JP6519269B2 - Electrostatic image developing toner, electrostatic image developer, toner cartridge, process cartridge, image forming apparatus, and image forming method - Google Patents

Description

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

  As a toner used to develop an electrostatic charge image, for example, Patent Document 1 states that “mechanical impact force is used in an aqueous solvent containing 0.1 to 30% by weight of resin particles containing at least a binder resin. A toner having toner particles produced through the step of fixing pigment particles to the surface of resin particles, wherein the toner contains at least a binder resin and a colorant and has a number average particle diameter of 0.5 to 6.0 μm. And the coefficient of variation of the number distribution of 0.1 to 20%, and the content of the pigment particles in the toner to the toner particles satisfies a specific relationship, and the pigment particles in the vicinity of the surface of the toner particles Are disclosed as being fixed at 80 to 100%.

For example, in Patent Document 2, “the binder resin and the carbon black are contained, and the surface of the carbon black is coated with a release agent, and the volume resistance value of the release agent is 10 ¹¹ Ω · cm or more. Disclosed is a toner for developing an electrostatic charge image.

JP 2000-330333 A JP, 2012-118420, A

  An object of the present invention is to provide a toner for developing an electrostatic charge image having a smaller dielectric loss factor as compared with the case of using pigment particles (that is, a pigment having no coating layer) in which the pigment component is exposed on the surface.

The above object is achieved by the present invention described below. That is,
The invention according to <1> is a toner for electrostatic charge image development, which comprises a coated pigment particle having a pigment and a coating layer containing a polyester resin provided on the surface of the pigment.

The invention according to <2> is the toner for developing an electrostatic charge image according to <1> , wherein the coated pigment particles are particles obtained by melting and emulsifying a mixture of a pigment and a polyester resin.

The invention according to <3> is the toner for developing an electrostatic charge image according to <1> , wherein the coated pigment particles are particles obtained by cooling a mixture of a pigment and a melt of a polyester resin.

The invention according to <4> is an electrostatic charge image developer containing the toner for electrostatic charge image development according to any one of <1> to <3> .

The invention according to <5> is a toner cartridge which contains the toner for developing an electrostatic charge image according to any one of <1> to <3> , and is detachably mounted to an image forming apparatus.

The invention according to <6> contains an electrostatic charge image developer according to <4>, and develops the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer. A process cartridge which is detachably mounted to the image forming apparatus.

The invention according to <7>, and the image carrier, a charging unit that charges the surface of the image carrier, and the electrostatic image forming means for forming an electrostatic image on the charged surface of the image carrier, <4 And a developing unit for containing the electrostatic charge image developer described in 1. and developing the electrostatic charge image formed on the surface of the image carrier with the electrostatic charge image developer as a toner image, and the surface of the image carrier An image forming apparatus comprising: transfer means for transferring the toner image formed on the surface of the recording medium onto the surface of the recording medium; and fixing means for fixing the toner image transferred onto the surface of the recording medium.

The invention according to <8> comprises 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 the electrostatic charge described in <4>. A developing step of developing an electrostatic charge image formed on the surface of the image carrier as a toner image with an image developer, and a transfer step of transferring the toner image formed on the surface of the image carrier onto the surface of a recording medium And a fixing step of fixing the toner image transferred to the surface of the recording medium.

According to the invention relating to <1> , < 2 > , and < 3 > , an electrostatic charge image developing toner having a smaller dielectric loss factor is provided as compared to the case where pigment particles having a pigment component exposed on the surface are used. .

According to the invention relating to <4> , an electrostatic charge image developer having a smaller dielectric loss factor is provided as compared to the case of including a toner for electrostatic charge image development using pigment particles having a pigment component exposed on the surface.

According to the invention as set forth in <5> , a toner cartridge is provided which accommodates a toner for developing an electrostatic charge image having a small dielectric loss factor as compared with the case where pigment particles having a pigment component exposed on the surface are used.

According to the invention relating to <6> , < 7 > , or < 8 > , compared to the case of using an electrostatic charge image developer containing a toner for electrostatic charge image development using pigment particles having a pigment component exposed on the surface Thus, it is possible to provide a process cartridge, an image forming apparatus, or an image forming method in which a decrease in transfer efficiency is suppressed.

FIG. 2 is a cross-sectional view schematically showing an example of a glitter toner particle in the present embodiment. 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. It is an upper surface schematic block diagram which shows an example of the apparatus used for the melt emulsification method in this embodiment.

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

[Toner for electrostatic image development]
A toner for developing an electrostatic charge image according to this embodiment (hereinafter sometimes referred to simply as "toner") is a coated pigment particle having a pigment and a coating layer containing a polyester resin provided on the surface of the pigment. ,including.

Here, the pigment used in the toner usually functions as a colorant and is also a component that can affect the electrical properties.
Therefore, when the pigment is exposed from the surface of the toner, the dielectric loss factor tends to increase. The toner having a large dielectric loss factor is lowered in resistance by being placed under an alternating electric field. Therefore, when an image is formed by applying an alternating voltage using a toner having a large dielectric loss factor, the toner is less likely to be charged, which may lower the transfer efficiency.
Under these circumstances, toners with smaller dielectric loss factors are currently desired.
Therefore, as in the toner according to the present embodiment, by using the coated pigment particles, the presence of the coating layer covering the surface of the pigment suppresses the exposure of the pigment itself from the surface of the toner. As a result, it has been found that the toner has a small dielectric loss factor.
In addition, in the coated pigment particle, the aggregation of the pigment in the toner is also easily suppressed by the presence of the coating layer covering the surface of the pigment. Therefore, it is considered that the toner containing the coated pigment particles can also suppress an increase in the dielectric loss factor due to the aggregation of the pigment.
In addition, by using a polyester resin for the covering layer, the affinity is expressed between the polar group possessed by the pigment surface and the polar portion such as water molecules on the pigment surface and the ester group portion of the polyester resin, Aggregation of the pigment by the polar portion of the pigment is suppressed, and the dispersibility of the pigment is improved.
In addition, the toner having a small dielectric loss factor can stabilize the charge amount, and can suppress a decrease in transfer efficiency. As a result, for example, in the case of a black toner, an image with a small lightness (L *) and an image with a high degree of blackness can be formed.

On the other hand, as a pigment used for a toner, there is a luster pigment used for the purpose of forming an image having luster such as metallic luster (hereinafter referred to as "glint").
When the pigment in the coated pigment particle is a bright pigment, the bright pigment is often a metal pigment, and the exposure of the bright pigment from the surface of the toner has a large influence on the electrical properties.
Therefore, as in the toner according to the exemplary embodiment, the use of the coated pigment particle provided with the coating layer covering the surface of the bright pigment has a high effect of suppressing the dielectric loss factor to a low level.
Further, the luster pigment (metal pigment) is also easily influenced by chemicals used in toner production because of its material (for example, oxidation, alkalization, clouding, etc. of the surface of the luster pigment). Therefore, by using coated pigment particles provided with a coating layer, the chemical resistance of the bright pigment (metal pigment) can be enhanced, and can be contained in the toner without reducing the function of the bright pigment.
From these facts, by using the coated pigment particles containing the bright pigment, it becomes a toner having a small dielectric loss factor, the reduction of the transfer efficiency of the toner is suppressed, and it is easy to form a bright image.

The coated pigment particles in the present embodiment will be described below.
The first embodiment is an embodiment in which the pigment in the coated pigment particles is a known pigment used for colored toner, and the second embodiment is an embodiment in which the pigment in the coated pigment particles is a bright pigment. Explain to.

[Coated pigment particle of the first aspect]
First, the coated pigment particles of the first aspect (hereinafter, referred to as "coated pigment particles (1)") will be described.
The coated pigment particles (1) preferably have a coating layer that covers the surface of the pigment more, and most preferably a coating layer that covers the entire surface of the pigment, that is, a coverage of 100%.
Such coverage is confirmed by a fluorescent X-ray analyzer.
The specific confirmation method of the coverage is as follows.
First, using a pressure molding machine, a compression pressure of 10 tons (10,000 kg) is applied to 5 g of the coated pigment particles (1) to prepare a disk with a diameter of 5 cm, and this is used as a measurement sample.
The measurement conditions are measured as tube voltage 40 KV, tube current 90 mA, and measurement time 5 minutes using a fluorescent X-ray analyzer (XRF-1500) manufactured by Shimadzu Corporation.
As a result, the ratio of the pigment-derived element to the resin-derived element (specifically, carbon) was measured, and the coverage was 100% when the pigment-derived element amount was 10% or less with respect to the carbon amount.
The reason why the ratio is 10% or less is that fluorescent X-rays detect elements in the depth direction as well.

Further, in the coated pigment particles (1), it is preferable that one pigment is contained in one coated pigment particle (1) from the viewpoint of reducing the dielectric loss factor in addition to the coloring performance.
Such a form can be confirmed by observing the cut surface of the coated pigment particle (1).
For example, an image in which about 10 to 20 cut coated pigment particles (1) can be observed is photographed by TEM, and particles corresponding to 50% by number from the large side of the particles are observed. If 80% or more of particles observed contain one pigment, it can be judged that one coated pigment particle (1) contains one pigment. In the case of particles, it is not always possible to cut the center of particles in order to make the particles to be observed up to 50% by number from the large side of the particles. To reduce the errors that occur.

In the coated pigment particle (1), the ratio of the coated layer in the coated pigment particle (1) from the point of increasing the coverage and obtaining the coated pigment particle (1) having a smaller dielectric loss factor: {coating layer / (coating layer 80 mass% or more and 98 mass% or less are preferable, and 90 mass% or more and 98 mass% or less are more preferable.
Here, the mass of the pigment and the coating layer can be measured by the following method.
The conditions of the fluorescent X-ray measurement in the above-described method of checking the coverage are changed to a measurement time of 30 minutes, the carbon amount is the mass of the coating layer, and the pigment-derived element amount is the mass of the pigment.

As a pigment which comprises coated pigment particle (1), the well-known pigment used for a colored toner is used.
Specifically, for example, carbon black, chrome yellow, Hansa yellow, benzidine yellow, slen yellow, quinoline yellow, pigment yellow, permanent orange GTR, pyrazolone orange, balkan orange, watch young red, permanent red, permanent carmine 3B, brilliant Carmine 6B, Dupont oil red, pyrazolone red, resole red, rhodamine B lake, lake red C, pigment red, rose bengal, aniline blue, ultramarine blue, chalco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine blue, pigment green, phthalocyanine green, Various pigments such as malachite green oxalate may be mentioned.
Among these, carbon black, in particular, amorphous carbon black is preferable.
Carbon black is likely to have a large dielectric loss factor by being exposed on the surface of the toner, and therefore, the effect of reducing the dielectric loss factor is easily exhibited by using coated pigment particles.
These pigments may be used alone or in combination of two or more.

The covering layer which comprises covering pigment particle (1) contains polyester resin.
As a polyester resin used here, an amorphous polyester resin is mentioned as a preferable thing from the point of the adhesive strength with respect to the pigment surface.
In addition, "crystallinity" of a resin means not having a step-like endothermic change but having a clear endothermic peak in differential scanning calorimetry (DSC), and specifically, a temperature rising rate of 10 (° C. It means that the half value width of the endothermic peak when it measures with / min) is less than 10 ° C.
On the other hand, “amorphous” of the resin means that the half width exceeds 10 ° C., exhibits a step-like endothermic change, or that no clear endothermic peak is observed.

Amorphous Polyester Resin As the amorphous polyester resin, for example, a condensation polymer of polyvalent carboxylic acid and polyvalent alcohol can be mentioned. In addition, as an amorphous polyester resin, a commercial item may be used 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.

40 degreeC or more and 70 degrees C or less are preferable, and, as for the glass transition temperature (Tg) of amorphous polyester resin, 45 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 describes in the determination method of the glass transition temperature of JISK7121-1987 "the transition temperature method of plastics". It is determined by the “extrapolated glass transition start temperature” of

  5,000 or more and 80,000 or less are preferable, and, as for the weight average molecular weight (Mw) of amorphous polyester resin, 10,000 or more and 70,000 or less are more preferable.

The molecular weight distribution Mw / Mn of the amorphous polyester resin is preferably 2.5 or more and 30 or less, and more preferably 3 or more and 10 or less.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin are measured by gel permeation chromatography (GPC). The molecular weight measurement by GPC uses a Tosoh GPC · HLC-8120 GPC as a measuring device, a Tosoh SC-8020 as a data processing device, and two Tosoh columns · TSKgel SuperHM-H (6.0 mm ID, 15 cm) , Tetrahydrofuran (THF) was used as an eluent. The measurement conditions are: sample concentration 0.5%, flow rate 0.6 ml / min, sample injection amount 10 μl, measurement temperature 40 ° C., using an RI (Refractive Index) detector (differential refractive index detector) It measured.
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.
Here, the molecular weight calibration curve (calibration curve) can be obtained by Tosoh Corp. “polystylene standard sample TSKstandard”: “A-500”, “F-1”, “F-10”, “F-80”, “F It prepares from ten samples of -380 "," A-2500 "," F-4 "," F-40 "," F-128 ", and" F-700 ".

Amorphous polyester resins are obtained by known production methods. 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 does not melt | dissolve or miscible with reaction temperature, you may add and dissolve the solvent of a high boiling point as a solubilizing agent. 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 coating layer in the coating pigment particles (1) may contain other resins besides the amorphous polyester resin described above.
Examples of other resins include crystalline polyester resins and various resins used as binder resins for toners (resins described in the column of binder resins described later).
The total content of resin components (amorphous polyester resin and other resins) in the coating layer is preferably 70% by mass or more, and 80% by mass or more, from the viewpoint of obtaining coated pigment particles (1) having a small dielectric loss factor. Is more preferable, and 85% by mass or more is more preferable.

The coating layer in the coating pigment particle (1) may contain the following components as an additive in addition to the polyester resin.
Examples of the additive include surfactants, fillers such as water glass and titania, charge control agents, lubricants and the like.

Next, a method of producing the coated pigment particle (1) will be described.
The coated pigment particles (1) may be produced by any method as long as it can produce a form in which the surface of the pigment is coated with a coating layer containing a polyester resin.
In view of the ease of formation of particles having a high coverage and the ease of forming an embodiment in which one pigment is contained in one coated pigment particle (1), it is preferable to use the melt emulsification method described below preferable.
Specifically, the melt emulsification method is a method in which, first, a mixture of a pigment and a polyester resin is prepared, and then the prepared mixture is emulsified and dispersed using a surfactant and a basic substance.
The mixture preparation step and the emulsification dispersion step of this method will be described in detail below.
Here, although the example which used amorphous polyester resin as polyester resin contained in a coating layer is demonstrated, it is not limited to this example.

Mixture Preparation Step In the mixture preparation step, a mixture containing at least a pigment and an amorphous polyester resin is prepared.
It is preferable that kneading | mixing at this time is performed using various heating kneaders in the container which can be sealed.
Examples of the heating kneader include batch type kneaders such as a kneader and a Banbury mixer, and an extruder having a plurality of shafts such as a single-screw extruder and a twin-screw extruder.
In kneading, a resin medium which does not melt at the above-mentioned heating temperature may be used.

The heating temperature for kneading is preferably in the range of glass transition temperature (Tg) + 20 ° C. to Tg + 100 ° C. of non-crystalline polyester resin, and glass transition temperature (Tg) + 35 ° C. or more to Tg + 60 ° C. of non-crystalline polyester resin Is more preferable.
In addition, when the polyester resin used for a coating layer is crystalline polyester resin, the heating temperature at the time of kneading | mixing has the preferable range of melting temperature (Tm) or more of crystalline polyester resin and Tm + 40 degrees C or less, and crystalline polyester The range of the melting temperature (Tm) + 5 ° C. or more and Tm + 25 ° C. or less of the resin is more preferable.

Emulsifying and dispersing step Subsequently, a surfactant and a basic substance are added to the mixture prepared as described above, and water is further added to neutralize the polyester resin, thereby adjusting the acid value and emulsifying particles. As a result, coated pigment particles (1) in which the polyester resin is coated on the surface of the pigment are formed.
In this step, an aqueous dispersion containing the coated pigment particles (1) is obtained.

  The surfactant used in the emulsifying and dispersing step is preferably an ionic surfactant, and specifically, surfactants such as sulfate ester salts, sulfonates, and soaps can be used. Specifically, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium dodecyl ether sulfate, sodium alkyl ether sulfate, sodium polyoxyethylene dodecyl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium alkyl naphthalene sulfonate, dialkyl sulfosuccinic acid Sodium, sodium alkyl diphenyl oxide sulfonate, and their potassium salts, ammonium salts and the like are used.

Further, as the basic substance used in the emulsification and dispersion process, sodium hydroxide, potassium hydroxide, ammonia, monomethylamine, diethylamine, trimethylamine, sodium metasilicate, sodium sesquisilicate, sodium orthosilicate (sodium orthosilicate), sodium carbonate Sodium bicarbonate, sodium sesquicarbonate, sodium orthophosphate (sodium orthophosphate), sodium pyrophosphate, sodium tripolyphosphate, sodium tetraphosphate, sodium hexametaphosphate, and their potassium salts, ammonium salts, etc. Japanese agents are mentioned.
These may be used alone or in combination of two or more.

Further, in the emulsification and dispersion step, when using an amorphous polyester resin, the range of the glass transition temperature (Tg) + 20 ° C to Tg + 100 ° C of the amorphous polyester resin, more preferably Tg + 35 ° C to Tg + 60 ° C It is preferable to maintain the temperature in the system in the range of
When a crystalline polyester resin is used, the temperature in the system is preferably maintained in the range of melting temperature (Tm) to Tm + 40 ° C., more preferably Tm + 5 ° C. to Tm + 25 ° C. of the crystalline polyester resin. It is preferable to keep
In particular, the temperature in the system is maintained in the range of 80 ° C. or more and 110 ° C. or less during the emulsification and dispersion process from the viewpoint of softening of the polyester resin by heating, pressurization by boiling of water, and excessive hydrolysis suppression of the polyester resin. Is preferable.

It is preferable that the mixture preparation process and the emulsification dispersion process as described above be performed using the apparatus shown in FIG.
Here, FIG. 4 is a schematic top view showing an example of an apparatus used for the melt emulsification method in the present embodiment.
The apparatus 300 shown in FIG. 4 includes a tank 310, two screw type stirring blades 320 for stirring the raw material supplied into the tank 310, and a jacket 330 which covers the outer periphery of the tank and heats the inside of the tank.
A mixture preparation process and an emulsification dispersion process using this apparatus will be described by taking one example.
In the tank 310, first, a pigment, a polyester resin, and a resin medium are supplied. The jacket 330 is set to the above-described heating temperature range, and the inside of the tank 310 is heated. And two screw type | mold stirring blade 320 rotates to an arrow direction by operation | movement of a motor, and stirs and mixes the pigment in the tank 310, a polyester resin, and the resin media (mixture preparation process).
After kneading is completed by heating and stirring, a surfactant and a basic substance are further supplied into the tank 310, and then the temperature in the tank 310 is maintained at, for example, a temperature of 80 ° C. or more and 110 ° C. or less. Water is supplied into the tank 310 (emulsification and dispersion step).
As described above, the mixture preparation step and the emulsification dispersion step are performed by the apparatus shown in FIG. 4 to prepare coated pigment particles (1).

The volume average particle diameter of the coated pigment particles (1) produced as described above is preferably 50 nm or more and 500 nm or less, more preferably 70 nm or more and 300 nm or less, and 100 nm or more and 200 nm or less More preferable.
The volume average particle size of the coated pigment particles (1) in the aqueous dispersion is measured by Nanotrac UPA manufactured by Nikkiso Co., Ltd.

[Coated pigment particles of the second aspect]
Subsequently, the coated pigment particles of the second aspect (hereinafter, referred to as "coated pigment particles (2)") will be described.
The coated pigment particles (2) preferably have a coating layer that covers the surface of the bright pigment more, and most preferably, covers the entire surface of the bright pigment, that is, a coating layer having a coverage of 100%. It is.
Such coverage is confirmed by X-ray fluorescence measurement.
Specifically, it is confirmed by the same fluorescent X-ray measurement as the confirmation of the coverage in the above-mentioned coated pigment particle (1), and the measurement conditions are also the same, and calculated from the amount of carbon and the amount of elements unique to the luster pigment Be done.

Further, in the coated pigment particles (2), it is preferable that one pigment is contained in one coated pigment particle (2) from the viewpoint of reducing the dielectric loss factor in addition to the coloring performance.
Such a form can be confirmed by observing the cut surface of the coated pigment particle.
The specific confirmation method is the same as the method described in the above-mentioned coated pigment particle (1).

In the coated pigment particle (2), the ratio of the coated layer in the coated pigment particle (2) from the point of increasing the coverage and obtaining the coated pigment particle (2) having a smaller dielectric loss factor: {coating layer / (coating layer 5 mass% or more and 30 mass% or less are preferable, and 8 mass% or more and 20 mass% or less are more preferable.
In addition, the mass of a pigment and a coating layer is measured by the method similar to the method described by the above-mentioned coating pigment particle (1).

Examples of the bright pigment constituting the coated pigment particle (2) include known bright pigments used for the purpose of forming an image having brightness such as metallic gloss.
Examples of the luster pigment include metal powders of aluminum (metal of Al alone), brass, bronze, nickel, stainless steel, zinc, etc .; mica coated with titanium oxide, yellow iron oxide etc .; barium sulfate, layered silicate, Coated flaky inorganic crystal substrate such as layered aluminum silicate; single crystal plate-like titanium oxide; basic carbonate; bismuth oxy oxychloride; natural guanine; flaky glass powder; metal-deposited flaky glass powder etc There is no particular limitation as long as it is one having luster.
Among the bright pigments, metal powders are preferred, particularly in terms of specular reflection intensity, and among them, aluminum is most preferred.
Such bright pigments are often scaly (flat).

The coating layer constituting the coated pigment particles (2) contains a polyester resin.
As a polyester resin used here, a coating of a pigment surface is easy, and a crystalline polyester resin is mentioned as a preferable thing from the point which is easy to suppress aggregation of a pigment.

Crystalline Polyester Resin Examples of crystalline polyester resins include polycondensates of polyvalent carboxylic acids and polyvalent alcohols. In addition, as crystalline polyester resin, you may use a commercial item and you may use what was synthesize | combined.
Here, in order to easily form a crystal structure, the crystalline polyester resin is preferably a polycondensate using a polymerizable monomer having a linear aliphatic group rather than a polymerizable monomer having an aromatic group.

Examples of polyvalent carboxylic acids include aliphatic dicarboxylic acids (eg oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid). Acids, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid etc., aromatic dicarboxylic acids (eg phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid) And dibasic acids such as acids, etc., anhydrides thereof, or lower (eg, 1 to 5 carbon atoms) alkyl esters thereof.
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 carboxylic acids include aromatic carboxylic acids (eg, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, etc.), Anhydrides or lower (for example, 1 or more and 5 or less carbon atoms) alkyl esters thereof can be mentioned.
As the polyvalent carboxylic acid, a dicarboxylic acid having a sulfonic acid group and a dicarboxylic acid having an ethylenic double bond may be used in combination with these dicarboxylic acids.
The polyvalent carboxylic acids may be used alone or in combination of two or more.

Examples of polyhydric alcohols include aliphatic diols (for example, straight-chain aliphatic diols having 7 to 20 carbon atoms in the main chain portion). Examples of aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8- Octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18- Examples include octadecanediol and 1,14-eicosanedecanediol. Among these, as the aliphatic diol, 1,8-octanediol, 1,9-nonanediol and 1,10-decanediol are preferable.
The polyhydric alcohol may be used in combination with a diol and a trivalent or higher alcohol having a crosslinked or branched structure. Examples of trihydric or higher alcohols include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like.
A polyhydric alcohol may be used individually by 1 type, and may use 2 or more types together.

  Here, in the polyhydric alcohol, the content of the aliphatic diol is preferably 80 mol% or more, preferably 90 mol% or more.

The melting temperature (Tm) of the crystalline polyester resin is preferably 40 ° C. to 80 ° C., more preferably 50 ° C. to 75 ° C., and still more preferably 55 ° C. to 75 ° C.
The melting temperature is determined from the “melting peak temperature” described in the method for 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). .
For differential scanning calorimetry (DSC), a differential scanning calorimeter with an automatic cooler (DSC-60A, manufactured by Shimadzu Corporation) is used.

  The weight average molecular weight (Mw) of the crystalline polyester resin is preferably 5,000 or more and 50,000 or less.

  The crystalline polyester resin can be obtained, for example, by well-known production methods, as with non-crystalline polyester.

The coating layer in the coating pigment particles (2) may contain other resins in addition to the crystalline polyester resin described above.
Examples of other resins include amorphous polyester resins, and various resins used as binder resins for toners (resins described in the section of binder resin described later).

The coating layer in the coating pigment particle (2) may contain the following components as an additive in addition to the polyester resin.
As an additive, surfactant, a mold release agent, a charge control agent, a lubricant etc. are mentioned, for example.

Next, a method of producing the coated pigment particle (2) will be described.
The coated pigment particles (2) may be produced by any method as long as it can produce a form in which the surface of the bright pigment is coated with a coating layer containing a polyester resin.
It is preferable to use the following method from the viewpoint of easy formation of particles having a high coverage rate and easy formation of an embodiment in which one pigment is contained in one coated pigment particle (2).
Specifically, first, a mixture of a pigment and a melt of a polyester resin is prepared, and then the prepared mixture is cooled.
The mixture preparation step and the cooling step of this method will be described in detail below.
Here, although the example which used crystalline polyester resin as polyester resin contained in a coating layer is demonstrated, it is not limited to this example.

Mixture Preparation Step In the mixture preparation step, a mixture containing at least a pigment and a melt of a crystalline polyester resin is prepared.
The liquid mixture is prepared by heating in a reaction vessel using a hydrocarbon solvent such as mineral spirit and stirring the pigment and the crystalline polyester resin to a temperature higher than the melting temperature (Tm) of the polyester resin. To be done.
In addition, in the case of preparation of a liquid mixture, you may use surfactant further.
As the surfactant used here, a polymeric surfactant is preferable from the viewpoint of the dispersibility of the bright pigment.

The heating temperature at the time of producing a mixture is preferably in the range of the melting temperature (Tm) of the crystalline polyester resin + 10 ° C. or more and 40 ° C. or less.
In addition, when the polyester resin used for a coating layer is amorphous polyester resin, the heating temperature at the time of producing a mixture is the glass transition temperature (Tg) +30 degreeC or more +60 degreeC or less of amorphous polyester resin. A range is preferred.
Also, heating is performed until the crystalline polyester resin is completely melted.

Cooling Step Subsequently, the mixture prepared as described above is cooled while being stirred.
By this cooling, the crystalline polyester resin is deposited on the surface of the bright pigment, and a dispersion liquid containing the coated pigment particles (2) is obtained.

  The dispersion containing the coated pigment particles (2) obtained as described above is subjected to solid-liquid separation, and the resulting solid is dried to obtain coated pigment particles (2).

The volume average particle diameter of the coated pigment particles (2) produced as described above is preferably 0.1 μm to 100 μm, more preferably 1 μm to 50 μm, and 1 μm to 30 μm. Is more preferred.
The volume average particle size of the coated pigment particles (2) is measured by Coulter Multisizer II manufactured by Beckman Coulter.

Next, the toner according to the present embodiment will be described.
The toner according to the present embodiment may be composed only of toner particles including the above-mentioned coated pigment particles (1) or (2), or may be composed of the toner particles and an external additive.
Hereinafter, components constituting toner particles will be described.

[Toner particle]
The toner particles used in the present invention contain, in addition to the coated pigment particles (1) or (2), a binder resin, and if necessary, a releasing agent and other additives.
The toner particles containing the coated pigment particles (2) may be referred to as "bright toner particles" to distinguish them from the toner particles containing the coated pigment particles (1). Unless otherwise specified, "toner particles" is a general expression of toner particles including coated pigment particles (1) or (2).

-Coated pigment particles (1) or (2)-
When the coated pigment particles (1) in the toner particles are contained, the content of the coated pigment particles (1) is 1% by mass or more based on the entire toner particles from the viewpoint of suppression of dielectric loss factor and securing of coloring properties. 30 mass% or less is preferable, and 3 mass% or more and 15 mass% or less are more preferable.
In addition, in the case of the glitter toner particle including the coated pigment particle (2), the content of the coated pigment particle (2) is 1 part by mass or more and 50 parts by mass with respect to the entire toner particle from the viewpoint of securing the glitter. The amount is preferably not more than 15 parts by mass and more preferably 15 parts by mass or more and 25 parts by mass or less.

-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.
When a polyester resin is used as the binder resin, since the coating layer of the coating pigment particles (1) or (2) contains the same polyester resin, the affinity between the two becomes high. It is preferable in the manufacture suitability of particle | grains. In particular, in the case of toner particles using a polyester resin as a binder resin, when producing toner particles by the aggregation and coalescence method described later, the amount of addition of the coagulant can be suppressed to a low level, and the generation of coarse powder is suppressed. It is preferable from the viewpoint of
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 describes in the determination method of the glass transition temperature of JISK7121-1987 "the transition temperature method of plastics". It is determined by the “extrapolated glass transition start temperature” of

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 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 does not melt | dissolve or miscible with reaction temperature, you may add and dissolve the solvent of a high boiling point as a solubilizing agent. 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 or more and 95% by mass or less, more preferably 50% by mass or more and 90% by mass or less, and 60% by mass or more and 85% by mass or less 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 of the release agent is also determined by the same method as the melting temperature of the resin.

  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.
In addition to the coated pigment particles (1) or (2) as the coloring agent, various dyes may be used in combination.
Examples of dyes include acridine dyes, xanthene dyes, azo dyes, benzoquinone dyes, azine dyes, anthraquinone dyes, anthraquinone dyes, thioindico dyes, dioxazine dyes, thiazine dyes, azomethine dyes, indigo dyes, phthalocyanine dyes, aniline black dyes, polymethine dyes, triphenylmethane And various dyes such as diphenylmethane dyes and thiazoles dyes.
These dyes may be used alone or in combination of two or more.

The volume average particle diameter (D50v) of the toner particles is preferably 2 μm or more and 10 μm or less, and more preferably 4 μm or more and 8 μm or less, as long as it is a toner particle including the coated pigment particle (1).
In the case of a glitter toner particle containing the coated pigment particle (2), the volume average particle diameter (D50v) is preferably 1 μm to 30 μm, more preferably 3 μm to 20 μm, and still more preferably 5 μm to 15 μm.

In addition, various average particle diameters of toner particles and various particle size distribution indexes are measured using Coulter Multisizer II (manufactured by Beckman Coulter Co., Ltd.), and electrolytic solution is measured using ISOTON-II (manufactured by Beckman Coulter Co.) Ru.
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 in terms of volume and number, and the particle size of cumulative 16% is the volume particle size D16v, number particle size The particle diameter of D16p and cumulative 50% is defined as volume average particle diameter D50v, cumulative number average particle diameter D50p, and particle diameter of 84% cumulative, as volume particle diameter D84v and number particle diameter D84p.
Using these, the volume average particle size distribution index (GSDv) is calculated as (D84 v / D 16 v) ^1/2 , and the number average particle size distribution index (GSD p) is calculated as (D 84 p / D 16 p) ^1/2 .

  In the case of toner particles containing the coated pigment particles (1), the shape factor SF1 of the toner particles is preferably 110 or more and 150 or less, and more preferably 120 or more and 140 or less.

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

In the case of the bright toner particle containing the coated pigment particle (2), it is preferable to exhibit the following physical properties.
・ Ratio (A / B)
The photoluminescent toner particles, when forming a solid image, receive the reflectance A at a light receiving angle of + 30 ° and the light receiving angle measured when the incident light of an incident angle of −45 ° is irradiated to the image by a variable angle photometer. The ratio (A / B) to the reflectance B at an angle of −30 ° is preferably 2 or more and 100 or less.

That the ratio (A / B) is 2 or more indicates that there is more reflection on the opposite side (angle + side) to the incident side than on the side (angle-side) on which incident light is incident. That is, it indicates that irregular reflection of incident light is suppressed. When irregular reflection occurs in which incident light is reflected in various directions, when the reflected light is visually confirmed, the color looks dull. Therefore, when the ratio (A / B) is less than 2, the gloss may not be confirmed even when the reflected light is viewed, and the glitter may be inferior.
On the other hand, when the ratio (A / B) exceeds 100, the viewing angle at which the reflected light can be visually recognized becomes too narrow, and since the specular reflection light component is large, it may appear dark depending on the viewing angle. In addition, bright toner particles having a ratio (A / B) of more than 100 are also difficult to produce.

  The ratio (A / B) is more preferably 50 or more and 100 or less, still more preferably 60 or more and 90 or less, and particularly preferably 70 or more and 80 or less.

Here, the incident angle and the light receiving angle will be described first. In the measurement by the variable angle photometer in the present embodiment, the incident angle is set to −45 ° because the measurement sensitivity is high for an image in a wide range of glossiness.
Further, the reason why the light receiving angles are set to -30 ° and + 30 ° is that the measurement sensitivity is the highest for evaluating an image with a brilliance and an image without a brilliance.

Next, a method of measuring the ratio (A / B) will be described.
In the present embodiment, when measuring the ratio (A / B), first, a "solid image" is formed by the following method. A developer containing bright toner particles as a sample is filled into a developer of DocuCentre-III C7600 manufactured by Fuji Xerox Co., Ltd., and recording paper (OK top coat + paper, manufactured by Oji Paper Co., Ltd.) A solid image having a toner coverage of 4.5 g / m ² is formed at a fixing temperature of 190 ° C. and a fixing pressure of 4.0 kg / cm ² . The "solid image" refers to an image having a printing rate of 100%.
Incident light with an incident angle of -45 ° on the solid image is made incident on the image area of the formed solid image using a spectral variable colorimeter GC5000L manufactured by Nippon Denshoku Kogyo Co., Ltd. as a variable angle photometer and received. The reflectance A at an angle of + 30 ° and the reflectance B at a light receiving angle of -30 ° are measured. The reflectance A and the reflectance B were measured at intervals of 20 nm for light of wavelengths in the range of 400 nm to 700 nm, and were taken as the average value of the reflectance at each wavelength. The ratio (A / B) is calculated from these measurement results.

From the viewpoint of satisfying the above-described ratio (A / B), it is desirable that the glitter toner particles according to the exemplary embodiment satisfy the following requirements (1) to (2).
(1) The equivalent circle equivalent diameter D is larger than the average maximum thickness C of the glitter toner particles. (2) When a cross section in the thickness direction of the glitter toner particles is observed, the cross section of the glitter toner particles in the cross section The number of coated pigment particles (2) in which the angle between the long axis direction and the long axis direction of the coated pigment particles (2) is in the range of -30 ° to + 30 ° is the total coated pigment particles (2) observed 60% or more

Here, FIG. 1 is a cross-sectional view schematically showing glittering toner particles satisfying the above requirements (1) to (2). The schematic view shown in FIG. 1 is a cross-sectional view of the glitter toner particles in the thickness direction.
The glitter toner particle 101 shown in FIG. 1 is a flat glitter toner particle having a circle equivalent diameter larger than the thickness L, and contains a coated pigment particle (2) 102 containing a scaly glitter pigment There is.

As shown in FIG. 1, if the glitter toner particles 101 are flat with a circle equivalent diameter larger than the thickness L, they are pushed down to the surface of the recording medium by the contact and pressure at the time of fixing in the fixing step of image formation. The scaly (flat) coated pigment particles (2) 102 are considered to be aligned so that the flat surface side thereof faces the recording medium surface.
Therefore, among the scaly coated pigment particles (2) contained in the glitter toner, the length of the major axis direction of the section of the glitter toner particles and the coated pigment particles (2) shown in the above (2) The coated pigment particles (2) satisfying the requirement of “the angle with the axial direction is in the range of −30 ° to + 30 °” are considered to be aligned such that the surface side having the largest area faces the recording medium surface. When light is irradiated to the image thus formed, the ratio of the coated pigment particles (2) irregularly reflected to the incident light is suppressed, so that the range of the aforementioned ratio (A / B) is achieved. It is considered to be a thing. In addition, when the ratio of the coated pigment particles (2) irregularly reflected to the incident light is suppressed, the reflected light intensity largely changes depending on the viewing angle, and thus more ideal brightness can be obtained.

・ Average maximum thickness C and average equivalent circle diameter D
As shown in the above (1), it is preferable that the glitter toner particles include glitter toner particles having an average equivalent circle diameter D larger than the average maximum thickness C. The ratio (C / D) of the average maximum thickness C to the average equivalent circle diameter D is more preferably in the range of 0.001 to 0.500, and the range of 0.010 to 0.200 is further preferable. Desirably, the range of 0.050 or more and 0.100 or less is particularly desirable.
When the ratio (C / D) is 0.001 or more, the strength of the bright toner particles is secured, breakage due to stress at the time of image formation is suppressed, and charging is caused by exposure of the coated pigment particles (2). And the resulting fog is suppressed. On the other hand, excellent brightness is obtained by being 0.500 or less.

The average maximum thickness C and the average equivalent circular diameter D are measured by the following method.
The bright toner particles are placed on a smooth surface and subjected to vibration so as to be dispersed uniformly. The maximum thickness C and the equivalent circular diameter D of the surface viewed from the top are measured by 1000 magnifications of 1000 bright toner particles with a color laser microscope “VK-9700” (manufactured by Keyence Corporation), Calculated by finding their arithmetic mean value.

The angle between the major axis direction of the cross section of the glitter toner particle and the major axis direction of the coated pigment particle (2), as shown in (2), when observing the cross section in the thickness direction of the glitter toner particle, The total number of coated pigment particles (2) in which the angle between the long axis direction in the cross section of the glitter toner particles and the long axis direction of the coated pigment particles (2) is in the range of -30 ° to + 30 ° It is desirable that it is 60% or more of the coated pigment particles (2). Furthermore, the number is more preferably 70% or more and 95% or less, and particularly preferably 80% or more and 90% or less.
When the above number is 60% or more, excellent luster can be obtained.

Here, a method of observing the cross section of the glitter toner particle will be described.
After embedding the glittering toner particles with a bisphenol A liquid epoxy resin and a curing agent, a cutting sample is prepared. Next, a cutting sample is cut at −100 ° C. using a cutting machine using a diamond knife (in this embodiment, LEICA Ultra Microtome (made by Hitachi Technologies)) to prepare a sample for observation . The observation sample is observed by a transmission electron microscope (TEM) to observe the cross section of the bright toner particles at a magnification of about 5000 times. A coated pigment particle in which the angle between the major axis direction of the cross section of the glitter toner particle and the major axis direction of the coated pigment particle (2) is in the range of -30 ° to + 30 ° for 1000 observed glitter toner particles Count the number of (2) using image analysis software and calculate the ratio.

  "The major axis direction in the cross section of the glitter toner particle" indicates a direction orthogonal to the thickness direction of the glitter toner particle having a larger equivalent circle diameter D than the above-mentioned average maximum thickness C. The long axis direction of the coated pigment particles (2) represents the length direction of the bright pigment particles.

(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 with respect to 100 parts by mass of the inorganic particles.

  As external additives, resin particles (resin particles such as polystyrene, PMMA, melamine resin, etc.), cleaning activators (for example, metal salts of higher fatty acids represented by zinc stearate, particles of fluorine-based polymer), etc. It can be mentioned.

  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 producing toner particles-
A method of producing toner particles in the present embodiment will be described.
The toner particles may be produced by any of dry production method (for example, kneading and pulverization method) and wet production 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.

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 of obtaining toner particles including the coated pigment particles (1) or (2) and the releasing agent is described, the releasing agent is used as needed. Of course, other additives besides the release agent may be used.

-Resin particle dispersion preparation process-
First, a resin particle dispersion liquid in which resin particles to be a binder resin are dispersed is prepared.
In addition to the resin particle dispersion, for example, a coated pigment particle dispersion in which the coated pigment particles (1) or (2) are dispersed, and a release agent particle in which the releasing agent particles are dispersed are used in the aggregated particle forming step described later. A template particle dispersion is prepared.

  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.

  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 addition, in the same manner as the resin particle dispersion, for example, a coated pigment particle dispersion and a releasing agent particle dispersion are also prepared. That is, regarding the volume average particle diameter of the particles in the resin particle dispersion, the dispersion medium, the dispersion method, and the content of the particles, the coated pigment particles (1) or (2) dispersed in the coated pigment particle dispersion, The same applies to release agent particles dispersed in a template particle dispersion.
In addition, as a covering pigment particle dispersion containing a covering pigment particle (1), you may use the aqueous dispersion containing the covering pigment particle (1) obtained when producing a covering pigment particle (1) as it is. .

-Aggregated particle formation process-
Next, the resin particle dispersion, the coated pigment particle dispersion, and the release agent particle dispersion are mixed.
Then, the resin particles, the coated pigment particles, and the release agent particles, which have a diameter close to the diameter of the toner particles to be targeted, are hetero-aggregated with the resin particles, the coated pigment 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 to a temperature not higher than the glass transition temperature of the resin particles (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 To form agglomerated particles.
In the aggregated particle forming step, for example, the above coagulant is added at room temperature (for example, 25 ° C.) while stirring the mixed dispersion with a rotary shear type homogenizer, and the pH of the mixed dispersion is acidic (for example, pH 2 to 5). The above heating may be carried out after adjusting to (1) and adding a dispersion stabilizer as required.

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 the second aggregated particles, and the step of heating the second aggregated particle dispersion liquid in which the second aggregated particles are dispersed to fuse and unite the second aggregated particles And toner particles may be produced.

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, lyophilization, flash jet drying, fluid drying, vibration-type fluid drying, etc. may be performed.

<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 coating resin and matrix resin, for example, polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic acid copolymer Examples thereof include polymers, straight silicone resins comprising an organosiloxane bond or modified products thereof, fluoro resins, polyesters, polycarbonates, phenol resins, epoxy resins and the like.
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 mixing a core material of a carrier and a solution for forming a coating layer in a kneader coater, and removing a solvent may, for example, 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 that accommodates the electrostatic charge image developer according to the present embodiment and is provided with a developing unit 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. 2 is a schematic configuration view showing an image forming apparatus according to the present embodiment.
The image forming apparatus shown in FIG. 2 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, and has a charge of the same polarity (negative polarity) as the charged charge on the photosensitive member 1Y, and the developer roll (the 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.
Although the image forming apparatus using toners of four colors of yellow, magenta, cyan, and black has been described above, for example, some or all of the image forming units 10Y, 10M, 10C, and 10K Change to an image forming unit using a developer containing a developer, or add an image forming unit using a developer containing a bright toner in addition to the image forming units 10Y, 10M, 10C, and 10K. The image forming apparatus may form an image having glitter.

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 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. 3 is a schematic configuration view showing a process cartridge according to the present embodiment.
The process cartridge 200 shown in FIG. 3 is provided around the photosensitive member 107 (an example of an image carrier) and the photosensitive member 107 by, for example, 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. 3, 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.

  The image forming apparatus shown in FIG. 2 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 are each developing devices (colors 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 invention will be described in more detail based on examples, but the present invention is not limited by the following examples. In addition, unless there is particular notice, all "parts" mean a "mass part."

<Preparation of Coated Pigment Particles (1)>
(Preparation of Coated Pigment Particles (1) -1)
-Preparation of amorphous polyester resin-
-Dimethyl adipate: 74 parts-Dimethyl terephthalate: 192 parts-Bisphenol A ethylene oxide adduct: 216 parts-Ethylene glycol: 38 parts-Tetrabutoxytitanate (catalyst): 0.037 parts A two-necked flask obtained by heating and drying the above components And introduce nitrogen gas into the vessel and keep it in an inert atmosphere, raising temperature while stirring, then carry out co-condensation polymerization reaction at 160 ° C for 7 hours, then raise to 220 ° C while gradually reducing pressure to 10 Torr. Warm and hold for 4 hours. The pressure was once returned to normal pressure, 9 parts of trimellitic anhydride was added, the pressure was gradually reduced again to 10 Torr, and the amorphous polyester resin was synthesized by maintaining the temperature at 220 ° C. for 1 hour.
The glass transition temperature (Tg) of the amorphous polyester resin was 63.5 ° C.

The coated pigment particle (1) -1 was produced using the apparatus 300 shown in FIG.
First, in the tank 310 shown in FIG. 4, 280 parts of the non-crystalline polyester resin produced as described above as a polyester resin, 20 parts of carbon black as a pigment, and resin media (a styrene resin manufactured by Asahi Kasei Chemicals Co., Ltd. Resin modified product): 100 parts are added, two screw type stirtable interface blades 320 are rotated at a stirring rotational speed of 50 rpm, the inside of the tank 310 is heated to 110 ° C. by the jacket 330, and heated for 20 minutes while stirring. The polyester resin and the pigment were kneaded.
At this time, the resin medium is dispersed in the softened mixture while maintaining its shape.
Thereto were added 25 parts of an anionic surfactant (Neogen RK manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and 6 parts of a potassium hydroxide aqueous solution (concentration 5%) as a basic substance.
Then, 700 parts of pure water was gradually added so that the internal temperature of the tank 310 did not fall below 95 ° C.
When the addition was completed, the mixture was emulsified and dispersed to obtain an aqueous dispersion (solid content 33%) containing the coated pigment particles (1) -1.
The coated pigment particles (1) -1 in the obtained aqueous dispersion were measured using Nanotrac UPA manufactured by Nikkiso Co., Ltd., and had a monomodal molecular weight distribution with a volume average particle diameter of 150 nm. .
Moreover, when the coverage of the coating layer in coating pigment particle (1) -1 was confirmed by the above-mentioned method, it was 100%.
Furthermore, when the coated pigment particles (1) -1 were confirmed by the above-mentioned method, it was found that one coated pigment particle contained one pigment.
In addition, the ratio of the coating layer in the coated pigment particle (1) -1: {coating layer / (coating layer + pigment)} × 100 was determined as described above, and was 93% by mass.

(Preparation of Coated Pigment Particles (1) -2)
Coated pigment particles in the same manner as in the preparation of the coated pigment particles (1) -1 except that 249 parts of the amorphous polyester resin as the polyester resin and 150 parts of the cyan cake containing 66% of water as the pigment were used. An aqueous dispersion (34% of solid content) containing (1) -2 was obtained.
The coated pigment particles (1) -2 in the obtained aqueous dispersion were measured using Nanotrac UPA manufactured by Nikkiso Co., Ltd., and had a monomodal molecular weight distribution with a volume average particle diameter of 150 nm. .
Moreover, when the coverage of the coating layer in coating pigment particle (1) -2 was confirmed by the above-mentioned method, it was 100%.
Furthermore, when the coated pigment particles (1) -2 were confirmed by the above-mentioned method, it was found that one coated pigment particle contained one pigment.
In addition, the percentage of the coating layer in the coated pigment particles (1) -2 was determined as follows: {coating layer / (coating layer + pigment)} × 100 as described above, and it was 83 mass%.

(Preparation of Coated Pigment Particles (1) -3)
Non-crystalline polyester resin as polyester resin: using 285 parts, and using carbon black: 15 parts as pigment, in the same manner as in the case of the coated pigment particles (1) -1, water dispersion containing the coated pigment particles (1) -3 A liquid (solid content 33%) was prepared.
It was 150 nm when the volume average particle diameter of coating pigment particle (1) -3 in the obtained water dispersion liquid was measured by the above-mentioned method.
Moreover, when the coverage of the coating layer in coating pigment particle (1) -3 was confirmed by the above-mentioned method, it was 100%.
Furthermore, when the coated pigment particles (1) -3 were confirmed by the above-mentioned method, it was found that one coated pigment particle contained one pigment.
In addition, in the case of the coated pigment particles (1) -3, the ratio of the coated layer in: {coated layer / (coated layer + pigment)} × 100 was determined as described above, and was 96% by mass.

(Preparation of Coated Pigment Particles (1) -4)
Water dispersed including coated pigment particles (1) -4 in the same manner as the coated pigment particles (1) -1 except that 221 parts of amorphous polyester resin is used as the polyester resin and 62 parts of carbon black is used as the pigment A liquid (solid content 33%) was prepared.
It was 150 nm when the volume average particle diameter of coating pigment particle (1) -4 in the obtained water dispersion liquid was measured by the above-mentioned method.
Moreover, it was 94% when the coverage of the coating layer in coating pigment particle (1) -4 was confirmed by the above-mentioned method.
Furthermore, when the coated pigment particles (1) -4 were confirmed by the above-mentioned method, it was found that one coated pigment particle contained one pigment.
In addition, in the coated pigment particles (1) -4, the ratio of the coated layer in: {coated layer / (coated layer + pigment)} × 100 was determined as described above, and was 78% by mass.

(Preparation of Coated Pigment Particles a)
In the same manner as in the case of the coated pigment particle (1) -1, except that 250 parts of polymethyl methacrylate (Mw: 80,000) manufactured by Soken Chemical Co., Ltd. is used instead of polyester resin and 22 parts of carbon black is used as a pigment An aqueous dispersion (solid content 33%) containing coated pigment particles a was prepared.
The volume average particle diameter of the coated pigment particles a in the obtained aqueous dispersion was measured by the method described above, to be 150 nm.
Moreover, when the coverage of the coating layer in coating pigment particle | grain a was confirmed by the above-mentioned method, it was 100%.
Furthermore, when the coated pigment particles a were confirmed by the above-mentioned method, it was found that one coated pigment particle contained one pigment.
In addition, the coated pigment particle a was 92% by mass when the ratio of the coated layer in: {coated layer / (coated layer + pigment)} × 100 was determined as described above.

<Preparation of each dispersion>
(Preparation of Crystalline Polyester Resin Particle Dispersion)
In a heat-dried three-necked flask, 45 mol parts of 1,9-nonanediol, 55 mol parts of dodecanedicarboxylic acid and 0.05 mol parts of dibutyltin oxide as a catalyst are added, and then the air in the container is made nitrogen by pressure reduction operation. The gas was brought into an inert atmosphere and mechanically stirred at 180 ° C. for 2 hours under stirring and reflux. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure, and the mixture was stirred for 5 hours. When it became viscous, air cooling was performed to stop the reaction, and a crystalline polyester resin was synthesized. It was 25,000 when the weight average molecular weight (Mw) of the obtained crystalline polyester resin was measured by gel permeation chromatography (polystyrene conversion). Next, 3,000 parts of the obtained crystalline polyester resin, 10,000 parts of ion-exchanged water, and surfactant sodium dodecylbenzenesulfonate were added to the emulsification tank of a high-temperature, high-pressure emulsification device (Cavitron CD1010, slit: 0.4 mm) After charging 90 parts, heat to melt at 130 ° C., disperse at 110 ° C., flow rate 3 L / m, 10,000 rotation for 30 minutes, and let it pass through a cooling tank to make crystalline polyester resin particle dispersion (high temperature · high pressure The emulsifying device (Cavitron CD1010, slit 0.4 mm, manufactured by Cavitron) was recovered to obtain a liquid crystalline polyester resin particle dispersion (solid content 15%).

(Preparation of Amorphous Polyester Resin Particle Dispersion)
15 moles of polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) propane and 85 moles of polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 10 parts by mole of terephthalic acid, 67 parts by mole of fumaric acid, 3 parts by mole of n-dodecenyl succinic acid, 20 parts by mole of trimellitic acid, and these acid components (terephthalic acid, n-dodecenyl succinic acid, trimellitic acid, 0.05 mol part of dibutyltin oxide is added to the total number of moles of fumaric acid, nitrogen gas is introduced into the vessel and temperature is maintained while maintaining inert atmosphere, then 12 at 150 ° C to 230 ° C. The cocondensation reaction was allowed to proceed for 20 hours from time. Thereafter, the pressure was gradually reduced at 210 ° C. to 250 ° C. to synthesize an amorphous polyester resin. The weight average molecular weight Mw of this resin was 65,000. Next, 3,000 parts of the obtained amorphous polyester resin, 10,000 parts of ion-exchanged water, surfactant dodecylbenzenesulfonic acid, in an emulsification tank of a high-temperature, high-pressure emulsification apparatus (Cavitron CD1010, slit: 0.4 mm) After charging 90 parts of sodium, the mixture is heated and melted at 130 ° C., dispersed at 10,000 rpm at a flow rate of 3 L / m at 110 ° C. for 30 minutes, and allowed to pass through a cooling tank to disperse amorphous polyester resin particles (high temperature A high-pressure emulsification device (Cavitron CD1010, slit 0.4 mm, manufactured by Cavitron) was recovered to obtain a non-crystalline polyester resin particle dispersion (solid content 15%).

(Preparation of Colorant Dispersion)
-Carbon black: 50 parts (Morgal L: Made by Cabot)
-Nonionic surfactant: 5 parts (noni pole 400: Sanyo Chemical Industries, Ltd. product)
Ion-exchanged water: 200 parts or more of the components are mixed, dissolved, dispersed for 10 minutes using a homogenizer (Ultratarax T50: manufactured by IKA), and colorant (carbon black) particles having an average particle diameter of 250 nm. Was prepared (20% solid content).

(Preparation of releasing agent particle dispersion)
Paraffin wax HNP9 (melting temperature 75 ° C: made by Nippon Seikei Co., Ltd.): 46 parts Cationic surfactant Neogen RK (made by Daiichi Kogyo Seiyaku Co., Ltd.): 5 parts Ion exchange water: 200 parts or more The mixture was heated to 100 ° C., sufficiently dispersed with IKA UltraTarax T50, and dispersed with a pressure discharge type Gorin homogenizer to obtain a release agent particle dispersion having a center diameter of 200 nm and a solid content of 20%. .

[Example (1) -1]
[Preparation of Toner Particles (1) -1]
Amorphous polyester resin particle dispersion: 256.8 parts Crystalline polyester resin particle dispersion: 33.2 parts Aqueous dispersion of coated pigment particles (1) -1: 25 parts Release agent particle dispersion 35 parts or more of the components were thoroughly mixed and dispersed in a round stainless steel flask using UltraTurrax T50. Next, 0.20 parts of polyaluminum chloride was added thereto, and the dispersing operation was continued with UltraTurrax. The flask was heated to 48 ° C. while stirring with a heating oil bath. After holding at 48 ° C. for 60 minutes, 70.0 parts of the non-crystalline polyester resin particle dispersion was added thereto. Thereafter, the pH of the system is adjusted to 8.0 with a 0.5 mol / L aqueous sodium hydroxide solution, and then the stainless steel flask is closed and heated to 96 ° C. while continuing stirring using a magnetic seal for 3 hours. I kept it. After completion of the reaction, the reaction solution is cooled, filtered, sufficiently washed with ion exchange water, and subjected to solid-liquid separation by Nutsche suction filtration. This was further dispersed in 1,000 parts of ion-exchanged water at 30 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five times, and when the pH of the filtrate became 7.5 and the electric conductivity became 7.0 μS / cm, No. 4 was filtered by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper. Vacuum drying was then continued for 12 hours.
The particle diameter of the obtained toner particles (1) -1 was measured by Coulter Multisizer II (manufactured by Beckman Coulter, Inc.), and the volume average particle diameter was 6.3 μm. In addition, the shape factor SF1 of the particles obtained from shape observation by Ruzex was 122.

[Example (1) -2]
[Preparation of Toner Particles (1) -2]
Amorphous polyester resin particle dispersion: 256.8 parts Crystalline polyester resin particle dispersion: 33.2 parts Aqueous dispersion of coated pigment particles (1) -2: 35 parts Releasant particle dispersion In a round stainless steel flask, 35 parts or more of the above was sufficiently mixed and dispersed with UltraTurrax T50. Next, 0.20 parts of polyaluminum chloride was added thereto, and the dispersing operation was continued with UltraTurrax. The flask was heated to 48 ° C. while stirring with a heating oil bath. After holding at 48 ° C. for 60 minutes, 70.0 parts of the non-crystalline polyester resin particle dispersion was added thereto. Thereafter, the pH of the system is adjusted to 8.0 with a 0.5 mol / L aqueous sodium hydroxide solution, and then the stainless steel flask is closed and heated to 96 ° C. while continuing stirring using a magnetic seal for 3 hours. I kept it. Thereafter, the same washing and drying process as those of toner particle (1) -1 were carried out to obtain toner particle (1) -2.
The volume average particle diameter of the obtained toner particles (1) -2 was 7.0 μm. In addition, the shape factor SF1 was 125.

[Example (1) -3]
[Preparation of Toner Particles (1) -3]
Amorphous polyester resin particle dispersion: 256.8 parts Crystalline polyester resin particle dispersion: 33.2 parts Aqueous dispersion of coated pigment particles (1) -3: 45 parts Release agent particle dispersion Toner particles (1) -3 were obtained in the same manner as in the preparation of toner particles (1) -1 except that 35 parts or more of the components were used.
The volume average particle diameter of the obtained toner particles (1) -3 was 6.1 μm. In addition, the shape factor SF1 was 127.

[Example (1) -4]
[Preparation of Toner Particles (1) -4]
Amorphous polyester resin particle dispersion: 256.8 parts Crystalline polyester resin particle dispersion: 33.2 parts Aqueous dispersion of coated pigment particles (1) -4: 15 parts Releasant particle dispersion Toner particles (1) -4 were obtained in the same manner as in preparation of toner particles (1) -1 except that 30 parts or more of the components were used.
The volume average particle diameter of the obtained toner particles (1) -4 was 6.3 μm. In addition, the shape factor SF1 was 119.

[Comparative Example (1) -1]
[Preparation of Toner Particles (1) -C1]
Amorphous polyester resin particle dispersion: 256.8 parts Crystalline polyester resin particle dispersion: 33.2 parts Colorant dispersion: 27.4 parts Releasing agent particle dispersion: 35 parts or more The mixture was thoroughly mixed and dispersed with Ultra-Turrax T50 in a stainless steel flask. Next, 0.20 parts of polyaluminum chloride was added thereto, and the dispersing operation was continued with UltraTurrax. The flask was heated to 48 ° C. while stirring with a heating oil bath. After holding at 48 ° C. for 60 minutes, 70.0 parts of the non-crystalline polyester resin particle dispersion was added thereto. Thereafter, the pH of the system is adjusted to 8.0 with a 0.5 mol / L aqueous sodium hydroxide solution, and then the stainless steel flask is closed and heated to 96 ° C. while continuing stirring using a magnetic seal for 3 hours. I kept it. After completion of the reaction, the reaction solution is cooled, filtered, sufficiently washed with ion exchange water, and subjected to solid-liquid separation by Nutsche suction filtration. This was further dispersed in 1,000 parts of ion-exchanged water at 30 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five times, and when the pH of the filtrate became 7.5 and the electric conductivity became 7.0 μS / cm, No. 4 was filtered by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper. Vacuum drying was then continued for 12 hours.
The particle diameter of the obtained toner particles (1) -C1 was measured by Coulter Multisizer II (manufactured by Beckman Coulter, Inc.), and the volume average particle diameter was 5.8 μm. In addition, the shape factor SF1 of the particles obtained from shape observation by Ruzex was 122.

[Comparative example (1) -2]
[Preparation of Toner Particles (1) -C2]
Amorphous polyester resin particle dispersion: 257 parts Crystalline polyester resin particle dispersion: 33 parts Aqueous dispersion of coated pigment particles a: 25 parts Releasing agent particle dispersion: 25 parts Toner particles (1) -C2 were obtained in the same manner as in the preparation of toner particles (1) -1 except that the toner particles were added.
The volume average particle diameter of the obtained toner particles (1) -C2 was 6.0 μm. In addition, the shape factor SF1 was 126.

«Evaluation»
<Measurement of dielectric loss factor>
-Preparation of Toner-
With respect to 50 parts of each toner particle obtained as described above, 1.5 parts of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY 50) and hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) are prepared. It was added to 0 part and mixed for 3 minutes at a peripheral speed of 30 m / s using a Henschel mixer to obtain a toner.

Subsequently, the dielectric loss factor of the obtained toner was measured as follows.
Five parts of the toner particles were pelletized, set between electrodes (SE-71 type solid electrode, manufactured by Ando Electric Co., Ltd.), and measured at 5 V with an LCR meter (type 4274A, manufactured by Yokogawa Hewlett Packard). The dielectric loss factor is determined by the following equation (1).
Dielectric loss factor ε ′ ′ = [14.39 / (W × D ² )] × G _X × T _X × 10 ¹² (1)
Here, W = 2πf (f: measurement frequency 100 kHz), D: electrode diameter (cm) G _x : conductivity (S), T _x : sample thickness (cm).
The measurement results are shown in Table 1.
The smaller the dielectric loss factor, the better, but for practical use it is preferably 0.05 or less.

<Measurement of lightness L *>
[Preparation of developer]
Ferrite particles (average particle size: 50 μm): 100 parts Toluene: 14 parts Styrene-methacrylate copolymer (component ratio (molar ratio): 90/10: Mw = 80000): 2 parts Carbon black (R330: 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 the coating solution and ferrite particles are put into a vacuum degassing type kneader Then, it was stirred at 60 ° C. for 30 minutes. Thereafter, the pressure was reduced while degassing while heating, and the carrier was obtained by drying.

Next, 100 parts of the carrier and 5 parts of each of the above toners were stirred at 40 rpm for 20 minutes using a V-blender, and the developer was obtained by sieving with a sieve having a mesh of 177 μm.
The toner particles contained in the toner used when preparing the developer are shown in Table 1.

[Measurement of lightness L *]
The following operations, image formation, and measurement were performed using the obtained developer. Work, imaging, and measurement were performed under the environment of temperature 25 ° C. and humidity 60% RH.
As an image forming apparatus for forming an evaluation image, DocuCentre Color 400 manufactured by Fuji Xerox Co., Ltd. was prepared, and each developer was placed in the developing device. Using this image forming apparatus, a 5 cm × 5 cm solid image (toning amount: 4.0 g / m ² ) was formed. During image formation, the fixing temperature was 190 ° C., and the fixing pressure was 4.0 kg / m ² . As a recording medium, coated paper (OS coated paper W manufactured by Fuji Xerox Co., Ltd.) having a glossiness of 40% was used.
The lightness of the formed solid image was measured using an X-Rite X-Rite 939. At this time, the lightness L * is expressed as white 100 and black 0. In the case of the black developer, the lightness L * is 15 or less, and in the case of the cyan developer, the lightness L * is 40 or more.
The measurement results are shown in Table 1.

<Preparation of Coated Pigment Particles (2)>
-Preparation of crystalline polyester resin A-
・ 1,9-nonanediol: 47 molar parts ・ dodecanedicarboxylic acid: 53 molar parts ・ dibutyl tin oxide: 0.05 molar parts The above material components are charged into a 3 L reaction vessel, nitrogen gas is enclosed in the vessel, After setting it under an active atmosphere, the temperature was raised to 180 ° C. and stirring was performed for 2 hours. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure, and stirred for 5 hours. When it became viscous, the reaction was stopped by air cooling to terminate the reaction, and a crystalline polyester resin A was synthesized.
The weight average molecular weight (Mw) of this crystalline polyester resin A was 30,000, and its melting temperature (Tm) was 73.degree.

-Preparation of crystalline polyester resin B-
A crystalline polyester resin B was synthesized in the same manner as in the preparation of the crystalline polyester resin A except that 1,6-hexanediol was used instead of 1,9-nonanediol.
The weight average molecular weight (Mw) of this crystalline polyester resin B was 22,000, and the melting temperature (Tm) was 68.degree.

(Preparation of Coated Pigment Particles (2) -1)
Mineral spirit: 380 parts Aluminum pigment (Showa Aluminum Powder Co., Ltd., 2173 EA): 100 parts Crystalline polyester resin A: 20 parts Polymeric surfactant (Kao Corporation, Homogen L-18): 2 Part The above material was charged into a 3 L glass reaction vessel and stirred at 200 rpm, and the entire reaction vessel was heated to 85 ° C. with a water bath and held for 60 minutes until the crystalline resin was completely dissolved. After that, cooling to 40 ° C. at a cooling rate of 0.7 ° C./min while maintaining a suitable stirring state, a crystalline polyester resin is deposited on the surface of the aluminum pigment, and a dispersion of coated pigment particles (2) -1 is obtained. Obtained.
The dispersion is then coarsely removed with a 40 micron nylon screen, the slurry is filtered to remove it as a wet cake, spread on a vat, dried in a vacuum drier at 40 ° C. for 16 hours, and solid coated Pigment particles (2) -1 were obtained.
The volume average particle size of the obtained coated pigment particles (2) -1 was 6 μm.
Moreover, it was 100% when the coverage of the coating layer in coating pigment particle (2) -1 was confirmed by the above-mentioned method.
Furthermore, when the coated pigment particle (2) -1 was confirmed by the above-mentioned method, it was found that one coated pigment particle contained one pigment.
In addition, the proportion of the covering layer in the covering pigment particle (2) -1: {coating layer / (coating layer + pigment)} × 100 was determined as described above, and it was 17% by mass.

(Preparation of Coated Pigment Particles (2) -2)
Solid coated pigment particles (2) -2 are obtained by the same method as the preparation of coated pigment particles (2) -1 except that the amount of the crystalline polyester resin A and the polymeric surfactant is reduced to half respectively. The
The volume average particle size of the obtained coated pigment particles (2) -2 was 6 μm.
Moreover, it was 100% when the coverage of the coating layer in coating pigment particle (2) -2 was confirmed by the above-mentioned method.
Furthermore, when the coated pigment particles (2) -2 were confirmed by the above-mentioned method, it was found that one coated pigment particle contained one pigment.
In addition, the proportion of the covering layer in the covering pigment particle (2) -2: {coating layer / (coating layer + pigment)} × 100 was determined as described above, and it was 9% by mass.

(Preparation of Coated Pigment Particles (2) -3)
Solid coated pigment particles (2) -3 were obtained by the same method as the preparation of coated pigment particles (2) -1 except that crystalline polyester resin B was used instead of crystalline polyester resin A.
The volume average particle size of the obtained coated pigment particles (2) -3 was 6 μm.
Moreover, when the coverage of the coating layer in coating pigment particle (2) -3 was confirmed by the above-mentioned method, it was 100%.
Furthermore, when the coated pigment particles (2) -3 were confirmed by the above-mentioned method, it was found that one coated pigment particle contained one pigment.
In addition, the ratio of the coating layer in the coated pigment particles (2) -3: {coating layer / (coating layer + pigment)} × 100 was determined as described above and was 17% by mass.

(Preparation of Coated Pigment Particles (2) -4)
Preparation of coated pigment particles (2) -1 except using a pearl pigment (Pearl Grays MM-100R manufactured by Nippon Koken Co., Ltd.) instead of the aluminum pigment used for producing coated pigment particles (2) -1 Coated pigment particles (2) -4 were produced in the same manner.
The volume average particle size of the obtained coated pigment particles (2) -4 was 11 μm.
It was 100% when the coverage of the coating layer in coating pigment particle (2) -4 was confirmed by the above-mentioned method.
Furthermore, when the coated pigment particles (2) -4 were confirmed by the above-mentioned method, it was found that one coated pigment particle contained one pigment.
In addition, the proportion of the covering layer in the covering pigment particles (2) -4: {coating layer / (coating layer + pigment)} × 100 was determined as described above, and it was 17% by mass.

(Preparation of Coated Pigment Particles b)
Aluminum pigment (Showa Aluminum Powder Co., Ltd. 2173EA): 100 parts Mineral spirit: 500 parts After removing the solvent from the paste of the aluminum pigment, add the above solvent and stir, temperature is adjusted while flowing nitrogen gas The temperature was raised to 80 ° C. Then, acrylic acid: 1.9 parts, epoxidized polybutadiene: 6.3 parts, trimethylolpropane triacrylate: 7.8 parts, divinylbenzene: 2.8 parts, and azobisisobutyronitrile: 1.2 parts Was added and polymerized at 80 ° C. for 5 hours. Thereafter, the slurry was filtered to take out the cake, and the cake was dried at 150 ° C. for 3 hours to obtain pigment particles (coated pigment particles b) provided with a coating layer with an acrylic resin.
The volume average particle size of the obtained coated pigment particles b was 6 μm.
Moreover, when the coverage of the coating layer in coating pigment particle b was confirmed by the above-mentioned method, it was 100%.
Furthermore, when the coated pigment particles b were confirmed by the above-mentioned method, it was found that one coated pigment particle contained one pigment.
In addition, the ratio of the coated layer in the coated pigment particle b: {coated layer / (coated layer + pigment)} × 100 was determined as described above and was 17% by mass.

<Preparation of each dispersion>
(Preparation of Amorphous Polyester Resin Dispersion)
Polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) propane: 10 molar parts Polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane: 90 Molar part-Terephthalic acid: 30 molar parts-Fumaric acid: 67 molar parts-n-dodecenyl succinic acid: 3 molar parts-Trimellitic acid: 5 molar parts-Dibutyltin oxide: 0.05 molar parts ^* (*: acid component (terephthalate Amount relative to the total number of moles of acid, n-dodecenylsuccinic acid, trimellitic acid and fumaric acid)
The above components are placed in a heat-dried two-necked flask, nitrogen gas is introduced into the vessel, the temperature is maintained under an inert atmosphere, and then cocondensation is allowed to occur at 150 ° C. to 230 ° C. for 12 hours to 20 hours. The pressure was gradually reduced at 210 ° C. to 250 ° C. to synthesize an amorphous polyester resin. The weight average molecular weight Mw of this amorphous polyester resin was 25,000, and the glass transition temperature (Tg) was 71 ° C.
Next, 3,000 parts of the obtained non-crystalline polyester resin, 7,000 parts of ion-exchanged water, surfactant (dodecyl benzene sulfone) in an emulsification tank of a high-temperature, high-pressure emulsification device (Cavitron CD1010, slit: 0.4 mm) After charging 90 parts of sodium acid sodium), the mixture is heated and melted at 130 ° C, dispersed at 10,000 rpm at a flow rate of 3 L / m at 110 ° C, for 30 minutes, and allowed to pass through a cooling tank to disperse amorphous polyester resin particles (High-temperature, high-pressure emulsification device (Cavitron CD1010: slit 0.4 mm) was recovered to obtain a non-crystalline polyester resin particle dispersion (solid content concentration: 30% by weight). The volume average particle diameter of the resin particles in the inside was 160 nm.

(Preparation of releasing agent particle dispersion)
Carnauba wax (Toa Kasei Co., Ltd. RC-160): 50 parts Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd. Neogen RK): 1.0 part Ion-exchanged water: 200 parts The above materials were charged into a pressure vessel and heated to 110 ° C. while stirring, and dispersion treatment equivalent to 10 passes was performed with a high pressure homogenizer to prepare a release agent particle dispersion.

[Example (2) -1]
(Production of Luminescent Toner Particles (2) -1)
-Ion exchange water: 380 parts-Coated pigment particles (2)-1: 20 parts-Amorphous polyester resin particle dispersion: 180 parts-Releasing agent particle dispersion: 30 parts-Anionic surfactant (1st part) Industrial pharmaceuticals Co., Ltd. product Neogen RK): 0.5 parts The above ion-exchange water and the above-mentioned anionic surfactant are placed in a 3 L cylindrical stainless steel container, and the coated pigment particles (2) -1 are added thereto and stirred. After the coated pigment particles (2) -1 were wetted with the above, the remaining materials were added, and dispersed and mixed for 1 minute with a homogenizer (manufactured by IKA, Ultralarux T50). Next, 1.25 parts of a 1% aqueous solution of aluminum sulfate was dropped as a coagulant, and the mixture was dispersed and mixed for 5 minutes to obtain a coagulated slurry.
Then, a stirrer and a thermometer were placed in the container, and while stirring was continued moderately, the heating was gradually performed with a mantle heater and maintained at 45 ° C. for 1 hour. Under the present circumstances, the volume average particle diameter of the aggregation particle | grains measured using Multisizer II was 7.4 micrometers.
Next, 60 parts of non-crystalline polyester resin particle dispersion is added, the temperature is raised to 50 ° C., and the resin particles are attached to the surface of the aggregated particles, the aggregated particles grow to 9.3 μm, and an optical microscope However, it was confirmed that the thickness of the resin coating layer increased.
Thereafter, the pH of the agglomerated particle slurry was adjusted to 8.0, the temperature was raised to 80 ° C., and while maintaining the degree of integration with an optical microscope, it was held for an appropriate time and cooled.
The resulting toner slurry was coarse-grained removed with a nylon mesh, filtered, and cake-washed with ion-exchanged water, and then dried with a vacuum dryer for 12 hours.
The volume average particle diameter of thus obtained glittering toner particles (2) -1 was 10.8 μm.
In addition, the amount of coarse powder which was 30 μm or more was 0.7% by mass with respect to the total amount of the obtained toner particles.

[Example (2) -2]
(Production of Bright Toner Particles (2) -2)
In the same manner as in preparation of glitter toner particles (2) -1, except that coated pigment particles (2) -2 were used instead of coated pigment particles (2) -1, glitter toner particles (2)- I got two.
The volume average particle diameter of the resulting bright toner particles (2) -2 was 11.0 μm.
Further, the amount of coarse powder was 0.5% by mass with respect to the total amount of toner particles obtained.

[Example (2) -3]
(Production of Luminescent Toner Particles (2) -3)
In the same manner as in the preparation of the glitter toner particle (2) -1 except that the coated pigment particle (2) -3 was used instead of the coated pigment particle (2) -1, the glitter toner particle (2)- I got three.
The volume average particle diameter of thus obtained glittering toner particles (2) -3 was 10.8 μm.
Further, the amount of coarse powder was 1.4% by mass with respect to the total amount of toner particles obtained.

Example (2) -4
(Production of Luminescent Toner Particles (2) -4)
In the same manner as in the preparation of the glitter toner particle (2) -1, except that the coated pigment particle (2) -4 is used instead of the coated pigment particle (2) -1, the glitter toner particle (2)- I got four.
The volume average particle diameter of thus obtained glittering toner particles (2) -4 was 20.0 μm.
Further, the amount of coarse powder was 3.3% by mass with respect to the total amount of toner particles obtained.

[Comparative Example (2) -1]
(Preparation of Bright Toner Particles (2) -C1)
A glitter toner particle (2) -C1 was obtained by the same procedure except that the coated pigment particle b was used instead of the coated pigment particle (2) -1 in the preparation of the glitter toner particle (2) -1. .
The volume average particle diameter of the resulting bright toner particles (2) -C1 was 10.5 μm.
The amount of coarse powder was 0.6% by mass based on the total amount of toner particles obtained.
In addition, the filtrate when the toner slurry is filtered is cloudy, and in the coated pigment particles a, the acrylic resin is not properly attached to the surface of the aluminum pigment, and the acrylic resin is peeled from the aluminum pigment. It was guessed that.

[Comparative Example (2) -2]
(Preparation of Bright Toner Particles (2) -C2)
The same procedure as in the preparation of the luster toner particle (2) -1, except that the coated pigment particle b is used instead of the coated pigment particle (2) -1 and the 1% aqueous solution of aluminum sulfate is increased to 2.00 parts Thus, bright toner particles (2) -C2 were obtained.
The volume average particle diameter of the resulting bright toner particles (2) -C2 was 10.9 μm.
Further, the amount of coarse powder was 3.5% by mass with respect to the total amount of the obtained toner particles.
In addition, the cloudiness of the filtrate at the time of filtering toner slurry was not seen equivalent to Example (2) -1-(2) -3.

[Comparative Example (2) -3]
(Preparation of Bright Toner Particles (2) -C3)
[Pigment particles c]
Aluminum pigment (2173EA manufactured by Showa Aluminum Powder Co., Ltd.): 100 parts Anionic surfactant (Neogen R manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 1.5 parts Ion exchange water: 900 parts The above materials are mixed and emulsified and dispersed. The dispersion liquid (10% solid content) of pigment particles c, in which the bright pigment (aluminum pigment) is dispersed, is dispersed for 1 hour using a machine CAVITRON (CR1010 manufactured by Pacific Kiko Co., Ltd.), and then coated pigment Solid pigment particles c were obtained in the same manner as in the preparation of the particles (2) -1.
The same procedure as in the preparation of the bright toner particle (2) -1, except that the pigment particle c is used instead of the coated pigment particle (2) -1, and the aqueous solution of aluminum sulfate is adjusted to 2.5 parts Thus, bright toner particles (2) -C3 were obtained.
The volume average particle diameter of the bright toner particles (2) -C3 was 12.9 μm.
The amount of coarse powder was 3.0% by mass with respect to the total amount of toner particles obtained.
In addition, the cloudiness of the filtrate at the time of filtering toner slurry was not seen equivalent to Example (2) -1-(2) -3.

«Evaluation»
<Measurement of dielectric loss factor>
-Preparation of Toner-
To 100 parts of each toner particle obtained as described above, 1.5 parts of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 1.0 part of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) Using a sample mill, mixed and blended at 10000 rpm for 30 seconds. Thereafter, the resultant was sieved with a vibrating sieve having an opening of 45 μm to obtain a bright toner.

Subsequently, the dielectric loss factor of the resulting bright toner was measured as follows.
5 parts of the glittering toner particles are pellet-molded, set between electrodes [SE-71 type solid electrode, made by Ando Electric Co., Ltd.] and measured at 5 V with an LCR meter (type 4274A, made by Yokogawa Hewlett Packard) did. The dielectric loss factor is determined by the following equation (1).
Dielectric loss factor ε ′ ′ = [14.39 / (W × D ² )] × G _X × T _X × 10 ¹² (1)
Here, W = 2πf (f: measurement frequency 100 kHz), D: electrode diameter (cm) G _x : conductivity (S), T _x : sample thickness (cm).
The measurement results are shown in Table 2.
The smaller the dielectric loss factor, the better. However, practically, in the case of a glitter toner particle, it is preferably 0.007 or less.

<Evaluation of brightness>
[Preparation of developer]
Ferrite particles (volume average particle size: 35 μm): 100 parts Toluene: 14 parts Methyl methacrylate-perfluorooctylethyl acrylate copolymer (critical surface tension: 24 dyn / cm): 1.6 parts Carbon black Name: VXC-72, manufactured by Cabot, volume resistivity: 100 Ωcm or less: 0.12 parts Crosslinked melamine resin particles (average particle size: 0.3 μm, toluene insoluble): 0.3 parts First, methyl methacrylate permeator Carbon black was diluted in toluene and added to a fluorooctylethyl acrylate copolymer and dispersed by a sand mill. Next, the above components other than ferrite particles were dispersed in this with a stirrer for 10 minutes to prepare a coating layer forming solution. Next, the solution for forming a coating layer and ferrite particles are placed in a vacuum degassing type kneader, stirred for 30 minutes at a temperature of 60 ° C., and then depressurized to distill off toluene to form a resin coating layer to obtain a carrier. The

Next, 36 parts of the bright toner and 414 parts of the carrier were placed in a 2 liter V blender, stirred for 20 minutes, and then sieved at 212 μm to prepare a developer.
The toner particles contained in the toner used when producing the developer are shown in Table 2.

[Evaluation of brightness]
The obtained developer was filled in a developer of Docu Center Color 400 manufactured by Fuji Xerox Co., Ltd., and left for 24 hours in an environment of a temperature of 35 ° C. and a humidity of 75%.
Thereafter, a 1 cm × 10 cm solid image (toning amount 4.5 g / m ² ) is prepared on recording paper (OK top coat + paper, manufactured by Oji Paper Co., Ltd.), fixing temperature 190 ° C., fixing pressure One thousand continuous images were formed at 4.0 kg / cm ² and a process speed of 180 mm / s.
With regard to the brightness of the obtained 1000th image, the first image and the brightness were compared and visually confirmed based on the following criteria. The evaluation results are shown in Table 2.
-Evaluation criteria-
G4: There is no difference in the brightness between the 1st and 1000th sheets.
The 1000th sheet is slightly inferior in luminosity to the G3: th sheet.
The 1000th on the G2: 1st sheet is somewhat inferior in brilliance or darkness can be confirmed, but is within the allowable range.
The 1000th sheet is inferior in luminosity to the G1: 1st sheet, or dark and unacceptable.

1Y, 1M, 1C, 1K photoconductors (an example of an image carrier)
2Y, 2M, 2C, 2K charging rolls (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 101 Bright Toner Particles 102 Coated Pigment Particles (2)
107 Photosensitive body (an example of an 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 118 Opening 117 for exposure Case 200 Process cartridge 300 Recording paper (an example of recording medium)
P recording paper (an example of recording medium)

Claims (6)

A bright pigment, coated pigment particles having a coating layer containing a crystalline polyester resin provided on the surface of the bright pigment, and, seen including a binder resin containing a amorphous polyester resin,
The ratio of the covering layer in the covering pigment particles: {coating layer / (coating layer + brightness pigment)} × 100 is 5% by mass or more and 30% by mass or less . An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 1 . A toner for electrostatic image development according to claim 1 is accommodated.
A toner cartridge that is attached to and removed from the image forming apparatus. And a developing unit for containing the electrostatic charge image developer according to claim 2 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;
3. A developing unit for containing the electrostatic charge image developer according to claim 2, 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 2 ;
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: