JP2018021956A - 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 can adjust a granular feeling of a photoluminescent image.SOLUTION: A photoluminescent toner contains resin particles each containing a binder resin; at least part of the resin particles contains a photoluminescent pigment; the resin particles have a large diameter-side volume granularity distribution index (upper GSDv) of 1.40 or more and 1.60 or less, and a small diameter-side volume granularity distribution index (lower GSDv) of 1.40 or more and 1.60 or less, or a first peak is present within a range of 8 μm or more and 20 μm or less in a granularity distribution of the resin particles and a second peak is present within a range of 2 μm or more and less than 8 μm; the ratio of the resin particles containing the photoluminescent pigment in the resin particles having a particle diameter of 3 μm or more and 6 μm or less is 50 number % or more.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 offices and general homes, there is an increasing demand for reproducing a glittering image having a metallic color included in a subject with a copy or a printer.
The glitter of the glitter image is exhibited by the reflection of light by the glitter pigment contained in the glitter toner. In order to exhibit the glitter, the surface area of each glitter pigment must be increased, and therefore, the glitter pigment is often used in a scaly shape (see, for example, Patent Document 1).

JP 2013-156343 A

Two types of glossiness (flop index: FI value) and graininess (Sparkle Grade) are known as indicators of the brightness of glitter images.
The FI value of the glitter image is a value mainly determined by the orientation of the glitter pigment in the glitter image. Therefore, it was possible to adjust the FI value (that is, glossiness) of the glitter image by controlling the orientation of the glitter pigment contained in the glitter toner transferred onto the recording medium. Examples of a method for controlling the orientation of the glitter pigment include a method of adjusting a fixing pressure, a fixing temperature, a fixing speed, and the like.
On the other hand, the sparkle grade of the glitter image is a value determined mainly by the particle size distribution of the glitter pigment in the glitter image. However, although it was possible to adjust the particle size distribution of the glitter pigment used as a raw material in the production process of the glitter toner, it is possible to change the particle size distribution of the glitter pigment contained in the glitter toner after the production. I couldn't. Therefore, it is difficult to adjust the graininess of the glitter image.

  The present invention has been made in view of the above-described conventional technology, as compared with the case where the resin particle has one peak in the particle size distribution and the upper GSDv and the lower GSDv of the resin particle are less than 1.40. An object of the present invention is to provide a glitter toner capable of adjusting the graininess of a glitter image.

Specific means for achieving the above object are as follows.
That is, the invention according to claim 1
Containing resin particles including a binder resin,
At least a part of the resin particles contains a glitter pigment,
The large particle volume particle size distribution index (upper GSDv) of the resin particles is 1.40 or more and 1.60 or less,
The small particle volume particle size distribution index (lower GSDv) of the resin particles is 1.40 or more and 1.60 or less,
A glittering toner in which the proportion of resin particles containing the glitter pigment in the resin particles having a particle diameter of 3 μm or more and 6 μm or less is 50% by number or more.

The invention according to claim 2
Containing resin particles including a binder resin,
At least a part of the resin particles contains a glitter pigment,
In the particle size distribution of the resin particles, a first peak exists in a range of 8 μm or more and 20 μm or less, and a second peak exists in a range of 2 μm or more and less than 8 μm,
A glittering toner in which the proportion of resin particles containing the glitter pigment in the resin particles having a particle diameter of 3 μm or more and 6 μm or less is 50% by number or more.

The invention according to claim 3
The glitter toner according to claim 2, wherein a difference between a particle diameter of the first peak and a particle diameter of the second peak is 6 μm or more and 12 μm or less.

The invention according to claim 4
The first peak is present in a range of 9 μm or more and 12 μm or less, and the second peak is present in a range of 2 μm or more and 5 μm or less in the particle size distribution of the glitter pigment. The glitter toner described in 1.

The invention according to claim 5
An electrostatic charge image developer comprising the glitter toner according to any one of claims 1 to 4.

The invention according to claim 6
Containing the glitter toner according to any one of claims 1 to 4,
A toner cartridge to be attached to and detached from the image forming apparatus.

The invention according to claim 7 provides:
A developing means for accommodating the electrostatic charge image developer according to claim 5 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer,
A process cartridge attached to and detached from the image forming apparatus.

The invention according to claim 8 provides:
An image carrier,
Charging means for charging the surface of the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
Developing means for containing the electrostatic charge image developer according to claim 5 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;
Control means for adjusting a sparkle grade of the toner image in accordance with designated information by controlling at least one of a developing bias applied in the developing means and a transfer bias applied in the transfer means;
An image forming apparatus comprising:

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 5 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer;
An intermediate transfer member on which a toner image formed on the surface of the image carrier is primarily transferred;
Primary transfer means for primarily transferring a toner image formed on the surface of the image carrier to the intermediate transfer member;
Secondary transfer means for secondary transfer of the toner image primarily transferred to the intermediate transfer body onto the surface of the recording medium;
Fixing means for fixing the toner image transferred to the surface of the recording medium;
By controlling at least one of the developing bias applied in the developing unit, the primary transfer bias applied in the primary transfer unit, and the secondary transfer bias applied in the secondary transfer unit, the specified information is obtained. Control means for adjusting the sparkle grade of the toner image according to
An image forming apparatus comprising:

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 image formed on the surface of the image carrier as a toner image by the electrostatic image developer according to claim 5;
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;
Have
An image forming method in which a sparkle grade of the toner image is adjusted according to designated information by controlling at least one of a developing bias applied in the developing step and a transfer bias applied in the transferring step.

The invention according to claim 11 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 image formed on the surface of the image carrier as a toner image by the electrostatic image developer according to claim 5;
A primary transfer step in which a toner image formed on the surface of the image carrier is primarily transferred to an intermediate transfer member;
A secondary transfer step of secondarily transferring the toner image primarily transferred to the intermediate transfer body onto the surface of the recording medium;
Fixing the toner image transferred to the surface of the recording medium,
By controlling at least one of the development bias applied in the development step, the primary transfer bias applied in the primary transfer step, and the secondary transfer bias applied in the secondary transfer step, the specified information is obtained. An image forming method in which a sparkle grade of the toner image is adjusted accordingly.

According to the invention according to claim 1 or claim 2, compared with the case where there is one peak in the particle size distribution of the resin particles and the upper GSDv and lower GSDv of the resin particles are less than 1.40, the glitter image A glittering toner capable of adjusting the graininess is provided.
According to the third aspect of the present invention, the graininess of the glitter image is compared with the case where the difference between the particle diameter of the first peak and the particle diameter of the second peak is less than 6 μm or more than 12 μm. Becomes easier to adjust.
According to the fourth aspect of the present invention, the graininess of the glitter image is more easily adjusted compared to the case where the first peak and the second peak are not present in the particle size distribution of the glitter pigment.
According to the fifth aspect of the present invention, the graininess of the glitter image is improved as compared with the case where the resin particle has one peak in the particle size distribution and the upper GSDv and the lower GSDv of the resin particles are less than 1.40. An adjustable electrostatic charge image developer is provided.
According to the invention of claim 6, compared to the case where the resin particle has one peak in the particle size distribution and the upper GSDv and lower GSDv of the resin particles are less than 1.40, the graininess of the glitter image is improved. A toner cartridge is provided that contains an adjustable glitter toner.
According to the seventh aspect of the present invention, the graininess of the glitter image is improved as compared with the case where the resin particle has one peak in the particle size distribution and the upper GSDv and the lower GSDv of the resin particle are less than 1.40. A process cartridge containing an adjustable electrostatic charge image developer is provided.
According to the inventions according to claim 8 and claim 9, compared to the case where there is one peak in the particle size distribution of the resin particles and the upper GSDv and lower GSDv of the resin particles are less than 1.40, the glitter image An image forming apparatus using an electrostatic charge image developer capable of adjusting the graininess of the image is provided.
According to the invention according to claim 10 and claim 11, compared with the case where there is one peak in the particle size distribution of the resin particles and the upper GSDv and lower GSDv of the resin particles are less than 1.40, the glitter image An image forming method using an electrostatic image developer capable of adjusting the graininess of the image is provided.

FIG. 3 is a cross-sectional view schematically showing the glitter toner of the present embodiment. It is a figure explaining the state of a screw about an example of a screw extruder used for manufacture of the luster toner of this 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 the process cartridge of this embodiment.

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

<Brightness toner>
The glitter toner of the first embodiment (hereinafter sometimes referred to as first glitter toner) contains resin particles containing a binder resin, and at least a part of the resin particles contains a glitter pigment. A large-diameter side volume particle size distribution index (upper GSDv) of the resin particles is 1.40 to 1.60, and a small-diameter side volume particle size distribution index (lower GSDv) of the resin particles is 1.40 to 1. The ratio of the resin particles containing the glitter pigment to the resin particles having a particle diameter of 60 or less and a particle diameter of 3 μm or more and 6 μm or less is 50% by number or more.
The glitter toner of the second embodiment (hereinafter sometimes referred to as second glitter toner) contains resin particles containing a binder resin, and at least a part of the resin particles is glitter. In the particle size distribution of the resin particles, the first peak is present in the range of 8 μm to 20 μm, the second peak is present in the range of 2 μm to less than 8 μm, and the particle diameter is 3 μm to 6 μm. The ratio of the resin particles containing the glitter pigment in the resin particles is 50% by number or more.
Hereinafter, the first glitter toner and the second glitter toner may be collectively referred to as the glitter toner of this embodiment.

In the present embodiment, the upper GSDv and the lower GSDv are values calculated based on the following equations.
Upper GSDv = (D84v / D50v) ^1/2
Lower GSDv = (D50v / D16v) ^1/2
In the above formula, D16v, D50v, and D84v are respectively a cumulative distribution from the small diameter side based on the particle size distribution, and a particle size (D16v) that is cumulative 16% and a particle size that is cumulative 50% on a volume basis. (D50v) and a particle size (D84v) of 84% cumulative.

According to the glitter toner of this embodiment, the graininess of the glitter image is adjusted. The reason is not clear, but can be considered as follows.
The graininess of the glitter image is a value mainly determined by the particle size distribution of the glitter pigment in the glitter image. Although it was possible to adjust the particle size distribution of the glitter pigment used as a raw material in the production process of the glitter toner, the particle size distribution of the glitter pigment contained in the glitter toner can be changed after production. There wasn't. Therefore, it is difficult to adjust the graininess of the glitter image.
The present inventors have noted that the particle size of the resin particles contained in the glitter toner is related to the ease of transfer in the transfer process and the ease of development in the development process.
That is, the larger the particle diameter of the resin particles contained in the glitter toner, the larger the charge amount per resin particle. Therefore, by increasing the developing bias, for example, the AC component in the developing process, highly charged resin particles (that is, resin particles having a large particle size) can easily move, while low charged resin particles (that is, small particle size). Resin particles) tend to be difficult to develop under the influence of charge injection. By utilizing this phenomenon, the particle size distribution of the resin particles forming the toner image formed on the image carrier is changed from the particle size distribution of the resin particles contained in the glittering toner by controlling the development bias. It becomes possible.

Further, the larger the particle diameter of the resin particles contained in the glitter toner, the larger the charge amount per resin particle. However, when the charge amount per resin particle increases, the electrostatic adhesion force of the resin particles increases. Will increase. In the transfer process (primary transfer process and secondary transfer process), a relatively high transfer electric field is required to transfer resin particles having a large particle size. On the other hand, when the transfer electric field is increased, the resin particles having a small particle diameter tend to be difficult to transfer due to the influence of charge injection because the charge amount is relatively low. Note that the glitter toner contains a glitter pigment mainly composed of a metal, and therefore, dielectric breakdown is likely to occur as compared with a color toner including an organic colorant. Due to the dielectric breakdown, the charge escapes from the toner and tends to be difficult to transfer. Since the resin particles having a small particle size have a smaller amount of charge compared to the resin particles having a large particle size, it is considered that the influence of the dielectric breakdown on the ease of transfer is large.
By utilizing this phenomenon and controlling the transfer electric field, the particle size distribution of the resin particles contained in the toner image after transfer in the transfer process (primary transfer process and secondary transfer process) is included in the toner image before transfer. It becomes possible to change from the particle size distribution of the resin particles.
Generally, the particle diameter of the resin particles contained in the glitter toner tends to have a correlation with the particle diameter of the glitter pigment contained in the resin particles. That is, the particle diameter of the glitter pigment contained in the resin particles having a relatively large particle diameter tends to be small while the particle diameter of the glitter pigment contained in the resin particles having a relatively small particle diameter is large. For this reason, adjusting the particle size distribution of the resin particles constituting the toner image means adjusting the particle size distribution of the glitter pigment contained in the toner image.
By adjusting the particle size distribution of the resin particles contained in the toner image, the particle size distribution of the glitter pigment contained in the toner image is adjusted, and as a result, the sparkle grade of the toner image can be adjusted according to the specified information. It becomes possible.

In order to adjust the particle size distribution of the resin particles contained in the toner image, it is important that the particle size distribution of the resin particles contained in the glitter toner is wide. Therefore, in the first glittering toner, the large-diameter side volume particle size distribution index (upper GSDv) of the resin particles is 1.40 to 1.60, and the small-diameter side volume particle size distribution index (lower GSDv) of the resin particles is It was decided that it was 1.40 or more and 1.60 or less. In the second glittering toner, the first peak is present in the range of 8 μm or more and 20 μm or less and the second peak is present in the range of 2 μm or more and less than 8 μm in the particle size distribution of the resin particles. When the resin particles contained in the first glitter toner and the second glitter toner satisfy the above-described conditions, the particle size distribution of the resin particles contained in the toner image can be easily adjusted.
In the glitter toner of this embodiment, the ratio of the resin particles containing the glitter pigment to the resin particles having a particle diameter of 3 μm or more and 6 μm or less is 50% by number or more. In general, the smaller the particle size of the resin particles, the higher the proportion of resin particles that do not contain a luster pigment. Therefore, when the proportion of resin particles not containing the glitter pigment in the resin particles having a relatively small particle diameter is large, the particle size distribution of the glitter pigment to be adjusted by adjusting the particle size distribution of the resin particles is desired. It may not be distributed. If the ratio of the resin particles containing the glitter pigment to the resin particles having a particle diameter of 3 μm or more and 6 μm or less is 50% by number or more, the particle size distribution of the glitter pigment is adjusted by adjusting the particle size distribution of the resin particles. It becomes easy.

Sparkle grade, which is an index of graininess, is an index of glittering feeling in metallic prints. The higher the numerical value (higher graininess), the higher the glittering feeling and the gorgeous impression. Images are obtained.
Sparkle grade can be measured using a multi-angle spectrocolorimeter (BYK-mac) manufactured by Toyo Seiki Seisakusho.

The glitter toner of this embodiment contains resin particles containing a binder resin, and at least a part of the resin particles contains a glitter pigment. The resin particles may contain other additives such as a release agent as necessary. Hereinafter, the resin particles containing the glitter pigment and the resin particles not containing the glitter pigment may be collectively referred to as toner particles.
Further, the glittering toner of this embodiment may include an external additive as necessary.

-Bright pigment-
Examples of bright pigments include metal pigments such as aluminum, brass, bronze, nickel, stainless steel, and zinc; mica coated with titanium oxide, yellow iron oxide, etc .; aluminosilicate, basic carbonate, barium sulfate, titanium oxide Flaky crystals or plate crystals such as bismuth oxychloride; flaky glass powder, flaky glass powder deposited by metal deposition, and the like. Among these, a metal pigment is desirable from the viewpoint of specular reflection intensity, and a flat-shaped metal pigment is more desirable from the viewpoint of higher specular reflection intensity. Among the metal pigments, an aluminum pigment is desirable from the viewpoint of easily obtaining a flat powder. The surface of the metal pigment may be coated with silica, acrylic resin, polyester resin or the like.

  The volume average particle diameter of the glitter pigment is preferably 3 μm to 20 μm, more preferably 4.5 μm to 18 μm, and particularly preferably 6 μm to 16 μm.

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

  The particle size distribution of the glitter pigment is not particularly limited. For example, the first peak may exist in the range of 9 μm to 12 μm, and the second peak may exist in the range of 2 μm to 5 μm. preferable. When the glitter pigment has a particle size distribution having a first peak and a second peak, the upper GSDv and the lower GSDv of the resin particles contained in the first glitter toner tend to be easily within the specified range. is there. Further, the glitter pigment exhibits a particle size distribution having the first peak and the second peak, so that the particle size distribution of the resin particles contained in the second glitter toner exhibits the above-described two peaks. Tend to be.

  The content of the glitter pigment in the toner of the exemplary embodiment is preferably 1 part by mass or more and 70 parts by mass or less, and more preferably 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the binder resin.

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

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

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

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

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

The glass transition temperature (Tg) of the polyester resin is preferably 50 ° C. or higher and 80 ° C. or lower, and more preferably 50 ° C. or higher and 65 ° C. or lower.
The glass transition temperature is obtained from a DSC curve obtained by differential scanning calorimetry (DSC), more specifically, according to JIS K-7121-1987 “Method for measuring glass transition temperature”. It is calculated | required by description "extrapolated glass transition start temperature" of description.

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

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

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

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

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 determined by the “melting peak temperature” described in the method for determining the melting temperature in JIS K-7121-1987 “Method for measuring the transition temperature of plastic” from the DSC curve obtained by differential scanning calorimetry (DSC). Ask.

  The content of the release agent is, for example, preferably 1% by mass 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 known additives such as a magnetic material, a charge control agent, and inorganic powder. These additives are contained in the toner particles as internal additives.

-Physical properties of glitter toner-
Further, the volume average particle diameter of the glitter toner of the present embodiment is preferably 1 μm or more and 30 μm or less, and more preferably 3 μm or more and 20 μm or less.

  The glitter toner of the present embodiment has a reflectance at a light receiving angle of + 30 ° measured when a solid image is formed and irradiated with incident light having an incident angle of −45 ° by a goniophotometer. The ratio (A / B) between A and the reflectance B at a light receiving angle of −30 ° is preferably 1.5 or more and 60 or less.

When the ratio (A / B) is 1.5 or more, the reflection on the side opposite to the incident side (angle + side) is more appropriate than the reflection on the side on which incident light is incident (angle-side). This means that there are many, that is, irregular reflection of 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 (A / B) is less than 1.5, the gloss may not be confirmed even when the reflected light is visually recognized, and the glitter may be slightly inferior.
On the other hand, if the ratio (A / B) exceeds 60, the color of the background may be difficult to see.

  The ratio (A / B) is more preferably 5 or more and 50 or less, and further preferably 10 or more and 40 or less.

Measurement of the ratio (A / B) with a goniophotometer First, the incident angle and the light receiving angle will be described. 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 (A / B) will be described.
In this embodiment, when measuring the ratio (A / B), a “solid image” is first formed by the following method. The developer used as a sample is filled in a developing unit of DocuCentre-III C7600 manufactured by Fuji Xerox Co., Ltd., and recording paper (OK topcoat + paper, manufactured by Oji Paper Co., Ltd .: glossiness 75, whiteness 85. 0) A solid image having a toner application amount of 4.5 g / m ² is formed at a fixing temperature of 190 ° C. and a fixing pressure of 4.0 kgf / cm ² .
Using a spectral variable angle color difference meter GC5000L manufactured by Nippon Denshoku Industries Co., Ltd. as a variable angle photometer, incident light having an incident angle of −45 ° is incident on the solid image. The reflectance A at an angle of + 30 ° and the reflectance B at a light receiving angle of −30 ° are measured. The reflectance A and 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 (A / B) is calculated from these measurement results.

The glitter toner of the present embodiment desirably satisfies the following requirements (1) to (2) from the viewpoint of satisfying the ratio (A / B) described above.
(1) The average equivalent circle diameter D is longer than the average maximum thickness C of the toner. (2) When the cross section in the thickness direction of the toner is observed, the long axis direction of the toner and the length of the bright pigment The number of glitter pigments having an angle with the axial direction in the range of −30 ° to + 30 ° is 60% or more of the total glitter pigments observed.

Here, FIG. 1 is a sectional view schematically showing a toner that satisfies the requirements (1) and (2). The schematic diagram shown in FIG. 1 is a cross-sectional view in the thickness direction of the toner.
The toner 2 shown in FIG. 1 is a flat toner having an equivalent circle diameter longer than the thickness L, and contains a scale-like metal pigment 4 which is a kind of glitter pigment.

・ Average maximum thickness C and average equivalent circle diameter D
As shown in (1) above, it is desirable that the glossy toner of this embodiment has an average equivalent circle diameter D longer than the 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, more preferably in the range of 0.010 to 0.200. Desirably, the range from 0.050 to 0.100 is particularly desirable.
When the ratio (C / D) is 0.001 or more, the strength of the glittering toner is ensured, breakage due to stress during image formation is suppressed, and charging due to exposure of the glittering pigment is reduced. Resulting fog 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 is placed on a smooth surface, and is vibrated and dispersed so that there is no unevenness. For 1000 toners, the color laser microscope “VK-9700” (manufactured by Keyence Corporation) was magnified 1000 times to measure the maximum thickness C and the equivalent circle diameter D of the surface viewed from above, and the arithmetic average of them. Calculate by finding the value.

The angle between the major axis direction in the cross section of the toner and the major axis direction of the glitter pigment As shown in (2) above, when the cross section in the thickness direction of the toner is observed, It is desirable that the number of glitter pigments having an angle with the major axis direction of the glitter pigment in a range of −30 ° to + 30 ° is 60% or more of all the glitter pigments to be observed. Furthermore, the number is more preferably 70% or more and 95% or less, and particularly preferably 80% or more and 90% or less.
When the number is 60% or more, excellent glitter can be obtained.

Here, a method for observing the cross section of the toner will be described.
After embedding the toner 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 (in this embodiment, a LEICA ultramicrotome (manufactured by Hitachi Technologies)) to prepare an observation sample. A cross section of the toner is observed with a transmission electron microscope (TEM) at a magnification of about 5000 times. Using the image analysis software, the number of glitter pigments in which the angle between the major axis direction of the toner cross section and the major axis direction of the glitter pigment is in the range of −30 ° to + 30 ° with respect to the 1,000 toners observed. And calculate the ratio.

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

-Production of glitter toner-
The glittering toner of this embodiment may be produced by adding an external additive to the toner particles after the toner particles are produced.
The method for producing the toner particles is not particularly limited, and the toner particles are produced by a known dry method such as a kneading and pulverizing method, a wet method such as an aggregation coalescence method or a dissolution suspension method.

The kneading and pulverization method involves mixing each material such as a luster pigment, then melt-kneading the above materials using a kneader, an extruder, etc., roughly pulverizing the obtained melt-kneaded product, and then using a jet mill or the like. This is a method of pulverizing and obtaining toner particles having a target particle size by an air classifier.
More specifically, the kneading and pulverizing method is divided into a kneading step of kneading a toner forming material containing a glitter pigment and a binder resin, and a pulverizing step of pulverizing the kneaded product. As needed, you may have other processes, such as a cooling process of cooling the kneaded material formed by the kneading process.
Each process related to the kneading / pulverizing method will be described in detail.

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

  Examples of the kneader used in the kneading step include a single screw extruder, a twin screw extruder, and the like. Hereinafter, as an example of a kneader, a kneader having a feed screw portion and two kneading portions will be described with reference to the drawings, but the present invention is not limited to this.

FIG. 2 is a view for explaining the state of the screw in an example of the screw extruder used in the kneading step in the method for producing the glittering toner of the present embodiment.
The screw extruder 11 includes a barrel 12 having a screw (not shown), an inlet 14 for injecting a toner forming material as a raw material of the toner into the barrel 12, and an aqueous medium added to the toner forming material in the barrel 12. A liquid addition port 16 for discharging the toner, and a discharge port 18 for discharging the kneaded material formed by kneading the toner forming material in the barrel 12.

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

  The barrel 12 is provided with temperature control means (not shown) that is different for each block. That is, the temperature may be controlled at different temperatures from the block 12A to the block 12J. FIG. 2 shows a state in which the temperature of the block 12A and the block 12B is controlled to t0 ° C., the temperature of the block 12C to the block 12E is controlled to t1 ° C., and the temperature of the block 12F to the block 12J is controlled to t2 ° C. Yes. Therefore, the toner forming material of the kneading part NA is heated to t1 ° C., and the toner forming material of the kneading part NB is heated to t2 ° C.

  When a toner forming material including a binder resin, a bright pigment, and a release agent as necessary is supplied from the injection port 14 to the barrel 12, the toner forming material is sent to the kneading portion NA by the feed screw portion SA. . At this time, since the temperature of the block 12C is set to t1 ° C., the toner forming material is fed into the kneading portion NA in a state of being heated and changed into a molten state. Since the temperatures of the block 12D and the block 12E are also set to t1 ° C., the toner forming material is melt-kneaded at the temperature of t1 ° C. in the kneading portion NA. The binder resin and the release agent are in a molten state at the kneading portion NA and are subjected to shearing by the screw.

Next, the toner forming material that has been kneaded in the kneading part NA is sent to the kneading part NB by the feed screw part SB.
Next, the aqueous medium is added to the toner forming material by injecting the aqueous medium into the barrel 12 from the liquid addition port 16 in the feed screw portion SB. Further, FIG. 2 shows a mode in which the aqueous medium is injected in the feed screw part SB. However, the present invention is not limited to this, and the aqueous medium may be injected in the kneading part NB, and the feed screw part SB and the kneading part NB. In both cases, an aqueous medium may be injected. That is, the position and the injection location for injecting the aqueous medium are selected as necessary.

As described above, when the aqueous medium is injected into the barrel 12 from the liquid addition port 16, the toner forming material and the aqueous medium in the barrel 12 are mixed, and the toner forming material is cooled by the latent heat of vaporization of the aqueous medium, The temperature of the toner forming material is maintained.
Finally, the kneaded material formed by being melt-kneaded by the kneading part NB is transported to the discharge port 18 by the feed screw part SC and discharged from the discharge port 18.
As described above, the kneading step using the screw extruder 11 shown in FIG. 2 is performed.

-Cooling process-
The cooling step is a step of cooling the kneaded product formed in the kneading step. In the cooling step, cooling is performed from the temperature of the kneaded product at the end of the kneading step to 40 ° C. or lower at an average temperature decrease rate of 4 ° C./sec or higher. It is preferable to do. When the cooling rate of the kneaded product is low, the mixture finely dispersed in the binder resin in the kneading step (the bright pigment and, if necessary, an internal additive such as a release agent internally added in the toner particles) The mixture) may recrystallize and the dispersion diameter may increase. On the other hand, quenching at the above average temperature drop rate is preferable because the dispersion state immediately after the end of the kneading process is maintained as it is. The average temperature decreasing rate refers to the average value of the temperature decreasing rate from the temperature of the kneaded product at the end of the kneading process (for example, t2 ° C. when using the screw extruder 11 in FIG. 2) to 40 ° C.
Specific examples of the cooling method in the cooling step include a method using a rolling roll in which cold water or brine is circulated, a sandwiching cooling belt, and the like. When cooling is performed by the above method, the cooling rate is determined by the speed of the rolling roll, the flow rate of brine, the supply amount of the kneaded material, the slab thickness at the time of rolling the kneaded material, and the like. The slab thickness is preferably 1 mm or more and 3 mm or less.

-Crushing process-
The kneaded product cooled in the cooling step is pulverized in the pulverization step, and particles are formed. In the pulverization step, for example, a mechanical pulverizer or a jet pulverizer is used.

-Classification process-
The particles obtained by the pulverization step may be classified by a classification step in order to obtain toner particles having a volume average particle diameter in a target range, if necessary. In the classification process, conventionally used centrifugal classifiers, inertia classifiers, etc. are used, and fine powder (particles smaller than the target particle size) and coarse powder (target particle size). Larger particles) are removed.

-External addition process-
To the obtained toner particles, inorganic particles typified by silica, titania, and aluminum oxide may be added and adhered for the purpose of charge adjustment, fluidity provision, charge exchangeability and the like. These are performed by, for example, a V-type blender, a Henschel mixer, a Redige mixer, or the like, and may be attached in stages. The addition amount of the external additive is preferably in the range of 0.1 to 5 parts by mass, more preferably in the range of 0.3 to 2 parts by mass with respect to 100 parts by mass of the toner particles.

-Sieving process-
You may provide a sieving process after the said external addition process as needed. Specific examples of the sieving method include a gyro shifter, a vibration sieving machine, and a wind sieving machine. By sieving, coarse particles of the external additive and the like are removed, and generation of streaks on the photosensitive member and scumming in the apparatus are suppressed.

  In this embodiment, an aggregation coalescence method may be used in which the shape of the toner particles and the particle diameter of the toner particles can be easily controlled, and the control range of the toner particle structure such as a core-shell structure is wide. Hereinafter, a method for producing toner particles by the aggregation coalescence method will be described in detail.

  The agglomeration and coalescence method according to this embodiment is a resin particle dispersion preparation step for emulsifying the raw material constituting the toner particles to form resin particles, an agglomeration step for forming aggregates of the resin particles, and the aggregates A fusion process.

(Resin particle dispersion preparation process)
The resin particle dispersion can be prepared by using a general polymerization method, such as emulsion polymerization, suspension polymerization, dispersion polymerization, or the like. In addition, a solution in which an aqueous medium and a binder resin are mixed is used. Alternatively, emulsification may be performed by applying a shearing force with a disperser. At that time, particles may be formed by heating to lower the viscosity of the resin component. A dispersant may be used for stabilizing the dispersed resin particles. Furthermore, if the resin is oily and dissolves in a solvent with a relatively low solubility in water, the resin is dissolved in those solvents and dispersed in water together with a dispersant and a polymer electrolyte, and then heated or decompressed. By evaporating the solvent, a resin particle dispersion is produced.

Examples of the aqueous medium include water such as distilled water and ion-exchanged water; alcohols; and the like. Water is preferable.
Examples of the dispersant used in the resin particle dispersion preparation step include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, sodium polyacrylate, and sodium polymethacrylate; dodecylbenzene Anionic surfactants such as sodium sulfonate, sodium octadecyl sulfate, sodium oleate, sodium laurate, potassium stearate, cationic surfactants such as laurylamine acetate, stearylamine acetate, lauryltrimethylammonium chloride, lauryldimethylamine Zwitterionic surfactants such as oxides, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polymers Surfactants such as nonionic surfactants such as polyoxyethylene alkyl amines; and the like are; tricalcium phosphate, aluminum hydroxide, calcium sulfate, calcium carbonate, inorganic salts such as barium carbonate.

  Examples of the disperser used for preparing the emulsion include a homogenizer, a homomixer, a pressure kneader, an extruder, and a media disperser. As the size of the resin particles, the average particle diameter (volume average particle diameter) is desirably 1.0 μm or less, more desirably 60 nm or more and 300 nm or less, and further desirably 150 nm or more and 250 nm or less. . When the thickness is 60 nm or more, the resin particles tend to be unstable particles in the dispersion, and thus the resin particles may be easily aggregated. If the particle size is 1.0 μm or less, the particle size distribution of the toner may become narrow.

  In preparing the release agent dispersion, the release agent is dispersed in water together with an ionic surfactant, a polymer electrolyte such as a polymer acid or a polymer base, and then heated to a temperature equal to or higher than the melting temperature of the release agent. Dispersion treatment is performed using a homogenizer or a pressure discharge type disperser to which a strong shearing force is applied while heating. By undergoing such treatment, a release agent dispersion is obtained. During the dispersion treatment, an inorganic compound such as polyaluminum chloride may be added to the dispersion. Examples of desirable inorganic compounds include polyaluminum chloride, aluminum sulfate, highly basic polyaluminum chloride (BAC), polyaluminum hydroxide, and aluminum chloride. Among these, polyaluminum chloride and aluminum sulfate are desirable.

By the dispersion treatment, a release agent dispersion liquid containing release agent particles having a volume average particle diameter of 1 μm or less is obtained. In addition, the more preferable volume average particle diameter of the release agent particles is 100 nm or more and 500 nm or less.
When the volume average particle diameter is 100 nm or more, the properties of the binder resin to be used are affected, but in general, the release agent component is easily taken into the toner. In the case of 500 nm or less, the state of dispersion of the release agent in the toner is good.

For the preparation of the glitter pigment dispersion, a known dispersion method can be used.For example, a general dispersion means such as a rotary shear type homogenizer, a ball mill having a medium, a sand mill, a dyno mill, or an optimizer can be employed. It is not limited. The glitter pigment is dispersed in water together with a polymer electrolyte such as an ionic surfactant, a polymer acid, or a polymer base. The dispersed pigment may have a volume average particle diameter of 20 μm or less, but if it is in the range of 3 μm or more and 16 μm or less, the dispersion of the glitter pigment in the toner is preferable without impairing the cohesiveness.
Also, a dispersion of the glitter pigment coated with the binder resin is prepared by dispersing and dissolving the glitter pigment and the binder resin in a solvent, mixing, and dispersing in water by phase inversion emulsification or shear emulsification. May be.

(Aggregation process)
In the agglomeration step, a dispersion of resin particles, a bright pigment dispersion, a release agent dispersion, etc. are mixed to form a mixed solution, which is heated to agglomerate at a temperature equal to or lower than the glass transition temperature of the resin particles. Form. Aggregated particles are often formed by acidifying the pH of the mixture under stirring. It becomes possible to make ratio (C / D) into a preferable range with the said stirring conditions. More specifically, the ratio (C / D) can be reduced by heating at a high speed and heating at the stage of forming aggregated particles, and the ratio can be reduced by heating at a lower speed and at a lower temperature. (C / D) can be increased. In addition, as pH, the range of 2-7 is desirable, and it is also effective in this case to use a flocculant.
Further, in the aggregation step, the release agent dispersion may be added and mixed at once with various dispersions such as a resin particle dispersion, or may be added in multiple portions.

  As the aggregating agent, a surfactant having a polarity opposite to that of the surfactant used for the dispersant, an inorganic metal salt, and a divalent or higher-valent metal complex are preferably used. In particular, the use of a metal complex is particularly desirable because the amount of the surfactant used can be reduced and the charging characteristics are improved.

  As the inorganic metal salt, an aluminum salt and a polymer thereof are particularly suitable. In order to obtain a narrower particle size distribution, the valence of the inorganic metal salt is bivalent than monovalent, trivalent than bivalent, trivalent than trivalent, and tetravalent than trivalent. Inorganic metal salt polymers are more suitable.

  Further, a toner having a configuration in which the surface of the core aggregated particles is coated with a resin may be prepared by additionally adding a resin particle dispersion when the aggregated particles have a desired particle size (coating step). In this case, the release agent and the glitter pigment are difficult to be exposed on the toner surface, which is desirable from the viewpoint of chargeability and developability. In the case of additional addition, a flocculant may be added or pH adjustment may be performed before additional addition.

(Fusion process)
In the fusion step, the agglomeration is stopped by increasing the pH of the suspension of the aggregated particles to a range of 3 to 9 under the stirring conditions in accordance with the aggregation step, and the glass transition temperature is higher than the glass transition temperature of the resin. The aggregated particles are fused by heating at a temperature.
Moreover, when it coat | covers with the said resin, this resin is also united and a core aggregated particle is coat | covered. The heating time may be performed to the extent that fusion is performed, and may be performed for about 0.5 hour to 10 hours.

Cool after fusion to obtain fused particles. Further, in the cooling step, crystallization may be promoted by reducing the cooling rate in the vicinity of the glass transition temperature (range of glass transition temperature ± 10 ° C.) of the resin, so-called slow cooling.
The fused particles obtained by fusing are made into toner particles through a solid-liquid separation process such as filtration, and a washing process and a drying process as necessary.

  To the obtained toner particles, inorganic oxides such as silica, titania, and aluminum oxide are added and adhered as external additives for the purpose of charge adjustment, fluidity provision, charge exchangeability and the like. Desirable external addition methods and addition amounts of external additives are as described above.

  In addition to the inorganic oxides described above, other components (particles) such as a charge control agent, organic particles, a lubricant, and an abrasive may be added as external additives.

  The charge control agent is not particularly limited, but a colorless or light-colored agent is desirably used. For example, quaternary ammonium salt compounds, nigrosine compounds, complexes of aluminum, chromium, triphenylmethane pigments, and the like can be given.

Examples of the organic particles include particles usually used as an external additive on the toner surface, such as vinyl resins, polyester resins, and silicone resins. These inorganic particles and organic particles are used as fluidity aids, cleaning aids, and the like.
Examples of the lubricant include fatty acid amides such as ethylene bis stearic acid amide and oleic acid amide, and fatty acid metal salts such as zinc stearate and calcium stearate.
As an abrasive | polishing agent, the above-mentioned silica, alumina, cerium oxide etc. are mentioned, for example.

Next, a method for producing toner particles by the dissolution suspension method will be described in detail.
In the dissolution suspension method, a binder resin, a bright pigment, and a material containing other components such as a release agent used as necessary are dissolved or dispersed in a solvent in which the binder resin can be dissolved. In this method, the liquid is granulated in an aqueous medium containing an inorganic dispersant, and then the solvent is removed to obtain toner particles.
Other components used in the dissolution suspension method include various components such as a charge control agent and organic particles in addition to a release agent.

  In the present embodiment, these binder resin, glitter pigment, and other components used as necessary are dissolved or dispersed in a solvent in which the binder resin can be dissolved. Whether or not the binder resin can be dissolved depends on the components of the binder resin, the molecular chain length, the degree of three-dimensionalization, etc., so it cannot be generally stated, but in general, toluene, xylene, hexane, etc. Halogenated hydrocarbons such as hydrocarbon, methylene chloride, chloroform, dichloroethane, dichloroethylene, alcohols or ethers such as ethanol, butanol, benzyl alcohol ethyl ether, benzyl alcohol isopropyl ether, tetrahydrofuran, tetrahydropyran, methyl acetate, ethyl acetate, butyl acetate Esters such as isopropyl acetate, acetone, methyl ethyl ketone, diisobutyl ketone, dimethyl oxide, diacetone alcohol, cyclohexanone, methylcyclohexanone, and other ketones or acetals are used.

  These solvents dissolve the binder resin and do not need to dissolve the glitter pigment and other components. The glitter pigment and other components only need to be dispersed in the binder resin solution. Although there is no restriction | limiting in the usage-amount of a solvent, What is necessary is just a viscosity which can be granulated in an aqueous medium. 10/90 to 50/50 (mass ratio of the former / the latter) is easily granulated by the ratio of the binder resin, the luster pigment and other materials (the former) to the solvent (the latter). From the viewpoint of typical toner particle yield.

  The binder resin, glitter pigment and other component liquid (toner mother liquid) dissolved or dispersed in a solvent are granulated to have a predetermined particle size in an aqueous medium containing an inorganic dispersant. The As the aqueous medium, water is mainly used. The inorganic dispersant is preferably selected from tricalcium phosphate, hydroxyapatite, calcium carbonate, titanium oxide and silica powder. The amount of the inorganic dispersant used is determined according to the particle size of the granulated particles, but generally it is preferably used in the range of 0.1% by mass to 15% by mass with respect to the toner mother liquor. . If the content is 0.1% by mass or more, granulation is easily performed, and if the content is 15% by mass or less, unnecessary fine particles are hardly generated and target particles are easily obtained in a high yield.

In order to granulate the toner mother liquor in an aqueous medium containing an inorganic dispersant, an auxiliary agent may be added to the aqueous medium. Such auxiliaries include known cationic type, anionic type and nonionic type surfactants, and those of the anionic type are particularly preferred. For example, there are sodium alkylbenzene sulfonate, sodium α-olefin sulfonate, sodium alkyl sulfonate, etc., and these are used in the range of 1 × 10 ⁻⁴ mass% to 0.1 mass% with respect to the toner mother liquor. preferable.

Granulation of the toner mother liquor in an aqueous medium containing an inorganic dispersant is preferably performed under shear. The toner mother liquid dispersed in the aqueous medium is desirably granulated to have an average particle size of 20 μm or less. Particularly, it is preferably 3 μm or more and 15 μm or less.
There are various dispersers as the apparatus provided with the shearing mechanism, and among them, a homogenizer is preferable. By using a homogenizer, a substance that is incompatible with each other (in this embodiment, an aqueous medium containing an inorganic dispersant and a toner mother liquor) is passed through a gap between the casing and the rotating rotor so that the liquid is contained in a liquid. And incompatible substances can be dispersed in the form of particles. As such a homogenizer, TK homomixer, line flow homomixer, auto homomixer (manufactured by Special Machine Industries Co., Ltd.), Silverson homogenizer (manufactured by Silverson), polytron homogenizer (manufactured by KINEMATICA AG), etc. There is.

  The stirring condition using the homogenizer is preferably 2 m / sec or more in terms of the peripheral speed of the rotor blades. If the peripheral speed is 2 m / sec or more, the particle formation tends to be good. In the present embodiment, the solvent is removed after the toner mother liquor is granulated in an aqueous medium containing an inorganic dispersant. The removal of the solvent may be performed at room temperature (25 ° C.) and normal pressure, but since it takes a long time to remove, the removal is performed under a temperature condition that is lower than the boiling point of the solvent and has a difference from the boiling point of 80 ° C. or less. Is preferred. The pressure may be normal pressure or reduced pressure, but when reducing the pressure, it is preferably 20 mmHg or more and 150 mmHg or less.

The toner particles are preferably washed with hydrochloric acid after removing the solvent. As a result, the inorganic dispersant remaining on the surface of the toner particles can be removed to obtain the original composition of the toner particles and improve the characteristics. Subsequently, powder toner particles can be obtained by dehydration and drying.
The toner particles obtained by the dissolution suspension method are subjected to inorganic oxidation represented by silica, titania, and aluminum oxide for the purpose of charge adjustment, fluidity provision, charge exchangeability and the like, as in the case of the aggregation and coalescence method. An object or the like is added and adhered as an external additive. In addition to the inorganic oxides described above, other components (particles) such as a charge control agent, organic particles, a lubricant, and an abrasive may be added as external additives.

Among the toner particle production methods described above, the toner particle production method is preferably an agglomeration coalescence method because toner particles exhibiting a particle size distribution close to that of the glitter pigment are easy to produce.
As described above, the particle size distribution of the glitter pigment used in the present embodiment has a first peak in the range of 9 μm to 12 μm and a second peak in the range of 2 μm to 5 μm. Preferably, such a bright pigment is obtained, for example, by mixing a bright pigment having a volume average particle size of 9 μm to 12 μm and a bright pigment having a volume average particle size of 2 μm to 5 μm. Also good.
Further, the first toner particles produced using the first bright pigment having a volume average particle diameter of 9 μm or more and 12 μm or less and a particle size distribution having one peak, and the volume average particle diameter of 2 μm or more and 5 μm or less. The glossy toner of this embodiment may be mixed with the second toner particles produced using the second glittering pigment having a single particle size distribution.

  Further, as a method for setting the ratio of toner particles (resin particles) containing a bright pigment to toner particles (resin particles) having a particle diameter of 3 μm or more and 6 μm or less to 50% by number or more, for example, the obtained toner particles Is a method of sieving using a specific gravity.

<Electrostatic image developer>
The electrostatic charge image developer of this embodiment contains at least the glitter toner of this embodiment.
The electrostatic image developer of this embodiment may be a one-component developer containing only the glitter toner of this embodiment, or may be a two-component developer mixed with the toner and a carrier.

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

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

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

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

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

<Image Forming Apparatus, Image Forming Method, Toner Cartridge, and Process Cartridge>
An image forming apparatus and an image forming method of the present embodiment will be described.
The image forming apparatus according to the first 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 charged surface of the image carrier, Developing means for containing the electrostatic charge image developer of the present embodiment and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer, and the surface of the image carrier A transfer means for transferring the toner image formed on the surface of the recording medium; a fixing means for fixing the toner image transferred to the surface of the recording medium; a developing bias applied by the developing means; and a transfer means. Control means for adjusting the sparkle grade of the toner image according to the designation information by controlling at least one of the applied transfer biases.
In the image forming apparatus according to the first 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 charged surface of the image carrier, and the electrostatic charge of the present embodiment. A development step of developing an electrostatic charge image formed on the surface of the image carrier as a toner image by an image developer, and a transfer step of transferring the toner image formed on the surface of the image carrier to the surface of a recording medium And a fixing step of fixing the toner image transferred to the surface of the recording medium, and controlling at least one of the developing bias applied in the developing step and the transfer bias applied in the transferring step Thus, the image forming method of the first embodiment is performed in which the sparkle grade of the toner image is adjusted according to the designation information.

The image forming apparatus according to the second embodiment includes an image carrier, a charging unit that charges the surface of the image carrier, and an electrostatic image forming unit that forms an electrostatic image on the charged surface of the image carrier. A developing unit that contains the electrostatic charge image developer according to the exemplary embodiment and develops the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic image developer; and the image carrier. An intermediate transfer body on which a toner image formed on the surface of the image is primarily transferred; a primary transfer means for primarily transferring the toner image formed on the surface of the image holding body to the intermediate transfer body; and a primary transfer to the intermediate transfer body. A secondary transfer means for secondary transfer of the transferred toner image onto the surface of the recording medium; a fixing means for fixing the toner image transferred onto the surface of the recording medium; a developing bias applied at the developing means; Mark on primary transfer means Control means for adjusting a sparkle grade of the toner image in accordance with designation information by controlling at least one of the primary transfer bias to be applied and the secondary transfer bias applied in the secondary transfer means. Prepare.
In the image forming apparatus of the second 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 charged surface of the image carrier, and the electrostatic charge of this embodiment. A developing process for developing an electrostatic image formed on the surface of the image carrier as a toner image by an image developer, and a primary transfer for primary transfer of the toner image formed on the surface of the image carrier to an intermediate transfer member A secondary transfer step of secondarily transferring the toner image primarily transferred to the intermediate transfer body onto the surface of the recording medium, and a fixing step of fixing the toner image transferred onto the surface of the recording medium. And controlling at least one of a developing bias applied in the developing step, a primary transfer bias applied in the primary transfer step, and a secondary transfer bias applied in the secondary transfer step. The image forming method of a second embodiment sparkle grade is adjustment of the toner image in accordance with the designation information is performed.
Hereinafter, the image forming apparatus of the first embodiment and the image forming apparatus of the second embodiment may be collectively referred to as the image forming apparatus of the present embodiment. Further, the image forming method of the first embodiment and the image forming method of the second embodiment may be collectively referred to as the image forming method of the present embodiment.

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

When the developing bias is controlled by the control unit according to the image forming apparatus of the present embodiment, for example, it is preferable to adjust the maximum amplitude (Vpp) of the AC component constituting the developing bias. By increasing Vpp, it is possible to increase the proportion of toner particles having a large particle size in the toner particles to be developed. Further, by reducing Vpp, it is possible to reduce the proportion of toner particles having a large particle size in the toner particles to be developed.
In the case where the transfer bias (at least one of the primary transfer bias and the secondary transfer bias) is controlled by the control unit according to the image forming apparatus of this embodiment, for example, it is preferable to adjust the applied voltage. By increasing the applied voltage, it is possible to increase the proportion of toner particles having a large particle size in the toner particles to be developed. Further, by reducing the applied voltage, it is possible to reduce the proportion of toner particles having a large particle size in the toner particles to be developed.
The sparkle grade of the toner image is adjusted by adjusting the ratio of the toner particles having a large particle size to the developed toner particles.

Hereinafter, an image forming apparatus and an image forming method of the present embodiment will be described with reference to the drawings. In the following description, the image forming apparatus of this embodiment will be described based on the image forming apparatus of the second embodiment provided with an intermediate transfer member.
FIG. 3 is a schematic configuration diagram illustrating an example of the image forming apparatus according to the present exemplary embodiment. The image forming apparatus shown in FIG. 3 has a tandem configuration in which a plurality of photoconductors as image carriers are provided, that is, a plurality of image forming units (image forming means) are provided. In the image forming apparatus shown in FIG. 3, the control unit adjusts the sparkle grade of the toner image according to the designated information by controlling the secondary transfer bias applied in the secondary transfer unit.

The image forming apparatus shown in FIG. 3 includes five image forming units 50Y, 50M, 50C, 50K, and 50B that form toner images of yellow, magenta, cyan, black, and glittering silver, respectively. Are arranged in parallel (in tandem). The image forming units are arranged in the order of the image forming units 50Y, 50M, 50C, 50K, and 50B from the upstream side in the rotation direction of the intermediate transfer belt 33. In addition, the image forming apparatus shown in FIG. 3 includes a control unit 60 that controls a secondary transfer bias applied to the secondary transfer roll 34 that is a secondary transfer unit.
Here, since each of the image forming units 50Y, 50M, 50C, 50K, and 50B has the same configuration except for the color of the toner in the stored developer, a yellow image is formed here. The image forming unit 50Y will be described as a representative. Note that the same reference numerals with magenta (M), cyan (C), black (K), and glittering silver (B) are attached to the same parts as the image forming unit 50Y instead of yellow (Y). Thus, the description of the image forming units 50M, 50C, 50K, and 50B is omitted. Further, the developer accommodated in the image forming unit 50B is the electrostatic charge image developer of this embodiment.

  The yellow image forming unit 50Y includes a photoconductor 11Y as an image carrier, and the photoconductor 11Y 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 11Y, for example, an organic photoreceptor having sensitivity in the infrared region is used.

  A charging roll (charging means) 18Y is provided above the photoconductor 11Y. A predetermined voltage is applied to the charging roll 18Y by a power source (not shown), and the surface of the photoconductor 11Y is predetermined. Charged to a certain potential.

  Around the photoreceptor 11Y, an exposure device (electrostatic charge image forming means) 19Y for exposing the surface of the photoreceptor 11Y to form an electrostatic charge image is disposed downstream of the charging roll 18Y in the rotation direction of the photoreceptor 11Y. Has been. Here, as the exposure device 19Y, an LED array that can be miniaturized 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. Of course there is no problem.

  Further, a developing device (developing unit) 20Y including a developer holding body that holds a yellow developer is disposed around the photoconductor 11Y on the downstream side in the rotation direction of the photoconductor 11Y with respect to the exposure device 19Y. The electrostatic charge image formed on the surface of the photoreceptor 11Y is visualized with yellow toner, and a toner image is formed on the surface of the photoreceptor 11Y.

  Below the photoconductor 11Y, an intermediate transfer belt (intermediate transfer body) 33 for primary transfer of a toner image formed on the surface of the photoconductor 11Y is below the five photoconductors 11Y, 11M, 11C, 11K, and 11B. It is arranged to cross over. The intermediate transfer belt 33 is pressed against the surface of the photoreceptor 11Y by a primary transfer roll (primary transfer means) 17Y. Further, the intermediate transfer belt 33 is stretched by three rolls of a drive roll 22, a support roll 13, and a bias roll 14, and is rotated in the direction of arrow B at a moving speed equal to the process speed of the photoreceptor 11Y. It has become. A yellow toner image is primarily transferred onto the surface of the intermediate transfer belt 33, and toner images of each color of magenta, cyan, black, and glittering silver are sequentially primary transferred.

  Around the photoreceptor 11Y, a cleaning device for cleaning the toner remaining on the surface of the photoreceptor 11Y and the retransferred toner downstream of the primary transfer roll 17Y in the rotation direction (arrow A direction) of the photoreceptor 11Y. 15Y is arranged. The cleaning blade in the cleaning device 15Y is attached so as to be in pressure contact with the surface of the photoreceptor 11Y in the counter direction.

  A secondary transfer roll (secondary transfer unit) 34 is pressed against the bias roll 14 that stretches the intermediate transfer belt 33 via the intermediate transfer belt 33. The toner image primarily transferred and laminated on the surface of the intermediate transfer belt 33 is recorded on 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 14 and the secondary transfer roll 34. Electrostatically transferred.

  Also, downstream of the secondary transfer roll 34, a fixing device (fixing means) for fixing the toner image transferred on the recording paper P onto the surface of the recording paper P by heat and pressure to form a permanent image. 35 is arranged.

  As the fixing device 35, 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 is represented by a fluororesin component or a silicone resin on the surface. And a cylindrical fixing roll is used.

  Next, the operation of each of the image forming units 50Y, 50M, 50C, 50K, and 50B that forms images of each color of yellow, magenta, cyan, black, and glittering silver will be described. Since the operations of the image forming units 50Y, 50M, 50C, 50K, and 50B are the same, the operation of the yellow image forming unit 50Y will be described as a representative example.

  In the yellow developing unit 50Y, the photoreceptor 11Y rotates in the direction of arrow A at a predetermined process speed. The surface of the photoconductor 11Y is negatively charged to a predetermined potential by the charging roll 18Y. Thereafter, the surface of the photoreceptor 11Y is exposed by the exposure device 19Y, and an electrostatic charge image corresponding to the image information is formed. Subsequently, the negatively charged toner is reversely developed by the developing device 20Y, and the electrostatic charge image formed on the surface of the photoreceptor 11Y is visualized on the surface of the photoreceptor 11Y to form a toner image. Thereafter, the toner image on the surface of the photoreceptor 11Y is primarily transferred onto the surface of the intermediate transfer belt 33 by the primary transfer roll 17Y. After the primary transfer, the transfer residual component such as toner remaining on the surface of the photoreceptor 11Y is scraped off and cleaned by the cleaning blade of the cleaning device 15Y, and is prepared for the next image forming process.

The above operations are performed in the image forming units 50Y, 50M, 50C, 50K, and 50B, and the toner images visualized on the surfaces of the photoreceptors 11Y, 11M, 11C, 11K, and 11B are successively in the middle. Multiple transfer is performed on the surface of the transfer belt 33. Toner images are transferred in multiple colors in the order of yellow, magenta, cyan, black, and glittering silver. In the two-color and three-color modes, only the toner images of the required colors are used in this order. Are singly or multiply transcribed.
In the image forming apparatus shown in FIG. 3, the order of multiple transfer of toner images is in the order of yellow, magenta, cyan, black, and glittering silver. In this embodiment, the image forming units 50Y, 50M, The order of multiple transfer of toner images may be changed by changing the positional relationship between 50C, 50K, and 50B.
Thereafter, the toner image singly or multiply transferred onto the surface of the intermediate transfer belt 33 is secondarily transferred onto the surface of the recording paper P conveyed from a paper cassette (not shown) by the secondary transfer roll 34. The secondary transfer bias applied to the secondary transfer roll 34 is controlled by the control unit 60 based on the designation information. Thereby, the sparkle grade of the toner image is adjusted.
Subsequently, the toner image is fixed on the surface of the recording paper P by heating and pressurizing the toner image in the fixing device 35. The toner remaining on the surface of the intermediate transfer belt 33 after the secondary transfer is cleaned by a belt cleaner 26 constituted by a cleaning blade for the intermediate transfer belt 33.

  In the present exemplary embodiment, the example in which the sparkle grade of the toner image is adjusted by controlling the secondary transfer bias applied to the secondary transfer roll 34 by the control unit 60 has been described. However, the present exemplary embodiment is not limited thereto. Is not to be done. For example, the control unit 60 controls at least one of the developing bias applied in the developing device 20B of the image forming unit 50B and the primary transfer bias applied in the primary transfer roll 17B, thereby adjusting the sparkle grade of the toner image. May be.

The yellow image forming unit 50Y includes a developing device 20Y including a developer holding body for holding a yellow developer, a photoconductor 11Y, a charging roll 18Y, and a cleaning device 15Y, which are integrated from the main body of the image forming apparatus. It is configured as a detachable process cartridge. Also, the image forming units 50M, 50C, 50K, and 50B are configured as process cartridges similarly to the image forming unit 50Y.
In FIG. 3, the toner image formed on the surface of the image carrier is transferred to the recording medium via the intermediate transfer member. In the first embodiment, the toner image is formed on the surface of the image carrier. The toner image may be directly transferred to a recording medium.

FIG. 4 is a schematic configuration diagram showing the process cartridge of the present embodiment.
The process cartridge 200 shown in FIG. 4 is provided around the photosensitive member 107 and the photosensitive member 107 by, for example, a housing 117 provided with an attachment rail 116 and an opening 118 for exposure. A charging roller 108 (an example of a charging unit), a developing device 111 (an example of a developing unit), and a photoconductor cleaning device 113 (an example of a cleaning unit) are integrally combined and held to form a cartridge. Yes.
In FIG. 4, 109 is an exposure device (an example of an electrostatic charge image forming unit), 112 is a transfer device (an example of a transfer unit), 115 is a fixing device (an example of a fixing unit), and 300 is a recording paper (a recording medium). An example).

  The toner cartridges 40Y, 40M, 40C, 40K, and 40B are cartridges that store toner of each color and are attached to and detached from the image forming apparatus. The toner cartridges 40Y, 40M, 40C, 40K, and 40B It is connected. When the toner stored in each toner cartridge becomes low, the toner cartridge is replaced.

  Hereinafter, although an example and a comparative example are given and this embodiment is described more concretely, this embodiment is not limited to the following examples. Unless otherwise specified, “part” and “%” are based on mass.

<< Preparation of Developer 1 >>
<Synthesis of Binder Resin 1>
-Dimethyl adipate: 74 parts-Dimethyl terephthalate: 192 parts-Bisphenol A ethylene oxide adduct: 216 parts-Ethylene glycol: 38 parts-Tetrabutoxy titanate (catalyst): 0.037 parts Place in a flask, introduce nitrogen gas into the container, keep the inert atmosphere and raise the temperature while stirring, then carry out a copolycondensation reaction at 160 ° C. for 7 hours, and then gradually increase the pressure to 220 ° C. while gradually reducing the pressure to 10 Torr. Warmed and held for 4 hours. Once the pressure was returned to normal pressure, 9 parts of trimellitic anhydride was added, the pressure was gradually reduced again to 10 Torr, and maintained at 220 ° C. for 1 hour to synthesize binder resin 1.
The glass transition temperature (Tg) of the binder resin 1 is measured using a differential scanning calorimeter (manufactured by Shimadzu Corporation: DSC-50) from room temperature (25 ° C.) to 150 ° C. under a temperature rising rate of 10 ° C./min. Was determined by The glass transition temperature was the temperature at the intersection of the extended line of the base line and the rising line in the endothermic part. The glass transition temperature of the binder resin 1 was 63.5 ° C.

<Preparation of resin particle dispersion 1>
・ Binder resin 1: 160 parts ・ Ethyl acetate: 233 parts ・ Sodium hydroxide aqueous solution (0.3N): 0.1 part The above ingredients were put in a 1000 ml separable flask and heated at 70 ° C. A resin mixed solution was prepared by stirring with Tokai Kagaku Co., Ltd. While this resin mixed liquid was further stirred at 90 rpm, 373 parts of ion exchange water was gradually added to carry out phase inversion emulsification and solvent removal to obtain a resin particle dispersion 1 (solid content concentration: 30%). The volume average particle size of the resin particle dispersion 1 is 162 nm.

<Preparation of release agent dispersion>
-Carnauba wax (manufactured by Toa Kasei Co., Ltd., RC-160): 50 parts-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK): 1.0 part-Ion-exchanged water: 200 parts After mixing and heating to 95 ° C. and dispersing using a homogenizer (Ultra Tlux T50, manufactured by IKA), dispersion treatment was performed for 360 minutes with a Manton Gorin high-pressure homogenizer (Gorin), and the volume average particle size was A release agent dispersion liquid (solid content concentration: 20%) prepared by dispersing release agent particles of 0.23 μm was prepared.

<Preparation of aluminum pigment dispersion 1>
100 parts of an aluminum pigment (Showa Aluminum Powder Co., Ltd., 2173EA) and 2000 parts of a zirconium oxide ball (diameter 2 mm) were placed in a ball mill, stirred at 150 rpm for 10 hours, and the aluminum pigment was pulverized to obtain an aluminum pigment 1 .
Next, 100 parts of an aluminum pigment (made by Showa Aluminum Powder Co., Ltd., 2173EA) and 2000 parts of a zirconium oxide ball (diameter 2 mm) are placed in a ball mill, stirred at 350 rpm for 10 hours, and the aluminum pigment is crushed to obtain aluminum pigment 2 Got.
・ Pulverized aluminum pigment 1:50 parts ・ Pulverized aluminum pigment 2:50 parts ・ Anionic surfactant (Daigen Kogyo Seiyaku Co., Ltd., Neogen R): 1.5 parts ・ Ion-exchanged water: 400 parts Aluminum pigment After removing the solvent from the paste, an aluminum pigment dispersion 1 in which the above is mixed and dispersed for about 1 hour using an emulsifying and dispersing machine Cavitron (manufactured by Taiheiyo Kiko Co., Ltd., CR1010) to disperse the aluminum pigment. (Solid content concentration: 20%) was prepared.
In addition, the 1st peak existed in 3 micrometers in the particle size distribution of the aluminum pigment contained in the aluminum pigment dispersion liquid 1, and the 2nd peak existed in 11 micrometers.

<Preparation of Toner 1>
-Resin particle dispersion 1: 100 parts-Release agent dispersion: 48 parts-Aluminum pigment dispersion 1: 180 parts-Nonionic surfactant (IGEPAL CA897): 1.40 parts The above raw material is a 2 L cylindrical stainless steel container The mixture was dispersed and mixed for 10 minutes while applying a shearing force at 4000 rpm with a homogenizer (manufactured by IKA, Ultra Turrax T50). Next, 300 parts of the resin particle dispersion 1 is added, and then 1.75 parts of a 10% aqueous nitric acid solution of polyaluminum chloride is gradually added dropwise. The homogenizer is rotated at 5000 rpm for 15 minutes to be mixed and mixed. A dispersion was obtained.
Thereafter, the raw material dispersion liquid is transferred to a kettle equipped with a stirring device using two paddle stirring blades and a thermometer, and heated with a mantle heater at a stirring speed of 810 rpm, and left at 54 ° C. for 30 minutes. did. At this time, the pH of the raw material dispersion was controlled in the range of 2.2 to 3.5 with 0.3N nitric acid or 1N sodium hydroxide aqueous solution. The agglomerated particles were formed by maintaining the above pH range for 2 hours.
Next, 100 parts of the resin particle dispersion 1 was added. The temperature was further raised to 56 ° C., and aggregated particles were prepared while confirming the size and form of the particles with an optical microscope and Multisizer II. Then, after raising pH to 8.0, it heated up to 67.5 degreeC. Further, the pH was lowered to 6.0 while maintaining the temperature at 67.5 ° C., and the heating was stopped after 1 hour, followed by cooling at a temperature lowering rate of 1.0 ° C./min. Thereafter, the mixture was sieved with a 20 μm mesh, washed repeatedly with water, and then dried with a vacuum dryer to obtain toner particles 1.
The upper GSDv of toner particles 1 (resin particles) was 1.5, and the lower GSDv was 1.5. Further, in the toner particles 1, the ratio of the toner particles containing aluminum pigment to the toner particles having a particle diameter of 3 μm or more and 6 μm or less was 85% by number. In the particle size distribution of the toner particles 1, a first peak was present at 5 μm and a second peak was present at 13 μm. The volume average particle diameter of the toner particles 1 is 9 μm.

To 100 parts of the toner particles 1 obtained, 2.0 parts of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) was mixed for 3 minutes at a peripheral speed of 30 m / s using a Henschel mixer. Thereafter, toner 1 was prepared by sieving with a vibrating sieve having an opening of 45 μm.
The obtained toner 1 had a volume average particle diameter of 12.2 μm.

<Creation of carrier>
Ferrite particles (volume average particle diameter: 35 μm): 100 parts Toluene: 14 parts Methyl methacrylate-perfluorooctylmethyl 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 fluorooctylmethyl 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, the coating layer forming solution and the ferrite particles are put in a vacuum degassing 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.

<Production of developer>
Toner 1:36 parts and carrier: 414 parts were put in a 2 liter V blender, stirred for 20 minutes, and then sieved at 212 μm to prepare Developer 1.

<Evaluation>
The obtained developer 1 is filled in a Color1000i Press developer manufactured by Fuji Xerox Co., Ltd., and an image is created on a recording medium (OK top coat + paper (trade name), manufactured by Oji Paper Co., Ltd.). did.
In the image formation, the secondary transfer bias is fixed to 2.5 kV, the AC component Vpp in the development bias is fixed to 1.0 kV, and the primary transfer bias is changed to 30 μA, 45 μA, and 60 μA to change the image A (30 μA). , Image B (45 μA) and Image C (60 μA) were formed. This was designated as Example 1.
Further, the primary transfer bias is fixed at 45 μA, the secondary transfer bias is fixed at 2.5 kV, and the AC component Vpp in the developing bias is changed to 0.6 kV, 1.0 kV, and 1.5 kV to change the image D (0.6 kV). ), Image E (1.0 kV) and image F (1.5 kV). This was designated Example 2.
Further, the primary transfer bias is fixed to 45 μA, the AC component Vpp in the development bias is fixed to 1.0 kV, and the secondary transfer bias is changed to 1.5 kV, 2.5 kV, and 4.0 kV to change the image G (1.5 kV). ), Image H (2.5 kV) and image I (4.0 kV). This was designated as Example 3.

The sparkle grade of each obtained image was measured using BYK-mac manufactured by Toyo Seiki Seisakusho. In addition, the sparkle grade in this embodiment is an arithmetic average of each sparkle grade in observation angles of 15 °, 45 °, and 75 °. Sparkle grades at observation angles of 15 °, 45 °, and 75 ° are calculated based on the following equations, respectively.
The measurement results are shown in Tables 1 to 3.

Sparkle Grade (15 °) = 0.35 × (dSi15 ° × dSa15 °) ^1/2 −0.8
Sparkle Grade (45 °) = 0.35 × (dSi45 ° × dSa45 °) ^1/2 −0.8
Sparkle Grade (75 °) = 0.35 × (dSi75 ° × dSa75 °) ^1/2 −0.8
Here, dSi means Sparkle intensity (strength), and dSa means Sparkle area (area).

<< Preparation of Developer 2 >>
<Preparation of aluminum pigment dispersion 2>
100 parts of aluminum pigment (Showa Aluminum Powder Co., Ltd., 2173EA) and 2000 parts of zirconium oxide balls (diameter 2 mm) were placed in a ball mill and stirred at 200 rpm for 10 hours to grind the aluminum pigment.
・ Pulverized aluminum pigment: 100 parts ・ Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R): 1.5 parts ・ Ion exchange water: 400 parts After removing the solvent from the aluminum pigment paste, the above The mixture was mixed and dispersed for about 1 hour using an emulsifying and dispersing machine Cavitron (manufactured by Taiheiyo Kiko Co., Ltd., CR1010) to prepare an aluminum pigment dispersion 2 (solid content concentration: 20%) in which the aluminum pigment was dispersed. .
In addition, there was one peak at 7 μm in the particle size distribution of the aluminum pigment contained in the aluminum pigment dispersion 2.
An aluminum pigment dispersion 2 was obtained through the above steps.
Toner particles 2 were obtained in the same manner as toner particles 1 except that the aluminum pigment dispersion 2 was used instead of the aluminum pigment dispersion 1. Developer 2 was obtained in the same manner as Developer 1 except that toner particles 2 were used instead of toner particles 1. Evaluation was performed under the same conditions as in Examples 1 to 3 except that Developer 2 was used instead of Developer 1. This was designated as Examples 4 to 6.
The upper GSDv of toner particles 2 (resin particles) was 1.5, and the lower GSDv was 1.5. Further, in the toner particles 2, the ratio of the toner particles containing aluminum pigment to the toner particles having a particle diameter of 3 μm or more and 6 μm or less was 85 number%. Further, in the particle size distribution of the toner particles 2, there was one peak at 9 μm. The volume average particle diameter of the toner particles 2 is 10 μm.

<< Preparation of Developer 3 >>
<Preparation of aluminum pigment dispersion 3>
100 parts of aluminum pigment (Showa Aluminum Powder Co., Ltd., 2173EA) and 2000 parts of zirconium oxide balls (diameter 2 mm) are placed in a ball mill, stirred at 80 rpm for 10 hours, and the aluminum pigment is pulverized to obtain aluminum pigment 1. It was.
Next, 100 parts of aluminum pigment (Showa Aluminum Powder Co., Ltd., 2173EA) and 2000 parts of zirconium oxide balls (diameter 2 mm) were placed in a ball mill, stirred at 400 rpm for 10 hours, and the aluminum pigment was crushed to obtain aluminum pigment 2 Got.
・ Pulverized aluminum pigment 1:50 parts ・ Pulverized aluminum pigment 2:50 parts ・ Anionic surfactant (Daigen Kogyo Seiyaku Co., Ltd., Neogen R): 1.5 parts ・ Ion-exchanged water: 400 parts Aluminum pigment After removing the solvent from the paste, an aluminum pigment dispersion 3 in which the above is mixed and dispersed for about 1 hour using an emulsifying and dispersing machine Cavitron (CR1010, manufactured by Taiheiyo Kiko Co., Ltd.) to disperse the aluminum pigment. (Solid content concentration: 20%) was prepared.
In addition, the 1st peak existed in 2 micrometer in the particle size distribution of the aluminum pigment contained in the aluminum pigment dispersion liquid 3, and the 2nd peak existed in 15 micrometers.
An aluminum pigment dispersion 3 was obtained through the above steps.
Toner particles 3 were obtained in the same manner as toner particles 1 except that aluminum pigment dispersion 3 was used instead of aluminum pigment dispersion 1. Developer 3 was obtained in the same manner as Developer 1, except that toner particles 3 were used instead of toner particles 1. Evaluation was performed under the same conditions as in Examples 1 to 3, except that Developer 3 was used instead of Developer 1. This was designated as Examples 7 to 9.
The upper GSDv of toner particles 3 (resin particles) was 1.5, and the lower GSDv was 1.5. Further, in the toner particles 3, the ratio of the toner particles containing aluminum pigment to the toner particles having a particle diameter of 3 μm or more and 6 μm or less was 85% by number. Further, in the particle size distribution of the toner particles 3, a first peak was present at 3 μm and a second peak was present at 17 μm. The volume average particle diameter of the toner particles 3 is 10 μm.

<< Preparation of Developer C1 >>
<Preparation of aluminum pigment dispersion C1>
In preparation of the aluminum pigment dispersion 1, an aluminum pigment dispersion C1 was prepared except for the pulverization step.
Toner particles C1 were obtained in the same manner as toner particles 1 except that the aluminum pigment dispersion C1 was used instead of the aluminum pigment dispersion 1. Developer C1 was obtained in the same manner as Developer 1, except that toner particle C1 was used instead of toner particle 1. Evaluation was made under the same conditions as in Examples 1 to 3 except that Developer C1 was used instead of Developer 1. This was designated as Comparative Examples 1 to 3.
The upper GSDv of the toner particles C1 (resin particles) was 1.2, and the lower GSDv was 1.3. Further, in the toner particle C1, the ratio of the toner particle containing aluminum pigment to the toner particle having a particle diameter of 3 μm or more and 6 μm or less was 85% by number. In addition, there was one peak at 9.0 μm in the particle size distribution of the toner particles C1. The volume average particle diameter of the toner particles C1 is 9.0 μm.

<< Preparation of Developer C2 >>
<Preparation of aluminum pigment dispersion C2>
100 parts of aluminum pigment (Showa Aluminum Powder Co., Ltd., 2173EA) and 2000 parts of zirconium oxide balls (diameter 2 mm) were placed in a ball mill and stirred at 200 rpm for 10 hours to grind the aluminum pigment.
・ Pulverized aluminum pigment: 100 parts ・ Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R): 1.5 parts ・ Ion exchange water: 400 parts After removing the solvent from the aluminum pigment paste, the above An aluminum pigment dispersion C2 (solid content concentration: 20%) was prepared by mixing and dispersing for about 1 hour using an emulsifying and dispersing machine Cavitron (manufactured by Taiheiyo Kiko Co., Ltd., CR1010). .
One peak was present at 7 μm in the particle size distribution of the aluminum pigment contained in the aluminum pigment dispersion C2.
An aluminum pigment dispersion C2 was obtained through the above steps.
Toner particles C2 were obtained in the same manner as toner particles 1 except that the aluminum pigment dispersion C2 was used in place of the aluminum pigment dispersion 1, and the stirring rotation speed during toner granulation was changed from 810 rpm to 660 rpm. Developer C2 was obtained in the same manner as Developer 1, except that toner particle C2 was used instead of toner particle 1. Evaluation was performed under the same conditions as in Examples 1 to 3 except that Developer C2 was used instead of Developer 1. This was designated as Comparative Examples 4 to 6.
The upper GSDv of the toner particles C2 (resin particles) was 1.7, and the lower GSDv was 1.7. In toner particle C2, the proportion of toner particles containing aluminum pigment in the toner particles having a particle diameter of 3 μm or more and 6 μm or less was 75% by number. In addition, there was one peak at 9 μm in the particle size distribution of the toner particles C2. The volume average particle diameter of the toner particles C2 is 10 μm.

  As is apparent from Table 1, the sparkle grade of each image in the example is larger than that in the comparative example by changing at least one of the primary transfer bias, the development bias, and the secondary transfer bias. You can see that it is changing. This means that the sparkle grade can be adjusted by changing at least one of the primary transfer bias, the development bias, and the secondary transfer bias by using the glitter toner of the present embodiment. To do.

DESCRIPTION OF SYMBOLS 11 Photoconductor 13 Support roll 14 Bias roll 15 Cleaning apparatus 17 Primary transfer roll 18 Charging roll 19 Exposure apparatus 20 Developing apparatus 22 Drive roll 26 Belt cleaner 34 Secondary transfer roll 35 Fixing device 40 Toner cartridge 50 Image forming unit 60 Control means P Recording paper

Claims (11)

Containing resin particles including a binder resin,
At least a part of the resin particles contains a glitter pigment,
The large particle volume particle size distribution index (upper GSDv) of the resin particles is 1.40 or more and 1.60 or less,
The small particle volume particle size distribution index (lower GSDv) of the resin particles is 1.40 or more and 1.60 or less,
A glittering toner in which the proportion of resin particles containing the glitter pigment in the resin particles having a particle diameter of 3 μm or more and 6 μm or less is 50% by number or more. Containing resin particles including a binder resin,
At least a part of the resin particles contains a glitter pigment,
In the particle size distribution of the resin particles, a first peak exists in a range of 8 μm or more and 20 μm or less, and a second peak exists in a range of 2 μm or more and less than 8 μm,
A glittering toner in which the proportion of resin particles containing the glitter pigment in the resin particles having a particle diameter of 3 μm or more and 6 μm or less is 50% by number or more.   The glitter toner according to claim 2, wherein a difference between a particle diameter of the first peak and a particle diameter of the second peak is 6 μm or more and 12 μm or less.   The first peak is present in a range of 9 μm or more and 12 μm or less, and the second peak is present in a range of 2 μm or more and 5 μm or less in the particle size distribution of the glitter pigment. The glitter toner described in 1.   An electrostatic charge image developer comprising the glitter toner according to any one of claims 1 to 4. Containing the glitter toner according to any one of claims 1 to 4,
A toner cartridge to be attached to and detached from the image forming apparatus. A developing means for accommodating the electrostatic charge image developer according to claim 5 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 5 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;
Control means for adjusting a sparkle grade of the toner image in accordance with designated information by controlling at least one of a developing bias applied in the developing means and a transfer bias applied in the transfer means;
An image forming apparatus comprising: 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 5 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer;
An intermediate transfer member on which a toner image formed on the surface of the image carrier is primarily transferred;
Primary transfer means for primarily transferring a toner image formed on the surface of the image carrier to the intermediate transfer member;
Secondary transfer means for secondary transfer of the toner image primarily transferred to the intermediate transfer body onto the surface of the recording medium;
Fixing means for fixing the toner image transferred to the surface of the recording medium;
By controlling at least one of the developing bias applied in the developing unit, the primary transfer bias applied in the primary transfer unit, and the secondary transfer bias applied in the secondary transfer unit, the specified information is obtained. Control means for adjusting the sparkle grade of the toner image according to
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 image formed on the surface of the image carrier as a toner image by the electrostatic image developer according to claim 5;
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;
Have
An image forming method in which a sparkle grade of the toner image is adjusted according to designated information by controlling at least one of a developing bias applied in the developing step and a transfer bias applied in the transferring step. 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 image formed on the surface of the image carrier as a toner image by the electrostatic image developer according to claim 5;
A primary transfer step in which a toner image formed on the surface of the image carrier is primarily transferred to an intermediate transfer member;
A secondary transfer step of secondarily transferring the toner image primarily transferred to the intermediate transfer body onto the surface of the recording medium;
Fixing the toner image transferred to the surface of the recording medium,
By controlling at least one of the development bias applied in the development step, the primary transfer bias applied in the primary transfer step, and the secondary transfer bias applied in the secondary transfer step, the specified information is obtained. An image forming method in which a sparkle grade of the toner image is adjusted accordingly.