JP2019061178A - Toner for electrostatic charge image development, toner set, electrostatic charge image developer, toner cartridge, process cartridge, image forming apparatus, and image forming method - Google Patents

Abstract

To provide a toner for electrostatic charge image development that is excellent in gradation when a multi-order color halftone image is formed.SOLUTION: A toner for electrostatic charge image development includes toner particles having a large diameter-side volume particle size distribution index (GSDv(90/50)) of 1.26 or less, a small diameter-side volume particle size distribution index (GSDp(50/10)) of 1.28 or less, where GSDv(90/50)/GSDp(50/10) is 0.96 or more and 1.01 or less, and an average circularity of 0.95 or more and 1.00 or less.SELECTED DRAWING: None

Description

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

  In recent years, the electrophotographic process has been widely used not only for copying machines but also for office network printers, personal computer printers, on-demand printing printers, etc. due to the development of devices in the information society and enhancement of communication networks. Regardless of color, high image quality, high speed, high reliability, small size, light weight, energy saving performance are increasingly demanded.

  In the electrophotographic process, usually, an electrostatic charge image is electrically formed by various means on a photosensitive member (image carrier) using a photoconductive substance, and this electrostatic charge image is used with a developer containing toner. Is developed, and the toner image on the photosensitive member is transferred to a recording medium such as paper directly via an intermediate transfer member or directly, and then the transferred image is fixed to the recording medium, and the fixed image is It is formed.

  Here, the volume average particle size distribution index (GSDv) is at most 1.3 and the volume average particle size distribution index (GSDv) in order to provide a toner for developing an electrostatic charge image having excellent chargeability and long life. Patent Document 1 discloses a toner for developing an electrostatic charge image characterized in that the ratio (GSDv / GSDp) of the number average particle size distribution index (GSDp) is at least 0.95. ).

  In addition, in order to provide a toner for developing an electrostatic charge image which brings excellent development and transfer performance, and gives excellent performance stability and high image quality and high reliability, the particle diameter distribution index GSDpS on the small diameter side is 1.27 or less Characteristic toner for developing electrostatic image: GSDpS = D50p / D16p (wherein, D50p is a particle size value that makes 50% of cumulative in particle number distribution, D16p is cumulative from the small diameter side in particle number distribution A particle size value of 16% is disclosed (see, for example, Patent Document 2).

Unexamined-Japanese-Patent No. 10-301323 JP 2001-255703 A

In color toner images, secondary and tertiary colors are generally used which overlap a plurality of colors such as magenta, yellow and cyan. In particular, it is easy to visually recognize the difference in the tonality of a toner image when a multi-color halftone image such as a secondary color halftone image or a tertiary color halftone image is formed in recent high quality images. There has been a demand for further improvement of the tonality of halftone images.
In Patent Documents 1 and 2, by controlling the particle size distribution of the toner, the gradation of the multi-order color image is good. However, when a light color such as halftone is formed, a subtle difference in tonality tends to be visible, so there is room for improvement with regard to tonality of a halftone image.
The present invention has been made in view of the above-described conventional circumstances, and it is an object of the present invention to provide a toner for developing an electrostatic charge image which is excellent in gradation when a multi-color halftone image is formed.

The specific means for achieving the said subject are as follows.
That is, the invention according to claim 1 is
The large diameter side volume particle size distribution index (GSDv (90/50)) is 1.26 or less,
The small-diameter side number particle size distribution index (GSDp (50/10)) is 1.28 or less,
GSDv (90/50) / GSDp (50/10) is 0.96 or more and 1.01 or less,
A toner for developing an electrostatic charge image comprising toner particles having an average circularity of 0.95 or more and 1.00 or less.

The invention according to claim 2 is
The air flow energy measured under the condition that the tip speed of the rotor blade is 100 mm / sec, the approach angle of the rotor blade is -5 °, and the air flow rate is 5 ml / min using a powder rheometer is 100 mJ to 300 mJ An electrostatic charge image developing toner according to claim 1.

The invention according to claim 3 is
The ratio of the aeration flow energy of aeration flow 5 ml / min to the aeration flow energy of aeration flow 80 ml / min (aeration flow 5 ml / min measurement time / aeration flow 80 ml / min measurement time) is 3 or more and 8 or less The toner for electrostatic image development according to claim 2.

The invention according to claim 4 is
The toner according to any one of claims 1 to 3, which is a magenta toner containing a magenta colorant or a cyan toner containing a cyan colorant.

The invention according to claim 5 is
The magenta colorant is C.I. I. Pigment red 122, C.I. I. Pigment red 185 and C.I. I. The toner for electrostatic image development according to claim 4, comprising at least one selected from the group consisting of C.I.

The invention according to claim 6 is
The cyan colorant is C.I. I. Pigment blue 15: 1, and C.I. I. The toner for developing an electrostatic charge image according to claim 4, comprising at least one selected from the group consisting of pigment blue 15: 3.

The invention according to claim 7 is
It has n kinds (n is an integer of 2 or more) of electrostatic charge image developing toner exhibiting different colors from one another,
At least one of the electrostatic image developing toners has a large diameter side volume particle size distribution index (GSDv (90/50)) of 1.26 or less and a small diameter side number particle size distribution index (GSDp (50/10)) It contains toner particles of 1.28 or less, GSDv (90/50) / GSDp (50/10) of 0.96 to 1.01, and having an average circularity of 0.95 to 1.00. Toner set.

The invention according to claim 8 is
All the toners for electrostatic image development have a large diameter side volume particle size distribution index (GSDv (90/50)) of 1.26 or less, and a small diameter side number particle size distribution index (GSDp (50/10)) It contains toner particles of 1.28 or less, GSDv (90/50) / GSDp (50/10) of 0.96 to 1.01, and having an average circularity of 0.95 to 1.00. The toner set according to claim 7.

The invention according to claim 9 is
Ventilation for each of the electrostatic image developing toners was measured using a powder rheometer at a tip speed of the rotary blade of 100 mm / sec, an entry angle of the rotary blade of -5 °, and a ventilation flow rate of 5 ml / min. The toner set according to claim 8, wherein the difference between the maximum value and the minimum value of the air flow energy at a flow rate of 5 ml / min is 80 mJ or less.

The invention according to claim 10 is
An electrostatic charge image developer containing the toner for electrostatic charge image development according to any one of claims 1 to 6.

The invention according to claim 11 is
A toner for electrostatic image development according to any one of claims 1 to 6 is contained,
A toner cartridge that is attached to and removed from the image forming apparatus.

The invention according to claim 12 is
11. A developing unit for containing the electrostatic charge image developer according to claim 10 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer.
Process cartridge that is attached to and detached from the image forming apparatus.

The invention according to claim 13 is
An image carrier,
Charging means for charging the surface of the image carrier;
Electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
11. A developing unit for containing the electrostatic charge image developer according to claim 10, and developing the electrostatic charge image formed on the surface of the image carrier as the toner image by the electrostatic charge image developer.
A transfer unit configured to transfer 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 14 is
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 by the electrostatic charge image developer according to claim 10.
Transferring the toner image formed on the surface of the image carrier to the surface of the 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 of claim 1, the toner particles have a GSDv (90/50) of more than 1.26, a GSDp (50/10) of more than 1.28, or GSDv (90/50) / GSDp Gradation when a multi-color halftone image is formed as compared with the case where 50/10) is less than 0.96 or more than 1.01 or the average circularity is less than 0.95 There is provided a toner for developing an electrostatic charge image which is excellent in properties.
According to the second aspect of the present invention, the tonality in the case of forming a multi-color halftone image is further improved as compared with the case where the aeration fluidity energy is less than 100 mJ or exceeds 300 mJ.
According to the invention of claim 3, the ratio of the aeration flow energy of the aeration flow rate 5 ml / min to the aeration flow energy of the aeration flow rate 80 ml / min (at the time of measurement of the aeration flow 5 ml / min / at the time of the aeration flow 80 ml / min) In the case where a multi-color halftone image is formed after forming a high-image-density toner image, the tonality is further improved as compared with the case where the value of 3) is less than 3 or more than 8.
According to the invention of claims 4 to 6, the gradation in the case of forming a multi-color halftone image is further improved.

According to the invention as set forth in claim 7, in any of n types of electrostatic charge image developing toners, GSDv (90/50) exceeds 1.26 or GSDp (50/10) exceeds 1.28. Compared with the case where toner particles having a GSDv (90/50) / GSDp (50/10) of less than 0.96 or more than 1.01 or an average circularity of less than 0.95 are included. Thus, a toner set having excellent gradation when forming a multi-color halftone image is provided.
According to the invention of claim 8, in any of n types of electrostatic charge image developing toners, GSDv (90/50) exceeds 1.26 or GSDp (50/10) exceeds 1.28. Compared with the case where toner particles having a GSDv (90/50) / GSDp (50/10) of less than 0.96 or more than 1.01 or an average circularity of less than 0.95 are included. Thus, the tonality in the case of forming a multi-color halftone image is further improved.
According to the invention as set forth in claim 9, in comparison to the case where the difference between the maximum value and the minimum value of the air flow fluidity energy of the air flow rate of 5 ml / min for each of the electrostatic charge image developing toner exceeds 80 mJ, The tonality in the case of forming the next color halftone image is further improved.

According to the invention of claim 10, the toner particles have a GSDv (90/50) of more than 1.26, a GSDp (50/10) of more than 1.28, or GSDv (90/50) / GSDp Gradation when a multi-color halftone image is formed as compared with the case where 50/10) is less than 0.96 or more than 1.01 or the average circularity is less than 0.95 Provided is an electrostatic charge image developer having excellent properties.
According to the invention of claim 11, the toner particles have a GSDv (90/50) exceeding 1.26, a GSDp (50/10) exceeding 1.28 or GSDv (90/50) / GSDp Gradation when a multi-color halftone image is formed as compared with the case where 50/10) is less than 0.96 or more than 1.01 or the average circularity is less than 0.95 There is provided a toner cartridge containing a toner for developing an electrostatic charge image, which has excellent properties.
According to the invention of claim 12, the toner particles have a GSDv (90/50) exceeding 1.26, a GSDp (50/10) exceeding 1.28, or GSDv (90/50) / GSDp Gradation when a multi-color halftone image is formed as compared with the case where 50/10) is less than 0.96 or more than 1.01 or the average circularity is less than 0.95 There is provided a process cartridge for containing an electrostatic charge image developer having excellent properties.
According to the invention of claim 13, the toner particles have a GSDv (90/50) exceeding 1.26, a GSDp (50/10) exceeding 1.28 or GSDv (90/50) / GSDp Gradation when a multi-color halftone image is formed as compared with the case where 50/10) is less than 0.96 or more than 1.01 or the average circularity is less than 0.95 There is provided an image forming apparatus using an electrostatic charge image developer having excellent properties.
According to the invention of claim 14, the toner particles have a GSDv (90/50) exceeding 1.26, a GSDp (50/10) exceeding 1.28, or GSDv (90/50) / GSDp Gradation when a multi-color halftone image is formed as compared with the case where 50/10) is less than 0.96 or more than 1.01 or the average circularity is less than 0.95 Provided is an image forming method using an electrostatic charge image developer having excellent properties.

It is a figure explaining the state of a screw about an example of the screw extruder used for manufacture of the toner which concerns on this embodiment. It is a figure for demonstrating the measuring method of the amount of flowable energy in a powder rheometer. It is a figure which shows the relationship of vertical load and energy gradient obtained by the powder rheometer. It is a schematic diagram for demonstrating the shape of the rotary blade used with a powder rheometer. FIG. 1 is a schematic configuration view showing an example of an image forming apparatus according to the present embodiment. It is a schematic block diagram which shows an example of the process cartridge which concerns on this embodiment.

  Hereinafter, embodiments of the toner for developing an electrostatic charge image, the toner set, the electrostatic charge image developer, the toner cartridge, the process cartridge, the image forming apparatus, and the image forming method of the present invention will be described in detail.

<Toner for electrostatic image development>
The toner for electrostatic image development (hereinafter, may be simply referred to as "toner") according to this embodiment has a large diameter volume particle size distribution index (GSDv (90/50)) of 1.26 or less, The small-diameter side number particle size distribution index (GSDp (50/10)) is 1.28 or less, GSDv (90/50) / GSDp (50/10) is 0.96 or more and 1.01 or less, and the average circularity Of toner particles is 0.95 or more and 1.00 or less.

The toner for developing an electrostatic charge image according to the present embodiment is excellent in gradation when a multi-color halftone image is formed. Although the reason is not clear, it is guessed as follows.
A multi-color halftone image consists of at least two toners forming a thin toner layer on a recording medium. In order to improve the tonality of a multi-color halftone image, it is necessary to form a toner layer by uniformly dispersing at least two color toners uniformly on a recording medium.
The toner according to this embodiment has GSDv (90/50) of 1.26 or less, GSDp (50/10) of 1.28 or less, and GSDv (90/50) / GSDp (50/10). Since the toner particles containing 0.96 to 1.01 and having an average circularity of 0.95 to 1.00 are included, the behavior of the toner particles tends to be uniform as compared with conventional toner particles. The toner containing such toner particles is particularly excellent in fluidity and charging characteristics. By improving the flowability and charging characteristics of the toner, it is easy to form a toner layer in which the toner is uniformly dispersed on the recording medium. As a result, it is presumed that a multi-color halftone image having excellent tonality is formed.

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

  The toner according to the exemplary embodiment is configured to include toner particles and, if necessary, an external additive.

(Toner particles)
The toner particles contain, for example, a binder resin, and, if necessary, a colorant, a release agent, and other additives.

-Binding resin-
As the binder resin, for example, styrenes (eg, styrene, parachlorostyrene, α-methylstyrene etc.), (meth) acrylates (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 (eg, 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) 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 above-mentioned vinyl resin, or The graft polymer etc. which are obtained by polymerizing a vinyl-type monomer in coexistence are also mentioned.
These binder resins may be used alone or in combination of two or more.

A polyester resin is suitable as the binder resin.
As polyester resin, a well-known polyester resin is mentioned, for example.

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

Examples of polyvalent carboxylic acids 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 (eg, cyclohexanedicarboxylic acid etc.), aromatic dicarboxylic acids (eg, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid etc.), their anhydrides, or their lower (eg, 1 or more carbon atoms) 5 or less) alkyl ester is mentioned. Among these, as polyvalent carboxylic acid, for example, aromatic dicarboxylic acid is preferable.
As the polyvalent carboxylic acid, a trivalent or higher carboxylic acid having a crosslinked or branched structure may be used in combination with the dicarboxylic acid. Examples of trivalent or higher carboxylic acids include trimellitic acid, pyromellitic acid, their anhydrides, or their lower (for example, 1 to 5 carbon atoms) alkyl esters.
The polyvalent carboxylic acids may be used alone or in combination of two or more.

Examples of polyhydric alcohols include aliphatic diols (eg ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol etc.), alicyclic diols (eg cyclohexanediol, cyclohexanedimethanol, Hydrogenated bisphenol A etc., aromatic diols (eg ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A etc) may be mentioned. 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 trivalent or higher polyhydric alcohol having a crosslinked structure or a branched structure may be used in combination with a diol. Examples of trihydric or higher polyhydric alcohols include glycerin, trimethylolpropane and pentaerythritol.
A polyhydric alcohol may be used individually by 1 type, and may use 2 or more types together.

50 degreeC or more and 80 degrees C or less are preferable, and, as for the glass transition temperature (Tg) of a polyester resin, 50 degrees C or more and 65 degrees C or less are more preferable.
In addition, a glass transition temperature is calculated | required from the DSC curve obtained by differential scanning calorimetry (DSC), and, more specifically, it is JIS K-7121-1987 "The method of measuring the glass transition temperature of the transition temperature of a plastics". It is determined by the "extrapolated glass transition initiation temperature" described.

The weight average molecular weight (Mw) of the polyester resin is preferably 5,000 or more and 1,000,000 or less, and more preferably 7,000 or more and 500000 or less.
The number average molecular weight (Mn) of the polyester resin is preferably 2000 or more and 100000 or less.
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 using a Tosoh GPC / HLC-8120 GPC as a measurement apparatus, a Tosoh column / TSKgel SuperHM-M (15 cm) in THF solvent. The weight average molecular weight and the number average molecular weight are calculated from the measurement results using a molecular weight calibration curve prepared from monodispersed polystyrene standard samples.

The polyester resin is obtained by a known production method. Specifically, for example, it is obtained by a method in which the polymerization temperature is set to 180 ° C. or more and 230 ° C. or less, the reaction system is reduced in pressure as necessary, and the reaction is performed while removing water and alcohol generated during condensation.
In addition, when the monomer of a raw material melt | dissolves or does not miscible at reaction temperature, you may be made to add and melt | dissolve the solvent of a high boiling point as a solubilizer. In this case, the polycondensation reaction is carried out while distilling off the solubilizer. When a monomer with poor compatibility is present in the copolymerization reaction, the monomer with poor compatibility and the acid or alcohol to be polycondensed are condensed in advance, and then it is used together with the main component. It is good to condense.

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

-Colorant-
As the colorant, conventionally known colorants corresponding to the color of toner can be used.
The tonality of a multi-color halftone image is likely to be degraded by the uneven distribution of toner on the recording medium, which exhibits a color that is easily visually recognized. Therefore, it is preferable that the toner according to the present embodiment is a magenta toner exhibiting a magenta color which is easily visible visually or a cyan toner exhibiting a cyan color. By suppressing the uneven distribution of the magenta toner or the cyan toner on the recording medium, the gradation of the multi-color halftone image can be easily improved.

Examples of cyan colorants include C.I. I. Pigment blue 1, 2, 3, 4, 5, 5, 6, 7, 7, 10, 11, 12, 13, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 23, 23, 60, 65, 73, 83, 180, C.I. I. Battian 1, 3, 20, etc., bitumen, cobalt blue, alkali blue lake, phthalocyanine blue, non-metal phthalocyanine blue, partially chlorinated phthalocyanine blue, cyan pigments of fast sky blue, indaslen blue BC, C.I. I. Cyan dyes such as solvent cyan 79 and 162 can be used.
As cyan colorants, C.I. I. Pigment blue 15: 1, and C.I. I. Pigment Blue 15: 3 is preferably included.

Examples of magenta colorants include C.I. I. Pigment red 1, 2, 3, 4, 5, 5, 6, 7, 8, 9, 10, 11, 12, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90 112, 114, 122, 123, 163, 184, 185, 202, 206, 207, 209, 238, etc., magenta pigments of pigment violet 19, C.I. I. Solvent Red 1, 3, 8, 23, 23, 24, 25, 30, 30, 49, 81, 82, 83, 84, 100, 109, 121, C . I. Disperse thread 9, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 18. 22, 23, 24, 27, 29, 32, 32, 34, and so on. Magenta dyes such as 35, 36, 37, 38, 39, 40, etc., etc., bengara, cadmium red, red lead, mercury sulfide, cadmium, permanent red 4R, resole red, pyrazolone red, watching red, calcium Salt, Lake Red D, Brilliant Carmine 6B, Eosin Lake, Rotamin Lake B, Alizarin Lake, Brilliant Carmine 3 B, etc. can be used.
As the magenta colorant, C.I. I. Pigment red 122, C.I. I. Pigment red 185 and C.I. I. It is preferable to contain at least 1 sort (s) selected from the group which consists of pigment red 238.

  Moreover, as a yellow coloring agent, for example, C.I. I. Pigment Yellow 2, 3, 15, 16, 16, 17, 74, 97, 180, 185, 139, etc. may be used.

Other coloring agents include carbon black (acetylene black, furnace black, thermal black, channel black, ketjen black), copper oxide, manganese dioxide, aniline black, titanium black, activated carbon, nonmagnetic ferrite, magnetite, etc. White coloring such as black colorant, titanium oxide, barium sulfate, lead oxide, zinc oxide, lead titanate, potassium titanate, barium titanate, barium titanate, strontium titanate, zirconia, antimony trioxide, lead white, zinc sulfide, barium carbonate, etc. Agents and the like.
The coloring agents may be used alone or in combination of two or more.

  As the coloring agent, a surface-treated coloring agent may be used if necessary, and may be used in combination with a dispersing agent. Moreover, a coloring agent may use multiple types together.

  As content of a coloring agent, 1 mass% or more and 30 mass% or less are preferable with respect to the whole toner particle, for example, and 3 mass% or more and 15 mass% or less are more preferable.

-Release agent-
As a mold release agent, for example, hydrocarbon wax; natural wax such as carnauba wax, rice wax, candelilla wax; synthesis such as montan wax or mineral / petroleum wax; ester wax such as fatty acid ester, montanic acid ester And the like. The release agent is not limited to this.

50 degreeC or more and 110 degrees C or less are preferable, and, as for the melting temperature of a mold release agent, 60 degrees C or more and 100 degrees C or less are more preferable.
The melting temperature is determined by the “melting peak temperature” described in the method of determining the melting temperature in JIS K-7121-1987 “Method for measuring transition temperature of plastic” from the DSC curve obtained by differential scanning calorimetry (DSC). Ask.

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

-Other additives-
Examples of other additives include well-known additives such as magnetic substances, charge control agents, and inorganic powders. These additives are contained in the toner particles as an internal additive.

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

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

  In the present embodiment, GSDv (90/50) of the toner particles is 1.26 or less, preferably 1.25 or less, and more preferably 1.24 or less. Further, the GSDv (90/50) of the toner particles may be 1.15 or more. When GSDv (90/50) of toner particles exceeds 1.26, since there are coarse toner particles of low charge, transfer to paper becomes uneven, and gradation in thin layer multi-color halftone decreases Can cause problems.

  In the present embodiment, GSDp (50/10) of the toner particles is 1.28 or less, preferably 1.27 or less, and more preferably 1.25 or less. In addition, GSDp (50/10) of the toner particles may be 1.16 or more. When GSDp (50/10) of toner particles exceeds 1.28, highly charged fine powder toner particles are present, so transfer to paper becomes uneven, and gradation in thin layer multi-color halftone decreases Can cause problems.

  In the present embodiment, GSDv (90/50) / GSDp (50/10) of the toner particles is 0.96 or more and 1.01 or less, preferably 0.97 or more and 1.01 or less, and 0.98 More preferably, it is 1.00 or less. When GSDv (90/50) / GSDp (50/10) of toner particles is less than 0.96, highly charged toner particles are present, and transfer to paper becomes uneven, resulting in thin multi-color halftone. May cause a problem that the tonality of the When GSDv (90/50) / GSDp (50/10) of toner particles exceeds 1.01, since there are coarse toner particles of low charge, transfer to paper becomes uneven and thin-layer multi-color halftone May cause a problem that the tonality at

In addition, various average particle diameters of toner particles, and various particle size distribution indexes (GSDv (90/50) and GSDp (50/10)) use Coulter Multisizer II (manufactured by Beckman Coulter, Inc.), and the electrolyte is ISOTON. -Measured using II (manufactured by Beckman Coulter).
In the measurement, 0.5 mg or more and 50 mg or less of a measurement sample is added to 2 ml of a 5% aqueous solution of surfactant (preferably sodium alkylbenzene sulfonate) as a dispersant. This is added to 100 ml or more and 150 ml or less of electrolyte solution.
The electrolytic solution in which the sample is suspended is dispersed for 1 minute with an ultrasonic disperser, and Coulter Multisizer II, using an aperture of 100 μm as the aperture diameter, the particle size distribution of particles of 2 μm to 60 μm in size. taking measurement. The number of particles to be sampled is 50,000.
With respect to the particle size range (channel) divided based on the particle size distribution to be measured, the cumulative distribution is drawn from the small diameter side of the volume and the number respectively, and the particle size of 10% cumulative is the volume particle size D10v, number particle size The particle diameter which becomes D10p and 50% of accumulation is defined as volume average particle diameter D50v, the number average particle diameter D50p, and the particle diameter which becomes 90% of accumulation as volume particle diameter D90v and number particle diameter D90p.
Using these, the large diameter side volume particle size distribution index (GSDv (90/50)) is calculated as (D90v / D50v) and the small diameter side number particle size distribution index (GSDp (50/10)) is calculated as (D50p / D10p) Be done.

In the present embodiment, when calculating the large diameter side volume particle size distribution index, D90v is used in place of D84v (grain diameter of 84% in cumulative) used for calculation of volume particle size distribution index (GSDv (84/16) The reason is the following factors.
The tonality of multi-color halftone to toner is affected even by very small amounts of coarse particles. Therefore, the amount of coarse powder (toner particles having a large particle diameter) contained in the toner particles is more sharply reflected on the value of the large-diameter-side volume particle size distribution index. It was confirmed that D90v and multi-order color halftone had strong correlation.
Further, in the present embodiment, when calculating the small particle size number particle size distribution index on the small diameter side, D10 p is replaced with D16 p (particle diameter of 16% in cumulative) used for calculating the number particle size distribution index (GSDp (84/16) The reason for using it is that the gradation of multi-order color halftone is affected even by a small amount of fine particles, so the amount of fine powder (toner particles with small particle diameter) contained in toner particles is more sensitive and the number particle size distribution index on the smaller diameter side The tonality of D10p and the multi-order color halftone was confirmed in detail, because there was a strong correlation between D10 p and the multi-order color halftone.

  The average circularity of the toner particles is 0.95 or more and 1.00 or less, preferably 0.95 or more and 0.98 or less, and 0.95 or more and 0.97 or less from the viewpoint of improving the cleaning property. Is more preferred. If the average circularity of the toner particles is less than 0.95, although it is good from the viewpoint of the cleaning ability, the transferability to the paper is not uniform due to the presence of irregular toner particles, like multi-color halftone In the case of such an image, there may be a problem that the tonality decreases.

The average circularity of the toner particles is determined by (circle equivalent circumference) / (perimeter length) [(perimeter of circle having the same projected area as the particle image) / (perimeter of particle projected image)]. Specifically, it is a value measured by the following method.
First, a toner particle to be measured is collected by suction, a flat flow is formed, and a strobe image is instantaneously flashed to take in a particle image as a still image, and a flow type particle image analysis device (Sysmex Corporation) It is determined by the company's FPIA-3000). And the number of samplings at the time of calculating | requiring an average circularity shall be 3500 pieces.
When the toner contains an external additive, the toner (developer) to be measured is dispersed in water containing a surfactant, and then subjected to ultrasonic treatment to obtain toner particles from which the external additive has been removed. .

(External additive)
Examples of the external additive include inorganic particles. As the inorganic particles, SiO ₂ , TiO ₂ , Al ₂ O ₃ , CuO, ZnO, SnO ₂ , CeO ₂ , CeO ₂ , Fe ₂ O ₃ , MgO, BaO, CaO, K ₂ O, Na ₂ O, ZrO ₂ , CaO. _{SiO 2, K 2 O · (} TiO 2) n, Al 2 O 3 · 2SiO 2, CaCO 3, MgCO 3, BaSO 4, MgSO 4 , and the like.

The surface of the inorganic particles as the external additive may be subjected to a hydrophobization treatment. The hydrophobization treatment is performed, for example, by immersing inorganic particles in a hydrophobization 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 alone or in combination of two or more.
The amount of the hydrophobic treatment agent is usually, for example, 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the inorganic particles.

  As external additives, resin particles (resin particles such as polystyrene, polymethyl methacrylate (PMMA), melamine resin, etc.), cleaning activators (for example, metal salts of higher fatty acids represented by zinc stearate, fluorine-based polymer Particles) and the like.

  The external addition amount of the external additive is, for example, preferably 0.01% by mass to 5% by mass, and more preferably 0.01% by mass to 2.0% by mass with respect to the toner particles.

(Method of manufacturing toner)
Next, a method of manufacturing the toner according to the present embodiment will be described.
The toner according to the exemplary embodiment is obtained by externally adding an external additive to toner particles after producing the toner particles.

The toner particles may be produced by any of dry method (for example, kneading and pulverizing method) and wet method (for example, aggregation and coalescence method, suspension polymerization method, dissolution and suspension method and the like). There are no particular limitations on the method for producing toner particles, and any known method may be employed.
Among these, toner particles are preferably obtained by an aggregation and coalescence method.

For example, the dissolution suspension method contains a particle dispersant, which is a liquid in which a raw material (binder resin, colorant, etc.) constituting toner particles is dissolved or dispersed in an organic solvent in which the binder resin can be dissolved. After dispersing in an aqueous solvent, the organic solvent is removed to granulate toner particles.
The aggregation and coalescence method is a method of obtaining toner particles through an aggregation step of forming aggregates of raw materials (resin particles, colorants, etc.) constituting toner particles, and a fusion step of coalescing the aggregates. .

  Among these, toner particles containing a urea-modified polyester resin as a binder resin may be obtained by the following dissolution and suspension method. In the following description of the dissolution and suspension method, a method for obtaining toner particles containing a non-modified polyester resin and a urea-modified polyester resin as a binder resin is described, but the toner particles use only a urea-modified polyester resin as a binder resin. May be included.

[Oil phase liquid preparation process]
An oil phase liquid is prepared by dissolving or dispersing toner particle materials containing an unmodified polyester resin, a polyester prepolymer having an isocyanate group, an amine compound, a colorant, and a release agent in an organic solvent (oil phase liquid preparation step) . This oil phase liquid preparation step is a step of dissolving or dispersing the toner particle material in an organic solvent to obtain a liquid mixture of toner material.

  The oil phase liquid is prepared by 1) dissolving or dispersing the toner material all at once in an organic solvent and preparing it 2) kneading the toner material in advance, then dissolving or dispersing the kneaded material in an organic solvent to prepare it. 3) Non-modified polyester resin, polyester prepolymer having isocyanate group, method of dissolving amine compound in organic solvent and dispersing colorant and mold release agent in this organic solvent, 4 ) After dispersing the coloring agent and the releasing agent in an organic solvent, a method of preparing by dissolving an unmodified polyester resin, a polyester prepolymer having an isocyanate group, an amine compound in the organic solvent, and preparing 5) an isocyanate group Toner particle materials (unmodified polyester resin, coloring agent and releasing agent) other than polyester prepolymers and amine compounds are dissolved or separated in an organic solvent After preparation, a polyester prepolymer having an isocyanate group and a method of dissolving and preparing an amine compound in the organic solvent, 6) a polyester prepolymer having an isocyanate group or toner particle materials other than an amine compound (unmodified polyester resin, After dissolving or dispersing the coloring agent and the releasing agent in an organic solvent, a method of preparing by dissolving a polyester prepolymer having an isocyanate group or an amine compound in the organic solvent may be mentioned. In addition, the preparation methods of oil phase liquid are not necessarily limited to these.

  Organic solvents for the oil phase liquid include ester solvents such as methyl acetate and ethyl acetate; ketone solvents such as methyl ethyl ketone and methyl isopropyl ketone; aliphatic hydrocarbon solvents such as hexane and cyclohexane; dichloromethane, chloroform, trichloroethylene etc. Halogenated hydrocarbon solvents and the like can be mentioned. These organic solvents dissolve the binder resin, and the proportion thereof dissolved in water is about 0% by mass to 30% by mass, and the boiling point is preferably 100 ° C. or less. Among these organic solvents, ethyl acetate is preferred.

[Suspension preparation process]
Next, the obtained oil phase liquid is dispersed in an aqueous phase liquid to prepare a suspension (suspension preparation step).
And reaction with the polyester prepolymer which has an isocyanate group, and an amine compound is performed with preparation of a suspension. Then, this reaction produces a urea-modified polyester resin. In addition, this reaction involves at least one of a crosslinking reaction of a molecular chain and an elongation reaction. In addition, you may perform reaction of the polyester prepolymer which has this isocyanate group, and an amine compound with the solvent removal process mentioned later.
Here, the reaction conditions are selected according to the reactivity between the isocyanate group structure of the polyester prepolymer and the amine compound. As one example, the reaction time is preferably 10 minutes to 40 hours, and more preferably 2 hours to 24 hours. The reaction temperature is preferably 0 ° C. or more and 150 ° C., and preferably 40 ° C. or more and 98 ° C. or less. In addition, you may use a well-known catalyst (Dibutyltin laurate, dioctyltin laurate, etc.) as needed for production | generation of urea modified polyester resin. That is, the catalyst may be added to the oil phase liquid or suspension.

  Examples of the aqueous phase liquid include aqueous phase liquids in which particle dispersants such as organic particle dispersants and inorganic particle dispersants are dispersed in an aqueous solvent. The aqueous phase liquid also includes an aqueous phase liquid in which the particle dispersant is dispersed in an aqueous solvent and the polymer dispersant is dissolved in an aqueous solvent. In addition, you may add well-known additives, such as surfactant, to a water phase liquid.

  Examples of the aqueous solvent include water (for example, ion-exchanged water, distilled water, pure water). The aqueous solvent is a solvent containing an organic solvent such as alcohol (methanol, isopropyl alcohol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) together with water. It may be.

  Examples of the organic particle dispersant include hydrophilic organic particle dispersants. Examples of the organic particle dispersant include particles of poly (meth) acrylic acid alkyl ester resin (for example, polymethyl methacrylate resin), polystyrene resin, poly (styrene-acrylonitrile) resin and the like. The organic particle dispersant also includes particles of styrene acrylic resin.

  As an inorganic particle dispersing agent, a hydrophilic inorganic particle dispersing agent is mentioned. Specific examples of the inorganic particle dispersant include particles of silica, alumina, titania, calcium carbonate, magnesium carbonate, tricalcium phosphate, clay, diatomaceous earth, bentonite and the like, and particles of calcium carbonate are preferable. The inorganic particle dispersant may be used alone or in combination of two or more.

The particle dispersant may be surface-treated with a polymer having a carboxyl group on the surface.
As the polymer having a carboxyl group, the carboxyl group of the α, β-monoethylenically unsaturated carboxylic acid or α, β-monoethylenically unsaturated carboxylic acid is selected depending on the alkali metal, alkaline earth metal, ammonia, amine or the like Copolymers of at least one selected from neutralized salts (alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts, etc.) and α, β-monoethylenically unsaturated carboxylic acid esters Be As the polymer having a carboxyl group, the carboxyl group of a copolymer of α, β-monoethylenically unsaturated carboxylic acid and α, β-monoethylenically unsaturated carboxylic acid ester is an alkali metal or alkaline earth metal And salts neutralized with ammonia, amines and the like (alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts and the like). The polymer having a carboxyl group may be used alone or in combination of two or more.

  Representative examples of α, β-monoethylenically unsaturated carboxylic acids include α, β-unsaturated monocarboxylic acids (acrylic acid, methacrylic acid, crotonic acid, etc.), α, β-unsaturated dicarboxylic acids (maleic acid) Acid, fumaric acid, itaconic acid etc. etc. are mentioned. Further, representative of α, β-monoethylenically unsaturated carboxylic acid esters are alkyl esters of (meth) acrylic acid, (meth) acrylates having an alkoxy group, (meth) acrylates having a cyclohexyl group, The (meth) acrylate which has a hydroxy group, polyalkylene glycol mono (meth) acrylate, etc. are mentioned.

  Examples of the polymer dispersant include hydrophilic polymer dispersants. As the polymer dispersant, specifically, a polymer dispersant having a carboxyl group and having no lipophilic group (hydroxypropoxy group, methoxy group, etc.) (for example, water-soluble such as carboxymethyl cellulose, carboxyethyl cellulose, etc.) Cellulose ether)).

  When the addition rate of the polymer dispersant is increased and added, the high concentration polymer dispersant is locally present, and fine powder particles are easily generated. Then, generation of fine powder particles and coarse powder particles can be suppressed by adding the polymer dispersant at a low concentration and reducing the addition rate.

[Solvent removal process]
Next, the organic solvent is removed from the obtained suspension to obtain a toner particle dispersion (solvent removal step). The solvent removal step is a step of removing the organic solvent contained in the droplets of the aqueous phase liquid dispersed in the suspension to generate toner particles. The removal of the organic solvent from the suspension may be performed immediately after the suspension preparation step, or may be performed after one minute or more after completion of the suspension preparation step.
In the solvent removal step, it is preferable to remove the organic solvent from the suspension by cooling or heating the obtained suspension to, for example, a range of 0 ° C. or more and 100 ° C. or less.

Specific methods for removing the organic solvent include the following methods.
(1) A method of forcibly renewing the gas phase on the suspension surface by blowing a gas flow on the suspension. In this case, gas may be blown into the suspension.
(2) A method of reducing the pressure. In this case, the gas phase on the suspension surface may be forcibly renewed by gas filling, or gas may be blown into the suspension.

  In the removal of the organic solvent, it is desirable in that the gas removal into the suspension can be accelerated and the removal of the solvent can be promoted. In particular, a plurality of gas injection points may be provided.

Through the above steps, toner particles are obtained.
Here, after completion of the solvent removing step, toner particles formed in the toner particle dispersion liquid are obtained as toner particles in a dried state through a known washing step, solid-liquid separation step, and drying step.
In the washing step, it is preferable to carry out substitution washing with ion exchange water sufficiently from the viewpoint of chargeability.
The solid-liquid separation step is not particularly limited, but it is preferable to apply suction filtration, pressure filtration, etc. from the viewpoint of productivity. Further, the drying step is also not particularly limited, but in view of productivity, it is preferable to perform freeze drying, flash drying, fluidized drying, vibration type fluidized drying and the like from the viewpoint of productivity.

The toner according to the exemplary embodiment is manufactured, for example, by adding an external additive to the obtained toner particles in a dry state and mixing them.
The mixing may be performed, for example, by a V blender, a Henschel mixer, a Loedige mixer, or the like.
Furthermore, if necessary, coarse particles of toner may be removed using a vibrating sieving machine, a wind sieving machine or the like.

In the kneading and pulverizing method, after mixing materials such as coloring agents, the above materials are melt-kneaded using a kneader, an extruder or the like, and the obtained melt-kneaded product is roughly pulverized and then pulverized by a jet mill or the like. The present invention is a method of obtaining toner particles having a target particle diameter by an air classifier.
The kneading and pulverizing method is more specifically divided into a kneading process of kneading a toner forming material containing a colorant and a binder resin, and a pulverizing process of grinding a kneaded material. If necessary, other steps such as a cooling step of cooling the kneaded material formed in the kneading step may be included.
Each process concerning the kneading and pulverizing method will be described in detail.

-Kneading process-
In the kneading step, the toner forming material containing a colorant and a binder resin is kneaded.
In the kneading step, it is desirable to add an aqueous medium (for example, water such as distilled water or ion exchanged water, alcohols, etc.) in an amount of 0.5 to 5 parts by mass with respect to 100 parts by mass of the toner .

  As a kneader used for a kneading | mixing process, a single-screw extruder, a twin-screw extruder, etc. are mentioned, for example. Hereinafter, as an example of the kneader, a kneader having a feed screw portion and two kneading portions will be described with reference to the drawings, but the present invention is not limited thereto.

FIG. 1 is a view for explaining the screw state of an example of a screw extruder used in the kneading step in the toner manufacturing method according to the present embodiment.
The screw extruder 11 adds a water-based medium to a barrel 12 having a screw (not shown), an inlet 14 for injecting a toner forming material which is a raw material of toner into the barrel 12, and a toner forming material in the barrel 12. And a discharge port 18 for discharging the kneaded material formed by kneading the toner forming material in the barrel 12.

  The barrel 12 transports the toner forming material injected from the injection port 14 to the kneading section NA in order from the side closer to the injection port 14, and the toner forming material is melt-kneaded in the first kneading step. Feed screw section SB for transporting the toner forming material melt-kneaded in the kneading section NA and the kneading section NA to the kneading section NB, and knee for melting and kneading the toner forming material in the second kneading step to form a kneaded material It is divided into a feeding portion NB and a feed screw portion SC for transporting the formed kneaded material to the discharge port 18.

Also, inside the barrel 12, temperature control means (not shown) different for each block is provided. That is, the temperature may be controlled to different temperatures from block 12A to block 12J. Note that FIG. 1 shows a state in which the temperatures of block 12A and block 12B are controlled to t0 ° C., the temperatures of block 12C to block 12E to t1 ° C., and the temperatures of block 12 F to block 12J to t2 ° C. There is. Therefore, the toner forming material of the kneading section NA is heated to t1.degree. C., and the toner forming material of the kneading section NB is heated to t2.degree.
As described above, the temperature t1 ° C. in the kneading portion NA is in the range of Ta-10 ° C. or more and Ta + 10 ° C. or less, and the temperature t2 ° C. in the kneading portion NB is in the range of Tm-10 ° C. or more and Tm + 20 ° C. or less is there. Further, the temperature of the endothermic peak when the toner was measured by DSC was Ta, and the melting temperature when the toner was similarly measured by DSC was Tm.

  When a toner forming material including a binder resin, a coloring agent, and a release agent as needed is supplied to the barrel 12 from the inlet 14, the toner forming material is sent by the feed screw portion SA to the kneading portion NA. At this time, since the temperature of the block 12C is set to t1.degree. C., the toner forming material is fed to the kneading portion NA in a state where it is heated and changed to the molten state. Then, since the temperatures of the blocks 12D and 12E are also set to t1.degree. C., the toner forming material is melt-kneaded at the temperature of t1.degree. C. at the kneading portion NA. The binder resin and the release agent are melted at the kneading section NA and are sheared by the screw.

Next, the toner forming material subjected to the kneading in the kneading section NA is sent to the kneading section NB by the feed screw section SB.
Next, in the feed screw portion SB, the aqueous medium is injected from the liquid addition port 16 into the barrel 12 to add the aqueous medium to the toner forming material. Although FIG. 1 shows a mode in which the aqueous medium is injected in the feed screw unit SB, the invention is not limited thereto. The aqueous medium may be injected in the kneading unit NB, and the feed screw unit SB and the kneading unit NB. An aqueous medium may be injected in both cases. That is, the injection position and injection position of the aqueous medium are selected as needed.

As described above, when the aqueous medium is injected from the liquid addition port 16 into the barrel 12, the toner forming material in the barrel 12 and the aqueous medium are mixed, and the latent heat of evaporation of the aqueous medium cools the toner forming material. The temperature of the toner forming material is maintained.
Finally, the kneaded material formed by melt-kneading by the kneading section NB is transported to the discharge port 18 by the feed screw section SC and discharged from the discharge port 18.
As described above, the kneading step using the screw extruder 11 shown in FIG. 1 is performed.

-Cooling process-
The cooling step is a step of cooling the kneaded material formed in the kneading step, and in the cooling step, the temperature of the kneaded material at the end of the kneading step is cooled to 40 ° C. or less at an average temperature decrease rate of 4 ° C./sec or more. It is preferable to do. When the cooling speed of the kneaded material is slow, a mixture finely dispersed in the binder resin in the kneading step (a mixture of a coloring agent and an internal additive such as a releasing agent internally added to toner particles as required) May recrystallize and the dispersion diameter may become large. On the other hand, it is preferable to rapidly quench at the above average temperature lowering rate, since the dispersed state immediately after the completion of the kneading step is maintained as it is. The above average temperature drop rate refers to the average value of the temperature at which the temperature of the kneaded material at the end of the kneading step (for example, t2 ° C. when using the screw extruder 11 of FIG. 1) is decreased to 40 ° C.
Specifically, as a cooling method in the cooling step, for example, a method using a rolling roll in which cold water or brine is circulated, a sandwich type cooling belt or the like can be mentioned. In addition, when cooling by the said method, the cooling speed is determined by the speed of a rolling roll, the flow volume of brine, the supply amount of kneaded material, the slab thickness at the time of rolling of a kneaded material, etc. The slab thickness is preferably as thin as 1 mm or more and 3 mm or less.

-Grinding process-
The kneaded material cooled by the cooling step is ground by the grinding step to form particles. In the pulverizing step, for example, a mechanical pulverizer, a jet pulverizer or the like is used. In addition, the particles may be heat treated with hot air or the like to make them spherical as required.

-Classification process-
The particles obtained by the pulverizing step may be classified by a classifying step to obtain toner particles having a particle size distribution within a target range, as necessary. In the classification step, conventionally used centrifugal classifiers, inertial classifiers and the like are used, and fine powder (particles smaller than the target particle size in the target range) and coarse powder (target particle size in the target range) Larger particles are removed.

-External addition process-
The obtained toner particles may be added and attached with inorganic particles typified by silica, titania, and aluminum oxide for the purpose of charge control, flowability impartation, charge exchangeability impartment and the like. These are performed, for example, by a V-type blender, a Henschel mixer, a Loedige mixer, etc., and may be attached in stages.

-Sift separation process-
A sieving process may be provided after the above-mentioned external addition process, if necessary. Specific examples of the sieving method include a gyro sifter, a vibrating sieving machine, and a wind sieving machine. By sieving, coarse powder and the like of the external additive are removed, and generation of streaks on the photosensitive member, dirt in the apparatus, and the like are suppressed.

In the present embodiment, it is easy to control the shape of the toner particles and the particle diameter of the toner particles, and an aggregation and coalescence method may be used in which the control range of the toner particle structure such as core shell structure is wide.
Hereinafter, the method of producing toner particles by the aggregation and coalescence method will be described in detail.

Specifically, for example, when toner particles are produced by the aggregation and coalescence method,
A step of preparing a resin particle dispersion in which resin particles to be a binder resin are dispersed (a resin particle dispersion preparing step), and in the resin particle dispersion (after mixing other particle dispersions as necessary) In the dispersion), a step of aggregating the resin particles (other particles as necessary) to form aggregated particles (aggregated particle formation step), and heating the aggregated particle dispersion in which the aggregated particles are dispersed And toner particles are produced through the step of fusing and coalescing aggregated particles to form toner particles (fusion and coalescence step).

The details of each step will be described below.
In the following description, although a method for obtaining toner particles including a colorant and a release agent is described, the colorant and the release agent are used as needed. Of course, other additives other than the colorant and the release agent may be used.

-Resin particle dispersion preparation process-
First, together with a resin particle dispersion in which resin particles to be a binder resin are dispersed, for example, a colorant particle dispersion in which colorant particles are dispersed and a release agent particle dispersion in which releasing agent particles are dispersed are prepared. Do.

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

Examples of the dispersion medium used for the resin particle dispersion include aqueous media.
Examples of the aqueous medium include water such as distilled water and ion exchange water, and alcohols. These may be used alone or in combination of two or more.

As surfactant, for example, anionic surfactant such as sulfate ester type, sulfonate type, phosphoric ester type, soap type; cationic surfactant such as amine salt type, quaternary ammonium salt type; polyethylene glycol And nonionic surfactants such as alkylphenol ethylene oxide adducts and polyhydric alcohols. Among these, anionic surfactants and cationic surfactants are particularly mentioned. Nonionic surfactants may be used in combination with anionic surfactants or cationic surfactants.
The surfactant may be used alone or in combination of two or more.

In the resin particle dispersion, as a method of dispersing the resin particles in a dispersion medium, for example, general dispersion methods such as a rotational shear type homogenizer, a ball mill having media, a sand mill, a dyno mill and the like can be mentioned. Further, 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.
In the phase inversion emulsification method, the 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 it, and then a water medium is obtained. Method of converting resin from W / O to O / W (so-called phase inversion) by introducing (W phase) to discontinuous phase and dispersing resin in the form of particles in water medium It is.

The volume average particle diameter 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.
The volume average particle diameter of the resin particles is the particle size distribution obtained by the measurement of a laser diffraction type particle size distribution measuring apparatus (for example, LA-700 manufactured by Horiba, Ltd.), and the particle size range (channel) divided is divided. With respect to the volume, the cumulative distribution is drawn from the small particle diameter side, and the particle diameter which becomes 50% of the cumulative with respect to all particles is measured as the volume average particle diameter D50v. The volume average particle diameter of particles in other dispersions is also measured in the same manner.

The particle size difference of the resin particles dispersed in the resin particle dispersion is preferably 80 nm or less, more preferably 70 nm or less, and still more preferably 60 nm or less. By setting the particle diameter difference of the resin particles to 80 nm or less, the cohesive force of the resin particles in the aggregated particle formation step becomes more uniform, so that the particle diameter of the toner particles is made uniform. GSDv (90/50) is 1. Under 26 or less, GSDp (50/10) tends to be 1.28 or less.
Here, the particle size difference of the resin particles refers to the particle size difference between the 10% particle diameter and the 90% particle diameter when the resin particle dispersion liquid is measured by Microtrac (Microtrac UPA 9340, manufactured by Nikkiso Co., Ltd.). Show. In addition, when mixing a plurality of resin particle dispersions, the particle diameter difference between the 10% particle diameter and the 90% particle diameter when the mixed resin particle dispersion is measured by Microtrac.

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

In the same manner as the resin particle dispersion, for example, a colorant particle dispersion and a releasing agent particle dispersion are also prepared. That is, with respect to 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 releasing agent particle dispersion The same applies to the releasing agent particles to be dispersed.
The particle diameter of each particle dispersed in the colorant particle dispersion or the release agent particle dispersion is preferably smaller when the particle diameter is mixed with the resin particle dispersion, and 10% particle diameter and 90% particle diameter The particle size difference is preferably 80 nm or less, more preferably 70 nm or less, and still more preferably 60 nm or less.

-Aggregated particle formation process-
Next, the colorant particle dispersion and the release agent particle dispersion are mixed together with the resin particle dispersion.
Then, the resin particles, the colorant particles, and the release agent particles, which have a diameter close to the diameter of the toner particles intended to hetero-aggregate the resin particles, the colorant particles, and the release agent particles in the mixed dispersion, To form agglomerated particles.

Specifically, for example, after adding an aggregating agent to the mixed dispersion, adjusting the pH of the mixed dispersion to acidic (for example, pH is 2 or more and 5 or less), and adding a dispersion stabilizer as necessary, Heat the resin particles to the temperature of the glass transition temperature (specifically, for example, the glass transition temperature of the resin particles-30 ° C or more and the glass transition temperature-10 ° C or less) to aggregate the particles dispersed in the mixed dispersion , Form agglomerated particles.
In the aggregation particle forming step, for example, the above coagulant is added at room temperature (for example, 25 ° C. or more and 30 ° C. or less) while stirring the mixed dispersion with a rotary shear type homogenizer, and the pH of the mixed dispersion is made acidic (eg, pH is After adjusting to 2 or more and 5 or less and adding a dispersion stabilizer as needed, the above-mentioned heating may be performed.
Also, before performing the above heating, the bubbles in the system are reduced by stirring for 0.5 hours or more and 2 hours or less while reducing the pressure to 60 kPa (abs) to 95 kPa (abs) and degassing the system. May be According to the findings of the present inventors, due to the presence of air bubbles in the system, agglomerated particles larger than the central particle size may be generated due to the aggregation caused by the air bubbles. Although the cause is unknown, aggregation caused by air bubbles may generate aggregated particles smaller than the central particle diameter. Therefore, it may be difficult to narrow the particle size distribution of the toner particles. By reducing air bubbles in the system, the particle size distribution of toner particles tends to be narrowed.

As the aggregating agent, for example, a surfactant having an opposite polarity to the surfactant used as a dispersing agent added to the mixed dispersion, an inorganic metal salt, and a divalent or higher metal complex can be mentioned. In particular, when a metal complex is used as the aggregating agent, the amount of surfactant used is reduced, and the charging characteristics are improved.
Additives that form a complex or similar bond with the metal ion of the flocculant may be used if desired. As the 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. Metal salt polymers and the like can be mentioned.
As the chelating agent, a water soluble chelating agent may be used. 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.
As addition amount of a chelating agent, 0.01 mass part or more and 5.0 mass parts or less are preferable with respect to 100 mass parts of resin particles, for example, 0.1 mass part or more and less than 3.0 mass parts are more preferable.

-Fusion and coalescence process-
Next, the aggregated particle dispersion liquid in which the aggregated particles are dispersed is heated, for example, to a temperature equal to or higher than the glass transition temperature of the resin particles (eg, 10 to 30 ° C. higher than the glass transition temperature of the resin particles) Are coalesced together to form toner particles.

Through the above steps, toner particles are obtained.
After obtaining the aggregated particle dispersion liquid in which the aggregated particles are dispersed, the aggregated particle dispersion liquid and the resin particle dispersion liquid in which the resin particles are dispersed are further mixed, and the resin particles are further added to the surface of the aggregated particles. The step of aggregation so as to adhere to form a second aggregated particle, and heating the second aggregated particle dispersion liquid in which the second aggregated particles are dispersed to fuse and unite the second aggregated particles The toner particles may be manufactured through the steps of forming toner particles of a core / shell structure.
When forming the second aggregated particles, it is preferable to increase the speed of adding the resin particle dispersion. The rate of adding the resin particle dispersion at the time of forming the second aggregated particles is preferably 80 parts by mass to 500 parts by mass per minute with respect to 500 parts by mass of the aggregated particle dispersion, and 100 parts by mass It is more preferable that the amount is equal to or more than 300 minutes by mass. When the rate of adding the resin particle dispersion is 80 parts by weight / minute or more and 500 parts by weight / minute or less, resin particles are uniformly dispersed in the system. As a result, the particle size of the aggregated particles becomes uniform, and the particle size distribution of the toner particles tends to be narrow.

Here, after completion of the coalescence and coalescence step, toner particles formed in the solution are subjected to a known washing step, solid-liquid separation step and drying step to obtain toner particles in a dried state.
In the washing step, it is preferable to carry out substitution washing with ion exchange water sufficiently from the viewpoint of chargeability. The solid-liquid separation step is not particularly limited, but it is preferable to apply suction filtration, pressure filtration, etc. from the viewpoint of productivity. Further, the drying step is also not particularly limited, but in view of productivity, it is preferable to perform freeze drying, flash drying, fluidized drying, vibration type fluidized drying and the like from the viewpoint of productivity.

  The toner according to the exemplary embodiment is manufactured, for example, by adding an external additive to the obtained toner particles in a dry state and mixing them. The mixing may be performed by, for example, a V blender, a Henschel mixer, a Loedige mixer, or the like. Furthermore, if necessary, coarse particles of toner may be removed using a vibrating sieving machine, a wind sieving machine or the like.

-Ventilation fluid energy-
The toner according to the present embodiment is measured using a powder rheometer under the condition that the tip speed of the rotary blade is 100 mm / sec, the approach angle of the rotary blade is -5 °, and the aeration flow rate is 5 ml / min. The aeration fluidity energy is preferably 100 mJ or more and 300 mJ or less, more preferably 100 mJ or more and 250 mJ or less, and still more preferably 100 mJ or more and 200 mJ or less. When the air flow energy is 100 mJ or more and 300 mJ or less, the flowability of the toner is further improved, and fine transfer becomes possible. As a result, the tonality of the multi-color halftone image becomes better.

  The toner according to the present embodiment has a ratio of air flow energy of 5 ml / min flow rate to air flow energy of 80 ml / min flow rate (5 ml / min measurement time / 80 ml / min measurement flow rate), The number is preferably 3 or more and 8 or less, more preferably 3 or more and 7 or less, and still more preferably 3 or more and 6 or less. In the case of forming a multi-color halftone image after forming a high-image-density toner image by setting the ratio (at a flow rate of 5 ml / min / at a flow rate of 80 ml / min) to 3 or more and 8 or less. The tonality is further improved.

Next, a method of measuring fluidity by using a powder rheometer will be described.
The powder rheometer is a flowability measuring device for directly determining the flowability by simultaneously measuring the rotational torque and the vertical load obtained by the spiral rotation of the rotary blade in the packed particles. By measuring both the rotational torque and the vertical load, it is possible to detect with high sensitivity the flowability including the characteristics of the powder itself and the influence of the external environment. In addition, since measurement is performed with the state of particle filling fixed, data with good reproducibility can be obtained.

  It measures using FT4 by freeman technology as a powder rheometer. In addition, in order to eliminate the influence of temperature and humidity before measurement, the developer (or toner) is used after being left for 8 hours or more at a temperature of 25 ° C. and a humidity of 45% RH.

  First, the developer (or toner) is placed in a split container with an inner diameter of 25 mm (a cylinder with a height of 22 mm is placed on a 25 mL container with a height of 61 mm so that it can be separated vertically) Fill the developer (or toner).

  After the developer (or toner) is filled, the sample is homogenized by gently stirring the filled developer (or toner). This operation is hereinafter referred to as conditioning.

  In conditioning, the rotors are gently stirred in a rotational direction that does not resist the developer (or toner) in the filled state, so that most of the excess air or partial stress is removed. Make the sample homogeneous. As a specific conditioning condition, the inside of the container is stirred at a tip speed of 40 mm / sec at an approach angle of 5 ° from a height of 70 mm to 2 mm from the bottom surface at an angle of 5 °.

  At this time, since the propeller-type rotor moves in the downward direction simultaneously with rotation, the tip draws a spiral, and the angle of the helical path drawn by the propeller tip at this time is called the entry angle.

  After repeating the conditioning operation four times, the container upper end of the split container is gently moved to scrape the developer (or toner) inside the vessel at a height of 61 mm to obtain a toner that fills the 25 mL container. The reason for carrying out the conditioning operation is that it is important to always obtain a powder with a constant volume in order to stably determine the amount of flowable energy.

  Furthermore, after performing the conditioning operation once, the rotational torque and the rotational speed when rotating at a tip speed of 100 mm / sec of the rotary wing while moving at a penetration angle of -5 ° from the bottom to a height of 55 mm to 2 mm from the bottom Measure the vertical load. The rotational direction of the propeller at this time is the opposite direction to the conditioning (clockwise as viewed from above).

The relationship between the rotational torque or the vertical load with respect to the height H from the bottom surface is shown in FIGS. 2 (A) and 2 (B). It is FIG. 3 which calculated | required the energy gradient (mJ / mm) with respect to the height H from rotational torque and a perpendicular | vertical load. The area (shaded area in FIG. 3) obtained by integrating the energy gradient in FIG. 3 is the fluidity energy amount (mJ). The section of height 2 mm to 55 mm from the bottom is integrated to determine the amount of fluidity energy.
Also, in order to reduce the influence of the error, the average value obtained by performing the cycle of this conditioning and energy measurement operation five times is taken as the fluidity energy amount (mJ).

  The rotor has a diameter of 23.5 mm of a two-bladed propeller type shown in FIG. 4 manufactured by freeman technology.

  And when measuring the rotational torque and the vertical load of the above-mentioned rotor blade, the amount of fluid energy measured while flowing in air at the target ventilation flow rate (ml / min) from the bottom of the container is "the amount of air flow fluidity energy" The flowable energy amount measured at a flow rate of 0 ml / min without aeration from the bottom of the container is the "basic flowable energy amount". In addition, inflow state of the aeration amount is controlled by FT4 made by freeman technology.

<Toner Set>
The toner set according to the present embodiment includes n kinds (n is an integer of 2 or more) of electrostatic charge image developing toners exhibiting different colors, and at least one of the electrostatic charge image developing toners has a large diameter side. Volume particle size distribution index (GSDv (90/50)) is 1.26 or less, small diameter number particle size distribution index (GSDp (50/10)) is 1.28 or less, GSDv (90/50) / GSDp (50/10) includes toner particles having an average circularity of 0.95 or more and 1.00 or less. That is, the toner set according to the present embodiment includes n kinds (n is an integer of 2 or more) of electrostatic charge image developing toners exhibiting different colors, and at least one of the electrostatic charge image developing toners is a toner. 1 is a toner according to an embodiment.
In the toner set according to the present embodiment, it is preferable that all of the electrostatic charge image developing toners be the toner according to the present embodiment.

  In the toner set according to the present embodiment, when any of the electrostatic charge image developing toners is the toner according to the present embodiment, the tip speed of the rotary blade is set to 100 mm / sec using a powder rheometer, and the approach angle of the rotary blade The difference between the maximum value and the minimum value of the air flow energy of the air flow 5 ml / min for each of the electrostatic image developing toners measured under the condition that the air flow rate is 5 ml / min and the air flow rate is 5 The absolute value of the difference between the air flow energy for the toner with the highest air flow energy value and the air flow energy for the toner with the lowest air flow energy value is preferably 80 mJ or less It is more preferably 60 mJ or less, and still more preferably 50 mJ or less. When the difference between the maximum value and the minimum value of the aeration fluidity energy is 80 mJ or less, the gradation of the multi-color halftone image becomes better.

<Electrostatic charge image developer>
The electrostatic charge image developer according to the present embodiment at least includes the toner according to the present embodiment.
The electrostatic charge image developer according to the present embodiment may be a one-component developer containing only the toner according to the present embodiment, or may be a two-component developer in which the toner and the carrier are mixed.

There is no restriction | limiting in particular as a carrier, A well-known carrier is mentioned. As the carrier, for example, a coated carrier obtained by coating a coating resin on the surface of a core material made of magnetic powder; a magnetic powder dispersion type carrier in which magnetic powder is dispersed / blended in a matrix resin; porous magnetic powder is impregnated with resin Resin impregnated carriers; and the like.
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 the core particles are 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.

As a coating resin and a matrix resin, for example, polyethylene, polypropylene, polystyrene, polyvinyl alcohol, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic acid ester Copolymers, straight silicone resins comprising an organosiloxane bond or modified products thereof, fluoro resins, polyesters, polycarbonates, phenol resins, epoxy resins and the like can be mentioned.
The coating resin and the matrix resin may contain other additives such as conductive particles.
Examples of conductive particles include particles of metals such as gold, silver and copper, carbon black, titanium oxide, zinc oxide, tin oxide, barium sulfate, aluminum borate, potassium titanate and the like.

Here, in order to coat the surface of the core material with a coating resin, a coating resin, and a method of coating with a solution for forming a coating layer in which various additives are dissolved in an appropriate solvent, if necessary, can 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.
As a specific resin coating method, an immersion method in which the core material is immersed in a solution for forming a coating layer, a spray method in which a solution for forming a coating layer is sprayed on the surface of the core material, and a state in which the core material is suspended by flowing air. A fluid bed method of spraying a solution for forming a coating layer, a kneader coater method of removing a solvent by mixing a core material of a carrier and a solution for forming a coating layer in a kneader coater, and the like can be mentioned.

  The mixing ratio (mass ratio) of toner and 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>
An 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, charging means for charging the surface of the image carrier, electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier, and electrostatic charge. Developing means for containing an image developer and developing an electrostatic charge image formed on the surface of the image carrier with the electrostatic charge image developer as a toner image, and a toner image formed on the surface of the image carrier as a recording medium And a fixing unit for fixing the toner image transferred to the surface of the recording medium. Then, the electrostatic charge image developer according to the present embodiment is applied as the electrostatic charge image developer.

  The image forming apparatus according to the present embodiment includes a charging step of 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, and an electrostatic charge according to the present embodiment. Developing the electrostatic charge image formed on the surface of the image carrier as a toner image with an image developer, and transferring the toner image formed on the surface of the image carrier onto the surface of the recording medium; And an image forming method (image forming method according to the present embodiment) including the fixing step of fixing the toner image transferred to the surface of the recording medium.

The image forming apparatus according to the present embodiment directly transfers the toner image formed on the surface of the image carrier to the recording medium; the toner image formed on the surface of the image carrier is an intermediate transfer member An intermediate transfer type device that performs primary transfer to the surface and secondarily transfers the toner image transferred to the surface of the intermediate transfer member to the surface of the recording medium; cleans the surface of the image carrier before charging after transferring the toner image A known image forming apparatus such as an apparatus provided with a cleaning means; an apparatus provided with a diselectrification means for diselectrifying the surface of the image holding member before electrification after transferring a toner image is applied.
In the case of an intermediate transfer type apparatus, for example, an intermediate transfer member to which a toner image is transferred on the surface, and a primary transfer on which the toner image formed on the surface of the image carrier is primarily transferred to the surface of the intermediate transfer member. A configuration is applied that includes: means; and secondary transfer means for secondary transfer of the toner image transferred to the surface of the intermediate transfer member to 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) which is detached 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 suitably used.

  Hereinafter, although an example of the image forming apparatus according to the present embodiment is shown, the present invention is not limited to this. The main parts shown in the figure will be described, and the description of the other parts will be omitted.

FIG. 5 is a schematic configuration view showing an image forming apparatus according to the present embodiment.
The image forming apparatus shown in FIG. 5 is an electrophotographic first to output an image of each color of yellow (Y), magenta (M), cyan (C) and black (K) based on color separated image data. The fourth image forming units 10Y, 10M, 10C, and 10K (image forming means) are provided. These image forming units (hereinafter sometimes referred to simply as “units”) 10Y, 10M, 10C, and 10K are arranged side by side at a predetermined distance from each other in the horizontal direction. The units 10Y, 10M, 10C, and 10K may be process cartridges that can be detached from the image forming apparatus.

Above the units 10Y, 10M, 10C, and 10K in the drawing, an intermediate transfer belt 20 as an intermediate transfer member is extended through the units. The intermediate transfer belt 20 is wound around a drive roll 22 and a support roll 24 in contact with the inner surface of the intermediate transfer belt 20, which are spaced apart from each other in the left to right direction in FIG. The vehicle travels in the direction toward the unit 10K. A force is applied to the support roll 24 in a direction away from the drive roll 22 by a spring or the like (not shown), and a tension is applied to the intermediate transfer belt 20 wound around both. Further, 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.
Also, yellow, magenta, cyan and black contained in the toner cartridges 8Y, 8M, 8C and 8K in the developing devices (developing means) 4Y, 4M, 4C and 4K of the units 10Y, 10M, 10C and 10K, respectively. The toner including 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 the yellow image disposed on the upstream side in the traveling direction of the intermediate transfer belt The 10Y will be described as a representative. The second to fourth reference numerals are attached to parts equivalent to the first unit 10Y by substituting magenta (M), cyan (C) and black (K) instead of yellow (Y). The description of the units 10M, 10C, and 10K is omitted.

The first unit 10Y has a photoreceptor 1Y acting as an image carrier. A charging roll (an example of a charging unit) 2Y for charging the surface of the photosensitive member 1Y to a predetermined potential around the photosensitive member 1Y and a laser beam 3Y based on an image signal obtained by color separation of the charged surface Exposure apparatus (an example of an electrostatic charge image forming unit) 3 for forming an electrostatic charge image, a developing apparatus (an example of a development unit) 4Y for developing an electrostatic charge image by supplying toner charged to the electrostatic charge image Primary transfer roll 5Y for transferring a toner image onto intermediate transfer belt 20 (an example of a primary transfer means), and photoreceptor cleaning device (an example of a cleaning means) 6Y for removing toner remaining on the surface of photoreceptor 1Y after 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 supply (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 supply varies the transfer bias applied to each primary transfer roll under 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 photosensitive member 1Y is charged to a potential of -600 V to -800 V by the charging roll 2Y.
The photoreceptor 1 </ ^b > Y is formed by laminating a photosensitive layer on a conductive (for example, volume resistivity at 20 ° C .: 1 × 10 ⁻⁶ Ωcm or less) substrate. This photosensitive layer usually has a high resistance (resistance of a general resin), but has the property that the specific resistance of the portion irradiated with the laser beam changes when the laser beam 3Y is irradiated. Therefore, the laser beam 3Y is output to the charged surface of the photosensitive member 1Y through the exposure device 3 in accordance with the yellow image data sent from the 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 of a yellow image pattern is formed on the surface of the photoreceptor 1Y.

The electrostatic image is an image formed on the surface of the photosensitive member 1Y by charging, and the specific resistance of the irradiated portion of the photosensitive layer is reduced by the laser beam 3Y, and the charge on the surface of the photosensitive member 1Y flows On the other hand, it is a so-called negative latent image which is formed by the residual charge of the portion not irradiated with the laser beam 3Y.
The electrostatic charge image formed on the photosensitive member 1Y is rotated to a predetermined development position as the photosensitive member 1Y travels. Then, at this developing position, the electrostatic charge image on the photosensitive member 1Y is made visible (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 a yellow toner and a carrier is accommodated. The yellow toner is frictionally charged by being stirred inside the developing device 4Y, has a charge of the same polarity (negative polarity) as the charged charge on the photosensitive member 1Y, and is used as a developer roll (developer holding member One example is held on top. Then, as the surface of the photosensitive member 1Y passes through the developing device 4Y, the yellow toner is electrostatically attached to the electrostatic latent image portion on the surface of the photosensitive member 1Y, and the latent image is developed by the yellow toner . The photoreceptor 1Y on which the yellow toner image is formed is subsequently traveled 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 photosensitive member 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 photosensitive member 1Y toward the primary transfer roll 5Y is applied to the toner image. The toner image on 1 Y is transferred onto the intermediate transfer belt 20. The transfer bias applied at this time is the (+) 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 photosensitive member 1Y is removed and collected by the photosensitive member 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 according to the first unit.
Thus, the intermediate transfer belt 20 to which the yellow toner image is transferred in 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 multiples. Ru.

  The intermediate transfer belt 20 on which toner images of four colors are multiply transferred through the first to fourth units is disposed on the intermediate transfer belt 20 and the image holding surface side of the intermediate transfer belt 20 and the support roll 24 in contact with the inner surface of the intermediate transfer belt. It leads to the secondary transfer part comprised from the secondary transfer roll (an example of a secondary transfer means) 26 which was carried out. On the other hand, recording paper (an example of a recording medium) P is fed at a predetermined timing to a gap where the secondary transfer roll 26 and the intermediate transfer belt 20 contact via a supply mechanism, and the secondary transfer bias is a support roll. 24 is applied. The transfer bias applied at this time is the same as the polarity (−) of the toner (−), and the electrostatic force from the intermediate transfer belt 20 to the recording paper P is applied to 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 unit (not shown) that detects the resistance of the secondary transfer portion, and is voltage controlled.

  Thereafter, the recording paper P is sent to the pressure contact portion (nip portion) of the pair of fixing rolls in the fixing device (an example of the fixing means) 28, the toner image is fixed on the recording paper P, and a fixed image is formed.

Examples of the recording paper P to which the toner image is transferred include plain paper used for electrophotographic copying machines, printers and the like. As the recording medium, in addition to the recording paper P, an OHP sheet or the like can also be mentioned.
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 obtained by coating the surface of plain paper with a resin or the like, art paper for printing, etc. are suitably used. Be done.

  The recording paper P for which the fixing of the color image is completed is carried out toward the discharge unit, and a series of color image forming operations are completed.

<Process cartridge / Toner cartridge>
The process cartridge according to the present embodiment will be described.
The process cartridge according to the present embodiment contains the electrostatic charge image developer according to the present embodiment, and develops the electrostatic charge image formed on the surface of the image carrier as the toner image by the electrostatic charge image developer. The process cartridge is detachably mounted to an image forming apparatus.

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

  Hereinafter, although an example of the process cartridge according to the present embodiment is shown, the present invention is not limited to this. The main parts shown in the figure will be described, and the description of the other parts will be omitted.

FIG. 6 is a schematic configuration view showing a process cartridge according to the present embodiment.
The process cartridge 200 shown in FIG. 6 includes, for example, a photosensitive member 107 (an example of an image carrier) and a periphery of the photosensitive member 107 by a housing 117 provided with a mounting rail 116 and an opening 118 for exposure. A charging roller 108 (an example of the charging means), a developing device 111 (an example of the developing means), and a photosensitive member cleaning device 113 (an example of the cleaning means) are integrally combined and held. There is.
In FIG. 6, 109 is an exposure device (an example of electrostatic charge image forming means), 112 is a transfer device (an example of transfer means), 115 is a fixing device (an example of fixing means), 300 is a recording sheet (recording medium). An example is shown.

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

  Note that the image forming apparatus shown in FIG. 5 is an image forming apparatus having a configuration in which toner cartridges 8Y, 8M, 8C, 8K are detachably mounted, and developing devices 4Y, 4M, 4C, 4K And a toner supply pipe (not shown). Further, when the amount of toner contained in the toner cartridge is reduced, the toner cartridge is replaced.

  Hereinafter, the present embodiment will be more specifically described by way of examples and comparative examples, but the present embodiment is not limited to the following examples. In addition, unless there is particular notice, "part" and "%" are mass references.

(Preparation of Resin Particle Dispersion (1))
Terephthalic acid: 30 mol parts Fumaric acid: 70 mol parts Bisphenol A ethylene oxide adduct: 5 mol parts Bisphenol A propylene oxide adduct: 95 mol parts

The above material is charged into a 5-liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectification column, the temperature is raised to 220 ° C. in 1 hour, and 100 parts of the above material is added. Then, 1 part of titanium tetraethoxide was added. The temperature was raised to 230 ° C. taking 0.5 hour while distilling off the water formed, and the dehydration condensation reaction was continued at this temperature for 1 hour, and then the reaction product was cooled. Thus, a polyester resin having a weight average molecular weight of 18,000, an acid value of 15 mg KOH / g, and a glass transition temperature of 60 ° C. was synthesized.
40 parts of ethyl acetate and 25 parts of 2-butanol are put in a container equipped with a temperature control means and a nitrogen substitution means to make a mixed solvent, then 100 parts of polyester resin is gradually put in and dissolved, and 2% here An aqueous ammonia solution (equivalent to three times the molar amount of the acid value of the resin) was added and stirred for 30 minutes.
Next, the inside of the container was replaced with dry nitrogen, and the temperature was maintained at 45 ° C., and 400 parts of ion exchanged water was dropped at a rate of 4 parts / minute while stirring the mixture to perform emulsification. After completion of the dropwise addition, the emulsion was returned to room temperature (20 ° C. to 25 ° C.) to obtain a resin particle dispersion in which resin particles having a volume average particle diameter of 200 nm are dispersed. Ion-exchanged water was added to the resin particle dispersion to adjust the solid content to 30% to obtain resin particle dispersion (1). The particle size difference of the resin particles was 55 nm.

(Preparation of Resin Particle Dispersion (2))
In the preparation of resin particle dispersion (1), the concentration of the aqueous ammonia solution added is changed to a 2% aqueous ammonia solution and changed to a 4% aqueous ammonia solution, and further, ion exchange water is changed to dripping at a rate of 4 parts / min. It was changed to dripping at a rate of part / minute to obtain a resin particle dispersion. Ion exchange water was added to the resin particle dispersion to adjust the solid content to 30% to obtain a resin particle dispersion (2). The particle size difference of the resin particles was 75 nm.

(Preparation of Resin Particle Dispersion (3))
The concentration of the aqueous ammonia solution added in the preparation of resin particle dispersion 1 is changed to a 2% aqueous ammonia solution to change it to a 10% aqueous ammonia solution, and further, ion exchange water is changed to 4 parts / min. It changed into dripping at the speed of the minute, and obtained the resin particle dispersion liquid. Ion-exchanged water was added to the resin particle dispersion to adjust the solid content to 30% to obtain resin particle dispersion (3). The particle size difference of the resin particles was 95 nm.

(Preparation of Cyan Colored Particle Dispersion)
C. I. Pigment Blue 15: 3: 50 parts Ion surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.): 5 parts Ion-exchanged water: 192.9 parts The above components are mixed and 240 MPa is applied by Ultimizer (manufactured by Sugino Machine Co., Ltd.) The mixture was treated for 10 minutes to prepare a cyan colored particle dispersion (solids concentration: 20%).

(Preparation of Magenta Colored Particle Dispersion)
As a colorant, C.I. I. A magenta colored particle dispersion (solid content concentration: 20%) was prepared in the same manner as in the preparation of the cyan colored particle dispersion except that the pigment was changed to Pigment Red 122.

(Preparation of Yellow Colored Particle Dispersion)
As a colorant, C.I. I. A yellow colored particle dispersion (solid content concentration: 20%) was prepared in the same manner as in the preparation of the cyan colored particle dispersion except that the pigment was changed to Pigment Yellow 74.

(Preparation of releasing agent particle dispersion)
· Paraffin wax (HNP-9 manufactured by Nippon Seiwa Co., Ltd.): 100 parts · Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK): 1 part · Ion-exchanged water: 350 parts

  The above materials are mixed, heated to 100 ° C., dispersed using a homogenizer (Ultra Talax T50 manufactured by IKA), and then dispersed using a Manton Gaulin high pressure homogenizer (manufactured by Gaulin) to separate the particles with a volume average particle diameter of 200 nm. A release agent particle dispersion (solid content 20%) in which the mold agent particles were dispersed was obtained.

Preparation of Magenta Toner 1
Ion-exchanged water: 185 parts Resin particle dispersion (1): 190 parts Magenta colored particle dispersion: 35 parts Releasing agent particle dispersion: 40 parts Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd. ): Neogen RK, 20%): 2.8 parts The above components are placed in a 3-liter reaction vessel equipped with a thermometer, a pH meter, and a stirrer, and the temperature is controlled externally by a mantle heater, and the temperature is 30 ° C, It hold | maintained for 30 minutes at 150 rpm of stirring rotation speed. Thereafter, a 0.3 N nitric acid aqueous solution was added to adjust the pH in the aggregation step to 3.0.
A PAC aqueous solution in which 1.5 parts of PAC (manufactured by Oji Paper Co., Ltd .: 30% powder product) was dissolved in 15 parts of ion-exchanged water was added while dispersing with a homogenizer (manufactured by IKA Japan: Ultra Tarax T 50) . After degassing while stirring at 65 ° C. (abs) at 30 ° C. for 1 hour, the temperature is raised to 50 ° C., and the particle size is measured with Coulter Multisizer II (aperture diameter: 50 μm, manufactured by Coulter Co.) It measured and set volume average particle diameter to 5.0 micrometers. Thereafter, 93 parts of the resin particle dispersion (1) was additionally added at an addition rate of 150 parts / minute to make the resin particles adhere (shell structure) to the surface of the aggregated particles.
Subsequently, 20 parts of a 10% aqueous solution of NTA (nitrilotriacetic acid) metal salt (Kyrest 70: manufactured by Chelest Co., Ltd.) was added, and then the pH was adjusted to 9.0 using a 1N aqueous sodium hydroxide solution. Thereafter, the temperature is raised to 90 ° C. at a temperature rising rate of 0.05 ° C./min and held at 90 ° C. for 3 hours, followed by cooling and filtering to obtain coarse toner particles. This is further re-dispersed in ion-exchanged water, and filtration is repeated to wash the filtrate until the electric conductivity of the filtrate becomes 20 μS / cm or less, and then vacuum-dried in an oven at 40 ° C. for 5 hours. The toner particles were obtained. The volume average particle diameter of the obtained toner particles was 6.1 μm.
A sample mill is prepared by adding 1.5 parts of hydrophobic silica (RY50, manufactured by Nippon Aerosil Co., Ltd.) and 1.0 parts of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., T805) to 100 parts of the obtained toner particles. The mixture was mixed at 10000 rpm for 30 seconds. Thereafter, the magenta toner 1 was manufactured by sieving with a vibrating sieve having an opening of 45 μm.
Various parameters for the obtained toner particles and magenta toner 1 are summarized in Table 1.

Preparation of Magenta Toner 2
In the preparation of the magenta toner 1, the resin particle dispersion (1) was changed to a resin particle dispersion (2), and the preparation was performed in the same manner as the magenta toner 1 to prepare a magenta toner 2.
Various parameters of the obtained toner particles and the magenta toner 2 are summarized in Table 1.

Preparation of Magenta Toner 3
In the preparation of the magenta toner 2, 185 parts of ion exchange water were changed to 215 parts of ion exchange water, and the preparation was performed in the same manner as the magenta toner 2 to prepare a magenta toner 3.
Various parameters of the obtained toner particles and the magenta toner 3 are summarized in Table 1.

Preparation of Magenta Toner 4
In the preparation of the magenta toner 1, the retention was changed to holding at 90 ° C. for 3 hours and changed to holding at 90 ° C. for 2 hours, and the preparation was performed in the same manner as the magenta toner 1 to prepare a magenta toner 4.
Various parameters for the obtained toner particles and the magenta toner 4 are summarized in Table 1.

Preparation of Magenta Toner 5
In the preparation of the magenta toner 3, the retention was changed to holding at 90 ° C. for 3 hours and changed to holding at 90 ° C. for 2 hours, and the preparation was performed in the same manner as the magenta toner 3 to prepare the magenta toner 5.
Various parameters of the obtained toner particles and the magenta toner 5 are summarized in Table 1.

Preparation of Magenta Toner 6
In the preparation of the magenta toner 1, the pressure reduction condition after addition of the PAC aqueous solution is changed to 65 kPa (abs), and the pressure reduction condition after addition of the PAC aqueous solution is changed to 95 kPa. Made.
Various parameters of the obtained toner particles and the magenta toner 6 are summarized in Table 1.

Preparation of Magenta Toner 7
In the preparation of the magenta toner 1, 185 parts of ion exchange water was changed to 289 parts of ion exchange water, and the preparation was performed in the same manner as the magenta toner 1 to prepare a magenta toner 7.
Various parameters of the obtained toner particles and the magenta toner 7 are summarized in Table 1.

Preparation of Magenta Toner 8
In preparation of Magenta toner 1, 1.5 parts of hydrophobic silica (RY50, manufactured by Nippon Aerosil Co., Ltd.) and 100 parts of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., T805) with respect to 100 parts of toner particles Of the toner particles, and 3.0 parts of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 2.0 parts of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805). The magenta toner 8 was manufactured in the same manner as in the above.
Various parameters for the obtained toner particles and the magenta toner 8 are summarized in Table 1.

Preparation of Magenta Toner 9
In preparation of Magenta toner 1, 1.5 parts of hydrophobic silica (RY50, manufactured by Nippon Aerosil Co., Ltd.) and 100 parts of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., T805) with respect to 100 parts of toner particles And 100 parts of toner particles, and 0.6 parts of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 0.4 parts of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805). The magenta toner 9 was manufactured in the same manner as in the above.
Various parameters of the obtained toner particles and magenta toner 9 are summarized in Table 1.

<Preparation of Magenta Toner 10>
Styrene-butyl acrylate copolymer (copolymerization ratio (mass ratio) = 80: 20, weight average molecular weight Mw = 1300,000, glass transition temperature Tg = 59 ° C.): 88 parts Magenta pigment (C.I. Pigment) Red 122): 6 parts Low molecular weight polypropylene (softening temperature: 148 ° C.): 6 parts The above materials were mixed by a Henschel mixer, and this was heat-kneaded by an extruder. After cooling, the kneaded product is coarsely pulverized / finely pulverized, and the pulverized product is further classified, and stored for 20 hours in an environment of 53 ° C. to obtain toner particles having a volume average particle diameter of 6.2 μm.
A sample mill is prepared by adding 1.5 parts of hydrophobic silica (RY50, manufactured by Nippon Aerosil Co., Ltd.) and 1.0 parts of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., T805) to 100 parts of the obtained toner particles. The mixture was mixed and blended at 10000 rpm for 30 seconds. Thereafter, the magenta toner 10 was manufactured by sieving with a vibrating sieve having an opening of 45 μm.
Various parameters for the obtained toner particles and the magenta toner 10 are summarized in Table 1.

<Preparation of Magenta Toner 11>
(Preparation of unmodified polyester resin)
Bisphenol A- ethylene oxide adduct 160 parts Bisphenol A- propylene oxide adduct: 15 parts Terephthalic acid: 220 parts by dry well the composition of the monomer was added to _{N 2} substituted three-necked flask, _{N 2} The mixture was heated to 180.degree. C. while insufflation to dissolve, and then thoroughly mixed. After addition of 0.1 part of dibutyltin oxide, the temperature in the system was raised to 205 ° C., and the reaction was allowed to proceed while maintaining the temperature. While collecting a small amount of sample on the way to measure the molecular weight, the reaction progress was controlled by temperature control and moisture recovery under a reduced pressure atmosphere to obtain a desired condensate.

(Preparation of polyester prepolymer)
Bisphenol A- ethylene oxide adduct 182 parts Bisphenol A- propylene oxide adduct: 21 parts Terephthalic acid: 7 parts of isophthalic acid: 85 parts well dried by the monomers were charged into _{N 2} substituted 3-necked flask After being dissolved by heating to 180 ° C. while supplying N ₂ , the mixture was sufficiently mixed. After 0.4 parts of dibutyltin oxide was added, the temperature in the system was raised to 205 ° C., and the reaction was allowed to proceed while maintaining the temperature. While collecting a small amount of sample on the way to measure the molecular weight, the reaction progress was controlled by temperature control and moisture recovery under a reduced pressure atmosphere to obtain a desired condensate. Next, the temperature was lowered to 175 ° C., 8 parts of phthalic anhydride was added, and reaction was performed by stirring under a reduced pressure atmosphere for 3 hours.
In a separate 3-neck flask dried well and substituted with N ₂ , 330 parts of the condensate obtained above, 25 parts of isophorone diisocyanate, and 410 parts of ethyl acetate are placed in a container, and N ₂ is supplied while The mixture was heated at 70 ° C. for 5 hours to obtain a polyester prepolymer having an isocyanate group (hereinafter, “isocyanate-modified polyester prepolymer”).

(Preparation of ketimine compounds)
-Methyl ethyl ketone: 20 parts-Isophorone diamine: 15 parts The above materials were placed in a container and stirred at 58 ° C under heating to obtain a ketimine compound.

(Preparation of Magenta Pigment Dispersion for Oil Phase Liquid)
Magenta pigment (C.I. Pigment Red 122): 15 parts Ethyl acetate: 65 parts Solsperse 5000 (manufactured by Nippon Lubrizol Corporation): 1.2 parts The above components are mixed and dissolved / dispersed using a sand mill. A magenta pigment dispersion for oil phase liquid was obtained.

(Preparation of releasing agent dispersion for oil phase liquid)
-Paraffin wax (melting temperature: 89 ° C): 20 parts-Ethyl acetate: 220 parts With the above components cooled to 18 ° C, wet ground with a microbead disperser (DCP mill), and a release agent for oil phase liquid A dispersion was obtained.

(Preparation of oil phase liquid)
Magenta pigment dispersion for oil phase liquid: 32 parts Bentonite (manufactured by Wako Pure Chemical Industries, Ltd.): 8 parts Ethyl acetate: 58 parts The above components were charged and sufficiently mixed by stirring. Unmodified polyester resin: 140 parts Releasable agent dispersion for oil phase liquid: 75 parts was added to the obtained mixed liquid, and the mixture was sufficiently stirred to prepare an oil phase liquid.

(Preparation of Styrene Acrylic Resin Particle Dispersion (1))
Styrene: 75 parts n-butyl acrylate: 115 parts methacrylic acid: 75 parts methacrylic acid polyoxyalkylene sulfuric acid ester Na (Eleminol RS-30, manufactured by Sanyo Chemical Industries, Ltd.): 8 parts dodecanethiol: 4 parts The above components were charged into a reaction vessel and thoroughly mixed with stirring. Ion exchange water: 800 parts and ammonium persulfate: 1.2 parts were rapidly added to the above mixture, and the mixture was dispersed and emulsified with a homogenizer (Ultratarax T50, manufactured by IKA) while maintaining at room temperature or less to obtain a white emulsion. . The temperature inside the system was raised to 70 ° C. while stirring while feeding N _2, and the emulsion polymerization was continued for 5 hours. Further, 18 parts of a 1% aqueous solution of ammonium persulfate was gradually dropped, and the mixture was maintained at 70 ° C. for 2 hours to complete the polymerization.

(Preparation of water phase liquid)
Styrene acrylic resin particle dispersion (1): 50 parts 2% aqueous solution of Cellogen BS-H (CMC, Dai-ichi Kogyo Seiyaku Co., Ltd.): 170 parts Anionic surfactant (Dowfax 2A1, manufactured by Dow): 3 parts of ion-exchanged water: 230 parts The above components were sufficiently stirred and mixed to prepare an aqueous phase liquid.

Oil phase liquid: 370 parts Isocyanate modified polyester prepolymer: 25 parts Ketimine compound: 1.5 parts The above components are charged into a round bottom stainless steel flask and stirred for 2 minutes with a homogenizer (Ultratarax: manufactured by IKA) After preparing a mixed oil phase liquid, 900 parts of aqueous phase liquid was added to the same flask, and the mixture was quickly forcedly emulsified with a homogenizer (8500 rpm) for about 2 minutes. Next, this emulsion was stirred using a paddle stirrer under normal temperature and normal pressure (1 atm) for about 15 minutes to advance particle formation and urea modification reaction of the polyester resin. Thereafter, the suspension was stirred at 75 ° C. for 8 hours while the solvent was distilled off under reduced pressure or removed under normal pressure while bubbling nitrogen into the suspension at a rate of 2 m ³ / h to complete the urea modification reaction.
After cooling to normal temperature, the suspension of product particles was taken out, sufficiently washed with ion exchanged water, and subjected to solid-liquid separation by Nutsche suction filtration. Next, it was re-dispersed in ion-exchanged water at 35 ° C. and washed with stirring for 15 minutes. After this washing operation was repeated several times, solid-liquid separation was carried out by Nutsche-type suction filtration, and freeze-dried under vacuum to obtain toner particles.
A sample mill is prepared by adding 1.5 parts of hydrophobic silica (RY50, manufactured by Nippon Aerosil Co., Ltd.) and 1.0 parts of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., T805) to 100 parts of the obtained toner particles. The mixture was mixed at 10000 rpm for 30 seconds. Thereafter, the magenta toner 11 was manufactured by sieving with a vibrating sieve having an opening of 45 μm.
Various parameters of the obtained toner particles and the magenta toner 11 are summarized in Table 1.

Preparation of Magenta Toner 12
(Preparation of Styrene Acrylic Resin Dispersion)
-Styrene: 308 parts-n-butyl acrylate: 100 parts-acrylic acid: 4 parts-dodecanethiol: 3 parts-propanediol diacrylate: 1.5 parts The above components are mixed and dissolved to give an anionic surfactant. 6 parts of ammonium persulfate is added to an aqueous solution in which 4 parts of (Daiichi Kogyo Seiyaku Co., Ltd. product: Neogen SC) is dissolved in 550 parts of ion-exchanged water and emulsified in a flask and then mixed for 10 minutes. The aqueous solution dissolved in 350 parts of ion-exchanged water was charged and nitrogen substitution was carried out, and while stirring the inside of the flask, the contents were heated with an oil bath until the temperature reached 75 ° C., and the emulsion polymerization was continued for 5 hours. Thus, a styrene acrylic resin dispersion (resin particle concentration: 40%) obtained by dispersing resin particles having an average particle diameter of 195 nm and a weight average molecular weight (Mw) of 41000 was obtained. The glass transition temperature of the amorphous styrene acrylic resin was 52 ° C.
In the preparation of the magenta toner 1, 190 parts of the resin particle dispersion (1) was changed to 190 parts of a styrene acrylic resin dispersion, and the preparation was performed in the same manner as the magenta toner 1 to prepare a magenta toner 12.
Various parameters of the obtained toner particles and the magenta toner 12 are summarized in Table 1.

Preparation of Magenta Toner 13
In the preparation of the magenta toner 1, the pressure reduction condition after addition of the PAC aqueous solution is changed to 65 kPa (abs), and the pressure reduction condition after addition of the PAC aqueous solution is changed to 98 kPa (abs). Toner 13 was produced.
Various parameters of the obtained toner particles and the magenta toner 13 are summarized in Table 1.

<Preparation of Magenta Toner 14>
In the preparation of the magenta toner 1, 185 parts of ion exchange water were changed to 335 parts of ion exchange water, and the preparation was performed in the same manner as the magenta toner 1 to prepare a magenta toner 14.
Various parameters of the obtained toner particles and the magenta toner 14 are summarized in Table 1.

Preparation of Magenta Toner 15
In the preparation of the magenta toner 1, the retention was changed to 90 ° C. for 3 hours, and the retention was changed to 90 ° C. for 1.5 hours. The preparation was performed in the same manner as the magenta toner 1 to prepare a magenta toner 15.
Various parameters for the obtained toner particles and the magenta toner 15 are summarized in Table 1.

Preparation of Magenta Toner 16
In the preparation of the magenta toner 3, the retention was changed to holding at 90 ° C. for 3 hours and changed to holding at 90 ° C. for 1.5 hours, and the preparation was performed in the same manner as the magenta toner 3 to prepare a magenta toner 16.
Various parameters for the obtained toner particles and the magenta toner 16 are summarized in Table 1.

Preparation of Magenta Toner 17
In preparation of Magenta toner 6, 1.5 parts of hydrophobic silica (RY50, manufactured by Nippon Aerosil Co., Ltd.) and 100 parts of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., T805) per 100 parts of toner particles Of the hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and the hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) by 2.0 parts, and the magenta toner 6 The magenta toner 17 was manufactured in the same manner as in the above.
Various parameters for the obtained toner particles and the magenta toner 17 are summarized in Table 1.

Preparation of Magenta Toner 18
In the preparation of the magenta toner 7, the retention was changed to holding at 90 ° C. for 3 hours and changed to holding at 90 ° C. for 2 hours, and the preparation was performed in the same manner as the magenta toner 7 to prepare a magenta toner 18.
Various parameters for the obtained toner particles and the magenta toner 18 are summarized in Table 1.

Preparation of Magenta Toner 19
In the preparation of the magenta toner 6, the retention was changed to holding at 90 ° C. for 3 hours and changed to holding at 90 ° C. for 4 hours, and the preparation was performed in the same manner as the magenta toner 6 to prepare a magenta toner 19.
Various parameters for the obtained toner particles and the magenta toner 19 are summarized in Table 1.

Preparation of Magenta Toner 20
In the preparation of magenta toner 7, 1.5 parts of hydrophobic silica (RY50, manufactured by Nippon Aerosil Co., Ltd.) and 100 parts of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., T805) per 100 parts of toner particles Of the hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and the hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) by 2.0 parts, and the magenta toner 7 The magenta toner 20 was manufactured in the same manner as in the above.
Various parameters of the obtained toner particles and the magenta toner 20 are summarized in Table 1.

<Preparation of Magenta Toner 21>
<Production of Toner>
Ion-exchanged water: 215 parts Resin particle dispersion (3): 190 parts Magenta colored particle dispersion: 35 parts Releasing agent particle dispersion: 40 parts Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd. ): Neogen RK, 20%): 2.8 parts The above components are placed in a 3-liter reaction vessel equipped with a thermometer, a pH meter, and a stirrer, and the temperature is controlled externally by a mantle heater, and the temperature is 30 ° C, It hold | maintained for 30 minutes at 150 rpm of stirring rotation speed. Thereafter, a 0.3 N nitric acid aqueous solution was added to adjust the pH in the aggregation step to 3.0.
A PAC aqueous solution in which 1.5 parts of PAC (manufactured by Oji Paper Co., Ltd .: 30% powder product) was dissolved in 15 parts of ion-exchanged water was added while dispersing with a homogenizer (manufactured by IKA Japan: Ultra Tarax T 50) . Thereafter, while stirring, the temperature was raised to 50 ° C., and the particle diameter was measured by Coulter Multisizer II (aperture diameter: 50 μm, manufactured by Coulter Corp.), and the volume average particle diameter was set to 5.0 μm. Thereafter, 93 parts of the resin particle dispersion (3) was additionally added at an addition rate of 70 parts / minute to make the resin particles adhere (shell structure) to the surface of the aggregated particles.
Subsequently, 20 parts of a 10% aqueous solution of NTA (nitrilotriacetic acid) metal salt (Kyrest 70: manufactured by Chelest Co., Ltd.) was added, and then the pH was adjusted to 9.0 using a 1N aqueous sodium hydroxide solution. Thereafter, the temperature is raised to 90 ° C. at a temperature rising rate of 0.05 ° C./min and held at 90 ° C. for 2 hours, followed by cooling and filtering to obtain coarse toner particles. This is further re-dispersed in ion-exchanged water, and filtration is repeated to wash the filtrate until the electric conductivity of the filtrate becomes 20 μS / cm or less, and then vacuum-dried in an oven at 40 ° C. for 5 hours. The toner particles were obtained. The volume average particle diameter of the obtained toner particles was 6.1 μm.
A sample mill is prepared by adding 1.5 parts of hydrophobic silica (RY50, manufactured by Nippon Aerosil Co., Ltd.) and 1.0 parts of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., T805) to 100 parts of the obtained toner particles. The mixture was mixed at 10000 rpm for 30 seconds. Thereafter, the magenta toner 21 was manufactured by sieving with a vibrating sieve having an opening of 45 μm.
Various parameters for the obtained toner particles and the magenta toner 21 are summarized in Table 1.

<Preparation of Cyan Toner 1>
In the preparation of the magenta toner 1, the magenta colored particle dispersion was changed to a cyan colored particle dispersion, and the cyan toner 1 was prepared in the same manner as the magenta toner 1.
Various parameters for the obtained toner particles and cyan toner 1 are summarized in Table 1.

<Preparation of Cyan Toner 2>
In the preparation of the magenta toner 21, the magenta colored particle dispersion was changed to a cyan colored particle dispersion, and the cyan toner 2 was prepared in the same manner as the magenta toner 21.
Various parameters of the obtained toner particles and cyan toner 2 are summarized in Table 1.

<Preparation of Yellow Toner 1>
In the preparation of the magenta toner 1, the magenta colored particle dispersion was changed to a yellow colored particle dispersion, and the preparation was performed in the same manner as the magenta toner 1 to prepare a yellow toner 1.
Various parameters for the obtained toner particles and yellow toner 1 are summarized in Table 1.

<Preparation of Yellow Toner 2>
In the preparation of the magenta toner 21, the magenta colored particle dispersion was changed to a yellow colored particle dispersion, and the yellow toner 2 was prepared in the same manner as the magenta toner 21.
Various parameters for the obtained toner particles and yellow toner 2 are summarized in Table 1.

  The toners and carriers obtained as described above were placed in a V blender at a toner: carrier ratio of 8:92 (mass ratio) and stirred for 20 minutes to obtain developers.

In addition, the carrier manufactured as follows was used.
Ferrite particles (volume average particle size: 50 μm): 100 parts Toluene: 14 parts Styrene-methyl methacrylate copolymer: 2 parts (component ratio: 90/10, Mw = 80000)
Carbon black (R330: manufactured by Cabot Co., Ltd.): 0.2 parts First, the above components except ferrite particles are stirred with a stirrer for 10 minutes to prepare a dispersed coating solution, and then this coating solution and ferrite particles The reaction solution was placed in a vacuum degassing type kneader and stirred at 60 ° C. for 30 minutes, and then the pressure was reduced while degassing while heating, and the carrier was obtained by drying.

[Evaluation]
The developer obtained as described above was filled in the developing device of the image forming apparatus "DocuCentre color 400 manufactured by Fuji Xerox Co., Ltd." as described in Table 2. By this image forming apparatus, 10000 solid images having an image density of 100% were output under an environment of a temperature of 35 ° C. and a humidity of 85% RH. Then, the electrophotographic society test chart No. Output 5-1. The L ^* value was determined using X-Rite X-Rite 939 (aperture diameter 4 mm) at 10 locations for each of the +0.1 to +1.8 multi-order color halftone image portions in the output image. Further, the applied toner amount (g / m ² ) of the measured multi-color halftone image portion was determined.
Here, the L ^* value was plotted against the amount of applied toner (g / m ² ), and a two-order polynomial approximation was performed to obtain R2.
-Evaluation criteria-
A: R 2 obtained is 0.99 or more and 1.0 or less B: R 2 obtained is 0.98 or more and less than 0.99 C: R 2 obtained is 0.96 or more and less than 0.98 (permissible range for practical use)
D: R2 obtained is less than 0.96 A level at which tonality is unacceptable in multi-order color halftone visually.

1Y, 1M, 1C, 1K, photoconductor (example of 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 devices (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 the cleaning means)
8Y, 8M, 8C, 8K Toner Cartridges 10Y, 10M, 10C, 10K Image Forming Unit 20 Intermediate Transfer Belt (Example of Intermediate Transfer Member)
22 Drive roll 24 Support roll 26 Secondary transfer roll (an example of secondary transfer means)
30 Intermediate Transfer Cleaning Device 107 Photoconductor (Example of Image Carrier)
108 Charging roll (an example of charging means)
109 Exposure apparatus (an example of electrostatic charge image forming means)
111 Development device (an example of development means)
112 Transfer device (an example of transfer means)
113 Photosensitive member cleaning device (an example of the cleaning means)
115 Fixing device (an example of fixing means)
116 Mounting rail 117 Housing 118 Opening for exposure 200 Process cartridge 300 Recording paper (an example of recording medium)
P recording paper (an example of recording medium)

Claims (14)

The large diameter side volume particle size distribution index (GSDv (90/50)) is 1.26 or less,
The small-diameter side number particle size distribution index (GSDp (50/10)) is 1.28 or less,
GSDv (90/50) / GSDp (50/10) is 0.96 or more and 1.01 or less,
A toner for developing an electrostatic charge image comprising toner particles having an average circularity of 0.95 or more and 1.00 or less.   The air flow energy measured under the condition that the tip speed of the rotor blade is 100 mm / sec, the approach angle of the rotor blade is -5 °, and the air flow rate is 5 ml / min using a powder rheometer is 100 mJ to 300 mJ An electrostatic charge image developing toner according to claim 1.   The ratio of the aeration flow energy of aeration flow 5 ml / min to the aeration flow energy of aeration flow 80 ml / min (aeration flow 5 ml / min measurement time / aeration flow 80 ml / min measurement time) is 3 or more and 8 or less The toner for electrostatic image development according to claim 2.   The toner according to any one of claims 1 to 3, which is a magenta toner containing a magenta colorant or a cyan toner containing a cyan colorant.   The magenta colorant is C.I. I. Pigment red 122, C.I. I. Pigment red 185 and C.I. I. The toner for electrostatic image development according to claim 4, comprising at least one selected from the group consisting of C.I.   The cyan colorant is C.I. I. Pigment blue 15: 1, and C.I. I. The toner for developing an electrostatic charge image according to claim 4, comprising at least one selected from the group consisting of pigment blue 15: 3. It has n kinds (n is an integer of 2 or more) of electrostatic charge image developing toner exhibiting different colors from one another,
At least one of the electrostatic image developing toners has a large diameter side volume particle size distribution index (GSDv (90/50)) of 1.26 or less and a small diameter side number particle size distribution index (GSDp (50/10)) It contains toner particles of 1.28 or less, GSDv (90/50) / GSDp (50/10) of 0.96 to 1.01, and having an average circularity of 0.95 to 1.00. Toner set.   All the toners for electrostatic image development have a large diameter side volume particle size distribution index (GSDv (90/50)) of 1.26 or less, and a small diameter side number particle size distribution index (GSDp (50/10)) It contains toner particles of 1.28 or less, GSDv (90/50) / GSDp (50/10) of 0.96 to 1.01, and having an average circularity of 0.95 to 1.00. The toner set according to claim 7.   Ventilation for each of the electrostatic image developing toners was measured using a powder rheometer at a tip speed of the rotary blade of 100 mm / sec, an entry angle of the rotary blade of -5 °, and a ventilation flow rate of 5 ml / min. The toner set according to claim 8, wherein the difference between the maximum value and the minimum value of the air flow energy at a flow rate of 5 ml / min is 80 mJ or less.   An electrostatic charge image developer containing the toner for electrostatic charge image development according to any one of claims 1 to 6. A toner for electrostatic image development according to any one of claims 1 to 6 is contained,
A toner cartridge that is attached to and removed from the image forming apparatus. 11. A developing unit for containing the electrostatic charge image developer according to claim 10 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer.
Process cartridge that is attached to and detached from the image forming apparatus. An image carrier,
Charging means for charging the surface of the image carrier;
Electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
11. A developing unit for containing the electrostatic charge image developer according to claim 10, and developing the electrostatic charge image formed on the surface of the image carrier as the toner image by the electrostatic charge image developer.
A transfer unit configured to transfer 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: 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 by the electrostatic charge image developer according to claim 10.
Transferring the toner image formed on the surface of the image carrier to the surface of the recording medium;
A fixing step of fixing the toner image transferred to the surface of the recording medium;
An image forming method comprising: