JP2016156963A - Toner set for electrostatic charge image development, electrostatic charge image developer set, toner cartridge set, process cartridge set, image forming apparatus, and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner set for electrostatic charge image development that is excellent in photoluminescence of a vermilion image that presents photoluminescence.SOLUTION: There is provided a toner set for electrostatic charge image development containing: a photoluminescent toner that contains a photoluminescent pigment; and a red toner that has a color difference ΔE from PANTONE 199C in a CIE 1976 Labcolor system of 30 or less.SELECTED DRAWING: Figure 2

Description

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

  In electrophotographic image formation, colors are generally reproduced using toners of four colors, yellow, magenta, cyan, and black. Also, glitter toner is used to form an image having metallic luster.

For example, Patent Document 1 includes a glitter toner containing a glitter pigment and at least one color toner including a colorant, and the storage elastic modulus of the glitter toner at 120 ° C. is G′A, When the storage elastic modulus at 120 ° C. of the toner is G′B, the ratio of G′A to G′B (G′A / G′B) is 1 ≦ G′A / G′B ≦ 10 A toner set that satisfies the requirements is disclosed.
Patent Document 2 includes at least a first glitter toner containing at least a glitter pigment, and at least a second glitter toner including at least a glitter pigment and exhibiting a color different from that of the first glitter toner. A toner set is disclosed.

JP 2014-134636 A JP 2014-021300 A

  The present invention provides an electrostatic charge image development that is superior in the glitter of a vermilion red image exhibiting brilliancy compared to the case of forming a vermilion red image exhibiting brilliancy by using only yellow toner and magenta toner as color toners and brilliant toner. It is an object to provide a toner set for use.

The above problem is solved by the following means. That is,
The invention according to claim 1
A glitter toner containing a glitter pigment;
A red toner containing a colorant and having a color difference ΔE of 30 or less from PANTONE 199C in the color system when forming a solid image; and CIE1976L ^* a ^* b ^*
A toner set for developing electrostatic images.

The invention according to claim 2
The red toner is
C. I. Pigment Yellow 74,
C. I. PigmentRed 48: 1, C.I. I. Pigment Red 48: 3, C.I. I. PigmentRed 57: 1 and C.I. I. At least one selected from the group consisting of PigmentRed 184;
The toner set for developing electrostatic images according to claim 1, comprising:

The invention according to claim 3
The red toner is
C. as a yellow colorant I. Contains only Pigment Yellow 74,
C. as a red colorant I. PigmentRed 48: 1, C.I. I. Pigment Red 48: 3, C.I. I. Pigment Red 57: 1 or C.I. I. Containing only one of PigmentRed 184,
The toner set for developing electrostatic images according to claim 1 or 2.

The invention according to claim 4
A first electrostatic charge image developer comprising a glitter toner containing a glitter pigment;
A second electrostatic charge image developer containing a red toner that contains a colorant and has a color difference ΔE of 30 or less from PANTONE 199C in the color system when forming a solid image, and CIE1976L ^* a ^* b ^*
An electrostatic charge image developer set.

The invention according to claim 5
The red toner is
C. I. Pigment Yellow 74,
C. I. PigmentRed 48: 1, C.I. I. Pigment Red 48: 3, C.I. I. PigmentRed 57: 1 and C.I. I. At least one selected from the group consisting of PigmentRed 184;
The electrostatic charge image developer set according to claim 4, comprising:

The invention according to claim 6
The red toner is
C. as a yellow colorant I. Contains only Pigment Yellow 74,
C. as a red colorant I. PigmentRed 48: 1, C.I. I. Pigment Red 48: 3, C.I. I. Pigment Red 57: 1 or C.I. I. Containing only one of PigmentRed 184,
The electrostatic charge image developer set according to claim 4 or 5.

The invention according to claim 7 provides:
While using the electrostatic image developing toner set according to any one of claims 1 to 3,
A first toner cartridge that contains the glitter toner and is attached to and detached from the image forming apparatus;
A second toner cartridge that contains the red toner and is attached to and detached from the image forming apparatus;
Including toner cartridge set.

The invention according to claim 8 provides:
While using the electrostatic charge image developer set of any one of Claims 4-6,
An image forming apparatus comprising: a developing unit that contains the first electrostatic charge image developer, and that develops the electrostatic charge image formed on the surface of the image carrier as a toner image with the first electrostatic charge image developer; A first process cartridge to be attached to and detached from,
An image forming apparatus comprising: a developing unit that accommodates the second electrostatic charge image developer and develops the electrostatic charge image formed on the surface of the image carrier as a toner image with the second electrostatic charge image developer. A second process cartridge to be attached to and detached from,
Including process cartridge set.

The invention according to claim 9 is:
While using the electrostatic charge image developer set of any one of Claims 4-6,
An image carrier,
Charging means for charging the surface of the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
First developing means for accommodating the first electrostatic charge image developer, and developing the electrostatic image formed on the surface of the image carrier as a toner image by the first electrostatic charge image developer;
A second developing unit that contains the second electrostatic charge image developer and develops the electrostatic image formed on the surface of the image carrier as a toner image by the second electrostatic charge image developer;
Transfer means for transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
Fixing means for fixing the toner image transferred to the surface of the recording medium;
An image forming apparatus comprising:

The invention according to claim 10 is:
While using the electrostatic charge image developer set of any one of Claims 4-6,
A charging step for charging the surface of the image carrier;
An electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged image carrier;
A first developing step of developing the electrostatic image formed on the surface of the image carrier as a toner image with the first electrostatic image developer;
A second developing step of developing the electrostatic image formed on the surface of the image carrier as a toner image with the second electrostatic image developer;
A transfer step of transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
A fixing step of fixing the toner image transferred to the surface of the recording medium;
An image forming method comprising:

According to the first aspect of the present invention, the brightness of the reddish red image exhibiting brilliantness compared with the case of forming the reddish image exhibiting brilliantness by using only the yellow toner and magenta toner as the color toner and the brilliant toner. An electrostatic charge image developing toner set excellent in the above is provided.
According to the second and third aspects of the invention, the toner set for developing an electrostatic charge image includes a low-priced red toner that satisfies the color difference ΔE as compared with a case where the yellow pigment and the red pigment other than the pigment are contained. Is provided.

According to the fourth aspect of the present invention, the brightness of the reddish red image exhibiting brilliancy is formed as compared with the case of forming the reddish image exhibiting brilliantness by using only the yellow toner and magenta toner as the color toner and the bright toner. An electrostatic charge image developer set excellent in the above is provided.
According to the inventions according to claims 5 and 6, there is provided an electrostatic charge image developer set including a low-priced red toner satisfying the color difference ΔE as compared with a case where the pigment other than the pigment is contained as a yellow pigment and a red pigment. Provided.

  According to the seventh, eighth, ninth, and tenth aspects of the present invention, the color toner exhibits brightness as compared with the case of forming a red-red image that exhibits brightness by using only the yellow toner and magenta toner as the color toner and the glitter toner. Provided are a toner cartridge set, a process cartridge set, an image forming apparatus, and an image forming method that are excellent in reddish red image glitter.

It is a figure which shows an example of the process of forming the image which shows a glittering property by the electrophotographic system using the conventional toner set. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to an exemplary embodiment. It is a schematic block diagram which shows an example of the process cartridge which concerns on this embodiment.

  Embodiments of the invention will be described below. These descriptions and examples illustrate embodiments and do not limit the scope of the invention.

  In the present specification, (meth) acryl means acrylic or methacrylic, (meth) acrylic acid means acrylic acid or methacrylic acid, and (meth) acrylo means acrylo or methacrylo.

<Toner set for developing electrostatic image>
The electrostatic image developing toner set (also referred to as “toner set”) according to the present embodiment includes a toner containing a bright pigment (also referred to as “bright toner”), a colorant, and a solid image. CIE 1976 L ^* a ^* b ^* red toner having a color difference ΔE with PANTONE 199C in the color system of 30 or less (also referred to as “specific red toner”).

In the present embodiment, the color difference ΔE with respect to the PANTONE 199C in the CIE 1976 L ^* a ^* b ^* color system relating to the red toner is defined by the following equation.

In the above _{formula, L 1, a 1, b} 1 and _{L 2,} a _{2, b} 2 ^{are, CIE1976L * a * b * L} * values in a color system, ^{a *} value, a ^{b *} value. L ₁ , a ₁ , and b ₁ are L ^* value, a ^* value, and b ^* value of PANTONE 199C, and are values obtained by measuring the color sample PANTONE 199C with a reflection spectral densitometer. L ₂ , a ₂ , and b ₂ are L ^* value, a ^* value, and b ^* value of an image formed with red toner, and are values obtained by measuring the image with a reflection spectral densitometer. The color sample PANTONE 199C is a color sample in which an image is formed on coated paper, and an image formed with red toner is also formed on the coated paper, and the color difference ΔE is measured.

In this embodiment, the coordinate value of the CIE 1976 L ^* a ^* b ^* color system of red toner is measured by the following method.
After mixing red toner as a sample with a carrier, the toner is put in a developing device of an image forming apparatus, and coated on paper at a fixing temperature of 190 ° C. and a fixing pressure of 4.0 kg / cm ² , and a toner loading of 4.5 g / m ^2. A solid image (image having a density of 100%) is formed.
Then, the coordinate values of the CIE1976L ^* a ^* b ^* color system of the formed solid image are measured arbitrarily at 10 locations using a reflection spectral densitometer, and the L ^* value, a ^* value, and b ^* value are measured. The average value is calculated.

  The toner set according to the present embodiment has a bright red color image exhibiting brilliancy compared to a case where a red toner image having high brilliancy is formed by using only yellow toner and magenta toner as color toners and brilliant toner. Excellent. The reason is not clear, but is presumed as follows.

  In electrophotographic image formation, colors are reproduced by combining four color toners of yellow, magenta, cyan, and black, and in order to add glitter to an image, it is common to combine glitter toner. is there. A red-red image exhibiting glitter is usually formed by using yellow toner and magenta toner as color toners and combining the glitter toner therewith. When forming a reddish image exhibiting brilliancy using an intermediate transfer type image forming apparatus, generally, yellow toner / magenta toner / brilliant toner is formed on the intermediate transfer member from the side closer to the surface. After sequentially superposing the toners to form a superimposed toner image, the superimposed toner image is transferred to a recording medium, and the superimposed toner image transferred onto the recording medium is fixed to obtain a fixed image.

  By the way, normally, the glitter pigment contained in the glitter toner has a flat shape, and it is desirable that the glitter toner particles have a flat shape reflecting the shape of the glitter pigment. In order for a fixed image on a recording medium to exhibit glitter (specifically, both a glittery feeling (sparkle feeling) and an optical effect in which the hue changes depending on the viewing angle), It is desirable that the pigment is oriented so that its long axis is parallel to or close to the surface of the recording medium. As the preceding stage, in the superimposed toner image transferred onto the recording medium, the glittering toner particles are oriented so that their major axes are aligned or close to one direction. Is desirable.

FIGS. 1A and 1B are diagrams for explaining the above state. In FIG. 1A, a superimposed toner image 70 is formed on the recording medium 90. The superimposed toner image 70 is formed by superimposing a yellow toner layer 40 including yellow toner particles 41, a magenta toner layer 50 including magenta toner particles 51, and a glitter toner layer 60 including glitter toner particles 61. ing. The glittering toner particles 61 are oriented so that their major axes are aligned or close to one direction. Thereby, the flat glitter pigment 62 contained in the glitter toner particles 61 is also oriented so that the directions of the major axes thereof are aligned in one direction or a state close thereto. In FIG. 1A, the major axis of the glittering toner particles 61 is oriented parallel to the surface of the recording medium 90, but the orientation direction is not limited to this.
The glittering toner particles 61 are arranged so as to face the surface of the recording medium 90 while maintaining the aligned state by the pressure at which the image is fixed, and the glittering pigment 62 is shown in FIG. As described above, it is considered that the long axis is aligned in a state parallel to or close to the surface of the recording medium 90 and fixed in the fixed image 80, and as a result, the fixed image is likely to exhibit glitter.

As a result of studies by the present inventors, when transferring the superimposed toner image on the intermediate transfer member to the recording medium, the larger the toner amount of the superimposed toner image, the more the color toner particles enter the glittering toner layer. There was a tendency to prevent the alignment so that the long axes of the glittering toner particles were aligned in one direction or in a state close thereto. Further, the disorder in the orientation of the glitter pigment due to the disorder in the orientation of the glitter toner particles is fixed when the superimposed toner image is fixed, and as a result, the fixed image is considered to hardly exhibit the glitter. It was.
FIGS. 1C and 1D are diagrams for explaining the above state. In the superimposed toner image 70 shown in FIG. 1C, the magenta toner particles 51 and the yellow toner particles 41 enter the glittering toner layer 60, so that the major axis of the glittering toner particles 61 is in one direction. It is prevented from being oriented so as to be in an aligned state or a state close thereto. Therefore, the flat glittering pigment 62 is also prevented from being oriented so that its major axis is aligned in one direction or a state close thereto.
As shown in FIG. 1D, after the fixing process, the glitter pigment 62 is fixed in the fixed image 80 in a state where the orientation is disturbed. If the orientation of the glitter pigment 62 is disturbed in the fixed image 80, the incident light is irregularly reflected, so that the fixed image hardly exhibits glitter.

  Due to the mechanism described above, when forming a reddish image exhibiting brilliancy, if the reddish color is reproduced by combining yellow toner and magenta toner, the toner amount of the superimposed toner image is relatively large, and the fixing is performed. It is presumed that the orientation of the glitter pigment is disturbed in the image, and as a result, the fixed image is less likely to exhibit glitter.

On the other hand, the toner set according to this embodiment has a red toner (specific red toner) having a color difference ΔE of 30 or less with respect to PANTONE 199C in the CIE1976L ^* a ^* b ^* color system when the solid image is formed, and glitter. By combining with toner, a red-red image exhibiting glitter is formed. In the toner set according to the present embodiment, the red color reproduction, which has been conventionally performed by combining only the yellow toner and the magenta toner, is performed by using at least the specific red toner, and the bright toner is combined therewith. It imparts glitter to the red image.
When the toner set according to the present embodiment is used, the amount of toner required for color reproduction is smaller than in the case of reproducing vermilion red by combining only yellow toner and magenta toner. Therefore, it is difficult for color toner particles to enter the glitter toner layer during the transfer of the superimposed toner image, and the orientation of the glitter toner particles in the superimposed toner image, and thus the orientation of the glitter pigment in the fixed image. As a result, it is considered that the reddish red image exhibiting the glitter is excellent in glitter.
Note that the toner set according to the present embodiment may be combined with at least one of yellow toner and magenta toner to form a reddish image exhibiting glitter. Even in this case, the amount of toner required for color reproduction can be reduced as compared with the case where color reproduction is conventionally performed by combining only yellow toner and magenta toner.

  In addition, the toner set according to the present embodiment has a vermilion image in which a vermilion image and a glitter image are formed adjacent to each other as compared with a vermilion image that is formed with only yellow toner and magenta toner. A decrease in glitter (also referred to as “dullness”) is suppressed at the boundary between adjacent glitter images. The boundary portion is a portion where the orientation of the glitter pigment is likely to be disturbed due to the influence of the toner of the reddish image as compared with the central portion of the glitter image. According to the toner set according to the present embodiment, Since the amount of toner in the red-red image is small, it is presumed that the disorder of the orientation of the glitter pigment is suppressed at the boundary portion, and as a result, the dullness at the boundary portion is suppressed.

In the toner set according to the present embodiment, the red toner has a color difference ΔE of 30 or less with respect to PANTONE 199C in the CIE1976L ^* a ^* b ^* color system when a solid image is formed. It is difficult to reproduce the red color of the toner whose color difference ΔE is out of the above range, even if only one color of the toner or other color toner (for example, at least one of yellow toner and magenta toner) is applied. . Therefore, the color difference ΔE of the red toner in the toner set according to the present embodiment for forming a reddish red image exhibiting brilliancy is in the above range. The color difference ΔE is preferably as small as possible.

  The glitter toner included in the toner set according to the present embodiment preferably includes toner particles in which a glitter pigment is bound by a binder resin (bright toner particles), and the toner particles include a release agent, Other internal additives may be further contained. The glitter toner may be a glitter toner by using glitter toner particles, or by adding an external additive to the glitter toner particles. The glitter toner preferably contains substantially no colorant in addition to the glitter pigment, and more preferably the colorant other than the glitter pigment is below the detection limit. The glitter toner is preferably a silver toner exhibiting a silver color.

  The specific red toner included in the toner set according to the present embodiment preferably includes toner particles (red toner particles) containing a colorant and a binder resin, and the toner particles include a release agent and other internal additives. An agent may be further contained. For the specific red toner, the red toner particles may be the specific red toner, or an external additive may be externally added to the red toner particles to be the specific red toner. The specific red toner is a non-brilliant toner, that is, a toner that does not substantially contain a glitter pigment. In the specific red toner, the content of the glitter pigment is preferably below the detection limit.

  The toner set according to the present embodiment is at least one selected from a yellow toner, a magenta toner, a cyan toner, a black toner, and a second glitter toner (for example, a golden toner including a colorant and a glitter pigment and exhibiting a gold color). The toner set may further include one.

  Hereinafter, the configuration of the toner in this embodiment will be described in detail.

[Toner particles]
The glitter toner particles preferably have a glitter pigment bound with a binder resin, and may further contain a release agent and other internal additives. The glitter toner particles preferably contain substantially no colorant in addition to the glitter pigment, and more preferably the colorant other than the glitter pigment is below the detection limit. The glitter toner particles are preferably silver toner particles exhibiting a silver color.
The red toner particles contain a colorant and a binder resin, and may further contain a release agent and other internal additives. The red toner particles are non-brilliant toner particles, that is, toner particles substantially free of a glitter pigment. In the red toner particles, the content of the glitter pigment is preferably below the detection limit.
Hereinafter, the components contained in the glitter toner particles and the components contained in the red toner particles will be described. In the following description, matters common to the glittering toner particles and the red toner particles will be collectively referred to as toner particles.

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

  The content of the glitter pigment in the glitter toner particles is, for example, 1% by mass to 70% by mass, 5% by mass to 50% by mass, and 5% by mass to 30% by mass.

-Colorant-
The red toner particles preferably contain at least one selected from a yellow pigment and an orange pigment and at least one selected from a red pigment from the viewpoint of controlling the color difference ΔE within a range of 30 or less. In view of the above, the red toner particles are C.I. I. Pigment Yellow 74, C.I. I. PigmentRed 48: 1, C.I. I. Pigment Red 48: 3, C.I. I. PigmentRed 57: 1 and C.I. I. C. at least one selected from the group consisting of PigmentRed 184; I. Pigment Yellow 155 and C.I. I. At least one selected from the group consisting of Pigment Yellow 185, C.I. I. PigmentRed 238 and C.I. I. C. at least one selected from the group consisting of PigmentRed 146; I. Pigment Orange 38 and C.I. I. Or PigmentRed 185 is preferred.

From the viewpoint of controlling the color difference ΔE to a range of 30 or less using a relatively inexpensive pigment, the red toner particles are C.I. I. Pigment Yellow 74, C.I. I. PigmentRed 48: 1, C.I. I. Pigment Red 48: 3, C.I. I. PigmentRed 57: 1, and C.I. I. And at least one selected from the group consisting of PigmentRed 184.
From the viewpoint of easily controlling the color difference ΔE within a range of 30 or less using a relatively inexpensive pigment, the red toner particles are C.I. I. Pigment Yellow 74 only, and C.I. I. PigmentRed 48: 1, C.I. I. Pigment Red 48: 3, C.I. I. PigmentRed 57: 1, or C.I. I. It is preferable to contain only one of PigmentRed184.

  Hereinafter, C.I. I. Pigment Yellow 74 is also referred to as “PY 74”. I. PigmentRed 48: 1 is also referred to as “PR48: 1”. I. PigmentRed48: 3 is also referred to as “PR48: 3”. I. PigmentRed 57: 1 is also referred to as “PR57: 1”. I. PigmentRed 184 is also referred to as “PR184”.

An embodiment containing PY74 and at least one of PR48: 1, PR48: 3, PR57: 1 and PR184 The red toner particles are composed of PY74 and PR48: 1, PR48: 3, PR57: 1 and PR184. When containing at least one selected from the group, it is preferable to adjust the content of these pigments from the viewpoint of improving the red color reproducibility.
In the present embodiment, red toner particles, red toner, toner set, red developer, and developer set are excellent in vermilion red color reproducibility and PANTONE 199C in CIE1976L ^* a ^* b ^* color system. The color difference ΔE may be confirmed as an index. The color difference ΔE is preferably as small as possible, preferably 30 or less, more preferably 20 or less, more preferably 10 or less, more preferably 8 or less, and more preferably 7 or less.

  The red toner particles have a PY74 content of 0.25% by mass or more and less than 3.75% by mass, and PR48: 1, PR48: 3, PR57: 1 and The total content of PR184 is preferably 3.75% by mass or more and less than 8.25% by mass.

  When the red toner particles contain only PY74 as the yellow colorant and only PR48: 1 as the red colorant, the content of each colorant is as follows (A1- It is preferable to satisfy any one of 1) to (A1-2), and it is preferable to satisfy any one of the following (A2-1) to (A2-2) from the viewpoint of superior red color reproducibility.

(A1-1) PY74 is 0.25% by mass or more and less than 0.75% by mass, and PR48: 1 is 3.75% by mass or more and less than 5.75% by mass (A1-2) PY74 is 0.75% by mass or more. Less than 1.25% by mass and PR48: 1 is 3.75% by mass or more and less than 5.25% by mass

(A2-1) PY74 is 0.25% by mass or more and less than 0.75% by mass, and PR48: 1 is 4.25% by mass or more and less than 5.25% by mass (A2-2) PY74 is 0.75% by mass or more. 1.25% by mass and PR48: 1 is 3.75% by mass or more and less than 4.75% by mass

  When the red toner particles contain only PY74 as the yellow colorant and only PR48: 3 as the red colorant, the content of each colorant is as follows (B1- It is preferable to satisfy any one of 1) to (B1-3), and it is preferable to satisfy any of the following (B2-1) to (B2-2) from the viewpoint of superior red color reproducibility.

(B1-1) PY74 is 0.25 mass% or more and less than 0.75 mass%, and PR48: 3 is 3.75 mass% or more and less than 5.75 mass% (B1-2) PY74 is 0.75 mass% or more. Less than 1.25% by mass, PR48: 3 is 3.75% by mass or more and less than 5.25% by mass (B1-3) PY74 is 1.25% by mass or more and less than 1.75% by mass, and PR48: 3 is 3 .75 mass% or more and less than 4.25 mass%

(B2-1) PY74 is 0.25 mass% or more and less than 0.75 mass%, and PR48: 3 is 4.25 mass% or more and less than 5.75 mass% (B2-2) PY74 is 0.75 mass% or more. Less than 1.25% by mass, and PR48: 3 is 3.75% by mass or more and less than 5.25% by mass.

  When the red toner particles contain only PY74 as the yellow colorant and only PR57: 1 as the red colorant, the content of each colorant is as follows (C1- It is preferable to satisfy any one of 1) to (C1-5), and it is preferable to satisfy any one of the following (C2-1) to (C2-3) from the viewpoint of superior red color reproducibility.

(C1-1) PY74 is 1.25 mass% or more and less than 1.75 mass%, and PR57: 1 is 5.25 mass% or more and less than 6.25 mass% (C1-2) PY74 is 1.75 mass% or more. 2.25% by mass and PR57: 1 is 4.75% by mass or more and less than 7.25% by mass (C1-3) PY74 is 2.25% by mass or more and less than 2.75% by mass, and PR57: 1 is 5 .25 mass% or more and less than 7.75 mass% (C1-4) PY74 is 2.75 mass% or more and less than 3.25 mass%, and PR57: 1 is 5.75 mass% or more and less than 7.75 mass% (C1 -5) PY74 is 3.25 mass% or more and less than 3.75 mass%, and PR57: 1 is 6.75 mass% or more and less than 7.75 mass%.

(C2-1) PY74 is 1.75% by mass or more and less than 2.25% by mass, and PR57: 1 is 5.25% by mass or more and less than 6.75% by mass (C2-2) PY74 is 2.25% by mass or more. 2.75% by mass and PR57: 1 is 5.25% by mass or more and less than 7.25% by mass (C2-3) PY74 is 2.75% by mass or more and less than 3.25% by mass, and PR57: 1 is 6 .25 mass% or more and less than 7.75 mass%

  When the red toner particles contain only PY74 as the yellow colorant and only PR184 as the red colorant, the content of each colorant is the following (D1-1) in that it is excellent in vermilion color reproducibility. It is preferable to satisfy any one of (D1-4), and it is preferable to satisfy any one of the following (D2-1) to (D2-3) from the viewpoint of superior red color reproducibility.

(D1-1) PY74 is 1.25 mass% or more and less than 1.75 mass%, and PR184 is 5.25 mass% or more and less than 6.25 mass% (D1-2) PY74 is 1.75 mass% or more and 2. Less than 25% by mass, PR184 is 5.25% by mass or more and less than 7.25% by mass (D1-3) PY74 is 2.25% by mass or more and less than 2.75% by mass, and PR184 is 5.25% by mass or more 7 Less than .75% by mass (D1-4) PY74 is not less than 2.75% by mass and less than 3.25% by mass, and PR184 is not less than 5.75% by mass and less than 8.25% by mass.

(D2-1) PY74 is 1.75 mass% or more and less than 2.25 mass%, and PR184 is 5.25 mass% or more and less than 7.25 mass% (D2-2) PY74 is 2.25 mass% or more and 2. Less than 75% by mass, PR184 is 5.75% by mass or more and less than 7.75% by mass (D2-3) PY74 is 2.75% by mass or more and less than 3.25% by mass, and PR184 is 6.25% by mass or more 7 Less than 75% by mass

The red toner particles may contain other colorants other than PY74, PR48: 1, PR48: 3, PR57: 1, and PR184. Other colorants may be pigments or dyes, and pigments are desirable from the viewpoint of light resistance and water resistance.
Examples of other colorants include white pigments such as SiO ₂ (silica), TiO ₂ (titania), and Al ₂ O ₃ (alumina); I. Red pigments and dyes such as CI Pigment Red 122 and Rose Bengal; I. Pigment yellow 97, C.I. I. CI yellow pigments and dyes such as CI Pigment Yellow 12, quinoline yellow and chrome yellow; green pigments and dyes such as malachite green oxalate; I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 3, blue pigments and dyes such as aniline blue, calcoyl blue, ultramarine blue, phthalocyanine blue, and methylene blue chloride; black pigments and dyes such as carbon black, lamp black, and nigrosine;

White pigments such as silica, titania, and alumina may be added to the red toner particles for purposes other than coloring (for example, toner charge control).
The total amount of the white pigment in the red toner particles is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, from the viewpoint of facilitating red color reproduction. The following is more desirable and 1% by mass or less is particularly desirable.

  The content of the colorant other than PY74, PR48: 1, PR48: 3, PR57: 1, PR184, and white pigment in the red toner particles is selected from the viewpoint of facilitating the red color reproduction. 1% by mass or less is desirable, 0.5% by mass or less is more desirable, 0.1% by mass or less is more desirable, and it is further desirable that it is substantially free, and it is further below the detection limit. Desirably, 0% by mass is particularly desirable.

  The total amount of PY74, PR48: 1, PR48: 3, PR57: 1, PR184, and white pigment in the total amount of the colorant in the red toner particles is 85% from the viewpoint of facilitating red-red color reproduction. % Or more is desirable, 90 mass% or more is more desirable, 95 mass% or more is further desirable, 99 mass% or more is further desirable, and 100 mass% (that is, PY74, PR48: 1, PR48: 3, PR57: 1, PR184). And no colorants other than white pigments) are particularly desirable.

  The total amount of PY74, PR48: 1, PR48: 3, PR57: 1, and PR184 in the total amount of the colorant in the red toner particles is 30% by mass or more from the viewpoint of facilitating red color reproduction. Desirably, 40% by mass or more is more desirable, 50% by mass or more is further desirable, 60% by mass or more is further desirable, 70% by mass is further desirable, 80% by mass is further desirable, 90% by mass is further desirable, and 100% by mass. (That is, no other colorant other than PY74, PR48: 1, PR48: 3, PR57: 1, and PR184) is particularly desirable.

-Binder resin-
Examples of the binder resin for toner particles include polyester resin, epoxy resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, polystyrene, styrene- (meth) acrylic acid alkyl copolymer, and styrene- (meth) acrylonitrile. Examples thereof include a copolymer, a styrene-butadiene copolymer, and a styrene-maleic anhydride copolymer. These resins may be used alone or in combination of two or more. The binder resin of the glitter toner particles and the binder resin of the non-brilliant toner particles may be the same or different.

  A polyester resin is suitable as the binder resin. As a polyester resin, the condensation polymer of polyhydric carboxylic acid and polyhydric alcohol is mentioned, for example. As the polyester resin, a commercially available product may be used, or a synthesized resin may be used.

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

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

The glass transition temperature (Tg) of the polyester resin is preferably 50 ° C. or higher and 80 ° C. or lower, and more preferably 50 ° C. or higher and 65 ° C. or lower.
The glass transition temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC). More specifically, it is determined by “extrapolated glass transition start temperature” described in JIS K7121-1987 “Method for Measuring Glass Transition Temperature”.

The weight average molecular weight (Mw) of the polyester resin is preferably from 5,000 to 1,000,000, and more preferably from 7,000 to 500,000.
The number average molecular weight (Mn) of the polyester resin is preferably 2,000 or more and 100,000 or less.
The molecular weight distribution Mw / Mn of the polyester resin is preferably 1.5 or more and 100 or less, and more preferably 2 or more and 60 or less.
The weight average molecular weight and number average molecular weight of the resin are measured by gel permeation chromatography (GPC). The molecular weight measurement by GPC is performed using HLC-8120 manufactured by Tosoh Corporation as a measuring device, TSKgel SuperHM-M15 cm manufactured by Tosoh Corporation as a column, and tetrahydrofuran as a solvent. The weight average molecular weight and the number average molecular weight are calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample from this measurement result.

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

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

The melting temperature of the release agent is preferably 50 ° C. or higher and 110 ° C. or lower, and more preferably 60 ° C. or higher and 100 ° C. or lower.
The melting temperature of the release agent is determined by the “melting peak temperature” described in the method for determining the melting temperature in JIS K7121-1987 “Method for measuring the transition temperature of plastic” from the DSC curve obtained by differential scanning calorimetry (DSC). Ask.

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

-Inorganic oxide particles-
The toner particles may include inorganic oxide particles. Examples of the inorganic oxide include SiO ₂ (silica), TiO ₂ (titania), Al ₂ O ₃ (alumina), CuO, ZnO, SnO ₂ , CeO ₂ , Fe ₂ O ₃ , MgO, BaO, CaO, K. Metal oxides such as ₂ O, Na ₂ O, ZrO ₂ , CaO.SiO ₂ , K ₂ O. (TiO ₂ ) n, Al ₂ O ₃ .2SiO ₂ , CaCO ₃ , MgCO ₃ , BaSO ₄ , MgSO ₄ Can be mentioned.
The surface of the inorganic oxide particles may not be previously hydrophobized or may be hydrophobized in advance.

  The content of the inorganic oxide particles in the toner particles is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, from the viewpoint of hardly affecting the color of the toner. % Or less is more desirable, and 1 mass% or less is particularly desirable.

-Other additives-
Examples of other additives include known additives such as a magnetic material, a charge control agent, and inorganic powder. These additives are contained in the toner particles as internal additives.

-Toner particle characteristics-
The toner particles may be toner particles having a single layer structure, or toner particles having a so-called core / shell structure composed of a core (core particle) and a coating layer (shell layer) covering the core. May be. The toner particles having a core / shell structure include, for example, a core that includes a binder resin and, if necessary, other additives such as a colorant and a release agent, and a binder resin. And a coating layer.

The volume average particle diameter (D50v) of the glittering toner particles is preferably 3 μm or more and 20 μm or less, and more preferably 7 μm or more and 15 μm or less.
The volume average particle size (D50v) of the red toner particles is preferably 2 μm or more and 10 μm or less, and more preferably 4 μm or more and 8 μm or less.

