JP2016139054A - 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 suppresses a reduction in photoluminescence and ensures a thermal storage property of a photoluminescent image when the image is fixed in a condition where deformation of toner particles is small.SOLUTION: A photoluminescent toner comprises: an amorphous resin; a plurality of flat photoluminescent pigments aligned in the same direction with each other; and a crystalline material that is interposed in a gap between at least one combination of the adjacent plurality of flat photoluminescent pigments from among the plurality of flat photoluminescent pigments.SELECTED DRAWING: Figure 1

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.

Conventionally, a toner containing a bright pigment such as a metal pigment is known for forming a bright image.
For example, Patent Document 1 states that “when a solid image is formed, the reflectance at a light receiving angle of + 30 ° measured when the image is irradiated with incident light having an incident angle of −45 ° by a goniophotometer. A toner having a ratio (A / B) of A to a reflectance B at a light receiving angle of −30 ° of 2 to 100 and containing polyalkylene as a release agent is disclosed.
Patent Document 2 states that “a binder resin having an acid value of less than 10 mg KOH / g and / or a precursor thereof (H) soluble in an organic solvent and an acid value hardly soluble in an organic solvent at the liquid temperature during the emulsification dispersion process. A toner composition solution dissolved or dispersed in the organic solvent containing at least 20 mg KOH / g or more and 50 mg KOH / g or less of a polyester polymer (L) and a metallic metallic pigment, in an aqueous medium in which resin fine particles are dispersed, An electrophotographic toner having host particles formed by at least emulsification or dispersion and convergence is disclosed.
Patent Document 3 states that “a toner for electrophotography containing at least a binder resin, a colorant, and a release agent, wherein the colorant is a metallic pigment. G ″) / storage elastic modulus (G ′) = tangent loss represented by tangent loss (tan δ) has a peak at 80 to 160 [° C.], and the peak value of tangent loss is 3 or more. A toner for electrophotographic development. Is disclosed.

JP 2012-032764 A JP 2013-057906 A JP2012-208142A

  An object of the present invention is to include an amorphous resin and a plurality of flat glitter pigments oriented in the same direction, in a state where the plurality of flat glitter pigments are in contact with each other and overlap each other. It is an object of the present invention to provide a glitter toner that suppresses a decrease in glitter of a glitter image and secures heat storage properties when fixed under conditions where the deformation of toner particles is small compared to the case where it exists.

  The above problem is solved by the following means. That is,

The invention according to claim 1
An amorphous resin, a plurality of flat glitter pigments oriented in the same direction, and at least one set of the plurality of flat glitters adjacent to each other among the plurality of flat glitter pigments A glittering toner having toner particles containing a crystalline substance interposed in a gap between the conductive pigments.

The invention according to claim 2
The glitter toner according to claim 1, wherein the crystalline substance is a hydrocarbon wax.

The invention according to claim 3
The glitter toner according to claim 2, wherein the amorphous resin is an amorphous polyester resin.

The invention according to claim 4
An electrostatic charge image developer comprising the glitter toner according to any one of claims 1 to 3.

The invention according to claim 5
Containing the glitter toner according to any one of claims 1 to 3,
A toner cartridge to be attached to and detached from the image forming apparatus.

The invention according to claim 6
A developing means for containing the electrostatic charge image developer according to claim 4 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 7 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;
Development means for containing the electrostatic charge image developer according to claim 4 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer;
Transfer means for transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
Fixing means for fixing the toner image transferred to the surface of the recording medium;
An image forming apparatus comprising:

The invention according to claim 8 provides:
A charging step for charging the surface of the image carrier;
An electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged image carrier;
A developing step of developing an electrostatic charge image formed on the surface of the image carrier as a toner image with the electrostatic charge image developer according to claim 4;
A transfer step of transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
A fixing step of fixing the toner image transferred to the surface of the recording medium;
An image forming method comprising:

According to the first aspect of the present invention, the amorphous resin and the plurality of flat glitter pigments oriented in the same direction are contacted with each other. Provided is a glitter toner that suppresses a decrease in glitter of a glitter image and secures heat storability when fixed under conditions where deformation of toner particles is small compared to the case where the toner particles exist in an overlapping state. .
According to the second aspect of the present invention, when the toner particles are fixed under the condition that the deformation of the toner particles is small as compared with the case where nothing is interposed in the gap between the plurality of flat-like glitter pigments, the glitter of the glitter image is obtained. A glossy toner that suppresses the deterioration of the property and secures the heat storage property is provided.
According to the invention of claim 3, when the amorphous resin is fixed under the condition that the deformation of the toner particles is small as compared with the case where the non-polyester resin is included, the reduction in the glitter of the glitter image is suppressed, and A glittering toner that ensures heat storage is provided.

  According to the invention according to claim 4, 5, 6, 7, or 8, the amorphous resin and a plurality of flat glitter pigments oriented in the same direction as each other, a plurality of flat When using a glitter toner that has toner particles that are in contact and overlapped with each other in the form of glitter pigment, the glitter of the glitter image is fixed when the toner particles are fixed under less deformation. There are provided an electrostatic charge image developer, a toner cartridge, a process cartridge, an image forming apparatus, and an image forming method in which the deterioration of the toner is suppressed and the heat storage property of the toner is ensured.

FIG. 3 is a cross-sectional view schematically illustrating an example of toner (toner particles) of the present embodiment. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to an exemplary embodiment. It is a schematic block diagram which shows an example of the process cartridge of this embodiment. FIG. 6 is a schematic diagram for explaining an estimation effect of toner according to the exemplary embodiment. It is a schematic diagram for explaining a conventional toner estimation action.

  Hereinafter, embodiments that are examples 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 this embodiment (hereinafter also referred to as “toner”) includes an amorphous resin and a plurality of flat glitter pigments (hereinafter simply referred to as “bright pigments”) oriented in the same direction. And a crystalline substance interposed in a gap between the plurality of flat glitter pigments adjacent to each other among the plurality of flat glitter pigments.

In the present specification, “crystallinity” refers to having a clear endothermic peak in differential scanning calorimetry (DSC), not a stepwise endothermic amount change. The half-value width of the endothermic peak when measured at 10 (° C./min) is within 10 ° C.
On the other hand, “amorphous” means that the half width exceeds 10 ° C., shows a step-like change in endothermic amount, or that no clear endothermic peak is observed.

  The toner according to the exemplary embodiment has the above-described configuration, and when the toner particles are fixed under a condition where deformation of the toner particles is small, a decrease in the glitter of the glitter image is suppressed and heat storage is ensured. The reason for this is not clear, but is presumed to be as follows.

  In recent years, with recent power savings and higher output speeds, for example, nip pressure (pressure applied to the recording medium by the fixing member when fixing), nip time (when fixing, the fixing member applies to the recording medium) There is a demand for fixing under a condition in which the pressure is applied) and the fixing temperature is reduced. For example, there is a demand for fixing at a low nip pressure, a low nip time, and a low fixing temperature by increasing the process speed and using an electromagnetic induction heating type fixing means. This fixing condition is characterized in that the amorphous resin as the binder resin in the toner particles is not sufficiently reduced in viscosity (melted) and is fixed in a state where the deformation of the toner particles is small.

  On the other hand, conventionally, in toner particles containing a plurality of glitter pigments, the plurality of glitter pigments are in contact with each other (see FIG. 5A).

  However, when the toner particles in this state are fixed under the condition that the deformation of the toner particles is small, as described above, the viscosity decrease (melting) of the amorphous resin as the binder resin in the toner particles is not sufficiently caused, and the fixing is performed. Since the pressure applied to the toner particles at that time is also low, it is difficult for the plurality of glitter pigments to be displaced from each other, and the overlap between the pigments may be difficult to eliminate (see FIG. 5B). Then, fixing is performed in a state close to that (see FIG. 5C). That is, the coverage of the glitter pigment on the recording medium may be low in the glitter image formed by fixing the plurality of glitter pigments while overlapping each other. For this reason, the glitter of the glitter image may be lowered.

  On the other hand, in the present embodiment, in the toner particles containing a plurality of bright pigments, among the plurality of flat bright pigments, the gaps between at least one pair of adjacent flat bright pigments. A crystalline substance is interposed (see FIG. 4A). Unlike the amorphous resin, the crystalline substance sufficiently reduces the viscosity (melts) of the crystalline substance even if the toner is fixed under the condition that the deformation of the toner particles is small. When the viscosity of the crystalline substance intervening in the gap between a plurality of flat glitter pigments is reduced, even if the pressure applied to the toner particles during fixing is low, the plurality of flat glitter pigments are misaligned. It becomes easier (see FIG. 4B). When the fixing is completed in this situation, a plurality of flat glitter pigments spread to increase the coverage of the glitter pigment on the recording medium in the glitter image formed (see FIG. 4C).

From the above, it is presumed that the toner according to the present embodiment suppresses the decrease in the glitter of the glitter image when it is fixed under the condition that the deformation of the toner particles is small.
Further, even if the glass transition temperature of the binder resin (amorphous resin) is lowered, when the fixing is performed under the condition that the deformation of the toner particles is small, the decrease in the glitter of the glitter image is suppressed. Storage stability deteriorates. On the other hand, in the toner according to the present exemplary embodiment, when the toner resin is fixed under the condition that deformation of the toner particles is small without lowering the glass transition temperature of the binder resin (amorphous resin), Is suppressed. For this reason, the fall of the glitter of a glitter image is suppressed after ensuring heat storage property.
That is, according to the present embodiment, both the glitter of the glitter image and the heat storage property of the toner can be achieved.

Here, the conditions under which the deformation of the toner particles is small include, for example, a nip pressure of 1.0 kg / cm ² or more and 2.0 kg / cm ² or less, a nip time of 40 milliseconds or less, and 130 ° C. or more and 170 ° C. or less. Examples include conditions that satisfy the fixing temperature. A typical example of the fixing unit that fixes the toner particles under a condition with little deformation is an electromagnetic induction heating type fixing unit.

  4 to 5, 2 represents toner particles, 4 represents a glitter pigment, 6 represents a crystalline substance, 8 represents a glitter image (fixed image), and P represents a recording medium. .

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

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

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

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

Next, a method for measuring the ratio (X / Y) will be described.
Incident light with an incident angle of −45 ° is incident on the image (glossy image) to be measured using a spectroscopic variable angle color difference meter GC5000L manufactured by Nippon Denshoku Industries Co., Ltd. as a variable angle photometer. Then, the reflectance X at the light receiving angle + 30 ° and the reflectance Y at the light receiving angle −30 ° are measured. Note that the reflectance X and the reflectance Y were measured at intervals of 20 nm for light having a wavelength in the range of 400 nm to 700 nm, and the average value of the reflectance at each wavelength was obtained. The ratio (X / Y) is calculated from these measurement results.
The ratio (X / Y) is a flop index value (FI value: Flop Index value) that is an index indicating the metallic luster measured according to ASTM E2194.

The toner according to the exemplary embodiment preferably satisfies the following requirements (1) to (2) from the viewpoint of satisfying the ratio (X / Y).
(1) The average equivalent circle diameter D is longer than the average maximum thickness C of the toner particles.
(2) When the cross section in the thickness direction of the toner particles is observed, the brightness in which the angle between the long axis direction of the toner particles and the long axis direction of the glitter pigment is in the range of −20 ° to + 20 °. The proportion of the luminescent pigment is 60% or more of the total bright pigment observed.

If the toner particles have a flat shape with a circle-equivalent diameter longer than the thickness (see FIG. 1), the flat surface of the toner particles is flat on the surface of the recording medium due to pressure during fixing in the image forming fixing process. It is thought that they are lined up to face each other.
Therefore, among the flat (scale-like) bright pigments contained in the toner particles, “the angle between the major axis direction in the cross section of the toner and the major axis direction of the bright pigment is shown in (2) above”. It is considered that the glitter pigments satisfying the requirement “in the range of −20 ° to + 20 °” are arranged so that the surface side having the maximum area faces the recording medium surface. When the image formed in this way is irradiated with light, the ratio of the glitter pigment that diffusely reflects the incident light is suppressed, so that the range of the ratio (X / Y) described above is achieved. It is done.

Hereinafter, details of the toner according to the exemplary embodiment will be described.
The toner according to this embodiment has toner particles. The toner may have an external additive that is externally added to the toner particles.

The toner particles will be described.
For example, as shown in FIG. 1, the toner particles include an amorphous resin as a binder resin, a plurality of glitter pigments, and at least one set of the plurality of flat glitter pigments. And a crystalline substance interposed in the gap between the flat glittering pigments. The toner particles may contain other additives. In FIG. 1, 2 represents toner particles, 4 represents a bright pigment, and 6 represents a crystalline substance.

-Binder resin-
An amorphous resin is applied as the binder resin.
Examples of the amorphous resin include known amorphous resins such as an amorphous polyester resin, an amorphous vinyl resin (for example, styrene / acrylic resin), an epoxy resin, a polycarbonate resin, and a polyurethane resin. Among these, amorphous polyester resins and amorphous vinyl resins (especially styrene / acrylic resins) are preferred, and amorphous polyester resins are more preferred from the viewpoint of toner fixing and charging properties.

  In particular, when a hydrocarbon wax is applied as the crystalline substance interposed in the gap between the glitter pigments, an amorphous polyester resin is preferable as the amorphous resin. Since the amorphous polyester resin has a hydrophilic ester bond in the molecular chain, the phase separation from the hydrophobic hydrocarbon wax is high. As a result, the releasability between the glitter pigments having the crystalline substance interposed therebetween is increased, and the glitter pigments are easily displaced from each other during fixing. For this reason, it becomes easy to suppress the fall of the glitter of a glitter image.

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

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

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

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

The weight average molecular weight (Mw) of the amorphous 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 amorphous polyester resin is preferably 2000 or more and 100,000 or less.
The molecular weight distribution Mw / Mn of the amorphous 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 amorphous polyester resin can be obtained by a known production method. Specifically, for example, the polymerization temperature is set to 180 ° C. or higher and 230 ° C. or lower, the pressure in the reaction system is reduced as necessary, and the reaction is performed while removing water and alcohol generated during the condensation.
In addition, when the monomer of the raw material is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point may be added and dissolved as a solubilizing agent. In this case, the polycondensation reaction is performed while distilling off the solubilizer. If a monomer with poor compatibility is present in the copolymerization reaction, the monomer with poor compatibility and the monomer and the acid or alcohol to be polycondensed are condensed in advance and then polymerized together with the main component. It is good to condense.

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

-Bright pigment-
The glitter pigment is contained in the toner particles in a plurality (two or more) per toner particle. The number of the glitter pigments is preferably 2 or more and 10 or less, more preferably 3 or more and 6 or less, from the viewpoint of suppressing the decrease in the glitter of the glitter image.

The number of glitter pigments is a value measured by the following method.
After embedding the toner particles with a bisphenol A liquid epoxy resin and a curing agent, a cutting sample is prepared. Next, the cutting sample is cut at −100 ° C. using a cutting machine using a diamond knife, for example, Ultracut UCT (manufactured by Leica), to prepare an observation sample. The observation sample is observed with a TEM at a magnification of about 5000 times.
Specifically, the cross section of the toner particles (cross section along the thickness direction of the toner particles) is observed, and the number of glitter pigments contained in one toner particle is counted. This operation is performed for 100 toner particles, and the average value is obtained as the number of glitter pigments contained in one toner particle.

The plurality of glitter pigments are oriented in the same direction in each toner particle. The phrase “the plurality of bright pigments are oriented in the same direction” means that the major axis directions of the plurality of bright pigments are oriented in the same direction.
Specifically, the angle θ between the orientation directions of the plurality of glitter pigments is preferably 20 ° or less, more preferably 15 ° or less, and still more preferably 10 ° or less. The angle θ represents an angle (acute angle) formed by an imaginary line along the major axis direction of each glittering pigment. Theoretically, the angle θ is preferably 0 ° or more.

The angle θ between the orientation directions of the plurality of glitter pigments is a value measured by the following method.
After embedding the toner particles with a bisphenol A liquid epoxy resin and a curing agent, a cutting sample is prepared. Next, the cutting sample is cut at −100 ° C. using a cutting machine using a diamond knife, for example, Ultracut UCT (manufactured by Leica), to prepare an observation sample. The observation sample is observed with a TEM at a magnification of about 5000 times. Specifically, the cross section of the toner particles (the cross section along the thickness direction of the toner particles) is observed, and among the orientation directions (major axis directions) of the plurality of bright pigments contained in one toner particle, the adjacent glitter Each angle formed by the pigments is determined. Further, this operation is performed for 100 toner particles, and the average value is obtained as the angle θ.

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

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

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

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

-Crystalline material-
The crystalline substance is present in the gap between at least one set of a plurality of flat-like bright pigments adjacent to each other. Specifically, the crystalline substance is interposed in the gap between the flat glittering pigments in a state of being separated from the amorphous resin and forming a domain (region). The crystalline substance may be present in the entire gap between the flat glittering pigments, or may be present in a part of the gap. The crystalline substance may be present in the gap between at least one set of adjacent bright pigments among the plurality of bright pigments, but is present in the gap between all adjacent bright pigments. It is good.
The crystalline substance may be present in a region other than the gap between the plurality of flat glitter pigments.

The confirmation of whether or not a crystalline substance is present in the gap between the glitter pigments is performed by the following method.
Specifically, the toner particles are embedded using a bisphenol A type liquid epoxy resin and a curing agent, and then a cutting sample is prepared. Next, it slices at -100 degreeC using the cutting machine using a diamond knife, for example, UltracutUCT (made by Leica). The sectioned sample is stained with a 0.5 wt% aqueous solution of ruthenium tetroxide to prepare an observation sample. The observation sample is observed with a TEM at a magnification of about 5000 times. In the cross section of the toner (cross section along the thickness direction of the toner particles), the crystalline substance domain is discriminated from the color contrast, and it is confirmed whether the crystalline substance is interposed in the gap between the glitter pigments.

  Examples of the crystalline substance include a release agent and a crystalline resin. Among these, as the crystalline substance, a release agent is preferable from the viewpoint of suppressing a decrease in the glitter of the glitter image. The crystalline resin may be contained in the toner particles together with the amorphous resin as a binder resin.

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.
Among these, as the release agent, hydrocarbon wax is preferable. Since the hydrocarbon wax has a low polarity, the releasability of the glitter pigments interspersed with the crystalline substance is increased, and the glitter pigments are easily displaced from each other at the time of fixing. For this reason, it becomes easy to suppress the fall of the glitter of a glitter image.

  The hydrocarbon wax is a wax having a skeleton composed of hydrocarbons. For example, a Fischer-Tropsch wax, a polyethylene wax (wax having a polyethylene skeleton), a polypropylene wax (wax having a polypropylene skeleton), and a paraffin wax. (Wax having a paraffin skeleton), microcrystalline wax and the like. Among these, Fischer-Tropsch wax is preferable as the hydrocarbon wax from the viewpoint of suppressing the decrease in the glitter of the glitter image.

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 from the DSC curve obtained by differential scanning calorimetry (DSC) according to the “melting peak temperature” described in JIS K-1987 “Method for measuring the transition temperature of plastics”.

  On the other hand, examples of the crystalline resin include known crystalline resins such as crystalline polyester resins and crystalline vinyl resins (for example, polyalkylene resins and long-chain alkyl (meth) acrylate resins). Among these, as the crystalline resin, a crystalline polyester resin is preferable from the viewpoint of suppression of reduction in glitter of a glitter image and low temperature fixability.

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

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

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

  Here, the polyhydric alcohol may have an aliphatic diol content of 80 mol% or more, and preferably 90 mol% or more.

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

  The weight average molecular weight (Mw) of the crystalline polyester resin is preferably 6,000 or more and 35,000 or less.

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

Here, the amount of the crystalline substance interposed in the gap between the adjacent flat glittering pigments enhances the releasability between the glittering pigments, and makes the glittering pigments easy to shift at the time of fixing. From the viewpoint of suppressing a decrease in the brightness of the image, it is preferable that the thickness be 0.3 μm ^{2 to} 3.0 μm ² (preferably 0.5 μm ^{2 to} 2.0 μm ² ).
The amount of the crystalline substance interposed in the gap between the adjacent flat glittering pigments is the amount of the crystalline substance existing in one gap, and is a value measured as follows. Specifically, the toner particles are embedded using a bisphenol A type liquid epoxy resin and a curing agent, and then a cutting sample is prepared. Next, it slices at -100 degreeC using the cutting machine using a diamond knife, for example, UltracutUCT (made by Leica). The sectioned sample is stained with a 0.5 wt% aqueous solution of ruthenium tetroxide to prepare an observation sample. The observation sample is observed with a TEM at a magnification of about 5000 times. In the cross section of the toner (cross section along the thickness direction of the toner particles), the crystalline substance domains are discriminated from the color contrast, and the area of the crystalline substance domains interposed in the gaps between the bright pigments is determined as the toner particles. Measurement was performed on 100 pieces, and the average value was defined as the amount of the crystalline substance.

  Of the crystalline substance, the content of the release agent contained in the entire toner particles is preferably 1% by mass or more and 20% by mass or less, and more preferably 5% by mass or more and 15% by mass or less with respect to the entire toner particles. preferable. Further, the content of the crystalline resin contained in the entire toner particles is preferably 2% by mass or more and 40% by mass or less, and preferably 2% by mass or more and 20% by mass or less, based on the entire binder resin. Is more preferable.

-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.

-Toner particle characteristics-
The toner particles may be toner particles having a single layer structure, or toner particles having a so-called core / shell structure composed of a core (core particle) and a coating layer (shell layer) covering the core. May be.
Here, the core / shell structure toner particles include, for example, a core portion including an amorphous resin, a bright pigment, and a crystalline substance, and a coating layer including an amorphous resin. It is good that it is comprised.

-Average maximum thickness C and average equivalent circle diameter D of toner particles
As shown in (1) above, the toner particles are preferably flat and have an average equivalent circle diameter D longer than their average maximum thickness C. The ratio (C / D) of the average maximum thickness C to the average equivalent circle diameter D is preferably in the range of 0.001 to 0.500, and more preferably in the range of 0.010 to 0.200. A range of 0.050 or more and 0.100 or less is particularly preferable.
When the ratio (C / D) is 0.001 or more, the strength of the toner is ensured, breakage due to stress during image formation is suppressed, charging is reduced due to exposure of the pigment, and fog is generated as a result. Is suppressed. On the other hand, when it is 0.500 or less, excellent glitter can be obtained.

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

The angle between the major axis direction of the cross section of the toner particles and the major axis direction of the glitter pigment particles As shown in the above (2), when the cross section in the thickness direction of the toner particles is observed, The ratio (number basis) of the glitter pigment particles in which the angle between the major axis direction and the major axis direction of the glitter pigment particles is in the range of −20 ° to + 20 ° is 60% of the total glitter pigment particles to be observed. The above is preferable. Furthermore, the ratio is more preferably 70% or more and 95% or more, and particularly preferably 80% or more and 90% or less.
When the ratio is 60% or more, excellent glitter can be obtained.

Here, a method for observing the cross section of the toner particles will be described.
After embedding the toner particles with a bisphenol A liquid epoxy resin and a curing agent, a cutting sample is prepared. Next, the cutting sample is cut at −100 ° C. using a cutting machine using a diamond knife, for example, Ultracut UCT (manufactured by Leica), to prepare an observation sample. The observation sample is observed with a TEM at a magnification of about 5000 times.
Specifically, the cross section of the toner particles (cross section along the thickness direction of the toner particles) is observed, and for the 100 toner particles observed, the long axis direction of the cross section of the toner particles and the long axis of the glitter pigment particles are observed. The number of glitter pigment particles having an angle with the direction in the range of −20 ° to + 20 ° is counted using image analysis software, and the ratio is calculated.

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

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

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

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

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

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

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

(Toner production method)
Next, a toner manufacturing method according to this embodiment will be described.
The toner according to the exemplary embodiment can be obtained, for example, by externally adding an external additive to the toner particles after the toner particles are manufactured.

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 / pulverizing method or a wet method such as an emulsion aggregation method or a dissolution suspension method.
However, in the toner particles, the emulsion aggregation method is used because a crystalline substance is interposed in the gap between at least one set of a plurality of flat glitter pigments adjacent to each other among the plurality of flat glitter pigments. preferable.

  The emulsion aggregation method includes an emulsification step of emulsifying raw materials constituting the toner particles to form resin particles and the like, an aggregation step of forming aggregates of the resin particles, and a fusion step of fusing the aggregates.

  The emulsion aggregation method includes an emulsification step of emulsifying the raw materials constituting the toner particles to form resin particles, an aggregation step of forming aggregates of the resin particles and the bright pigment, and a fusion step of fusing the aggregates. .

-Emulsification 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 emulsification step include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, sodium polyacrylate, and sodium polymethacrylate; sodium dodecylbenzenesulfonate, Anionic surfactants such as sodium octadecyl sulfate, sodium oleate, sodium laurate and potassium stearate; cationic surfactants such as laurylamine acetate, stearylamine acetate and lauryltrimethylammonium chloride; amphoteric such as lauryldimethylamine oxide Ionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene Surfactants such as nonionic surfactants such as 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 particles is desirable without loss of aggregation. .
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-
Examples of the aggregation step include the step shown in the following (A).
Step (A): 1) In a mixed dispersion of a crystalline substance particle dispersion and a glittering pigment dispersion, the mixed dispersion is heated to a temperature lower than the melting temperature of the crystalline substance to produce crystalline substance particles. A first agglomerate of the pigment and the luster pigment, and 2) in a mixed dispersion of the first agglomerate dispersion and the amorphous resin particle dispersion, the glass transition temperature of the amorphous resin particles being less than the glass transition temperature. Heating the mixed dispersion to a temperature to form a second aggregate that is aggregated such that amorphous resin particles adhere to the surface of the first aggregate.

  In the step (A), the glass transition temperature of the amorphous resin particles in the mixed dispersion of the first aggregate dispersion, the amorphous resin particle dispersion, and the crystalline substance particle dispersion is used. The mixed dispersion may be heated to a temperature lower than that to form a second aggregate that aggregates so that the amorphous resin particles and the crystalline substance particles adhere to the surface of the first aggregate.

  The step (A) is: 1) after forming the first aggregate, the first aggregate is heated to a temperature equal to or higher than the melting temperature of the crystalline substance particles to form fused particles, and 2) this fused particle dispersion. And the second resin particle dispersion liquid, the mixed dispersion liquid is heated to a temperature lower than the glass transition temperature of the amorphous resin particles, and the amorphous resin particles adhere to the surface of the fused particles. The step of forming the aggregated second aggregate may be used.

  In the step (A), after the second aggregated particles are formed, in the mixed liquid of the second aggregated particle dispersion and the amorphous resin particle dispersion, the temperature is lower than the glass transition temperature of the amorphous resin particles. The mixed dispersion may be heated to form a third aggregate that is aggregated so that amorphous resin particles further adhere to the surface of the second aggregate. In this case, the crystalline substance and the glitter pigment are difficult to be exposed on the surface of the toner particles, which is desirable from the viewpoint of chargeability and developability. When the second aggregated particle dispersion and the amorphous resin particle dispersion are mixed, an aggregating agent may be added to the second aggregated particle dispersion or the pH may be adjusted before mixing.

  In the step (A), for example, the orientation of the glitter pigment in the obtained toner particles is controlled by the stirring conditions of the mixed dispersion when forming the first aggregated particles. Further, for example, by adjusting the concentration of the bright pigment in the mixed dispersion, the number of bright pigments in the obtained toner particles is controlled. Further, for example, by adjusting the concentration of the crystalline substance in the mixed dispersion, the amount of the crystalline substance interposed in the gap between the glitter pigments is controlled.

Here, in the aggregation step, the formation of each aggregated particle is often performed by acidifying the pH of the mixed solution with stirring. It becomes possible to make ratio (C / D) into a preferable range with stirring conditions. More specifically, the ratio (C / D) can be reduced by heating at a high speed and heating at the stage of forming the agglomerated particles (particularly the second agglomerated particles), and the stirring can be performed at a lower speed and more The ratio (C / D) can be increased by heating at a low temperature. 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, it is preferable to add in a plurality of times together with various dispersions such as a resin particle dispersion because the uneven distribution of each component in the toner can be reduced. This is because agglomerated particles generally have a different charge order in the dispersion, and thus the order of formation of the agglomerated particles is generally different.

  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.
In this embodiment, it is desirable to use a polymer of a tetravalent inorganic metal salt containing aluminum in order to obtain a narrow particle size distribution.

-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 particles. The aggregated particles are fused by heating at a temperature.
The heating time may be as long as fusion is performed, and may be performed for about 0.5 hours 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, if necessary, a washing process and a drying process.

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

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

There is no restriction | limiting in particular as a carrier, A well-known carrier is mentioned. 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 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 copolymer. Examples thereof include a polymer, a straight silicone resin containing an organosiloxane bond or a modified product thereof, a fluororesin, a polyester, a polycarbonate, a phenol resin, and an epoxy resin.
The coating resin and 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>
The image forming apparatus / image forming method according to the present embodiment will be described.
The image forming apparatus according to the present embodiment includes an image carrier, a charging unit that charges the surface of the image carrier, an electrostatic image forming unit that forms an electrostatic image on the surface of the charged image carrier, and an electrostatic charge. Development means for containing an image developer and developing the electrostatic image formed on the surface of the image carrier as a toner image with the electrostatic image developer, and the toner image formed on the surface of the image carrier as a recording medium Transfer means for transferring to the surface of the recording medium, and fixing means for fixing the toner image transferred to the surface of the recording medium. The electrostatic charge image developer according to this embodiment is applied as the electrostatic charge image developer.

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

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

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

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

FIG. 2 is a schematic configuration diagram illustrating an example of an image forming apparatus according to this embodiment including a developing device to which the electrostatic charge image developer according to this embodiment is applied.
In FIG. 1, the image forming apparatus according to the present embodiment includes a photoconductor 20 as an image holding body that rotates in a predetermined direction, and around the photoconductor 20, there is a photoconductor 20 (an image holding body). A charging device 21 (an example of a charging unit), and an exposure device 22 (an example of an electrostatic image forming unit) as an electrostatic image forming device that forms an electrostatic image Z on the photoconductor 20. The developing device 30 (an example of a developing unit) that visualizes the electrostatic charge image Z formed on the photoconductor 20 and the toner image that is visualized on the photoconductor 20 are examples of a recording medium. A transfer device 24 (an example of a transfer unit) that transfers to the recording paper 28 and a cleaning device 25 (an example of a cleaning unit) that cleans residual toner on the photoreceptor 20 are sequentially disposed.

In the present embodiment, as shown in FIG. 2, the developing device 30 has a developing container 31 in which a developer G containing toner 40 is accommodated, and the developing container 31 faces the photoconductor 20 for development. In addition to opening the opening 32, a developing roll (developing electrode) 33 serving as a toner holding member is disposed facing the developing opening 32, and a developing bias determined by the developing roll 33 is applied, thereby exposing the photosensitive member. A developing electric field is formed in a region (developing region) sandwiched between the body 20 and the developing roll 33. Further, a charge injection roll (injection electrode) 34 as a charge injection member is provided in the developing container 31 so as to face the developing roll 33. In particular, in the present 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. Further, it is desirable that the rotation is performed with a peripheral speed difference (for example, 1.5 times or more), the toner 40 is sandwiched between the regions sandwiched between the charge injection roll 34 and the developing roll 33, and the charges are 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 photoconductor 20 is charged by the charging device 21, and the exposure device 22 writes the electrostatic charge image Z on the charged photoconductor 20, and the developing device 30 writes the electrostatic charge image. Z is visualized as a toner image. Thereafter, the toner image on the photoconductor 20 is conveyed to a transfer site, and the transfer device 24 electrostatically transfers the toner image on the photoconductor 20 to a recording paper 28 as a recording medium. The residual toner on the photoconductor 20 is cleaned by the cleaning device 25. Thereafter, the toner image on the recording paper 28 is fixed by a fixing device 36 (an example of a fixing unit), and an image is obtained.

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

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

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

FIG. 3 is a schematic configuration diagram showing a process cartridge according to the present embodiment.
The process cartridge 200 shown in FIG. 3 is provided around the 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. 2, 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).

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

  The image forming apparatus shown in FIG. 2 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 embodiment explains this embodiment in detail, this embodiment is not limited to these examples at all. In the following description, “part” and “%” are all based on mass unless otherwise specified.

<Preparation of amorphous resin particle dispersion (1)>
(Preparation of amorphous resin particle dispersion (1))
Dimethyl adipate: 30 parts Dimethyl terephthalate: 221 parts Bisphenol A ethylene oxide adduct: 85 parts Bisphenol A propylene oxide adduct: 106 parts Ethylene glycol: 41 parts Tetrabutoxy titanate (catalyst): 0. 042 copies,
The above components are placed in a heat-dried two-necked flask, and nitrogen gas is introduced into the container and heated while stirring in an inert atmosphere, and then subjected to a copolycondensation reaction at 160 ° C. for 7 hours, and then gradually up to 10 Torr. The temperature was raised to 220 ° C. while reducing the pressure to 3 hours. The pressure was returned to normal pressure, 21 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 amorphous polyester resin (1).
The glass transition temperature (Tg) of the amorphous polyester resin (1) is from room temperature (25 ° C.) to 150 ° C. using a differential scanning calorimeter (manufactured by Shimadzu Corporation: DSC-50) in accordance with ASTM D3418-8. It calculated | required by measuring on conditions with a temperature increase rate of 10 degree-C / min. 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 amorphous polyester resin (1) had a glass transition temperature of 59.8 ° C., a GPC mass average molecular weight Mw of 52,000, and a number average molecular weight Mn of 6,500.

-Amorphous polyester resin (1): 200 parts-Ethyl acetate: 340 parts-Sodium hydroxide aqueous solution (0.3M): 5.5 parts The above ingredients were placed in a 2000 ml separable flask and heated at 70 ° C. A resin mixture was prepared by stirring with a three-one motor (manufactured by Shinto Kagaku Co., Ltd.). While further stirring this resin mixture at 90 rpm, 550 parts of ion-exchanged water is gradually added, phase-inversion emulsified, and the solvent is removed to remove amorphous resin particle dispersion (1) (solid content concentration: 25%). Got. The volume average particle diameter of the resin particles in the amorphous resin particle dispersion (1) was 182 nm.

<Preparation of amorphous resin particle dispersion (2)>
・ Styrene 320 parts ・ N-butyl acrylate 120 parts ・ Acrylic acid 3 parts ・ Dodecanethiol 8 parts ・ Anionic surfactant (Dow Fax, Dow Fax) 12 parts
・ Ion exchange water 950 parts
Among the above components, styrene, n-butyl acrylate, acrylic acid, and dodecanethiol are mixed to prepare a solution, and this solution is dispersed and emulsified in a flask containing the anionic surfactant and ion-exchanged water (simple Multimer emulsion 1). 2 parts of an anionic surfactant was dissolved in 350 parts of ion exchange water and charged into a polymerization flask. The polymerization flask was sealed, a reflux tube was installed, and the inside of the polymerization flask was stirred while purging with nitrogen, and the polymerization flask was heated to 75 ° C. with a water bath and held for 45 minutes. A solution obtained by dissolving 7 parts of ammonium persulfate in 60 parts of ion-exchanged water is dropped into a polymerization flask over 12 minutes using a tube pump, and then the monomer emulsion 1 is dropped over 60 minutes using a tube pump. did. Thereafter, the polymerization flask was stirred for 4 hours while maintaining at 85 ° C., and the polymerization flask was cooled to 30 ° C. with ice water to complete the polymerization. As a result, an amorphous resin particle dispersion (2) (solid content concentration: 34%) was obtained. The mass average molecular weight Mw by GPC was 31,000, the number average molecular weight Mn was 4,200, and the volume average particle diameter of the resin particles in the amorphous resin particle dispersion (2) was 205 nm.

<Preparation of amorphous resin particle dispersion (3)>
Dimethyl adipate: 15 parts Dimethyl terephthalate: 251 parts Bisphenol A ethylene oxide adduct: 62 parts Bisphenol A propylene oxide adduct: 126 parts Ethylene glycol: 38 parts Tetrabutoxy titanate (catalyst): 0. 040 parts,
The above components are placed in a heat-dried two-necked flask, and nitrogen gas is introduced into the container and heated while stirring in an inert atmosphere, and then subjected to a copolycondensation reaction at 160 ° C. for 7 hours, and then gradually up to 10 Torr. The temperature was raised to 220 ° C. while reducing the pressure to 3 hours. The pressure was returned to normal pressure, 31 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 amorphous polyester resin (2).
The glass transition temperature (Tg) of the amorphous polyester resin (2) is from room temperature (25 ° C.) to 150 ° C. using a differential scanning calorimeter (manufactured by Shimadzu Corporation: DSC-50) in accordance with ASTM D3418-8. It calculated | required by measuring on conditions with a temperature increase rate of 10 degree-C / min. 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 amorphous polyester resin (2) had a glass transition temperature of 53.4 ° C., a mass average molecular weight Mw by GPC of 42,000, and a number average molecular weight Mn of 7,600.

Amorphous polyester resin (2): 200 parts Ethyl acetate: 340 parts Sodium hydroxide aqueous solution (0.3M): 5.5 parts The above ingredients were placed in a 2000 ml separable flask and heated at 70 ° C, A resin mixture was prepared by stirring with a three-one motor (manufactured by Shinto Kagaku Co., Ltd.). While further stirring this resin mixture at 90 rpm, 550 parts of ion-exchanged water was gradually added, phase-inversion emulsification, and solvent removal were performed to remove amorphous resin particle dispersion (3) (solid content concentration: 28%) Got. The volume average particle diameter of the resin particles in the resin particle dispersion (3) was 175 nm.

<Preparation of glitter pigment dispersion>
(Preparation of glitter pigment dispersion (1))
Aluminum pigment (Showa Aluminum Powder Co., Ltd., 2173EA): 100 parts Anionic surfactant (Taika BN2060): 1.5 parts Ion-exchanged water: 900 parts After removing the solvent from the aluminum pigment paste The above-mentioned mixture, dissolution, and dispersion for about 1 hour using an emulsifier-dispersing machine Cavitron (manufactured by Taiheiyo Kiko Co., Ltd., CR1010), and a glittering pigment dispersion in which a glittering pigment (aluminum pigment) is dispersed ( Solid content concentration: 10%) was prepared.

<Preparation of crystalline substance particle dispersion>
(Preparation of release agent dispersion)
-Preparation of release agent dispersion (1)-
・ Hydrocarbon wax (Nihon Seiki Co., Ltd. FNP0080, melting temperature = 80 ° C.): 270 parts ・ Anionic surfactant (Tainer Corporation BN2060): 12 parts ・ Ion-exchanged water: 21.6 parts And after the release agent was dissolved at an internal liquid temperature of 120 ° C. with a pressure discharge type homogenizer (Gorin homogenizer), the dispersion pressure was 5 MPa for 120 minutes, followed by dispersion at 40 MPa for 360 minutes. Upon cooling, a release agent dispersion (1) was obtained. The volume average particle diameter D50 of the release agent in this release agent dispersion was 225 nm. Thereafter, ion exchange water was added to adjust the solid content concentration to 20.0%.

-Preparation of release agent dispersion (2)-
Ester wax (Nippon Yushi Co., Ltd. WEP-8, melting temperature = 79 ° C.): 270 parts Anionic surfactant (Taika BN2060): 12 parts Ion exchange water: 21.6 parts And after the release agent was dissolved at an internal liquid temperature of 120 ° C. with a pressure discharge type homogenizer (Gorin homogenizer), the dispersion pressure was 5 MPa for 120 minutes, followed by dispersion at 40 MPa for 360 minutes. Upon cooling, a release agent dispersion (2) was obtained. The volume average particle diameter D50 of the release agent in this release agent dispersion was 231 nm. Thereafter, ion exchange water was added to adjust the solid content concentration to 20.0%.

(Preparation of crystalline resin particle dispersion)
-Preparation of crystalline resin particle dispersion (1)-
-Sebacic acid: 102 parts-1,9-nonanediol: 85 parts Lu The above monomer components are placed in a reaction vessel equipped with a stirrer, thermometer, condenser and nitrogen gas introduction tube, and the inside of the reaction vessel is replaced with dry nitrogen gas. After that, 0.47 parts of titanium tetrabutoxide (reagent) was added. After stirring and reacting at 170 ° C. for 3 hours under a nitrogen gas stream, the temperature was further raised to 210 ° C. over 1 hour, the pressure inside the reaction vessel was reduced to 3 kPa, and the stirring reaction was performed for 13 hours under reduced pressure to produce crystals. -Soluble polyester resin (1) was obtained.
The obtained crystalline polyester resin (1) had a melting temperature by DSC of 71.2 ° C., a mass average molecular weight Mw by GPC of 25,000, and a number average molecular weight Mn of 10,500.

-Crystalline polyester resin (1): 200 parts-Ethyl acetate: 520 parts-Sodium hydroxide aqueous solution (0.3M): 3.2 parts The above ingredients were placed in a 2000 ml separable flask and heated at 75 ° C, and three-one A resin mixed solution was prepared by stirring with a motor (manufactured by Shinto Kagaku Co., Ltd.). While further stirring this resin mixture at 90 rpm, 450 parts of ion-exchanged water is gradually added, phase-inversion emulsification, and solvent removal are performed to obtain a crystalline resin particle dispersion (1) (solid content concentration: 28%). Obtained. The volume average particle diameter of the resin particles in the crystalline resin particle dispersion (1) was 175 nm.

<Example 1>
-Release agent dispersion (1): 80 parts-Bright pigment dispersion (1): 380 parts-Anionic surfactant (BN2060 manufactured by Teica): 3 parts The above raw materials are placed in a 3 L cylindrical stainless steel container, The mixture was dispersed and mixed for 10 minutes by applying a shearing force at 4000 rpm with a homogenizer (manufactured by IKA, Ultra Turrax T50). Next, 15 parts of a 10% nitric acid aqueous solution of polyaluminum chloride as a flocculant was gradually dropped, and the homogenizer was rotated at 5000 rpm for 15 minutes and mixed to obtain a raw material dispersion.
Thereafter, the raw material dispersion was transferred to a container equipped with a stirrer using two paddle stirring blades and a thermometer, the stirring rotation speed was set to 350 rpm, and heating with a mantle heater was started, and the mixture was left at 54 ° C. At this time, the pH of the raw material dispersion was controlled in the range of 2.2 to 3.5 with 0.3 M nitric acid or 1 M sodium hydroxide aqueous solution. The first agglomerated particles were formed under the above conditions for about 2 hours.
Next, 584 parts of amorphous resin particle dispersion (1) was additionally added to form second aggregated particles. The temperature was further raised to 56 ° C., and the second aggregated particles were arranged while confirming the size and form of the particles. Then, after raising pH to 8.0, it heated up to 87 degreeC. After confirming that the aggregated particles were fused with an optical microscope, the pH was lowered to 6.0 while maintaining at 87 ° C., and the heating was stopped after 1 hour, followed by cooling at a temperature lowering rate of 1.0 ° C./min. Thereafter, it was sieved with a 40 μm mesh, washed repeatedly with water, and then dried with a vacuum dryer to obtain toner particles. The obtained toner particles had a volume average particle diameter of 11.0 μm. In addition, it was confirmed that the toner particles are flat and have an average equivalent circle diameter D longer than the average maximum thickness C thereof.

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

(Creation of carrier)
Ferrite particles (volume average particle diameter: 35 μm): 100 parts Toluene: 14 parts Methyl methacrylate-perfluorooctylethyl acrylate copolymer (critical surface tension: 24 dyn / cm): 1.6 parts Carbon black (Product name: VXC-72, manufactured by Cabot Corporation, volume resistivity: 100 Ωcm or less): 0.12 parts / crosslinked melamine resin particles (average particle size: 0.3 μm, toluene insoluble): 0.3 parts To the polymer, carbon black was diluted with toluene and added with a sand mill. Next, each of the above components other than the ferrite particles was dispersed for 10 minutes with a stirrer to prepare a coating layer forming solution. Next, this coating layer forming solution and ferrite particles are put in a vacuum degassing type kneader and stirred at a temperature of 60 ° C. for 30 minutes, and then the pressure is reduced to distill off toluene to form a resin coating layer to obtain a carrier. It was.

(Development of developer)
36 parts of the toner and 414 parts of the carrier were put in a 2 liter V blender, stirred for 20 minutes, and then sieved at 212 μm to prepare a developer.

<Example 2>
Toner particles (2) were produced as follows. A developer was prepared in the same manner as in Example 1 except that the toner particles (2) were used.

(Preparation of toner particles (2))
The same operation was carried out except that the amount of the glitter pigment dispersion (1) was changed to 260 parts and the amount of the amorphous resin particle dispersion (1) was changed to 632 parts in the production of the toner particles (1). As a result, toner particles were obtained. The resulting toner particles had a volume average particle size of 10.6 μm. In addition, it was confirmed that the toner particles are flat and have an average equivalent circle diameter D longer than the average maximum thickness C thereof.

<Example 3>
Toner particles (3) were produced as follows. A developer was prepared in the same manner as in Example 1 except that the toner particles (3) were used.

(Production of toner particles (3))
In the production of the toner particles (1), the same operation was performed except that the amount of the glitter pigment dispersion (1) was changed to 520 parts and the amount of the amorphous resin particle dispersion (1) was changed to 528 parts. And toner particles were obtained. The obtained toner particles had a volume average particle diameter of 10.8 μm. In addition, it was confirmed that the toner particles are flat and have an average equivalent circle diameter D longer than the average maximum thickness C thereof.

<Example 4>
Toner particles (4) were produced as follows. A developer was prepared in the same manner as in Example 1 except that this toner particle (4) was used.

(Production of toner particles (4))
In the production of the toner particles (1), the amount of the glitter pigment dispersion (1) is changed to 340 parts, and the release agent dispersion (2) is replaced with amorphous resin particles instead of the release agent dispersion (1). A toner particle was obtained in the same manner as described above except that the amount of the dispersion (1) was changed to 600 parts. The obtained toner particles had a volume average particle diameter of 10.9 μm. In addition, it was confirmed that the toner particles are flat and have an average equivalent circle diameter D longer than the average maximum thickness C thereof.

<Example 5>
Toner particles (5) were produced as follows. A developer was prepared in the same manner as in Example 1 except that the toner particles (5) were used.

(Production of toner particles (5))
In the production of the toner particles (1), the amount of the glitter pigment dispersion (1) is 360 parts, and the amorphous resin particle dispersion (1) is replaced with 435 parts of the amorphous resin particle dispersion (2). A toner particle was obtained by carrying out the same operation except that it was changed to. The obtained toner particles had a volume average particle diameter of 11.0 μm. In addition, it was confirmed that the toner particles are flat and have an average equivalent circle diameter D longer than the average maximum thickness C thereof.

<Example 6>
Toner particles (6) were produced as follows. Then, a developer was prepared in the same manner as in Example 1 except that this toner particle (6) was used.

(Production of toner particles (6))
Toner particles (6) were obtained in the same manner as toner particles (1) except that the following composition was used to form the first aggregated particles.
-Release agent dispersion (1): 80 parts-Bright pigment dispersion (1): 380 parts-Crystalline resin dispersion (1): 50 parts-Anionic surfactant BN2060): 3 parts The obtained toner particles had a volume average particle diameter of 11.1 μm. In addition, it was confirmed that the toner particles are flat and have an average equivalent circle diameter D longer than the average maximum thickness C thereof.

<Example 7>
Toner particles (7) were produced as follows. A developer was prepared in the same manner as in Example 1 except that this toner particle (7) was used.

(Production of toner particles (7))
In the production of the toner particles (6), the amount of the glitter pigment dispersion (1) is 360 parts, the amount of the release agent dispersion (1) is 90 parts, and the amount of the crystalline resin dispersion (1) is 35. The same operation was carried out except that the amount of the amorphous resin particle dispersion (1) was changed to 7 parts and 544 parts to obtain toner particles. The obtained toner particles had a volume average particle diameter of 10.7 μm. In addition, it was confirmed that the toner particles are flat and have an average equivalent circle diameter D longer than the average maximum thickness C thereof.

<Example 8>
Toner particles (8) were produced as follows. A developer was prepared in the same manner as in Example 1 except that the toner particles (8) were used.

(Production of toner particles (8))
In the production of the toner particles (6), the amount of the glitter pigment dispersion (1) is 300 parts, the amount of the release agent dispersion (1) is 40 parts, and the amount of the crystalline resin dispersion (1) is 7. The same operation was carried out except that the amount of the amorphous resin particle dispersion (1) was changed to 1 part and 640 parts, and toner particles were obtained. The obtained toner particles had a volume average particle diameter of 10.9 μm. In addition, it was confirmed that the toner particles are flat and have an average equivalent circle diameter D longer than the average maximum thickness C thereof.

<Comparative Example 1>
Comparative toner particles (C1) were produced as follows. A developer was prepared in the same manner as in Example 1 except that this comparative toner particle (C1) was used.

(Production of comparative toner particles (C1))
-Amorphous resin particle dispersion (1): 175 parts-Bright pigment dispersion (1): 380 parts-Anionic surfactant (BN2060 manufactured by Teika): 3 parts The above raw materials are put into a 3 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 Tarrax T50). Next, 15 parts of a 10% nitric acid aqueous solution of polyaluminum chloride as a flocculant was gradually dropped, and the homogenizer was rotated at 5000 rpm for 15 minutes and mixed to obtain a raw material dispersion.
Thereafter, the raw material dispersion was transferred to a container equipped with a stirring device using two paddle stirring blades and a thermometer, heated with a mantle heater at a stirring speed of 350 rpm, and left at 54 ° C. The pH of the raw material dispersion was controlled in the range of 2.2 to 3.5. Holding for about 2 hours under the above conditions, aggregated particles were formed.
Next, 200 parts of the amorphous resin particle dispersion (1) and 80 parts of the release agent dispersion (1) are added, and after standing for 10 minutes, 209 parts of the amorphous resin particle dispersion (1) is further added. 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. Thereafter, the pH was raised to 8.0 in order to fuse the aggregated particles, and then the temperature was raised to 87 ° C. After confirming that the aggregated particles were fused with an optical microscope, the pH was lowered to 6.0 while maintaining at 87 ° C., and the heating was stopped after 1 hour, followed by cooling at a temperature lowering rate of 1.0 ° C./min. Thereafter, it was sieved with a 40 μm mesh, washed repeatedly with water, and then dried with a vacuum dryer to obtain toner particles. The obtained toner particles had a volume average particle diameter of 11.1 μm. In addition, it was confirmed that the toner particles are flat and have an average equivalent circle diameter D longer than the average maximum thickness C thereof.

<Comparative example 2>
Comparative toner particles (C2) were produced as follows. A developer was prepared in the same manner as in Example 1 except that this comparative toner particle (C2) was used.

(Preparation of comparative toner particles (C2))
-Glitter pigment dispersion (1): 340 parts-Anionic surfactant (BN2060, manufactured by Teika): 3 parts The above raw materials are placed in a 3 L cylindrical stainless steel container, and homogenizer (IKA, Ultra Turrax T50) is used. The mixture was dispersed and mixed for 10 minutes while applying a shearing force at 4000 rpm. Next, 15 parts of a 10% nitric acid aqueous solution of polyaluminum chloride as a flocculant was gradually dropped, and the homogenizer was rotated at 5000 rpm for 15 minutes and mixed to obtain a raw material dispersion.
Thereafter, the raw material dispersion was transferred to a vessel equipped with a stirrer using two paddle stirring blades and a thermometer, the stirring rotation speed was set to 350 rpm, and heating with a mantle heater was started, and the mixture was left at 45 ° C. The pH was controlled in the range of 2.2 to 3.5. This state was maintained for about 2 hours.
Next, a mixture of 600 parts of the amorphous resin particle dispersion (1) and 80 parts of the release agent dispersion (1) was additionally added. The temperature was further raised to 56 ° C. Thereafter, the pH was raised to 8.0, and then the temperature was raised to 87 ° C. After confirming that the aggregated particles were fused with an optical microscope, the pH was lowered to 6.0 while maintaining at 87 ° C., and the heating was stopped after 1 hour, followed by cooling at a temperature lowering rate of 1.0 ° C./min. Thereafter, it was sieved with a 40 μm mesh, washed repeatedly with water, and then dried with a vacuum dryer to obtain toner particles. The obtained toner particles had a volume average particle diameter of 10.7 μm. In addition, it was confirmed that the toner particles are flat and have an average equivalent circle diameter D longer than the average maximum thickness C thereof.
<Comparative Example 3>
Comparative toner particles (C3) were produced as follows. A developer was prepared in the same manner as in Example 1 except that this comparative toner particle (C3) was used.

(Preparation of comparative toner particles (C3))
-Bright pigment dispersion (1): 360 parts-Anionic surfactant (BN2060, manufactured by Teika): 3 parts The above raw materials are placed in a 3 L cylindrical stainless steel container, and homogenizer (IKA, Ultra Turrax T50) is used. The mixture was dispersed and mixed for 10 minutes while applying a shearing force at 4000 rpm. Next, 15 parts of a 10% nitric acid aqueous solution of polyaluminum chloride as a flocculant was gradually dropped, and the homogenizer was rotated at 5000 rpm for 15 minutes and mixed to obtain a raw material dispersion.
Thereafter, the raw material dispersion was transferred to a vessel equipped with a stirrer using two paddle stirring blades and a thermometer, the stirring rotation speed was set to 350 rpm, and heating with a mantle heater was started, and the mixture was left at 45 ° C. The pH of the raw material dispersion was controlled in the range of 2.2 to 3.5. The above conditions were maintained for about 2 hours.
Next, a mixture of 529 parts of the amorphous resin particle dispersion (3) and 80 parts of the release agent dispersion (1) was additionally added. The temperature was further raised to 52 ° C., and aggregated particles were arranged while confirming the size and form of the particles. Thereafter, the pH was raised to 8.0, and then the temperature was raised to 83 ° C. After confirming that the aggregated particles were fused with an optical microscope, the pH was lowered to 6.0 while maintaining at 83 ° C., and the heating was stopped after 1 hour, followed by cooling at a temperature lowering rate of 1.0 ° C./min. Thereafter, it was sieved with a 40 μm mesh, washed repeatedly with water, and then dried with a vacuum dryer to obtain toner particles. The obtained toner particles had a volume average particle diameter of 10.9 μm. In addition, it was confirmed that the toner particles are flat and have an average equivalent circle diameter D longer than the average maximum thickness C thereof.

<Evaluation test>
(Various measurements)
For the toner (toner particles) prepared in each example, the number θ of the bright pigments and the angle θ between the orientation directions of the bright pigments were measured according to the method described above.
In addition, with respect to the toner (toner particles) produced in each example, whether a crystalline substance is present in the gap between at least one pair of adjacent bright pigments among the plurality of bright pigments is described according to the method described above. confirmed. And the amount of crystalline substance intervening in the gap between adjacent flat glittering pigments (indicated as “intervening amount” in the table)

(Formation of solid images)
A solid image was formed by the following method.
The developer obtained in each example was manufactured by Fuji Xerox Co., Ltd. “Apeos Port IV C3370 (equipped with an electromagnetic induction heating type fixing device, fixing device nip pressure 1.6 kg / cm ² , nip time 35 seconds, fixing temperature 150 Device) set to “° C.”), and a solid image with a toner loading of 3.5 g / m ² is formed on a white recording medium (OK topcoat + paper, manufactured by Oji Paper Co., Ltd.). Form. The “solid image” refers to an image with a printing rate of 100%.

(Measurement of luster: ratio (X / Y) [FI value])
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 (X / Y) [FI value] was calculated from these measurement results. The results are shown in Table 1. The higher the FI value, the higher the glitter feeling. If the FI value is 6 or more, the majority of observers can feel a metallic feeling. When the FI value is less than 6, the dull feeling is strong and it is difficult to feel the glitter.

(Heat storage)
The thermal storability of the developer obtained in each example was evaluated as follows.
The toner obtained in each example was allowed to stand for about 24 hours in an environment of 50 ° C./50% RH, and then a toner powder tester (Hosokawa Micron Corporation) in which sieves having openings of 53 μm, 45 μm, and 38 μm were arranged in series from the top. Made on a 53 μm sieve, and vibrated for 90 seconds with an amplitude of 1 mm. The toner weight on each sieve after vibration was measured, and 0.5, 0.3, and 0.1 from the top were measured. A value obtained by adding the weights and dividing by the sample amount before the measurement was expressed as a percentage.
The results are shown in Table 1. If the value expressed as a percentage is 35% or less, the heat storage property can be used without any problem in practice. Therefore, “A ○” means 35% or less, and “Bx” means 35% or more. displayed.

From the above results, it can be seen that the present example obtained better results with respect to the evaluation of the glittering property than the comparative example.
Moreover, in the present Example, it turns out that the favorable result was obtained also about evaluation of heat storage property.

2 Toner particles 4 Bright pigments 20 and 107 Photosensitive member (an example of an image carrier)
21 Charging device (an example of charging means)
22, 109 Exposure apparatus (an example of electrostatic charge image forming means)
24, 112 Transfer device (an example of transfer means)
25 Cleaning device (an example of cleaning means)
28, 300 Recording paper (recording medium)
30, 111 developing device (an example of developing means)
31 Developing container 32 Developing opening 33 Developing roll 34 Charge injection roll 36, 115 Fixing device (an example of fixing means)
40 Toner 108 Charging roll (an example of charging means)
113 photoconductor cleaning device (an example of cleaning means)
116 Mounting rail 117 Housing 118 Opening 200 for exposure Process cartridge

Claims (8)

  An amorphous resin, a plurality of flat glitter pigments oriented in the same direction, and at least one set of the plurality of flat glitters adjacent to each other among the plurality of flat glitter pigments A glittering toner having toner particles containing a crystalline substance interposed in a gap between the conductive pigments.   The glitter toner according to claim 1, wherein the crystalline substance is a hydrocarbon wax.   The glitter toner according to claim 2, wherein the amorphous resin is an amorphous polyester resin.   An electrostatic charge image developer comprising the glitter toner according to any one of claims 1 to 3. Containing the glitter toner according to any one of claims 1 to 3,
A toner cartridge to be attached to and detached from the image forming apparatus. A developing means for containing the electrostatic charge image developer according to claim 4 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;
Development means for containing the electrostatic charge image developer according to claim 4 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer;
Transfer means for transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
Fixing means for fixing the toner image transferred to the surface of the recording medium;
An image forming apparatus comprising: A charging step for charging the surface of the image carrier;
An electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged image carrier;
A developing step of developing an electrostatic charge image formed on the surface of the image carrier as a toner image with the electrostatic charge image developer according to claim 4;
A transfer step of transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
A fixing step of fixing the toner image transferred to the surface of the recording medium;
An image forming method comprising: