JP2016070988A - Toner for electrostatic charge image development, electrostatic charge image developer, toner cartridge, process cartridge, image forming apparatus, and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge image development that suppresses the occurrence of a phenomenon where a toner is attached to a non-image part (fogging) and a reduction in image density.SOLUTION: There is provided a toner for electrostatic charge image development including toner particles having an external additive including silica particles surface-treated with oil externally added thereto, the toner particles containing a binder resin and a mold release agent and having a sea-island structure having a sea part including the binder resin and island parts including the mold release agent, where the degree of maldistribution B of the island parts including the mold release agent is represented by the following formula (1): degree of maldistribution B=2d/D, where D represents the equivalent circle diameter (μm) of the toner in observation of the cross section of the toner, and d represents the distance (μm) from the center of gravity of the toner to the center of gravity of the island parts including the mold release agent in the observation of the cross section of the toner; the most frequent value of the distribution of the degree of maldistribution B is 0.75 or more and 0.98 or less; and the skewness of the distribution of the degree of maldistribution B is -1.10 or more and -0.50 or less.SELECTED DRAWING: None

Description

  The present invention relates to an electrostatic charge image developing toner, an electrostatic charge image developer, a toner cartridge, a process cartridge, an image forming apparatus, and an image forming method.

  Methods for visualizing image information, such as electrophotography, are currently used in various fields. In electrophotography, an electrostatic charge image is formed as image information on the surface of an image carrier by charging and electrostatic charge image formation. Then, a toner image is formed on the surface of the image holding member by a developer containing toner, the toner image is transferred to a recording medium, and then the toner image is fixed on the recording medium. Through these steps, the image information is visualized as an image.

  For example, Patent Document 1 states that “wax is encapsulated in the form of fine particles in the toner, the wax is present from the vicinity of the surface of the toner to the entire interior, and the concentration of the wax existing in the vicinity of the surface of the toner is within the toner. A dry toner that is greater than the concentration of wax present. Further, Patent Document 1 discloses that in the kneading and pulverizing method, an uneven distribution control resin having both a portion close to the polarity of the binder resin and a portion close to the polarity of the release agent is used.

  Patent Document 2 states that “the wax content is 3.0 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the binder resin, and the degree of wax uneven distribution in the depth direction of the toner. Is controlled ". Patent Document 2 discloses that “the position of the wax is arranged near the surface by controlling the hydrophilicity / hydrophobicity difference between the binder resin and the wax dissolved in the solvent”.

JP 2004-145243 A JP 2011-158758 A

  An object of the present invention is to provide toner particles in which the mode of distribution of the uneven distribution degree B of the island portion including the release agent is less than 0.75 and the skewness of the distribution of the uneven distribution degree B exceeds −0.50. Compared with the case of having an external additive containing silica particles surface-treated with oil, a phenomenon in which toner adheres to a non-image area (hereinafter referred to as “fogging”) when image output continues in a low temperature and low humidity environment. The toner for developing an electrostatic image that suppresses both the occurrence of the occurrence of the image charge and the decrease in image density.

  The above problem is solved by the following means.

The invention according to claim 1
It has a sea-island structure including a binder resin and a release agent, and has a sea part containing the binder resin and an island part containing the release agent, and includes the release agent represented by the following formula (1) Toner particles having a mode of distribution of the uneven distribution degree B in the island portion of 0.75 or more and 0.98 or less, and a skewness of the distribution of the uneven distribution degree B of −1.10 or more and −0.50 or less,
An external additive comprising silica particles surface-treated with oil;
A toner for developing an electrostatic charge image.
Formula (1): Unevenness B = 2d / D
(In formula (1), D represents the equivalent-circle diameter (μm) of the toner particles in the cross-sectional observation of the toner particles. D represents the center of gravity of the island portion including the release agent from the center of gravity of the toner particles in the cross-sectional observation of the toner particles. The distance (μm) is shown.)

The invention according to claim 2
The toner for developing an electrostatic charge image according to claim 1, wherein the silica particles have a volume average particle diameter of 30 nm to 200 nm.

The invention according to claim 3
The electrostatic image developing toner according to claim 1, wherein the amount of free oil of the silica particles is 1% by mass or more and 10% by mass or less.

The invention according to claim 4
An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 1.

The invention according to claim 5
An electrostatic charge image developing toner according to any one of claims 1 to 3 is accommodated,
A toner cartridge to be attached to and detached from the image forming apparatus.

The invention according to claim 6
A developing means for containing the electrostatic charge image developer according to claim 4 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer,
A process cartridge attached to and detached from the image forming apparatus.

The invention according to claim 7 provides:
An image carrier,
Charging means for charging the surface of the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
Development means for containing the electrostatic charge image developer according to claim 4 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer;
Transfer means for transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
Fixing means for fixing the toner image transferred to the surface of the recording medium;
An image forming apparatus comprising:

The invention according to claim 8 provides:
A charging step for charging the surface of the image carrier;
An electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged image carrier;
A developing step of developing an electrostatic charge image formed on the surface of the image carrier as a toner image with the electrostatic charge image developer according to claim 4;
A transfer step of transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
A fixing step of fixing the toner image transferred to the surface of the recording medium;
An image forming method comprising:

According to the invention according to claim 1, the mode of distribution of the uneven distribution degree B of the island portion including the release agent is less than 0.75, and the skewness of the distribution of the uneven distribution degree B exceeds −0.50. Compared with the case of having toner particles and an external additive containing silica particles surface-treated with oil, both the occurrence of fogging and the decrease in image density when image output continues in a low-temperature and low-humidity environment. An electrostatic charge image developing toner is provided.
According to the second aspect of the present invention, when the image output continues in a low-temperature and low-humidity environment as compared with the volume average particle diameter of the silica particles being less than 30 nm, static generation that suppresses both generation of fog and a decrease in image density. A charge image developing toner is provided.
According to the third aspect of the present invention, when image output continues in a low-temperature and low-humidity environment as compared with the case where the amount of free oil of silica particles is less than 1% by mass, generation of fogging and reduction in image density are reduced. An electrostatic charge image developing toner that suppresses both is provided.

  According to the invention according to claim 4, 5, 6, 7, or 8, the mode of the distribution of the uneven distribution degree B of the island portion including the release agent is less than 0.75, and the distribution of the uneven distribution degree B is Compared with the case where an electrostatic charge image developing toner having toner particles having a skewness exceeding −0.50 and an external additive containing silica particles surface-treated with oil is used, an image is produced in a low temperature and low humidity environment. Thus, an electrostatic charge image development, a toner cartridge, a process cartridge, an image forming apparatus, or an image forming method that suppresses both occurrence of fogging and a decrease in image density when the output is continued.

1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to an exemplary embodiment. It is a schematic block diagram which shows an example of the process cartridge which concerns on this embodiment. It is a schematic diagram for demonstrating the power feed addition method. FIG. 6 is a diagram illustrating a distribution of a degree of uneven distribution B of a release agent domain in the toner according to the exemplary embodiment.

  Hereinafter, an embodiment which is an example of the present invention will be described in detail.

(Static image developing toner)
The toner for developing an electrostatic charge image (hereinafter referred to as “toner”) according to this embodiment includes toner particles containing a binder resin and a release agent, and silica particles surface-treated with oil (hereinafter “oil-treated silica”). And an external additive including a “particle”.

The toner particles have a sea-island structure having a sea part containing a binder resin and an island part containing a release agent.
In this sea-island structure, the mode of distribution of the uneven distribution degree B of the island portion including the releasing agent represented by the formula (1) is not less than 0.75 and not more than 0.98, and the distribution distribution of the uneven distribution degree B is distorted. The degree is from −1.10 to −0.50.
Formula (1): Unevenness B = 2d / D
(In formula (1), D represents the equivalent-circle diameter (μm) of the toner particles in the cross-sectional observation of the toner particles. D represents the center of gravity of the island portion including the release agent from the center of gravity of the toner particles in the cross-sectional observation of the toner particles. The distance (μm) is shown.)

  With the toner according to the present embodiment, when the image continues to be output in a low-temperature and low-humidity environment (for example, in an environment of a temperature of 10 ° C. and a humidity of 15% RH, the image output to A4 paper is 100,000 Both the occurrence of fog (a phenomenon in which toner adheres to a non-image portion) and a decrease in image density are suppressed. The reason is not clear, but is presumed to be as follows.

When the oil-treated silica particles are externally added to the toner particles, the oil adheres to the surface of the toner particles. The oil adhering to the toner particles adsorbs moisture. The oil that has adsorbed the moisture becomes a conduction path for the charge, and the charge exchange property of the toner particles is improved. As a result, generation of fog due to poor charge exchangeability (charging failure) of the toner is easily suppressed.
However, when image output continues at low temperature and low humidity, the humidity in the image forming apparatus decreases, and the amount of moisture adsorbed on the oil (or the amount of moisture adsorbed) also decreases. For this reason, even if the oil-treated silica particles are externally added to the toner particles, if image output continues under low temperature and low humidity, it is difficult to suppress the occurrence of fog due to toner charge exchange failure (charging failure).

On the other hand, it is known that a release agent is unevenly distributed in the surface layer portion of toner particles. In the toner particles in which the release agent is unevenly distributed in the surface layer portion, the resistance of the surface layer portion is reduced and the charge exchange property is improved. As a result, generation of fog due to poor charge exchangeability (charging failure) of the toner is easily suppressed.
However, the toner particles in which the release agent is unevenly distributed in the surface layer portion have high internal resistance, so that when the image output is continued under low temperature and low humidity, the toner particles are likely to accumulate excessively and excessively. Charging (charging up) is likely to cause a decrease in image density.

  Here, the uneven distribution degree B of the island part including the release agent (hereinafter also referred to as “release agent domain”) is an index indicating how far the center of gravity of the release agent domain is separated from the center of gravity of the toner particles. is there. The uneven distribution degree B indicates that the larger the value is, the closer the release agent domain is to the toner surface, and the smaller the value is, the closer the release agent domain is to the center of the toner particle. The mode of distribution of the uneven distribution degree B indicates a portion where the release agent domain is most present in the radial direction of the toner particles. On the other hand, the skewness of the distribution of the uneven distribution degree B indicates the symmetry of the distribution. Specifically, the skewness of the distribution of the uneven distribution degree B indicates the degree of tailing of the distribution from the mode value. That is, the skewness of the distribution of the uneven distribution degree B indicates how much distribution of the release agent domain exists from the most numerous parts in the radial direction of the toner particles.

  That is, the mode value of the distribution of the uneven distribution degree B of the release agent domains is in the range of 0.75 or more and 0.98 or less means that the release agent domains are most present in the surface layer portion of the toner particles. It is shown that. When the skewness of the distribution of the uneven distribution degree B of the release agent domain is in the range of −1.10 or more and −0.50 or less, the release agent domain is directed from the surface layer portion of the toner particle toward the inside. , It is distributed with a gradient (see FIG. 4).

  As described above, the toner particles satisfying the above-described range of the distribution mode B of the distribution degree B of the uneven distribution degree of the release agent domain have a gradient and the inside of the toner particle having a gradient while the release agent domain is most present in the surface layer portion. The toner particles are distributed toward the surface layer. That is, the toner particles having a gradient in the distribution of the release agent domains are reduced in resistance inside and at the surface layer by the release agent.

  In addition, when oil-treated silica particles are externally added to toner particles having a gradient in the release agent domain distribution, the oil adheres to the surface of the toner particles, and the moisture adsorbed on the oil releases the surface layer of the toner particles. Selectively supplied to the agent domain. Thereafter, the moisture is supplied into the toner particles via the release agent domains distributed from the release agent domains in the surface layer portion of the toner particles to the inside of the toner particles. For this reason, it is considered that the toner particles are further reduced in resistance both in the surface layer portion and inside due to moisture. And since oil adheres to the surface of the toner particles, the water content in the surface layer portion and the inside is hardly lowered even under low temperature and low humidity.

  For this reason, even when image output continues at low temperature and low humidity, the toner particles are easily maintained in a state where the resistance of the surface layer and the inside is low, and excessive charging (charge-up) is suppressed along with charge exchange. It becomes easy to be done.

  From the above, it is presumed that the toner according to the present embodiment suppresses both the occurrence of fogging and the decrease in image density when image output continues in a low temperature and low humidity environment.

  Conventionally, a toner (JP-A-2004-145243, for example), which uses a difference in hydrophilicity / hydrophobicity between a binder resin dissolved in a solvent and a release agent to place the release agent near the surface (JP 2004-145243, etc.), Known is a toner (Japanese Unexamined Patent Publication No. 2011-158758, etc.) in which the position of the release agent is arranged near the surface by a kneading and pulverization method using an uneven distribution control resin having both a portion close to polarity and a portion close to the polarity of the release agent ing. However, in any toner, the position of the release agent in the toner is controlled by the physical properties of the material, and the distribution of the release agent domain of the toner cannot be given a gradient.

  Hereinafter, details of the toner according to the exemplary embodiment will be described.

(Toner particles)
The toner particles have a sea-island structure having a sea part containing a binder resin and an island part containing a release agent. That is, the toner particles have a sea-island structure in which the release agent exists in an island shape in the continuous phase of the binder resin. Note that the release agent domain is preferably not present in the central portion (center of gravity) of the toner in the cross-sectional observation of the toner from the viewpoint of suppressing defective peeling.

  In the toner particles having the sea-island structure, the mode of distribution of the degree of uneven distribution B of the release agent domain (island portion including the release agent) is 0.75 or more and 0.98 or less, which suppresses occurrence of fogging and image. From the viewpoint of suppressing the decrease in concentration, 0.80 or more and 0.95 or less are preferable, and 0.85 or more and 0.90 or less are more preferable. In particular, from the viewpoint of heat storage properties of the toner, the mode of distribution of the uneven distribution degree B of the release agent domain is preferably 0.98 or less.

  The skewness of the distribution of the uneven distribution degree B of the release agent domain (the island part including the release agent) is −1.10 or more and −0.50 or less, from the viewpoint of suppressing the occurrence of fog and the reduction of image density. -1.00 or more and -0.60 or less are preferable, and -0.95 or more and -0.65 or less are more preferable.

Here, a method for confirming the sea-island structure of toner particles will be described.
The sea-island structure of the toner particles is confirmed by, for example, a method of observing the cross section of the toner particles with a transmission electron microscope, or a method of observing the cross section of the toner particles with ruthenium tetroxide and observing with a scanning electron microscope. A method of observing with a scanning electron microscope is preferable in that the release agent domain in the cross section of the toner particles can be observed more clearly. The scanning electron microscope may be any model well known to those skilled in the art, and examples thereof include SU8020 manufactured by Hitachi High-Tech, JSM-7500F manufactured by JEOL.
A specific observation method is as follows. First, after embedding toner particles to be measured in an epoxy resin, the epoxy resin is cured. The cured product is thinned by a microtome equipped with a diamond blade to obtain an observation sample in which the cross section of the toner particles is exposed. The observation sample of the flakes is dyed with ruthenium tetroxide, and the cross section of the toner particles is observed with a scanning electron microscope. By this observation method, a sea-island structure in which a release agent having a luminance difference (contrast) exists in an island shape is observed in the cross section of the toner particle due to a difference in the degree of dyeing in the continuous phase of the binder resin. .

Next, a method for measuring the uneven distribution degree B of the release agent domain will be described.
The measurement of the uneven distribution degree B of the release agent domain is performed as follows. First, using a sea-island structure confirmation method, an image is recorded at a magnification at which the cross section of one toner particle can be viewed. The recorded image is subjected to image analysis under the condition of 0.010000 μm / pixel using image analysis software (WinROOF manufactured by Mitani Corporation). By this image analysis, the shape of the cross section of the toner particles is extracted based on the luminance difference (contrast) between the epoxy resin used for embedding and the binder resin of the toner particles. Based on the extracted cross-sectional shape of the toner particles, a projected area is obtained. Then, the equivalent circle diameter is obtained from this projected area. The equivalent circle diameter is calculated by the formula: 2√ (projected area / π). The obtained equivalent circle diameter is defined as equivalent circle diameter D of the toner particles in the cross-sectional observation of the toner particles.
On the other hand, the position of the center of gravity is obtained based on the cross-sectional shape of the extracted toner particles. Subsequently, the shape of the release agent domain is extracted based on the luminance difference (contrast) between the binder resin and the release agent, and the position of the center of gravity of the release agent domain is obtained. Specifically, for each of the center of gravity positions, the number of pixels in the region is n, and the xy coordinates of each pixel are x _i , y _i (i = , N), the x coordinate of the center of gravity is obtained by dividing the sum of each x _i coordinate value by n, and the y coordinate of the center of gravity is obtained by dividing the sum of each y _i coordinate value by n. Then, the distance between the centroid position of the cross section of the toner particles and the centroid position of the release agent domain is obtained. The obtained distance is defined as a distance d from the center of gravity of the toner particle to the center of gravity of the island portion including the release agent in the cross-sectional observation of the toner particle.
Finally, the uneven distribution degree B of the release agent domain is obtained from each circle-equivalent diameter D and the distance d by Equation (1): uneven distribution degree B = 2d / D. Then, the same operation as described above is performed for each of the plurality of release agent domains existing in the cross section of one toner particle, and the uneven distribution degree B of the release agent domains is obtained.

Next, a method for calculating the mode of the distribution of the uneven distribution degree B of the release agent domain will be described.
First, the above-described degree of uneven distribution B of the release agent domain is measured for 200 toner particles. The data of the degree of uneven distribution B of each obtained release agent domain is subjected to statistical analysis processing in a data interval from 0 to 0.01 to obtain the distribution of the degree of uneven distribution B. The mode of the obtained distribution, that is, the value of the data section that appears most frequently in the distribution of the uneven distribution degree B of the release agent domain is obtained. And the value of this data section is made the mode value of the distribution of the uneven distribution degree B of the release agent domain.

Next, a method for calculating the skewness of the distribution of the uneven distribution degree B of the release agent domain will be described.
First, as described above, the distribution of the uneven distribution degree B of the release agent domain is obtained. The skewness of the distribution of the uneven distribution degree B is obtained based on the obtained following formula. In the following formula, the skewness is Sk, the number of data of the uneven distribution degree B of the release agent domain is n, and the value of the data of the uneven distribution degree B of each release agent domain is x _i (i = 1, 2,... n) The average value of the entire data of the uneven distribution degree B of the release agent domain is x (x with an upper bar), and the standard deviation of the entire data of the uneven distribution degree B of the release agent domain is s.

  A method for satisfying the distribution characteristics of the uneven distribution degree B of the release agent domain in the toner particles will be described in the toner manufacturing method.

Hereinafter, the components of the toner particles will be described.
The toner particles include a binder resin and a release agent. Specifically, the toner particles have toner particles containing a binder resin and a release agent. The toner particles may contain other additives such as a colorant.

-Binder resin-
Examples of the binder resin include styrenes (eg, styrene, parachlorostyrene, α-methylstyrene, etc.), (meth) acrylic acid esters (eg, methyl acrylate, ethyl acrylate, n-propyl acrylate, acrylic acid). n-butyl, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, etc.), ethylenically unsaturated nitriles (for example, acrylonitrile, Methacrylonitrile, etc.), vinyl ethers (eg, vinyl methyl ether, vinyl isobutyl ether, etc.), vinyl ketones (vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone, etc.), olefins (eg, ethylene, propylene, etc.) Emissions, a homopolymer of a monomer such as butadiene) and the like, or a vinyl-based resin composed of these monomers with two or more combinations copolymer.
As the binder resin, for example, epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, non-vinyl resin such as modified rosin, a mixture of these with the vinyl resin, or these Examples also include a graft polymer obtained by polymerizing a vinyl monomer in the coexistence.
These binder resins may be used alone or in combination of two or more.

A polyester resin is suitable as the binder resin.
Examples of the polyester resin include known polyester resins.

  As a polyester resin, the condensation polymer of polyhydric carboxylic acid and polyhydric alcohol is mentioned, for example. In addition, as a polyester resin, a commercial item may be used and what was synthesize | combined may be used.

Examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids (eg, oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, alkenyl succinic acid, adipic acid, sebacic acid, etc.) Alicyclic dicarboxylic acids (for example, cyclohexanedicarboxylic acid), aromatic dicarboxylic acids (for example, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, etc.), their anhydrides, or lower (for example, having 1 or more carbon atoms) 5 or less) alkyl esters. Among these, as polyvalent carboxylic acid, aromatic dicarboxylic acid is preferable, for example.
The polyvalent carboxylic acid may be used in combination with a dicarboxylic acid or a trivalent or higher carboxylic acid having a crosslinked structure or a branched structure. Examples of the trivalent or higher carboxylic acid include trimellitic acid, pyromellitic acid, anhydrides thereof, and lower (for example, having 1 to 5 carbon atoms) alkyl esters.
Polyvalent carboxylic acid may be used individually by 1 type, and may use 2 or more types together.

