JP2017062410A - Photoluminescent toner, electrostatic charge image developer, toner cartridge, process cartridge, image forming apparatus, and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoluminescent toner that provides high photoluminescence to an image, and suppresses a phenomenon (fogging) where a toner scatters from an image part to a non-image part when a toner image with high image height is transferred to a recording medium in a high-temperature and high-humidity environment.SOLUTION: There is provided a photoluminescent toner comprising toner particles including a binder resin and a flat photoluminescent pigment, where the binder resin has a ratio of the weight average molecular weight (Mw) to the peak top molecular weight (Mp) (Mw/Mp) of 1.2 or more and 2.5 or less, and a value of the peak top molecular weight (Mp) of 3000 or more and 10000 or less.SELECTED DRAWING: None

Description

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

  In recent years, the use of glitter toner containing a glitter pigment has been studied for the purpose of forming an image having a brightness such as metallic luster.

  As such a glittering toner, for example, Patent Document 1 discloses that a binder resin having an acid value of less than 10 mgKOH / g and / or a precursor thereof (H And a toner composition solution dissolved or dispersed in the organic solvent containing at least a polyester polymer (L) having an acid value of 20 mgKOH / g or more and 50 mgKOH / g or less, which is hardly soluble in an organic solvent, and a metallic metallic pigment, A toner having base particles formed by at least emulsifying or dispersing and converging in an aqueous medium in which fine particles are dispersed, the base particles having an acid value of 20 mg KOH which is hardly soluble in an organic solvent containing a metal pigment The binder resin (H) having an acid value of less than 10 mgKOH / g, wherein the domain of the polyester-based polymer (L) having an acid value of less than or equal to 50 mgKOH / g is soluble in an organic solvent. Electrophotographic toners ", characterized by being dispersed in the matrix have been disclosed.

JP 2013-57906 A

  An object of the present invention is to provide a ratio of the weight average molecular weight (Mw) to the peak top molecular weight (Mp) of the binder resin (Mw / Mp) in a bright toner having toner particles containing a binder resin and a flat bright pigment. Mp) is less than 1.2 or more than 2.5, or higher peak high molecular weight (Mp) than the case where the value of the peak top molecular weight (Mp) of the binder resin is less than 3000 or more than 10,000, while obtaining high image brightness. An object of the present invention is to provide a glittering toner that suppresses a phenomenon (fogging) in which toner is scattered from an image portion to a non-image portion when a toner image having a high image height is transferred to a recording medium under an environment.

  The above problem is solved by the following means.

The invention according to claim 1
The ratio (Mw / Mp) to the peak top molecular weight (Mp) in the weight average molecular weight (Mw) is 1.2 or more and 2.5 or less, and the peak top molecular weight (Mp) value is 3000 or more and 10,000 or less. A resin ring,
A flat luster pigment,
A glittering toner having toner particles containing.

The invention according to claim 2
The glitter toner according to claim 1, wherein the toner particles include a polyester resin as the binder resin.

The invention according to claim 3
The glittering toner according to claim 1, wherein the toner particles include a crystalline polyester resin as the binder resin.

The invention according to claim 4
The glitter toner according to any one of claims 1 to 3, wherein the toner particles contain a urea-modified polyester resin as the binder resin.

The invention according to claim 5
An oil phase liquid adjusting step of adjusting an oil phase liquid, wherein the toner particles are a mixed liquid obtained by mixing the organic solvent that dissolves the binder resin, the binder resin, and the glitter pigment; The suspension obtained by dispersing in a medium to adjust the suspension, and the solvent removal step of removing the organic solvent from the suspension are obtained. The glitter toner according to any one of the items.

The invention according to claim 6
An electrostatic charge image developer comprising the glitter toner according to claim 1.

The invention according to claim 7 provides:
Containing the glitter toner according to any one of claims 1 to 5,
The toner cartridge is detachable from the image forming apparatus.

The invention according to claim 8 provides:
A developing means for containing the electrostatic charge image developer according to claim 6 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer,
It is a process cartridge that can be attached to and detached from the image forming apparatus.

The invention according to claim 9 is:
An image carrier,
Charging means for charging the surface of the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
Developing means for containing the electrostatic charge image developer according to claim 6 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer;
Transfer means for transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
Fixing means for fixing the toner image transferred to the surface of the recording medium;
An image forming apparatus.

The invention according to claim 10 is:
A charging step for charging the surface of the image carrier;
An electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged image carrier;
A developing step of developing an electrostatic charge image formed on the surface of the image carrier as a toner image with the electrostatic charge image developer according to claim 6;
A transfer step of transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
A fixing step of fixing the toner image transferred to the surface of the recording medium;
Is an image forming method.

  According to the invention of claim 1, in the glitter toner having toner particles including the binder resin and the flat glitter pigment, the peak top molecular weight (Mp) in the weight average molecular weight (Mw) of the binder resin. When the ratio (Mw / Mp) is less than 1.2 or more than 2.5, or when the value of the peak top molecular weight (Mp) of the binder resin is less than 3000 or more than 10,000, high image brightness is obtained. A glittering toner that suppresses a phenomenon (fogging) of toner scattering from an image portion to a non-image portion when a toner image having a high image height is transferred to a recording medium in a high temperature and high humidity environment is provided.

  According to the second aspect of the present invention, compared with the case where the toner particles contain only a styrene acrylic resin as the binder resin, the toner having a high image height in a high-temperature and high-humidity environment while obtaining higher image brightness. A glittering toner that suppresses the phenomenon (fogging) of toner scattering from an image area to a non-image area when an image is transferred to a recording medium is provided.

  According to the invention of claim 3, compared to the case where the toner particles contain only amorphous polyester resin as a binder resin, a toner image having a high image height is transferred to a recording medium in a high temperature and high humidity environment. A glittering toner that suppresses a phenomenon (fogging) in which toner is scattered from an image portion to a non-image portion during the process is provided.

  According to the fourth aspect of the invention, compared to the case where the toner particles contain only unmodified polyester resin as the binder resin, images having low image density were continuously formed while obtaining high image glitter. There is provided a glittering toner that suppresses a phenomenon (fogging) in which toner is scattered from an image portion to a non-image portion when a toner image having a high image height is subsequently transferred to a recording medium in a high temperature and high humidity environment.

  According to the invention of claim 5, the oil phase liquid for adjusting the oil phase liquid in which the toner particles are a mixed liquid obtained by mixing the organic solvent that dissolves the binder resin, the binder resin, and the glitter pigment. It was obtained through an adjustment step, a suspension adjustment step of dispersing an oil phase liquid in an aqueous medium to adjust a suspension, and a solvent removal step of removing the organic solvent from the suspension. In a bright toner having toner particles containing a binder resin and a flat glitter pigment, the ratio (Mw / Mp) of the binder resin to the peak top molecular weight (Mp) in the weight average molecular weight (Mw) is 1. .2 or more than 2.5, or when the peak top molecular weight (Mp) value of the binder resin is less than 3000 or more than 10,000, while obtaining high image brightness, the image is obtained in a high temperature and high humidity environment. Tall tona From the image section to the non-image portion suppresses brilliant toner phenomenon (fogging) of the toner is scattered is provided when transferring an image on a recording medium.

  According to the invention according to claim 6, 7, 8, 9, or 10, in the glitter toner having toner particles including the binder resin and the flat glitter pigment, the weight average molecular weight (Mw) of the binder resin. ) A glossy toner having a ratio (Mw / Mp) to a peak top molecular weight (Mp) of less than 1.2 or more than 2.5, or a peak top molecular weight (Mp) value of a binder resin of less than 3000 or more than 10,000 Compared to the case where glitter toner is applied, the toner scatters from the image area to the non-image area when a toner image having a high image height is transferred to a recording medium in a high temperature and high humidity environment while obtaining high image glitter. An electrostatic charge image developer, toner cartridge, process cartridge, image forming apparatus, or image forming method for suppressing a phenomenon (fogging) is provided.

FIG. 3 is a cross-sectional view schematically illustrating an example of toner particles according to the exemplary embodiment. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to an exemplary embodiment. It is a schematic block diagram which shows an example of the process cartridge which concerns on this embodiment.

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

<Brightness toner>
The glitter toner according to the exemplary embodiment (hereinafter may be referred to as “toner”) is a ratio (hereinafter referred to as “ratio”) of a weight average molecular weight (hereinafter also referred to as “Mw”) to a peak top molecular weight (hereinafter also referred to as “Mp”). Mw / Mp) ”) is 1.2 or more and 2.5 or less, and Mp value is 3000 or more and 10,000 or less, and toner particles containing a flat glitter pigment Have.

  The toner according to the present exemplary embodiment has an image height (hereinafter referred to as “pile height”) in an environment of high temperature and high humidity (for example, a temperature of 28 ° C. or higher and a humidity of 85% or higher) while obtaining high image brightness with the above configuration. ), A phenomenon (fogging) in which toner scatters from an image portion to a non-image portion when a toner image having a high toner density is transferred to a recording medium. The reason is presumed as follows.

  When a color metallic image is formed by combining glitter toner and color toner, for example, a toner image of glitter toner and a toner image of color toner are formed on an intermediate transfer member in an overlapping manner to form a toner image having a high pile height. obtain. When the toner image having a high pile height is transferred from the intermediate transfer member to the recording medium in a high temperature and high humidity environment, the toner in the image area scatters to the non-image area, resulting in image defects such as fogging. There is a case.

The reason for the occurrence of the fogging is considered to be the presence of toner particles of glittering toner having reduced chargeability.
The glitter toner includes a pigment having high conductivity such as a metal pigment as the glitter pigment, and therefore the electrification property tends to be lower than that of a normal color toner. In particular, the toner particles of the glitter toner have a flat glitter pigment encapsulated in the binder resin, so the toner particles themselves are also flat, and when the mechanical load is applied, The toner particles exposed to the surface are likely to be generated. When the glitter pigment is exposed on the surface of the toner particles, the chargeability of the toner particles is greatly reduced.

When the glossy toner whose chargeability of the toner particles is greatly reduced as described above and a toner image having a high pile height is formed on an intermediate transfer member and transferred to a recording medium, the fog is likely to occur.
Specifically, for example, when a color metallic image is obtained by fixing a toner image laminated in the order of colored toner and glitter toner from the recording medium side to the recording medium, the toner image formed on the intermediate transfer member is: The glitter toner and the color toner are laminated in this order from the intermediate transfer member side. At this time, if the toner image of the glitter toner contains toner particles having a significantly reduced chargeability, not only the toner particles themselves of the glitter toner having a decreased chargeability, but also the colored toner laminated on the glitter toner. The toner particles are also scattered and fogging is likely to occur.

On the other hand, in this embodiment, the value of Mp is 3000 or more and 10,000 or less, and the value of the ratio (Mw / Mp) is 1.2 or more and 2.5 or less. Therefore, compared with the case where the value of ratio (Mw / Mp) is smaller than the said range, there are few components with a molecular weight smaller than a peak top molecular weight.
When there are few low molecular weight components (components with low molecular weight), the mechanical strength is higher than when there are many low molecular weight components, and exposure of the glittering pigment due to mechanical load is unlikely to occur.
Further, for example, in the case of toner particles obtained by granulating after the binder resin is dissolved in an organic solvent, if the low molecular weight component is small, the viscosity of the resin solution in which the binder resin is dissolved in the organic solvent is unlikely to decrease. . Therefore, compared to the case where the viscosity of the resin solution is too low, the resin solution easily takes in the bright pigment during granulation, the resin layer is not too thin, and toner particles with the bright pigment exposed are less likely to be generated.

  As described above, in the present embodiment, since the number of toner particles to which the glitter pigment is exposed is small, it is presumed that the fogging caused by the toner particles having greatly reduced chargeability is suppressed.

Moreover, in this embodiment, since the value of Mp is 3000 or more and 10,000 or less, and the value of ratio (Mw / Mp) is 1.2 or more and 2.5 or less, the value of ratio (Mw / Mp) is the said value. Compared to a case where the molecular weight is larger than the range, there are few components having a molecular weight larger than the peak top molecular weight.
In this embodiment, since the high molecular weight component contained in the binder resin is small, the binder resin is easily melted even when an image having a high pile height is fixed, and the glitter pigment is oriented in a state almost parallel to the recording medium. Therefore, it is easy to obtain high image brightness.

  In addition, for example, in the case of toner particles obtained by granulation after dissolving the binder resin in an organic solvent, since the high molecular weight component contained in the binder resin is small, compared to the case where the high molecular weight component is large, The viscosity of the resin solution in which the binder resin is dissolved in the organic solvent is not easily increased. If the viscosity of the resin solution becomes too high, it becomes easier for the resin solution to incorporate many glitter pigment particles at the time of granulation, but in this embodiment, toner particles in which a plurality of glitter pigment particles are incorporated together. Is difficult to generate. When a toner image having a high pile height is formed and fixed on the recording medium, the plurality of glitter pigments in the toner particles are aligned with each other, as in the case where one toner particle includes a plurality of glitter pigment particles. It is presumed that high glitter can be obtained because it is difficult to prevent interference.

In this embodiment, since the value of Mp is in the above range, the binder resin is easily melted and the glitter pigment is easily oriented even when an image having a high pile height is fixed as compared with the case where the value is larger than the above range. Therefore, it is estimated that high image brightness can be obtained.
Further, in this embodiment, since the value of Mp is in the above range, the low molecular weight component contained in the binder resin is less than that in the case where the value is smaller than the above range. It is estimated that toner scattering (fogging) due to the reduction is suppressed.

  As described above, the toner according to the present embodiment has the above-described configuration to obtain a high image brightness and to transfer a toner image having a high image height to a recording medium in a high-temperature and high-humidity environment. It is estimated that the phenomenon (fogging) in which toner is scattered is suppressed.

  The Mw and Mp of the binder resin are measured by gel permeation chromatography (GPC). The molecular weight measurement by GPC is performed using a Tosoh GPC / HLC-8120GPC as a measuring device, using two Tosoh columns / TSKgel SuperHM-H (6.0 mmID × 15 cm), and a tetrahydrofuran (THF) solvent. Specifically, a solution obtained by mixing a toner and a solvent to dissolve the toner in a solvent (tetrahydrofuran) and removing components insoluble in the solvent is used as a measurement sample. As other measurement conditions, the sample concentration is 0.5 mass%, the flow rate is 0.6 ml / min, the sample injection amount is 10 μl, the measurement temperature is 40 ° C., and the RI detector is used. The calibration curve is “polystylen standard sample TSK standard” manufactured by Tosoh Corporation: “A-500”, “F-1”, “F-10”, “F-80”, “F-380”, “A-2500”. ”,“ F-4 ”,“ F-40 ”,“ F-128 ”, and“ F-700 ”.

When the binder resin includes a plurality of resins, the Mw and Mp of the binder resin are Mw and Mp calculated from the molecular weight distribution in the plurality of resins as a whole.
The Mp of the binder resin is 3000 or more and 10,000 or less, preferably 4000 or more and 7000 or less, and more preferably 5000 or more and 6000 or less.
The ratio (Mw / Mp) of the binder resin is 1.2 or more and 2.5 or less, preferably 1.2 or more and 2.0 or less, and more preferably 1.2 or more and 1.5 or less.
The Mw of the binder resin is not particularly limited as long as the ratio (Mw / Mp) is in the above range, but for example, 3600 to 25000 is mentioned, 4600 to 20000 is preferred, and 5600 to 15000 is more preferred.

As a method for controlling the ratio (Mw / Mp) and Mp of the binder resin within the above ranges, for example, addition amounts of monomers, additives, solvents, etc. used in the synthesis of the resin, and synthesis conditions (temperature, time, etc.) ).
In particular, when the binder resin includes “a urea-modified polyester resin obtained by a reaction between an isocyanate group-containing polyester prepolymer and an amine compound” described later, for example, the mixing ratio of the urea-modified polyester resin and the other resin By adjusting the ratio of the isocyanate group of the polyester prepolymer and the amino group of the amine compound used for the synthesis of the urea-modified polyester resin, adjusting the reaction time of the polyester prepolymer and the amine compound, the ratio of the binder resin (Mw / Mp) and Mp may be controlled.

Here, “brightness” in the toner according to the present embodiment indicates that the image formed with the bright toner has a brightness such as a metallic luster when visually recognized.
Specifically, when a solid image is formed, the toner according to the exemplary embodiment has a light receiving angle of + 30 ° measured when incident light having an incident angle of −45 ° is irradiated to the image by a goniophotometer. It is preferable that the ratio (X / Y) of the reflectance X at the light receiving angle and the reflectance Y at the light receiving angle of −30 ° is 2 or more and 100 or less.

A ratio (X / Y) of 2 or more indicates that there is more reflection on the side opposite to the incident side (angle + side) than on the side on which incident light enters (angle-side). That is, the irregular reflection of the incident light is suppressed. When irregular reflection occurs in which incident light is reflected in various directions, the color looks dull when the reflected light is visually confirmed. Therefore, when the ratio (X / Y) is less than 2, gloss may not be confirmed even when the reflected light is viewed, and the glitter may be inferior.
On the other hand, if the ratio (X / Y) exceeds 100, the viewing angle at which the reflected light can be visually recognized becomes too narrow, and the specularly reflected light component is large, so that it may appear black depending on the viewing angle. Further, a toner having a ratio (X / Y) exceeding 100 is difficult to manufacture.

  The ratio (X / Y) is more preferably 4 or more and 50 or less, further preferably 6 or more and 20 or less, and more preferably 8 or more and 15 or less from the viewpoint of glitter and toner productivity. It is particularly preferred.

-Measurement of ratio (X / Y) with goniophotometer-
Here, the incident angle and the light receiving angle will be described first. In this embodiment, when measuring with a goniophotometer, the incident angle is set to −45 ° because the measurement sensitivity is high for an image in a wide range of glossiness.
The reason why the light receiving angles are set to −30 ° and + 30 ° is that the measurement sensitivity is highest in evaluating an image having a glitter feeling and an image having no glitter feeling.

Next, a method for measuring the ratio (X / Y) will be described.
Incident light with an incident angle of −45 ° is incident on the image (glossy image) to be measured using a spectroscopic variable angle color difference meter GC5000L manufactured by Nippon Denshoku Industries Co., Ltd. as a variable angle photometer. Then, the reflectance X at the light receiving angle + 30 ° and the reflectance Y at the light receiving angle −30 ° are measured. Note that the reflectance X and the reflectance Y were measured at intervals of 20 nm for light having a wavelength in the range of 400 nm to 700 nm, and the average value of the reflectance at each wavelength was obtained. The ratio (X / Y) is calculated from these measurement results.

The toner according to the exemplary embodiment preferably satisfies the following requirements (1) to (2) from the viewpoint of satisfying the ratio (X / Y).
(1) The average equivalent circle diameter D is longer than the average maximum thickness C of the toner particles.
(2) When the cross section in the thickness direction of the toner particles is observed, the brightness in which the angle between the long axis direction of the toner particles and the long axis direction of the glitter pigment is in the range of −30 ° to + 30 °. The proportion of the luminescent pigment is 60% or more of the total bright pigment observed.

If the toner particles have a flat shape with a circle-equivalent diameter longer than the thickness (see FIG. 1), the flat surface of the toner particles is flat on the surface of the recording medium due to pressure during fixing in the image forming fixing process. It is thought that they are lined up to face each other. In FIG. 1, 2 denotes toner particles, 4 denotes a bright pigment, and L denotes the thickness of the toner particles.
Therefore, among the flat (scale-like) bright pigments contained in the toner particles, “the angle between the major axis direction in the cross section of the toner particles and the major axis direction of the bright pigment is shown in (2) above”. Is considered to be lined up so that the surface side having the maximum area faces the recording medium surface. When the image formed in this way is irradiated with light, the ratio of the glitter pigment that diffusely reflects the incident light is suppressed, so that the range of the ratio (X / Y) described above is achieved. It is done.

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

  The toner according to this embodiment has toner particles. The toner may have an external additive externally added to the toner particles as necessary.

(Toner particles)
The toner particles include a binder resin and a flat glitter pigment. The toner particles may contain a release agent and other additives as necessary.

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

A polyester resin is suitable as the binder resin.
Examples of the polyester resin include known amorphous polyester resins. A polyester resin may use a crystalline polyester resin together with an amorphous polyester resin. However, the crystalline polyester resin is preferably used in the range of 2 mass% to 40 mass% (preferably 2 mass% to 20 mass%) with respect to the total binder resin.

When a polyester resin is included in the toner particles as a binder resin, a high image brightness can be obtained, and a high image height toner image can be transferred from the image area to the non-image area in a high temperature and high humidity environment. Suppresses the phenomenon of toner scattering (fogging). The reason is presumed as follows.
Specifically, since the ester bonds of the polyester resin easily form hydrogen bonds, the cohesive force between the toner particles is increased, and toner scattering is less likely to occur. In addition, since the binder resin easily melts at the fixing temperature of the polyester resin, it is easy to obtain a fixed image in which the glitter pigment is oriented almost parallel to the recording medium, and high image glitter is obtained.

When crystalline polyester resin is included in the toner particles as a binder resin, the toner scatters from the image area to the non-image area when a high-height image is transferred to a recording medium in a high-temperature and high-humidity environment. (Fogging) is suppressed. The reason is presumed as follows.
Specifically, in the case of toner particles obtained by granulating after the binder resin is dissolved in an organic solvent, if the binder resin contains a crystalline polyester resin, the resin in which the binder resin is dissolved in the organic solvent The viscosity of the solution decreases, and the application of shearing force by stirring during granulation becomes nearly uniform. For this reason, the method of taking up the particles of the glitter pigment by the resin solution is also almost uniform, and the difference in charge amount between the toner particles is reduced, so that toner scattering (fogging) is suppressed.

The “crystallinity” of the resin means that it has a clear endothermic peak in differential scanning calorimetry (DSC) rather than a stepwise endothermic amount change. Specifically, the temperature rise rate is 10 (° C. / Min) indicates that the half-value width of the endothermic peak is 10 ° C. or less.
On the other hand, “amorphous” of the resin means that the half width exceeds 10 ° C., shows a stepwise endothermic change, or does not show a clear endothermic peak.

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

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

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

The glass transition temperature (Tg) of the amorphous polyester resin is preferably 50 ° C. or higher and 80 ° C. or lower, and more preferably 50 ° C. or higher and 65 ° C. or lower.
The glass transition temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC), and more specifically described in the method for determining the glass transition temperature in JIS K 7121-1987 “Method for Measuring Plastic Transition Temperature”. Of “extrapolated glass transition start temperature”.

The weight average molecular weight Mw of the amorphous polyester resin is preferably 4600 or more and 20000 or less, and more preferably 5600 or more and 15000 or less.
The peak top molecular weight Mp of the amorphous polyester resin is preferably 4000 or more and 7000 or less, and more preferably 5000 or more and 6000 or less.
The number average molecular weight Mn of the amorphous polyester resin is preferably 2000 or more and 5000 or less, and more preferably 2500 or more and 4000 or less.

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

Crystalline polyester resin Examples of the crystalline polyester resin include a polycondensate of a polyvalent carboxylic acid and a polyhydric alcohol. In addition, as a crystalline polyester resin, a commercial item may be used and what was synthesize | combined may be used.
Here, since the crystalline polyester resin easily forms a crystal structure, a polycondensate using a polymerizable monomer having a linear aliphatic group is preferable to a polymerizable monomer having an aromatic group.

Examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids (for example, oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid. Acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, etc.), aromatic dicarboxylic acid (eg phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid) Dibasic acids such as acids), anhydrides thereof, or lower (for example, having 1 to 5 carbon atoms) alkyl esters.
The polyvalent carboxylic acid may be used in combination with a dicarboxylic acid or a trivalent or higher carboxylic acid having a crosslinked structure or a branched structure. Examples of the trivalent carboxylic acid include aromatic carboxylic acids (for example, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, etc.), these Examples thereof include anhydrides and lower (for example, having 1 to 5 carbon atoms) alkyl esters thereof.
As the polyvalent carboxylic acid, a dicarboxylic acid having a sulfonic acid group or a dicarboxylic acid having an ethylenic double bond may be used in combination with these dicarboxylic acids.
Polyvalent carboxylic acid may be used individually by 1 type, and may use 2 or more types together.

Examples of the polyhydric alcohol include aliphatic diols (for example, linear aliphatic diols having a main chain portion having 7 to 20 carbon atoms). Examples of the aliphatic diol 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-eicosandecanediol. Among these, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol are preferable as the aliphatic diol.
The polyhydric alcohol may be used in combination with a diol and a trivalent or higher alcohol having a crosslinked structure or a branched structure. Examples of the trivalent or higher alcohol 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, the polyhydric alcohol may have an aliphatic diol content of 80 mol% or more, and preferably 90 mol% or more.

The melting temperature of the crystalline polyester resin is preferably 50 ° C. or higher and 100 ° C. or lower, more preferably 55 ° C. or higher and 90 ° C. or lower, and further preferably 60 ° C. or higher and 85 ° C. or lower.
The melting temperature is determined from the “melting peak temperature” described in the method for determining the melting temperature of JIS K7121-1987 “Method for measuring the transition temperature of plastic” from the DSC curve obtained by differential scanning calorimetry (DSC).

The weight average molecular weight Mw of the crystalline polyester resin is preferably 15000 or more and 40000 or less, and more preferably 20000 or more and 30000 or less.
The peak top molecular weight Mp of the crystalline polyester resin is preferably 15000 or more and 40000 or less, and more preferably 20000 or more and 30000 or less.
The number average molecular weight Mn of the crystalline polyester resin is preferably 3000 or more and 20000 or less, and more preferably 5000 or more and 15000 or less.

  The crystalline polyester resin can be obtained by, for example, a well-known manufacturing method, similarly to the amorphous polyester resin.

  Here, examples of the polyester resin include modified polyester resins in addition to the above-described unmodified polyester resins. The modified polyester resin is a polyester resin in which a bonding group other than an ester bond is present, or a polyester resin in which a resin component different from the polyester resin component is bonded by a covalent bond or an ionic bond. Examples of the modified polyester include a resin in which a functional group such as an isocyanate group that reacts with an acid group or a hydroxyl group is introduced at the terminal, and a resin in which the terminal is modified by reacting with an active hydrogen compound.

  As the modified polyester resin, a urea-modified polyester resin is particularly preferable. By using a resin containing a urea-modified polyester resin as a binder resin and having a ratio (Mw / Mp) and Mp within the above ranges, a low image density (for example, an image density of 5) is obtained while obtaining high image brightness. % Or less), when toner images with a high image height are transferred to a recording medium in a high-temperature and high-humidity environment, the toner scatters from the image area to the non-image area (fogging). Suppress. This is because the inclusion of the urea-modified polyester resin increases the elasticity of the toner particles, and is considered to suppress the exposure of the glitter pigment due to the stress on the toner when images with low image density are continuously formed. It is. In this respect, the content of the urea-modified polyester resin is preferably 5% by mass or more and 50% by mass or less, and more preferably 8% by mass or more and 50% by mass or less with respect to the total binder resin.

  The urea-modified polyester resin is preferably a urea-modified polyester resin obtained by a reaction between a polyester resin having an isocyanate group (polyester prepolymer) and an amine compound (at least one of a crosslinking reaction and an extension reaction). Note that the urea-modified polyester resin may contain a urethane bond together with a urea bond.

  Examples of the polyester prepolymer having an isocyanate group include a polyester which is a polycondensate of a polyvalent carboxylic acid and a polyhydric alcohol, and a prepolymer obtained by reacting a polyvalent isocyanate compound with a polyester having active hydrogen. . Examples of the group having active hydrogen in the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like, and alcoholic hydroxyl groups are preferable.

  In the polyester prepolymer having an isocyanate group, examples of the polyvalent carboxylic acid and polyhydric alcohol include the same compounds as the polyvalent carboxylic acid and polyhydric alcohol described in the polyester resin.

Examples of the polyvalent isocyanate compound include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; the polyisocyanates such as phenol derivatives, oximes, caprolactam What blocked with the blocking agent is mentioned.
A polyvalent isocyanate compound may be used individually by 1 type, and may use 2 or more types together.

  The ratio of the polyvalent isocyanate compound is preferably 1/1 or more and 5/1 or less as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester prepolymer having a hydroxyl group. Preferably it is 1.2 / 1 or more and 4/1 or less, More preferably, it is 1.5 / 1 or more and 2.5 / 1 or less. When [NCO] / [OH] is set to 1/1 or more and 5/1 or less, the exposure of the glitter pigment is suppressed, and the fog accompanying the decrease in the charging property of the glitter toner is easily suppressed. In addition, when [NCO] / [OH] is 5/1 or less, a decrease in low-temperature fixability is easily suppressed.

  In the polyester prepolymer having an isocyanate group, the content of the component derived from the polyvalent isocyanate compound is preferably 0.5% by mass or more and 40% by mass or less, more preferably, based on the entire polyester prepolymer having an isocyanate group. 1 mass% or more and 30 mass% or less, More preferably, they are 2 mass% or more and 20 mass% or less. When the content of the component derived from the polyvalent isocyanate is 0.5% by mass or more and 40% by mass or less, the exposure of the glitter pigment is suppressed, and the fog accompanying the decrease in the charging property of the glitter toner is easily suppressed. Note that when the content of the component derived from the polyvalent isocyanate is 40% by mass or less, a decrease in low-temperature fixability is easily suppressed.

  The number of isocyanate groups contained per molecule of the polyester prepolymer having an isocyanate group is preferably 1 or more on average, more preferably 1.5 or more and 3 or less, and even more preferably 1.8 or more on average. .5 or less. When the number of isocyanate groups is 1 or more per molecule, the molecular weight of the urea-modified polyester resin after the reaction is increased, the exposure of the glitter pigment is suppressed, and the fog accompanying the decrease in the charging property of the glitter toner is easily suppressed. .

  Examples of the amine compound that reacts with the polyester prepolymer having an isocyanate group include diamine, trivalent or higher polyamine, amino alcohol, amino mercaptan, amino acid, and compounds in which these amino groups are blocked.

Examples of the diamine include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, isophoronediamine, etc. ); And aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.) and the like.
Examples of the trivalent or higher polyamine include diethylenetriamine and triethylenetetramine.
Examples of amino alcohols include ethanolamine and hydroxyethylaniline.
Examples of amino mercaptans include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of amino acids include aminopropionic acid and aminocaproic acid.
These amino group-blocked ones include ketimine compounds obtained from amine compounds such as diamines, trivalent or higher polyamines, amino alcohols, amino mercaptans, amino acids and ketone compounds (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), Examples include oxazoline compounds.
Of these amine compounds, ketimine compounds are preferred.
An amine compound may be used individually by 1 type, and may use 2 or more types together.

Note that the urea-modified polyester resin is a polyester resin having an isocyanate group (polyester prepolymer) by a stopper that stops at least one of a crosslinking reaction and an extension reaction (hereinafter also referred to as “crosslinking / extension reaction stopper”). It may be a resin in which the molecular weight after the reaction is adjusted by adjusting the reaction with the amine compound (at least one of a crosslinking reaction and an extension reaction).
Examples of the crosslinking / elongation reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those blocked (ketimine compounds).

  The ratio of the amine compound is preferably 1/2 or more and 2 as an equivalent ratio [NCO] / [NHx] of the isocyanate group [NCO] in the polyester prepolymer having an isocyanate group and the amino group [NHx] in the amines. / 1 or less, more preferably from 1 / 1.5 to 1.5 / 1, and even more preferably from 1 / 1.2 to 1.2 / 1. When [NCO] / [NHx] is within the above range, the molecular weight of the urea-modified polyester resin after the reaction is increased, exposure of the glitter pigment is suppressed, and fog associated with a decrease in chargeability of the glitter toner is easily suppressed.

  The glass transition temperature of the urea-modified polyester resin is preferably 40 ° C. or higher and 65 ° C. or lower, and more preferably 45 ° C. or higher and 60 ° C. or lower. The number average molecular weight is preferably 2500 or more and 50000 or less, and more preferably 2500 or more and 30000 or less. The weight average molecular weight is preferably 10,000 to 500,000, more preferably 30,000 to 100,000.

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

-Bright pigment-
Examples of the bright pigment include pigments (bright pigments) that can give a bright feeling such as metallic luster. Specific examples of the bright pigment include metal powders such as aluminum (metal of Al alone), brass, bronze, nickel, stainless steel, zinc; mica coated with titanium oxide, yellow iron oxide, etc .; barium sulfate, layered silica Coated flaky inorganic crystal substrates such as silicates and layered aluminum silicates; single crystal plate-like titanium oxide; basic carbonates; bismuth oxychloride chloride; natural guanine; flaky glass powder; A powder etc. are mentioned and there will be no restriction | limiting in particular if it has glitter.
Among the bright pigments, metal powder is preferable from the viewpoint of specular reflection strength, and aluminum is most preferable among them.

The shape of the glitter pigment is a flat shape (scale shape).
The average length in the major axis direction of the glitter pigment is preferably 1 μm or more and 30 μm or less, more preferably 3 μm or more and 20 μm or less, and further preferably 5 μm or more and 15 μm or less.
The ratio of the average length in the major axis direction (aspect ratio) when the average length in the thickness direction of the glitter pigment is 1 is preferably 5 or more and 200 or less, more preferably 10 or more and 100 or less, More preferably, it is 30 or more and 70 or less.

  Each average length and aspect ratio of the glitter pigment are measured by the following methods. Using a scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation), a photograph of the pigment particles was taken at a measurable magnification (300 to 100,000 times), and the resulting pigment particle image was two-dimensional. In such a state, the length in the major axis direction and the length in the thickness direction of each particle are measured, and the average length and the aspect ratio in the major axis direction of the glitter pigment are calculated.

  The content of the glitter pigment is, for example, preferably from 1 part by weight to 50 parts by weight, and more preferably from 15 parts by weight to 25 parts by weight with respect to 100 parts by weight of the toner particles.

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

The melting temperature of the release agent is preferably 50 ° C. or higher and 110 ° C. or lower, and more preferably 60 ° C. or higher and 100 ° C. or lower.
The melting temperature is obtained from the DSC curve obtained by differential scanning calorimetry (DSC) according to “melting peak temperature” described in JIS K 1721-1987 “Method for measuring the melting temperature of plastics”. .

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

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

  Examples of the charge control agent include quaternary ammonium salt compounds, nigrosine compounds, dyes containing complexes of aluminum, iron, chromium, and triphenylmethane pigments.

  As the inorganic particles, for example, known inorganic particles such as silica particles, titanium oxide particles, alumina particles, cerium oxide particles, or those obtained by hydrophobizing the surface thereof may be used alone or in combination of two or more. Good. Among these, silica particles having a refractive index smaller than that of the binder resin are preferably used. Further, the silica particles may be subjected to various surface treatments, and for example, those subjected to surface treatment with a silane coupling agent, a titanium coupling agent, a silicone oil or the like are preferably used.

  Examples of other colorants other than the luster pigment include known colorants, and are selected according to the target color. In addition, as another coloring agent, the coloring agent surface-treated as needed may be used, and you may use together with a dispersing agent.

-Toner particle characteristics-
The toner particles may be toner particles having a single layer structure, or toner particles having a so-called core / shell structure composed of a core (core particle) and a coating layer (shell layer) covering the core. May be.
The toner particles having a core / shell structure are composed of, for example, a core containing a bright pigment, a binder resin, and, if necessary, other additives such as a release agent, and a coating layer containing the binder resin. It is good to have.

-Average maximum thickness C and average equivalent circle diameter D of toner particles
The toner particles are preferably flat and have an average equivalent circle diameter D longer than their average maximum thickness C. The ratio (C / D) of the average maximum thickness C to the average equivalent circle diameter D is preferably in the range of 0.001 to 0.500, and more preferably in the range of 0.010 to 0.200. A range of 0.050 or more and 0.100 or less is particularly preferable.
When the ratio (C / D) is 0.001 or more, the strength of the toner is ensured, breakage due to stress during image formation is suppressed, charging is reduced due to exposure of the pigment, and fog is generated as a result. Is suppressed. On the other hand, when it is 0.500 or less, excellent glitter can be obtained.

The average maximum thickness C and the average equivalent circle diameter D are measured by the following methods.
The toner particles are placed on a smooth surface and shaken to disperse the toner particles without unevenness. For 1000 toner particles, the maximum thickness C of the glittering toner particles and the equivalent circle diameter D of the surface viewed from above are measured by a color laser microscope “VK-9700” (manufactured by Keyence Corporation). And it calculates by calculating | requiring those arithmetic mean values.

The angle between the major axis direction of the toner particle cross section and the major axis direction of the glitter pigment When the section of the toner particle in the thickness direction is observed, the major axis direction of the toner particle and the length of the glitter pigment are measured. It is preferable that the ratio (based on the number) of the glitter pigment in which the angle with the axial direction is in the range of −30 ° to + 30 ° is 60% or more of the total glitter pigment to be observed. Further, the ratio is more preferably 70% or more and 95% or less, and particularly preferably 80% or more and 90% or less.
When the ratio is 60% or more, excellent glitter can be obtained.

Here, a method for observing the cross section of the toner particles will be described.
After embedding the toner particles with a bisphenol A liquid epoxy resin and a curing agent, a cutting sample is prepared. Next, the cutting sample is cut at −100 ° C. using a cutting machine using a diamond knife, for example, an ultramicrotome apparatus (Ultracut UCT, manufactured by Leica) (to produce an observation sample). Observation is performed with a field emission scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation) at a magnification at which about 1 to 10 toner particles can be seen in one field of view.
Specifically, the cross section of the toner particles (the cross section along the thickness direction of the toner particles) is observed, and for the 100 toner particles observed, the long axis direction of the cross section of the toner particles and the long axis direction of the glitter pigment. The number of glitter pigments with an angle between −30 ° and + 30 ° is determined by using, for example, image analysis software such as image analysis software (Wim ROOF) manufactured by Mitani Corporation or an output sample of the observation image and a protractor And calculate the ratio.

  The “major axis direction in the cross section of the toner particles” means a direction orthogonal to the thickness direction of the toner particles having an average equivalent circle diameter D longer than the average maximum thickness C described above. The “long axis direction” represents the length direction of the glitter pigment.

  The volume average particle diameter of the toner particles is desirably 1 μm or more and 30 μm or less, and more desirably 3 μm or more and 20 μm or less.

The volume average particle diameter D _50v of the toner particles is the volume and number of the particle size range (channel) divided based on the particle size distribution measured by a measuring device such as Multisizer II (Coulter). Each is obtained by drawing a cumulative distribution from the small diameter side. The particle diameter that is 16% cumulative is defined as volume D _16v and number D _16p , the particle diameter that is cumulative 50% is _defined as volume D _50v and number D _50p , and the particle diameter that is cumulative 84% is defined as volume D _84v and number D _84p . . Using these, the volume average particle size distribution index (GSDv) is calculated as ( _D84v / _D16v ) ^1/2 .

(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 , 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 an external additive is preferably subjected to a hydrophobic treatment. The hydrophobic treatment is performed, for example, by immersing inorganic particles in a hydrophobic treatment agent. The hydrophobizing agent is not particularly limited, and examples thereof include silane coupling agents, silicone oils, titanate coupling agents, aluminum coupling agents and the like. These may be used individually by 1 type and may use 2 or more types together.
The amount of the hydrophobizing agent is usually 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the inorganic particles, for example.

  Examples of external additives include resin particles (resin particles such as polystyrene, polymethyl methacrylate (PMMA), and melamine resin), cleaning activators (for example, metal salts of higher fatty acids typified by zinc stearate, fluorine-based high molecular weight substances). Particle) and the like.

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

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

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

For example, the dissolution suspension method includes a particle dispersant obtained by dissolving or dispersing a raw material (resin particles, glitter pigment, etc.) constituting toner particles in an organic solvent in which the binder resin can be dissolved. In this method, toner particles are granulated by dispersing in an aqueous solvent and then removing the organic solvent.
The emulsion aggregation method is a method for obtaining toner particles through an aggregation process for forming aggregates of raw materials (resin particles, glitter pigment, etc.) constituting the toner particles and a fusion process for fusing the aggregates. .

Among these, toner particles containing a urea-modified polyester resin as a binder resin are preferably obtained by the following dissolution suspension method.
The dissolution suspension method includes, for example, an oil phase liquid adjustment step of adjusting an oil phase liquid, which is a mixed liquid obtained by mixing the organic solvent that dissolves the binder resin, the binder resin, and the glitter pigment, and an oil phase. A suspension adjusting step of adjusting the suspension by dispersing the liquid in an aqueous medium; and a solvent removing step of removing the organic solvent from the suspension.
Examples of the organic solvent for dissolving the binder resin include ester solvents such as methyl acetate and ethyl acetate; ketone solvents such as methyl ethyl ketone and methyl isopropyl ketone; aliphatic hydrocarbon solvents such as hexane and cyclohexane; dichloromethane, Examples thereof include halogenated hydrocarbon solvents such as chloroform and trichloroethylene. The organic solvent that dissolves the binder resin is one that dissolves the binder resin and has a ratio of dissolving in water (water solubility at 25 ° C.) of about 0% by mass to 30% by mass. It is preferable that the boiling point is 100 ° C. or lower. Among these organic solvents, ethyl acetate is preferable as the organic solvent for dissolving the binder resin.

In the dissolution suspension method, the binder resin is dissolved in an organic solvent, and then the organic solvent is removed in the presence of the glitter pigment to obtain toner particles in which the binder resin is coated with the glitter pigment. Therefore, depending on the viscosity of the resin solution (that is, oil phase liquid) in which the binder resin is dissolved in the organic solvent, the structure and characteristics of the toner particles obtained through the suspension adjustment step and the solvent removal step differ as follows: Conceivable.
Specifically, as described above, if the viscosity of the oil phase liquid is too low, it is difficult for the oil phase liquid to take in the particles of the bright pigment in the suspension adjustment step, and the binder resin particles not containing the bright pigment or Thus, it is easy to obtain toner particles with a small amount of binder resin. On the other hand, if the viscosity of the oil phase liquid is too high, the oil phase liquid can easily take in a large amount of glitter pigment particles, and toner particles including a plurality of glitter pigment particles can be easily obtained.

From the above viewpoint, the viscosity of the oil phase liquid is, for example, 0.05 Pa · s or more and 1.5 Pa · s or less, preferably 0.1 Pa · s or more and 1.0 Pa · s or less, and preferably 0.2 Pa · s or more. 0.8 Pa · s or less is more preferable.
The viscosity of the oil phase liquid varies depending on the type, molecular weight, molecular weight distribution, and concentration of the binder resin, and the type, molecular weight, and molecular weight distribution of the binder resin are as described above.
As a density | concentration of the binder resin in an oil phase liquid, 30 mass% or more and 70 mass% or less are mentioned, for example, 35 mass% or more and 65 mass% or less are preferable, and 40 mass% or more and 60 mass% or less are more preferable.

Hereinafter, although the specific example of the dissolution suspension method is shown, it is not limited to this.
In the following description of the dissolution suspension method, a method for obtaining toner particles containing a release agent will be described. The release agent is included in the toner particles as necessary. Although a method for obtaining toner particles containing an unmodified polyester resin and a urea-modified polyester resin as a binder resin will be described, the toner particles may contain only a urea-modified polyester resin as a binder resin.

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

  The oil phase liquid is prepared by 1) a method in which toner materials are collectively dissolved or dispersed in an organic solvent, and 2) after kneading the toner materials in advance and then dissolving or dispersing the kneaded material in an organic solvent. 3) A method of adjusting by dissolving an unmodified polyester resin, a polyester prepolymer having an isocyanate group, an amine compound in an organic solvent, and then dispersing a glittering pigment and a release agent in the organic solvent. 4) A method in which a glittering pigment and a release agent are dispersed in an organic solvent, and then an unmodified polyester resin, a polyester prepolymer having an isocyanate group, and an amine compound are dissolved in the organic solvent. 5) Organic toner particle materials (unmodified polyester resin, glitter pigment, and release agent) other than polyester prepolymers having isocyanate groups and amine compounds 6) A method for preparing a polyester prepolymer having an isocyanate group and an amine compound in this organic solvent after dissolving or dispersing in the medium, and 6) a toner particle material other than the polyester prepolymer having an isocyanate group or the amine compound. Non-modified polyester resin, glitter pigment, and release agent) are dissolved or dispersed in an organic solvent, and then prepared by dissolving a polyester prepolymer having an isocyanate group or an amine compound in the organic solvent. It is done. The method for preparing the oil phase liquid is not limited to these.

  The organic solvent of the oil phase liquid is not particularly limited as long as it is an organic solvent that dissolves the binder resin. For example, ester solvents such as methyl acetate and ethyl acetate; ketone solvents such as methyl ethyl ketone and methyl isopropyl ketone; hexane, Aliphatic hydrocarbon solvents such as cyclohexane; Halogenated hydrocarbon solvents such as dichloromethane, chloroform, and trichloroethylene. These organic solvents are those that dissolve the binder resin, have a ratio of dissolving in water of about 0% by mass to 30% by mass, and preferably have a boiling point of 100 ° C. or less. Of these organic solvents, ethyl acetate is preferred.

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

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

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

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

  Examples of the inorganic particle dispersant include hydrophilic inorganic particle dispersants. Specific examples of the inorganic particle dispersant include particles of silica, alumina, titania, calcium carbonate, magnesium carbonate, tricalcium phosphate, clay, diatomaceous earth, bentonite, and the like, but calcium carbonate particles are preferable. An inorganic particle dispersing agent may be used individually by 1 type, and may use 2 or more types together.

The particle dispersant may be surface-treated with a polymer having a carboxyl group on the surface.
As the polymer having a carboxyl group, the carboxyl group of an α, β-monoethylenically unsaturated carboxylic acid or α, β-monoethylenically unsaturated carboxylic acid is an alkali metal, alkaline earth metal, ammonium, amine, or the like. And a copolymer of at least one selected from neutralized salts (alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts, etc.) and α, β-monoethylenically unsaturated carboxylic acid esters. It is done. As the polymer having a carboxyl group, the carboxyl group of a copolymer of an α, β-monoethylenically unsaturated carboxylic acid and an α, β-monoethylenically unsaturated carboxylic acid ester is an alkali metal or an alkaline earth metal. And salts neutralized with ammonium, amine, etc. (alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts, etc.). The said polymer which has a carboxyl group may be used individually by 1 type, and may use 2 or more types together.

  Typical α, β-monoethylenically unsaturated carboxylic acids include α, β-unsaturated monocarboxylic acids (acrylic acid, methacrylic acid, crotonic acid, etc.), α, β-unsaturated dicarboxylic acids (maleic acid). Acid, fumaric acid, itaconic acid, etc.). Representative examples of α, β-monoethylenically unsaturated carboxylic acid esters include alkyl esters of (meth) acrylic acid, (meth) acrylates having an alkoxy group, (meth) acrylates having a cyclohexyl group, Examples include (meth) acrylate having a hydroxy group, polyalkylene glycol mono (meth) acrylate, and the like.

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

[Solvent removal step]
Next, the organic solvent is removed from the obtained suspension to obtain a toner particle dispersion (solvent removal step). In this solvent removal step, the organic solvent contained in the droplets of the aqueous phase liquid dispersed in the suspension is removed to generate toner particles. The removal of the organic solvent from the suspension may be performed immediately after the suspension preparation step, or may be performed after 1 minute or more has elapsed after completion of the suspension preparation step.
In the solvent removal step, the organic solvent is preferably removed from the suspension by cooling or heating the obtained suspension in a range of, for example, 0 ° C. or more and 100 ° C. or less.

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

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

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

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

There is no restriction | limiting in particular as a carrier, A well-known carrier is mentioned. Examples of carriers include a coated carrier in which the surface of a core made of magnetic powder is coated with a resin; a magnetic powder-dispersed carrier in which magnetic powder is dispersed in a matrix resin; and a porous magnetic powder impregnated with resin. Resin impregnated type carriers; and the like.
The magnetic powder-dispersed carrier and the resin-impregnated carrier may be carriers in which the constituent particles of the carrier are used as a core and the surface is coated with a resin.

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

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

  In order to coat the surface of the core material with a resin, a method of coating with a coating layer forming solution in which a coating resin and various additives (used as necessary) are dissolved in an appropriate solvent may be mentioned. The solvent is not particularly limited, and may be selected in consideration of the type of resin used, application suitability, and the like. Specific resin coating methods include a dipping method in which a core material is immersed in a coating layer forming solution; a spray method in which the coating layer forming solution is sprayed on the surface of the core material; Examples thereof include a fluidized bed method in which a coating layer forming solution is sprayed; a kneader coater method in which a carrier core material and a coating layer forming solution are mixed in a kneader coater, and then the solvent is removed.

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

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

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

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

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

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

  FIG. 2 is a schematic configuration diagram illustrating the image forming apparatus according to the present embodiment. The image forming apparatus according to the present embodiment has a tandem configuration in which a plurality of photoconductors as image holding members, that is, a plurality of image forming units (image forming units) are provided, and an intermediate transfer member is used as an intermediate transfer member. The image forming apparatus is an intermediate transfer type image forming apparatus including a belt.

As shown in FIG. 2, the image forming apparatus according to the present embodiment includes an image forming unit 150B that forms a metallic toner image using the developer according to the present embodiment, and each color of yellow, magenta, cyan, and black. The four image forming units 150Y, 150M, 150C, and 150K that form the toner images are arranged in parallel (tandem) at intervals. The image forming units are arranged in the order of the image forming units 150K, 150C, 150M, 150Y, and 150B from the downstream side in the rotation direction of the intermediate transfer belt 133.
Here, each of the image forming units 150B, 150Y, 150M, 150C, and 150K has the same configuration except for the color of the toner in the developer stored therein, and therefore, here, image formation for forming a metallic image is performed. The unit 150B will be described as a representative. It should be noted that reference numerals with yellow (Y), magenta (M), cyan (C), and black (K) are attached to the same parts as the image forming unit 150K in place of metallic (B). Description of the image forming units 150Y, 150M, 150C, and 150K is omitted.

  The metallic image forming unit 150B includes a photoconductor 111B as an image holding member, and the photoconductor 111B is rotationally driven at a predetermined process speed by a driving unit (not shown) along the direction of an arrow A shown in the drawing. It has become so. As the photoreceptor 111B, for example, an organic photoreceptor having sensitivity in the infrared region is used.

  A charging roll (charging means) 118B is provided above the photoconductor 111B, and a predetermined voltage is applied to the charging roll 118B by a power source (not shown), so that the surface of the photoconductor 111B is predetermined. Charged to a certain potential.

An exposure device (electrostatic image forming means) 119B that exposes the surface of the photoconductor 111B to form an electrostatic image on the downstream side in the rotation direction of the photoconductor 111B from the charging roll 118B is disposed around the photoconductor 111B. Has been.
Here, as the exposure device 119B, an LED array that can be reduced in size is used in terms of space, but the present invention is not limited to this, and an electrostatic charge image forming unit using another laser beam or the like is used. May be. However, the wavelength of the light source is within the spectral sensitivity region of the photoreceptor. For example, when a semiconductor laser is used, near infrared having an oscillation wavelength near 780 nm is the mainstream, but the wavelength is not limited to this wavelength, and an oscillation wavelength laser of 600 nm range or a blue laser has an oscillation wavelength of 400 nm to 450 nm. A laser may also be used. A surface-emitting laser light source that can output a multi-beam is also effective for forming a color image.

  Around the photosensitive member 111B, a developing device (developing unit) 120B including a developer holding member that holds a metallic developer is disposed downstream of the exposure device 119B in the rotation direction of the photosensitive member 111B. The electrostatic charge image formed on the surface of the photoconductor 111B is visualized with a metallic toner, and a toner image is formed on the surface of the photoconductor 111B.

Below the photoconductor 111B, an intermediate transfer belt 133 to which a toner image formed on the surface of the photoconductor 111B is primarily transferred is disposed so as to extend below the five photoconductors 111B, 111Y, 111M, 111C, and 111K. ing. The intermediate transfer belt 133 is pressed against the surface of the photoreceptor 111B by a primary transfer roll 117B (primary transfer unit).
The intermediate transfer belt 133 is supported by three rolls of a drive roll 112, a support roll 113, and a bias roll 114, and is rotated in the direction of arrow B at a moving speed equal to the process speed of the photosensitive member 111B. ing. The drive roll 112 also serves as an intermediate transfer member charge removing unit that removes charges accumulated on the intermediate transfer belt 133.
A metallic toner image is primarily transferred onto the surface of the intermediate transfer belt 133, and further, toner images of each color of yellow, magenta, cyan, and black are sequentially primary transferred, stacked, and then neutralized by the driving roll 112.

  A belt cleaner 116 for cleaning the outer peripheral surface of the intermediate transfer belt 133 is provided on the opposite side of the support roll 113 via the intermediate transfer belt 133 so as to be in pressure contact with the support roll 113. Further, on the upstream side in the rotation direction of the intermediate transfer belt 133 with respect to the belt cleaner 116, a voltage that is an arrangement unit that generates an electric field with the intermediate transfer belt 133 by generating a potential difference with the support roll 113. An application device 160 is provided.

The intermediate transfer belt 133 preferably contains a polyimide resin or a polyamideimide resin because the belt itself has high strength and can satisfy durability. Further, the surface resistivity of the intermediate transfer belt 133 is preferably in the range of 1 × 10 ⁹ Ω / □ to 1 × 10 ¹⁴ Ω / □. In order to control the surface resistivity, the intermediate transfer belt 133 contains a conductive filler as necessary. Examples of the conductive filler include metals or alloys such as carbon black, graphite, aluminum, and copper alloys, metal oxides such as tin oxide, zinc oxide, potassium titanate, tin oxide-indium oxide, and tin oxide-antimony oxide composite oxide. Or a conductive polymer such as polyaniline is used alone or in combination of two or more. Among these, carbon black is preferable as the conductive filler in terms of cost. Moreover, you may add processing aids, such as a dispersing agent and a lubricant, as needed.

  Further, around the photosensitive member 111B, toner remaining on the surface of the photosensitive member 111B or re-transferred (retransferred) toner is located downstream of the primary transfer roll 117B in the rotation direction (arrow A direction) of the photosensitive member 111B. A cleaning device 115B for cleaning is disposed. The cleaning device 115B is a cleaning blade type device as described above. The cleaning blade in the cleaning device 115B is attached so as to be in pressure contact with the surface of the photoreceptor 111B in the counter direction.

  The material of the cleaning blade is not particularly limited, and various elastic bodies are used. Specific elastic bodies include elastic bodies such as polyurethane elastic bodies, silicone rubber, and chloroprene rubber.

  As the polyurethane elastic body, a polyurethane synthesized through an addition reaction of an isocyanate with a polyol and various hydrogen-containing compounds is generally used. This uses a polyether polyol such as polypropylene glycol and polytetramethylene glycol as a polyol component, and a polyester polyol such as an adipate polyol, a polycaprolactam polyol, and a polycarbonate polyol, and a tolylene diisocyanate as an isocyanate component. Aromatic polyisocyanates such as 4,4′-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, toluidine diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate; Prepare a urethane prepolymer, add a curing agent to it, inject it into the mold, After bridge curing, it is produced by aging at room temperature (25 ° C.). As the curing agent, a dihydric alcohol such as 1,4-butanediol and a trihydric or higher polyhydric alcohol such as trimethylolpropane or pentaerythritol are usually used in combination.

  If the rubber hardness of the cleaning blade (according to JIS K6253-3: 2012 durometer type A) is 50 ° or more, the cleaning blade is less likely to be worn, and toner slip-out is unlikely to occur. If the rubber hardness is 100 ° or less, since the cleaning blade is not too hard, the wear of the image carrier is unlikely to proceed, and the cleaning performance is unlikely to deteriorate.

Also, if the 300% modulus, which indicates the tensile stress when the sample elongation is 300%, is 80 kgf / cm ² or more, the blade edge is easily deformed and is not easily torn off. Slip-off is unlikely to occur. On the other hand, if it is 550 kgf / cm ² or less, the followability due to the deformation of the cleaning blade is unlikely to deteriorate with respect to the surface shape of the image carrier, and therefore, poor cleaning due to poor contact is unlikely to occur.
Further, a cleaning blade having a rebound resilience (hereinafter simply referred to as a rebound resilience) of 4% or more as defined in the rebound resilience test method of JIS K-6255: 1996 is liable to cause reciprocation of toner scraping of the blade edge. Slip-off is unlikely to occur. Further, a cleaning blade having a rebound resilience of 85% or less is less likely to cause blade squeal and blade curl.

  Further, the amount of biting of the cleaning blade (the amount of deformation of the cleaning blade caused by being pressed against the surface of the image carrier) cannot be generally specified, but is preferably about 0.8 mm to 1.6 mm. More preferably, it is about 0 mm or more and 1.4 mm or less. Further, the contact angle of the cleaning blade to the image holding member (the angle formed between the tangent to the surface of the image holding member and the cleaning blade) cannot be generally specified, but is preferably about 18 ° to 28 °.

  A secondary transfer roll (secondary transfer unit) 134 is pressed against the bias roll 114 that supports the intermediate transfer belt 133 via the intermediate transfer belt 133. The toner image primarily transferred and laminated on the surface of the intermediate transfer belt 133 is applied to the surface of the recording paper (recording medium) P fed from a paper cassette (not shown) at the pressure contact portion between the bias roll 114 and the secondary transfer roll 134. Electrostatically transferred. At this time, since the toner image transferred and laminated on the intermediate transfer belt 133 has the metallic toner image at the bottom (lowermost layer), the toner image transferred on the surface of the recording paper P is the metallic toner image. Becomes the top (top layer).

  Also, downstream of the secondary transfer roll 134, a fixing device (fixing means) for fixing the toner image, which has been multiple-transferred on the recording paper P, onto the surface of the recording paper P by heat and pressure to form a permanent image. 135 is arranged.

  As the fixing device 135, for example, a low surface energy material typified by a fluororesin component or a silicone resin is used on the surface, and a fixing belt having a belt shape and a fluororesin component or a silicone resin typified on the surface are used. And a cylindrical fixing roll is used.

  Next, operations of the image forming units 150B, 150Y, 150M, 150C, and 150K that form images of metallic, yellow, magenta, cyan, and black are described. Since the operations of the image forming units 150B, 150Y, 150M, 150C, and 150K are the same, the operation of the metallic image forming unit 150B will be described as a representative example.

  In the metallic image forming unit 150B, the photoreceptor 111B rotates in the direction of arrow A at a predetermined process speed. The surface of the photoconductor 111B is negatively charged to a predetermined potential by the charging roll 118B. Thereafter, the surface of the photoreceptor 111B is exposed by the exposure device 119B, and an electrostatic charge image corresponding to the image information is formed. Subsequently, the negatively charged toner is reversely developed by the developing device 120B, and the electrostatic charge image formed on the surface of the photoreceptor 111B is visualized on the surface of the photoreceptor 111B to form a toner image. Thereafter, the toner image on the surface of the photoreceptor 111B is primarily transferred onto the surface of the intermediate transfer belt 133 by the primary transfer roll 117B. After the primary transfer, the transfer residual component such as toner remaining on the surface of the photoreceptor 111B is scraped off and cleaned by the cleaning blade of the cleaning device 115B to prepare for the next image forming process.

  The above operations are performed by the image forming units 150B, 150Y, 150M, 150C, and 150K, and the toner images visualized on the surfaces of the photoreceptors 111B, 111Y, 111M, 111C, and 111K are successively transferred to the intermediate transfer belt. Multiple transfer is performed on the 133 surface. In the color mode, the toner images of each color are multiplex-transferred in the order of metallic, yellow, magenta, cyan, and black. In the two-color and three-color modes, only the toner images of the required colors are in this order. Single or multiple transcription is performed. Then, the intermediate transfer belt 133 on which the toner image is transferred singly or multiple times is discharged by the drive roll 112.

  Thereafter, the toner image singly or multiply transferred onto the surface of the intermediate transfer belt 133 is secondarily transferred onto the surface of the recording paper P conveyed from a paper cassette (not shown) by the secondary transfer roll 134, and then the fixing device 135. It is fixed by heating and pressurizing. The toner remaining on the surface of the intermediate transfer belt 133 after the secondary transfer is subjected to a process of causing the toner to rise on the surface of the intermediate transfer belt 133 by a voltage application device 160 that is an arrangement unit that generates an electric field with the intermediate transfer belt 133. Thereafter, the belt is cleaned by a belt cleaner 116 constituted by a cleaning blade for the intermediate transfer belt 133.

  The metallic image forming unit 150B includes a developing device 120B including a developer holding body for holding a metallic-color electrostatic charge image developer, a photoconductor 111B, a charging roll 118B, and a cleaning device 115B, which form an image. It is configured as a process cartridge that is detachable from the apparatus body. The image forming units 150Y, 150M, 150C, and 150K are also configured as process cartridges in the same manner as the image forming unit 150B.

  The toner cartridges 140B, 140Y, 140M, 140C, and 140K are cartridges that store toner of each color and are attached to and detached from the image forming apparatus, and are connected to a developing device corresponding to each color by a toner supply pipe (not shown). Has been. When the toner stored in each toner cartridge becomes low, the toner cartridge is replaced.

  In this embodiment, the image forming units are arranged in the order of the image forming units 150K, 150C, 150M, 150Y, and 150B from the downstream side in the rotation direction of the intermediate transfer belt 133. However, the present invention is not limited to this. They may be arranged in the order of 150K, 150C, 150M, and 150Y.

  In the present embodiment, the charging rolls 118B, 118Y, 118M, 118C, and 118K are used as the charging device, but the charging roller 118B, 118Y, 118M, 118C, and 118K are not limited thereto, and for example, contact using a charging brush, a charging film, a charging rubber blade, a charging tube, or the like. Known chargers such as a type charger, a non-contact type roll charger, a scorotron charger using a corona discharge and a corotron charger are also used.

  In this embodiment, the primary transfer roll is used as the primary transfer means, and the secondary transfer roll is used as the secondary transfer means. However, the present invention is not limited to this. For example, contact transfer using a belt, a film, a rubber blade, or the like. A known transfer charger such as a charger, a scorotron transfer charger using corona discharge, a corotron transfer charger, or the like may be used.

  The image forming apparatus according to the present embodiment includes an alignment unit that raises the transfer residual toner on the surface of the intermediate transfer body with respect to the surface of the intermediate transfer body. A configuration may be further provided with arrangement means for waking up, or a configuration without these arrangement means may be provided.

  The image forming apparatus according to the present embodiment has a tandem configuration in which a plurality of image forming units are provided. However, the present invention is not limited thereto, and only the image forming unit that forms a toner image using the developer according to the present embodiment. It is good also as a structure provided.

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

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

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

FIG. 3 is a schematic configuration diagram showing a process cartridge according to the present embodiment.
The process cartridge 200 shown in FIG. 3 is provided around the photoreceptor 207 (an example of an image carrier) and the periphery of the photoreceptor 207, for example, by a housing 217 provided with an attachment rail 216 and an opening 218 for exposure. A charging roll 208 (an example of a charging unit), a developing device 211 (an example of a developing unit), and a photoconductor cleaning device 213 (an example of a cleaning unit) are integrally combined and held to form a cartridge. Yes.
In FIG. 3, reference numeral 209 denotes an exposure apparatus (an example of an electrostatic image forming unit), 212 denotes a primary transfer roll (an example of a primary transfer unit), 220 denotes an intermediate transfer belt (an example of an intermediate transfer member), and 222 denotes an intermediate transfer. Driving roll also serving as a belt neutralizing unit (an example of an intermediate transfer member neutralizing unit), 224 is a support roll, 226 is a secondary transfer roll (an example of a secondary transfer unit), 228 is a fixing device (an example of a fixing unit), 300 Indicates a recording sheet (an example of a recording medium).

Next, the toner cartridge according to this embodiment will be described.
The toner cartridge according to the present exemplary embodiment may be configured to store the toner according to the present exemplary embodiment and be attached to and detached from the image forming apparatus. Note that the toner cartridge according to the present embodiment only needs to contain at least toner, and may contain developer, for example, depending on the mechanism of the image forming apparatus.

  Hereinafter, although an embodiment explains this embodiment in detail, this embodiment is not limited to these examples at all. In the following description, “part” and “%” are all based on mass unless otherwise specified.

(Preparation of unmodified amorphous polyester resin (1))
-Terephthalic acid: 1243 parts-Bisphenol A ethylene oxide adduct: 1830 parts-Bisphenol A propylene oxide adduct: 840 parts After mixing the above ingredients at 180 ° C, add 3 parts of dibutyltin oxide and heat at 220 ° C. While removing water, an unmodified amorphous polyester was obtained. The obtained non-modified amorphous polyester resin has a glass transition temperature Tg of 60 ° C., an acid value of 3 mgKOH / g, a hydroxyl value of 1 mgKOH / g, a weight average molecular weight Mw of 9500, a number average molecular weight Mn of 3100, and a peak top molecular weight. Mp was 5700.

(Preparation of unmodified crystalline polyester resin (1))
-Sebacic acid: 102 parts-1,9-nonanediol: 85 parts Lu The above components are placed in a reaction vessel equipped with a stirrer, thermometer, condenser and nitrogen gas introduction tube, and the reaction vessel is replaced with dry nitrogen gas. After that, 0.47 parts of titanium tetrabutoxide (reagent) was added. After stirring and reacting at 170 ° C. for 3 hours under a nitrogen gas stream, the temperature was further raised to 210 ° C. over 1 hour, the pressure in the reaction vessel was reduced to 3 kPa, and the stirring reaction was performed for 13 hours under reduced pressure. A modified crystalline polyester resin was obtained. The obtained unmodified crystalline polyester resin had a melting temperature by DSC of 71.2 ° C., a weight average molecular weight Mw by GPC of 25000, a number average molecular weight Mn of 10500, and a peak top molecular weight Mp of 25000.

(Preparation of polyester prepolymer (1))
-Terephthalic acid: 1243 parts-Bisphenol A ethylene oxide adduct: 1830 parts-Bisphenol A propylene oxide adduct: 840 parts After mixing the above ingredients at 180 ° C, add 3 parts of dibutyltin oxide and heat at 220 ° C. While distilling off water, a polyester prepolymer was obtained. 350 parts of the obtained polyester prepolymer, 50 parts of tolylene diisocyanate and 450 parts of ethyl acetate were put in a container, and this mixture was heated at 130 ° C. for 3 hours to obtain a polyester prepolymer (1) having an isocyanate group (hereinafter referred to as “isocyanate”). Modified polyester prepolymer (1) ") was obtained. The weight average molecular weight Mw of the isocyanate-modified polyester prepolymer (1) was 5000, the number average molecular weight Mn was 3100, and the peak top molecular weight Mp was 4500.

(Preparation of ketimine compound (1))
A container was charged with 50 parts of methyl ethyl ketone and 150 parts of hexamethylenediamine, and stirred at 60 ° C. to obtain a ketimine compound (1).

(Preparation of glitter pigment dispersion (1))
Aluminum pigment (flat luster pigment, Showa Aluminum Powder Co., Ltd., 2173EA): 100 parts Ethyl acetate: 500 parts Mixing the above components, filtering the mixture and further mixing with 500 parts of ethyl acetate After repeating the process five times, the pigment dispersion liquid (1) in which the glitter pigment (aluminum pigment) is dispersed by dispersing for about 1 hour using an emulsifier / disperser Cavitron (manufactured by Taiheiyo Kiko Co., Ltd., CR1010) Solid content concentration: 10%) was obtained.

(Preparation of release agent dispersion (1))
Paraffin wax (melting temperature 89 ° C.): 30 parts Ethyl acetate: 270 parts In the state where the above components are cooled to 10 ° C., they are wet pulverized by a microbead type disperser (DCP mill), and a release agent dispersion (1 )

(Preparation of oil phase liquid (1))
Unmodified amorphous polyester resin (1): 136 parts Unmodified crystalline polyester resin (1): 12 parts Bright pigment dispersion (1): 500 parts Ethyl acetate: 56 parts The above ingredients are mixed by stirring. Thereafter, 75 parts of the release agent dispersion (1) was added to the resulting mixture and stirred to obtain an oil phase liquid (1).

(Preparation of styrene acrylic resin particle dispersion (1))
-Styrene: 370 parts-n-butyl acrylate: 30 parts-Acrylic acid: 4 parts-Dodecanethiol: 24 parts-Carbon tetrabromide: 4 parts The above components were mixed and dissolved into a nonionic surfactant ( Dispersed in a flask in an aqueous solution in which 6 parts of Sanyo Chemical Industries, Ltd .: Nonipol 400) and 10 parts of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) were dissolved in 560 parts of ion-exchanged water. After emulsification and mixing for 10 minutes, an aqueous solution in which 4 parts of ammonium persulfate was dissolved in 50 parts of ion-exchanged water was added thereto, and after nitrogen substitution, the contents were kept at 70 ° C. while stirring the flask. The mixture was heated in an oil bath until it became, and emulsion polymerization was continued for 5 hours. Thus, a styrene acrylic resin particle dispersion liquid (1) (resin particle concentration: 40% by mass) obtained by dispersing resin particles having an average particle diameter of 180 nm and a weight average molecular weight (Mw) of 15,500 was obtained. The glass transition point of the styrene acrylic resin particles was 59 ° C.

(Preparation of aqueous phase liquid (1))
-Styrene acrylic resin particle dispersion (1): 60 parts-2% aqueous solution of Serogen BS-H (Daiichi Kogyo Seiyaku Co., Ltd.): 200 parts-Ion-exchanged water: 200 parts A liquid (1) was obtained.

<Example 1>
-Production of toner particles (1)-
・ Oil phase liquid (1): 300 parts ・ Isocyanate-modified polyester prepolymer (1): 45 parts ・ Ketimine compound (1): 0.9 part The above ingredients are put in a container, and a homogenizer (Ultra Turrax: manufactured by IKA) After stirring for 2 minutes to obtain an oil phase liquid (1P), 1000 parts of the aqueous phase liquid (1) was added to the container and stirred for 20 minutes with a homogenizer. Next, this mixed solution is stirred with a propeller type stirrer at room temperature (25 ° C.) and normal pressure (1 atm) for 48 hours to react the isocyanate-modified polyester prepolymer (1) with the ketimine compound (1), and urea While producing | generating the modified polyester resin, the organic solvent was removed and the granular material was formed. Next, the granular material was washed with water, dried and classified to obtain toner particles (1). The volume average particle diameter of the toner particles was 12 μm.

-Preparation of glitter toner (1)-
Toner particles (1): 100 parts, hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50): 1.5 parts, and hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805): 1.0 part of sample mill For 30 seconds at 10,000 rpm. Thereafter, the toner was sieved with a vibration sieve having an opening of 45 μm to obtain a glittering toner (1).

<Example 2>
Toner particles (1) were prepared in the same manner as toner particles (1) except that 20 parts of isocyanate-modified polyester prepolymer (1) and 0.5 parts of ketimine compound (1) were used. )
Then, a bright toner (2) was obtained in the same manner as the bright toner (1) except that the toner particles (2) were used.

<Example 3>
Toner particles (1) were prepared in the same manner as toner particles (1) except that 98 parts of the isocyanate-modified polyester prepolymer (1) and 2.5 parts of the ketimine compound (1) were used. )
Then, a glittering toner (3) was obtained in the same manner as the glittering toner (1) except that the toner particles (3) were used.

<Example 4>
Toner particles (1) were prepared in the same manner as toner particles (1) except that 30 parts of isocyanate-modified polyester prepolymer (1) and 0.5 parts of ketimine compound (1) were used. )
Then, a bright toner (4) was obtained in the same manner as the bright toner (1) except that the toner particles (4) were used.

<Example 5>
Toner particles (1) were prepared in the same manner as toner particles (1) except that 120 parts of isocyanate-modified polyester prepolymer (1) and 2.0 parts of ketimine compound (1) were used. )
Then, a glittering toner (5) was obtained in the same manner as the glittering toner (1) except that the toner particles (5) were used.

<Example 6>
Toner particles (1) and toner particles (1) were prepared except that the oil phase liquid (1) was 400 parts, the isocyanate-modified polyester prepolymer (1) was 0 parts, and the ketimine compound (1) was 0 parts. Similarly, toner particles (6) were obtained.
Then, a bright toner (6) was obtained in the same manner as the bright toner (1) except that the toner particles (6) were used.

<Comparative Example 1>
Toner particles (1) were prepared in the same manner as toner particles (1) except that 40 parts of the isocyanate-modified polyester prepolymer (1) and 1.3 parts of the ketimine compound (1) were used. )
Then, a bright toner (C1) was obtained in the same manner as the bright toner (1) except that the toner particles (C1) were used.

<Comparative example 2>
Toner particles (C2) were prepared in the same manner as toner particles (1) except that 100 parts of isocyanate-modified polyester prepolymer (1) and 1.0 parts of ketimine compound (1) were used. )
Then, a glittering toner (C2) was obtained in the same manner as the glittering toner (1) except that the toner particles (C2) were used.

<Comparative Example 3>
Toner particles (1) were prepared in the same manner as toner particles (1) except that 10 parts of isocyanate-modified polyester prepolymer (1) and 0.2 parts of ketimine compound (1) were used. )
Then, a glittering toner (C3) was obtained in the same manner as the glittering toner (1) except that the toner particles (C3) were used.

<Comparative example 4>
Toner particles (1) were prepared in the same manner as toner particles (1) except that the isocyanate-modified polyester prepolymer (1) was 120 parts and the ketimine compound (1) was 3.0 parts. )
Then, a glittering toner (C4) was obtained in the same manner as the glittering toner (1) except that the toner particles (C4) were used.

<Measurement / Evaluation>
(Measurement of molecular weight)
Mw and Mp in the binder resin of the glitter toner obtained in each example were measured according to the method described above. The results are shown in Table 1.

(Preparation of metallic developer)
The glittering toner obtained in each example: 36 parts and carrier: 414 parts were put into a 2 liter V blender, stirred for 20 minutes, and then sieved at 212 μm to prepare each metallic developer. In addition, the carrier obtained by the method shown below was used.

-Production of carrier-
Ferrite particles (volume average particle diameter: 35 μm): 100 parts Toluene: 14 parts Methyl methacrylate-perfluorooctylethyl acrylate copolymer (critical surface tension: 24 dyn / cm): 1.6 parts Carbon black (product) 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-par To the fluorooctylethyl acrylate copolymer, carbon black was diluted with toluene and dispersed with a sand mill. Next, each of the above components other than the ferrite particles was dispersed for 10 minutes with a stirrer to prepare a coating layer forming solution. Next, this coating layer forming solution and ferrite particles are put in a vacuum degassing type kneader and stirred at a temperature of 60 ° C. for 30 minutes, and then the pressure is reduced to distill off toluene to form a resin coating layer to obtain a carrier. It was.

(Preparation of colored toner and colored developer)
-Preparation of yellow developer-
As a yellow pigment, C.I. I. A yellow toner (1) was obtained in the same manner as the bright toner (1) except that Pigment Yellow 74 (monoazo pigment, manufactured by Dainichi Seika, Seika Fast Yellow 2054) was used.
A yellow developer was obtained in the same manner as the metallic developer except that the yellow toner (1) was used instead of the glitter toner.

(Evaluation)
The obtained metallic developer and the obtained yellow developer were filled in a developing device of “color 800 press remodeling machine” manufactured by Fuji Xerox Co., Ltd.
Using this modified machine, the amount of yellow toner applied to the image area on the paper of OK top coat paper (basis weight 127: manufactured by Oji Paper Co., Ltd.) in a high temperature and high humidity environment of 28 ° C. and 85% humidity is 3. A toner image of 0 g / m ^{2 and} a toner image having a glossy toner loading amount of 3.0 g / m ^{2 on} the image portion are laminated in this order from the paper side, the fixing temperature is 190 ° C., and the load at fixing is 4.0 kg / m. After outputting 50000 images with a density of 2% (color metallic image) fixed together at cm ^{2, the applied} amount of the toner image with the yellow toner applied to 8.0 g / m ^{2 and} the applied amount of the glitter toner A belt-like solid image (color metallic image) obtained by laminating toner images of 4.5 g / m ² in this order from the paper side and fixing them together at a fixing temperature of 190 ° C. and a load of 4.0 kg / cm ² during fixing. 10,000 sheets It was.

(Measurement of brightness: ratio (X / Y))
For the solid image output to the 5th sheet and the solid image output to the 10000th sheet among the belt-shaped solid images, using a spectroscopic variable angle color difference meter GC5000L manufactured by Nippon Denshoku Industries Co., Ltd. as a variable angle photometer, Incident light with an incident angle of −45 ° is incident on the solid image, and the reflectance A at the light receiving angle + 30 ° and the reflectance B at the light receiving angle −30 ° are measured. The reflectance A and reflectance B were measured at intervals of 20 nm for light having a wavelength in the range of 400 nm to 700 nm, and the average value of the reflectance at each wavelength was used. The ratio (X / Y) was calculated from these measurement results. The results are shown in Table 1.
The higher the ratio (X / Y), the higher the glitter feeling, and the lower the ratio (X / Y), the stronger the dull feeling and the less the feeling of glitter.

(Observation of toner scattering (fogging) on non-image area)
Among the strip-shaped solid images, for the solid image output for the fifth image and the solid image output for the 10,000th image, the boundary portion of the image (the boundary portion between the image portion and the non-image portion on the upstream side and the downstream side in the traveling direction) ) Fog (scattering of the toner from the image area to the non-image area) was visually observed and evaluated based on the following evaluation criteria. The results are shown in Table 1.
A (◎): No fogging is observed on both upstream and downstream sides B (◯): Slight fogging is observed on the upstream side, but not observed on the downstream side C (Δ): Fog is observed on both the upstream and downstream sides D (x) that is confirmed but is within the allowable range: The fog exceeds the allowable range

From the above results, in this embodiment, compared with the comparative example, a high image brightness is obtained, and a non-image is formed from the image portion when a toner image having a high image height is transferred to a recording medium in a high temperature and high humidity environment. It can be seen that the phenomenon of toner scattering (fogging) is suppressed.
In particular, the glitter toners of Examples 1 to 5 that contain urea-modified polyester resin in the toner particles have lower image density images than the glitter toner of Example 6 that does not contain urea-modified polyester resin in the toner particles. It can be seen that the phenomenon (fogging) in which toner is scattered from the image portion to the non-image portion when a toner image having a high image height is transferred to a recording medium in a high-temperature and high-humidity environment after being continuously formed is suppressed. .

2 Toner particles 4 Bright pigments 111B, 111Y, 111M, 111C, 111K, 207 Photoconductor 112, 222 Drive roll 113, 224 Support roll 114 Bias roll 115B, 115Y, 115M, 115C, 115K Cleaning device 116 Belt cleaner 117B, 117Y 117M, 117C, 117K, 212 Primary transfer roll 118B, 118Y, 118M, 118C, 118K, 208 Charging roll 119B, 119Y, 119M, 119C, 119K, 209 Exposure device 120B, 120Y, 120M, 120C, 120K, 211 Developing device 133, 220 Intermediate transfer belt 134, 226 Secondary transfer roll 135, 228 Fixing device 140B, 140Y, 140M, 140C, 140K Toner cartridge 150B, 150Y, 150M, 150C, 150K Image forming unit 160 Voltage application device 200 Process cartridge 213 Photoconductor cleaning device 216 Mounting rail 217 Housing 218 Opening 300, P Recording paper

Claims (10)

The ratio (Mw / Mp) to the peak top molecular weight (Mp) in the weight average molecular weight (Mw) is 1.2 or more and 2.5 or less, and the peak top molecular weight (Mp) value is 3000 or more and 10,000 or less. A resin ring,
A flat luster pigment,
Bright toner having toner particles containing   The glitter toner according to claim 1, wherein the toner particles include a polyester resin as the binder resin.   The glitter toner according to claim 1, wherein the toner particles include a crystalline polyester resin as the binder resin.   The glitter toner according to any one of claims 1 to 3, wherein the toner particles include a urea-modified polyester resin as the binder resin.   An oil phase liquid adjusting step of adjusting an oil phase liquid, wherein the toner particles are a mixed liquid obtained by mixing the organic solvent that dissolves the binder resin, the binder resin, and the glitter pigment; The suspension obtained by dispersing in a medium to adjust the suspension, and the solvent removal step of removing the organic solvent from the suspension are obtained. The glitter toner according to any one of the above items.   An electrostatic charge image developer comprising the glitter toner according to any one of claims 1 to 5. Containing the glitter toner according to any one of claims 1 to 5,
A toner cartridge to be attached to and detached from the image forming apparatus. A developing means for containing the electrostatic charge image developer according to claim 6 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer,
A process cartridge attached to and detached from the image forming apparatus. An image carrier,
Charging means for charging the surface of the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
Developing means for containing the electrostatic charge image developer according to claim 6 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer;
Transfer means for transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
Fixing means for fixing the toner image transferred to the surface of the recording medium;
An image forming apparatus comprising: A charging step for charging the surface of the image carrier;
An electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged image carrier;
A developing step of developing an electrostatic charge image formed on the surface of the image carrier as a toner image with the electrostatic charge image developer according to claim 6;
A transfer step of transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
A fixing step of fixing the toner image transferred to the surface of the recording medium;
An image forming method comprising: