JP2013072944A - Toner for electrostatic charge image development and manufacturing method of the same, electrostatic charge image developer, toner cartridge, process cartridge, image forming method, and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge image development that provides images having photoluminescence, and suppresses the occurrence of scratches on a surface of an image holding body.SOLUTION: A toner for electrostatic latent image development contains a binder resin and an aluminum pigment; and a ratio of the content of Al elements A(atm%) and the content of C elements B(atm%)(A/B) measured by an X-ray photoelectron spectroscopy (XPS) is 0 to 0.03. The aluminum pigment preferably has the average particle diameter of 3 μm to 20 μm, and preferably accounts for 10 to 40 weight% of a toner for electrostatic charge image development.

Description

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

For the purpose of forming an image having a brightness such as a metallic luster, glittering toner is used.
Patent Document 1 discloses a toner having a metallic color tone and containing a metallic pigment, wherein the metallic pigment includes a) a fatty acid, at least one acid amide, at least one acid salt, and an olefin-based material. An organic layer selected from natural waxes, synthetic waxes, polymers, and combinations thereof, the organic layer comprising a charge control agent and optionally a colorant, b) optionally silicate, titanate, or A toner comprising an aluminate coating, wherein the toner is optionally coated with a hydrophobic fumed metal oxide is disclosed.
Patent Document 2 discloses a toner containing at least a binder resin and a colorant, and the colorant contains silver in flat glass flakes having an average thickness of 2 to 5 μm and an average length in the longitudinal direction of 15 to 500 μm. A gold toner for electrostatic latent image development is disclosed which is a coated glitter pigment.
Patent Document 3 discloses a toner for developing an electrostatic image characterized by containing at least a binder resin and a metal powder sufficient to exhibit a metallic luster, and Patent Document 4 discloses a fixing resin, An electrophotographic toner comprising a colorant and a toner compounding agent, wherein the colorant is a pigment obtained by coating a thin layer of titanium dioxide on a flaky inorganic crystal substrate. Toner is disclosed.

Special table 2009-501349 JP 2003-207941 A JP-A-62-67558 JP-A-62-100769

An object of the present invention is to provide a toner for developing an electrostatic charge image that can form an image having a glittering property and suppresses the occurrence of scratches on the surface of an image carrier.
Here, “brightness” indicates that the image formed with the toner has a brightness such as a metallic luster when viewed visually.

The above problems have been solved by means described in the following <1> and <4> to <9>. It is described below together with <2> and <3> which are preferred embodiments.
<1> A binder resin and an aluminum pigment are contained, and the ratio (A / B) of the Al element content A (atm%) and the C element content B (atm%) by X-ray photoelectron spectroscopy (XPS) ) Is 0 to 0.03, an electrostatic charge image developing toner,
<2> The electrostatic charge image developing toner according to <1>, wherein the aluminum pigment has a volume average particle size of 3 μm to 20 μm.
<3> The electrostatic image developing toner according to <1> or <2>, wherein the content of the aluminum pigment in the electrostatic image developing toner is 10 to 40% by weight,
<4> A step of preparing an aluminum pigment dispersion or an aluminum pigment dispersion simultaneously emulsified with a resin, and a step of adding a toner constituent material to the dispersion in several times <1> to <3> a method for producing a toner for developing an electrostatic charge image according to any one of
<5><1> to <3> The electrostatic charge image developer comprising the electrostatic charge image developing toner according to any one of the above and a carrier.
<6> Any of <1> to <3> can be attached to and detached from an image forming apparatus including at least a developing unit that develops an electrostatic charge image to form a toner image. A toner cartridge containing the electrostatic image developing toner according to claim 1;
<7> The toner for developing an electrostatic charge image according to any one of <1> to <3> is accommodated, and a toner holder that holds and transports the toner for developing an electrostatic charge image is provided. Process cartridges,
<8> A latent image forming step for forming an electrostatic latent image on the surface of the image carrier, and the electrostatic latent image formed on the surface of the image carrier is an electrostatic charge according to any one of <1> to <3>. Developing with a developer containing image developing toner to form a toner image, transferring step for transferring the toner image to the surface of the transfer target, and fixing the toner image transferred to the surface of the transfer target An image forming method comprising at least a fixing step;
<9> The image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on a surface of the image carrier, and the electrostatic latent image according to any one of <1> to <3>. Developing means for developing a toner image by developing with a developer containing toner for developing an electrostatic charge image; transfer means for transferring the toner image to the surface of the transfer body; and the toner image transferred to the surface of the transfer body. An image forming apparatus comprising at least fixing means for fixing.

According to the invention described in <1> above, it is possible to form an image having glitter as compared with the case where the present configuration is not provided, and a static in which generation of scratches on the surface of the image carrier is suppressed. A charge image developing toner is provided.
According to the invention described in the above <2>, the toner for developing an electrostatic charge image capable of forming an image having further excellent glitter as compared with the case where the volume average particle diameter of the aluminum pigment is less than 3 μm or more than 20 μm. Is provided.
According to the invention described in the above <3>, the electrostatic charge capable of forming an image having further excellent glitter as compared with the case where the content of the aluminum pigment is less than 10% by weight or more than 40% by weight. An image developing toner is provided.
According to the invention described in <4> above, it is possible to form an image having glitter as compared with the case where the present configuration is not provided, and a static in which generation of scratches on the surface of the image carrier is suppressed. A method for producing a toner for developing a charge image is provided.
According to the invention described in <5> above, it is possible to form an image having brilliancy as compared with the case where the present configuration is not provided, and a static in which generation of scratches on the surface of the image carrier is suppressed. A charge image developer is provided.
According to the invention described in <6> above, it is possible to form an image having brilliancy as compared with the case where the present configuration is not provided, and to reduce the occurrence of scratches on the surface of the image carrier. A toner cartridge containing toner for developing a charge image is provided.
According to the invention described in <7> above, it is possible to form an image having glitter as compared with the case where the present configuration is not provided, and a static in which generation of scratches on the surface of the image carrier is suppressed. A process cartridge containing charge image developing toner is provided.
According to the invention described in <8> above, an image having excellent glitter can be obtained and the occurrence of scratches on the surface of the image carrier is suppressed as compared with the case where the present configuration is not provided. An image forming method is provided.
According to the invention described in <9>, an image having excellent glitter can be obtained and the occurrence of scratches on the surface of the image carrier is suppressed as compared with the case where the present configuration is not provided. An image forming apparatus is provided.

1 is a schematic configuration diagram illustrating an image forming apparatus to which the exemplary embodiment is applied. It is a schematic block diagram which shows an example of the process cartridge which concerns on this embodiment.

Embodiments of the present invention will be described below. This embodiment is an example for carrying out the present invention, and the present invention is not limited to this embodiment.
In the present specification, the description of “lower limit to upper limit” representing a numerical range represents “lower limit or higher and lower limit or lower”, and the description of “upper limit to lower limit” represents “lower limit or higher and lower limit or higher”. That is, it represents a numerical range including an upper limit and a lower limit.

1. Toner for developing an electrostatic image The toner for developing an electrostatic image of the present embodiment (hereinafter also simply referred to as “toner”) contains a binder resin and an aluminum pigment, and contains Al element by X-ray photoelectron spectroscopy (XPS). The ratio (A / B) of the content A (atm%) of C and the content B (atm%) of C element is 0 to 0.03.
In order to impart glitter to the toner, it has been studied to include an aluminum pigment in the toner. In order for the resulting image to exhibit high glitter, it is important to increase the amount of aluminum pigment and to incorporate the toner in the toner with the aluminum pigment particle size being somewhat large. This is because the bright pigment needs to reflect light in a wide wavelength region with respect to light in the visible region. If the reflection wavelength is biased, the amount of reflection of light having a specific wavelength is reduced, resulting in an image with inferior luster.
This is different from what color toners using normal magenta, yellow, cyan pigments, etc. recognize as colored toners by absorbing and reflecting a specific wavelength region. Colored toners have improved transparency and vivid color development by making the pigment dispersion diameter as small as possible, so the particle size is much smaller than 400 nm, which is the lower limit of about 400 nm to 850 nm in the visible region. There is a need to. On the other hand, since the bright pigment needs to reflect incident light over a wider wavelength region, it is necessary to make the dispersion diameter larger than 850 nm.

As a result of intensive studies, the present inventors have found that a toner using an aluminum pigment having a large particle size has a problem in the inclusion property of the aluminum pigment in order to express desired glitter. Specifically, it has been found that the presence of an aluminum pigment not coated with a resin on the toner surface causes a problem of directly contacting the photoconductor (image carrier) and causing the photoconductor to wear and deteriorate. That is, although there is a possibility that the colored toner pigments may be worn or deteriorated with respect to the photoreceptor, since the pigment dispersion diameter is small as described above, the generated wear is small and the deterioration is not remarkable. It has been found that the particle size is large, and particularly when the surface of the photoreceptor is scratched, it tends to be visible as it is.
In the present embodiment, by adopting the above-described configuration, the ratio of the aluminum pigment existing on the toner surface is controlled to suppress wear and deterioration of the photoreceptor.

(Al element content and C element content)
In this embodiment, the ratio (A / B) of the Al element content A (atm%) to the C element content B (atm%) by X-ray photoelectron spectroscopy (XPS) in the toner is 0 to 0. .03. When A / B is 0 to 0.03, wear and deterioration of the photoreceptor are suppressed.
A / B is preferably 0 to 0.025, more preferably 0 to 0.02, and still more preferably 0 to 0.015.

Here, X-ray photoelectron spectroscopy (XPS) is an analysis of the energy of photoelectrons emitted when a solid surface is irradiated with a constant energy of X-rays. By obtaining the above, the kind, concentration, etc. of atoms in the substance are measured. The detection depth is about several nm, which is the escape depth of photoelectrons. Therefore, the concentration of atoms in the vicinity of the toner surface (several nm from the surface) is measured by XPS.
In this embodiment, A / B is set to the above range by reducing the Al element concentration in the vicinity of the surface of the toner by improving the inclusion property of the aluminum pigment in the toner.
For measurement of toner by XPS, JPS-9000MX manufactured by JEOL Ltd. is used.

Hereinafter, materials constituting the toner of the exemplary embodiment will be described in detail.
(Pigment)
The toner according to the exemplary embodiment contains an aluminum pigment as pigment particles having glitter. The aluminum pigment is preferably aluminum or an aluminum alloy. In the case of using an aluminum alloy, another metal element or non-metal element that can be added to aluminum is not particularly limited as long as it has a function such as having a metallic luster, but silver, gold, platinum, Examples thereof include nickel, chromium, tin, zinc, indium, titanium, copper, and the like, and at least one of these simple substances or alloys thereof and mixtures thereof is preferably used.

  The method for producing the aluminum pigment includes, for example, the metal or alloy layer of the composite pigment base material and the release resin having a structure in which a release resin layer and a metal or alloy layer are sequentially laminated on a sheet-like substrate surface. An example is a method in which scale-like (flat plate-like) particles are obtained by peeling off from the sheet-like substrate, pulverizing and refining with the interface of the layers as a boundary.

In the present embodiment, the pigment is preferably scaly (tabular) particles.
The scale-like particles are particles having a substantially flat surface (XY plane) and a substantially uniform thickness (Z). Here, the major axis on the plane of the scaly particles is defined as X, the minor axis is defined as Y, and the thickness is defined as Z. The XY plane is a surface that gives the maximum projected area.
When the major axis on the plane of the tabular grains is X, the minor axis is Y, and the thickness is Z, R ₅₀ is the number average particle diameter of the equivalent circle diameter determined from the area of the XY plane of the scaly grains. It is.
The equivalent circle diameter is the diameter of the circle when assuming that the substantially flat surface (XY plane) of the tabular grain is a circle having the same projected area as the projected area of the grain. When the substantially flat surface (XY plane) of a tabular grain is a polygon, the diameter of the circle obtained by converting the projected surface of the polygon into a circle is the equivalent circle diameter of the tabular grain. It is said.

R ₅₀ of the aluminum pigment is preferably 5 to 25 μm, more preferably 7 to 20 μm, and still more preferably 10 to 16 μm from the viewpoint of glitter.
Moreover, the R ₅₀ of the aluminum pigment, the relationship between the thickness d, in order to ensure a high gloss, it is preferable that R ₅₀ / d> 5. R ₅₀ / d is more preferably 6 or more, and still more preferably 8 or more.
The R ₅₀ can be measured using a particle image analyzer, and examples thereof include a flow particle image analyzer FPIA-2100, FPIA-300, and FPIA-3000S manufactured by Sysmex Corporation.
The thickness d can be measured by an SEM image.

In the toner according to the exemplary embodiment, from the viewpoint of brightness, the content of the aluminum pigment is preferably 10 to 40% by weight with respect to 100% by weight of the toner described later, and 15 to 35% by weight. More preferably, it is more preferably 20 to 30% by weight.
The content of the aluminum pigment is specified with respect to the total weight of the toner including the external additive when the external additive is added to the toner base particles. Since the amount is generally small relative to the toner base particles, the content in the toner base particles may be approximated.

In this embodiment, from the viewpoint of glitter, the volume average particle diameter of the aluminum pigment is preferably 3 to 20 μm, more preferably 7 to 20 μm, and still more preferably 10 to 16 μm.
In the present embodiment, the volume average particle size is measured using Coulter Multisizer II (manufactured by Beckman-Coulter), and the measured particle size distribution is divided into divided particle size ranges (channels). ), A cumulative distribution is drawn from the small diameter side with respect to the volume, and the particle size at which 50% is accumulated is defined as the volume average particle size.

  The aluminum pigment in the toner is generally insoluble in water and organic solvents. Therefore, after removing the external additive of the toner by sieving, etc., the binder resin and release agent in the toner are dissolved with an appropriate organic solvent, and the aluminum pigment is recovered by centrifuging or filtering. From the recovered amount of aluminum pigment, the content of aluminum pigment in the toner is measured.

(Binder resin)
Examples of the binder resin used in the present embodiment include ethylene resins such as polyester, polyethylene, and polypropylene; styrene resins such as polystyrene and α-polymethylstyrene; and (meth) acrylic resins such as polymethyl methacrylate and polyacrylonitrile. Resin; Polyamide resin, polycarbonate resin, polyether resin and copolymer resins thereof may be used. Among these, it is desirable to use a polyester resin.
In the following, polyester resins that are particularly preferably used will be described.

  The polyester resin is synthesized mainly from an acid (polyhydric carboxylic acid) component and an alcohol (polyhydric alcohol) component. In the present embodiment, the “acid-derived constituent component” refers to a component before synthesis of the polyester resin. Refers to a component that was an acid component, and “alcohol-derived component” refers to a component that was an alcohol component before the synthesis of the polyester resin.

<Acid-derived components>
The acid-derived component is not particularly limited, and aliphatic dicarboxylic acids and aromatic carboxylic acids are preferably used. Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, 1,9-nonanedicarboxylic acid, and 1,10-decanedicarboxylic acid. 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, etc. Or lower alkyl esters and acid anhydrides thereof, but are not limited thereto. Examples of the aromatic carboxylic acid include lower alkyl esters and acid anhydrides of aromatic carboxylic acids such as terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, and naphthalenedicarboxylic acid. Moreover, alicyclic carboxylic acids, such as cyclohexane dicarboxylic acid, etc. are mentioned. In order to secure better fixing properties, it is preferable to use a trivalent or higher carboxylic acid (trimellitic acid or acid anhydride thereof) together with a dicarboxylic acid in order to form a crosslinked structure or a branched structure. Specific examples of the alkenyl succinic acid include dodecenyl succinic acid, dodecyl succinic acid, stearyl succinic acid, octyl succinic acid, octenyl succinic acid and the like.

<Constituents derived from alcohol>
The alcohol-derived constituent component is not particularly limited, and examples of the aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol and the like can be mentioned. In addition, diethylene glycol, triethylene glycol, neopentyl glycol, glycerin, alicyclic diols such as cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A Aromatic diols such as are used. In order to secure good fixing properties, a trihydric or higher polyhydric alcohol (glycerin, trimethylolpropane, pentaerythritol) may be used in combination with the diol in order to form a crosslinked structure or a branched structure.
As the polyester resin that can be used in the present embodiment, an amorphous polyester resin or a crystalline polyester resin can be easily obtained by a combination of these polycondensable monomers.

  As the polyvalent carboxylic acid used to obtain the crystalline polyester resin, among the carboxylic acids, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid Maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid, n-octyl succinic acid, n-octenyl succinic acid, These acid anhydrides or acid chlorides can be mentioned.

  Examples of the polyol used for obtaining the crystalline polyester resin include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,4. , Butenediol, neopentyl glycol, 1,5-pentane glycol, 1,6-hexane glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol and the like. .

  As such a crystalline polycondensation resin, 1,9-nonanediol and 1,10-decanedicarboxylic acid, or a polyester resin obtained by reacting cyclohexanediol and adipic acid, 1,6-hexanediol Resin obtained by reacting glycine and sebacic acid, polyester resin obtained by reacting ethylene glycol and succinic acid, polyester resin obtained by reacting ethylene glycol and sebacic acid, 1,4-butanediol and Mention may be made of polyester resins obtained by reacting with succinic acid. Among these, polyester resins obtained by reacting 1,9-nonanediol and 1,10-decanedicarboxylic acid, and 1,6-hexanediol and sebacic acid are more preferable.

In addition, as the polyvalent carboxylic acid used to obtain the non-crystalline polyester resin in the present embodiment, among the above polyvalent carboxylic acids, dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, tetrachloro Phthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylene diacetic acid, m-phenylene diglycolic acid, p-phenylene diglycolic acid, o-phenylene diglycolic acid, diphenylacetic acid, diphenyl-p, p Examples include '-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, and cyclohexanedicarboxylic acid. Examples of the polyvalent carboxylic acid other than dicarboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid. Moreover, you may use what derived the carboxyl group of these carboxylic acid into the acid anhydride, the acid chloride, or ester.
Among these, it is preferable to use terephthalic acid or its lower ester, diphenylacetic acid, cyclohexanedicarboxylic acid, or the like. The lower ester refers to an ester of an aliphatic alcohol having 1 to 8 carbon atoms.

Moreover, as a polyol used in order to obtain the non-crystalline polyester resin in this embodiment, among the above polyols, in particular, polytetramethylene glycol, bisphenol A, bisphenol Z, hydrogenated bisphenol A, cyclohexane dimethanol and the like. It is preferable to use it.
Further, a polycondensate of hydroxycarboxylic acid can be used as the amorphous resin.
Hydroxycarboxylic acid is a compound having both a hydroxyl group and a carboxyl group in the molecule. Examples of the hydroxycarboxylic acid include aromatic hydroxycarboxylic acids and aliphatic hydroxycarboxylic acids, but it is preferable to use aliphatic hydroxycarboxylic acids.
Specific examples include hydroxyheptanoic acid, hydroxyoctanoic acid, hydroxydecanoic acid, hydroxyundecanoic acid, and lactic acid. Of these, lactic acid is preferably used.

  In order to produce one type of polycondensation resin, each of the polyvalent carboxylic acid and polyol may be used alone or in combination of two or more, each of which may be used alone or in combination of two or more. You may use each. Moreover, when using hydroxycarboxylic acid in order to produce 1 type of polycondensation resin, 1 type may be used individually, 2 or more types may be used, and polyvalent carboxylic acid and a polyol may be used together.

  The method for producing the polyester resin is not particularly limited, and may be produced by a general polyester polymerization method in which an acid component and an alcohol component are reacted. Examples thereof include direct polycondensation and transesterification. What is necessary is just to produce it properly according to a kind. The molar ratio (acid component / alcohol component) when the acid component reacts with the alcohol component varies depending on the reaction conditions and the like, and cannot be generally stated, but is usually about 1/1.

  The polyester resin may be produced, for example, at a polymerization temperature of 180 ° C. or higher and 230 ° C. or lower, and may be reacted while removing the water and alcohol generated during condensation by reducing the pressure in the reaction system as necessary. . If the monomer is not dissolved or compatible at the reaction temperature, the polymerization reaction may be partially accelerated or slowed down, and many uncolored particles may be generated. It may be added and dissolved as a solubilizer. In the polycondensation reaction, the dissolution auxiliary solvent may be distilled off. 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 before the polymerization with the main component. It may be condensed.

  Catalysts that may be used in the production of the polyester resin include alkali metal compounds such as sodium and lithium; alkaline earth metal compounds such as magnesium and calcium; metals such as zinc, manganese, antimony, titanium, tin, zirconium, and germanium Compound: Phosphorous acid compound, phosphoric acid compound, amine compound and the like. Among these, for example, it is preferable to use a tin-containing catalyst such as tin, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin oxide, and diphenyltin oxide.

  In the present embodiment, a compound having a hydrophilic polar group may be used as long as it is copolymerizable as a resin for an electrostatic charge image developing toner. Specific examples include dicarboxylic acid compounds in which an aromatic ring such as sulfonyl-terephthalic acid sodium salt or 3-sulfonylisophthalic acid sodium salt is directly substituted when the resin used is a polyester.

The toner according to the exemplary embodiment preferably contains a crystalline polyester resin as a binder resin. Of the crystalline polyester resins, aromatic crystalline resins are generally higher than the melting temperature range described later, and are preferably aliphatic crystalline polyester resins.
The content of the crystalline polyester resin in the toner according to the exemplary embodiment is preferably 2% by weight to 30% by weight, and more preferably 4% by weight to 25% by weight.

The melting temperature of the crystalline polyester resin is preferably in the range of 50 ° C. to 100 ° C., preferably in the range of 55 ° C. to 95 ° C., and more preferably in the range of 60 ° C. to 90 ° C. preferable.
Here, for the measurement of the melting temperature of the crystalline polyester resin, a differential scanning calorimeter was used, and JIS K-7121 was measured at a temperature rising rate of 10 ° C. per minute from room temperature (20 ° C.) to 180 ° C. : It can obtain | require as a melting peak temperature of the input compensation differential scanning calorimetry shown to 87. The crystalline polyester resin may show a plurality of melting peaks, but in the present embodiment, the maximum peak is regarded as the melting temperature.
“Crystallinity” as shown in the above “crystalline polyester” means that in differential scanning calorimetry (DSC), it has a clear endothermic peak, not a stepwise endothermic change. Means that the half-value width of the endothermic peak when measured at a heating rate of 10 ° C./min is within 15 ° C., and so on. The crystalline polyester resin is a polymer obtained by copolymerizing other components with respect to the main chain. When the other components are 50% by weight or less, this copolymer is also called crystalline polyester.
On the other hand, a resin having an endothermic peak with a half-value width exceeding 15 ° C. or a resin having no clear endothermic peak means non-crystalline (amorphous), and so on.

On the other hand, the glass transition temperature (Tg) of the amorphous polyester resin is preferably 30 ° C. or higher, more preferably 30 to 100 ° C., and still more preferably 50 to 80 ° C.
Within the above numerical range, the cohesive strength of the binder resin itself in the high temperature range is good, so that it has excellent hot offset at the time of fixing, and sufficient melting can be obtained. Is preferable because it is difficult to rise.
Here, the glass transition temperature of the non-crystalline polyester resin refers to a value measured by a method (DSC method) defined in ASTM D3418-82.
Moreover, the measurement of the glass transition temperature in this embodiment can be measured by, for example, “DSC-20” (manufactured by Seiko Denshi Kogyo Co., Ltd.) according to the differential scanning calorimetry, and specifically, about 10 mg of a sample. Is heated at a constant rate of temperature increase (10 ° C./min), and the glass transition temperature is obtained from the intersection of the baseline and the endothermic peak tilt line.

  In the toner according to the exemplary embodiment, the resin other than the polyester resin is not particularly limited. Specifically, styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, ethyl acrylate, acrylic acid acrylic monomers such as n-propyl, butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, etc. Methacrylic monomers; Ethylenically unsaturated acid monomers such as acrylic acid, methacrylic acid and sodium styrenesulfonate; Vinyl nitriles such as acrylonitrile and methacrylonitrile; Vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether Vinyl vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; homopolymers of olefin monomers such as ethylene, propylene and butadiene, and copolymers obtained by combining two or more of these monomers , Or a mixture thereof, and further, an epoxy resin, a polyester resin, a polyurethane resin, a polyamide resin, a cellulose resin, a polyether resin, and the like, a non-vinyl condensation resin, or a mixture of them with the vinyl resin, and their coexistence Examples thereof include graft polymers obtained by polymerizing vinyl monomers below. These resins may be used alone or in combination of two or more.

  The total content of the binder resin in the toner is preferably 50 to 90% by weight, more preferably 60 to 85% by weight, and still more preferably 70 to 80% by weight. It is preferable for the content of the binder resin to be within the above range because exposure of the aluminum pigment can be suppressed while maintaining desired glitter.

(Release agent)
The toner according to the exemplary embodiment may contain a release agent as necessary. Examples of the release agent include paraffin wax such as low molecular weight polypropylene and low molecular weight polyethylene; silicone resin; rosins; rice wax; carnauba wax;
The melting temperature of these release agents is preferably 50 ° C. or higher and 100 ° C. or lower, and more preferably 60 ° C. or higher and 95 ° C. or lower.
These release agents may be used alone or in combination of two or more. The content of the release agent in the toner is preferably from 0.5% by weight to 15% by weight, and more preferably from 1.0% by weight to 12% by weight.

(Other additives)
In addition to the components described above, various components such as an internal additive, a charge control agent, inorganic powder (inorganic particles), and organic particles may be added to the toner according to the exemplary embodiment as necessary. .

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

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

<External additive>
In this embodiment, it is preferable to add an external additive to the toner base particles.
It is not particularly limited, as the external additive, for _{example, SiO 2, TiO 2, Al} 2 O 3, CuO, ZnO, SnO 2, CeO 2, Fe 2 O 3, MgO, BaO, CaO, K Inorganic oxide particles such as ₂ O, Na ₂ O, ZrO ₂ , CaO.SiO ₂ , K ₂ O. (TiO ₂ ) _n , Al ₂ O ₃ .2SiO ₂ , CaCO ₃ , MgCO ₃ , BaSO ₄ , MgSO ₄ Is mentioned.
Of the inorganic oxide particles, silica particles and titania particles are particularly desirable. In addition, it is desirable that the surface of the inorganic oxide particles is previously hydrophobized. This hydrophobization treatment improves the powder fluidity of the toner, and is more effective for improving the environmental dependency of charging and carrier contamination.

Polyolefin resins such as polyethylene, polypropylene; polyvinyl and polyvinylidene resins such as polystyrene, acrylic resin, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether and polyvinyl ketone; Examples thereof include vinyl-vinyl acetate copolymer; styrene-acrylic acid copolymer; straight silicone resin composed of organosiloxane bond or a modified product thereof; polyester; polycarbonate: fluororesin. A cured resin particle can be obtained by simultaneously using a crosslinking component such as divinylbenzene together with the resin formation.
Examples of thermosetting resins include phenol resins; amino resins such as urea-formaldehyde resins, melamine resins, benzoguanamine resins, urea resins, polyamide resins; epoxy resins, and the like.

An external additive may be used individually by 1 type, and may use 2 or more types together.
The total amount of external additives added is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 4 parts by weight, based on 100 parts by weight of toner base particles. More preferably, it is 3 to 2 parts by weight.

(Toner characteristics)
The toner according to the exemplary embodiment has a volume average particle diameter D50 of preferably 1 μm or more and 30 μm or less, more preferably 3 μm or more and 20 μm or less, and further preferably 5 μm or more and 10 μm or less.
In addition, the volume average particle diameter D50 is a volume and a number with respect to a particle size range (channel) divided based on a particle size distribution measured by a measuring instrument such as Multisizer II (manufactured by Beckman-Coulter). The cumulative distribution is drawn from the small diameter side, the particle size to be accumulated 16% is volume D16v, several D16p, the particle size to be accumulated 50% is volume D50v, several D50p, the particle size to be accumulated 84% is volume D84v, number D84p. It is defined as Using these, the volume average particle size distribution index (GSDv) is calculated as (D84v / D16v) ^1/2 .

(Toner production method)
The toner according to the exemplary embodiment is manufactured by a known method such as a wet method or a dry method, but it is particularly preferable that the toner is manufactured by a wet method. Examples of the wet method include a melt suspension method, an emulsion aggregation method, and a dissolution suspension method. Among these, it is preferable to manufacture by an emulsion aggregation method.
Here, the emulsion aggregation method is to prepare each dispersion (emulsion, pigment dispersion, etc.) containing components (binder resin, colorant, etc.) contained in the toner, and mix and mix these dispersions. And then the aggregated particles are not less than the melting temperature or glass transition temperature of the binder resin (in the case of producing a toner containing both the crystalline resin and the amorphous resin, This is a method in which the toner components are aggregated and united by heating to a glass transition temperature or higher) of the crystalline resin.

In this embodiment, in particular, a step of preparing an aluminum pigment dispersion or an aluminum pigment dispersion simultaneously emulsified with a resin (hereinafter also referred to as a dispersion preparation step), and a number of toner constituent materials in the dispersion. It is preferable to have a step of adding in steps (hereinafter also referred to as an addition step). Here, the toner constituent material means a constituent material of toner excluding an aluminum pigment, and specifically, a binder resin and a release agent are exemplified. In addition, the above-described internal additives may be added.
In the dispersion preparation step, an aluminum pigment dispersion or an aluminum pigment dispersion simultaneously emulsified with a resin is prepared. Among these, it is preferable to prepare an aluminum pigment dispersion that is simultaneously emulsified with the resin. The aluminum pigment dispersion can be prepared, for example, by dispersing an aluminum pigment using a surfactant.
Examples of surfactants used for the purpose of dispersing aluminum pigments, mold release agents, binder resins, etc., agglomerating them, or stabilizing them include sulfate ester, sulfonate, phosphate ester, An anionic surfactant such as a soap and a cationic surfactant such as an amine salt type or a quaternary ammonium salt type can be used. It is also effective to use a nonionic surfactant such as polyethylene glycol, alkylphenol ethylene oxide adduct, and polyhydric alcohol. As these dispersing means, general means such as a rotary shear type homogenizer, a ball mill having a medium, a sand mill, a dyno mill and the like can be used.

  In the exemplary embodiment, the toner manufacturing method preferably includes the adding step a plurality of times. The number of addition steps may be appropriately selected within a range in which a desired A / B (a ratio of Al element content and C element content) is obtained. It is more preferably 7 times, and further preferably 3 to 6 times.

In this embodiment, when the aluminum pigment dispersion is prepared in the dispersion step, the aluminum pigment is first agglomerated, and then the binder resin dispersion and the release agent dispersion are added in the addition step. Each time, an aggregating agent is added to cause heteroaggregation, and then the addition process including the addition of the aggregating agent is repeated a plurality of times to form aggregated particles corresponding to the toner diameter, and then the system is bonded to the binder resin. It is preferable to obtain toner particles by combining the individual particles constituting the aggregated particles by heating to a glass transition temperature or a temperature higher than the melting point.
In addition, when preparing an aluminum pigment dispersion that is simultaneously emulsified with the resin in the dispersion step, heteroaggregation is caused in the dispersion, and then a binder resin dispersion and a release agent dispersion are added in the addition step. In addition, it is preferable to add a flocculant for each addition to cause heteroaggregation.

  The method for dispersing and granulating the binder resin in the aqueous medium can be selected from known methods such as forced emulsification, self-emulsification, and phase inversion emulsification. Of these, the self-emulsification method and the phase inversion emulsification method are preferably applied in consideration of the energy required for emulsification, the particle size controllability and stability of the resulting emulsion, and the phase inversion emulsification method is particularly preferred.

  As a flocculant, besides a surfactant, an inorganic salt or a divalent or higher metal salt can be suitably used. In particular, when a metal salt is used, it is preferable in characteristics such as cohesion control and toner chargeability. The metal salt compound used for aggregation is obtained by dissolving a general inorganic metal compound or a polymer thereof in a resin particle dispersion, but the metal elements constituting the inorganic metal salt are a periodic table (long period table). 2A, 3A, 4A, 5A, 6A, 7A, 8, 1B, 2B, and 3B, and those having a valence of 2 or more and soluble in the form of ions in the resin particle aggregation system. Good. Specific examples of preferred inorganic metal salts include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, aluminum sulfate, and polyaluminum chloride, polyaluminum hydroxide, calcium polysulfide. And inorganic metal salt polymers. Among these, an aluminum salt and a polymer thereof are particularly preferable. In general, in order to obtain a sharper particle size distribution, it is preferable that the valence of the inorganic metal salt is bivalent rather than monovalent, and trivalent or more valent than bivalent. A type of inorganic metal salt polymer is more suitable.

In the dispersion step and the addition step, for example, a stirring blade that forms a laminar flow having two paddles is used, and stirring is performed at a high stirring speed (for example, 500 rpm or more and 1500 rpm or less), thereby producing a glittering pigment. The particles are aligned in the major axis direction in the aggregated particles, and the aggregated particles are also aggregated in the major axis direction, so that the toner becomes flat. Finally, after alkalizing for particle stabilization, the temperature is raised to the glass transition temperature (Tg) or more of the toner to coalesce the aggregated particles. In the coalescence step, coalescence is performed at a lower temperature (for example, 60 ° C. or more and 80 ° C. or less), so that the movement accompanying the rearrangement of the material is reduced and the orientation of the pigment is maintained.
In addition, as said stirring speed, 650 rpm or more and 1,130 rpm or less are further preferable, and 760 rpm or more and 870 rpm or less are especially preferable. Further, the coalescence temperature in the coalescence step is more preferably 63 ° C. or more and 75 ° C. or less, and particularly preferably 65 ° C. or more and 70 ° C. or less.

2. Developer The toner according to the exemplary embodiment may be used as it is as a one-component developer, or may be mixed with a carrier and used as a two-component developer.
The carrier that can be used in the two-component developer is not particularly limited, and a known carrier is used. Examples thereof include magnetic metals such as iron oxide, nickel and cobalt, magnetic oxides such as ferrite and magnetite, resin-coated carriers having a resin coating layer on the surface of the core material, and magnetic dispersion carriers. Further, a resin-dispersed carrier in which a conductive material or the like is dispersed in a matrix resin may be used.

  Coating resins and matrix resins used for carriers include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic. Examples include, but are not limited to, acid copolymers, straight silicone resins composed of organosiloxane bonds or modified products thereof, fluororesins, polyesters, polycarbonates, phenol resins, and epoxy resins.

  Examples of the conductive material include metals such as gold, silver, and copper, carbon black, titanium oxide, zinc oxide, barium sulfate, aluminum borate, potassium titanate, and tin oxide, but are not limited thereto. .

Examples of the core material of the carrier include magnetic metals such as iron, nickel, and cobalt, magnetic oxides such as ferrite and magnetite, and glass beads. However, in order to use the carrier for the magnetic brush method, it is a magnetic material. It is preferable. The volume average particle size of the carrier core material is preferably 10 μm or more and 500 μm or less, more preferably 30 μm or more and 100 μm or less.
Further, in order to coat the surface of the carrier core material with a resin, a method of coating with a coating layer forming solution in which the coating resin and, if necessary, various additives are dissolved 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 an immersion method in which the carrier core material is immersed in the coating layer forming solution, a spray method in which the coating layer forming solution is sprayed onto the surface of the carrier core material, and the carrier core material is fluidized air. A fluidized bed method in which the coating layer forming solution is sprayed in a state of being suspended by the above, a kneader coater method in which the carrier core material and the coating layer forming solution are mixed in a kneader coater, and the solvent is removed.

  The mixing ratio (weight ratio) between the toner according to the exemplary embodiment and the carrier in the two-component developer is preferably in the range of toner: carrier = 1: 100 or more and 30: 100 or less, and 3: 100 or more and 20: 100. The following ranges are more preferable.

3. Image Forming Apparatus FIG. 1 is a schematic configuration diagram showing an embodiment of an image forming apparatus including a developing device to which toner according to the present embodiment is applied.
In FIG. 1, the image forming apparatus according to the present embodiment has a photosensitive drum 20 as an image holding body that rotates in a predetermined direction, and the photosensitive drum 20 is charged around the photosensitive drum 20. The charging device 21, the exposure device 22 as a latent image forming device for forming the electrostatic latent image Z on the photosensitive drum 20, and the electrostatic latent image Z formed on the photosensitive drum 20 are visible. A developing device 30 that forms an image, a transfer device 24 that transfers a toner image visualized on the photosensitive drum 20 to a recording paper 28 that is a transfer target, and residual toner on the photosensitive drum 20 are cleaned. The cleaning device 25 is sequentially arranged.

In the present embodiment, as shown in FIG. 1, the developing device 30 has a developing housing 31 in which a developer G containing toner 40 is accommodated, and the developing housing 31 faces the photosensitive drum 20 for development. A developing roll (developing electrode) 33 serving as a toner holding member facing the developing opening 32 and applying a predetermined developing bias to the developing roll 33. A developing electric field is formed in the developing region between the photosensitive drum 20 and the developing roll 33. Further, a charge injection roll (injection electrode) 34 as a charge injection member is provided in the development housing 31 so as to face the development roll 33. In particular, in this embodiment, the charge injection roll 34 also serves as a toner supply roll for supplying the toner 40 to the developing roll 33.
Here, the rotation direction of the charge injection roll 34 may be selected. However, in consideration of the toner supply property and the charge injection characteristic, the charge injection roll 34 has the same direction at the portion facing the developing roll 33. In addition, it is preferable that the rotation is performed with a peripheral speed difference (for example, 1.5 times or more), the toner 40 is sandwiched between the charge injection roll 34 and the developing roll 33, and the charge is injected while being rubbed.

Next, the operation of the image forming apparatus according to the embodiment will be described.
When the image forming process is started, first, the surface of the photosensitive drum 20 is charged by the charging device 21, and the exposure device 22 writes the electrostatic latent image Z on the charged photosensitive drum 20, and the developing device 30 then The electrostatic latent image Z is visualized as a toner image. Thereafter, the toner image on the photoconductive drum 20 is conveyed to a transfer site, and the transfer device 24 electrostatically transfers the toner image on the photoconductive drum 20 to a recording paper 28 that is a transfer target. The residual toner on the photosensitive drum 20 is cleaned by the cleaning device 25. Thereafter, the toner image on the recording paper 28 is fixed by a fixing device (not shown) to obtain an image.

(Process cartridge, toner cartridge)
FIG. 2 is a schematic configuration diagram illustrating an example of a process cartridge according to the present embodiment. The process cartridge according to the present embodiment is characterized in that the toner according to the present embodiment described above is accommodated, and a toner holder that holds and conveys the toner is provided.

  A process cartridge 200 shown in FIG. 2 includes a photoconductor 107 as an image carrier, a charging roller 108, a developing device 111 that accommodates the toner according to the above-described embodiment, a photoconductor cleaning device 113, and an opening for exposure. 118 and an opening 117 for static elimination exposure are combined and integrated using a mounting rail 116. The process cartridge 200 is detachably attached to an image forming apparatus main body including a transfer device 112, a fixing device 115, and other components not shown, and the image forming apparatus together with the image forming apparatus main body. It constitutes.

  The process cartridge 200 shown in FIG. 2 includes a charging device 108, a developing device 111, a cleaning device 113, an opening 118 for exposure, and an opening 117 for static elimination exposure. May be combined. In the process cartridge according to the present embodiment, in addition to the developing device 111, the photosensitive member 107, the charging device 108, the cleaning device (cleaning means) 113, the opening 118 for exposure, and the opening for static elimination exposure. 117, at least one selected from the group consisting of 117.

  Next, the toner cartridge according to this embodiment will be described. The toner cartridge according to this embodiment is detachably attached to the image forming apparatus, and at least the toner cartridge that stores toner to be supplied to the developing unit provided in the image forming apparatus is described above. The toner according to the present exemplary embodiment is characterized. Note that the toner cartridge according to the present embodiment only needs to contain at least toner, and may contain developer, for example, depending on the mechanism of the image forming apparatus.

  The image forming apparatus shown in FIG. 1 is an image forming apparatus having a configuration in which a toner cartridge (not shown) can be freely attached and detached, and the developing device 30 is connected to the toner cartridge by a toner supply pipe (not shown). . Further, when the amount of toner stored in the toner cartridge is low, this toner cartridge may be replaced.

  Hereinafter, although an Example and a comparative example are given and this embodiment is described in detail in detail, this embodiment is not limited to the following examples. In the following description, “parts” represents “parts by weight” and “%” represents “% by weight” unless otherwise specified.

(Measuring method)
<Measurement of pigment particle size>
The volume average particle diameter of the pigment particles was measured using Coulter Multisizer II (manufactured by Beckman-Coulter). As the electrolytic solution, ISOTON-II (manufactured by Beckman-Coulter) was used.
First, the toner was dissolved in THF (tetrahydrofuran), the insoluble matter was extracted by filtration and dried to obtain a measurement sample. In the measurement, 0.5 mg to 50 mg of a measurement sample was added to 2 ml of a 5% aqueous solution of a surfactant, preferably sodium alkylbenzenesulfonate as a dispersant, and this was added to 100 ml to 150 ml of the electrolytic solution. The electrolytic solution in which the measurement sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 minute. Using the Coulter Multisizer II type, an aperture having an aperture diameter of 100 μm is used. The particle size distribution of the following range of particles was measured. The number of particles to be measured was 50,000.
For the measured particle size distribution, a cumulative distribution is drawn from the smaller diameter side with respect to the divided particle size range (channel), and the particle size at which 50% is accumulated is defined as the volume average particle size.

<Measurement of pigment content>
The pigment content was measured by first ultrasonically treating the toner to separate the external additive from the toner base particles. Next, the weight of the separated toner base particles was measured and designated as A (g). The mother particles were dissolved in THF, and the insoluble matter, that is, the aluminum pigment was extracted by filtration and dried. After drying, the weight of the aluminum pigment was measured to obtain B (g). The content of the aluminum pigment was calculated from A and B.

<XPS measurement>
The amount of Al and C on the toner surface was measured by XPS (X-ray photoelectron spectroscopy). The measurement conditions by XPS were as follows.
X-ray photoelectron spectrometer: JPS-9000MX manufactured by JEOL Ltd.
・ X-ray source: MgKα ray ・ Acceleration voltage: 10.0 kV
・ Emission current: 20mA
-Pass energy of photoelectron energy analyzer: 30V
The surface atomic concentration was estimated from the peak intensity of each element of Al, O, N, S, Na, and C (rounding up to the nearest thousand in consideration of measurement error). The surface atom concentration was calculated using a relative photosensitivity factor provided by JASCO. Background correction and area (Area) were derived according to the analysis application software made by JEOL.

<Method of measuring endothermic peak temperature and glass transition temperature of resin>
The glass transition temperature (Tg) of the resin was measured using a differential scanning calorimeter (manufactured by Shimadzu Corporation: DSC-60A) in accordance with ASTM D3418. For the sample, an aluminum pan was used, an empty pan was set as a control, the temperature was increased at a temperature increase rate of 10 ° C./min, held at 200 ° C. for 5 minutes, and liquid nitrogen was used from 200 ° C. to 0 ° C. The temperature was lowered at 10 ° C./min, held at 0 ° C. for 5 minutes, and again heated from 0 ° C. to 200 ° C. at 10 ° C./min. The analysis was performed from the endothermic curve during the second temperature increase, and the onset temperature was set to Tg for the amorphous polyester resin, and the endothermic peak temperature was set from the maximum peak for the crystalline polyester resin.

<Method for measuring weight average molecular weight and molecular weight distribution of resin>
In the present embodiment, the molecular weight of the binder resin or the like is determined under the following conditions. GPC uses “HLC-8120GPC, SC-8020 (manufactured by Tosoh Corp.)”, column uses “TSKgel, SuperHM-H (Tosoh Corp. 6.0 mmID × 15 cm)”, two eluents THF (tetrahydrofuran) was used. As experimental conditions, an experiment was performed using a sample concentration of 0.5%, a flow rate of 0.6 ml / min, a sample injection amount of 10 μl, a measurement temperature of 40 ° C., and an IR detector. In addition, the calibration curve is “polystylen standard sample TSK standard” manufactured by Tosoh Corporation: “A-500”, “F-1”, “F-10”, “F-80”, “F-380”, “A” -2500 "," F-4 "," F-40 "," F-128 ", and" F-700 ".

<Method of measuring volume average particle diameter of toner>
The volume average particle diameter of the toner was measured using a Coulter Multisizer II (manufactured by Beckman-Coulter). As the electrolytic solution, ISOTON-II (manufactured by Beckman-Coulter) was used.
As a measuring method, first, 0.5 mg to 50 mg of a measurement sample is added to 2 ml of a 5% aqueous solution of a surfactant, preferably sodium alkylbenzenesulfonate as a dispersant, and this is added to 100 ml to 150 ml of the electrolytic solution. Added. The electrolytic solution in which the measurement sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 minute. Using the Coulter Multisizer II type, an aperture having an aperture diameter of 100 μm is used. The particle size distribution of the following range of particles was measured. The number of particles to be measured was 50,000.
For the measured particle size distribution, a cumulative distribution is drawn from the smaller diameter side with respect to the divided particle size range (channel), and the particle size at which 50% is accumulated is defined as the volume average particle size.

<Measurement method of volume average particle diameter of carrier>
The volume average particle diameter of the carrier was measured using a laser diffraction / scattering particle size distribution analyzer (LS Particle Size Analyzer: LS13 320, manufactured by Beckman Coulter, Inc.). For the particle size range (channel) obtained by dividing the obtained particle size distribution, the volume cumulative distribution was subtracted from the small particle size side, and the particle size at 50% cumulative was taken as the volume average particle size.

(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
The above components were placed in a heat-dried two-necked flask, and nitrogen gas was introduced into the container and the temperature was raised while stirring in an inert atmosphere, followed by a copolycondensation reaction at 160 ° C. for 7 hours, and then 10 Torr (1 The temperature was raised to 220 ° C. while gradually reducing the pressure to 0.333 kPa) and held for 4 hours. Once the pressure was returned to normal pressure, 9 parts of trimellitic anhydride was added, and the pressure was gradually reduced again to 10 Torr (1.33 kPa) and maintained at 220 ° C. for 1 hour to synthesize polyester resin 1 (binder resin 1).
The obtained polyester resin 1 had a glass transition temperature of 58 ° C. and a weight average molecular weight of 22,000.

(Preparation of binder resin dispersion 1)
・ Binder resin 1: 160 parts ・ Ethyl acetate: 233 parts ・ Sodium hydroxide aqueous solution (0.3 N): 0.1 part The above ingredients were put into a separable flask and heated at 70 ° C. And a resin mixed solution was prepared. While further stirring this resin mixture, 373 parts of ion-exchanged water was gradually added to effect phase inversion emulsification, and the solvent was removed to obtain a resin particle dispersion 1 (solid content concentration 30%).

(Synthesis of binder resin 2)
After putting 43.4 parts of dimethyl sebacate, 32.8 parts of 1,10-decanediol, 27 parts of dimethyl sulfoxide, and 0.03 part of dibutyltin oxide as a catalyst into a heat-dried three-necked flask The air in the container was put under an inert atmosphere with nitrogen gas by a depressurization operation, and the mixture was stirred at 180 ° C. for 4 hours by mechanical stirring. Dimethyl sulfoxide was distilled off under reduced pressure, and then the temperature was gradually raised to 220 ° C. under reduced pressure and stirred for 1.5 hours. When it became viscous, it was air-cooled to stop the reaction, and aliphatic. 65 parts of a crystalline polyester resin (binder resin 2) was synthesized. The melting temperature of the obtained crystalline polyester resin (binder resin 2) was 76 ° C.

(Preparation of binder resin dispersion 2)
Prepare 160 parts of crystalline polyester resin (binder resin 2), 233 parts of ethyl acetate, and 0.1 part of sodium hydroxide aqueous solution (0.3N), and put them in a separable flask at 70 ° C. The mixture was heated and stirred with a three-one motor (manufactured by Shinto Kagaku Co., Ltd.) to prepare a resin mixture. While further stirring this resin mixture, 373 parts of ion exchange water was gradually added, phase-inversion emulsified, and solvent removal was performed to obtain a crystalline polyester resin dispersion (binder resin dispersion 2). The volume average particle diameter of the resin particles in the crystalline polyester resin dispersion (binder resin dispersion 2) was 170 nm, and the solid content concentration was 30%.

(Preparation of glitter pigment dispersion)
<Preparation of glitter pigment dispersion 1>
Aluminum pigment (Showa Aluminum Powder Co., Ltd., 260EA, average particle size 10 μm): 100 parts Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R): 1.5 parts Ion-exchanged water: 400 parts After removing the solvent from the aluminum pigment paste and mixing with the above-mentioned activator and ion-exchanged water, it was dispersed for about 1 hour using an emulsifier-dispersing machine Cavitron (CR1010, manufactured by Taiheiyo Kiko Co., Ltd.). A glittering pigment dispersion 1 (pigment dispersion diameter 10 μm) in which pigment particles (aluminum pigment) are dispersed was prepared (solid content concentration 20%).

<Preparation of glitter pigment dispersion 2>
Aluminum pigment (Showa Aluminum Powder Co., Ltd., 260EA, average particle size 10 μm): 100 parts Binder resin: 100 parts Ethyl acetate: 233 parts Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd.) , Neogen R): 1.5 parts · Ion-exchanged water: 800 parts A solvent obtained by removing the solvent from the aluminum pigment paste, 100 parts of the binder resin 1, 233 parts of ethyl acetate, and an aqueous sodium hydroxide solution (0. 3N) 0.1 parts were prepared, and these were put in a separable flask, heated at 70 ° C., and stirred by a three-one motor (manufactured by Shinto Kagaku Co., Ltd.) to prepare a mixed solution. While further stirring this mixed solution, 800 parts of ion-exchanged water was gradually added, phase-inversion emulsification was performed, and the solvent was removed to obtain a glittering pigment dispersion 2 coated with a resin. The solid content concentration was 20%.

<Preparation of glitter pigment dispersion 3>
The aluminum pigment was changed to an aluminum pigment (Showa Aluminum Powder Co., Ltd. 210EA, average particle size 9 μm). The solvent was removed from the aluminum pigment paste, and the pigment was mechanically pulverized and classified to an average particle size of 8.2 μm using a star mill (manufactured by Ashizawa Finetech Co., Ltd., LMZ). Then, after mixing and dissolving with the above-mentioned activator and ion exchange water, it is dispersed for about 1 hour using an emulsifying disperser Cavitron (manufactured by Taiheiyo Kiko Co., Ltd., CR1010) to disperse glitter pigment particles (aluminum pigment). The resulting bright pigment dispersion 3 (pigment dispersion diameter 8.2 μm) was prepared (solid content concentration 20%).

<Preparation of glitter pigment dispersion 4>
The aluminum pigment was changed to an aluminum pigment (Showa Aluminum Powder Co., Ltd., 220EA, average particle size 17 μm). Thereafter, the pigment was pulverized by a star mill until the average particle size became 13.8 μm. In the other steps, the glitter pigment dispersion 4 was prepared through the same steps as the preparation of the glitter pigment dispersion 1 (solid content concentration 20%).

<Preparation of glitter pigment dispersion 5>
The aluminum pigment was changed to an aluminum pigment (Showa Aluminum Powder Co., Ltd. 210EA, average particle size 9 μm). Thereafter, the pigment was pulverized with a star mill until the average particle size became 7.8 μm. In other steps, the glitter pigment dispersion 5 was prepared through the same steps as the preparation of the glitter pigment dispersion 1 (solid content concentration 20%).

<Preparation of glitter pigment dispersion 6>
The aluminum pigment was changed to an aluminum pigment (Showa Aluminum Powder Co., Ltd., 220EA, average particle size 17 μm). Thereafter, the pigment was pulverized by a star mill until the average particle size became 14.2 μm. In other steps, the glitter pigment dispersion 6 was prepared through the same steps as the preparation of the glitter pigment dispersion 1 (solid content concentration 20%).

<Preparation of glitter pigment dispersion 7>
The aluminum pigment was changed to an aluminum pigment (Showa Aluminum Powder Co., Ltd., 2173EA, average particle size 6 μm). Thereafter, the pigment was pulverized by a star mill until the average particle size became 5.2 μm. In other steps, the glitter pigment dispersion 7 was prepared through the same steps as the preparation of the glitter pigment dispersion 1 (solid content concentration 20%).

<Preparation of luster pigment dispersion 8>
The aluminum pigment was changed to an aluminum pigment (Showa Aluminum Powder Co., Ltd., 220EA, average particle size 17 μm). In other steps, the glittering pigment dispersion 8 was prepared through the same steps as the glittering pigment dispersion 1 (pigment dispersion diameter 16.8 μm, solid content concentration 20%).

<Preparation of glitter pigment dispersion 9>
The aluminum pigment was changed to an aluminum pigment (Showa Aluminum Powder Co., Ltd., 2173EA, average particle size 6 μm). Thereafter, the pigment was pulverized by a star mill until the average particle size became 4.8 μm. In other steps, the bright pigment dispersion 9 was prepared through the same steps as the preparation of the bright pigment dispersion 1 (solid content concentration 20%).

<Preparation of glitter pigment dispersion 10>
The aluminum pigment was changed to an aluminum pigment (produced by Showa Aluminum Powder Co., Ltd., 525EA, average particle size 20 μm). Thereafter, the pigment was pulverized with a star mill until the average particle size became 17.2 μm. In other steps, the glitter pigment dispersion 10 was prepared through the same steps as the preparation of the glitter pigment dispersion 1 (solid content concentration 20%).

<Preparation of glitter pigment dispersion 11>
The aluminum pigment was changed to an aluminum pigment (Showa Aluminum Powder Co., Ltd., 2173EA, average particle size 6 μm). Thereafter, the pigment was pulverized by a star mill until the average particle size became 3.2 μm. In other steps, the glitter pigment dispersion 11 was prepared through the same steps as the preparation of the glitter pigment dispersion 1 (solid content concentration 20%).

<Preparation of glitter pigment dispersion 12>
The aluminum pigment was changed to an aluminum pigment (produced by Showa Aluminum Powder Co., Ltd., 525EA, average particle size 20 μm). In other steps, the glitter pigment dispersion 12 was prepared through the same steps as the preparation of the glitter pigment dispersion 1 (solid content concentration 20%).

<Preparation of glitter pigment dispersion 13>
Aluminum pigment (Showa Aluminum Powder Co., Ltd., 525EA, average particle size 20 μm): 100 parts Binder resin 1: 100 parts Ethyl acetate: 233 parts Anionic surfactant (Daiichi Kogyo Seiyaku, Neogen R): 1.5 parts ・ Ion-exchanged water: 800 parts Removed solvent from aluminum pigment paste, 100 parts of binder resin 1, 233 parts of ethyl acetate, aqueous sodium hydroxide solution (0.3 N) 0.1 parts were prepared, placed in a separable flask, heated at 70 ° C., and stirred by a three-one motor (manufactured by Shinto Kagaku Co., Ltd.) to prepare a mixed solution. While further stirring this mixed liquid, 800 parts of ion-exchanged water was gradually added, phase-inversion emulsification was performed, and the solvent was removed to obtain a glittering pigment dispersion 13 coated with a resin. The solid content concentration was 20%.

<Preparation of glitter pigment dispersion 14>
The aluminum pigment was changed to an aluminum pigment (Showa Aluminum Powder Co., Ltd., 2173EA, average particle size 6 μm). Thereafter, the pigment was pulverized by a star mill until the average particle size became 2.8 μm. In the other steps, the glitter pigment dispersion 14 was prepared through the same steps as the preparation of the glitter pigment dispersion 1 (solid content concentration 20%).

<Preparation of glitter pigment dispersion 15>
The aluminum pigment was changed to an aluminum pigment (Showa Aluminum Powder Co., Ltd., 625EA, average particle size 22 μm). In other steps, the glitter pigment dispersion 15 was prepared through the same steps as the preparation of the glitter pigment dispersion 1 (dispersion diameter 22 μm, solid content concentration 20%).

(Preparation of release agent dispersion)
Carnauba wax (Toa Kasei Co., Ltd., RC-160, Tm68 ° C.): 50 parts Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK): 1.0 parts Ion exchange water : 200 parts or more were mixed and heated to 95 ° C. and dispersed using a homogenizer (IKA, Ultra Tarrax T50). A release agent dispersion liquid (solid content concentration 20%) prepared by dispersing release agent particles having a volume average particle diameter of 0.23 μm was prepared.

Example 1
<Preparation of Toner 1>
-Binder resin dispersion 1: 232 parts-Release agent dispersion: 72 parts-Bright pigment dispersion 1: 140 parts Put the bright pigment dispersion 1 in a cylindrical stainless steel container and homogenizer (Ultra, manufactured by IKA). The mixture was dispersed and mixed for 10 minutes while applying a shear force at 4,000 rpm by Lalux T50). Subsequently, 0.35 part of a 10% nitric acid aqueous solution of polyaluminum chloride as a flocculant was gradually added dropwise, and the homogenizer was rotated at 5,000 rpm and dispersed for 15 minutes to prepare a raw material dispersion.
Thereafter, the raw material dispersion liquid is transferred to a polymerization vessel equipped with a stirring device using two paddle stirring blades for forming a laminar flow and a thermometer, and heated with a mantle heater at a stirring rotational speed of 810 rpm. First, the temperature was raised to around Tg of the resin while stirring. During this temperature increase, the addition of 1.4 parts of the other toner materials (binder resin dispersion, release agent dispersion) and flocculant was repeated five times so that the aluminum pigment was coated with a multilayer resin. Particles were formed. The toner material and the flocculant were equally divided according to the number of additions. 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 about 2 hours.
Thereafter, the pH was raised to 8.0 in order to fuse the aggregated particles, and then the temperature was raised to a temperature not lower than Tg of the binder resin and not higher than Tm of the release agent. After confirming that the aggregated particles were fused with an optical microscope, the pH was lowered to 6.0 while maintaining the above temperature, 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 obtained toner particles 1 had a volume average particle diameter of 15.2 μm.

  To 100 parts by weight of toner particles 1 obtained, 1.5 parts by weight of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 1.0% of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) are prepared. The parts by weight were mixed and blended at 10,000 rpm for 30 seconds using a sample mill. Thereafter, toner 1 was prepared by sieving with a vibrating sieve having an opening of 45 μm. At this time, the volume average particle diameter of the toner 1 measured using Multisizer II (aperture diameter: 50 μm, manufactured by Beckman Coulter, Inc.) was 14.4 μm.

<Creation of carrier>
-Toluene: 14 parts-Styrene-methyl methacrylate copolymer (component ratio: 80/20 (weight ratio), weight average molecular weight: 70,000): 2 parts-MZ500 (zinc oxide, manufactured by Titanium Industry Co., Ltd.): 0.6 parts The above components were mixed and stirred with a stirrer for 10 minutes to prepare a coating layer forming solution in which zinc oxide was dispersed. Next, this coating solution and 100 parts of ferrite particles (volume average particle size: 38 μm) are put in a vacuum degassing kneader and stirred at 60 ° C. for 30 minutes, and then degassed by further reducing pressure while heating. The carrier was prepared by drying.

<Preparation of Developer 1>
The developer 1 was prepared by placing 1 part of the toner 1 and 100 parts of the carrier in a V blender, stirring for 20 minutes, and then sieving at 212 μm.

(Examples 2-40, Comparative Examples 1-2)
The toner was manufactured by the method described in Example 1 except that the method for manufacturing the glittering toner described in Example 1 was changed as follows.

  In Example 2, the amount of the glitter pigment dispersion 1 of Example 1 was changed from 140 parts to 118 parts.

  In Example 3, the amount of the glitter pigment dispersion 1 of Example 1 was changed from 140 parts to 163 parts.

  In Example 4, the amount of the glitter pigment dispersion 1 of Example 1 was changed from 140 parts to 98 parts, and the number of additions was changed from 5 times to 4 times.

  In Example 5, the glittering pigment dispersion 1 of Example 1 was changed to the glittering pigment dispersion 2, the amount used was changed from 140 parts to 377 parts, and the amount of binder resin dispersion used was 232 parts. To 106 parts.

  In Example 6, the amount of the glitter pigment dispersion 1 of Example 1 was changed from 140 parts to 57 parts, and the number of additions was changed from 5 times to 4 times.

  In Example 7, the amount of the glitter pigment dispersion 1 of Example 1 was changed from 140 parts to 257 parts, and the number of additions was changed from 5 times to 6 times.

  In Example 8, the amount of the glitter pigment dispersion 1 of Example 1 was changed from 140 parts to 36 parts, and the number of additions was changed from 5 times to 2 times.

  In Example 9, the amount of the glitter pigment dispersion liquid of Example 1 was changed from 140 parts to 304 parts, and the number of additions was changed from 5 times to 7 times.

  In Example 10, the glittering pigment dispersion 1 of Example 1 was changed to the glittering pigment dispersion 3.

  In Example 11, the glitter pigment dispersion 1 of Example 1 was changed to the glitter pigment dispersion 3, and the number of additions was changed from 5 times to 4 times.

  In Example 12, the glitter pigment dispersion 1 of Example 1 was changed to the glitter pigment dispersion 4.

  In Example 13, the glitter pigment dispersion 1 of Example 1 was changed to the glitter pigment dispersion 4, and the number of additions was changed from 5 to 6.

  In Example 14, the glitter pigment dispersion 1 of Example 1 was changed to the glitter pigment dispersion 5.

  In Example 15, the glittering pigment dispersion 1 of Example 1 was changed to the glittering pigment dispersion 5, and the number of additions was changed from 5 times to 4 times.

  In Example 16, the glitter pigment dispersion 1 of Example 1 was changed to the glitter pigment dispersion 6.

  In Example 17, the glitter pigment dispersion 1 of Example 1 was changed to the glitter pigment dispersion 6, and the number of additions was changed from 5 to 6.

  In Example 18, the glitter pigment dispersion 1 of Example 1 was changed to the glitter pigment dispersion 7, and the number of additions was changed from 5 to 4.

  In Example 19, the glitter pigment dispersion 1 of Example 1 was changed to the glitter pigment dispersion 7, and the number of additions was changed from 5 to 6.

  In Example 20, the glitter pigment dispersion 1 of Example 1 was changed to the glitter pigment dispersion 8, and the number of additions was changed from 5 to 3.

  In Example 21, the glitter pigment dispersion 1 of Example 1 was changed to the glitter pigment dispersion 8.

  In Example 22, the number of additions of the glitter pigment dispersion 1 of Example 1 to the glitter pigment dispersion 9 was changed from 5 times to 4 times.

  In Example 23, the glitter pigment dispersion 1 of Example 1 was changed to the glitter pigment dispersion 9, and the number of additions was changed from 5 to 6.

  In Example 24, the glitter pigment dispersion 1 of Example 1 was changed to the glitter pigment dispersion 8, and the number of additions was changed from 5 to 6.

  In Example 25, the glitter pigment dispersion 1 of Example 1 was changed to the glitter pigment dispersion 10, and the number of additions was changed from 5 to 6.

  In Example 26, the glitter pigment dispersion 1 of Example 1 was changed to the glitter pigment dispersion 10, and the number of additions was changed from 5 to 7.

  In Example 27, the glitter pigment dispersion 1 of Example 1 was changed to the glitter pigment dispersion 11, and the number of additions was changed from 5 times to 4 times.

  In Example 28, the glitter pigment dispersion 1 of Example 1 was changed to the glitter pigment dispersion 11 and the number of additions was changed from 5 to 2 times.

  In Example 29, the glitter pigment dispersion 1 of Example 1 was changed to the glitter pigment dispersion 12, and the number of additions was changed from 5 to 7.

  In Example 30, the glitter pigment dispersion 1 of Example 1 was changed to the glitter pigment dispersion 12, and the number of additions was changed from 5 times to 8 times.

  In Example 31, the glitter pigment dispersion 1 of Example 1 was changed to the glitter pigment dispersion 11, the amount of the glitter pigment dispersion 11 was changed from 140 parts to 36 parts, and the number of additions was 5 times. Changed to 3 times.

  In Example 32, the glittering pigment dispersion liquid 1 of Example 1 was changed to the glittering pigment dispersion liquid 11, the amount of the glittering pigment dispersion liquid 11 was changed from 140 parts to 36 parts, and the number of additions was 5 times. Changed to 2 times.

  In Example 33, the glitter pigment dispersion 1 of Example 1 was changed to the glitter pigment dispersion 12, the amount of the glitter pigment dispersion 12 was changed from 140 parts to 304 parts, and the number of additions was five times. Changed to 8 times.

  In Example 34, the glitter pigment dispersion 1 of Example 1 was changed to the glitter pigment dispersion 12, the amount of the glitter pigment dispersion 12 was changed from 140 parts to 304 parts, and the number of additions was five times. Changed to 10 times.

  In Example 35, the glitter pigment dispersion 1 of Example 1 was changed to the glitter pigment dispersion 14, and the number of additions was changed from 5 to 3.

  In Example 36, the glitter pigment dispersion 1 of Example 1 was changed to the glitter pigment dispersion 14, and the number of additions was changed from 5 to 2 times.

  In Example 37, the glitter pigment dispersion 1 of Example 1 was changed to the glitter pigment dispersion 15, and the number of additions was changed from 5 times to 10 times.

  In Example 38, the glitter pigment dispersion 1 of Example 1 was changed to the glitter pigment dispersion 15, and the number of additions was changed from 5 to 8.

  In Example 39, the binder resin dispersion 1 of Example 1 was changed from 232 parts to 170 parts, and the binder resin dispersion liquid 2 was changed to 62 parts.

  In Comparative Example 1, the bright pigment dispersion liquid 1 of Example 1 was changed to the bright pigment dispersion liquid 11. Furthermore, all the raw materials except the binder resin dispersion to be added are put into a cylindrical stainless steel container, and dispersed and mixed for 10 minutes while applying a shearing force at 4,000 rpm with a homogenizer (IKA's Ultra Lalux T50). did. Next, 1.75 parts of a 10% nitric acid aqueous solution of polyaluminum chloride as a flocculant was gradually added dropwise, and the homogenizer was rotated at 5,000 rpm for 15 minutes to be mixed. Thereafter, after forming aggregated particles, 100 parts of the binder resin dispersion 1 was additionally added.

  In Comparative Example 2, the glitter pigment dispersion 1 of Example 1 was used as the glitter pigment dispersion 13, the amount of the glitter pigment dispersion 13 used was changed from 140 parts to 280 parts, and the binder resin dispersion 1 was used. The amount was changed from 232 parts to 138 parts. Furthermore, all the raw materials except the binder resin dispersion to be added are put into a cylindrical stainless steel container, and dispersed and mixed for 10 minutes while applying a shearing force at 4,000 rpm with a homogenizer (IKA's Ultra Lalux T50). did. Next, 1.75 parts of a 10% nitric acid aqueous solution of polyaluminum chloride as a flocculant was gradually added dropwise, and the homogenizer was rotated at 5,000 rpm for 15 minutes to be mixed. Thereafter, after forming aggregated particles, 1: 100 parts of a binder resin dispersion was additionally added.

(Example 40)
-Binder resin dispersion 1: 380 parts-Release agent dispersion: 72 parts-Brilliant pigment dispersion 1: 140 parts All the above toner materials are put in a cylindrical stainless steel container and homogenizer (manufactured by IKA, Ultra Turrax T50). The mixture was dispersed and mixed for 10 minutes while applying a shearing force at 4,000 rpm. Subsequently, 1.75 parts of a 10% nitric acid aqueous solution of polyaluminum chloride as a flocculant was gradually added dropwise, and the homogenizer was rotated at 5,000 rpm and dispersed for 15 minutes to prepare a raw material dispersion. Subsequent granulation was performed as in Example 1 except for the additional addition of toner material. After the toner is dried, it is mixed with 100 parts of the binder resin dispersion that has been freeze-dried in advance, and a sample mill (manufactured by Kyoritsu Riko Co., Ltd., SK-M10 type) is used to mechanically transfer the resin to the toner. Adhesion was performed to obtain a glittering toner 40 covered with resin. In addition, the sample mill was performed 10 times for 60 seconds at 10,000 rpm. The subsequent external addition process and the like were performed in the same manner as in Example 1.

(Evaluation test)
<Photoreceptor wear evaluation method>
Using a DocuCenter Color 400CP (Fuji Xerox Co., Ltd.), first, 10,000 solid patterns were continuously output at low temperature and low humidity (20 ° C., 30% RH). After being left for 24 hours in a low temperature and low humidity (20 ° C., 30% RH) environment, 5,000 solid patterns were output in a high humidity (28 ° C., 60% RH) environment. After being left in a high humidity (28 ° C., 60% RH) environment for 24 hours, it was returned to a low temperature, low humidity (20 ° C., 30% RH) environment again, and 20,000 solid patterns were output. The worn state of the photoreceptor after output was visually evaluated. G2 and above are practical levels.
G6 Glossy as new.
G5 No flaws are visually confirmed.
G4 1-2 places, very small scratches.
G3 Several small scratches occurred.
G2 Partially small scratches.
G1 Scratches on the entire surface.

<Illumination evaluation method>
A developer as a sample is filled in a developing device of DocuCenter Color 400CP (Fuji Xerox Co., Ltd.), recording paper (rough paper, Oji Paper Co., Ltd.), fixing temperature 200 ° C., fixing pressure 4.0 Kg. / cm ^2, at a process speed 220 mm / s, the amount of applied toner to form a solid image of 4.5 g / cm ^2. With respect to the obtained solid image, the glossiness was visually evaluated based on the following criteria. JISK5600-4-3: 1999 "Coating paint general test method-Part 4: Visual characteristics of paint-Section 3: Visual comparison of color" Brightness by visual observation under natural lighting (natural daylighting) Sex was evaluated. In addition, evaluation evaluated particle | grain feeling (effect of the glittering glitter) and optical effect (change of the hue by the viewing angle). G2 and above are practical levels.
G5 Particle feeling and optical effect are harmonized.
G4 Slightly grainy and has optical effects.
G3 Normal feeling.
G2 I feel blurry.
G1 No particle feeling or optical effect.
The evaluation results are shown in the following table.

20 Photosensitive drum 21 Charging device 22 Exposure device 24 Transfer device 25 Cleaning device 28 Recording paper 30 Development device 31 Development housing 32 Development opening 33 Development roll 34 Charge injection roll 40 Toner 107 Photoconductor (image carrier)
108 Charging roller 111 Developing device (developing means)
112 Transfer device 113 Photoconductor cleaning device (cleaning means)
115 Fixing device (fixing means)
116 Mounting rail 117 Opening portion 118 for static elimination exposure Opening portion 200 for exposure Process cartridge 300 Recording paper (transfer object)
G Developer Z Electrostatic latent image

Claims (9)

Contains binder resin and aluminum pigment,
The ratio (A / B) of the Al element content A (atm%) and the C element content B (atm%) by X-ray photoelectron spectroscopy (XPS) is 0 to 0.03. Yes Toner for developing electrostatic images.   The electrostatic image developing toner according to claim 1, wherein the volume average particle diameter of the aluminum pigment is 3 μm to 20 μm.   The electrostatic image developing toner according to claim 1, wherein the content of the aluminum pigment in the electrostatic image developing toner is 10 to 40% by weight. A step of preparing an aluminum pigment dispersion or an aluminum pigment dispersion simultaneously emulsified with a resin; and
The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 3, further comprising a step of adding the toner constituent material to the dispersion in several times.   An electrostatic image developer comprising: the electrostatic image developing toner according to claim 1; and a carrier. It is detachable from an image forming apparatus having at least developing means for developing an electrostatic charge image to form a toner image,
A toner cartridge containing the electrostatic image developing toner according to claim 1 as toner to be supplied to the developing unit. While containing the electrostatic image developing toner according to any one of claims 1 to 3,
A process cartridge comprising a toner holder for holding and transporting the toner for developing an electrostatic image. A latent image forming step for forming an electrostatic latent image on the surface of the image carrier;
A developing step of developing the electrostatic latent image formed on the surface of the image carrier with a developer containing the electrostatic charge image developing toner according to claim 1 to form a toner image;
A transfer step of transferring the toner image onto the surface of the transfer target; and
An image forming method comprising at least a fixing step of fixing the toner image transferred onto the surface of the transfer target. An image carrier,
An electrostatic latent image forming means for forming an electrostatic latent image on the surface of the image carrier;
Developing means for developing the electrostatic latent image with a developer containing the electrostatic image developing toner according to claim 1 to form a toner image;
Transfer means for transferring the toner image onto the surface of the transfer target;
An image forming apparatus comprising: a fixing unit configured to fix the toner image transferred to the surface of the transfer medium.

Images