Examples of the polyhydric alcohol include aliphatic diols (for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, etc.), alicyclic diols (for example, cyclohexanediol, cyclohexanedimethanol, Hydrogenated bisphenol A, etc.) and aromatic diols (for example, ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, etc.). Among these, as the polyhydric alcohol, for example, aromatic diols and alicyclic diols are preferable, and aromatic diols are more preferable.
As the polyhydric alcohol, a trihydric or higher polyhydric alcohol having a crosslinked structure or a branched structure may be used together with the diol. Examples of the trihydric or higher polyhydric alcohol include glycerin, trimethylolpropane, and pentaerythritol.
A polyhydric alcohol may be used individually by 1 type, and may use 2 or more types together.

The glass transition temperature (Tg) of the polyester resin is preferably 50 ° C. or higher and 80 ° C. or lower, and more preferably 50 ° C. or higher and 65 ° C. or lower.
The glass transition temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC), and more specifically, described in the method for determining the glass transition temperature in JIS K-1987 “Method for Measuring Transition Temperature of Plastics”. It is determined by “extrapolated glass transition start temperature”.

The weight average molecular weight (Mw) of the polyester resin is preferably from 5,000 to 1,000,000, and more preferably from 7,000 to 500,000.
The number average molecular weight (Mn) of the polyester resin is preferably from 2,000 to 100,000.
The molecular weight distribution Mw / Mn of the polyester resin is preferably 1.5 or more and 100 or less, and more preferably 2 or more and 60 or less.
The weight average molecular weight and the number average molecular weight are measured by gel permeation chromatography (GPC). The molecular weight measurement by GPC is performed with a THF solvent using a Tosoh GPC / HLC-8120GPC as a measuring device and a Tosoh column / TSKgel SuperHM-M (15 cm). The weight average molecular weight and the number average molecular weight are calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample from this measurement result.

The polyester resin is obtained by a well-known manufacturing method. Specifically, for example, the polymerization temperature is set to 180 ° C. or higher and 230 ° C. or lower, the pressure in the reaction system is reduced as necessary, and the reaction is performed while removing water and alcohol generated during the condensation.
In addition, when the monomer of the raw material is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point may be added and dissolved as a solubilizing agent. In this case, the polycondensation reaction is performed while distilling off the solubilizer. If a monomer with poor compatibility is present in the copolymerization reaction, the monomer with poor compatibility and the monomer and the acid or alcohol to be polycondensed are condensed in advance and then polymerized together with the main component. It is good to condense.

  The content of the binder resin is, for example, preferably 40% by weight to 95% by weight, more preferably 50% by weight to 90% by weight, and more preferably 60% by weight to 85% by weight with respect to the entire toner particles. Further preferred.

-Release agent-
Examples of mold release agents include hydrocarbon waxes; natural waxes such as carnauba wax, rice wax, and candelilla wax; synthetic or mineral / petroleum waxes such as montan wax; and ester waxes such as fatty acid esters and montanic acid esters. And so on. The release agent is not limited to this.

  Among these, as the release agent, hydrocarbon wax (wax having a hydrocarbon as a skeleton) is preferable. Hydrocarbon wax is suitable because it easily forms a release agent domain and easily oozes out on the surface of toner particles at the time of fixing.

  The content of the release agent is, for example, preferably 1% by mass to 20% by mass and more preferably 5% by mass to 15% by mass with respect to the entire toner particles.

-Colorant-
Examples of the colorant include carbon black, chrome yellow, hansa yellow, benzidine yellow, sren yellow, quinoline yellow, pigment yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brilliant carmine 3B, and brilliant. Carmine 6B, Dupont Oil Red, Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C, Pigment Red, Rose Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Pigment Blue, Phthalocyanine Green, Various pigments such as malachite green oxalate, or acridine, xanthene, , Benzoquinone, azine, anthraquinone, thioindico, dioxazine, thiazine, azomethine, indico, phthalocyanine, aniline black, polymethine, triphenylmethane, diphenylmethane, thiazole, and other dyes Etc.
A colorant may be used individually by 1 type and may use 2 or more types together.

  As the colorant, a surface-treated colorant may be used as necessary, or it may be used in combination with a dispersant. A plurality of colorants may be used in combination.

  The content of the colorant is, for example, preferably 1% by mass or more and 30% by mass or less, and more preferably 3% by mass or more and 15% by mass or less with respect to the entire toner particles.

-Other additives-
Examples of other additives include known additives such as a magnetic material, a charge control agent, and inorganic powder. These additives are contained in the toner particles as internal additives.

-Toner particle characteristics-
The toner particles may be toner particles having a single layer structure, or toner particles having a so-called core / shell structure composed of a core (core particle) and a coating layer (shell layer) covering the core. May be.
Here, the core-shell structure toner particles include, for example, a core portion including a binder resin, a release agent, and, if necessary, other additives such as a colorant, and a binder resin. It is good to be comprised with the comprised coating layer.

  The volume average particle diameter (D50v) of the toner particles is preferably 2 μm or more and 10 μm or less, and more preferably 4 μm or more and 8 μm or less.

The various average particle diameters and various particle size distribution indexes of the toner particles are measured using Coulter Multisizer II (manufactured by Beckman-Coulter), and the electrolyte is measured using ISOTON-II (manufactured by Beckman-Coulter). The
In the measurement, 0.5 mg to 50 mg of a measurement sample is added as a dispersant to 2 ml of a 5% aqueous solution of a surfactant (preferably sodium alkylbenzenesulfonate). This is added to 100 ml or more and 150 ml or less of the electrolytic solution.
The electrolyte in which the sample is suspended is dispersed for 1 minute with an ultrasonic disperser, and the particle size distribution of particles having a particle size in the range of 2 μm to 60 μm is measured using a 100 μm aperture with a Coulter Multisizer II. taking measurement. The number of particles to be sampled is 50,000.
For the particle size range (channel) divided based on the measured particle size distribution, the cumulative distribution is drawn from the smaller diameter side to the volume and number, respectively, and the particle size to be 16% is the volume particle size D16v, the number particle size D16p, a particle size that is 50% cumulative is defined as a volume average particle size D50v, a cumulative number average particle size D50p, and a particle size that is 84% cumulative is defined as a volume particle size D84v and a number particle size D84p.
Using these, the volume average particle size distribution index (GSDv) is calculated as (D84v / D16v) ^1/2 and the number average particle size distribution index (GSDp) is calculated as (D84p / D16p) ^1/2 .

  The shape factor SF1 of the toner particles is preferably 110 or more and 150 or less, and more preferably 120 or more and 140 or less.

The shape factor SF1 is obtained by the following formula.
Formula: SF1 = (ML ² / A) × (π / 4) × 100
In the above formula, ML represents the absolute maximum length of the toner, and A represents the projected area of the toner.
Specifically, the shape factor SF1 is quantified mainly by analyzing a microscope image or a scanning electron microscope (SEM) image using an image analyzer, and is calculated as follows. That is, by capturing an optical microscope image of particles dispersed on the surface of a slide glass into a Luzex image analyzer using a video camera, obtaining the maximum length and projected area of 100 particles, calculating by the above formula, and obtaining the average value can get.

(External additive)
The external additive includes oil-treated silica particles. The oil-treated silica particles are silica particles that have been surface-treated with oil.

The silica particles to be subjected to the oil treatment may be silica, that is, particles mainly composed of SiO ₂ , and may be crystalline or amorphous. The silica particles may be particles produced from a silicon compound such as water glass or alkoxysilane, or may be particles obtained by pulverizing quartz.
Specifically, examples of the silica particles include sol-gel silica particles, aqueous colloidal silica particles, alcoholic silica particles, famed silica particles obtained by a gas phase method, and fused silica particles.

  Examples of the oil to be surface-treated on the silica particles include one or more compounds selected from the group consisting of lubricating oils and fats. Specific examples of the oil include silicone oil, paraffin oil, fluorine oil, and vegetable oil. Oil may be used by 1 type and may be used multiple types.

Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, and amino-modified. Examples include silicone oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, acrylic, methacryl-modified silicone oil, and α-methylstyrene-modified silicone oil.
Examples of paraffin oil include liquid paraffin.
Examples of the fluorine oil include fluorine oil and fluorine chloride oil.
Examples of the mineral oil include machine oil.
Examples of vegetable oils include rapeseed oil and palm oil.

  Among these oils, silicone oil is preferable from the viewpoint of suppression of fog generation and suppression of decrease in image density. When silicone oil is applied, it becomes easy to surface-treat the silica particles in a state where the oil is almost uniform in a thin film shape.

  The volume average particle size of the oil-treated silica particles is preferably 30 nm or more and 200 nm or less, more preferably 30 nm or more and 180 nm or less, and further preferably 30 nm or more and 150 nm or less, from the viewpoint of suppression of fog generation and suppression of image density reduction.

The volume average particle diameter of the oil-treated silica particles is a value measured by the following method.
100 primary particles of oil-treated silica particles are observed with a SEM (Scanning Electron Microscope) apparatus. Next, the longest diameter and the shortest diameter for each particle are measured by image analysis of primary particles, and the equivalent sphere diameter is measured from this intermediate value. The 50% diameter (D50v) in the cumulative frequency of the obtained sphere equivalent diameter on a volume basis is defined as the volume average particle diameter of the oil-treated silica particles.

  The amount of free oil in the oil-treated silica particles is preferably 1% by mass or more and 10% by mass or less, more preferably 3% by mass or more and 10% by mass or less, from the viewpoint of suppression of fog generation and reduction in image density. More preferred is 10% by mass or less.

The amount of free oil in the oil-treated silica particles is a value measured by the following method.
Proton NMR measurement is performed on the oil-treated silica particles using AL-400 (magnetic field 9.4T (H nucleus 400 MHz) manufactured by JEOL). A sample, a deuterated chloroform solvent, and TMS as a reference substance are filled into a sample tube (diameter 5 mm) made of zirconia. Set this sample tube, and measure, for example, frequency: Δ87 kHz / 400 MHz (= Δ20 ppm), measurement temperature: 25 ° C., integration frequency: 16 times, resolution 0.24 Hz (32000 points), peak derived from free oil Use the calibration curve from the intensity to convert to free oil.
For example, when dimethyl silicone oil is used as the oil, NMR measurement of untreated silica particles and dimethyl silicone oil (fluctuate about 5 levels) is performed, and a calibration curve between the oil release amount and the NMR peak intensity is obtained. Create And the amount of free oil is calculated using a calibration curve.

  In addition, when increasing the amount of free oil of an oil process silica particle, an oil process is performed in multiple times, for example. In order to reduce the amount of free oil in the oil-treated silica particles, for example, a step of drying after immersion in a solvent is repeatedly performed.

  The amount of the oil-treated silica particles is 2% by mass to 30% by mass with respect to the total mass of the silica particles (non-oil-treated silica particles) from the viewpoint of suppressing the generation of fog and suppressing the decrease in image density. Is preferably 5% by mass or more and 20% by mass or less, and more preferably 8% by mass or more and 15% by mass or less.

  The external addition amount (addition amount) of the oil-treated silica particles is preferably 0.5% by mass or more and 5.0% by mass or less, and more preferably 0.8% by mass or more and 3.0% by mass with respect to the total mass of the toner particles. The following is more preferable.

As the external additive, other external additives other than the oil-treated silica particles may be applied.
As other external additives, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, Examples thereof include inorganic particles (inorganic particles other than oil-treated silica particles) such as chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Examples of other external additives include resin particles such as fluororesin and silicone resin, and particles of metal salts of higher fatty acids represented by zinc stearate.

  In addition, the surface of the inorganic particle as another external additive is preferably subjected to a hydrophobic treatment. The hydrophobic treatment is performed, for example, by immersing inorganic particles in a hydrophobic treatment agent. The hydrophobizing agent is not particularly limited, and examples thereof include silane coupling agents, silicone oils, titanate coupling agents, aluminum coupling agents and the like. These may be used individually by 1 type and may use 2 or more types together.

  The external addition amount (addition amount) of the other external additives is preferably 0.01% by mass or more and 5% by mass or less, and preferably 0.01% by mass or more and 2.0% by mass with respect to the total mass of the toner particles. The following is more preferable.

(Toner production method)
Next, a toner manufacturing method according to this embodiment will be described.
The toner according to the exemplary embodiment can be obtained by externally adding an external additive to the toner particles after the toner particles are manufactured.

The toner particles may be produced by any of a dry production method (for example, a kneading and pulverizing method) and a wet production method (for example, an aggregation coalescence method, a suspension polymerization method, a dissolution suspension method, etc.). The production method of the toner particles is not particularly limited, and a known production method is adopted.
Among these, it is preferable to obtain toner particles by an aggregation and coalescence method.

  In particular, from the viewpoint of obtaining a toner (toner particle) satisfying the distribution characteristics of the uneven distribution degree B of the release agent domain described above, the toner particle is preferably produced by the following aggregation and coalescence method. In the following aggregation and coalescence method, a method for producing a toner (toner particles) including a colorant will be described. The colorant is an additive contained in the toner particles as necessary.

Specifically, a step of preparing each dispersion (dispersion preparation step),
A first resin particle dispersion in which first resin particles to be a binder resin are dispersed and a colorant particle dispersion in which colorant particles (hereinafter also referred to as “colorant particles”) are mixed are obtained. A step of aggregating each particle in the dispersed liquid to form first agglomerated particles (first agglomerated particle forming step);
After obtaining the first agglomerated particle dispersion in which the first agglomerated particles are dispersed, the mixture in which the second resin particles to become the binder resin and the release agent particles (hereinafter also referred to as “release agent particles”) are dispersed. The dispersion is sequentially added to the first aggregated particle dispersion while gradually increasing the concentration of the release agent particles in the mixed dispersion, and second resin particles and release agent particles are further added to the surface of the first aggregated particles. A step of agglomerating to form second agglomerated particles (second agglomerated particle forming step);
After obtaining the second aggregated particle dispersion in which the second aggregated particles are dispersed, the second aggregated particle dispersion and the third resin particle dispersion in which the third resin particles serving as the binder resin are further dispersed Mixing and aggregating so that the third resin particles further adhere to the surface of the second aggregated particles to form third aggregated particles (third aggregated particle forming step);
Heating the third agglomerated particle dispersion in which the third agglomerated particles are dispersed, fusing and coalescing the third agglomerated particles to form toner particles (fusing and coalescing step);
Through this process, it is preferable to produce toner particles.

  The method for producing toner particles is not limited to the above. For example, the resin particle dispersion and the colorant particle dispersion are mixed, and the particles are aggregated in the obtained mixed dispersion. Next, in the aggregation process, the release agent particle dispersion is added to the mixed dispersion while gradually increasing the addition rate or increasing the concentration of the release agent particles, and further the aggregation of each particle is advanced. To form agglomerated particles. Then, the aggregated particles may be fused and combined to form toner particles.

  Details of each step will be described below.

-Each dispersion preparation process-
First, it prepares with each dispersion liquid used by the aggregation coalescence method. Specifically, the first resin particle dispersion in which the first resin particles to be the binder resin are dispersed, the colorant particle dispersion in which the colorant particles are dispersed, and the second resin particles to be the binder resin are dispersed. The second resin particle dispersion, the third resin particle dispersion in which the third resin particles as the binder resin are dispersed, and the release agent particle dispersion in which the release agent particles are dispersed are prepared.
In each dispersion preparation step, the first resin particles, the second resin particles, and the third resin particles are referred to as “resin particles”.

  Here, the resin particle dispersion is prepared, for example, by dispersing resin particles in a dispersion medium using a surfactant.

Examples of the dispersion medium used for the resin particle dispersion include an aqueous medium.
Examples of the aqueous medium include water such as distilled water and ion exchange water, and alcohols. These may be used individually by 1 type and may use 2 or more types together.

Examples of the surfactant include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol And nonionic surfactants such as polyphenols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, an anionic surfactant and a cationic surfactant are particularly mentioned. The nonionic surfactant may be used in combination with an anionic surfactant or a cationic surfactant.
Surfactant may be used individually by 1 type and may use 2 or more types together.

Examples of the method for dispersing the resin particles in the dispersion medium in the resin particle dispersion include a general dispersion method such as a rotary shear homogenizer, a ball mill having media, a sand mill, and a dyno mill. Depending on the type of resin particles, the resin particles may be dispersed in the resin particle dispersion using, for example, a phase inversion emulsification method.
The phase inversion emulsification method is a method in which a resin to be dispersed is dissolved in a hydrophobic organic solvent in which the resin is soluble, and a base is added to the organic continuous phase (O phase) to neutralize the aqueous medium. (W phase) is added to convert the resin from W / O to O / W (so-called phase inversion) to form a discontinuous phase and disperse the resin in an aqueous medium in the form of particles. It is.

The volume average particle size of the resin particles dispersed in the resin particle dispersion is, for example, preferably 0.01 μm to 1 μm, more preferably 0.08 μm to 0.8 μm, and further preferably 0.1 μm to 0.6 μm. preferable.
In addition, the volume average particle diameter of the resin particles is a particle size distribution (channel) obtained by using a particle size distribution obtained by measurement with a laser diffraction particle size distribution measuring apparatus (for example, LA-700 manufactured by Horiba, Ltd.). The cumulative distribution is subtracted from the small particle diameter side with respect to the volume, and the particle diameter that becomes 50% cumulative with respect to all particles is measured as the volume average particle diameter D50v. The volume average particle size of particles in other dispersions is also measured in the same manner.

  As content of the resin particle contained in a resin particle dispersion liquid, 5 to 50 mass% is preferable, for example, and 10 to 40 mass% is more preferable.

  For example, a colorant particle dispersion and a release agent particle dispersion are also prepared in the same manner as the resin particle dispersion. In other words, regarding the volume average particle diameter of the particles in the resin particle dispersion, the dispersion medium, the dispersion method, and the content of the particles, the colorant particles dispersed in the colorant particle dispersion and the release agent particle dispersion The same applies to the release agent particles to be dispersed.

-First aggregated particle forming step-
Next, the first resin particle dispersion and the colorant particle dispersion are mixed.
Then, in this mixed dispersion, the first resin particles and the colorant particles are heteroaggregated to form first aggregated particles including the first resin particles and the colorant particles.

Specifically, for example, the flocculant is added to the mixed dispersion, and the pH of the mixed dispersion is adjusted to acidic (for example, the pH is 2 or more and 5 or less), and a dispersion stabilizer is added as necessary. Particles heated to the glass transition temperature of the first resin particles (specifically, for example, the glass transition temperature of the first resin particles −30 ° C. or more and the glass transition temperature −10 ° C. or less) and dispersed in the mixed dispersion liquid Are aggregated to form first aggregated particles.
In the first agglomerated particle forming step, for example, the flocculant is added at room temperature (for example, 25 ° C.) while stirring the mixed dispersion with a rotary shearing homogenizer, and the pH of the mixed dispersion is acidic (for example, pH is 2 or more). 5 or less) and, if necessary, after adding a dispersion stabilizer, the heating may be performed.

Examples of the flocculant include a surfactant having a polarity opposite to that of the surfactant used as the dispersant added to the mixed dispersion, an inorganic metal salt, and a divalent or higher-valent metal complex. In particular, when a metal complex is used as the flocculant, the amount of the surfactant used is reduced, and the charging characteristics are improved.
If necessary, an additive that forms a complex or a similar bond with the metal ion of the flocculant may be used. As this additive, a chelating agent is preferably used.

Examples of inorganic metal salts include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and inorganic substances such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. Examples thereof include metal salt polymers.
A water-soluble chelating agent may be used as the chelating agent. Examples of the chelating agent include oxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid, iminodiacid (IDA), nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), and the like.
The addition amount of the chelating agent is preferably 0.01 parts by mass or more and 5.0 parts by mass or less, and more preferably 0.1 parts by mass or more and less than 3.0 parts by mass with respect to 100 parts by mass of the first resin particles. .

-Second aggregated particle forming step-
Next, after obtaining the first agglomerated particle dispersion in which the first agglomerated particles are dispersed, the mixed dispersion in which the second resin particles and the releasing agent particles are dispersed is used as the release agent particles in the mixed dispersion. Sequentially added to the first aggregated particle dispersion while increasing the concentration.
The second resin particles may be the same type as the first resin particles or different types.

  Then, in the dispersion liquid in which the first aggregated particles, the second resin particles, and the release agent particles are dispersed, the second resin particles and the release agent particles are aggregated on the surface of the first aggregated particles. Specifically, for example, in the first aggregated particle forming step, when the first aggregated particles reach the target particle size, the concentration of the release agent particles is gradually increased in the first aggregated particle dispersion, A mixed dispersion in which the second resin particles and the release agent particles are dispersed is added, and the dispersion is heated at a temperature equal to or lower than the glass transition temperature of the second resin particles.

  Through this step, aggregated particles in which the second resin particles and the release agent particles are attached to the surface of the first aggregated particles are formed. That is, the second aggregated particles in which the aggregates of the second resin particles and the release agent particles are attached to the surface of the first aggregated particles are formed. At this time, the mixed dispersion in which the second resin particles and the release agent particles are dispersed is sequentially added to the first aggregated particle dispersion while gradually increasing the concentration of the release agent particles in the mixed dispersion. On the surface of the first aggregated particles, the concentration (existence ratio) of the release agent particles gradually increases toward the outside in the particle diameter direction, and the aggregates of the second resin particles and the release agent particles adhere.

  Here, as a method for adding the mixed dispersion, it is preferable to use a power feed addition method. By utilizing this power feed addition method, the mixed dispersion can be added to the first aggregated particle dispersion while gradually increasing the concentration of the release agent particles in the mixed dispersion.

  Hereinafter, a method for adding a mixed dispersion using a power feed addition method will be described with reference to the drawings.

  FIG. 3 shows an apparatus used for the power feed addition method. In FIG. 3, 311 indicates the first aggregated particle dispersion, 312 indicates the second resin particle dispersion, and 313 indicates the release agent particle dispersion.

  The apparatus shown in FIG. 3 contains a first storage tank 321 in which first aggregated particles are dispersed and contains a first aggregated particle dispersion, and a second resin particle dispersion in which second resin particles are dispersed. The second storage tank 322 and the third storage tank 323 that stores the release agent particle dispersion in which the release agent particles are dispersed.

The first storage tank 321 and the second storage tank 322 are connected by a first liquid feeding pipe 331. A first liquid feed pump 341 is interposed in the middle of the path of the first liquid feed pipe 331. By driving the first liquid feed pump 341, the dispersion liquid stored in the second storage tank 322 is sent to the dispersion liquid stored in the first storage tank 321 through the first liquid supply pipe 331.
A first stirring device 351 is disposed in the first storage tank 321. When the dispersion liquid stored in the second storage tank 322 is fed to the dispersion liquid stored in the first storage tank 321 by the driving of the first stirring device 351, each dispersion liquid is agitated and stirred in the first storage tank 321. Mixed.

The second storage tank 322 and the third storage tank 323 are connected by a second liquid feeding pipe 332. In the middle of the path of the second liquid feeding pipe 332, a second liquid feeding pump 342 is interposed. By driving the second liquid feed pump 342, the dispersion liquid stored in the third storage tank 323 is sent to the dispersion liquid stored in the second storage tank 322 through the second liquid supply pipe 332.
A second stirring device 352 is disposed in the second storage tank 322. When the dispersion liquid stored in the third storage tank 323 is fed to the dispersion liquid stored in the second storage tank 322 by driving the second stirring device 352, each dispersion liquid is stirred and mixed in the second storage tank 322. Mixed.

  In the apparatus shown in FIG. 3, first, a first aggregated particle forming step is performed in the first storage tank 321 to produce a first aggregated particle dispersion, and the first aggregated particle dispersion is added to the first storage tank 321. Accommodate. Note that the first aggregated particle dispersion may be stored in the first storage tank 321 after the first aggregated particle forming step is performed in another tank to produce the first aggregated particle dispersion.

In this state, the first liquid pump 341 and the second liquid pump 342 are driven. By this driving, the second resin particle dispersion liquid stored in the second storage tank 322 is fed to the first aggregated particle dispersion liquid stored in the first storage tank 321. Then, each dispersion liquid is stirred and mixed in the first storage tank 321 by driving the first stirring device 351.
On the other hand, the release agent particle dispersion liquid stored in the third storage tank 323 is fed to the second resin particle dispersion liquid stored in the second storage tank 322. Then, each dispersion liquid is stirred and mixed in the second storage tank 322 by driving the second stirring device 352.

  At this time, the release agent particle dispersion is sequentially fed to the second resin particle dispersion stored in the second storage tank 322, and the concentration of the release agent particles gradually increases. Therefore, the second storage tank 322 stores the mixed dispersion liquid in which the second resin particles and the release agent particles are dispersed, and the mixed dispersion liquid is stored in the first storage tank 321. It is sent to one aggregated particle dispersion. The mixed dispersion is fed continuously while the concentration of the release agent particle dispersion in the mixed dispersion is increased.

Thus, by using the power feed addition method, the mixed dispersion liquid in which the second resin particles and the release agent particles are dispersed while gradually increasing the concentration of the release agent particles in the first aggregated particle dispersion liquid. Can be added.
In the power feed addition method, the distribution characteristics of the release agent domains of the toner are adjusted by adjusting the liquid feed start timing and the liquid feed speed of the respective dispersions stored in the second storage tank 322 and the third storage tank 323. Is adjusted. Further, in the power feed addition method, the distribution of the toner release agent domain can also be adjusted by adjusting the liquid feeding speed during the liquid feeding of the respective dispersions stored in the second storage tank 322 and the third storage tank 323. Characteristics are adjusted.

  Specifically, for example, the mode of the distribution of the degree of uneven distribution B of the release agent domain is adjusted by the timing when the release agent particle dispersion liquid has been fed from the third storage tank 323 to the second storage tank 322. The More specifically, for example, before the liquid feeding from the second storage tank 322 to the first storage tank 321 is completed, the release agent particle dispersion liquid is fed from the third storage tank 323 to the second storage tank 322. When is finished, the concentration of the release agent particles in the mixed dispersion in the second storage tank 322 does not increase beyond that point. Thereby, the mode value of the distribution of the uneven distribution degree B of the release agent domain becomes small.

  Further, for example, the skewness of the distribution of the uneven distribution degree B of the release agent domain is determined by the timing of sending each dispersion liquid from the second storage tank 322 and the third storage tank 323 and the first storage tank from the second storage tank 322. It is adjusted by the liquid feeding speed at which the dispersion liquid is fed to 321. More specifically, for example, the liquid feed start timing of the release agent particle dispersion from the third storage tank 323 and the liquid feed start timing of the dispersion liquid from the second storage tank 322 are advanced, and the second storage tank 322 When the liquid feeding speed of the dispersion liquid is reduced, the release agent particles are arranged from the inner side to the outer side of the particles in the formed aggregated particles. Thereby, the skewness of the distribution of the uneven distribution degree B of the release agent domain is increased.

  In addition, the power feed addition method demonstrated above is not necessarily limited to the said method. For example, 1) Separately, a storage tank in which the second resin particle dispersion is stored, and a storage tank in which the second resin particles and the release agent particle dispersion are dispersed are provided, and the liquid feeding speed is changed. A method of feeding each dispersion liquid from each storage tank to the first storage tank 321, a separate storage tank containing the release agent particle dispersion liquid, and mixing in which the second resin particles and the release agent particle dispersion liquid are dispersed Various methods may be employed, such as a method of providing a storage tank containing the dispersion liquid and feeding each dispersion liquid from each storage tank to the first storage tank 321 while changing the liquid feeding speed.

  As described above, the second aggregated particles aggregated so that the second resin particles and the release agent particles adhere to the surface of the first aggregated particles are obtained.

-Third aggregated particle forming step-
Next, after obtaining the second aggregated particle dispersion in which the second aggregated particles are dispersed, the second aggregated particle dispersion, and the third resin particle dispersion in which the third resin particles serving as the binder resin are dispersed, , Are further mixed.
In addition, the 3rd resin particle may be the same kind as the 1st or 2nd resin particle, and a different kind may be sufficient as it.

Then, the third resin particles are aggregated on the surface of the second aggregated particles in the dispersion liquid in which the second aggregated particles and the third resin particles are dispersed. Specifically, for example, in the second aggregated particle forming step, when the second aggregated particle reaches a target particle size, the third resin particle dispersion is added to the second aggregated particle dispersion. The dispersion is heated below the glass transition temperature of the third resin particles.
Then, the progress of aggregation is stopped by adjusting the pH of the dispersion to a range of, for example, about 6.5 to 8.5.

-Fusion / unification process-
Next, with respect to the third aggregated particle dispersion in which the third aggregated particles are dispersed, for example, the glass transition temperature of the first, second, and third resin particles is higher than (for example, the first, second, and third resin particles). And a third aggregated particle is fused and united to form toner particles.

Through the above steps, toner particles are obtained.
In the toner particles (toner) obtained by the above steps, the distribution characteristic of the degree of uneven distribution B of the release agent domain falls within the above range.

Here, after completion of the coalescence / union process, toner particles formed in the solution are dried through a known washing process, solid-liquid separation process, and drying process to obtain toner particles.
In the washing step, it is preferable to sufficiently carry out substitution washing with ion-exchanged water from the viewpoint of chargeability. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, etc. are preferably performed from the viewpoint of productivity. Also, the drying process is not particularly limited, but from the viewpoint of productivity, freeze drying, flash jet drying, fluidized drying, vibration fluidized drying, or the like is preferably performed.

  The toner according to the exemplary embodiment is manufactured, for example, by adding an external additive to the obtained dry toner particles and mixing them. Mixing may be performed, for example, with a V blender, a Henschel mixer, a Ladyge mixer, or the like. Furthermore, if necessary, coarse toner particles may be removed using a vibration classifier, a wind classifier, or the like.

<Electrostatic image developer>
The electrostatic charge image developer according to the exemplary embodiment includes at least the toner according to the exemplary embodiment.
The electrostatic image developer according to this embodiment may be a one-component developer including only the toner according to this embodiment, or may be a two-component developer mixed with the toner and a carrier.

There is no restriction | limiting in particular as a carrier, A well-known carrier is mentioned. As a carrier, for example, a coated carrier in which the surface of a core made of magnetic powder is coated with a coating resin; a magnetic powder dispersion type carrier in which magnetic powder is dispersed and mixed in a matrix resin; a porous magnetic powder is impregnated with a resin Resin impregnated type carriers; and the like.
Note that the magnetic powder-dispersed carrier and the resin-impregnated carrier may be a carrier in which the constituent particles of the carrier are used as a core material and coated with a coating resin.

  Examples of the magnetic powder include magnetic metals such as iron, nickel, and cobalt, and magnetic oxides such as ferrite and magnetite.

Examples of the coating resin and matrix resin include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic acid copolymer. Examples thereof include a polymer, a straight silicone resin containing an organosiloxane bond or a modified product thereof, a fluororesin, a polyester, a polycarbonate, a phenol resin, and an epoxy resin.
The coating resin and matrix resin may contain other additives such as conductive particles.
Examples of the conductive particles include particles of metals such as gold, silver, and copper, carbon black, titanium oxide, zinc oxide, tin oxide, barium sulfate, aluminum borate, and potassium titanate.

Here, in order to coat the surface of the core material with the coating resin, a method of coating with a coating layer forming solution obtained by dissolving the coating resin and, if necessary, various additives in an appropriate solvent may be mentioned. The solvent is not particularly limited, and may be selected in consideration of the coating resin to be used, coating suitability, and the like.
Specific resin coating methods include a dipping method in which the core material is immersed in the coating layer forming solution, a spray method in which the coating layer forming solution is sprayed on the surface of the core material, and a state in which the core material is suspended by flowing air. Examples thereof include a fluidized bed method in which a coating layer forming solution is sprayed, a kneader coater method in which a carrier core material and a coating layer forming solution are mixed in a kneader coater, and the solvent is removed.

  The mixing ratio (mass ratio) of the toner and the carrier in the two-component developer is preferably toner: carrier = 1: 100 to 30: 100, and more preferably 3: 100 to 20: 100.

<Image Forming Apparatus / Image Forming Method>
The image forming apparatus / image forming method according to the present embodiment will be described.
The image forming apparatus according to the present embodiment includes an image carrier, a charging unit that charges the surface of the image carrier, an electrostatic image forming unit that forms an electrostatic image on the surface of the charged image carrier, and an electrostatic charge. Development means for containing an image developer and developing the electrostatic image formed on the surface of the image carrier as a toner image with the electrostatic image developer, and the toner image formed on the surface of the image carrier as a recording medium Transfer means for transferring to the surface of the recording medium, and fixing means for fixing the toner image transferred to the surface of the recording medium. The electrostatic charge image developer according to this embodiment is applied as the electrostatic charge image developer.

  In the image forming apparatus according to this embodiment, a charging process for charging the surface of the image carrier, an electrostatic charge image forming process for forming an electrostatic image on the surface of the charged image carrier, and an electrostatic charge according to this embodiment. A developing step of developing an electrostatic charge image formed on the surface of the image carrier as a toner image with an image developer; a transfer step of transferring the toner image formed on the surface of the image carrier to the surface of the recording medium; An image forming method (an image forming method according to the present embodiment) including a fixing step of fixing the toner image transferred onto the surface of the recording medium is performed.

The image forming apparatus according to the present embodiment is a direct transfer type apparatus that directly transfers a toner image formed on the surface of an image carrier to a recording medium; the toner image formed on the surface of the image carrier is transferred to an intermediate transfer member An intermediate transfer type apparatus that primarily transfers the toner image transferred to the surface of the intermediate transfer body and then secondary transfer the toner image to the surface of the recording medium; after the toner image is transferred, the surface of the image carrier before charging is cleaned. An apparatus provided with a cleaning unit; a known image forming apparatus such as an apparatus provided with a charge removing unit that discharges the surface of an image holding member by irradiating a discharge light after charging a toner image and before charging is applied.
In the case of an intermediate transfer type apparatus, the transfer means includes, for example, an intermediate transfer body on which a toner image is transferred to the surface, and a primary transfer that primarily transfers the toner image formed on the surface of the image holding body to the surface of the intermediate transfer body. And a secondary transfer unit that secondarily transfers the toner image transferred onto the surface of the intermediate transfer member onto the surface of the recording medium.

  In the image forming apparatus according to the present embodiment, for example, the part including the developing unit may have a cartridge structure (process cartridge) that is detachable from the image forming apparatus. As the process cartridge, for example, a process cartridge including a developing unit containing the electrostatic charge image developer according to the present embodiment is preferably used.

  Hereinafter, an example of the image forming apparatus according to the present embodiment will be described, but the present invention is not limited thereto. In addition, the main part shown to a figure is demonstrated and the description is abbreviate | omitted about others.

FIG. 1 is a schematic configuration diagram illustrating an image forming apparatus according to the present embodiment.
The image forming apparatus shown in FIG. 1 is a first to first electrophotographic method that outputs yellow (Y), magenta (M), cyan (C), and black (K) images based on color-separated image data. Fourth image forming units 10Y, 10M, 10C, and 10K (image forming means) are provided. These image forming units (hereinafter sometimes simply referred to as “units”) 10Y, 10M, 10C, and 10K are arranged in parallel at a predetermined distance from each other in the horizontal direction. The units 10Y, 10M, 10C, and 10K may be process cartridges that are detachable from the image forming apparatus.

Above each of the units 10Y, 10M, 10C, and 10K, an intermediate transfer belt 20 as an intermediate transfer member is extended through each unit. The intermediate transfer belt 20 is provided by being wound around a drive roll 22 and a support roll 24 that are in contact with the inner surface of the intermediate transfer belt 20 that are spaced apart from each other in the left to right direction in the drawing. The vehicle travels in the direction toward the unit 10K. The support roll 24 is applied with a force in a direction away from the drive roll 22 by a spring or the like (not shown), and tension is applied to the intermediate transfer belt 20 wound around the support roll 24. An intermediate transfer member cleaning device 30 is provided on the side of the image carrier of the intermediate transfer belt 20 so as to face the drive roll 22.
Further, each of the developing devices (developing means) 4Y, 4M, 4C, and 4K of the units 10Y, 10M, 10C, and 10K has yellow, magenta, cyan, and black contained in the toner cartridges 8Y, 8M, 8C, and 8K. The toner including the four color toners is supplied.

  Since the first to fourth units 10Y, 10M, 10C, and 10K have the same configuration, here, the first unit that forms a yellow image disposed on the upstream side in the intermediate transfer belt traveling direction. 10Y will be described as a representative. It should be noted that reference numerals with magenta (M), cyan (C), and black (K) are attached to the same parts as those of the first unit 10Y instead of yellow (Y). Description of the units 10M, 10C, and 10K will be omitted.

The first unit 10Y includes a photoreceptor 1Y that functions as an image holding member. Around the photoreceptor 1Y, a charging roll (an example of a charging unit) 2Y that charges the surface of the photoreceptor 1Y to a predetermined potential, and the charged surface is exposed by a laser beam 3Y based on the color-separated image signal. Then, an exposure device (an example of an electrostatic image forming unit) 3 that forms an electrostatic image, and a developing device (an example of a developing unit) 4Y that develops the electrostatic image by supplying toner charged to the electrostatic image, developed A primary transfer roll 5Y (an example of a primary transfer unit) that transfers a toner image onto the intermediate transfer belt 20, and a photoconductor cleaning device (an example of a cleaning unit) 6Y that removes toner remaining on the surface of the photoconductor 1Y after the primary transfer. Are arranged in order.
The primary transfer roll 5Y is disposed inside the intermediate transfer belt 20, and is provided at a position facing the photoreceptor 1Y. Further, a bias power source (not shown) for applying a primary transfer bias is connected to each of the primary transfer rolls 5Y, 5M, 5C, and 5K. Each bias power source varies the transfer bias applied to each primary transfer roll under the control of a control unit (not shown).

Hereinafter, an operation of forming a yellow image in the first unit 10Y will be described.
First, prior to operation, the surface of the photoreceptor 1Y is charged to a potential of −600V to −800V by the charging roll 2Y.
The photoreceptor 1Y is formed by laminating a photosensitive layer on a conductive substrate (for example, volume resistivity at 20 ° C .: 1 × 10 ⁻⁶ Ωcm or less). This photosensitive layer usually has a high resistance (general resin resistance), but has a property that the specific resistance of the portion irradiated with the laser beam changes when irradiated with the laser beam 3Y. Therefore, a laser beam 3Y is output to the surface of the charged photoreceptor 1Y via the exposure device 3 in accordance with yellow image data sent from a control unit (not shown). The laser beam 3Y is applied to the photosensitive layer on the surface of the photoreceptor 1Y, whereby an electrostatic charge image having a yellow image pattern is formed on the surface of the photoreceptor 1Y.

The electrostatic charge image is an image formed on the surface of the photoreceptor 1Y by charging, and the specific resistance of the irradiated portion of the photosensitive layer is lowered by the laser beam 3Y, and the charged charge on the surface of the photoreceptor 1Y flows. On the other hand, this is a so-called negative latent image formed by the charge remaining in the portion not irradiated with the laser beam 3Y.
The electrostatic charge image formed on the photoreceptor 1Y is rotated to a predetermined development position as the photoreceptor 1Y travels. At this development position, the electrostatic charge image on the photoreceptor 1Y is visualized (developed image) as a toner image by the developing device 4Y.

  In the developing device 4Y, for example, an electrostatic charge image developer containing at least yellow toner and a carrier is accommodated. The yellow toner is triboelectrically charged by being agitated inside the developing device 4Y, and has a charge of the same polarity (negative polarity) as the charged electric charge on the photoreceptor 1Y, and has a developer roll (a developer holding member). Example) is held on. As the surface of the photoreceptor 1Y passes through the developing device 4Y, the yellow toner is electrostatically attached to the latent image portion on the surface of the photoreceptor 1Y, and the latent image is developed with the yellow toner. . The photoreceptor 1Y on which the yellow toner image is formed continues to run at a predetermined speed, and the toner image developed on the photoreceptor 1Y is conveyed to a predetermined primary transfer position.

When the yellow toner image on the photoreceptor 1Y is conveyed to the primary transfer, a primary transfer bias is applied to the primary transfer roll 5Y, and an electrostatic force from the photoreceptor 1Y toward the primary transfer roll 5Y is applied to the toner image, so that the photoreceptor is exposed. The toner image on 1Y is transferred onto the intermediate transfer belt 20. The transfer bias applied at this time has a (+) polarity opposite to the polarity (−) of the toner, and is controlled to +10 μA by the control unit (not shown) in the first unit 10Y, for example.
On the other hand, the toner remaining on the photoreceptor 1Y is removed and collected by the photoreceptor cleaning device 6Y.

Further, the primary transfer bias applied to the primary transfer rolls 5M, 5C, and 5K after the second unit 10M is also controlled in accordance with the first unit.
Thus, the intermediate transfer belt 20 onto which the yellow toner image has been transferred by the first unit 10Y is sequentially conveyed through the second to fourth units 10M, 10C, and 10K, and the toner images of the respective colors are superimposed and transferred in a multiple manner. The

  The intermediate transfer belt 20 on which the four color toner images are transferred in multiple ways through the first to fourth units is disposed on the image transfer surface side of the intermediate transfer belt 20, the support roll 24 in contact with the inner surface of the intermediate transfer belt 20. The secondary transfer roll (an example of a secondary transfer unit) 26 is formed to a secondary transfer portion configured. On the other hand, recording paper (an example of a recording medium) P is fed at a predetermined timing into a gap where the secondary transfer roll 26 and the intermediate transfer belt 20 are in contact with each other via a supply mechanism, and the secondary transfer bias is supplied to the support roll. 24. The transfer bias applied at this time is a (−) polarity that is the same polarity as the polarity (−) of the toner, and an electrostatic force from the intermediate transfer belt 20 toward the recording paper P is applied to the toner image, so The toner image is transferred onto the recording paper P. The secondary transfer bias at this time is determined according to the resistance detected by a resistance detection means (not shown) for detecting the resistance of the secondary transfer portion, and is voltage-controlled.

  Thereafter, the recording paper P is fed into the pressure contact portions (nip portions) of a pair of fixing rolls in a fixing device (an example of a fixing unit) 28, and the toner image is fixed on the recording paper P to form a fixed image.

Examples of the recording paper P to which the toner image is transferred include plain paper used in electrophotographic copying machines, printers, and the like. In addition to the recording paper P, the recording medium may be an OHP sheet.
In order to further improve the smoothness of the image surface after fixing, the surface of the recording paper P is also preferably smooth. For example, coated paper with the surface of plain paper coated with resin, art paper for printing, etc. are preferably used. Is done.

  The recording paper P on which the color image has been fixed is carried out toward the discharge unit, and a series of color image forming operations is completed.

<Process cartridge / toner cartridge>
The process cartridge according to this embodiment will be described.
The process cartridge according to the present embodiment accommodates the electrostatic image developer according to the present embodiment, and develops the electrostatic image formed on the surface of the image carrier as a toner image by the electrostatic image developer. And a process cartridge that can be attached to and detached from the image forming apparatus.

  Note that the process cartridge according to the present embodiment is not limited to the above-described configuration, and other means such as a developing device and other units such as an image carrier, a charging unit, an electrostatic charge image forming unit, and a transfer unit, if necessary. And at least one selected from the above.

  Hereinafter, an example of the process cartridge according to the present embodiment will be shown, but the present invention is not limited to this. In addition, the main part shown to a figure is demonstrated and the description is abbreviate | omitted about others.

FIG. 2 is a schematic configuration diagram showing a process cartridge according to the present embodiment.
The process cartridge 200 shown in FIG. 2 is provided around the photoconductor 107 and the photoconductor 107 by, for example, a housing 117 provided with an attachment rail 116 and an opening 118 for exposure. A charging roller 108 (an example of a charging unit), a developing device 111 (an example of a developing unit), and a photoconductor cleaning device 113 (an example of a cleaning unit) are integrally combined and held to form a cartridge. Yes.
In FIG. 2, 109 is an exposure device (an example of an electrostatic charge image forming unit), 112 is a transfer device (an example of a transfer unit), 115 is a fixing device (an example of a fixing unit), and 300 is a recording paper (a recording medium). An example).

Next, the toner cartridge according to this embodiment will be described.
The toner cartridge according to the present exemplary embodiment is a toner cartridge that accommodates the toner according to the present exemplary embodiment and is detachable from the image forming apparatus. The toner cartridge contains toner for replenishment to be supplied to the developing means provided in the image forming apparatus.

  The image forming apparatus shown in FIG. 1 is an image forming apparatus having a configuration in which toner cartridges 8Y, 8M, 8C, and 8K are attached and detached, and the developing devices 4Y, 4M, 4C, and 4K are each developing devices (colors). And a toner supply pipe (not shown). Further, when the amount of toner stored in the toner cartridge becomes low, the toner cartridge is replaced.

  Hereinafter, although an Example and a comparative example are given and this embodiment is described in detail in detail, this embodiment is not limited to these Examples at all. The “part” means “part by mass” unless otherwise specified.

<Preparation of resin particle dispersion>
[Preparation of resin particle dispersion (1)]
・ Terephthalic acid: 30 mol part ・ Fumaric acid: 70 mol part ・ Bisphenol A ethylene oxide adduct: 5 mol part ・ Bisphenol A propylene oxide adduct: 95 mol part Stirrer, nitrogen introduction tube, temperature sensor, and rectifying column The above material was charged into a 5 liter flask equipped with the above, and the temperature was raised to 210 ° C. over 1 hour, and 1 part of titanium tetraethoxide was added to 100 parts of the material. The temperature was raised to 230 ° C. over 0.5 hours while distilling off the produced water, and the dehydration condensation reaction was continued at that temperature for 1 hour, and then the reaction product was cooled. Thus, a polyester resin (1) having a weight average molecular weight of 18,500, an acid value of 14 mgKOH / g, and a glass transition temperature of 59 ° C. was synthesized.

In a container equipped with temperature control means and nitrogen replacement means, 40 parts of ethyl acetate and 25 parts of 2-butanol are added to make a mixed solvent, and then 100 parts of polyester resin (1) is gradually added and dissolved therein. A 10% by mass aqueous ammonia solution (corresponding to 3 times the molar ratio with respect to the acid value of the resin) was added and stirred for 30 minutes.
Next, the inside of the container was replaced with dry nitrogen, the temperature was kept at 40 ° C., and 400 parts of ion-exchanged water was added dropwise at a rate of 2 parts / minute while stirring the mixed solution to carry out emulsification. After completion of the dropwise addition, the emulsion is returned to room temperature (20 ° C. to 25 ° C.), and stirred for 48 hours with dry nitrogen to reduce ethyl acetate and 2-butanol to 1,000 ppm or less. A resin particle dispersion in which resin particles having a diameter of 200 nm were dispersed was obtained. Ion exchange water was added to the resin particle dispersion to adjust the solid content to 20% by mass to obtain a resin particle dispersion (1).

<Preparation of colorant particle dispersion>
[Preparation of Colorant Particle Dispersion (1)]
Cyan pigment C.I. I. Pigment Blue 15: 3 (Copper Phthalocyanine DIC, trade name: FASTOGEN BLUE LA5380): 70 parts, anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK): 5 parts, ion-exchanged water: 200 Part The above materials were mixed and dispersed for 10 minutes using a homogenizer (Ultra Turrax T50 manufactured by IKA). Ion exchanged water was added so that the solid content in the dispersion was 20% by mass to obtain a colorant particle dispersion (1) in which colorant particles having a volume average particle diameter of 190 nm were dispersed.

<Preparation of release agent particle dispersion>
[Preparation of release agent particle dispersion (1)]
-Paraffin wax (Nippon Seiwa Co., Ltd. HNP-9) 100 parts-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK) 1 part-Ion-exchanged water 350 parts After heating to 100 ° C. and dispersing using a homogenizer (Ultra Turrax T50 manufactured by IKA), dispersion treatment is performed using a Menton Gorin high-pressure homogenizer (manufactured by Gorin), and release agent particles having a volume average particle diameter of 200 nm are dispersed. A release agent particle dispersion (1) (solid content 20% by mass) was obtained.

<Preparation of toner particles>
[Production of Toner Particles (1)]
The round stainless steel flask and the container A are connected by the tube pump A, and the liquid stored in the container A is sent to the flask by driving the tube pump A, and the container A and the container B are connected by the tube pump B. A device (see FIG. 3) for feeding the liquid stored in the container B to the container A by driving the tube pump B was prepared. And the following operation was implemented using this apparatus.

-Resin particle dispersion (1): 500 parts-Colorant particle dispersion (1): 40 parts-Anionic surfactant (TaycaPower): 2 parts The above materials are placed in a round stainless steel flask and 0.1N After adjusting the pH to 3.5 by adding nitric acid, 30 parts of an aqueous nitric acid solution having a polyaluminum chloride concentration of 10% by mass was added. Subsequently, after dispersing at 30 ° C. using a homogenizer (IKA Ultra Turrax T50), the particle size of the aggregated particles is grown while raising the temperature at a rate of 1 ° C./30 minutes in a heating oil bath. It was.
On the other hand, 150 parts of the resin particle dispersion (1) was put into a container A of a polyester bottle, and 25 parts of the release agent particle dispersion (1) was put into the container B. Next, the liquid feeding speed of the tube pump A is set to 0.7 part / minute, the liquid feeding speed of the tube pump B is set to 0.14 part / minute, and the inside of the round stainless steel flask during the formation of aggregated particles is set. When the temperature reached 37.0 ° C., the tube pumps A and B were driven to start feeding each dispersion liquid. Thereby, while gradually increasing the concentration of the release agent particles, the mixed dispersion in which the resin particles and the release agent particles were dispersed was fed from the container A to the round stainless steel flask in which aggregated particles were being formed.
Then, the feeding of each dispersion liquid to the flask was completed, and the liquid was held for 30 minutes from the time when the temperature in the flask reached 48 ° C., thereby forming second aggregated particles.

  Thereafter, 50 parts of the resin particle dispersion (1) was gently added and held for 1 hour, and the pH was adjusted to 8.5 by adding a 0.1N aqueous sodium hydroxide solution. Heated to 0 ° C. and held for 5 hours. Thereafter, the mixture was cooled to 20 ° C. at a rate of 20 ° C./min, filtered, sufficiently washed with ion exchange water, and dried to obtain toner particles (1) having a volume average particle diameter of 6.0 μm.

[Production of Toner Particles (2)]
In preparation of the toner particles (1), the liquid feeding speed of the tube pump A is set to 0.56 parts / minute, the liquid feeding speed of the tube pump B is set to 0.11 parts / minute, and the temperature in the flask is 32. The toner particles (2) were obtained in the same manner as the toner particles (1) except that the tube pumps A and B were driven when the temperature reached 1 ° C.

[Production of Toner Particles (3)]
In the production of the toner particles (1), the liquid feeding speed of the tube pump A is set to 0.68 parts / minute, the liquid feeding speed of the tube pump B is set to 0.15 parts / minute, and the temperature in the flask is 33. The toner particles (3) were obtained in the same manner as the toner particles (1) except that the tube pumps A and B were driven when the temperature reached 8 ° C.

[Production of Toner Particles (4)]
In the production of the toner particles (1), the liquid feeding speed of the tube pump A is set to 0.82 parts / minute, the liquid feeding speed of the tube pump B is set to 0.17 parts / minute, and the temperature in the flask is 39. The toner particles (4) were obtained in the same manner as the toner particles (1) except that the tube pumps A and B were driven when the temperature reached 4 ° C.

[Production of Comparative Toner Particles (C1)]
In the production of the toner particles (1), the liquid feeding speed of the tube pump A is set to 0.79 parts / minute, the liquid feeding speed of the tube pump B is set to 0.11 parts / minute, and the temperature in the flask is 30. Comparative toner particles (C1) were obtained in the same manner as the toner particles (1) except that the tube pumps A and B were driven when the temperature reached 6 ° C.

[Production of Comparative Toner Particles (C2)]
In the production of the toner particles (1), the liquid feeding speed of the tube pump A is set to 0.49 parts / minute, the liquid feeding speed of the tube pump B is set to 0.10 parts / minute, and the temperature in the flask is 30. Comparative toner particles (C2) were obtained in the same manner as the toner particles (1) except that the tube pumps A and B were driven when the temperature reached 2 ° C.

[Production of Comparative Toner Particles (C3)]
In preparation of the toner particles (1), the liquid feeding speed of the tube pump A is set to 1.02 parts / minute, the liquid feeding speed of the tube pump B is set to 0.19 parts / minute, and the temperature in the flask is 39. Comparative toner particles (C3) were obtained in the same manner as the toner particles (1) except that the tube pumps A and B were driven when the temperature reached 4 ° C.

<Preparation of surface-treated silica particles>
[Preparation of oil-treated silica particles (1)]
After SiCl ₄ , hydrogen gas, and oxygen gas are mixed in the mixing chamber of the combustion burner, they are burned at a temperature of 1000 ° C. or higher and 3000 ° C. or lower. Silica particles were obtained by removing silica powder from the burned gas. At this time, silica particles (R1) having a volume average particle diameter of 136 nm were obtained by setting the molar ratio of hydrogen gas to oxygen gas to 1.3: 1.
100 parts of silica particles (R1) and 500 parts of ethanol were placed in an evaporator and stirred for 15 minutes while maintaining the temperature at 40 ° C. Next, 10 parts of dimethyl silicone oil was added to 100 parts of silica particles and stirred for 15 minutes, and then 10 parts of dimethyl silicone oil was further added to 100 parts of silica particles and stirred for 15 minutes. Finally, the temperature was raised to 90 ° C. and ethanol was dried under reduced pressure. Thereafter, the treated product was taken out and further vacuum-dried at 120 ° C. for 30 minutes to obtain an oil treatment having a volume average particle size of 136 nm and a free oil amount of 10% by mass. Silica particles 1 were obtained.

[Preparation of oil-treated silica particles 2]
Oil treatment with a volume average particle size of 180 nm and a free oil amount of 10% by mass under the same conditions and method as the oil-treated silica particles (1) except that the molar ratio of hydrogen gas to oxygen gas is 1.2: 1 Silica particles 2 were obtained.

[Preparation of oil-treated silica particles (3)]
Oil treatment with a volume average particle size of 32 nm and a free oil amount of 10% by mass under the same conditions and method as the oil-treated silica particles (1) except that the molar ratio of hydrogen gas to oxygen gas is 1.5: 1 Silica particles 2 were obtained.

[Preparation of oil-treated silica particles (4)]
100 parts of silica particles (R1) and 500 parts of ethanol used for the production of oil-treated silica particles (1) were placed in an evaporator and stirred for 15 minutes while maintaining the temperature at 40 ° C. Next, 6 parts of dimethyl silicone oil was added to 100 parts of silica particles and stirred for 15 minutes. Finally, the temperature was raised to 90 ° C. and ethanol was dried under reduced pressure. Thereafter, the treated product was taken out and further vacuum-dried at 120 ° C. for 30 minutes to obtain oil-treated silica particles having a volume average particle size of 136 nm and a free oil amount of 3% by mass. Got (4)

[Production of HMDS treated silica particles (C1)]
100 parts of silica particles (R1) and 500 parts of ethanol used for the production of oil-treated silica particles (1) were placed in an evaporator and stirred for 15 minutes while maintaining the temperature at 40 ° C. Next, 20 parts of hexamethyldisilazane (HMDS) was added to 100 parts of silica particles and stirred for 15 minutes. Finally, the temperature was raised to 90 ° C., and ethanol was dried under reduced pressure. Then, the treated product was taken out, further vacuum-dried at 120 ° C. for 30 minutes, and treated with hexamethyldisilazane and treated with hexamethyldisilazane. Particles (C1) were obtained.

<Examples 1-7, Comparative Examples 1-4>
[Production of toner]
100 parts of the toner particles of the type shown in Table 1 and the surface-treated silica particles of the type and number of parts shown in Table 1 were mixed using a Henschel mixer (circumferential speed 30 m / second, 3 minutes) to obtain each toner.

(Development of developer)
・ Ferrite particles (average particle size 50 μm) 100 parts ・ Toluene 14 parts ・ Styrene / methyl methacrylate copolymer (copolymerization ratio 15/85) 3 parts ・ Carbon black 0.2 parts A carrier was obtained by dispersing to prepare a dispersion, putting the dispersion together with ferrite particles in a vacuum degassing kneader, and drying under reduced pressure while stirring.

  Then, 8 parts of each toner was mixed with 100 parts of the carrier to obtain a developer.

<Various measurements>
With respect to the toner of the developer obtained in each example, the mode value and the skewness of the distribution of the uneven distribution degree B of the release agent domain were measured according to the method described above. The results are shown in Table 1.
With respect to the oil-treated silica particles of the developer toner obtained in each example, the volume average particle size (denoted as “D50v” in the table) and the amount of free oil were measured according to the method described above. The results are shown in Table 1.

<Evaluation>
The following evaluation was performed using the developer obtained in each example. The results are shown in Table 1.

(Evaluation of fog and image density)
The developer obtained in each example was left for 3 days in an environment of low temperature and low humidity (temperature 10 ° C., humidity 15% RH). Thereafter, the developer was filled in a developing device of 700 Digital Color Press (manufactured by Fuji Xerox Co., Ltd.). And the following evaluation was implemented using this apparatus in the environment of low temperature and low humidity (temperature 10 degreeC, humidity 15% RH).

  First, a patch of 100% solid image of 5 cm × 5 cm was prepared on C2 paper manufactured by Fuji Xerox Co., Ltd. The density of the prepared patch was measured, and this was defined as density 1. Here, this density was measured with an image densitometer X-Rite 938 (manufactured by X-Rite).

  Next, an image with an image density of 40% was output continuously on C2 paper for 100,000 sheets. Here, the density of the output background portion of the 100,000th sheet was measured in the same manner as the density 1, and also visually confirmed. The measured density was evaluated as fog density.

  Next, 100,000 images of an image density of 1% were output continuously on C2 paper. Thereafter, a patch of a 100% solid image of 5 cm × 5 cm was prepared, and the density of this patch was measured in the same manner as density 1, and this was set to density 2.

And it evaluated based on the following evaluation criteria based on fog density and visual observation. The allowable range up to G3 was set.
-Evaluation criteria for fogging-
G1 (◎): The fog density is less than 0.2, and no partial fog is observed even visually.
G2 (◯): The fog density is less than 0.2, but slight fog is visually observed.
G3 (Δ): The fog density is less than 0.2, but partial fog is visually observed.
G4 (x): fog density is 0.2 or more.

Further, the difference between the concentration 2 and the concentration 1 was obtained, and this was taken as the Δ concentration. That is, Δ concentration = concentration 2−concentration 1. The allowable range up to G3 was set.
-Evaluation criteria for concentration reduction-
G1 (◯): 0 <Δconcentration ≦ 0.2
G2 (△): 0.2 <△ concentration ≦ 0.3
G3 (×): 0.3 <Δ concentration

  From the above results, it can be seen that in this embodiment, both fog and image density evaluation are better than those in the comparative example.

1Y, 1M, 1C, 1K photoconductor (an example of an image carrier)
2Y, 2M, 2C, 2K charging roll (an example of charging means)
3. Exposure device (an example of electrostatic charge image forming means)
3Y, 3M, 3C, 3K Laser beams 4Y, 4M, 4C, 4K Developing device (an example of developing means)
5Y, 5M, 5C, 5K primary transfer roll (an example of primary transfer means)
6Y, 6M, 6C, 6K Photoconductor cleaning device (an example of cleaning means)
8Y, 8M, 8C, 8K Toner cartridge 10Y, 10M, 10C, 10K Image forming unit 20 Intermediate transfer belt (an example of an intermediate transfer member)
22 Drive roll 24 Support roll 26 Secondary transfer roll (an example of secondary transfer means)
30 Intermediate transfer member cleaning device 107 Photosensitive member (an example of an image holding member)
108 Charging roll (an example of charging means)
109 Exposure apparatus (an example of electrostatic charge image forming means)
111 Developing device (an example of developing means)
112 Transfer device (an example of transfer means)
113 photoconductor cleaning device (an example of cleaning means)
115 Fixing device (an example of fixing means)
116 Attachment rail 118 Opening 117 for exposure 117 Case 200 Process cartridge 300 Recording paper (an example of recording medium)
P Recording paper (an example of a recording medium)

Claims (8)

It has a sea-island structure including a binder resin and a release agent, and has a sea part containing the binder resin and an island part containing the release agent, and includes the release agent represented by the following formula (1) Toner particles having a mode of distribution of the uneven distribution degree B in the island portion of 0.75 or more and 0.98 or less, and a skewness of the distribution of the uneven distribution degree B of −1.10 or more and −0.50 or less,
An external additive comprising silica particles surface-treated with oil;
A toner for developing an electrostatic charge image.
Formula (1): Unevenness B = 2d / D
(In formula (1), D represents the equivalent-circle diameter (μm) of the toner particles in the cross-sectional observation of the toner particles. D represents the center of gravity of the island portion including the release agent from the center of gravity of the toner particles in the cross-sectional observation of the toner particles. The distance (μm) is shown.)   The toner for developing an electrostatic charge image according to claim 1, wherein the silica particles have a volume average particle diameter of 30 nm to 200 nm.   The electrostatic image developing toner according to claim 1, wherein the amount of free oil of the silica particles is 1% by mass or more and 10% by mass or less.   An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 1. An electrostatic charge image developing toner according to any one of claims 1 to 3 is accommodated,
A toner cartridge to be attached to and detached from the image forming apparatus. A developing means for containing the electrostatic charge image developer according to claim 4 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer,
A process cartridge attached to and detached from the image forming apparatus. An image carrier,
Charging means for charging the surface of the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
Development means for containing the electrostatic charge image developer according to claim 4 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer;
Transfer means for transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
Fixing means for fixing the toner image transferred to the surface of the recording medium;
An image forming apparatus comprising: A charging step for charging the surface of the image carrier;
An electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged image carrier;
A developing step of developing an electrostatic charge image formed on the surface of the image carrier as a toner image with the electrostatic charge image developer according to claim 4;
A transfer step of transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
A fixing step of fixing the toner image transferred to the surface of the recording medium;
An image forming method comprising: