JP6825276B2 - Toner set, electrostatic charge image developer set, toner cartridge set, process cartridge, image forming apparatus, and image forming method - Google Patents

Description

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

A brilliant toner is used for the purpose of forming an image having a brilliance such as metallic luster.

Here, when a solid image is formed, the reflectance A and the light receiving angle −30 at the light receiving angle + 30 ° measured when the image is irradiated with the incident light having an incident angle −45 ° by a variable angle photometer. A toner having a reflectance (A / B) of 2 or more and 100 or less at ° is disclosed (see, for example, Patent Document 1).
Further, it has a brilliant toner containing a brilliant pigment and a colored toner containing a colorant, and the heat absorption amount of the brilliant toner is 1.2 times or more and 5 times or less of the heat absorption amount of the colored toner. Toner sets are disclosed (see, for example, Patent Document 2).

Japanese Unexamined Patent Publication No. 2012-032765 Japanese Unexamined Patent Publication No. 2016-126199

A brilliant image section (hereinafter, also referred to as "metallic image section") made of brilliant toner and a colored image section (hereinafter, also referred to as "color image section") made of colored toner are superimposed to form a colored brilliant image section (hereinafter, also referred to as "color image section"). When forming a "metallic image portion having color"), particularly when forming a fine line-shaped image, a metallic image portion that does not overlap with the color image portion is formed at the end of the fine line-shaped image. There was a case that it ended up.

The problem to be solved by the present invention is that the heat absorption amount QA / heat absorption amount QB in Equation 1 is 0 when a fine line image portion is formed as a metallic image portion having color by using a colored toner and a brilliant toner. It is an object of the present invention to provide a toner set that suppresses the formation of a metallic image portion that does not overlap with the color image portion at the widthwise end portion of the fine line-shaped image portion as compared with the case of 0.05 or more.

Specific means for achieving the above-mentioned problems are as follows.
That is, the invention according to < 1 > is
A brilliant toner containing brilliant toner particles containing a flat brilliant pigment and a binder resin, and a brilliant toner.
A colored toner containing colored toner particles containing a colorant and a crystalline resin, and a peak temperature ± 5 of the endothermic peak A of the crystalline resin contained in the brilliant toner particles detected by differential scanning calorimetry. A toner set in which the endothermic QA in the region of ° C. and the endothermic QB of the endothermic peak B of the crystalline resin contained in the colored toner particles in the region of ± 5 ° C. satisfy the following formula 1.
Equation 1: 0 ≤ heat absorption QA / heat absorption QB <0.05

The invention according to < 2 > is
The toner set according to < 1 > , wherein the content of the crystalline resin with respect to the total mass of the colored toner particles is 3% by mass or more and 40% by mass or less.

The invention according to < 3 > is
The toner set according to < 1 > or < 2 > , wherein the heat absorption amount QB is 2.0 J / g or more and 40 J / g or less.

The invention according to < 4 > is
The toner set according to any one of < 1 > to < 3 > , wherein the heat absorption amount QC of the colored toner, which is measured by differential scanning calorimetry, is 5.0 J / g or more and 60 J / g or less.

The invention according to < 5 > is
In any one of < 1 > to < 4 > , the first electrostatic charge image developer containing the brilliant toner in the toner set and
Of the toner set for static charge image development according to any one of < 1 > to < 4 >, a second electrostatic charge image developer containing the colored toner, and
Static charge image developer set with.

The invention according to < 6 > is
Of the toner set for static charge image development according to any one of < 1 > to < 4 > , the first toner cartridge containing the brilliant toner and the first toner cartridge.
A second toner cartridge containing the colored toner in the electrostatic charge image developing toner set according to any one of < 1 > to < 4 > , and
Have,
A toner cartridge set that can be attached to and detached from the image forming device.

The invention according to < 7 > is
The first developing means containing the first electrostatic image developing agent among the electrostatic image developing agent sets according to < 5 > , and
The second developing means containing the second electrostatic image developing agent in the electrostatic image developing agent set according to < 5 > , and
With
A process cartridge that is attached to and detached from the image forming device.

The invention according to < 8 > is
Of the toner set for static charge image development according to any one of < 1 > to < 4 > , the first image forming means for forming a brilliant image with the brilliant toner, and
Of the toner set for static charge image development according to any one of < 1 > to < 4 > , a second image forming means for forming a colored image with the colored toner, and
A transfer means for transferring the glittering image and the colored image onto a recording medium, and
A fixing means for fixing the glittering image and the colored image on the recording medium, and
An image forming apparatus comprising.

The invention according to < 9 > is
The first image forming step of forming a brilliant image with the brilliant toner in the toner set for static charge image development according to any one of < 1 > to < 4 > .
The second image forming step of forming a colored image with the colored toner in the electrostatic charge image developing toner set according to any one of < 1 > to < 4 > .
A transfer step of transferring the glittering image and the colored image onto a recording medium, and
A fixing step of fixing the brilliant image and the colored image on the recording medium, and
An image forming method having.

According to the invention according to < 1 > , as compared with the case where the heat absorption amount QA / heat absorption amount QB in the above formula 1 is 0.05 or more, the color image portion and the color image portion are formed at the widthwise end portion of the thin line image portion. A toner set in which the formation of non-overlapping metallic image portions is suppressed is provided.

According to the invention according to < 2 > , as compared with the case where the content of the crystalline resin with respect to the total mass of the colored toner particles is less than 3% by mass, the color is colored at the end portion in the width direction of the fine line image portion. Provided is a toner set in which the formation of a metallic image portion that does not overlap with the image portion is suppressed.

According to the invention according to < 3 > , as compared with the case where the heat absorption amount QB is less than 2.0 J / g, a metallic image that does not overlap with the color image portion at the widthwise end portion of the thin line image portion. A toner set in which the formation of portions is suppressed is provided.

According to the invention according to < 4 > , as compared with the case where the heat absorption amount QC of the colored toner is less than 5.0 J / g, the metallic image portion does not overlap with the color image portion at the widthwise end of the thin line image portion. A toner set in which the formation of an image portion is suppressed is provided.

According to the invention according to < 5 > , as compared with the case where the heat absorption amount QA / heat absorption amount QB in the above formula 1 is 0.05 or more, the color image portion and the color image portion are formed at the widthwise end portion of the thin line image portion. Provided is a static charge image developer set in which the formation of non-overlapping metallic image portions is suppressed.

According to the invention according to < 6 > , as compared with the case where the heat absorption amount QA / heat absorption amount QB in the above formula 1 is 0.05 or more, the color image portion and the color image portion are formed at the widthwise end portion of the thin line image portion. A toner cartridge set in which the formation of non-overlapping metallic image portions is suppressed is provided.

According to the invention according to < 7 > , as compared with the case where the heat absorption amount QA / heat absorption amount QB in the above formula 1 is 0.05 or more, the color image portion and the color image portion are formed at the widthwise end portion of the fine line image portion. A process cartridge is provided in which the formation of non-overlapping metallic image portions is suppressed.

According to the invention according to < 8 > , as compared with the case where the heat absorption amount QA / heat absorption amount QB in the above formula 1 is 0.05 or more, the color image portion and the color image portion at the widthwise end portion of the thin line image portion. An image forming apparatus is provided in which the formation of non-overlapping metallic image portions is suppressed.

According to the invention according to < 9 > , as compared with the case where the heat absorption amount QA / heat absorption amount QB in the above formula 1 is 0.05 or more, the color image portion and the color image portion are formed at the widthwise end portion of the thin line image portion. An image forming method is provided in which the formation of non-overlapping metallic image portions is suppressed.

It is sectional drawing which shows typically an example of the brilliant toner particle of this embodiment. It is a schematic block diagram which shows an example of the image forming apparatus of this embodiment. It is a schematic block diagram which shows an example of the process cartridge which concerns on this embodiment.

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

<Toner set>
The toner set according to the present embodiment includes a brilliant toner containing brilliant toner particles containing a flat brilliant pigment and a binder resin, and a colored toner containing colored toner particles containing a colorant and a crystalline resin. The heat absorption QA in the region of the peak temperature ± 5 ° C. of the heat absorption peak A of the crystalline resin contained in the brilliant toner particles, which is detected by differential scanning calorimetry, and is contained in the colored toner particles. The heat absorption amount QB in the region of the peak temperature ± 5 ° C. of the heat absorption peak B of the crystalline resin satisfies the following formula 1.
Equation 1: 0 ≤ heat absorption QA / heat absorption QB <0.05
When 0 ≦ heat absorption QA / heat absorption QB <0.05, the brilliant toner particles do not contain a crystalline resin, or the content of the crystalline resin in the brilliant toner particles is a colored toner particle. It means that it is smaller than the content of the crystalline resin in.
When the brilliant toner particles do not contain a crystalline resin, the heat absorption amount QA is 0, and the heat absorption amount QA / heat absorption amount QB is also 0.

Examples of the colored toner that can be contained in the toner set of the present embodiment include known toners such as magenta toner, cyan toner, yellow toner, black toner, red toner, green toner, blue toner, orange toner, and violet toner. Toner.

In addition, in this embodiment, "brightness" means having a brilliance such as metallic luster when the image formed by the brilliant toner of this embodiment is visually recognized.

When a fine line image (for example, a line image having a width of 60 μm) is formed as a metallic image portion having color by using a toner set containing a flat brilliant pigment and a colored toner. In some cases, the formation of a metallic image portion that does not overlap with the color image portion was observed at the end portion of the thin line-shaped image portion.

It is considered that the flat-shaped bright pigment contained in the bright toner particles is oriented when the toner is fixed to form a metallic image portion.
The orientation of the brilliant pigment means that the surface side where the area of the flat brilliant pigment is maximized faces the surface of the recording medium.
The bright pigment is, for example, flat particles having a volume average particle size of 1.0 μm or more and 10 μm or less, and a colorant contained in the colored toner particles (for example, a volume average particle size of 200 nm or more and 500 nm). Below).
Due to the orientation of the bright pigment and the large volume average particle size of the bright pigment, the metallic image portion is more likely to spread along the surface of the recording medium than the color image portion. It is considered that the area of is likely to be larger than the area of the color image portion.
When forming a metallic image portion having color, the glittering toner and the colored toner are superposed on the recording medium and then fixed to form the image portion, but the metallic image portion is formed rather than the area of the color image portion. It is presumed that when the area of is increased, a metallic image portion that does not overlap with the color image portion is formed at the end portion of the image portion.
In particular, when a fine line-shaped image portion is formed as a metallic image portion having color, the length of the color image portion in the width direction of the thin line-shaped image portion becomes small, so that the length of the thin line-shaped image portion in the width direction It is considered that a metallic image portion that does not overlap with the color image portion is likely to be formed at the end portion.

On the other hand, according to the toner set according to the present embodiment, when a fine line-shaped image portion is formed as a metallic image portion having color by using a colored toner and a brilliant toner, the width direction of the fine line-shaped image portion is formed. The formation of a metallic image portion that does not overlap with the color image portion (hereinafter, also simply referred to as “formation of a metallic image portion that does not overlap with the color image portion”) at the end portion of the is suppressed. The reason is presumed as follows.
When the colored toner and the brilliant toner contained in the toner set satisfy 0 ≦ heat absorption QA / heat absorption QB <0.05, the amount of crystalline resin contained in the colored toner particles is included in the brilliant toner particles. More than the amount of crystalline resin.
As a result, the viscosity of the colored toner at the time of melting becomes lower than the viscosity of the brilliant toner at the time of melting, and the molten colored toner is more likely to spread along the surface of the recording medium as compared with the molten brilliant toner, and the color is colored. It is considered that the area of the image portion tends to be larger than the area of the metallic image portion.
If the area of the color image portion is larger than the area of the metallic image portion, it is considered that the formation of the metallic image portion that does not overlap with the color image portion is suppressed.
As a result, it is presumed that the metallic image portion that does not overlap with the color image portion becomes difficult to be visually recognized at the end portion in the width direction of the thin line.

(Heat absorption QA / Heat absorption QB)
In the toner set of the present embodiment, the heat absorption amount QA / heat absorption amount QB satisfies the following formula 1.
Equation 1: 0 ≤ heat absorption QA / heat absorption QB <0.05
The heat absorption amount QA / heat absorption amount QB is 0 or more and less than 0.05, and is more preferably 0 or more and 0.03 or less, more preferably 0 or more, from the viewpoint of suppressing the formation of a metallic image portion that does not overlap with the color image portion. It is more preferably 0.015 or less, and particularly preferably 0.

The endothermic amount QA is the amount of heat absorption in the region of the peak temperature ± 5 ° C. of the heat absorption peak A in the differential scanning calorimetry of the brilliant toner, and the amount of heat absorption increases when the amount of crystalline resin contained in the brilliant toner particles is large. To increase.
The endothermic amount QB is the amount of heat absorption in the region of the peak temperature ± 5 ° C. of the heat absorption peak B in the differential scanning calorimetry of the colored toner, and the amount of heat absorption increases when the amount of crystalline resin contained in the colored toner particles is large. ..
Therefore, it is possible to adjust the value of the heat absorption amount QA / heat absorption amount QB by adjusting the amount of the crystalline resin contained in the brilliant toner particles and the amount of the crystalline resin contained in the colored toner particles. is there.
The fact that the heat absorption amount QA / heat absorption amount QB is 0 means that the heat absorption amount QA is 0, and that the brilliant toner does not have a peak of the crystalline resin in the differential scanning calorimetry.
For example, since the brilliant toner does not contain the crystalline resin, the heat absorption amount QA / heat absorption amount QB becomes 0.
When the endothermic peak A is present, the endothermic peak A is the endothermic peak of the crystalline resin detected by the differential scanning calorimetry in the brilliant toner.
From the viewpoint of low temperature fixability, the endothermic peak A is preferably present in the range of 60 ° C. or higher and 80 ° C. or lower, and more preferably in the range of 65 ° C. or higher and 75 ° C. or lower.
If the endothermic peak A is not confirmed in the differential scanning calorimetry, the endothermic QA is assumed to be 0.
The endothermic peak B is the endothermic peak of the crystalline resin detected by differential scanning calorimetry in the colored toner.
From the viewpoint of low temperature fixability, the endothermic peak B is preferably present in the range of 60 ° C. or higher and 80 ° C. or lower, and more preferably in the range of 65 ° C. or higher and 75 ° C. or lower.
In the present embodiment, when the endothermic peak of the crystalline resin is described, the peak derived from the compatible portion between the crystalline resin and the non-crystalline resin is not included.

The peak temperatures of the endothermic peak A and the endothermic peak B, and the amount of heat absorption (heat absorption amount QA and heat absorption amount QB) in the region of each peak temperature ± 5 ° C. are measured by differential scanning calorimetry.
Specifically, a differential scanning calorimeter is used, the melting temperature of a mixture of indium and zinc is used to correct the temperature of the detection unit of the apparatus, and the heat of fusion of indium is used to correct the calorific value. The sample (brilliant toner) is placed in an aluminum pan, the aluminum pan containing the sample and an empty aluminum pan for control are set, and the temperature is measured at a heating rate of 10 ° C./min.
The DSC curve is obtained by plotting the measurement result with time on the horizontal axis and change in calorific value on the vertical axis. From the obtained DSC curve, the peak temperature and the amount of heat absorption in the region of the peak temperature ± 5 ° C. are calculated. When calculating the amount of heat absorption, the baseline on the DSC curve is determined as a line connecting the measured values at 20 ° C and 130 ° C with a straight line, and the distance from the baseline to the DSC curve in the region of peak temperature ± 5 ° C is determined. The amount of heat absorbed is calculated by summing up.
When multiple peaks are fused, the lowest endothermic temperature between the adjacent peaks on the low temperature side is the separation temperature on the low temperature side, and the lowest endothermic temperature between the adjacent peaks on the high temperature side is the high temperature side. Judge the peak as the separation temperature of. The heat absorption amount of the crystalline resin is calculated from the difference between the heat absorption amounts of the first differential scanning calorimetry and the second differential scanning calorimetry. The second differential scanning calorimetry is carried out under the same conditions as the first measurement after the temperature is lowered at 50 ° C./min and held for 5 min after the first differential scanning calorimetry. In the present embodiment, the peak at which the endothermic peak disappears in the second differential scanning calorimetry is the peak of the crystalline resin.

The heat absorption amount QA is preferably 0 J / g or more and 2.0 J / g or less, and more preferably 0 J / g or more and 1.0 J / g or less, from the viewpoint of suppressing the formation of a metallic image portion that does not overlap with the color image portion. It is preferable, 0 J / g or more and 0.5 J / g or less is more preferable, and 0 is particularly preferable.
The heat absorption amount QB is preferably 2.0 J / g or more and 40 J / g or less, and more preferably 4.0 J / g or more and 30 J / g or less, from the viewpoint of suppressing the formation of a metallic image portion that does not overlap with the color image portion. It is preferable, and more preferably 8.0 J / g or more and 20 J / g or less.
In particular, when the heat absorption amount QB is within the above range, the heat absorption amount of the colored toner becomes large and the amount of heat transferred to the glitter toner at the time of fixing becomes small, so that the decrease in the viscosity of the glitter toner melted by fixing is suppressed. It is considered that the formation of the metallic image portion that does not overlap with the color image portion is further suppressed by suppressing the expansion of the area of the metallic image portion.

(Heat absorption QS of brilliant toner)
The heat absorption amount QS of the brilliant toner is preferably 2.0 J / g or more and 25 J / g or less, preferably 4.0 J / g or more and 20 J / g, from the viewpoint of suppressing the formation of a metallic image portion that does not overlap with the color image portion. It is more preferably g or less, and further preferably 6.0 J / g or more and 15 J / g or less.
The heat absorption amount QS is measured by differential scanning calorimetry (DSC). Specifically, the heat absorption of the toner uses a differential scanning calorimeter, the melting temperature of the mixture of indium and zinc is used to correct the temperature of the detector of the device, and the heat of fusion of indium is used to correct the calorific value. .. The sample (toner) is placed in an aluminum pan, the aluminum pan containing the sample and an empty aluminum pan for control are set, and the temperature is measured at a heating rate of 10 ° C./min. The endothermic amount is calculated from the endothermic portion of the DSC curve obtained by the measurement.

(Heat absorption QC of colored toner)
The heat absorption amount QC of the colored toner is preferably 5.0 J / g or more and 60 J / g or less, preferably 10 J / g or more and 50 J / g or less, from the viewpoint of suppressing the formation of a metallic image portion that does not overlap with the color image portion. More preferably, it is more preferably 15 J / g or more and 40 J / g or less.
The heat absorption amount QC is measured by the same method as the heat absorption amount QS.
When the heat absorption amount QC is within the above range, the heat absorption amount of the colored toner becomes large and the amount of heat transferred to the glitter toner at the time of fixing becomes small, so that the decrease in the viscosity of the glitter toner melted by fixing is suppressed, and the metallic image. It is considered that the formation of the metallic image portion that does not overlap with the color image portion is further suppressed by suppressing the expansion of the area of the portion.

The ratio of the heat absorption amount QS to the heat absorption amount QC (heat absorption amount QS / heat absorption amount QC) is 0.03 ≦ heat absorption amount QS / from the viewpoint of suppressing the formation of a metallic image portion that does not overlap with the color image portion. The heat absorption amount QC ≦ 20 is preferable, 0.1 ≦ heat absorption amount QS / heat absorption amount QC ≦ 1.5 is more preferable, and 0.3 ≦ heat absorption amount QS / heat absorption amount QC ≦ 1.0 is further preferable.

(Bright toner)
The brilliant toner of the present embodiment that constitutes the toner set of the present embodiment will be described below.
Specifically, the brilliant toner according to the present embodiment has a light receiving angle measured when a solid image is formed and the image is irradiated with incident light having an incident angle of −45 ° by a variable angle photometer. The ratio (X / Y) of the reflectance X at + 30 ° to the reflectance Y at the light receiving angle −30 ° is preferably 2 or more and 100 or less.

A ratio (X / Y) of 2 or more means that the incident light is reflected more on the opposite side (angle + side) than on the incident side (angle-side). That is, it means that the diffused reflection of the incident light is suppressed. When diffuse reflection occurs in which the 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, the gloss may not be confirmed even when the reflected light is visually recognized, and the brilliance may be inferior.
On the other hand, when the ratio (X / Y) exceeds 100, the viewing angle at which the reflected light can be visually recognized becomes too narrow, and the specular reflected light component is large, so that the reflected light may appear blackish depending on the viewing angle.

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

<Measurement of ratio (X / Y) with a variable angle photometer>
Here, first, the incident angle and the light receiving angle will be described. In the present embodiment, the incident angle is set to −45 ° when the measurement is performed by the angle photometer, because the measurement sensitivity is high for an image having a wide range of glossiness.
Further, the light receiving angles are set to −30 ° and + 30 ° because the measurement sensitivity is the highest for evaluating an image with a brilliant feeling and an image without a shining feeling.

Next, a method of measuring the ratio (X / Y) will be described.
A spectroscopic variable angle color difference meter GC5000L manufactured by Nippon Denshoku Kogyo Co., Ltd. is used as a variable angle photometer for the image to be measured (bright image), and incident light with an incident angle of −45 ° is incident on the image. Then, the reflectance X at the light receiving angle + 30 ° and the reflectance Y at the light receiving angle −30 ° are measured. 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 were taken as the average value of the reflectance at each wavelength. The ratio (X / Y) is calculated from these measurement results.

The toner according to the present embodiment preferably satisfies the following requirements (1) and (2) from the viewpoint of satisfying the above-mentioned ratio (X / Y).
(1) The average circle equivalent diameter D is longer than the average maximum thickness C of the brilliant toner particles.
(2) When observing a cross section of the brilliant toner particles in the thickness direction, the angle between the long axis direction of the brilliant toner particles and the long axis direction of the brilliant pigment is -30 ° to + 30 °. The proportion of brilliant pigments in the range is 60% or more of the total brilliant pigments observed.

When the brilliant toner particles have a flat shape in which the equivalent circle diameter is longer than the thickness (see FIG. 1), the flat brilliant toner particles have a flat surface due to the pressure at the time of fixing in the fixing step of image formation. It is considered that the sides are lined up so as to face the surface of the recording medium. In FIGS. 1 and 2, 2 indicates the thickness of the brilliant toner particles, 4 indicates the brilliant pigment, and L indicates the thickness of the brilliant toner particles.
Therefore, among the flat (scaly) bright pigments contained in the bright toner particles, the "long-axis direction in the cross section of the toner and the long-axis direction of the bright pigment" shown in (2) above It is considered that the bright pigments satisfying the requirement that the angle is in the range of −30 ° to + 30 ° are arranged so that the surface side having the maximum area faces the surface of the recording medium. When the image formed in this way is irradiated with light, it is considered that the above-mentioned ratio (X / Y) range is achieved because the ratio of the bright pigment that diffusely reflects the incident light is suppressed. Be done.

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

The brilliant toner particles contained in the brilliant toner according to the present embodiment include a brilliant pigment and a binder resin. The glittering toner particles according to the present embodiment may contain other components, if necessary.

<Glittering toner particles>
[Average maximum thickness C and average circle equivalent diameter D of brilliant toner particles]
It is preferable that the brilliant toner particles are flat and have an average circle equivalent diameter D longer than the average maximum thickness C. The ratio (C / D) of the average maximum thickness C to the average circle equivalent diameter D is more preferably in the range of 0.001 or more and 0.700 or less, and further in the range of 0.100 or more and 0.600 or less. It is preferable, and the range of 0.300 or more and 0.450 or less is particularly preferable.
When the ratio (C / D) is 0.001 or more, the strength of the brilliant toner particles is ensured, fracture due to stress during image formation is suppressed, and the charge is reduced due to the exposure of the pigment, and as a result. The fog that occurs is suppressed. On the other hand, when it is 0.700 or less, excellent brilliance can be obtained.

The average maximum thickness C and the average circle equivalent diameter D are measured by the following methods.
Glittering toner particles are placed on a smooth surface and vibrated to disperse them evenly. The maximum thickness C of the brilliant toner particles and the equivalent circle diameter D of the surface seen from above were magnified 1000 times by the color laser microscope "VK-9700" (manufactured by KEYENCE) for 1000 brilliant toner particles. Is measured, and it is calculated by calculating the arithmetic mean value of them.

[Angle between the long axis direction of the brilliant toner particles and the long axis direction of the brilliant pigment]
When observing the cross section of the bright toner particles in the thickness direction, the angle between the long axis direction of the bright toner particles and the long axis direction of the bright pigment is in the range of -30 ° to + 30 °. The ratio (number basis) of the bright pigments is preferably 60% or more of the total observed bright pigments. Further, the above ratio is more preferably 70% or more and 95% or less, and particularly preferably 80% or more and 90% or less.
When the above ratio is 60% or more, excellent brilliance can be obtained.

Here, a method of observing the cross section of the glittering toner particles will be described.
After embedding the glittering toner particles with a bisphenol A type liquid epoxy resin and a curing agent, a sample for cutting is prepared. Next, a cutting machine using a diamond knife, for example, an ultramicrotome device (UltracutUCT, manufactured by Leica) is used to cut the cutting sample at −100 ° C. to prepare an observation sample. The observation sample is observed with, for example, an ultra-high resolution field emission scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation) at a magnification at which about 1 to 10 bright toner particles can be seen in one field of view.
Specifically, the cross section of the brilliant toner particles (the cross section along the thickness direction of the brilliant toner particles) is observed, and the observed 100 brilliant toner particles are subjected to the long axis direction in the cross section of the brilliant toner particles. The number of bright pigments whose angle between the and the long axis direction of the bright pigment is in the range of -30 ° to + 30 ° can be determined by image analysis software such as image analysis software (Win ROOF) manufactured by Mitani Shoji Co., Ltd. or observation. Count using the image output sample and the divider to calculate the ratio.

The volume average particle size of the brilliant toner particles is preferably 3 μm or more and 30 μm or less, and more preferably 5 μm or more and 20 μm or less.

The volume average particle size D50v of the brilliant toner particles is the volume and number with respect to the particle size range (channel) divided based on the particle size distribution measured by a measuring instrument such as Multisizer II (manufactured by Coulter). Can be obtained by drawing a cumulative distribution from the small diameter side. The cumulative 16% particle size is defined as volume D16v and number D16p, the cumulative 50% particle size is defined as volume D50v and number D50p, and the cumulative 84% particle size is defined as volume D84v and number D84p. Using these, the volume particle size distribution index (GSDv) is calculated as (D84v / D16v) ^1/2 .

The ratio (aspect ratio) of the average length in the major axis direction when the average length in the thickness direction of the brilliant toner particles is 1, is preferably 1.5 or more and 15 or less, and 2 or more and 10 or less. More preferably, it is more preferably 3 or more and 8 or less.
The average length in the thickness direction and the average length in the major axis direction of the brilliant toner particles are such that the brilliant toner particles are placed on a smooth surface and vibrated to disperse them evenly. About 1,000 bright toner particles, magnified 1,000 times by a color laser microscope "VK-9700" (manufactured by KEYENCE), the maximum thickness of the bright toner particles and the long axis of the surface seen from above. It is calculated by measuring the length in the direction and calculating the arithmetic mean value of them.

The components constituting the brilliant toner according to the present embodiment will be described below.

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

Examples of the binder resin include an amorphous resin and a crystalline resin.
In the brilliant toner according to the present embodiment, the content of the crystalline resin is 0% by mass or more with respect to the total mass of the brilliant toner particles from the viewpoint of suppressing the formation of the metallic image portion that does not overlap with the color image portion. It is preferably 2.0% by mass or less, more preferably 0% by mass or more and 1.0% by mass or less, and further preferably 0% by mass.

The "crystallinity" of the resin means that the resin has an endothermic peak that disappears when the differential scanning calorimetry (DSC) is performed for the second time. After the first measurement of differential scanning calorimetry, the temperature is lowered at 50 ° C./min and held for 5 minutes, and then the temperature is raised at a rate of 10 (° C./min) as in the first measurement. , It means that the peak area of the endothermic peak is 10% or less. The baseline for calculating the peak area is set as a line connecting the measured values at 20 ° C and 130 ° C with a straight line, and when multiple peaks are fused, the peak division is with the adjacent peak on the low temperature side. The lowest endothermic temperature between them is set as the separation temperature on the low temperature side, and the lowest endothermic temperature between the adjacent peaks on the high temperature side is set as the separation temperature on the high temperature side.
On the other hand, the "amorphous" of the resin means that it does not have the above-mentioned crystallinity.

As the binder resin, a polyester resin is suitable.
Examples of the polyester resin include known amorphous polyester resins. As the polyester resin, a crystalline polyester resin may be used in combination with the amorphous polyester resin. However, the preferable range of the content of the crystalline polyester resin is the same as the preferable range of the content of the crystalline resin described above.

-Amorphous polyester resin Examples of the amorphous polyester resin include a condensed polymer of a polyvalent carboxylic acid and a polyhydric alcohol. As the amorphous polyester resin, a commercially available product may be used, or a synthetic resin may be used.

Examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids (for example, 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 acid (eg cyclohexanedicarboxylic acid, etc.), aromatic dicarboxylic acid (eg, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, etc.), these anhydrides, or their lower grades (eg, 1 or more carbon atoms). (5 or less) Alkyl ester can be mentioned. Among these, as the polyvalent carboxylic acid, for example, an aromatic dicarboxylic acid is preferable.
As the polyvalent carboxylic acid, a trivalent or higher carboxylic acid having a crosslinked structure or a branched structure may be used in combination with the dicarboxylic acid. Examples of the trivalent or higher carboxylic acid include trimellitic acid, pyromellitic acid, anhydrides thereof, and lower (for example, 1 to 5 carbon atoms) alkyl esters thereof.
The polyvalent carboxylic acid may be used alone or in combination of two or more.

Examples of the polyhydric alcohol include aliphatic diols (eg ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, etc.), alicyclic diols (eg cyclohexanediol, cyclohexanedimethanol, etc. Hydrogenated bisphenol A, etc.), aromatic diols (for example, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, etc.) can be mentioned. Among these, as the polyhydric alcohol, for example, an aromatic diol and an alicyclic diol are preferable, and an aromatic diol is more preferable.
As the polyhydric alcohol, a trihydric or higher polyhydric alcohol having a crosslinked structure or a branched structure may be used in combination with the diol. Examples of the trihydric or higher polyhydric alcohol include glycerin, trimethylolpropane, and pentaerythritol.
The polyhydric alcohol may be used alone or in combination of two or more.

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 obtained from the DSC curve obtained by differential scanning calorimetry (DSC), and more specifically described in JIS K 7121-1987 "Method for measuring transition temperature of plastics". It is obtained by the "external glass transition start temperature" of.

The weight average molecular weight (Mw) of the amorphous polyester resin is preferably 5000 or more and 1,000,000 or less, and more preferably 7,000 or more and 500,000 or less.
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 by using Tosoh's GPC / HLC-8120GPC as a measuring device, using Tosoh's column TSKgel SuperHM-M (15 cm), and using a THF solvent. The weight average molecular weight and the number average molecular weight are calculated from this measurement result using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample.

Amorphous polyester resin is obtained by a well-known manufacturing method. Specifically, for example, the polymerization temperature is set to 180 ° C. or higher and 230 ° C. or lower, the pressure inside the reaction system is reduced as necessary, and the reaction is carried out while removing water and alcohol generated during condensation.
When the raw material monomer is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point may be added as a dissolution aid to dissolve the monomer. In this case, the polycondensation reaction is carried out while distilling off the dissolution aid. If there is a monomer with poor compatibility, it is advisable to condense the monomer with poor compatibility with the monomer and the acid or alcohol to be polycondensed in advance, and then polycondensate with the main component. ..

-Crystalline polyester resin Examples of the crystalline polyester resin include a polycondensate of a polyvalent carboxylic acid and a polyhydric alcohol. As the crystalline polyester resin, a commercially available product may be used, or a synthetic resin may be used.
Here, since the crystalline polyester resin easily forms a crystal structure, a polycondensate using a polymerizable monomer having a linear aliphatic is preferable to a polymerizable monomer having an aromatic.

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-nonandicarboxylic acid, and 1,10-decandicarboxylic acid. Acids, 1,12-dodecanedicarboxylic acids, 1,14-tetradecandicarboxylic acids, 1,18-octadecanedicarboxylic acids, etc., aromatic dicarboxylic acids (eg, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid) Examples thereof include dibasic acids such as acids), anhydrides thereof, and lower (for example, 1 to 5 carbon atoms) alkyl esters thereof.
As the polyvalent carboxylic acid, a trivalent or higher carboxylic acid having a crosslinked structure or a branched structure may be used in combination with the dicarboxylic acid. 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.). Anhydrides or lower (for example, 1 to 5 carbon atoms) alkyl esters thereof can be mentioned.
As the polyvalent carboxylic acid, a dicarboxylic acid having a sulfonic acid group and a dicarboxylic acid having an ethylenic double bond may be used in combination with these dicarboxylic acids.
The polyvalent carboxylic acid may be used alone or in combination of two or more.

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

Here, the polyhydric alcohol preferably has an aliphatic diol content of 80 mol% or more, 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 DSC curve obtained by differential scanning calorimetry (DSC) by the "melting peak temperature" described in the method for determining the melting temperature in JIS K7121-1987 "Method for measuring transition temperature of plastics".

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 well-known manufacturing method, like the amorphous polyester resin, for example.

Here, examples of the amorphous polyester resin or the crystalline polyester resin (hereinafter, collectively referred to simply as “polyester resin”) include modified polyester resins in addition to the above-mentioned unmodified polyester resins. The modified polyester resin is a polyester resin having a bonding group other than an ester bond, or a polyester resin in which a resin component different from the polyester resin component is bonded by a covalent bond or an ionic bond. Examples of the modified polyester include a polyester resin in which a functional group such as an isocyanate group that reacts with an acid group or a hydroxyl group is introduced at the end, and a resin in which the end is modified by reacting an active hydrogen compound.

As the modified polyester resin, a urea-modified polyester resin is particularly preferable. The content of the urea-modified polyester resin is preferably 10% by mass or more and 30% by mass or less, and more preferably 15% by mass or more and 25% by mass or less with respect to the total binder resin.

The urea-modified polyester resin is preferably a urea-modified polyester resin obtained by reacting a polyester resin having an isocyanate group (polyester prepolymer) with an amine compound (at least one reaction of a cross-linking reaction and an extension reaction). The urea-modified polyester may contain a urethane bond as well as a urea bond.

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

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

Polyisocyanate compounds include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethyl caproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatics. Diisocyanate (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); aromatic aliphatic diisocyanate (α, α, α', α'-tetramethylxylylene diisocyanate, etc.); isocyanurates; Examples include those blocked with a blocking agent.
The polyisocyanate compound may be used alone or in combination of two or more.

The ratio of the polyisocyanate compound is preferably 1/1 or more and 5/1 or less, as the equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester prepolymer having a hydroxyl group. It is preferably 1.2 / 1 or more and 4/1 or less, and more preferably 1.5 / 1 or more and 2.5 / 1 or less. When [NCO] / [OH] is set to 5 or less, the decrease in low temperature fixability is easily suppressed.

In the polyester prepolymer having an isocyanate group, the content of the component derived from the polyhydric isocyanate compound is preferably 0.5% by mass or more and 40% by mass or less, more preferably, with respect to the entire polyester prepolymer having an isocyanate group. It is 1% by mass or more and 30% by mass or less, more preferably 2% by mass or more and 20% by mass or less.

The number of isocyanate groups contained in one molecule of the polyester prepolymer having an isocyanate group is preferably 1 or more on average, more preferably 1.5 or more and 3 or less on average, and still more preferably 1.8 or more on average 2. .5 or less.

Examples of the amine compound that reacts with the polyester prepolymer having an isocyanate group include diamines, trivalent or higher polyamines, amino alcohols, amino mercaptans, amino acids, and compounds in which these amino groups are blocked.

Examples of diamines include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, etc.); alicyclic diamines (4,4'-diamino-3,3'-dimethyldicyclohexylmethane, diaminecyclohexane, isophorone). Diamines, etc.); and aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.) and the like.
Examples of the triamine or higher polyamine include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of amino acids include aminopropionic acid and aminocaproic acid.
Blocking these amino groups includes amine compounds such as diamines, trivalent or higher polyamines, aminoalcohols, aminomercaptans, and amino acids, and ketimine compounds obtained from ketone compounds (acetones, methyl ethyl ketones, methyl isobutyl ketones, etc.). Examples include oxazoline compounds.
Of these amine compounds, ketimine compounds are preferred.
The amine compound may be used alone or in combination of two or more.

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

The ratio of the amine compound is preferably 1/2 or more as the equivalent ratio [NCO] / [NHx] of the isocyanate group [NCO] in the polyester prepolymer having an isocyanate group and the amino group [NHx] in the amines. It is 1/1 or less, more preferably 1 / 1.5 or more and 1.5 / 1 or less, and further preferably 1 / 1.2 or more and 1.2 / 1 or less.

The glass transition temperature of the urea-modified polyester resin is preferably 40 ° C. or higher and 65 ° C. or lower, and more preferably 45 ° C. or higher and 60 ° C. or lower. The number average molecular weight is preferably 2500 or more and 50,000 or less, and more preferably 2500 or more and 30,000 or less. The weight average molecular weight is preferably 10,000 or more and 500,000 or less, and more preferably 30,000 or more and 100,000 or less.

The total content of the crystalline resin and the amorphous resin is, for example, 40% by mass or more and 95% by mass or less, more preferably 50% by mass or more and 90% by mass or less, more preferably 60% by mass or less, based on the entire glittering toner particles. More preferably, it is by mass% or more and 85% by mass or less.

-Glittering pigment-
Examples of the brilliant pigment include pigments (brilliant pigments) that can impart a brilliant feeling such as metallic luster. Specifically, as the glitter pigment, for example, metal powders such as aluminum (metal of Al alone), brass, bronze, nickel, stainless steel, zinc, etc .; mica coated with titanium oxide, yellow iron oxide, etc.; barium sulfate, layered Kay Coated flaky inorganic crystal substrate such as acid salt and silicate of layered aluminum; monocrystalline plate-shaped titanium oxide; basic carbonate; bismuth acid oxychloride; natural guanine; flaky glass powder; metal-deposited flaky glass There is no particular limitation as long as it has a brilliant property such as powder.

Among the bright pigments, metal powder is preferable, and aluminum is most preferable, particularly from the viewpoint of specular reflection intensity.

The shape of the brilliant pigment according to the present embodiment is flat (scaly) from the viewpoint of having high brilliance in the fixed image.
Hereinafter, the flat-shaped bright pigment will be described.
The average length of the flat bright pigment in the major axis direction 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 (aspect ratio) of the average length in the major axis direction when the average length in the thickness direction of the bright pigment is 1, is preferably 5 or more and 200 or less, more preferably 10 or more and 100 or less. More preferably, it is 30 or more and 70 or less.

Each average length and aspect ratio of the glitter pigment is measured by the following method. Using a scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation), a photograph of the pigment particles is taken at a measurable magnification (300 to 100,000 times), and the obtained image of the pigment particles is two-dimensional. In this 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 aspect ratio in the major axis direction of the bright pigment are calculated.

The volume average particle size of the bright pigment is preferably 1.0 μm or more and 20.0 μm or less, and more preferably 2.0 μm or more and 15.0 μm or less.
When the volume average particle size of the brilliant pigment is 1.0 μm or more, the brilliance of the obtained image is excellent.
When the volume average particle size of the bright pigment is 20.0 μm or less, the charging characteristics of the obtained toner are excellent and transfer unevenness is suppressed.

The volume average particle size of the bright pigment is measured as follows.
Cumulative 50% of the volume is drawn from the small diameter side for each particle size range (channel) divided based on the particle size distribution measured by a measuring instrument such as Multisizer II (manufactured by Coulter). The particle size is the volume average particle size.
As a method for measuring the volume average particle size of the glitter pigment in the toner particles after production, the toner resin is sufficiently mixed and stirred with a solvent capable of dissolving only the toner resin without dissolving the glitter pigment. After dissolving in, the bright pigment is solid-liquid separated, and the volume average particle size is measured by the same particle size distribution measuring device as described above.

The content of the brilliant pigment with respect to the total mass of the brilliant toner particles is preferably 1% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 50% by mass or less, and 5% by mass or more and 40% by mass. It is more preferably mass% or less.

The brilliant toner in this embodiment may contain a colorant and a mold release agent.

-Colorant-
As the colorant, a colorant similar to the colorant used for the coloring toner described later is used.

When the brilliant toner contains a colorant, the content of the colorant is, for example, 0% by mass or more and 20% by mass or less, preferably 3.0% by mass or more and 15% by mass or less, based on the entire brilliant toner particles. The following is more preferable.

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

The melting temperature of the release agent is preferably 50 ° C. or higher and 110 ° C. or lower, and more preferably 60 ° C. or higher and 100 ° C. or lower.
The melting temperature is determined from the DSC curve obtained by differential scanning calorimetry (DSC) by the "melting peak temperature" described in the method for determining the melting temperature in JIS K 7121-1987 "Method for measuring transition temperature of plastics". ..

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

-Other additives-
Examples of other additives include well-known additives such as magnetic materials, charge control agents, and inorganic powders. These additives are contained in the glittering toner particles as an internal additive.

(External agent)
The brilliant toner may have an 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 should be hydrophobized. The hydrophobizing treatment is performed, for example, by immersing the inorganic particles in a hydrophobizing agent. The hydrophobizing agent is not particularly limited, and examples thereof include a silane-based coupling agent, a silicone oil, a titanate-based coupling agent, and an aluminum-based coupling agent. These may be used alone or in combination of two or more.
The amount of the hydrophobizing agent is usually, for example, 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the inorganic particles.

Examples of the external additive include resin particles (resin particles such as polystyrene, polymethylmethacrylate (PMMA), and melamine resin), cleaning activators (for example, metal salts of higher fatty acids typified by zinc stearate, fluoropolymers). Particles) and the like.

The amount of the external additive is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.01% by mass or more and 2.0% by mass or less, based on the total mass of the glittering toner particles. preferable.

<Colored toner>
Next, the components constituting the colored toner according to the present embodiment will be described.
The colored toner according to the present embodiment contains colored toner particles containing a colorant and a crystalline resin.

-Colorant-
Colorants include, for example, carbon black, chrome yellow, Hansa yellow, benzine yellow, slene yellow, quinoline yellow, pigment yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brilliant carmine 3B, brilliant. Carmin 6B, Dupont Oil Red, Pyrazolon Red, Resole Red, Rhodamin B Lake, Lake Red C, Pigment Red, Rose Bengal, Aniline Blue, Ultra Marine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Pigment Blue, Phthalocyanine Green, Various pigments such as malachite green oxalate, or aclysine, xanthene, azo, benzoquinone, azine, anthraquinone, thioindico, dioxazine, thiazine, azomethine, indico, phthalocyanine, aniline black Examples thereof include various dyes such as system, polymethine type, triphenylmethane type, diphenylmethane type and thiazole type.
One type of colorant may be used alone, or two or more types may be used in combination.

As the colorant, a surface-treated colorant may be used if necessary, or may be used in combination with a dispersant. Further, a plurality of kinds of colorants may be used in combination.

The content of the colorant is, for example, preferably 1% by mass or more and 30% by mass or less, and more preferably 3% by mass or more and 15% by mass or less with respect to the entire colored toner particles.

-Crystalline resin-
The colored toner particles according to this embodiment contain a crystalline resin.
The content of the crystalline resin with respect to the total mass of the colored toner particles is preferably 3% by mass or more and 40% by mass or less, more preferably 5% by mass or more and 35% by mass or less, and 10% by mass or more and 25% by mass or less. It is more preferably% or less.
The crystalline resin is not particularly limited as long as it is a resin having known crystallinity, and specific examples thereof include polyester resin and vinyl resin, but from the viewpoint of facilitating fixing in a low temperature range. Polyester resin is preferred.

The crystalline polyester resin has the same meaning as the crystalline polyester resin used in the above-mentioned bright toner, and the preferred embodiment is also the same.

Moreover, the colored toner used in this embodiment may contain an amorphous resin.
As the amorphous resin used in the present embodiment, a known amorphous binding resin for toner particles can be used, and for example, a styrene-acrylic resin, a polyester resin, or the like can be used. As the amorphous resin, it is preferable to use an amorphous polyester resin.
The amorphous polyester resin has the same meaning as the amorphous resin used in the above-mentioned bright toner, and the preferred embodiment is also the same.

The volume average particle size of the colored toner particles of the present embodiment is preferably 1 μm or more and 10 μm or less, more preferably 2 μm or more and 8 μm or less, and further preferably 3 μm or more and 6 μm or less.
The volume average particle diameter of the colored toner particles is measured by the same method as the volume average particle diameter of the glittering toner particles described above.

The average circularity of the colored toner particles is preferably 0.94 or more and 1.00 or less, and more preferably 0.95 or more and 0.98 or less.

The average circularity of the colored toner particles is obtained by (circumferential peripheral length) / (peripheral length) [(circumferential length of a circle having the same projected area as the particle image) / (peripheral length of the particle projected image)]. Specifically, it is a value measured by the following method.
First, a flow-type particle image analyzer (a flow-type particle image analyzer that collects colored toner particles to be measured by suction, forms a flat flow, and instantly emits strobe light to capture a particle image as a still image and analyze the particle image. Obtained by FPIA-2100) manufactured by Sysmex. Then, the number of samplings when calculating the average circularity is set to 3500.
When the colored toner has an external additive, the colored toner (developer) to be measured is dispersed in water containing a surfactant, and then ultrasonic treatment is performed to remove the external additive. Get the particles.

(External agent)
The colored toner may have an external additive.
The external additive used is synonymous with the external additive used in the brilliant toner, and the preferred embodiment is also the same.

<Toner manufacturing method>
The brilliant toner and the colored toner of the present embodiment (hereinafter, may be simply referred to as “toners” together) may be referred to as brilliant toner particles or colored toner particles (hereinafter, collectively referred to as “toner particles”). ) May be produced by adding an external additive to the toner particles.
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 / crushing method, a wet method such as an emulsion aggregation method, a dissolution suspension method, or a suspension polymerization method.
In the kneading / crushing method, after mixing each material including a colorant, the above materials are melt-kneaded using a kneader, an extruder, etc., and the obtained melt-kneaded product is roughly crushed and then jet milled. This is a method of obtaining toner particles having a target particle size by crushing with a wind classifier.
Among these methods, an emulsion aggregation method in which the shape of toner particles and the particle size of toner particles can be easily controlled and the control range of the toner particle structure such as a core-shell structure is wide is desirable. Hereinafter, a method for producing toner particles by the emulsion aggregation method will be described in detail.

The emulsification / aggregation method of the present embodiment fuses an emulsification step of emulsifying a raw material constituting the toner particles to form resin particles (emulsified particles), an aggregation step of forming an aggregate of the resin particles, and an aggregate. It has a fusion step.

(Emulsification process)
The resin particle dispersion is prepared by a general polymerization method, for example, an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, or the like, or a solution in which an aqueous medium and a binder resin are mixed. In addition, it may be emulsified by applying a shearing force with a disperser. At that time, the particles may be formed by heating to reduce the viscosity of the resin component. Further, a dispersant may be used to stabilize the dispersed resin particles. Further, if the resin is oily and dissolves in a solvent having a relatively low solubility in water, the resin is dissolved in those solvents, particles are dispersed in water together with a dispersant and a polymer electrolyte, and then heated or depressurized. By evaporating the solvent, a resin particle dispersion is prepared.

Examples of the aqueous medium include distilled water, water such as ion-exchanged water; alcohols; and the like, but 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 dodecylbenzene sulfonate, Anionic surfactants such as sodium octadecyl sulfate, sodium oleate, sodium laurylate, potassium stearate, cationic surfactants such as laurylamine acetate, stearylamine acetate, and lauryltrimethylammonium chloride, and both sexes such as lauryldimethylamine oxide. Surfactants such as ionic surfactants, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, nonionic surfactants such as polyoxyethylene alkyl amines; tricalcium phosphate, aluminum hydroxide, calcium sulfate, carbon dioxide Inorganic salts such as calcium and barium carbonate; and the like.

Examples of the disperser used for producing the emulsion include a homogenizer, a homomixer, a pressurized kneader, an extruder, a media disperser and the like. As for the size of the resin particles, the average particle size (volume average particle size) is preferably 1.0 μm or less, more preferably 60 nm or more and 300 nm or less, and further preferably 150 nm or more and 250 nm or less. .. At 60 nm or more, the resin particles tend to become unstable particles in the dispersion liquid, so that the resin particles may easily aggregate. If it is 1.0 μm or less, the particle size distribution of the toner may be narrowed.

When preparing the release agent dispersion, the release agent is dispersed in water together with an ionic surfactant and a polymer electrolyte such as a polymer acid or a polymer base, and then the temperature is raised to a temperature higher than the melting temperature of the release agent. Along with heating, dispersion processing is performed using a homogenizer or a pressure discharge type disperser to which a strong shearing force is applied. By undergoing such a treatment, a release agent dispersion liquid can be obtained. At the time of the dispersion treatment, an inorganic compound such as polyaluminum chloride may be added to the dispersion liquid. Desirable inorganic compounds include, for example, polyaluminum chloride, aluminum sulfate, highly basic polyaluminum chloride (BAC), polyaluminum hydroxide, aluminum chloride and the like. Among these, polyaluminum chloride, aluminum sulfate and the like are desirable. The release agent dispersion is used in the emulsion aggregation method, but the release agent dispersion may also be used when the toner is produced by the suspension polymerization method.

By the dispersion treatment, a release agent dispersion liquid containing the release agent particles having a volume average particle diameter of 1 μm or less can be obtained. The more desirable volume average particle size of the release agent particles is 100 nm or more and 500 nm or less.
When the volume average particle size is 100 nm or more, the release agent component is generally easily incorporated into the toner, although it is affected by the characteristics of the binder resin used. Further, when it is 500 nm or less, the dispersed state of the release agent in the toner becomes good.

Known dispersion methods can be used for the preparation of the colorant dispersion liquid and the bright pigment dispersion liquid, and for example, a rotary shear type homogenizer or a general dispersion means such as a ball mill having a medium, a sand mill, a dyno mill, or an ultimateizer is adopted. It can be done and is not restricted at all. The colorant is dispersed in water together with an ionic surfactant and a polymer electrolyte such as a polymer acid or a polymer base.
Further, the bright pigment and the binder resin are dispersed and dissolved in a solvent, mixed, and dispersed in water by phase inversion emulsification or shear emulsification to prepare a dispersion liquid of the bright pigment coated with the binder resin. You may.

(Aggregation process)
In the agglomeration step, a dispersion of resin particles, a colorant dispersion, a bright pigment dispersion, a release agent dispersion, etc. are mixed to form a mixed solution, which is heated at a temperature equal to or lower than the glass transition temperature of the resin particles. To agglomerate to form agglomerated particles. The formation of agglomerated particles is often done by acidifying the pH of the mixture under stirring. The pH is preferably in the range of 2 or more and 7 or less, and in this case, it is also effective to use a flocculant.
By adjusting the amount of the dispersion liquid of the resin particles containing the crystalline resin in the aggregation step between the case of producing the brilliant toner and the case of producing the colored toner, the heat absorption amount QA / heat absorption amount QB The value is adjusted to obtain the toner set of the present embodiment.

As the flocculant, a surfactant having a polarity opposite to that of the surfactant used in the dispersant, an inorganic metal salt, or a divalent or higher valent metal complex is preferably used. In particular, when a metal complex is used, the amount of the surfactant used can be reduced and the charging characteristics are improved, which is particularly desirable.

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 divalent rather than monovalent, trivalent rather than divalent, trivalent rather than trivalent, and even if the valence is the same, it is a polymerization type. Inorganic metal salt polymers are more suitable.
In the present 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.

Further, a toner having a structure in which the surface of the core agglomerated particles is coated with a resin may be produced by additionally adding a resin particle dispersion liquid when the agglomerated particles have a desired particle size (coating step). In this case, the release agent, the colorant, and the bright pigment are less likely to be exposed on the toner surface, which is a desirable configuration from the viewpoint of chargeability and developability. In the case of additional addition, a flocculant may be added or the pH may be adjusted before the additional addition.

(Fusion process)
In the fusion step, the progress of aggregation is stopped by raising the pH of the suspension of the aggregated particles to a range of 3 or more and 9 or less under the stirring conditions similar to the aggregation step, and the temperature is equal to or higher than the glass transition temperature of the resin. Aggregated particles are fused by heating at temperature. When coated with the resin, the resin is also fused to coat the core agglomerated particles. The heating time may be such that fusion is carried out, and may be performed for about 0.5 hours or more and 10 hours or less.

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

Inorganic oxides such as silica, titania, and aluminum oxide are added and adhered to the obtained toner particles as an external additive for the purpose of adjusting charge, imparting fluidity, imparting charge exchange property, and the like. These can be performed by, for example, a V-type blender, a Henschel mixer, a Ladyge mixer, or the like, and may be attached in stages. The amount of the external additive added is preferably in the range of 0.1 parts by mass or more and 5 parts by mass or less, and more preferably in the range of 0.3 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the toner particles.
Further, if necessary, coarse particles of toner may be removed after external addition using an ultrasonic sieving machine, a vibration sieving machine, a wind sieving machine, or the like.

In addition to the above-mentioned inorganic oxides and the like, other components (particles) such as charge control agents, organic particles, lubricants, and abrasives may be added as external additives.

The charge control agent is not particularly limited, but a colorless or light-colored agent is preferably used. Examples thereof include quaternary ammonium salt compounds, niglosin compounds, complexes such as aluminum, iron and chromium, and triphenylmethane pigments.

Examples of the organic particles include particles such as vinyl resin, polyester resin, and silicone resin, which are usually used as an additive on the surface of toner. In addition, these inorganic particles and organic particles are used as a fluidity aid, a cleaning aid, and the like.
Examples of the lubricant include fatty acid amides such as ethylene bisstearic acid amide and oleic acid amide, and fatty acid metal salts such as zinc stearate and calcium stearate.
Examples of the abrasive include the above-mentioned silica, alumina, cerium oxide and the like.

Next, a method for producing toner particles by the dissolution / suspension method will be described in detail.
In the dissolution / suspension method, a material containing a binder resin, a bright pigment, a colored pigment, and other components such as a release agent used as needed is dissolved in a solvent in which the binder resin can be dissolved. Alternatively, it is a method of obtaining toner particles by granulating the dispersed liquid in an aqueous medium containing an inorganic dispersant and then removing the solvent.
Examples of other components used in the dissolution / suspension method include various components such as an internal additive, a charge control agent, an inorganic powder (inorganic particles), and organic particles, in addition to a mold release agent.

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

These solvents dissolve the binder resin and do not need to dissolve bright pigments, colored pigments and other components. The bright pigment and other components need only be able to be dispersed in the solution of the binder resin.
The amount of the solvent used is not limited, but it may be any viscosity as long as it can be granulated in an aqueous medium. The ratio of the material containing the binder resin, the bright pigment, and other components (the former) to the solvent (the latter) is 10/90 to 50/50 (the mass ratio of the former / the latter) and the ease of granulation and It is preferable in terms of the yield of final toner particles.

The binder resin, bright pigment, colored pigment and other component liquids (toner mother liquor) dissolved or dispersed in the solvent have a predetermined particle size in an aqueous medium containing an inorganic dispersant. Is granulated. Water is mainly used as the water medium. The mixing ratio of the water medium and the toner mother liquor is preferably water medium / toner mother liquor = 90/10 to 50/50 (mass ratio).
As the inorganic dispersant, those selected from tricalcium phosphate, hydroxyapatite, calcium carbonate, titanium oxide and silica powder are preferable.
The amount of the inorganic dispersant used is determined according to the particle size of the granulated particles, but is generally preferably used in the range of 0.1% by mass or more and 15% by mass or less with respect to the toner mother liquor. .. If it is 0.1% by mass or more, granulation is likely to be performed well, and if it is 15% by mass or less, unnecessary fine particles are unlikely to be generated and the target particles can be easily obtained in high yield.

In order to improve the granulation from the toner mother liquor, an auxiliary agent may be further added to the aqueous medium containing the inorganic dispersant.
As the auxiliary agent, there are known cation type, anion type and nonion type surfactants, and the anion type is particularly preferable. For example, there are sodium alkylbenzene sulfonate, sodium α-olefin sulfonate, sodium alkyl sulfonate, etc., and these are used in the range of 1 × 10 ^-4 % by mass or more and 0.1% by mass or less with respect to the toner mother liquor. preferable.

Granulation from the toner mother liquor in an aqueous medium containing an inorganic dispersant is preferably performed under shearing.
At this time, it is desirable that the average particle size is 20 μm or less, and particularly preferably 3 μm or more and 15 μm or less.
There are various types of dispersers as devices provided with a shearing mechanism, and among them, a homogenizer is preferable. By using a homogenizer, substances that are incompatible with each other (in this embodiment, an aqueous medium containing an inorganic dispersant and a toner mother liquor) are passed through a gap between a casing and a rotating rotor, so that the liquid is contained in a certain liquid. Substances that are incompatible with and can be dispersed in the form of particles.
Specifically, as homogenizers, TK homomixer, line flow homomixer, auto homomixer (manufactured by Tokushu Kagaku Kogyo Co., Ltd.), Silberson homogenizer (manufactured by Silberson), polytron homogenizer (KINEMATICA AG) Made) and so on.
The stirring condition using the homogenizer is preferably 2 m / sec or more at the peripheral speed of the rotor blades. If the peripheral speed is 2 m / sec or more, the particle formation tends to be good.

After granulation as described above, the solvent is removed.
The solvent may be removed at normal temperature (25 ° C.) and normal pressure, but since it takes a long time to remove the solvent, the temperature conditions are lower than the boiling point of the solvent and the difference from the boiling point is 80 ° C. or less. It is preferable to carry out with. The pressure may be normal pressure or reduced pressure, but it is preferable to reduce the pressure at 20 mmHg or more and 150 mmHg or less.

Further, after removing the solvent, it is preferable to wash the toner particles with hydrochloric acid or the like. As a result, the inorganic dispersant remaining on the surface of the toner particles can be removed to obtain the original composition of the toner particles and improve the characteristics.
Then, if it is dehydrated and dried, powder toner particles can be obtained.

Further, the toner particles containing the urea-modified polyester resin as the binder resin may be obtained by the dissolution suspension method. In the following description of the dissolution / suspension method, a method for obtaining toner particles containing a release agent will be described, but the release agent is contained in the toner particles as needed. Further, the method of obtaining the toner particles containing the unmodified polyester resin and the urea-modified polyester resin as the binder resin will be described, but the toner particles may contain only the urea-modified polyester resin as the binder resin.
[Oil phase liquid preparation process]
An oil phase liquid is prepared by dissolving or dispersing a toner particle material containing an unmodified polyester resin, a polyester prepolymer having an isocyanate group, an amine compound, a bright pigment, a colored pigment and a mold release agent in an organic solvent (oil phase liquid). Preparation process). This oil phase liquid preparation step is a step of dissolving or dispersing the toner particle material in an organic solvent to obtain a mixed liquid of the toner material.

The oil phase liquid is prepared by 1) a method of preparing by dissolving or dispersing the toner material in an organic solvent all at once, and 2) kneading the toner material in advance and then dissolving or dispersing this kneaded compound in an organic solvent. 3) A method in which an unmodified polyester resin, a polyester prepolymer having an isocyanate group, and an amine compound are dissolved in an organic solvent, and then a bright pigment and a mold release agent are dispersed in the organic solvent to prepare the compound. 4) A method of preparing by dissolving a bright pigment, a colored pigment and a mold release agent in an organic solvent, and then dissolving an unmodified polyester resin, a polyester prepolymer having an isocyanate group, and an amine compound in the organic solvent. 5. After dissolving or dispersing toner particle materials (unmodified polyester resin, bright pigment, and mold release agent) other than the polyester prepolymer having an isocyanate group and the amine compound in an organic solvent, isocyanate is added to the organic solvent. Method for preparing by dissolving a polyester prepolymer having a group and an amine compound, 6) Toner particle material other than the polyester prepolymer having an isocyanate group or the amine compound (unmodified polyester resin, bright pigment, colored pigment and mold release agent) ) Is dissolved or dispersed in an organic solvent, and then a polyester prepolymer having an isocyanate group or an amine compound is dissolved in the organic solvent to prepare the compound. The method for preparing the oil phase liquid is not limited to these.

Examples of the organic solvent of the oil phase liquid include ester solvents such as methyl acetate and ethyl acetate; ketone solvents such as methyl ethyl ketone and methyl isopropyl ketone; aliphatic hydrocarbon solvents such as hexane and cyclohexane; and dichloromethane, chloroform, trichloroethylene and the like. Examples thereof include halogenated hydrocarbon solvents. It is preferable that these organic solvents dissolve the binder resin, dissolve in water at a rate of 0% by mass or more and 30% by mass or less, and have a boiling point of 100 ° C. or less. Among these organic solvents, ethyl acetate is preferable.

[Suspension preparation process]
Next, the obtained oil phase liquid is dispersed in the aqueous phase liquid to prepare a suspension (suspension preparation step).
Then, along with the preparation of the suspension, the reaction between the polyester prepolymer having an isocyanate group and the amine compound is carried out. Then, a urea-modified polyester resin is produced by this reaction. This reaction involves at least one of a molecular chain cross-linking reaction and an extension reaction. The reaction between the polyester prepolymer having an isocyanate group and the amine compound may be carried out together with the solvent removing step described later.
Here, the reaction conditions are selected based on the reactivity of the isocyanate group structure of the polyester prepolymer with the amine compound. As an example, the reaction time is preferably 10 minutes or more and 40 hours or less, and preferably 2 hours or more and 24 hours or less. The reaction temperature is preferably 0 ° C. or higher and 150 ° C., and preferably 40 ° C. or higher and 98 ° C. or lower. A known catalyst (dibutyltin laurate, dioctyltin laurate, etc.) may be used to produce the urea-modified polyester resin, if necessary. That is, the catalyst may be added to the oil phase liquid or suspension.

Examples of the aqueous phase liquid include an aqueous phase liquid in which a particle dispersant such as a resin particle dispersant and an inorganic particle dispersant is dispersed in an aqueous solvent. Further, as the aqueous phase liquid, an aqueous phase liquid in which a particle dispersant is dispersed in an aqueous solvent and a polymer dispersant is dissolved in an aqueous solvent can also be mentioned. A well-known additive such as a surfactant may be added to the aqueous phase liquid.

Examples of the aqueous solvent include water (usually ion-exchanged water, distilled water, pure water). The aqueous solvent is a solvent containing water and an organic solvent such as alcohol (methanol, isopropyl alcohol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellsolves (methylcellsolve, etc.), lower ketones (acetone, methylethylketone, etc.). There may be.

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

Examples of the inorganic particle dispersant include a hydrophilic inorganic particle dispersant. Specific examples of the inorganic particle dispersant include particles such as silica, alumina, titania, calcium carbonate, magnesium carbonate, tricalcium phosphate, clay, diatomaceous earth, and bentonite, and calcium carbonate particles are preferable. As the inorganic particle dispersant, one type may be used alone, or two or more types may be used in combination.

The surface of the particle dispersant may be surface-treated with a polymer having a carboxyl group.
As the polymer having a carboxyl group, the carboxyl group of α, β-monoethylene unsaturated carboxylic acid or α, β-monoethylene unsaturated carboxylic acid is composed of alkali metal, alkaline earth metal, ammonia, amine or the like. Examples include a copolymer of at least one selected from neutralized salts (alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts, etc.) and α, β-monoethylene unsaturated carboxylic acid esters. Be done. As the polymer having a carboxyl group, the carboxyl group of the copolymer of α, β-monoethylene unsaturated carboxylic acid and α, β-monoethylene unsaturated carboxylic acid ester is an alkali metal or an alkaline earth metal. , Alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts, etc., which are neutralized with ammonia, amines, etc. As the polymer having a carboxyl group, one type may be used alone, or two or more types may be used in combination.

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

Examples of the polymer dispersant include hydrophilic polymer dispersants. Specific examples of the polymer dispersant include water-soluble polymer dispersants (for example, carboxymethyl cellulose, carboxyethyl cellulose, etc.) having a carboxyl group and no parent oil group (hydroxypropoxy group, methoxy group, etc.). Sexual cellulose ether).

[Solvent removal step]
Next, the organic solvent is removed from the obtained suspension to obtain a toner particle dispersion (solvent removal step). This solvent removing step is a step of removing the organic solvent contained in the droplets of the aqueous phase liquid dispersed in the suspension to generate toner particles. The removal of the organic solvent from the suspension may be carried out immediately after the suspension preparation step, or may be carried out one minute or more after the completion of the suspension preparation step.
In the solvent removing step, it is preferable to remove the organic solvent from the suspension by cooling or heating the obtained suspension to, for example, 0 ° C. or higher and 100 ° C. or lower.

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

Toner particles are obtained through the above steps.
Here, after the solvent removal step is completed, the toner particles formed in the toner particle dispersion liquid are obtained as dried toner particles through a known washing step, solid-liquid separation step, and drying step.
In the cleaning step, it is preferable to sufficiently perform replacement cleaning with ion-exchanged water from the viewpoint of chargeability.
The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration and the like may be performed from the viewpoint of productivity. The drying step is also not particularly limited, but from the viewpoint of productivity, freeze-drying, air-flow drying, fluid drying, vibration-type fluid drying and the like may be performed.

<Static charge image developer set>
The electrostatic charge image developer set according to the present embodiment includes a first electrostatic charge image developer containing a brilliant toner in the toner set according to the present embodiment, and a colored toner among the toner sets according to the present embodiment. It has two electrostatic charge image developers.
Each electrostatic charge image developer may be a one-component developer containing only toner, or may be a two-component developer mixed with the toner and a carrier.

The carrier is not particularly limited, and examples thereof include known carriers. Examples of the carrier include a coating carrier in which the surface of a core material made of magnetic powder is coated with a coating resin; a magnetic powder dispersion type carrier in which magnetic powder is dispersed and blended in a matrix resin; and a porous magnetic powder impregnated with resin. Resin-impregnated carrier; etc.
The magnetic powder dispersion type carrier and the resin impregnated type carrier may be carriers 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, and styrene-acrylic acid. 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, an epoxy resin and the like.
The coating resin and the matrix resin may contain other additives such as conductive particles.
Examples of the conductive particles include metals such as gold, silver and copper, and particles such as 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 resin and, if necessary, a coating layer forming solution in which various additives are dissolved in an appropriate solvent can be mentioned. The solvent is not particularly limited, and may be selected in consideration of the coating resin to be used, coating suitability, and the like.
Specific resin coating methods include a dipping method in which the core material is immersed in a coating layer forming solution, a spray method in which the coating layer forming solution is sprayed on the core material surface, and a state in which the core material is suspended by flowing air. Examples thereof include a fluidized bed method in which a solution for forming a coating layer is sprayed, a kneader coater method in which a core material of a carrier and a solution for forming a coating layer are mixed in a kneader coater, and a 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 device / 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 is a first image forming means for forming a brilliant image by a brilliant toner in the toner set according to the present embodiment, and a colored image using a colored toner in the toner set according to the present embodiment. A second image forming means for forming the image, a transfer means for transferring the glittering image and the colored image onto the recording medium, and a fixing means for fixing the glittering image and the colored image on the recording medium are provided.
The image forming apparatus according to the present embodiment forms an image holder, a charging means for charging the surface of the image holder, and a static charge image on the surface of the charged image holder as the first and second image forming means. Even in the form provided with each image forming means having each of an electrostatic charge image forming means for forming a static charge image and a developing means for developing an electrostatic charge image formed on the surface of an image holder as a toner image by an electrostatic charge image developing agent. Good.
Further, the image forming apparatus according to the present embodiment includes an image holder, a charging means for charging the surface of the image holder, and a static charge image forming means for forming a static charge image on the surface of the charged image holder. Even in the form having first and second developing means for developing the electrostatic charge image formed on the surface of the image holder as a toner image by the static charge image developing agent as the first and second image forming means. Good.

In the image forming apparatus according to the present embodiment, the first image forming step of forming a brilliant image by the brilliant toner in the toner set according to the present embodiment and the colored image by the colored toner in the toner set according to the present embodiment. An image forming method having a second image forming step of forming the image, a transfer step of transferring the glittering image and the colored image onto the recording medium, and a fixing step of fixing the glittering image and the colored image on the recording medium ( The image forming method) according to this embodiment is carried out.

The image forming apparatus according to the present embodiment is a direct transfer type apparatus for directly transferring a toner image (a brilliant image, a colored image in the present embodiment) formed on the surface of an image holder to a recording medium; An intermediate transfer type device that primary transfers the toner image formed on the surface to the surface of the intermediate transfer body and secondarily transfers the toner image transferred to the surface of the intermediate transfer body to the surface of the recording medium; after the transfer of the toner image. , A device provided with a cleaning means for cleaning the surface of the image holder before charging; a well-known device provided with a static removing means for irradiating the surface of the image holder with static elimination light after transferring the toner image and before charging. The image forming apparatus of is applied.
In the case of an intermediate transfer type apparatus, the transfer means is, for example, an intermediate transfer body in which a toner image is transferred to the surface and a primary transfer in which a toner image formed on the surface of an image holder is primarily transferred to the surface of the intermediate transfer body. A configuration comprising means and secondary transfer means for secondary transfer of the toner image transferred to the surface of the intermediate transfer body to the surface of the recording medium is applied.

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 the following description, the main parts shown in the figure will be described, and the description thereof will be omitted for the others. In the following description, an example of the toner set according to the present embodiment will be described with reference to the brilliant toner as "silver toner".

FIG. 2 is a schematic configuration diagram showing an image forming apparatus according to the present embodiment, and is a diagram showing an image forming apparatus of a 5-unit tandem type and an intermediate transfer type.
The image forming apparatus shown in FIG. 2 is an electron that outputs an image of each color of yellow (Y), magenta (M), cyan (C), black (K), and silver (B) based on the color-separated image data. It is provided with photographic first to fifth image forming units 150Y, 150M, 150C, 150K, 150G (image forming means). These image forming units (hereinafter, may be simply referred to as "units") 150Y, 150M, 150C, 150K, and 150G are arranged side by side in the horizontal direction at a predetermined distance from each other. These units 150Y, 150M, 150C, 150K, 150G may be process cartridges that are attached to and detached from the image forming apparatus.

Below each unit 150Y, 150M, 150C, 150K, 150G, an intermediate transfer belt (an example of an intermediate transfer body) 133 extends through each unit. The intermediate transfer belt 133 is provided by being wound around a drive roll 113, a support roll 112, and an opposing roll 114 that are in contact with the inner surface of the intermediate transfer belt 133, and is provided in a direction from the first unit 150Y to the fifth unit 150B (FIG. In 2, it runs in the direction of arrow B). An intermediate transfer body cleaning device 116 is provided on the image holding surface side of the intermediate transfer belt 133 so as to face the drive roll 113. Further, on the upstream side of the intermediate transfer belt 133 in the rotation direction with respect to the intermediate transfer body cleaning device 116, a voltage is applied to generate an electric field between the intermediate transfer belt 133 and the intermediate transfer belt 133 by causing a potential difference with the support roll 113. A device 160 is provided.
Development equipment for each unit 150Y, 150M, 150C, 150K, 150G (example of developing means) 120Y, 120M, 120C, 120K, 120B, respectively, yellow contained in toner cartridges 140Y, 140M, 140C, 140K, 140B. , Magenta, cyan, black, and silver toners are supplied.

Since the first to fifth units 150Y, 150M, 150C, 150K, and 150B have the same configuration, operation, and operation, here, the yellow ones arranged on the upstream side in the traveling direction of the intermediate transfer belt. The first unit 150Y forming the image will be described as a representative.

The first unit 150Y has a photoconductor 111Y that acts as an image holder. Around the photoconductor 111Y, a charging roll (an example of charging means) 118Y that charges the surface of the photoconductor 111Y to a predetermined potential, and the charged surface are exposed by a laser beam based on a color-separated image signal. An exposure device (an example of a static charge image forming means) 119Y for forming an electrostatic charge image, a developing device (an example of a developing means) 120Y for supplying toner to a static charge image to develop an electrostatic charge image, and a developed toner image. A primary transfer roll (an example of a primary transfer means) 117Y to be transferred onto the intermediate transfer belt 133, and a photoconductor cleaning device (an example of a cleaning means) 115Y for removing toner remaining on the surface of the photoconductor 111Y after the primary transfer are arranged in order. Has been done.
The primary transfer roll 117Y is arranged inside the intermediate transfer belt 133, and is provided at a position facing the photoconductor 111Y. A bias power supply (not shown) for applying a primary transfer bias is connected to each of the primary transfer rolls 117Y, 117M, 117C, 117K, and 117B of each unit. Each bias power supply changes the value of the transfer bias applied to each primary transfer roll by control by a control unit (not shown).

Hereinafter, the operation of forming a yellow image in the first unit 150Y will be described.
First, prior to the operation, the surface of the photoconductor 111Y is charged to a potential of −600V to −800V by the charging roll 118Y.
The photoconductor 111Y is formed by laminating a photosensitive layer on a conductive substrate (for example, a volume resistivity of 1 × 10 ^-6 Ωcm or less at 20 ° C.). This photosensitive layer usually has a high resistivity (resistance of a general resin), but has a property that when a laser beam is irradiated, the specific resistance of the portion irradiated with the laser beam changes. Therefore, the surface of the charged photoconductor 111Y is irradiated with a laser beam from the exposure apparatus 119Y according to the image data for yellow sent from the control unit (not shown). As a result, an electrostatic charge image of the yellow image pattern is formed on the surface of the photoconductor 111Y.

The static charge image is an image formed on the surface of the photoconductor 111Y by charging, and the specific resistance of the irradiated portion of the photosensitive layer is lowered by the laser beam from the exposure apparatus 119Y, and the surface of the photoconductor 111Y is charged. It is a so-called negative latent image formed by the flow of the charged charge and the residual charge of the portion not irradiated with the laser beam.
The electrostatic charge image formed on the photoconductor 111Y rotates to a predetermined development position as the photoconductor 111Y travels. Then, at this developing position, the electrostatic charge image on the photoconductor 111Y is developed and visualized as a toner image by the developing device 120Y.

In the developing apparatus 120Y, for example, a static charge image developing agent containing at least yellow toner and a carrier is housed. The yellow toner is triboelectrically charged by being agitated inside the developing apparatus 120Y, has a charge having the same polarity (negative electrode property) as the charged charge on the photoconductor 111Y, and has a developing agent roll (developing agent holder). Example) It is held on. Then, as the surface of the photoconductor 111Y passes through the developing device 120Y, the yellow toner is electrostatically adhered to the statically eliminated latent image portion on the surface of the photoconductor 111Y, and the latent image is developed by the yellow toner. .. The photoconductor 111Y on which the yellow toner image is formed is continuously traveled at a predetermined speed, and the toner image developed on the photoconductor 111Y is conveyed to a predetermined primary transfer position.

When the yellow toner image on the photoconductor 111Y is conveyed to the primary transfer position, a primary transfer bias is applied to the primary transfer roll 117Y, and an electrostatic force from the photoconductor 111Y toward the primary transfer roll 117Y acts on the toner image to expose the toner image. The toner image on the body 111Y is transferred onto the intermediate transfer belt 133. The transfer bias applied at this time has a polarity (+) opposite to that of the toner (−), and is controlled to, for example, + 10 μA by a control unit (not shown) in the first unit 150Y.
On the other hand, the toner remaining on the photoconductor 111Y is removed by the photoconductor cleaning device 115Y and recovered.

The primary transfer bias applied to the primary transfer rolls 117M, 117C, 117K, 117B after the second unit 150M is also controlled according to the first unit.
In this way, the intermediate transfer belt 133 on which the yellow toner image is transferred by the first unit 150Y is sequentially conveyed through the second to fifth units 150M, 150C, 150K, and 150B, and the toner images of each color are superimposed and multiplexed. Transcribed.

The intermediate transfer belt 133 in which the toner images of five colors are multiple-transferred through the first to fifth units includes the intermediate transfer belt 133, the opposing roll 114 in contact with the inner surface of the intermediate transfer belt, and the image holding surface of the intermediate transfer belt 133. It leads to a secondary transfer unit composed of a secondary transfer roll (an example of the secondary transfer means) 134 arranged on the side. On the other hand, the recording paper (an example of the recording medium) P is fed to the gap where the secondary transfer roll 134 and the intermediate transfer belt 133 are in contact with each other via the supply mechanism at a predetermined timing, and the secondary transfer bias is applied to the opposing roll. It is applied to 114. The transfer bias applied at this time has a (-) polarity that is the same as the polarity (-) of the toner, and the electrostatic force from the intermediate transfer belt 133 toward the recording paper P acts on the toner image, and the transfer bias is applied on the intermediate transfer belt 133. The toner image of is transferred onto the recording paper P. The secondary transfer bias at this time is determined according to the resistance detected by the resistance detecting means (not shown) for detecting the resistance of the secondary transfer unit, and is voltage controlled.

After that, the recording paper P is sent to the pressure contact portion (nip portion) of the pair of fixing rolls in the fixing device (an example of the fixing means) 135, and the toner image is fixed on the recording paper P to form the fixing image. ..

Examples of the recording paper P for transferring the toner image include plain paper used in electrophotographic copying machines, printers, and the like. Examples of the recording medium include an OHP sheet and the like in addition to the recording paper P.
In order to further improve the smoothness of the image surface after fixing, it is preferable that the surface of the recording paper P is also smooth. Suitable for use.

The recording paper P for which the color image has been fixed is carried out toward the ejection unit, and a series of color image forming operations is completed.

The image forming apparatus shown in FIG. 2 is an image forming apparatus having a structure in which the toner cartridges 140Y, 140M, 140C, 140K, and 140B are attached and detached, and the developing apparatus 120Y, 120M, 120C, 120K, and 120B are the respective image forming apparatus. It is connected to a toner cartridge corresponding to the developing device (color) by a toner supply tube (not shown). Further, when the amount of toner contained in the toner cartridge is low, the toner cartridge is replaced.

<Process cartridge / toner cartridge set>
The process cartridge according to this embodiment will be described.
The process cartridge according to the present embodiment includes the first developing means containing the first static charge image developer among the electrostatic charge image developing agents set according to the present embodiment, and the electrostatic charge image developing agent set according to the present embodiment. A process cartridge including a second developing means containing the second static charge image developing agent, which is attached to and detached from an image forming apparatus.

The process cartridge according to the present embodiment is not limited to the above configuration, and includes a developing device and other means such as an image holder, a charging means, an electrostatic charge image forming means, and a transfer means, if necessary. It may be configured to include at least one selected from.

Hereinafter, an example of the process cartridge according to the present embodiment will be shown, but the present invention is not limited to this. The main parts shown in the figure will be described, and the other parts will be omitted.

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 photoconductor 207 (an example of an image holder) and the photoconductor 207 by, for example, a housing 217 provided with a mounting rail 216 and an opening 218 for exposure. The charged roll 208 (an example of the charging means), the developing device 211 (an example of the developing means), and the photoconductor cleaning device 213 (an example of the cleaning means) are integrally combined and held and configured to form a cartridge. There is.
In FIG. 3, 209 is an exposure device (an example of an electrostatic charge image forming means), 212 is a primary transfer roll (an example of a primary transfer means), 220 is an intermediate transfer belt (an example of an intermediate transfer body), and 222 is an intermediate transfer. A drive roll that also serves as a belt static elimination means (an example of an intermediate transfer static elimination means), 224 is a support roll, 226 is a secondary transfer roll (an example of a secondary transfer means), and 228 is a fixing device (an example of a fixing means), 300. Indicates a recording paper (an example of a recording medium).

Next, the toner cartridge set according to this embodiment will be described.
The toner cartridge set according to the present embodiment includes a first toner cartridge containing brilliant toner in the toner set according to the present embodiment and a second toner cartridge containing colored toner in the toner set according to the present embodiment. , A toner cartridge set that is attached to and detached from the image forming apparatus.
Each toner cartridge accommodates a replenishing toner for supplying to each developing means provided in the image forming apparatus.

Hereinafter, the present embodiment will be described in more detail based on the examples, but the present embodiment is not limited to the following examples. Unless otherwise specified, "parts" and "%" represent "parts by mass" and "% by mass".

(Synthesis of amorphous polyester resin)
-Dimethyl adipate: 74 parts-Dimethyl terephthalate: 192 parts-Bisphenol A ethylene oxide adduct: 216 parts-Ethylene glycol: 38 parts-Tetrabutoxytitanate (catalyst): 0.037 parts,
The above components are placed in a heat-dried two-necked flask, nitrogen gas is introduced into the container to maintain an inert atmosphere and the temperature is raised while stirring, followed by a co-condensation polymerization 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, and the temperature was maintained for 4 hours. Amorphous polyester resin was synthesized by returning to normal pressure once, adding 9 parts of trimellitic anhydride, gradually reducing the pressure to 10 Torr again, and holding at 220 ° C. for 1 hour.

(Preparation of amorphous polyester resin dispersion)
-Amorphous polyester resin: 160 parts-Ethyl acetate: 233 parts-Sodium hydroxide aqueous solution (0.3N): 0.1 parts Put the above components in a 1000 ml separable flask and heat at 70 ° C. A resin mixture was prepared by stirring by Shinto Kagaku Co., Ltd. While further stirring the resin mixture, 373 parts of ion-exchanged water was gradually added, phase-inverted emulsified, and the solvent was removed to obtain an amorphous polyester resin dispersion (solid content concentration: 30%).

(Synthesis of crystalline polyester resin 1)
1,10-decandicarboxylic acid: 50 mol%
-1,9-Nonanediol: 50 mol%
The above monomer component is placed in a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen gas introduction tube, the inside of the reaction vessel is replaced with dry nitrogen gas, and then titanium tetrabutoxide (reagent) is added to 100 parts of the monomer component. On the other hand, 0.25 copies were added. After a stirring reaction at 170 ° C. for 3 hours under a nitrogen gas stream, the temperature was further raised to 210 ° C. over 1 hour, the inside of the reaction vessel was reduced to 3 kPa, and the reaction was stirred under reduced pressure for 13 hours to crystallize. A sex polyester resin 1 was obtained.

(Synthesis of crystalline polyester resins 2-4)
Crystalline polyester resins 2 to 3 were synthesized in the same manner as the crystalline polyester resin 1 except that the dicarboxylic acids and diols used were changed as shown in Table 1 below.

(Preparation of crystalline polyester resin dispersion 1)
In a 3-liter reaction tank with a jacket (Tokyo Rikaki Co., Ltd .: BJ-30N) equipped with a condenser, a thermometer, a water dropping device, and an anchor wing, 300 parts of the crystalline polyeltel resin, 160 parts of methyl ethyl ketone (solvent), and 160 parts. 100 parts of isopropyl alcohol (solvent) was added, and the resin was dissolved while stirring and mixing at 100 rpm while maintaining the temperature at 70 ° C. in a water circulation type thermometer.
After that, the stirring speed was set to 150 rpm, the water circulation type constant temperature bath was set to 66 ° C., 17 parts of 10% ammonia water (reagent) was added over 10 minutes, and then 7 parts of ion-exchanged water kept at 66 ° C./ A total of 900 parts were added dropwise at a rate of 1 minute to invert the phase to obtain an emulsion.
Immediately, 800 parts of the obtained emulsion and 700 parts of ion-exchanged water were placed in a 2 liter eggplant flask and set in an evaporator (Tokyo University of Science, Inc.) equipped with a vacuum control unit via a trap ball. While rotating the eggplant flask, it was heated in a hot water bath at 60 ° C., and the pressure was reduced to 7 kPa while paying attention to sudden boiling to remove the solvent. When the amount of solvent recovered reached 1100 parts, the pressure was returned to normal pressure, and the eggplant flask was water-cooled to obtain a dispersion liquid. The obtained dispersion had no solvent odor. The volume average particle diameter D50v of the resin particles in this dispersion was 130 nm. Then, ion-exchanged water was added to adjust the solid content concentration to 20% by mass, and this was used as the crystalline polyester resin dispersion liquid 1.

(Preparation of crystalline polyester resin dispersion liquids 2 to 3)
In the preparation of the crystalline polyester resin dispersion liquid 1, the crystalline polyester resins 2 to 3 were prepared in the same manner except that the crystalline polyester resin 1 was changed to the crystalline polyester resins 2 to 4.

(Preparation of Bright Pigment Dispersion Solution 1)
-Aluminum pigment (manufactured by Showa Aluminum Powder Co., Ltd., 2173EA 6 μm): 100 parts-Anionic surfactant (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Neogen R): 1.5 parts-Ion-exchanged water: 400 parts Aluminum pigment paste The solvent was removed from the pigment, and the pigment was mechanically pulverized to 5.2 μm and classified using a star mill (LMZ, manufactured by Ashizawa Finetech Co., Ltd.). After that, it is mixed with the above-mentioned activator and ion-exchanged water and dispersed for about 1 hour using an emulsification disperser Cavitron (manufactured by Pacific Kiko Co., Ltd., CR1010) to disperse bright pigment particles (aluminum pigment). A bright pigment dispersion 1 was prepared (solid content concentration: 20% by mass). The pigment dispersion diameter was 5.2 μm.

(Preparation of Sian colorant dispersion)
・ C. I. Pigment Blue 15: 3 (copper phthalocyanine) (manufactured by Dainichiseika): 50 parts ・ Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku): 5 parts ・ Ion exchange water: 192.9 parts Mix the above components and mix. It was treated with an ultimateizer (manufactured by Sugino Machine Limited) at 240 MPa for 10 minutes to obtain a Sian colorant dispersion. The solid content concentration was 20% by mass.

(Preparation of magenta colorant dispersion)
・ C. I. Pigment Red 122 (quinacridone) (manufactured by Dainichi Seika): 50 parts ・ Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku): 5 parts ・ Ion-exchanged water: 192.9 parts The treatment was carried out at 240 MPa for 10 minutes with Sugino Machine Limited to obtain a magenta colorant dispersion. The solid content concentration was 20% by mass.

(Preparation of yellow colorant dispersion)
・ C. I. Pigment Yellow74 (manufactured by Dainichiseika): 50 parts ・ Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.): 5 parts ・ Ion-exchanged water: 192.9 parts Mixing the above components, Ultimateer (manufactured by Sugino Machine Limited) ) For 10 minutes at 240 MPa to obtain a yellow colorant dispersion. The solid content concentration was 20%.

(Preparation of release agent dispersion)
・ Carnauba wax (manufactured by Toa Kasei Co., Ltd., RC-160): 50 parts ・ Anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK): 1.0 parts ・ Ion-exchanged water: 200 parts or more The mixture was mixed and heated to 95 ° C., dispersed using a homogenizer (Ultratarax T50 manufactured by IKA), and then dispersed with a Manton Gorin high-pressure homogenizer (Gorin) for 360 minutes to obtain a volume average particle size. A release agent dispersion (solid content concentration: 20% by mass) prepared by dispersing the release agent particles having a size of 0.23 μm was prepared.

<Manufacturing of brilliant toner 1>
-Glittering pigment dispersion: 1: 150 parts-Amorphous polyester resin dispersion: 280 parts-Release release agent dispersion: 75 parts Put the above components in a 2 L cylindrical stainless steel container and homogenizer (made by IKA, Ultra Tarax). The mixture was dispersed and mixed for 10 minutes while applying a shearing force at 4000 rpm according to T50). Next, 1.75 parts of a 10% aqueous nitric acid solution of polyaluminum chloride was gradually added dropwise as a coagulant, and the homogenizer was dispersed at 5000 rpm for 15 minutes to prepare a raw material dispersion.
After that, the dispersion liquid was transferred to a stirrer equipped with a stirrer using a four paddle stirrer and a thermometer, the stirring speed was set to 1000 rpm, and heating was started with a mantle heater, and the agglomerated particles were heated at 54 ° C. Promoted growth. At this time, the pH of the dispersion was controlled in the range of 2.2 to 3.5 by using 0.3 mol / L nitric acid or 1 mol / L sodium hydroxide aqueous solution. It was kept in the above pH range for about 2 hours to form aggregated particles.
Next, 70 parts of the amorphous polyester resin dispersion was additionally added to attach the amorphous polyester resin particles to the surface of the aggregated particles. Further, the temperature was raised to 56 ° C., and the aggregated particles were prepared while checking the size and morphology of the particles with an optical microscope and Multisizer II. Then, 3.25 parts of a chelating agent (HIDS, manufactured by Nippon Shokubai Co., Ltd.) was added, and then the pH was adjusted to 7.8 with a 5% aqueous sodium hydroxide solution and held for 15 minutes. Then, the pH was raised to 8.0 in order to fuse the agglomerated particles, and then the temperature was raised to 67.5 ° C. After confirming that the agglomerated particles were fused with an optical microscope, the pH was lowered to 6.0 while maintaining at 67.5 ° C., heating was stopped after 1 hour, and the mixture was cooled at a temperature lowering rate of 1.0 ° C./min. Then, it was sieved with a 40 μm mesh, washed with water repeatedly, and then dried with a vacuum dryer to obtain toner particles. The volume average particle diameter of the obtained toner particles was 11.5 μm.
1.5 parts of colloidal silica (manufactured by Nippon Aerosil Co., Ltd., R972) was mixed with 100 parts of the obtained toner particles at a peripheral speed of 30 m / s for 2 minutes with a Henschel mixer to obtain a brilliant toner 1.

<Manufacturing of brilliant toner 2>
In the production of the brilliant toner 1, the amount of the amorphous polyester resin dispersion was changed from 280 parts to 245 parts, and further, the yellow colorant dispersion liquid: 45 parts and the magenta colorant dispersion liquid: 7.5 parts were added. The brilliant toner 2 was obtained by the same operation as in the production of the brilliant toner 1 except for the addition.

<Manufacturing of brilliant toner 3>
In the production of the brilliant toner 1, the amount of the amorphous polyester resin dispersion is changed from 280 parts to 273 parts, and 11.3 parts of the crystalline polyester resin dispersion 1 is used. The glittering toner 3 was obtained by the same operation as in the above.

<Manufacturing of brilliant toner 4>
Atypical polyester resin: 75 parts by mass, bright pigment (2173EA manufactured by Showa Aluminum Powder Co., Ltd.): 20 parts by mass of a mixture is kneaded with an extruder, crushed with a surface crushing type crusher, and then classified by wind force. Fine particles and coarse particles were classified by a machine to obtain toner particles.

Hereinafter, the brilliant toner 4 was manufactured by the same operation as in Example 1.

<Manufacturing of brilliant toner 5>
(Preparation of unmodified polyester resin (1))
-Terephthalic acid: 1243 parts-Bisphenol A ethylene oxide adduct: 1830 parts-Bisphenol A propylene oxide adduct: 840 parts After heating and mixing the above components at 180 ° C, add 3 parts of dibutyltin oxide and heat at 220 ° C. While distilling off water, an unmodified polyester resin was obtained. The glass transition temperature Tg of the obtained unmodified polyester resin was 60 ° C., the acid value was 3 mgKOH / g, and the hydroxyl value was 1 mgKOH / g.

(Preparation of polyester prepolymer (1))
-Terephthalic acid: 1243 parts-Bisphenol A ethylene oxide adduct: 1830 parts-Bisphenol A propylene oxide adduct: 840 parts After heating and mixing the above components at 180 ° C, add 3 parts of dibutyltin oxide and heat at 220 ° C. While distilling off water, polyester was obtained. 350 parts of the obtained polyester, 50 parts of tolylene diisocyanate, and 450 parts of ethyl acetate are placed in a container, and the mixture is heated at 130 ° C. for 3 hours to prepare a polyester prepolymer (1) having an isocyanate group (hereinafter, "isocyanate-modified polyester"). Prepolymer (1) ") was obtained.

(Preparation of ketimine compound (1))
50 parts of methyl ethyl ketone and 150 parts of hexamethylenediamine were placed in a container and stirred at 60 ° C. to obtain ketimine compound (1).

(Preparation of Bright Pigment Dispersion Liquid 2)
-Aluminum pigment (flat bright pigment, manufactured by Showa Aluminum Powder Co., Ltd., 2173EA): 100 parts-Ethyl acetate: 500 parts Mixing the above components, filtering the mixture and further mixing with 500 parts of ethyl acetate After repeating 5 times, the mixture was dispersed for about 1 hour using an emulsifying disperser Cavitron (CR1010 manufactured by Pacific Kiko Co., Ltd.), and the glitter pigment dispersion 2 (solid content) in which the glitter pigment (aluminum pigment) was dispersed was dispersed. Concentration: 10%) was obtained.

(Preparation of release agent dispersion liquid (1))
-Paraffin wax (melting temperature 89 ° C.): 30 parts-Ethyl acetate: 270 parts With the above components cooled to 10 ° C., wet pulverization is performed with a microbead type disperser (DCP mill), and a release agent dispersion liquid (1). ) Was obtained.

(Preparation of oil phase liquid (1))
-Unmodified polyester resin (1): 136 parts-Glittering pigment dispersion 2: 500 parts-Ethyl acetate: 56 parts After stirring and mixing the above components, 75 parts of the release agent dispersion (1) was added to the obtained mixture. In addition, the mixture was stirred to obtain an oil phase liquid (1).

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

(Preparation of aqueous phase liquid (1))
・ Styrene acrylic resin particle dispersion (1): 60 parts ・ 2% aqueous solution of cellogen BS-H (Daiichi Kogyo Seiyaku Co., Ltd.): 200 parts ・ Ion-exchanged water: 200 parts The above components are stirred and mixed, and the aqueous phase Liquid (1) was obtained.

-Preparation of toner particles (1)-
・ Oil phase liquid (1): 300 parts ・ Isocyanate-modified polyester prepolymer (1): 25 parts ・ Ketimine compound (1): 0.5 parts Put the above ingredients in a container and homogenizer (Ultratalax: manufactured by IKA). After stirring for 2 minutes to obtain an oil phase solution (1P), 1000 parts of the aqueous phase solution (1) was added to the container, and the mixture was stirred with a homogenizer for 20 minutes. Next, the mixed solution was stirred with a propeller-type stirrer at room temperature (25 ° C.) and normal pressure (1 atm) for 48 hours to react the isocyanate-modified polyester prepolymer (1) with the ketimine compound (1). A urea-modified polyester resin was produced, and the organic solvent was removed to form granules. Next, the granules were washed with water, dried and classified to obtain toner particles. The volume average particle size of the toner particles was 12.0 μm, and the aspect ratio was 6.0.

-Preparation of brilliant toner 5-
Toner particles: 100 parts, hydrophobic silica (manufactured by Nippon Aerosil, RY50): 1.5 parts, hydrophobic titanium oxide (manufactured by Nippon Aerosil, T805): 1.0 parts, at 10000 rpm by sample mill. Mixed for 30 seconds. Then, it was sieved with a vibrating sieve having an opening of 45 μm to obtain a brilliant toner 5.

<Manufacturing of brilliant toner 6>
In the production of the brilliant toner 1, the amount of the amorphous polyester resin dispersion 1 is changed to 255 parts, and 37.5 parts of the crystalline polyester resin dispersion 1 is used, which is the same as the production of the brilliant toner 1. A brilliant toner 6 was obtained by the above operation.

Hereinafter, manufacturing methods for colored toners such as Sian toner, magenta toner, and yellow toner will be described.

<Manufacturing of Sian Toner 1>
・ Sian colorant dispersion: 37.5 parts ・ Amorphous polyester resin dispersion: 330 parts ・ Crystalline polyester resin dispersion 1: 37.5 parts ・ Release agent dispersion: 75 parts 2L cylinder of the above components The mixture was placed in a stainless steel container and dispersed and mixed for 10 minutes while applying a shearing force at 4000 rpm with a homogenizer (Ultratalax T50 manufactured by IKA). Next, 1.75 parts of a 10% aqueous nitric acid solution of polyaluminum chloride was gradually added dropwise as a coagulant, and the homogenizer was dispersed at 5000 rpm for 15 minutes to prepare a raw material dispersion.
After that, the raw material dispersion was transferred to a polymerization kettle equipped with a stirring device using a stirring blade of four paddles and a thermometer, the stirring speed was set to 600 rpm, and heating was started with a mantle heater, and agglomerated particles were formed at 50 ° C. Promoted the growth of. At this time, the pH of the dispersion was controlled in the range of 2.2 to 3.5 by using 0.3 mol / L nitric acid or 1 mol / L sodium hydroxide aqueous solution. It was kept in the above pH range for about 2 hours to form aggregated particles.
Next, 70 parts of the amorphous polyester resin dispersion was additionally added to attach the amorphous polyester resin particles to the surface of the aggregated particles. Further, the temperature was raised to 52 ° C., and the aggregated particles were prepared while checking the size and morphology of the particles with an optical microscope and Multisizer II. Then, 2.25 parts of a chelating agent (HIDS, manufactured by Nippon Shokubai Co., Ltd.) was added, and then the pH was adjusted to 7.8 with a 5 mass% sodium hydroxide aqueous solution and held for 15 minutes. Then, the pH was raised to 8.0 in order to fuse the agglomerated particles, and then the temperature was raised to 67.5 ° C. After confirming that the agglomerated particles were fused with an optical microscope, the pH was lowered to 6.0 while maintaining at 67.5 ° C., heating was stopped after 1 hour, and the mixture was cooled at a temperature lowering rate of 1.0 ° C./min. Then, it was sieved with a 20 μm mesh, washed with water repeatedly, and then dried with a vacuum dryer to obtain toner particles. The volume average particle diameter of the obtained toner particles was 5.5 μm.
1.5 parts of colloidal silica (manufactured by Nippon Aerosil Co., Ltd., R972) was mixed with 100 parts of the obtained toner particles at a peripheral speed of 30 m / s for 2 minutes with a Henschel mixer to obtain Sian Toner 1.

<Manufacturing of Sian Toner 2>
In the production of Sian Toner 1, except that the amount of amorphous polyester resin dispersion used was changed from 330 parts to 305 parts and the amount of crystalline polyester resin dispersion 1 used was changed from 37.5 parts to 75 parts. The cyan toner 2 was obtained by the same operation as in the production of.

<Manufacturing of Sian Toner 3>
In the production of Sian Toner 1, Sian except that the amount of amorphous polyester resin dispersion used was changed from 330 parts to 180 parts and the amount of crystalline polyester resin dispersion 1 used was changed from 37.5 parts to 262.5 parts. The cyan toner 3 was obtained by the same operation as in the production of the toner 1.

<Manufacturing of Sian Toner 4>
In the production of the Sian Toner 1, the Sian Toner 4 was operated in the same manner as in the production of the Sian Toner 1 except that the crystalline polyester resin dispersion liquid 1: 37.5 parts was changed to the crystalline polyester resin dispersion liquid 2: 75 parts. Got

<Manufacturing of Sian Toner 5>
In the production of the Sian Toner 1, the Sian Toner 5 was operated in the same manner as in the production of the Sian Toner 1 except that the crystalline polyester resin dispersion liquid 1: 37.5 parts was changed to the crystalline polyester resin dispersion liquid 3: 75 parts. Got

<Manufacturing of Sian Toner 6>
In the production of the glitter toner 4 , 8.7 parts by mass of a crystalline polyester resin was added to make a glitter pigment (2173EA manufactured by Showa Aluminum Powder Co., Ltd.): 20 parts by mass and a Sian colorant dispersion: 5 parts by mass. A cyan toner 6 was obtained by the same operation as in the production of the brilliant toner 4 except for the modification.

<Manufacturing of Sian Toner 7>
In the production of the brilliant toner 5 , the brilliant pigment dispersion liquid: 2: 500 parts was changed to the Sian colorant dispersion liquid: 125 parts, and the content of the crystalline resin with respect to the total mass of the toner particles was the value shown in Table 3. The Sian toner 7 was obtained by the same operation as that of the brilliant toner 5 except that the crystalline resin was added so as to be .

<Manufacturing of Magenta Toner 1>
In the production of Sian Toner 1, the Sian colorant dispersion: 37.5 parts was changed to the magenta colorant dispersion: 37.5 parts, and the crystalline polyester resin dispersion: 1: 37.5 parts was changed to crystalline polyester. The magenta toner 1 was obtained by the same operation as in the production of the cyan toner 1 except that the resin dispersion was changed to 1:75 parts .

<Manufacturing of Yellow Toner 1>
In the production of Sian Toner 1, the Sian colorant dispersion: 37.5 parts was changed to the yellow colorant dispersion: 37.5 parts, and the crystalline polyester resin dispersion: 1: 37.5 parts was changed to crystalline polyester. The yellow toner 1 was obtained by the same operation as in the production of the cyan toner 1 except that the resin dispersion was changed to 1:75 parts .

<Manufacturing of carriers>
-Ferrite particles (volume average particle size: 35 μm): 100 parts-Toluene: 14 parts-Perfluorooctyl ethyl acrylate-methyl methacrylate copolymer (critical surface tension: 24 dyn / cm, copolymerization ratio 2: 8, weight average molecular weight 77000): 1.6 parts, carbon black (trade name: VXC-72, manufactured by Cabot, volume resistance: 100 Ωcm or less): 0.12 parts, crosslinked melamine resin particles (average particle size: 0.3 μm, toluene insoluble) ): 0.3 part First, carbon black was diluted with toluene and dispersed in a perfluorooctyl ethyl acrylate-methyl methacrylate copolymer with a sand mill. Next, each of the above components other than the ferrite particles was dispersed therein with a stirrer for 10 minutes to prepare a coating layer forming liquid. Next, the coating layer forming liquid and the ferrite particles were placed in a vacuum degassing type kneader, stirred at a temperature of 60 ° C. for 30 minutes, and then reduced pressure to distill off toluene to form a resin coating layer to obtain carriers. ..

<Preparation of developer>
For each brilliant toner, each Sian toner, magenta toner, and yellow toner, 36 parts of toner and 414 parts of carrier were put in a V blender, stirred for 20 minutes, and then sieved at 212 μm to prepare a developer. Made.

<Evaluation>
-Measurement of heat absorption QA, heat absorption QB, heat absorption QS, heat absorption QC-
A differential scanning calorimeter [MacScience: DSC3110, thermal analysis system 001] is used, the melting temperature of the mixture of indium and zinc is used to correct the temperature of the detector of the device, and the heat of fusion of indium is used to correct the calorific value. Was used. The sample (toner) is placed in an aluminum pan, the aluminum pan containing the sample and an empty aluminum pan for control are set, and the heat absorption peak temperature, heat absorption amount QA or heat absorption amount is set at a heating rate of 10 ° C./min. QB and heat absorption QS or heat absorption QC were measured respectively.
Table 2 shows the results of heat absorption for each toner.

-Evaluation of brilliance-
A developer of Color 1000 Press manufactured by Fuji Xerox Co., Ltd. was filled with a developer and fixed on coated paper (OK top coat + paper, surface roughness Rz = 1.98 μm, manufactured by Oji Paper Co., Ltd.). At a temperature of 180 ° C. (pressure roll temperature of 100 ° C.), a fine linear image portion of 60 μm was formed.
In each Example and Comparative Example, the brilliant toner and the colored toner contained in the developer used are shown in Table 3. Further, in Table 3, the numerical value in the column of the amount of crystalline resin indicates the content of the crystalline resin with respect to the total mass of the toner particles.
For the obtained fine line-shaped image portion, an image obtained by a microscope (manufactured by Leica) is image-analyzed, and the ratio of the total area of the metallic image portion that does not overlap with the color image portion to the total area of the metallic image portion having color. Was measured. The measurement results are shown in the column of microscopic images in Table 3. The smaller the ratio, the more the formation of the metallic image portion that does not overlap with the color image portion at the widthwise end of the fine line image portion is suppressed, and if it is 15 area% or less, the color is obtained when the image is visually observed. Almost no formation of a metallic image part that does not overlap with the image part can be seen.

From Table 3, when the heat absorption amount QA / heat absorption amount QB is 0 or more and less than 0.05, the formation of the metallic image portion that does not overlap with the color image portion at the widthwise end portion of the thin line image portion is suppressed. I understand.
Further, when the content of the crystalline resin with respect to the total mass of the colored toner particles is 3% by mass or more and 40% by mass or less, the metallic image does not overlap with the color image portion at the widthwise end portion of the fine line image portion. It can be seen that the formation of the portion is further suppressed.
Further, when the heat absorption amount QB is 2.0 J / g or more and 40 J / g or less, the formation of a metallic image portion that does not overlap with the color image portion at the widthwise end portion of the thin line image portion is further suppressed. I understand.
When the heat absorption amount QC of the colored toner is 5.0 J / g or more and 60 J / g or less, the formation of the metallic image portion that does not overlap with the color image portion at the widthwise end portion of the fine line image portion is further suppressed. I understand.

2 Bright toner particles 4 Bright pigments 111Y, 111M, 111C, 111K, 111B, 207 Photoreceptor 113, 222 Drive roll 112, 224 Support roll 114 Opposing roll 115Y, 115M, 115C, 115K, 115B Cleaning device 116 Intermediate transfer Cleaning device 117Y, 117M, 117C, 117K, 117B, 212 Primary transfer roll 118Y, 118M, 118C, 118K, 118B, 208 Charging roll 119Y, 119M, 119C, 119K, 119B, 209 Exposure device 120Y, 120M, 120C, 120K, 120B, 211 Developer 133 Intermediate Transfer Belt 134, 226 Secondary Transfer Roll 135, 228 Fixing Device 140Y, 140M, 140C, 140K, 140B Toner Cartridge 150Y, 150M, 150C, 150K, 150B Image Formation Unit 200 Process Cartridge 213 Photoreceptor Cleaning device 216 Mounting rail 217 Housing 218 Opening 300, P Recording paper

Claims (8)

A brilliant toner containing brilliant toner particles containing a flat brilliant pigment and a binder resin, and a brilliant toner.
Has a colored toner containing colored toner particles containing a colorant and a crystalline resin.
The content of the crystalline resin with respect to the total mass of the colored toner particles is 3% by mass or more and 40% by mass or less.
The endothermic QA in the region of the peak temperature ± 5 ° C. of the endothermic peak A of the crystalline resin contained in the brilliant toner particles detected by the differential scanning calorimetry, and the crystalline resin contained in the colored toner particles. A toner set in which the endothermic amount QB in the region of the peak temperature ± 5 ° C. of the endothermic peak B satisfies the following formula 1.
Equation 1: 0 ≤ heat absorption QA / heat absorption QB <0.05 The toner set according to claim 1, wherein the heat absorption amount QB is 2.0 J / g or more and 40 J / g or less. The toner set according to claim 1 or 2 , wherein the heat absorption amount QC of the colored toner measured by differential scanning calorimetry is 5.0 J / g or more and 60 J / g or less. The first electrostatic charge image developer containing the brilliant toner in the toner set according to any one of claims 1 to 3 .
The second electrostatic charge image developing agent containing the colored toner in the toner set for developing an electrostatic charge image according to any one of claims 1 to 3 .
Static charge image developer set with. The first toner cartridge containing the brilliant toner in the toner set for developing an electrostatic charge image according to any one of claims 1 to 3 .
A second toner cartridge containing the colored toner in the toner set for static charge image development according to any one of claims 1 to 3 .
Have,
A toner cartridge set that can be attached to and detached from the image forming device. The first developing means containing the first electrostatic image developing agent in the electrostatic image developing agent set according to claim 4 , and the first developing means.
The second developing means containing the second electrostatic image developing agent in the electrostatic image developing agent set according to claim 4 , and the second developing means.
With
A process cartridge that is attached to and detached from the image forming device. The first image forming means for forming a brilliant image by the brilliant toner in the electrostatic charge image developing toner set according to any one of claims 1 to 3 .
A second image forming means for forming a colored image with the colored toner in the toner set for static charge image development according to any one of claims 1 to 3 .
A transfer means for transferring the glittering image and the colored image onto a recording medium, and
A fixing means for fixing the glittering image and the colored image on the recording medium, and
An image forming apparatus comprising. The first image forming step of forming a brilliant image by the brilliant toner in the toner set for static charge image development according to any one of claims 1 to 3 .
The second image forming step of forming a colored image with the colored toner in the toner set for static charge image development according to any one of claims 1 to 3 .
A transfer step of transferring the glittering image and the colored image onto a recording medium, and
A fixing step of fixing the brilliant image and the colored image on the recording medium, and
An image forming method having.