L, inner diameter 208 mm, height 355 mm) equipped with a stirring device (double helical blade), heating / cooling device, concentrating device, and each raw material / auxiliary charging device A DBS aqueous solution was charged and mixed uniformly at an internal temperature of 7 ° C. for 5 minutes. Subsequently, while maintaining the internal temperature at 7 ° C. and continuing stirring at 250 rpm, 0.52 part of 5 mass% aqueous solution of ferrous sulfate was added as FeSO ₄ · 7H ₂ O over 5 minutes, and then the colorant The dispersion was added over 5 minutes, mixed uniformly at an internal temperature of 7 ° C., and a 0.5% by mass aqueous solution of aluminum sulfate was added dropwise over 8 minutes with the same conditions (solid to resin solids). Min is 0.10 parts). Thereafter, the internal temperature was raised to 55.0 ° C. while maintaining the rotational speed of 250 rpm, the volume median diameter (Dv50) was measured using a multisizer, and grown to 6.60 μm.

○ Shell coating process
Thereafter, with an internal temperature of 55.0 ° C. and a rotational speed of 250 rpm, a liquid in which 1.0 part of the polymer primary particle dispersion A2 and the charge control agent dispersion δ was mixed was added over 3 minutes and held as it was for 60 minutes. .
○ Circularization process
Subsequently, the rotational speed was reduced to 150 rpm (a peripheral speed of 1.56 m / sec at the tip of the stirring blade, a stirring speed reduced by 40% with respect to the rotational speed of the aggregation process), and then a 20% DBS aqueous solution (6 parts as solid content) was added. The mixture was added over 10 minutes, then heated to 84 ° C. over 30 minutes, and heating and stirring were continued until the average circularity reached 0.936. Thereafter, it was cooled to 30 ° C. over 20 minutes to obtain a slurry.

<Manufacture of toner R>
Thereafter, the toner R was changed in the same manner as in “Production of toner K” except that the amount of H2000 silica as an external additive was changed to 1.41 g and the amount of SMT150IB titania fine powder was changed to 0.56 g. Got.
○ Analysis process
The volume median diameter (Dv50) measured using a multisizer of the toner R obtained here is 6.60 μm, and “number% (Dns) of toner having a particle size of 2.00 μm to 3.56 μm” is The average circularity was 0.936 and the number variation coefficient was 21.8%.
The depression of the charge control agent on the toner surface was 1200 nm, and the charge control agent was present in ± R with respect to the toner surface.

Comparative Example 3
<Preparation of charge control agent dispersion ε>
10 parts of powder of charge control agent TN-105 (Hodogaya Chemical Co., Ltd.), 10 parts of anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen S-20A) in a 1 L stainless beaker with a stirring blade set Then, 80 parts of ion-exchanged water having an electric conductivity of 2 μS / cm was added and mixed well with stirring, and a charge control agent premix solution was obtained by preliminary dispersion.

  The premix solution was dispersed as a raw material slurry using a wet bead mill (a batch type tabletop sand mill manufactured by Kansai Paint Co., Ltd.). As dispersion media, zirconia beads having a diameter of 300 μm (true density 6.0 g / cm 3) were used and mixed with the raw material slurry 1 at a weight ratio of 5 to a total amount of 1200 g. A stainless steel disc-shaped stirring blade with a diameter of 7 cm and a thickness of 0.6 cm is fixed along the rotation center axis of the bead mill, and the premix solution is placed so that the blade is sufficiently immersed in the mixture of raw material slurry and beads. I set a beaker. This beaker was immersed in a constant temperature water bath, and 10 ° C. cooling water was circulated by a constant temperature cooler during the bead mill operation. The number of revolutions of the stirring blade was kept constant at 525 rpm, and the mixture was stirred for about 0.5 hours to obtain a dispersion when the particle size reached a predetermined level.

  The beads and filtrate were completely separated with a 100 mesh stainless steel sieve to obtain a charge control agent dispersion. This dispersion was diluted with UPA (manufactured by Nikkiso Co., Ltd., UPA-150) to an appropriate concentration in water in which several μL of the above anionic surfactant was dropped, and the particle size distribution of the particles was measured in a measurement time of 100 seconds. did. The volume particle size distribution median diameter of the obtained particles was 550 nm.

<Manufacture of toner mother particles S>
The component of the toner base particle K is 9.0 parts of the colorant dispersion quinacridone, and the agglomeration process (core material agglomeration process / shell coating process), circularization process, washing process, and drying process of “manufacturing the toner base particle K” 1 except that the “core material agglomeration step”, “shell coating step” and “circularization step” were changed as described below in the same manner as in “Production of toner mother particles K” in Example 1. Particles S were obtained.

○ Core material aggregation process
Polymer primary particle dispersion A1 and 20% in a mixer (volume 12 L, inner diameter 208 mm, height 355 mm) equipped with a stirring device (double helical blade), heating / cooling device, concentrating device, and each raw material / auxiliary charging device A DBS aqueous solution was charged and mixed uniformly at an internal temperature of 7 ° C. for 5 minutes. Subsequently, while maintaining the internal temperature at 7 ° C. and continuing stirring at 250 rpm, 0.52 part of 5 mass% aqueous solution of ferrous sulfate was added as FeSO ₄ · 7H ₂ O over 5 minutes, and then the colorant The dispersion was added over 5 minutes, mixed uniformly at an internal temperature of 7 ° C., and a 0.5% by mass aqueous solution of aluminum sulfate was added dropwise over 8 minutes with the same conditions (solid to resin solids). Min is 0.10 parts). Thereafter, the internal temperature was raised to 55.0 ° C. while maintaining the rotational speed of 250 rpm, and the volume median diameter (Dv50) was measured using a multisizer to grow it to 6.83 μm.

○ Shell coating process
Thereafter, a liquid in which 1.0 part of the polymer primary particle dispersion A2 and the charge control agent dispersion ε was mixed was added over 3 minutes while maintaining the internal temperature at 55.0 ° C. and the rotation speed of 250 rpm, and the mixture was held as it was for 60 minutes. .
○ Circularization process
Subsequently, the rotational speed was reduced to 150 rpm (a peripheral speed of 1.56 m / sec at the tip of the stirring blade, a stirring speed reduced by 40% with respect to the rotational speed of the aggregation process), and then a 20% DBS aqueous solution (6 parts as solid content) was added. The mixture was added over 10 minutes, then heated to 84 ° C. over 30 minutes, and heating and stirring were continued until the average circularity reached 0.944. Thereafter, it was cooled to 30 ° C. over 20 minutes to obtain a slurry.

<Manufacture of toner S>
Thereafter, the toner S was prepared in the same manner as in “Production of Toner K” except that the amount of H2000 silica as an external additive was changed to 1.41 g and the amount of SMT150IB titania fine powder was changed to 0.56 g. Got.
○ Analysis process
The volume median diameter (Dv50) measured using a multisizer of the toner S obtained here is 6.83 μm, and “number% (Dns) of toner having a particle size of 2.00 μm to 3.56 μm” is The average circularity was 0.944 and the number variation coefficient was 22.8%.
The depression of the charge control agent on the toner surface was 1200 nm, and the charge control agent was present in ± R with respect to the toner surface.

Comparative Example 4
<Preparation of Charge Control Resin (CCR) Dispersion ζ>
10 parts powder of charge control resin FC2521NJ (manufactured by Fujikura Kasei), 10 parts of an anionic surfactant (Neogen S-20A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), conductivity 2 μS 80 parts of ion-exchanged water / cm was added and well mixed by stirring, and a charge control agent premix solution was obtained by preliminary dispersion.

  The premix solution was dispersed as a raw material slurry using a wet bead mill (a batch type tabletop sand mill manufactured by Kansai Paint Co., Ltd.). As dispersion media, zirconia beads having a diameter of 300 μm (true density 6.0 g / cm 3) were used and mixed with the raw material slurry 1 at a weight ratio of 5 to a total amount of 1200 g. A stainless steel disc-shaped stirring blade with a diameter of 7 cm and a thickness of 0.6 cm is fixed along the rotation center axis of the bead mill, and the premix solution is placed so that the blade is sufficiently immersed in the mixture of raw material slurry and beads. I set a beaker. This beaker was immersed in a constant temperature water bath, and 10 ° C. cooling water was circulated by a constant temperature cooler during the bead mill operation. The number of revolutions of the stirring blade was kept constant at 1490 rpm, and the mixture was stirred for about 2 hours.

The beads and filtrate were completely separated with a 100 mesh stainless steel sieve to obtain a charge control agent dispersion. This dispersion was diluted with UPA (manufactured by Nikkiso Co., Ltd., UPA-150) to an appropriate concentration in water in which several μL of the above anionic surfactant was dropped, and the particle size distribution of the particles was measured in a measurement time of 100 seconds. did. The volume particle size distribution median diameter of the obtained particles was 66 nm.

<Manufacture of toner mother particles T>
The component of the toner base particle K is 9.0 parts of the colorant dispersion quinacridone, and the agglomeration process (core material agglomeration process / shell coating process), circularization process, washing process, and drying process of “manufacturing the toner base particle K” 1 except that the “core material agglomeration step”, “shell coating step” and “circularization step” were changed as described below in the same manner as in “Production of toner mother particles K” in Example 1. Particles T were obtained.

○ Core material aggregation process
Polymer primary particle dispersion A1 and 20% in a mixer (volume 12 L, inner diameter 208 mm, height 355 mm) equipped with a stirring device (double helical blade), heating / cooling device, concentrating device, and each raw material / auxiliary charging device A DBS aqueous solution was charged and mixed uniformly at an internal temperature of 7 ° C. for 5 minutes. Subsequently, while maintaining the internal temperature at 7 ° C. and continuing stirring at 250 rpm, 0.52 part of 5 mass% aqueous solution of ferrous sulfate was added as FeSO ₄ · 7H ₂ O over 5 minutes, and then the colorant The dispersion was added over 5 minutes, mixed uniformly at an internal temperature of 7 ° C., and a 0.5% by mass aqueous solution of aluminum sulfate was added dropwise over 8 minutes with the same conditions (solid to resin solids). Min is 0.10 parts). Thereafter, the internal temperature was raised to 55.0 ° C. while maintaining the rotational speed of 250 rpm, the volume median diameter (Dv50) was measured using a multisizer, and grown to 5.71 μm.

○ Shell coating process
Thereafter, a liquid obtained by mixing 0.5 part of the polymer primary particle dispersion A2 and the charge control agent dispersion ε was added over 3 minutes while maintaining the internal temperature at 55.0 ° C. and the rotation speed of 250 rpm, and held for 60 minutes. .
○ Circularization process
Subsequently, the rotational speed was reduced to 150 rpm (a peripheral speed of 1.56 m / sec at the tip of the stirring blade, a stirring speed reduced by 40% with respect to the rotational speed of the aggregation process), and then a 20% DBS aqueous solution (6 parts as solid content) was added. The mixture was added over 10 minutes, then heated to 84 ° C. over 30 minutes, and heating and stirring were continued until the average circularity reached 0.958. Thereafter, it was cooled to 30 ° C. over 20 minutes to obtain a slurry.

<Manufacture of toner T>
Thereafter, the toner T was prepared in the same manner as in “Production of toner K” except that the amount of H2000 silica as an external additive was changed to 1.41 g and the amount of SMT150IB titania fine powder was changed to 0.56 g. Got.
○ Analysis process
The volume median diameter (Dv50) measured using a multisizer of the toner T obtained here is 5.71 μm, and the “number% (Dns) of toner having a particle size of 2.00 μm to 3.56 μm” is The average circularity was 0.958 and the number variation coefficient was 22%.
Further, no depression of the charge control agent on the toner surface was observed, and the charge control agent was not present in ± R with respect to the toner surface.

Comparative Example 5
<Manufacture of toner mother particles U>
The component of the toner base particle K is 9.0 parts of the colorant dispersion quinacridone, and the agglomeration process (core material agglomeration process / shell coating process), circularization process, washing process, and drying process of “manufacturing the toner base particle K” 1 except that the “core material agglomeration step”, “shell coating step” and “circularization step” were changed as described below in the same manner as in “Production of toner mother particles K” in Example 1. Particle U was obtained.

○ Core material aggregation process
Polymer primary particle dispersion A1 and 20% in a mixer (volume 12 L, inner diameter 208 mm, height 355 mm) equipped with a stirring device (double helical blade), heating / cooling device, concentrating device, and each raw material / auxiliary charging device A DBS aqueous solution was charged and mixed uniformly at an internal temperature of 7 ° C. for 5 minutes. Subsequently, while maintaining the internal temperature at 7 ° C. and continuing stirring at 250 rpm, 0.52 part of 5 mass% aqueous solution of ferrous sulfate was added as FeSO ₄ · 7H ₂ O over 5 minutes, and then the colorant The dispersion was added over 5 minutes, and 1.0 part of the charge control agent dispersion β was uniformly mixed at an internal temperature of 7 ° C. over 3 minutes, and further 0.5 mass% aluminum sulfate with the same conditions. The aqueous solution was added dropwise over 8 minutes (the solid content relative to the resin solid content was 0.10 parts). Thereafter, the internal temperature was raised to 55.0 ° C. while maintaining the rotational speed of 250 rpm, the volume median diameter (Dv50) was measured using a multisizer, and grown to 7.06 μm.

○ Shell coating process
Thereafter, a liquid obtained by mixing 1 part of the polymer primary particle dispersion A2 and the charge control agent dispersion β was added over 3 minutes while maintaining the internal temperature at 55.0 ° C. and the rotation number of 250 rpm, and held for 60 minutes.
○ Circularization process
Subsequently, the rotational speed was reduced to 150 rpm (a peripheral speed of 1.56 m / sec at the tip of the stirring blade, a stirring speed reduced by 40% with respect to the rotational speed of the aggregation process), and then a 20% DBS aqueous solution (6 parts as solid content) was added. The mixture was added over 10 minutes, then heated to 84 ° C. over 30 minutes, and heating and stirring were continued until the average circularity reached 0.943. Thereafter, it was cooled to 30 ° C. over 20 minutes to obtain a slurry.

<Manufacture of toner U>
Thereafter, the toner U was changed to 1.41 g as an external additive, and the amount of SMT150IB titania fine powder was changed to 0.56 g. Got.
○ Analysis process
The volume median diameter (Dv50) measured using a multisizer of the toner U obtained here is 7.06 μm, and the “number% (Dns) of toner having a particle diameter of 2.00 μm to 3.56 μm” is The average circularity was 0.943 and the number variation coefficient was 21.2%.
Further, no depression of the charge control agent on the toner surface was observed, and the charge control agent was not present in ± R with respect to the toner surface.

Comparative Example 6
<Manufacture of toner mother particles V>
The component of the toner base particle K is 9.0 parts of the colorant dispersion quinacridone, and the agglomeration process (core material agglomeration process / shell coating process), circularization process, washing process, and drying process of “manufacturing the toner base particle K” 1 except that the “core material agglomeration step”, “shell coating step” and “circularization step” were changed as described below in the same manner as in “Production of toner mother particles K” in Example 1. Particle V was obtained.

○ Core material aggregation process
Polymer primary particle dispersion A1 and 20% in a mixer (volume 12 L, inner diameter 208 mm, height 355 mm) equipped with a stirring device (double helical blade), heating / cooling device, concentrating device, and each raw material / auxiliary charging device A DBS aqueous solution was charged and mixed uniformly at an internal temperature of 7 ° C. for 5 minutes. Subsequently, while maintaining the internal temperature at 7 ° C. and continuing stirring at 250 rpm, 0.52 part of 5 mass% aqueous solution of ferrous sulfate was added as FeSO ₄ · 7H ₂ O over 5 minutes, and then the colorant The dispersion was added over 5 minutes, mixed uniformly at an internal temperature of 7 ° C., and a 0.5% by mass aqueous solution of aluminum sulfate was added dropwise over 8 minutes with the same conditions (solid to resin solids). Min is 0.10 parts). Thereafter, the internal temperature was raised to 55.0 ° C. while maintaining the rotational speed of 250 rpm, the volume median diameter (Dv50) was measured using a multisizer, and grown to 6.56 μm.

○ Shell coating process
Thereafter, a liquid obtained by mixing 1.0 part of the polymer primary particle dispersion A2 and the charge control agent dispersion β was added over 3 minutes while maintaining the internal temperature at 55.0 ° C. and the rotation speed of 250 rpm, and held for 60 minutes. .
○ Circularization process
Subsequently, the rotational speed was reduced to 150 rpm (a peripheral speed of 1.56 m / second at the tip of the stirring blade, a stirring speed reduced by 40% with respect to the rotational speed of the aggregation process), and then a 20% DBS aqueous solution (6 parts as solid content) was added. The mixture was added over 10 minutes, then heated to 84 ° C. over 30 minutes, and heating and stirring were continued until the average circularity reached 0.945. Thereafter, it was cooled to 30 ° C. over 20 minutes to obtain a slurry.

<Manufacture of toner V>
Thereafter, the toner V was changed by the same external addition process as in “Production of Toner K” except that the amount of H2000 silica as an external additive was changed to 1.41 g and the amount of SMT150IB titania fine powder was changed to 0.56 g. Got.
○ Analysis process
The volume median diameter (Dv50) measured using a multisizer of toner V obtained here is 6.56 μm, and “number% (Dns) of toner having a particle size of 2.00 μm to 3.56 μm” is The average circularity was 0.945 and the number variation coefficient was 24.4%.

Further, the depression of the charge control agent on the toner surface was 350 nm, and the charge control agent was present within ± R with respect to the toner surface.
Example 7
<Preparation of colorant dispersion (monoazo yellow)>
In a container with a volume of 300 L equipped with a stirrer (propeller blade), 20 parts (40 kg) of monoazo yellow (manufactured by Clariant Japan, 5GX01), 1 part of 20% DBS aqueous solution, nonionic surfactant (manufactured by Kao Corporation, Emulgen 120 4 parts and 75 parts of ion-exchanged water having an electric conductivity of 2 μS / cm were added and predispersed to obtain a pigment premix solution. The volume average diameter (Mv) of monoazo yellow in the dispersion after pigment premixing measured with Nanotrac was 100 μm.

The pigment premix solution was supplied as a raw material slurry to a wet bead mill and circulated and dispersed. The inner diameter of the stator was φ75 mm, the separator diameter was φ60 mm, the distance between the separator and the disk was 15 mm, and zirconia beads having a diameter of 50 μm (true density 6.0 g / cm ³ ) were used as the dispersing medium. Since the effective internal volume of the stator is 0.5 L and the filling volume of the media is 0.35 L, the media filling rate is 70% by mass. The pigment premix liquid is continuously supplied from the supply port at a supply speed of 50 L / hr by a non-pulsating metering pump, and the rotor rotation speed is constant (peripheral speed at the rotor tip is 11 m / sec), and continuously from the discharge port The colorant dispersion (monoazo yellow) was obtained when it reached a predetermined particle size by being repeatedly circulated. The volume average diameter (Mv) of the colorant dispersion (monoazo yellow) measured with Nanotrac was 183 nm, and the solid content concentration was 24.0% by mass.

<Manufacture of toner mother particles W>
The component of the toner base particle K is 6.0 parts of a colorant dispersion monoazo yellow, and the agglomeration process (core material agglomeration process / shell coating process), circularization process, washing process, and drying of “manufacturing the toner base particle K”. In the process, except that the “core material aggregating process”, “shell covering process” and “circularization process” were changed as follows, the toner was prepared in the same manner as in “Production of toner base particles K” in Example 1. Base particles W were obtained.

○ Core material aggregation process
Polymer primary particle dispersion A1 and 20% in a mixer (volume 12 L, inner diameter 208 mm, height 355 mm) equipped with a stirring device (double helical blade), heating / cooling device, concentrating device, and each raw material / auxiliary charging device A DBS aqueous solution was charged and mixed uniformly at an internal temperature of 7 ° C. for 5 minutes. Subsequently, while maintaining the internal temperature at 7 ° C. and continuing stirring at 250 rpm, 0.52 part of 5 mass% aqueous solution of ferrous sulfate was added as FeSO ₄ · 7H ₂ O over 5 minutes, and then the colorant The dispersion was added over 5 minutes, mixed uniformly at an internal temperature of 7 ° C., and a 0.5% by mass aqueous solution of aluminum sulfate was added dropwise over 8 minutes with the same conditions (solid to resin solids). Min is 0.10 parts). Thereafter, the internal temperature was raised to 55.0 ° C. while maintaining the rotational speed of 250 rpm, the volume median diameter (Dv50) was measured using a multisizer, and grown to 5.72 μm.

○ Shell coating process
Thereafter, a liquid obtained by mixing 0.3 part of the polymer primary particle dispersion A2 and the charge control agent dispersion β was added over 3 minutes while maintaining the internal temperature at 55.0 ° C. and the rotation speed of 250 rpm, and held as it was for 60 minutes. .
○ Circularization process
Subsequently, the rotational speed was reduced to 150 rpm (a peripheral speed of 1.56 m / sec at the tip of the stirring blade, a stirring speed reduced by 40% with respect to the rotational speed of the aggregation process), and then a 20% DBS aqueous solution (6 parts as solid content) was added. The mixture was added over 10 minutes, then heated to 84 ° C. over 30 minutes, and heating and stirring were continued until the average circularity reached 0.944. Thereafter, it was cooled to 30 ° C. over 20 minutes to obtain a slurry.

<Toner W production>
Thereafter, the toner W was prepared by the same external addition process as in “Production of Toner K” except that the amount of H2000 silica as an external additive was changed to 1.41 g and the amount of SMT150IB titania fine powder was changed to 0.56 g. Got.
○ Analysis process
The volume median diameter (Dv50) measured by using the multisizer of the toner W obtained here is 5.72 μm, and “the number% (Dns) of toner having a particle size of 2.00 μm to 3.56 μm” is The average circularity was 0.944 and the number variation coefficient was 18.8%.
Further, the depression of the charge control agent on the toner surface was 350 nm, and the charge control agent was present within ± R with respect to the toner surface.

Comparative Example 7
<Manufacture of toner mother particle X>
The component of the toner base particle K is 6.0 parts of a colorant dispersion monoazo yellow, and the agglomeration process (core material agglomeration process / shell coating process), circularization process, washing process, and drying of “manufacturing the toner base particle K”. In the process, except that the “core material aggregating process”, “shell covering process” and “circularization process” were changed as follows, the toner was prepared in the same manner as in “Production of toner base particles K” in Example 1. Base particles X were obtained.

○ Core material aggregation process
Polymer primary particle dispersion A1 and 20% in a mixer (volume 12 L, inner diameter 208 mm, height 355 mm) equipped with a stirring device (double helical blade), heating / cooling device, concentrating device, and each raw material / auxiliary charging device A DBS aqueous solution was charged and mixed uniformly at an internal temperature of 7 ° C. for 5 minutes. Subsequently, while maintaining the internal temperature at 7 ° C. and continuing stirring at 250 rpm, 0.52 part of 5 mass% aqueous solution of ferrous sulfate was added as FeSO ₄ · 7H ₂ O over 5 minutes, and then the colorant The dispersion was added over 5 minutes, mixed uniformly at an internal temperature of 7 ° C., and a 0.5% by mass aqueous solution of aluminum sulfate was added dropwise over 8 minutes with the same conditions (solid to resin solids). Min is 0.10 parts). Thereafter, the internal temperature was raised to 55.0 ° C. while maintaining the rotational speed of 250 rpm, the volume median diameter (Dv50) was measured using a multisizer, and grown to 5.94 μm.

○ Shell coating process
Thereafter, the polymer primary particle dispersion A2 was added over 3 minutes while maintaining the internal temperature at 55.0 ° C. and the rotation speed at 250 rpm, and held as it was for 60 minutes.
○ Circularization process
Subsequently, the rotational speed was reduced to 150 rpm (a peripheral speed of 1.56 m / sec at the tip of the stirring blade, a stirring speed reduced by 40% with respect to the rotational speed of the aggregation process), and then a 20% DBS aqueous solution (6 parts as solid content) was added. The mixture was added over 10 minutes, then heated to 84 ° C. over 30 minutes, and heating and stirring were continued until the average circularity reached 0.938. Thereafter, it was cooled to 30 ° C. over 20 minutes to obtain a slurry.

<Toner X production>
Thereafter, the toner X was changed to 1.41 g as an external additive, and the toner X was prepared by the same external addition process as in “Production of toner K”, except that the amount of SMT150IB titania fine powder was changed to 0.56 g. Got.
○ Analysis process
The volume median diameter (Dv50) measured using a multisizer of toner X obtained here is 5.94 μm, and “number% (Dns) of toner having a particle diameter of 2.00 μm to 3.56 μm” is The average circularity was 0.938 and the number variation coefficient was 23.8%.

Example 8
<Preparation of colorant dispersion (phthalocyanine blue)>
In a container with an internal volume of 300 L equipped with a stirrer (propeller blade), 20 parts (40 kg) of phthalocyanine blue (manufactured by Clariant Japan, Hostaperm Blue B2G), 1 part of a 20% DBS aqueous solution, nonionic surfactant (manufactured by Kao Corporation, 4 parts of Emulgen 120) and 75 parts of ion-exchanged water having an electric conductivity of 2 μS / cm were added and predispersed to obtain a pigment premix solution. The volume average diameter (Mv) of phthalocyanine blue in the dispersion after pigment premixing measured with Nanotrac was about 90 μm.

The pigment premix solution was supplied as a raw material slurry to a wet bead mill and circulated and dispersed. The inner diameter of the stator was φ75 mm, the separator diameter was φ60 mm, the distance between the separator and the disk was 15 mm, and zirconia beads having a diameter of 50 μm (true density 6.0 g / cm ³ ) were used as the dispersing medium. Since the effective internal volume of the stator is 0.5 L and the filling volume of the media is 0.35 L, the media filling rate is 70% by mass. The pigment premix liquid is continuously supplied from the supply port at a supply speed of 50 L / hr by a non-pulsating metering pump, and the rotor rotation speed is constant (peripheral speed at the rotor tip is 11 m / sec), and continuously from the discharge port. The colorant dispersion (phthalocyanine blue) was obtained when it reached a predetermined particle size by being repeatedly circulated. The volume average diameter (Mv) of the colorant dispersion (phthalocyanine blue) measured with Nanotrac was 131 nm, and the solid content concentration was 24.1% by mass.

<Manufacture of toner mother particle Y>
The component of the toner base particle K is 4.4 parts of a colorant dispersion phthalocyanine blue, and the aggregation process (core material aggregation process / shell coating process), circularization process, cleaning process, and drying of “manufacturing the toner base particle K” In the process, except that the “core material aggregating process”, “shell covering process” and “circularization process” were changed as follows, the toner was prepared in the same manner as in “Production of toner base particles K” in Example 1. Base particles Y were obtained.

○ Core material aggregation process
Polymer primary particle dispersion A1 and 20% in a mixer (volume 12 L, inner diameter 208 mm, height 355 mm) equipped with a stirring device (double helical blade), heating / cooling device, concentrating device, and each raw material / auxiliary charging device A DBS aqueous solution was charged and mixed uniformly at an internal temperature of 7 ° C. for 5 minutes. Subsequently, while maintaining the internal temperature at 7 ° C. and continuing stirring at 250 rpm, 0.52 part of 5 mass% aqueous solution of ferrous sulfate was added as FeSO ₄ · 7H ₂ O over 5 minutes, and then the colorant The dispersion was added over 5 minutes, mixed uniformly at an internal temperature of 7 ° C., and a 0.5% by mass aqueous solution of aluminum sulfate was added dropwise over 8 minutes with the same conditions (solid to resin solids). Min is 0.10 parts). Thereafter, the internal temperature was raised to 55.0 ° C. while maintaining the rotational speed of 250 rpm, the volume median diameter (Dv50) was measured using a multisizer, and grown to 5.85 μm.

○ Shell coating process
Thereafter, a liquid obtained by mixing 0.3 part of the polymer primary particle dispersion A2 and the charge control agent dispersion β was added over 3 minutes while maintaining the internal temperature at 55.0 ° C. and the rotation speed of 250 rpm, and held as it was for 60 minutes. .
○ Circularization process
Subsequently, the rotational speed was reduced to 150 rpm (a peripheral speed of 1.56 m / sec at the tip of the stirring blade, a stirring speed reduced by 40% with respect to the rotational speed of the aggregation process), and then a 20% DBS aqueous solution (6 parts as solid content) was added. The mixture was added over 10 minutes, then heated to 84 ° C. over 30 minutes, and heating and stirring were continued until the average circularity reached 0.944. Thereafter, it was cooled to 30 ° C. over 20 minutes to obtain a slurry.

<Toner Y production>
Thereafter, the toner Y was changed in the same manner as in “Production of Toner K” except that the amount of H2000 silica as an external additive was changed to 1.41 g and the amount of SMT150IB titania fine powder was changed to 0.56 g. Got.
○ Analysis process
The volume median diameter (Dv50) measured using a multisizer of the toner Y obtained here is 5.85 μm, and “number% (Dns) of toner having a particle size of 2.00 μm to 3.56 μm” is The average circularity was 0.944 and the number variation coefficient was 19%.
Further, the depression of the charge control agent on the toner surface was 350 nm, and the charge control agent was present within ± R with respect to the toner surface.

Comparative Example 8
<Production of toner mother particle Z>
The component of the toner base particle K is 4.4 parts of a colorant dispersion phthalocyanine blue, and the aggregation process (core material aggregation process / shell coating process), circularization process, cleaning process, and drying of “manufacturing the toner base particle K” In the process, except that the “core material aggregating process”, “shell covering process” and “circularization process” were changed as follows, the toner was prepared in the same manner as in “Production of toner base particles K” in Example 1. Base particles Z were obtained.

○ Core material aggregation process
Polymer primary particle dispersion A1 and 20% in a mixer (volume 12 L, inner diameter 208 mm, height 355 mm) equipped with a stirring device (double helical blade), heating / cooling device, concentrating device, and each raw material / auxiliary charging device A DBS aqueous solution was charged and mixed uniformly at an internal temperature of 7 ° C. for 5 minutes. Subsequently, while maintaining the internal temperature at 7 ° C. and continuing stirring at 250 rpm, 0.52 part of 5 mass% aqueous solution of ferrous sulfate was added as FeSO ₄ · 7H ₂ O over 5 minutes, and then the colorant The dispersion was added over 5 minutes, mixed uniformly at an internal temperature of 7 ° C., and a 0.5% by mass aqueous solution of aluminum sulfate was added dropwise over 8 minutes with the same conditions (solid to resin solids). Min is 0.10 parts). Thereafter, the internal temperature was raised to 55.0 ° C. while maintaining the rotational speed of 250 rpm, the volume median diameter (Dv50) was measured using a multisizer, and grown to 5.26 μm.

○ Shell coating process
Thereafter, the polymer primary particle dispersion A2 was added over 3 minutes while maintaining the internal temperature at 55.0 ° C. and the rotation speed at 250 rpm, and held as it was for 60 minutes.
○ Circularization process
Subsequently, the rotational speed was reduced to 150 rpm (a peripheral speed of 1.56 m / sec at the tip of the stirring blade, a stirring speed reduced by 40% with respect to the rotational speed of the aggregation process), and then a 20% DBS aqueous solution (6 parts as solid content) was added. The mixture was added over 10 minutes, then heated to 84 ° C. over 30 minutes, and heating and stirring were continued until the average circularity reached 0.940. Thereafter, it was cooled to 30 ° C. over 20 minutes to obtain a slurry.

<Manufacture of toner Z>
Thereafter, the toner Z was prepared in the same manner as in “Production of toner K” except that the amount of H2000 silica as an external additive was changed to 1.41 g and the amount of SMT150IB titania fine powder was changed to 0.56 g. Got.
○ Analysis process
The volume median diameter (Dv50) measured using a multisizer of toner Z obtained here is 5.26 μm, and “number% (Dns) of toner having a particle diameter of 2.00 μm to 3.56 μm” is The average circularity was 0.940 and the number variation coefficient was 20.8%.

Comparative Example 9
<Production of toner mother particles ZZ>
The component of the toner base particle K is 4.4 parts of a colorant dispersion phthalocyanine blue, and the aggregation process (core material aggregation process / shell coating process), circularization process, cleaning process, and drying of “manufacturing the toner base particle K” In the process, except that the “core material aggregating process”, “shell covering process” and “circularization process” were changed as follows, the toner was prepared in the same manner as in “Production of toner base particles K” in Example 1. Base particles ZZ were obtained.

○ Core material aggregation process
Polymer primary particle dispersion A1 and 20% in a mixer (volume 12 L, inner diameter 208 mm, height 355 mm) equipped with a stirring device (double helical blade), heating / cooling device, concentrating device, and each raw material / auxiliary charging device A DBS aqueous solution was charged and mixed uniformly at an internal temperature of 7 ° C. for 5 minutes. Subsequently, while maintaining the internal temperature at 7 ° C. and continuing stirring at 250 rpm, 0.52 part of 5 mass% aqueous solution of ferrous sulfate was added as FeSO ₄ · 7H ₂ O over 5 minutes, and then the colorant The dispersion was added over 5 minutes, mixed uniformly at an internal temperature of 7 ° C., and a 0.5% by mass aqueous solution of aluminum sulfate was added dropwise over 8 minutes with the same conditions (solid to resin solids). Min is 0.10 parts). Thereafter, the internal temperature was raised to 55.0 ° C. while maintaining the rotational speed of 250 rpm, the volume median diameter (Dv50) was measured using a multisizer, and grown to 5.19 μm.

○ Shell coating process
Thereafter, the polymer primary particle dispersion A2 was added over 3 minutes while maintaining the internal temperature at 55.0 ° C. and the rotation speed at 250 rpm, and held as it was for 60 minutes.
○ Circularization process
Subsequently, the rotational speed was reduced to 150 rpm (a peripheral speed of 1.56 m / sec at the tip of the stirring blade, a stirring speed reduced by 40% with respect to the rotational speed of the aggregation process), and then a 20% DBS aqueous solution (6 parts as solid content) was added. The mixture was added over 10 minutes, then heated to 84 ° C. over 30 minutes, and heating and stirring were continued until the average circularity reached 0.943. Thereafter, it was cooled to 30 ° C. over 20 minutes to obtain a slurry.

<Manufacturing toner ZZ>
Thereafter, the toner ZZ was operated by the same external addition process as in “Production of toner K” except that the amount of H2000 silica as an external additive was changed to 1.41 g and the amount of SMT150IB titania fine powder was changed to 0.56 g. Got.
○ Analysis process
The volume median diameter (Dv50) measured by using the multisizer of the toner ZZ obtained here is 5.19 μm, and “number% (Dns) of toner having a particle size of 2.00 μm to 3.56 μm” is The average circularity was 0.943 and the number variation coefficient was 20.3%.

Comparative Example 9
<Manufacture of toner mother particles ZZZ>
The component of the toner base particle K is 4.4 parts of a colorant dispersion phthalocyanine blue, and the aggregation process (core material aggregation process / shell coating process), circularization process, cleaning process, and drying of “manufacturing the toner base particle K” In the process, except that the “core material aggregating process”, “shell covering process” and “circularization process” were changed as follows, the toner was prepared in the same manner as in “Production of toner base particles K” in Example 1. Base particles ZZZ were obtained.

○ Core material aggregation process
Polymer primary particle dispersion A1 and 20% in a mixer (volume 12 L, inner diameter 208 mm, height 355 mm) equipped with a stirring device (double helical blade), heating / cooling device, concentrating device, and each raw material / auxiliary charging device A DBS aqueous solution was charged and mixed uniformly at an internal temperature of 7 ° C. for 5 minutes. Subsequently, while maintaining the internal temperature at 7 ° C. and continuing stirring at 250 rpm, 0.52 part of 5 mass% aqueous solution of ferrous sulfate was added as FeSO ₄ · 7H ₂ O over 5 minutes, and then the colorant The dispersion was added over 5 minutes, mixed uniformly at an internal temperature of 7 ° C., and a 0.5% by mass aqueous solution of aluminum sulfate was added dropwise over 8 minutes with the same conditions (solid to resin solids). Min is 0.10 parts). Thereafter, the internal temperature was raised to 55.0 ° C. while maintaining the rotational speed of 250 rpm, the volume median diameter (Dv50) was measured using a multisizer, and grown to 5.31 μm.

○ Shell coating process
Thereafter, the polymer primary particle dispersion A2 was added over 3 minutes while maintaining the internal temperature at 55.0 ° C. and the rotation speed at 250 rpm, and held as it was for 60 minutes.
○ Circularization process
Subsequently, the rotational speed was reduced to 150 rpm (a peripheral speed of 1.56 m / sec at the tip of the stirring blade, a stirring speed reduced by 40% with respect to the rotational speed of the aggregation process), and then a 20% DBS aqueous solution (6 parts as solid content) was added. The mixture was added over 10 minutes, then heated to 84 ° C. over 30 minutes, and heating and stirring were continued until the average circularity reached 0.940. Thereafter, it was cooled to 30 ° C. over 20 minutes to obtain a slurry.

<Manufacturing Toner ZZZ>
Thereafter, the toner ZZZ was operated by the same external addition step as that of “Production of toner K” except that the amount of H2000 silica as an external additive was changed to 1.41 g and the amount of SMT150IB titania fine powder was changed to 0.56 g. Got.
○ Analysis process
The volume median diameter (Dv50) measured using the multi-sizer of toner ZZZ obtained here is 5.31 μm, and “number% (Dns) of toner having a particle size of 2.00 μm to 3.56 μm” is The average circularity was 0.940 and the number variation coefficient was 19.5%.

FIG. 2 is a diagram of the image forming apparatus used in the present invention. Among image transfer methods, the tandem method is more likely to cause color misregistration compared to four cycles. Further, in the tandem direct transfer system, contact between the photosensitive drum and the paper occurs, so that fine irregularities are likely to occur on the surface of the photosensitive drum, and toner fine powder easily fits into the irregularities, so that the image is easily affected. In such an image forming apparatus, that is, an image forming apparatus adopting a tandem belt conveying system, the present invention is particularly effective.

  On the other hand, the direct transfer method has excellent image reproducibility because the number of times of transfer is small. In an image forming apparatus that can provide such high image quality, the present invention is particularly effective.

  The toner of the present invention is less likely to cause stains, afterimages (ghosts), blurring (solid followability), etc. on the white background of the image, has good cleaning properties, and has a sharp charge amount distribution, and thus has excellent image stability. The particle size distribution is narrow, and even if the toner particle size is reduced, the amount of fine powder is small, so the bulk density is improved and the fixability is good. It is widely used in image forming methods by high resolution, long life, and high speed printing that have been made.

1 Electrostatic latent image carrier
2 Toner conveying member
3 Elastic blade (toner layer thickness regulating member)
4 Sponge roller (toner replenishment auxiliary member)
5 Stirring blade
6 Toner
7 Toner Hopper
8 Conveyor belt 9 Pressure roller 10 Laser 11 Toner cartridge 12 Fixing belt
13 Heat source

Claims (18)

A toner for developing an electrostatic charge image, wherein the toner contains a charge control agent, satisfies all of the following (1) to (3), and has a toner number variation coefficient of 24.0% or less.
(1) The volume median diameter (Dv50) is 4.0 μm or more and 7.5 μm or less.
(2) The relationship between the volume median diameter (Dv50) of toner and the number% (Dns) of toner having a particle diameter of 2.00 μm to 3.56 μm satisfies Dns ≦ 0.233EXP (17.3 / Dv50).
(3) The average dispersion diameter of the contained charge control agent is 500 nm or less. A toner for developing an electrostatic charge image, wherein the toner contains a charge control agent, satisfies all of the following (4) to (6), and has a toner number variation coefficient of 24.0% or less.
(4) The volume median diameter (Dv50) is 4.0 μm or more and 7.5 μm or less.
(5) The relationship between the volume median diameter (Dv50) of toner and the number% (Dns) of toner having a particle diameter of 2.00 μm to 3.56 μm satisfies Dns ≦ 0.233EXP (17.3 / Dv50).
(6) The average diameter of the dent when the charge control agent on the toner surface is removed is 500 nm or less.   The relationship between the volume median diameter (Dv50) of toner and the number% (Dns) of toner having a particle diameter of 2.00 μm to 3.56 μm satisfies Dns ≦ 0.11EXP (19.9 / Dv50). The toner for developing an electrostatic charge image according to claim 1 or 2.   The relationship between the volume median diameter (Dv50) of toner and the number% (Dns) of toner having a particle size of 2.00 μm to 3.56 μm satisfies 0.0517EXP (22.4 / Dv50) ≦ Dns. The toner for developing an electrostatic charge image according to claim 1 or 2.   The electrostatic charge image developing toner according to claim 1, wherein the toner has a volume median diameter (Dv50) of 5.0 μm or more.   5. The electrostatic image developing toner according to claim 1, wherein the number% (Dns) of the toner having a particle diameter of 2.00 μm to 3.56 μm is 6% by number or less.   6. The electrostatic image developing toner according to claim 1, wherein the toner has an average circularity of 0.93 or more.   The electrostatic charge image developing toner according to claim 1, wherein the charge control agent is present in the vicinity of the surface.   9. The charge control agent according to claim 1, wherein the charge control agent exists in a range of ± R centering on the toner surface, where R is an average diameter of the dent when the charge control agent is removed. Toner for developing electrostatic images.   10. The electrostatic image developing toner according to claim 1, wherein the toner is obtained by forming particles in an aqueous medium.   11. The toner for developing an electrostatic charge image according to claim 1, wherein the toner is produced by an emulsion polymerization aggregation method.   The toner for developing an electrostatic charge image according to any one of claims 1 to 11, wherein the toner is obtained by fixing or adhering resin fine particles to core particles.   The core particles are composed of at least polymer primary particles, and the ratio of the total amount of polar monomers in 100% by mass of all polymerizable monomers constituting the binder resin as the resin fine particles constitutes the core particles. 13. The toner for developing an electrostatic charge image according to claim 12, wherein the toner for developing an electrostatic charge image is smaller than a ratio of the total amount of polar monomers in 100% by mass of all polymerizable monomers constituting the binder resin as the polymer primary particles.   14. The electrostatic image developing toner according to claim 1, wherein the wax is contained in an amount of 4 to 20 parts by weight based on 100 parts by weight of the electrostatic image developing toner.   The toner for developing an electrostatic charge image according to any one of claims 1 to 14, wherein the toner is used for an image forming apparatus having a developing process speed of 100 mm / second or more on a latent image carrier. The toner for developing an electrostatic charge image according to any one of claims 1 to 15, wherein the toner is used for an image forming apparatus satisfying the following formula (7).
(7) Guaranteed lifetime number of sheets of developing machine filled with developer (sheets) x printing rate ≧ 400 (sheets)   The toner for developing an electrostatic charge image according to any one of claims 1 to 15, wherein the toner is used for an image forming apparatus having a resolution of 600 dpi or more on the latent image carrier.   The toner for developing an electrostatic charge image is obtained without a step of removing particles having a volume median diameter (Dv50) or less of the toner. The toner for developing an electrostatic charge image according to 1.

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