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

  The shape factor SF1 of the toner particles is preferably 110 or more and 150 or less, and more preferably 120 or more and 140 or less.

The shape factor SF1 is obtained by the following equation.
Formula: SF1 = (ML ² / A) × (π / 4) × 100
In the above formula, ML represents the absolute maximum length of the toner, and A represents the projected area of the toner.
Specifically, the shape factor SF1 is quantified mainly by analyzing a microscope image or a scanning electron microscope image using an image analyzer, and is calculated as follows. That is, by capturing an optical microscope image of particles dispersed on the surface of a slide glass into a Luzex image analyzer using a video camera, obtaining the maximum length and projected area of 100 particles, calculating by the above formula, and obtaining the average value can get.

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

The surface of the inorganic particles as an external additive is preferably subjected to a hydrophobic treatment. The hydrophobic treatment is performed, for example, by immersing inorganic particles in a hydrophobic treatment agent. The hydrophobizing agent is not particularly limited, and examples thereof include silane coupling agents, silicone oils, titanate coupling agents, aluminum coupling agents and the like. These may be used individually by 1 type and may use 2 or more types together.
The amount of the hydrophobizing agent is, 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 external additives include resin particles (resin particles such as polystyrene, PMMA, and melamine resin), cleaning activators (for example, metal salts of higher fatty acids typified by zinc stearate, particles of a fluorine-based high molecular weight substance), and the like. Can be mentioned.

  The external additive amount of the external additive is, for example, preferably 0.01% by mass or more and 5% by mass or less, and more preferably 0.01% by mass or more and 2% by mass or less with respect to the toner particles.

[Toner Production Method]
The glitter toner may be a toner obtained by producing glitter toner particles and using the toner particles as a toner, or by adding an external additive to the toner particles. Further, the specific red toner may be produced by producing red toner particles and using the toner particles as a toner, or by adding an external additive to the toner particles.

  The toner particles may be produced by any of a dry production method (for example, a kneading pulverization method) and a wet production method (for example, an aggregation coalescence method, a suspension polymerization method, a dissolution suspension method, etc.) There is no restriction | limiting in particular in these manufacturing methods, A well-known manufacturing method is employ | adopted. Among these, it is preferable to obtain toner particles by an aggregation coalescence method.

Specifically, for example, when producing glitter toner particles by an aggregation coalescence method,
A step of preparing a resin particle dispersion in which resin particles serving as a binder resin are dispersed (resin particle dispersion preparation step);
A step of preparing a bright pigment dispersion in which the bright pigment is dispersed (a bright pigment dispersion preparing step);
A step of aggregating the resin particles and the bright pigment in a dispersion obtained by mixing the resin particle dispersion and the bright pigment dispersion to form aggregated particles (aggregated particle forming step);
The aggregated particle dispersion liquid in which the aggregated particles are dispersed is heated, and the aggregated particles are fused and united to form toner particles (a uniting and uniting step), thereby producing glittering toner particles.
When the red toner particles are produced by the aggregation and coalescence method, in place of the glitter pigment dispersion preparation step, a step of preparing a colorant dispersion in which a colorant is dispersed (colorant dispersion preparation step) is performed. Instead of the glitter pigment dispersion, a colorant dispersion may be used to perform the aggregated particle formation step and the fusion / unification step.

  Details of each step will be described below. In the following description, a method for obtaining toner particles containing a release agent will be described. However, the release agent is used as necessary. Of course, you may use other additives other than a mold release agent.

-Preparation step of resin particle dispersion-
In the resin particle dispersion preparation step, a resin particle dispersion in which resin particles that are binder resins are dispersed is prepared. The resin particle dispersion is prepared, for example, by dispersing resin particles in a dispersion medium using a surfactant.

Examples of the dispersion medium used for the resin particle dispersion include an aqueous medium.
Examples of the aqueous medium include water such as distilled water and ion exchange water, and alcohols. These may be used individually by 1 type and may use 2 or more types together.

Examples of the surfactant include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol And nonionic surfactants such as polyphenols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, an anionic surfactant and a cationic surfactant are particularly mentioned. The nonionic surfactant may be used in combination with an anionic surfactant or a cationic surfactant.
Surfactant may be used individually by 1 type and may use 2 or more types together.

Examples of the method for dispersing the resin particles in the dispersion medium in the resin particle dispersion include general dispersion methods such as a rotary shear type homogenizer, a ball mill having a medium, a sand mill, and a dyno mill. Depending on the type of resin particles, the resin particles may be dispersed in the resin particle dispersion using, for example, a phase inversion emulsification method.
In the phase inversion emulsification method, a resin to be dispersed is dissolved in a hydrophobic organic solvent in which the resin is soluble, a base is added to the organic continuous phase (O phase), and the aqueous medium (W In this method, the resin is converted from W / O to O / W (so-called phase inversion) to form a discontinuous phase, and the resin is dispersed in the form of particles in an aqueous medium. .

The volume average particle size of the resin particles dispersed in the resin particle dispersion is preferably 0.01 μm or more and 1 μm or less, more preferably 0.08 μm or more and 0.8 μm or less, and further preferably 0.1 μm or more and 0.6 μm or less. .
The volume average particle size of the resin particles is a volume with respect to a divided particle size range (channel) using a particle size distribution obtained by measurement with a laser diffraction particle size distribution measuring apparatus (for example, LA-700 manufactured by HORIBA, Ltd.). A cumulative distribution is drawn from the side of the small particle diameter, and the particle diameter of 50% in volume with respect to all particles is defined as the volume average particle diameter D50v. The volume average particle size of the particles in the other dispersion is also measured in the same manner.

  5 mass% or more and 50 mass% or less are preferable, for example, and, as for content of the resin particle contained in the resin particle dispersion liquid, 10 mass% or more and 40 mass% or less are more preferable.

  In the same manner as the method for preparing the resin particle dispersion, a glitter pigment dispersion, a colorant dispersion, and a release agent dispersion are also prepared. That is, the dispersion medium, surfactant, dispersion method, particle volume average particle diameter, and particle content of the glitter pigment dispersion, the colorant dispersion, and the release agent dispersion are those of the resin particle dispersion. It is the same.

-Aggregated particle formation process-
When producing glitter toner particles, the resin particle dispersion and the glitter pigment dispersion are mixed, the resin particles and the glitter pigment are hetero-aggregated in the mixture dispersion, and the resin particles and the glitter pigment are combined. Aggregated particles are formed.
When producing red toner particles, the resin particle dispersion and the colorant dispersion are mixed, the resin particles and the colorant particles are heteroaggregated in the mixed dispersion, and the aggregation includes the resin particles and the colorant particles. Form particles.
In any of the above cases, the release agent dispersion may also be mixed to include the release agent in the aggregated particles.

Specifically, for example, a flocculant is added to the mixed dispersion, and the pH of the mixed dispersion is adjusted to acidic (for example, pH 2 to 5), and a dispersion stabilizer is added as necessary. The glass particles are heated to a temperature close to the glass transition temperature (specifically, for example, the glass transition temperature of the resin particles is −30 ° C. or higher and the glass transition temperature is −10 ° C. or lower), and the particles dispersed in the mixed dispersion are agglomerated. To form aggregated particles.
In the agglomerated particle forming step, for example, the agglomerated agent is added at room temperature (for example, 25 ° C.) while stirring the mixed dispersion with a rotary shearing homogenizer, and the pH of the mixed dispersion is adjusted to be acidic (for example, pH 2 to 5). In addition, heating may be performed after adding a dispersion stabilizer as necessary.

Examples of the flocculant include a surfactant having a polarity opposite to that of the surfactant contained in the mixed dispersion, an inorganic metal salt, and a bivalent or higher-valent metal complex. When a metal complex is used as the aggregating agent, the amount of the surfactant used is reduced and the charging characteristics are improved.
An additive that forms a complex or similar bond with the metal ion of the flocculant may be used together with the flocculant. As this additive, a chelating agent is preferably used.

Examples of inorganic metal salts include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate; inorganic metal salts such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide Polymer; and the like.
A water-soluble chelating agent may be used as the chelating agent. Examples of the chelating agent include oxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid; aminocarboxylic acids such as iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), and ethylenediaminetetraacetic acid (EDTA); .
For example, the addition amount of the chelating agent is preferably 0.01 parts by mass or more and 5.0 parts by mass or less, and more preferably 0.1 parts by mass or more and less than 3.0 parts by mass with respect to 100 parts by mass of the resin particles.

-Fusion / unification process-
Next, the agglomerated particle dispersion in which the agglomerated particles are dispersed is heated to, for example, a glass transition temperature or higher of the resin particles (for example, a temperature of 10 ° C. to 30 ° C. higher than the glass transition temperature of the resin particles). Fusing and coalescing to form toner particles.

Through the above steps, toner particles are obtained.
In addition, after obtaining the aggregated particle dispersion liquid in which the aggregated particles are dispersed, the aggregated particle dispersion liquid and the resin particle dispersion liquid in which the resin particles are dispersed are further mixed, and the resin particles are further added to the surface of the aggregated particles. A process of aggregating to adhere to form second aggregated particles, and heating the second aggregated particle dispersion in which the second aggregated particles are dispersed to fuse and coalesce the second aggregated particles. The toner particles may be manufactured through a step of forming toner particles having a core / shell structure.

After completion of the coalescence / union process, the toner particles formed in the solution are subjected to a known washing process, solid-liquid separation process, and drying process to obtain dried toner particles.
In the washing step, it is preferable to sufficiently perform substitution washing with ion-exchanged water from the viewpoint of chargeability. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, or the like is preferably performed from the viewpoint of productivity. Also, the drying process is not particularly limited, but from the viewpoint of productivity, freeze drying, flash jet drying, fluidized drying, vibration fluidized drying, or the like is preferably performed.

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

<Static image developer set>
The electrostatic image developer set (also referred to as “developer set”) according to this embodiment includes at least the toner set according to this embodiment.
That is, the developer set according to the present embodiment includes at least a first electrostatic image developer including a glitter toner containing a glitter pigment, and a second electrostatic image developer including a specific red toner. Including.
The developer set according to this embodiment includes a yellow developer, a magenta developer, a cyan developer, a black developer, and a second glitter developer (for example, a gold developer that includes a colorant and a glitter pigment and exhibits a gold color). A developer set further including at least one selected from (agent) may be used.

In the present embodiment, the first electrostatic charge image developer (also referred to as “bright developer”) may be a one-component developer including only a bright toner containing a bright pigment, A two-component developer in which a toner and a carrier are mixed may be used.
In the present embodiment, the second electrostatic image developer (also referred to as “red developer”) may be a one-component developer containing only a specific red toner, or the toner and a carrier are mixed. A two-component developer may be used.

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

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

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

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

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

<Image Forming Apparatus / Image Forming Method>
The image forming apparatus according to the present embodiment is applied with the developer set according to the present embodiment, and includes a mechanism for forming an image on the surface of the recording medium with at least a glitter developer and a red developer.
That is, the image forming apparatus according to the present embodiment includes an image carrier, a charging unit that charges the surface of the image carrier, and an electrostatic image forming unit that forms an electrostatic image on the charged surface of the image carrier. When,
First developing means for accommodating the first electrostatic charge image developer, and developing the electrostatic image formed on the surface of the image carrier as a toner image by the first electrostatic charge image developer;
A second developing unit that contains the second electrostatic charge image developer and develops the electrostatic image formed on the surface of the image carrier as a toner image by the second electrostatic charge image developer;
Transfer means for transferring the toner image formed on the surface of the image carrier to the surface of the recording medium, and fixing means for fixing the toner image transferred to the surface of the recording medium.
Hereinafter, items common to the first developing unit and the second developing unit will be collectively referred to as “developing unit”.

In the image forming apparatus according to this embodiment, the developer set according to this embodiment is used.
A charging step for charging the surface of the image carrier, and an electrostatic charge image forming step for forming an electrostatic image on the surface of the charged image carrier,
A first developing step of developing the electrostatic image formed on the surface of the image carrier as a toner image with the first electrostatic image developer;
A second developing step of developing the electrostatic image formed on the surface of the image carrier as a toner image with the second electrostatic image developer;
A transfer step for transferring the toner image formed on the surface of the image carrier to the surface of the recording medium and a fixing step for fixing the toner image transferred on the surface of the recording medium are performed.

  The image forming apparatus according to the present embodiment may be a method using one image carrier or a tandem method using a plurality of image carriers. When the image forming apparatus according to the present embodiment is a tandem system, the image forming apparatus includes a plurality of image carriers, a plurality of charging units corresponding to each of the plurality of image carriers, and a plurality of electrostatic charge images. A charging unit and an electrostatic charge image forming step are performed for each of the plurality of image holding members. When the image forming apparatus according to the present embodiment uses a single image carrier, the image forming apparatus repeats the charging process to the transfer process for the number of colors of toner used for image formation.

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

  In the image forming apparatus according to the present embodiment, for example, the part including the developing unit may have a cartridge structure (process cartridge) that is detachable from the image forming apparatus.

  The image forming apparatus according to this embodiment further uses at least one selected from a yellow developer, a magenta developer, a cyan developer, a black developer, and a second glitter developer (for example, a gold developer). It may be a forming device.

  Hereinafter, an example of the image forming apparatus according to the present embodiment will be described, but the present invention is not limited to this. In the following description, the main part shown in the figure will be described, and the description of other parts will be omitted. In the following description, an example of a toner set according to the present embodiment will be described by referring to the glitter toner as “silver toner” and the specific red toner as “red toner”.

FIG. 2 is a schematic configuration diagram illustrating the image forming apparatus according to the present embodiment, and is a diagram illustrating an image forming apparatus of a 6-tandem type and an intermediate transfer type.
The image forming apparatus shown in FIG. 2 is based on the color-separated image data and each color of yellow (Y), magenta (M), red (R), cyan (C), black (K), and silver (G). Electrophotographic first to sixth image forming units 10Y, 10M, 10R, 10C, 10K, and 10G (image forming means) that output images are provided. These image forming units (hereinafter sometimes simply referred to as “units”) 10Y, 10M, 10R, 10C, 10K, and 10G are arranged in parallel at a predetermined distance from each other in the horizontal direction. These units 10Y, 10M, 10R, 10C, 10K, and 10G may be process cartridges that are detachable from the image forming apparatus.

Under each unit 10Y, 10M, 10R, 10C, 10K, and 10G, an intermediate transfer belt (an example of an intermediate transfer member) 20 is extended through each unit. The intermediate transfer belt 20 is wound around a drive roll 22, a support roll 23, and a counter roll 24 that are in contact with the inner surface of the intermediate transfer belt 20, and travels in a direction from the first unit 10Y to the sixth unit 10G. It is supposed to be. An intermediate transfer member cleaning device 21 is provided on the image holding surface side of the intermediate transfer belt 20 so as to face the drive roll 22.
Each unit 10Y, 10M, 10R, 10C, 10K, and 10G developing device (an example of a developing unit) 4Y, 4M, 4R, 4C, 4K, and 4G includes toner cartridges 8Y, 8M, 8R, 8C, 8K, Each toner of yellow, magenta, red, cyan, black, and silver contained in 8G is supplied.

  Since the first to sixth units 10Y, 10M, 10R, 10C, 10K, and 10G have the same configuration, operation, and action, they are disposed upstream in the intermediate transfer belt traveling direction. The first unit 10Y that forms a yellow image will be described as a representative.

The first unit 10Y has a photoreceptor 1Y that functions as an image holding member. Around the photoreceptor 1Y, a charging roll (an example of a charging unit) 2Y for charging the surface of the photoreceptor 1Y to a predetermined potential, and the charged surface is exposed by a laser beam based on the color-separated image signal. An exposure device (an example of an electrostatic image forming unit) 3Y that forms an electrostatic charge image, a developing device (an example of a developing unit) 4Y that supplies toner to the electrostatic image and develops the electrostatic image, and a developed toner image A primary transfer roll (an example of a primary transfer unit) 5Y that is transferred onto the intermediate transfer belt 20 and a photoconductor cleaning device (an example of a cleaning unit) 6Y that removes toner remaining on the surface of the photoconductor 1Y after the primary transfer are sequentially arranged. Has been.
The primary transfer roll 5Y is disposed inside the intermediate transfer belt 20, and is provided at a position facing the photoreceptor 1Y. A bias power source (not shown) for applying a primary transfer bias is connected to the primary transfer rolls 5Y, 5M, 5R, 5C, 5K, and 5G of each unit. Each bias power source changes the value of the transfer bias applied to each primary transfer roll under the control of a control unit (not shown).

Hereinafter, an operation of forming a yellow image in the first unit 10Y will be described.
First, prior to operation, the surface of the photoreceptor 1Y is charged to a potential of −600V to −800V by the charging roll 2Y.
The photoreceptor 1Y is formed by laminating a photosensitive layer on a conductive base (for example, a volume resistivity of 1 × 10 ⁻⁶ Ωcm or less at 20 ° C.). This photosensitive layer usually has a high resistance (general resin resistance), but has a property of changing the specific resistance of the portion irradiated with the laser beam when irradiated with the laser beam. Therefore, a laser beam is irradiated from the exposure device 3Y to the surface of the charged photoreceptor 1Y in accordance with yellow image data sent from a control unit (not shown). Thereby, an electrostatic charge image of a yellow image pattern is formed on the surface of the photoreceptor 1Y.

The electrostatic charge image is an image formed on the surface of the photoreceptor 1Y by charging. The specific resistance of the irradiated portion of the photosensitive layer is lowered by the laser beam from the exposure device 3Y, and the surface of the photoreceptor 1Y is charged. This is a so-called negative latent image formed by the remaining charge flowing, while the charge remaining in the portion not irradiated with the laser beam remains.
The electrostatic charge image formed on the photoreceptor 1Y rotates to a predetermined development position as the photoreceptor 1Y travels. At this development position, the electrostatic charge image on the photoreceptor 1Y is developed and visualized as a toner image by the developing device 4Y.

  In the developing device 4Y, for example, an electrostatic charge image developer containing at least yellow toner and a carrier is accommodated. The yellow toner is triboelectrically charged by being agitated inside the developing device 4Y, and has a charge of the same polarity (negative polarity) as the charged electric charge on the photoreceptor 1Y, and has a developer roll (a developer holding member). Example) is held on. As the surface of the photoreceptor 1Y passes through the developing device 4Y, the yellow toner is electrostatically attached to the latent image portion on the surface of the photoreceptor 1Y, and the latent image is developed with the yellow toner. . The photoreceptor 1Y on which the yellow toner image is formed continues to run at a predetermined speed, and the toner image developed on the photoreceptor 1Y is conveyed to a predetermined primary transfer position.

When the yellow toner image on the photoreceptor 1Y is transported to the primary transfer position, a primary transfer bias is applied to the primary transfer roll 5Y, and an electrostatic force from the photoreceptor 1Y toward the primary transfer roll 5Y acts on the toner image, thereby causing the The toner image on the body 1Y is transferred onto the intermediate transfer belt 20. The transfer bias applied at this time has a (+) polarity opposite to the polarity (−) of the toner, and is controlled to, for example, +10 μA by the control unit (not shown) in the first unit 10Y.
On the other hand, the toner remaining on the photoreceptor 1Y is removed and collected by the photoreceptor cleaning device 6Y.

The primary transfer bias applied to the primary transfer rolls 5M, 5R, 5C, 5K, and 5G after the second unit 10M is also controlled according to the first unit.
Thus, the intermediate transfer belt 20 onto which the yellow toner image has been transferred by the first unit 10Y is sequentially conveyed through the second to sixth units 10M, 10R, 10C, 10K, and 10G, and the toner images of the respective colors are superimposed. Multiple transfer.

  The intermediate transfer belt 20 onto which the six color toner images have been transferred in a multiple manner through the first to sixth units includes the intermediate transfer belt 20, the opposing roll 24 in contact with the inner surface of the intermediate transfer belt, and the image holding surface of the intermediate transfer belt 20. To a secondary transfer portion composed of a secondary transfer roll (an example of secondary transfer means) 26 arranged on the side. On the other hand, recording paper (an example of a recording medium) P is fed at a predetermined timing into a gap where the secondary transfer roll 26 and the intermediate transfer belt 20 are in contact with each other via a supply mechanism, and the secondary transfer bias is opposed to the opposing roll. 24. The transfer bias applied at this time is a (−) polarity that is the same polarity as the polarity (−) of the toner, and an electrostatic force from the intermediate transfer belt 20 toward the recording paper P acts on the toner image, and the transfer bias is applied to the intermediate transfer belt 20. The toner image is transferred onto the recording paper P. The secondary transfer bias at this time is determined according to the resistance detected by a resistance detecting means (not shown) for detecting the resistance of the secondary transfer portion, and is voltage-controlled.

  Thereafter, the recording paper P is sent to a pressure contact portion (nip portion) of a pair of fixing rolls in a fixing device (an example of a fixing unit) 28, and the toner image is fixed on the recording paper P to form a fixed image. .

Examples of the recording paper P to which the toner image is transferred include plain paper used in electrophotographic copying machines, printers, and the like. As the recording medium, in addition to the recording paper P, an OHP sheet and the like are also included.
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. For example, coated paper in which the surface of plain paper is coated with resin, art paper for printing, etc. Preferably used.

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

<Process cartridge set / toner cartridge set>
The process cartridge set according to the present embodiment uses the developer set according to the present embodiment, accommodates the glitter developer, and toners the electrostatic charge image formed on the surface of the image carrier by the glitter developer. A first process cartridge that includes a developing unit that develops an image and is attached to and detached from the image forming apparatus, and a red developer are accommodated. The electrostatic image formed on the surface of the image carrier by the red developer is converted into a toner image. And a second process cartridge that is detachably attached to the image forming apparatus.

  In the process cartridge set according to the present embodiment, the first and second process cartridges are not limited to the above-described configuration. For example, an image holding member, a charging unit, and an electrostatic charge image forming unit, as necessary. And at least one selected from other means such as a transfer means and the transfer means.

  Hereinafter, examples of the first and second process cartridges in the process cartridge set according to the present embodiment will be described, but the present invention is not limited thereto. In the following description, the main part shown in the figure will be described, and the description of other parts will be omitted.

FIG. 3 is a schematic configuration diagram showing a process cartridge in the present embodiment.
The process cartridge 200 shown in FIG. 3 is provided around the photosensitive member 107 and the photosensitive member 107 by, for example, a housing 117 provided with an attachment rail 116 and an opening 118 for exposure. A charging roller 108 (an example of a charging unit), a developing device 111 (an example of a developing unit), and a photoconductor cleaning device 113 (an example of a cleaning unit) are integrally combined and held to form a cartridge. Yes.
In FIG. 3, 109 is an exposure device (an example of an electrostatic charge image forming unit), 112 is a transfer device (an example of a transfer unit), 115 is a fixing device (an example of a fixing unit), and 300 is a recording paper (an example of a recording medium). Is shown.

Next, the toner cartridge set according to the present embodiment will be described.
The toner cartridge set according to the present embodiment uses the toner set according to the present embodiment, and stores a glitter toner, a first toner cartridge that is attached to and detached from the image forming apparatus, a specific red toner, and an image. And a second toner cartridge that is detachably attached to the forming apparatus. The toner cartridge contains toner for replenishment to be supplied to the developing means provided in the image forming apparatus.

  The toner cartridge set according to the present embodiment includes, for example, a yellow toner cartridge that contains yellow toner and is attached to and detached from the image forming apparatus; a magenta toner cartridge that contains magenta toner and is attached to and detached from the image forming apparatus; and contains cyan toner A cyan toner cartridge that can be attached to and detached from the image forming apparatus; a black toner cartridge that contains black toner and a detachable toner image that can be attached to and detached from the image forming apparatus; The toner cartridge may further include at least one selected from the following.

  The image forming apparatus shown in FIG. 2 is an image forming apparatus having a configuration in which toner cartridges 8Y, 8M, 8R, 8C, 8K, and 8G constituting an example of the toner cartridge set according to the present embodiment are attached and detached, and a developing device 4Y, 4M, 4C, and 4K are connected to a toner cartridge corresponding to each color by a toner supply pipe (not shown). Further, when the amount of toner stored in the toner cartridge becomes low, the toner cartridge is replaced.

  Hereinafter, although an embodiment explains this embodiment in detail, this embodiment is not limited to these examples at all.

In the following, “part” and “%” are based on mass unless otherwise specified.
In the following, C.I. I. Pigment Yellow 74 is referred to as “PY 74”, and C.I. I. PigmentRed 48: 1 is referred to as “PR48: 1”, and C.I. I. PigmentRed48: 3 is referred to as “PR48: 3”, and C.I. I. PigmentRed 57: 1 is referred to as “PR57: 1”, and C.I. I. PigmentRed 184 is referred to as “PR184”, and C.I. I. PigmentRed 122 is referred to as “PR122”.

<Preparation of resin particle dispersion>
[Preparation of resin particle dispersion (1)]
・ Terephthalic acid: 30 mol part ・ Fumaric acid: 70 mol part ・ Bisphenol A ethylene oxide adduct: 5 mol part ・ Bisphenol A propylene oxide adduct: 95 mol part Stirrer, nitrogen introduction tube, temperature sensor, and rectifying column The above material was charged into a 5 liter flask equipped with the above, the temperature was raised to 220 ° C. over 1 hour, and 1 part of titanium tetraethoxide was added to 100 parts of the material. The temperature was raised to 230 ° C. over 0.5 hours while distilling off the produced water, and the dehydration condensation reaction was continued at that temperature for 1 hour, and then the reaction product was cooled. Thus, a polyester resin (1) having a weight average molecular weight of 18,000, an acid value of 15 mgKOH / g, and a glass transition temperature of 60 ° C. was synthesized. The acid value of the resin was measured by a neutralization titration method according to JIS K0070-1992.

In a container equipped with temperature control means and nitrogen replacement means, 40 parts of ethyl acetate and 25 parts of 2-butanol are added to make a mixed solvent, and then 100 parts of polyester resin (1) is gradually added and dissolved therein. A 10% by mass aqueous ammonia solution (corresponding to 3 times the molar ratio with respect to the acid value of the resin) was added and stirred for 30 minutes.
Next, the inside of the container was replaced with dry nitrogen, the temperature was kept at 40 ° C., and 400 parts of ion-exchanged water was added dropwise at a rate of 2 parts / minute while stirring the mixed solution to carry out emulsification. After completion of the dropwise addition, the emulsion is returned to room temperature (20 ° C. to 25 ° C.), and stirred for 48 hours with dry nitrogen to reduce ethyl acetate and 2-butanol to 1,000 ppm or less. A resin particle dispersion in which resin particles having a diameter of 200 nm were dispersed was obtained. Ion exchange water was added to the resin particle dispersion to adjust the solid content to 20% by mass to obtain a resin particle dispersion (1).

[Preparation of resin particle dispersion (2)]
Styrene: 310 parts n-butyl acrylate: 100 parts β-carboxyethyl acrylate: 9 parts 1,10-decanediol diacrylate: 1.5 parts Dodecanethiol: 3 parts Anionic surfactant in the flask A solution prepared by dissolving 4 parts (Dow Fax manufactured by Dow Chemical Co., Ltd.) in 550 parts of ion-exchanged water was added, and a mixed liquid in which the above raw materials were mixed was added and emulsified. While slowly stirring the emulsion for 10 minutes, 50 parts of ion-exchanged water in which 6 parts of ammonium persulfate had been dissolved was added. Next, after sufficiently replacing the nitrogen in the system, the flask was heated with an oil bath while stirring until the temperature in the system reached 75 ° C., and the emulsion polymerization was continued for 4 hours as it was. As a result, a resin particle dispersion in which resin particles having a weight average molecular weight of 33,000, a glass transition temperature of 53 ° C., and a volume average particle size of 250 nm were dispersed was obtained. Ion exchange water was added to the resin particle dispersion to adjust the solid content to 20% by mass to obtain a resin particle dispersion (2).

<Preparation of glitter pigment dispersion>
[Preparation of glitter pigment dispersion (1)]
Aluminum pigment (Toyo Aluminum Co., Ltd. 2173EA): 100 parts Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd. Neogen R): 1.5 parts Ion-exchanged water: 900 parts The solvent was removed from the aluminum pigment paste. Thereafter, the above-mentioned materials are mixed and dispersed for 1 hour using an emulsifier-dispersing machine Cavitron (CR1010 manufactured by Taiheiyo Kiko Co., Ltd.) to disperse the glitter pigment (aluminum pigment) (solid content 10%). ) Was prepared.

<Preparation of colorant dispersion>
[Preparation of Colorant Dispersion (Y1)]
-PY74 (Hansa Yellow 5GX01 manufactured by Clariant): 70 parts-Anionic surfactant (Neogen RK manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 1 part-Ion-exchanged water: 200 parts The above materials were mixed and a homogenizer (Ultra manufactured by IKA) Dispersion was carried out for 10 minutes using Turrax T50). Ion exchange water was added so that the solid content in the dispersion was 20% by mass to obtain a colorant dispersion (Y1) in which colorant particles having a volume average particle diameter of 190 nm were dispersed.

[Preparation of Colorant Dispersion (R1)]
PR48: 1 (Dyclicer Red 3109): 70 parts Anionic surfactant (Daigen Kogyo Seiyaku Genogen RK): 1 part Ion-exchanged water: 200 parts The above materials were mixed and homogenizer (IKA) The dispersion was carried out for 10 minutes using an ultra turrax T50). Ion exchange water was added so that the solid content in the dispersion was 20% by mass, and a colorant dispersion (R1) in which colorant particles having a volume average particle size of 190 nm were dispersed was obtained.

[Preparation of Colorant Dispersion (R2)]
・ PR48: 3 (FujiRed5R763 manufactured by Fuji Color Co., Ltd.): 70 parts ・ Anionic surfactant (Neogen RK manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 1 part ・ Ion-exchanged water: 200 parts The above materials were mixed and homogenizer (IKA) Dispersion was carried out for 10 minutes using an ultra turrax T50). Ion exchange water was added so that the solid content in the dispersion was 20% by mass to obtain a colorant dispersion (R2) in which colorant particles having a volume average particle diameter of 190 nm were dispersed.

[Preparation of Colorant Dispersion (R3)]
PR57: 1 (Fuji Carmine 6BNo. 50 manufactured by Fuji Dye Co., Ltd.): 70 parts Anionic surfactant (Neogen RK manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 1 part Ion-exchanged water: 200 parts The above materials are mixed and homogenizer (IKA Ultra Turrax T50) was dispersed for 10 minutes. Ion exchange water was added so that the solid content in the dispersion was 20% by mass to obtain a colorant dispersion (R3) in which colorant particles having a volume average particle diameter of 190 nm were dispersed.

[Preparation of Colorant Dispersion (R4)]
-PR184 (Clariant TonerMagenta F8B): 70 parts-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd. Neogen RK): 1 part-Ion-exchanged water: 200 parts The above materials are mixed and a homogenizer (Ultra manufactured by IKA) Dispersion was carried out for 10 minutes using Turrax T50). Ion exchange water was added so that the solid content in the dispersion was 20% by mass to obtain a colorant dispersion (R4) in which colorant particles having a volume average particle size of 190 nm were dispersed.

[Preparation of Colorant Dispersion (R5)]
PR122 (Chromofine Magenta 6887 manufactured by Dainichi Seika Kogyo Co., Ltd.): 70 parts Anionic surfactant (Neogen RK manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 1 part Ion-exchanged water: 200 parts The above materials are mixed, The mixture was dispersed for 10 minutes using a homogenizer (Ultra Tarrax T50 manufactured by IKA). Ion exchange water was added so that the solid content in the dispersion was 20% by mass, and a colorant dispersion (R5) in which colorant particles having a volume average particle diameter of 190 nm were dispersed was obtained.

<Preparation of release agent dispersion>
[Preparation of release agent dispersion (1)]
-Paraffin wax (HNP-9 manufactured by Nippon Seiwa Co., Ltd.): 100 parts-Anionic surfactant (Neogen RK manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 1 part-Ion-exchanged water: 350 parts And then dispersed using a homogenizer (Ultra Turrax T50 manufactured by IKA) and then dispersed using a Menton Gorin high-pressure homogenizer (manufactured by Gorin) to release the release agent particles having a volume average particle diameter of 200 nm. A mold dispersion (1) (solid content 20% by mass) was obtained.

<Preparation of carrier>
Ferrite particles (average particle size 50 μm): 100 parts Toluene: 14 parts Styrene / methyl methacrylate copolymer (copolymerization ratio 15/85): 2 parts Carbon black: 0.2 parts The above materials excluding ferrite particles Was dispersed in a sand mill to prepare a dispersion. The dispersion was placed in a vacuum degassing type kneader together with ferrite particles, and the carrier was obtained by drying under reduced pressure while stirring.

<Comparative Example 1>
[Preparation of glitter toner and glitter developer]
-Resin particle dispersion (1) (containing polyester resin): 450 parts-Release agent dispersion (1): 50 parts-Bright pigment dispersion (1): 21.7 parts-Nonionic surfactant (IGEPAL) CA897): 1.4 parts The above material was placed in a 2 L cylindrical stainless steel container, and dispersed and mixed for 10 minutes while applying a shearing force at 4000 rpm with a homogenizer (Ultra Turrax T50 manufactured by IKA). Next, 1.75 parts of a 10% nitric acid aqueous solution of polyaluminum chloride as a flocculant was gradually added dropwise, and the homogenizer was rotated at 5000 rpm for 15 minutes and mixed to prepare a raw material dispersion.
Next, the agglomerated particle dispersion is transferred to a polymerization kettle equipped with a stirrer using a two-paddle stirring blade for forming a laminar flow and a thermometer, and heated with a mantle heater at a stirring speed of 550 rpm. First, the growth of aggregated particles was promoted at 54 ° C. At this time, the pH of the raw material dispersion was controlled in the range of 2.2 to 3.5 with 0.3N nitric acid and 1N sodium hydroxide aqueous solution. The agglomerated particles were formed by maintaining the above pH range for about 2 hours. At this time, the volume average particle diameter of the aggregated particles measured using Multisizer II (aperture diameter: 50 μm, manufactured by Coulter) was 10.6 μm.
Next, 100 parts of the resin particle dispersion (1) was additionally added, and the resin particles were adhered to the surface of the aggregated particles. The temperature was raised to 56 ° C., and aggregated particles were prepared while confirming the size and form of the particles with an optical microscope and Multisizer II.
Thereafter, the pH was raised to 8.0 in order to coalesce the aggregated particles, and then the temperature was raised to 80 ° C. at a rate of 0.01 ° C./min. After confirming that the aggregated particles were coalesced with an optical microscope, the pH was lowered to 6.0 while maintaining at 80 ° C., heating was stopped after 2.5 hours, and the mixture was cooled at a rate of temperature decrease of 1.0 ° C./min. Thereafter, the mixture was sieved with a 20 μm mesh, washed repeatedly with water, and then dried with a vacuum dryer to obtain glittering toner particles (1). The volume average particle diameter of the glittering toner particles (1) was 12.5 μm.

  100 parts of glittering toner particles (1) and 1.5 parts of hydrophobic silica (RY50 manufactured by Nippon Aerosil Co., Ltd.) were mixed at 10,000 rpm for 30 seconds using a sample mill. Thereafter, the mixture was sieved with a vibration sieve having an opening of 45 μm to obtain a glittering toner (1).

  The glittering developer (1) was obtained by mixing 5 parts of the glittering toner (1) and 100 parts of the carrier.

[Preparation of yellow toner and yellow developer]
-Resin particle dispersion (1) (containing polyester resin): 425 parts-Colorant dispersion (Y1) (containing PY74): 25 parts-Release agent dispersion (1): 50 parts-Anionic surfactant ( (TaycaPower): 2 parts Place the above material in a round stainless steel flask, add 0.1N nitric acid to adjust the pH to 3.5, then add 30 parts of nitric acid aqueous solution with a polyaluminum chloride concentration of 10% by mass. did. Subsequently, the mixture was dispersed at 30 ° C. using a homogenizer (Ultra Turrax T50 manufactured by IKA), then heated to 45 ° C. in a heating oil bath and held for 30 minutes. Thereafter, 100 parts of the resin particle dispersion (1) was slowly added and held for 1 hour, and the pH was adjusted to 8.5 by adding a 0.1N sodium hydroxide aqueous solution. And heated for 5 hours. Thereafter, the mixture was cooled to 20 ° C. at a rate of 20 ° C./min, filtered, sufficiently washed with ion exchange water, and dried to obtain yellow toner particles (1) having a volume average particle diameter of 7.5 μm.

  100 parts of yellow toner particles (1) and 0.7 parts of dimethyl silicone oil-treated silica particles (RY200 manufactured by Nippon Aerosil Co., Ltd.) were mixed using a Henschel mixer to obtain yellow toner (1).

  5 parts of yellow toner (1) and 100 parts of carrier were mixed to obtain yellow developer (1).

[Preparation of magenta toner and magenta developer]
-Resin particle dispersion (1) (containing polyester resin): 420 parts-Colorant dispersion (R1) (containing PR48: 1): 30 parts-Release agent dispersion (1): 50 parts-Anionic surface activity Agent (TaycaPower): 2 parts The above material is placed in a round stainless steel flask, 0.1N nitric acid is added to adjust the pH to 3.5, and then 30 parts of a nitric acid aqueous solution having a polyaluminum chloride concentration of 10% by mass. Was added. Subsequently, the mixture was dispersed at 30 ° C. using a homogenizer (Ultra Turrax T50 manufactured by IKA), then heated to 45 ° C. in a heating oil bath and held for 30 minutes. Thereafter, 100 parts of the resin particle dispersion (1) was slowly added and held for 1 hour, and the pH was adjusted to 8.5 by adding a 0.1N sodium hydroxide aqueous solution. And heated for 5 hours. Thereafter, the mixture was cooled to 20 ° C. at a rate of 20 ° C./min, filtered, sufficiently washed with ion exchange water, and dried to obtain magenta toner particles (1) having a volume average particle diameter of 7.5 μm.

  100 parts of magenta toner particles (1) and 0.7 part of dimethyl silicone oil-treated silica particles (RY200 manufactured by Nippon Aerosil Co., Ltd.) were mixed using a Henschel mixer to obtain magenta toner (1).

  5 parts of magenta toner (1) and 100 parts of carrier were mixed to obtain a magenta developer (1).

<Example A1>
[Preparation of glitter toner and glitter developer]
As in Comparative Example 1, a glittering toner (1) and a glittering developer (1) were produced.

[Production of Red Toner and Red Developer]
Red toner particles (A1) were produced by the following production method so that the pigment content was as shown in Table 2.

Resin particle dispersion (1) (containing polyester resin): 423 parts Colorant dispersion (Y1) (containing PY74): 3 parts Colorant dispersion (R1) (containing PR48: 1): 24 parts Mold dispersion (1): 50 parts · Anionic surfactant (TaycaPower): 2 parts The above materials were placed in a round stainless steel flask, and 0.1N nitric acid was added to adjust the pH to 3.5. Thereafter, 30 parts of an aqueous nitric acid solution having a polyaluminum chloride concentration of 10% by mass was added. Subsequently, the mixture was dispersed at 30 ° C. using a homogenizer (Ultra Turrax T50 manufactured by IKA), then heated to 45 ° C. in a heating oil bath and held for 30 minutes. Thereafter, 100 parts of the resin particle dispersion (1) was slowly added and held for 1 hour, and the pH was adjusted to 8.5 by adding a 0.1N sodium hydroxide aqueous solution. And heated for 5 hours. Thereafter, the mixture was cooled to 20 ° C. at a rate of 20 ° C./min, filtered, sufficiently washed with ion exchange water, and dried to obtain red toner particles (A1) having a volume average particle diameter of 7.5 μm.

  100 parts of red toner particles (A1) and 0.7 parts of dimethyl silicone oil-treated silica particles (RY200 manufactured by Nippon Aerosil Co., Ltd.) were mixed using a Henschel mixer to obtain red toner (A1).

  5 parts of red toner (A1) and 100 parts of carrier were mixed to obtain a red developer (A1).

[Measurement of Color Difference ΔE of Red Developer (Red Toner)]
The following operations, image formation, and measurement were performed in an environment of a temperature of 25 ° C. and a humidity of 60% RH.
The red developer is put into a developing device of DocuCenter Color 400 manufactured by Fuji Xerox Co., Ltd., and a solid image (100% density image) (size 5 cm × 5 cm, toner applied amount) on coated paper (OS coated paper W manufactured by Fuji Xerox Co., Ltd.). 4.5 g / m ² ) was imaged. The fixing temperature was 190 ° C., and the fixing pressure was 4.0 kg / cm ² .
Then, the CIE1976L ^* a ^* b ^* color system coordinate values of the formed image were measured arbitrarily at 10 locations using X-Rite 939 (aperture diameter 4 mm) manufactured by X-Rite, and the L ^* value, a The average value of ^* value and b ^* value was calculated.

For PANTONE 199C (coated paper) of a commercially available color sample (PANTONE FORMULA GUIDE Solid Coated by PANTONE), CIE1976L ^* a ^* b ^* coordinate value of the color system was measured in the same manner as above, and the L ^* value, a ^* The average value of the value and the b ^* value was calculated to be L ^* = 46.25, a ^* = 74.16, and b ^* = 41.96.
The color difference ΔE between the red toner and PANTONE 199C was calculated based on the following formula.

L ₁ , a ₁ , and b ₁ are L ^* values, a ^* values, and b ^* values of the vermilion index, and L ₂ , a ₂ , and b ₂ are L ^* values of an image formed with red toner, a ^* Value, b ^* value.

<Example B1>
The colorant dispersion (R1) (containing PR48: 1) is changed to the colorant dispersion (R2) (containing PR48: 3), and the resin particle dispersion and the pigment content are as shown in Table 5; Toner particles, toner, and developer were prepared in the same manner as in Example A1, except that the amount of the colorant dispersion was adjusted to prepare red toner particles.

<Example C1>
The colorant dispersion (R1) (containing PR48: 1) is changed to the colorant dispersion (R3) (containing PR57: 1), and the resin particle dispersion and the pigment content are as shown in Table 8. Toner particles, toner, and developer were prepared in the same manner as in Example A1, except that the amount of the colorant dispersion was adjusted to prepare red toner particles.

<Example D1>
The colorant dispersion (R1) (containing PR48: 1) was changed to the colorant dispersion (R4) (containing PR184), and the resin particle dispersion and colorant were changed so that the pigment content was as shown in Table 11. Toner particles, toner, and developer were prepared in the same manner as in Example A1, except that red toner particles were prepared by adjusting each amount of the dispersion.

<Comparative Example 101>
[Preparation of glitter toner and glitter developer]
-Resin particle dispersion (2) (containing styrene-acrylic resin): 450 parts-Release agent dispersion (1): 50 parts-Bright pigment dispersion (1): 21.7 parts-Nonionic surfactant (IGEPAL CA897): 1.4 parts The above material was placed in a 2 L cylindrical stainless steel container, and dispersed and mixed for 10 minutes while applying a shearing force at 4000 rpm with a homogenizer (Ultra Turrax T50 manufactured by IKA). Next, 1.75 parts of a 10% nitric acid aqueous solution of polyaluminum chloride as a flocculant was gradually added dropwise, and the homogenizer was rotated at 5000 rpm for 15 minutes and mixed to prepare a raw material dispersion.
Next, the agglomerated particle dispersion is transferred to a polymerization kettle equipped with a stirrer using a two-paddle stirring blade for forming a laminar flow and a thermometer, and heated with a mantle heater at a stirring speed of 550 rpm. First, the growth of aggregated particles was promoted at 54 ° C. At this time, the pH of the raw material dispersion was controlled in the range of 2.2 to 3.5 with 0.3N nitric acid and 1N sodium hydroxide aqueous solution. The agglomerated particles were formed by maintaining the above pH range for about 2 hours. At this time, the volume average particle diameter of the aggregated particles measured using Multisizer II (aperture diameter: 50 μm, manufactured by Coulter) was 10.6 μm.
Next, 100 parts of the resin particle dispersion (2) was additionally added, and the resin particles were adhered to the surface of the aggregated particles. The temperature was raised to 56 ° C., and aggregated particles were prepared while confirming the size and form of the particles with an optical microscope and Multisizer II.
Thereafter, the pH was raised to 8.0 in order to coalesce the aggregated particles, and then the temperature was raised to 80 ° C. at a rate of 0.01 ° C./min. After confirming that the aggregated particles were coalesced with an optical microscope, the pH was lowered to 6.0 while maintaining at 80 ° C., heating was stopped after 2.5 hours, and the mixture was cooled at a rate of temperature decrease of 1.0 ° C./min. Thereafter, the mixture was sieved with a 20 μm mesh, washed repeatedly with water, and then dried with a vacuum dryer to obtain bright toner particles (101). The volume average particle diameter of the glittering toner particles (101) was 12.5 μm.

  100 parts of glittering toner particles (101) and 1.5 parts of hydrophobic silica (RY50 manufactured by Nippon Aerosil Co., Ltd.) were mixed at 10,000 rpm for 30 seconds using a sample mill. Thereafter, the mixture was sieved with a vibration sieve having an opening of 45 μm to obtain a glittering toner (101).

  A glittering developer (101) was obtained by mixing 5 parts of glittering toner (101) and 100 parts of carrier.

[Preparation of yellow toner and yellow developer]
Resin particle dispersion (2) (containing styrene-acrylic resin): 425 parts Colorant dispersion (Y1) (containing PY74): 25 parts Release agent dispersion (1): 50 parts It put into the stainless steel flask, and it mixed and disperse | distributed with the homogenizer (Ultra Turrax T50 by IKA). Next, 0.5 part of polyaluminum chloride was added, and the dispersing operation was continued with a homogenizer. Then, it heated to 50 degreeC, stirring with the oil bath for heating, and hold | maintained at 50 degreeC for 60 minutes. Thereafter, the pH of the system was adjusted to 5.5 with a 0.5N sodium hydroxide aqueous solution, the flask was sealed, heated to 95 ° C. while continuing stirring using a magnetic seal, and maintained for 5 hours. After completion of the reaction, the mixture was cooled, filtered, thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 L of ion-exchanged water at 40 ° C. and stirred for 15 minutes at 300 rpm and washed. This was repeated 5 times, and when the pH of the filtrate reached 6.6 and the electric conductivity was 12 μS / cm, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Vacuum drying was then continued for 12 hours. Thus, yellow toner particles (101) having a volume average particle diameter of 7.5 μm were obtained.

  100 parts of yellow toner particles (101) and 0.7 parts of dimethyl silicone oil-treated silica particles (RY200 manufactured by Nippon Aerosil Co., Ltd.) were mixed using a Henschel mixer to obtain yellow toner (101).

  5 parts of yellow toner (101) and 100 parts of carrier were mixed to obtain a yellow developer (101).

[Preparation of magenta toner and magenta developer]
Resin particle dispersion (2) (containing styrene-acrylic resin): 420 parts Colorant dispersion (R1) (containing PR48: 1): 30 parts Release agent dispersion (1): 50 parts It put into the round stainless steel flask, and it mixed and disperse | distributed with the homogenizer (Ultra Turrax T50 by IKA). Next, 0.5 part of polyaluminum chloride was added, and the dispersing operation was continued with a homogenizer. Then, it heated to 50 degreeC, stirring with the oil bath for heating, and hold | maintained at 50 degreeC for 60 minutes. Thereafter, the pH of the system was adjusted to 5.5 with a 0.5N sodium hydroxide aqueous solution, the flask was sealed, heated to 95 ° C. while continuing stirring using a magnetic seal, and maintained for 5 hours. After completion of the reaction, the mixture was cooled, filtered, thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 L of ion-exchanged water at 40 ° C. and stirred for 15 minutes at 300 rpm and washed. This was repeated 5 times, and when the pH of the filtrate reached 6.6 and the electric conductivity was 12 μS / cm, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Vacuum drying was then continued for 12 hours. Thus, magenta toner particles (101) having a volume average particle diameter of 7.5 μm were obtained.

  100 parts of magenta toner particles (101) and 0.7 part of dimethyl silicone oil-treated silica particles (RY200 manufactured by Nippon Aerosil Co., Ltd.) were mixed using a Henschel mixer to obtain magenta toner (101).

  5 parts of magenta toner (101) and 100 parts of carrier were mixed to obtain a magenta developer (101).

<Example A101>
[Preparation of glitter toner and glitter developer]
As in Comparative Example 101, a glitter toner (101) and a glitter developer (101) were produced.

[Production of Red Toner and Red Developer]
Red toner particles (A101) were produced by the following production method. The red toner particles (A101) have the same pigment content as the red toner particles (A1) in Example A1.

Resin particle dispersion (2) (containing styrene-acrylic resin): 427.5 parts Colorant dispersion (Y1) (containing PY74): 2.5 parts Colorant dispersion (R1) (containing PR48: 1) ): 20 parts, release agent dispersion (1): 50 parts The above materials were placed in a round stainless steel flask, and mixed and dispersed with a homogenizer (Ultra Turrax T50, manufactured by IKA). Next, 0.5 part of polyaluminum chloride was added, and the dispersing operation was continued with a homogenizer. Then, it heated to 50 degreeC, stirring with the oil bath for heating, and hold | maintained at 50 degreeC for 60 minutes. Thereafter, the pH of the system was adjusted to 5.5 with a 0.5N sodium hydroxide aqueous solution, the flask was sealed, heated to 95 ° C. while continuing stirring using a magnetic seal, and maintained for 5 hours. After completion of the reaction, the mixture was cooled, filtered, thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 L of ion-exchanged water at 40 ° C. and stirred for 15 minutes at 300 rpm and washed. This was repeated 5 times, and when the pH of the filtrate reached 6.6 and the electric conductivity was 12 μS / cm, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Vacuum drying was then continued for 12 hours. In this way, red toner particles (A101) having a volume average particle diameter of 7.5 μm were obtained.

  100 parts of red toner particles (A101) and 0.7 parts of dimethyl silicone oil-treated silica particles (RY200 manufactured by Nippon Aerosil Co., Ltd.) were mixed using a Henschel mixer to obtain red toner (A101).

  5 parts of red toner (A101) and 100 parts of carrier were mixed to obtain a red developer (A101).

[Measurement of Color Difference ΔE of Red Developer (Red Toner)]
In the same manner as in Example A1, the color difference ΔE of the red developer (red toner) was measured.

<Example B101>
The colorant dispersion liquid (R1) (containing PR48: 1) is changed to the colorant dispersion liquid (R2) (containing PR48: 3), and the resin particle dispersion liquid and coloring are made to have the same pigment content as in Example B1. Toner particles, toner, and developer were prepared in the same manner as in Example A101, except that red toner particles were prepared by adjusting each amount of the agent dispersion.

<Example C101>
The colorant dispersion liquid (R1) (containing PR48: 1) is changed to the colorant dispersion liquid (R3) (containing PR57: 1), and the resin particle dispersion liquid and coloring are made to have the same pigment content as in Example C1. Toner particles, toner, and developer were prepared in the same manner as in Example A101, except that red toner particles were prepared by adjusting each amount of the agent dispersion.

<Example D101>
The colorant dispersion (R1) (containing PR48: 1) was changed to the colorant dispersion (R4) (containing PR184), and the resin particle dispersion and the colorant dispersion were made the same as in Example D1. Toner particles, toner, and developer were prepared in the same manner as in Example A101, except that red toner particles were prepared by adjusting each amount of the liquid.

<Evaluation>
The following evaluations were performed using the developer sets of Comparative Example 1, Examples A1 to D1, Comparative Example 101, and Examples A101 to D101. The results are shown in Table 1.

The following operations, image formation, and measurement were performed in an environment of a temperature of 25 ° C. and a humidity of 60% RH.
As an image forming apparatus for forming an image for evaluation, DocuCentre Color 400 manufactured by Fuji Xerox Co., Ltd. was prepared, and each developer was put in the developing device. During image formation, the fixing temperature was 190 ° C. and the fixing pressure was 4.0 kg / cm ² . As the recording medium, coated paper (OS coated paper W manufactured by Fuji Xerox Co., Ltd.) having a glossiness of 40% was used. In addition, the said glossiness means the glossiness obtained by measuring at 60 degrees of JISK5600-4-7 (JISZ8741), and measured by the model 4430 micro-TRI-gloss by BYK-Gardner. .

First, a solid image (100% density image) (size 5 cm x 5 cm) that reproduces PANTONE 199C of a commercially available color sample (PANTONE FORMULA GUIDE Solid Coated by PANTONE) is formed with yellow toner, magenta toner, or red toner. Then, an image (size 5 cm × 5 cm, toner applied amount 4.0 g / m ² ) of only the glittering toner was formed so as to be adjacent thereto.

Next, a vermilion red image (solid image having a size of 5 cm × 5 cm) exhibiting glitter was formed. The loading amount of the glittering toner was set to 4.0 g / m ² , and the tint red color reproduced PANTONE 199C of the above color sample. The order of development (that is, the order in which the toner images are superimposed on the intermediate transfer member) was yellow toner / magenta toner / bright toner, or red toner / bright toner.

1) Luminance Illumination for color observation according to JIS K 5600-4-3: 1999 “General paint test method-Part 4: Visual characteristics of coating film-Section 3: Visual comparison of colors” (natural daylight illumination) ) Below, the glitter of the vermilion red image exhibiting the glitter was visually evaluated. The glitter was evaluated by observing a sparkle feeling (sparkling feeling) and an optical effect (change in hue depending on viewing angle) according to the following criteria. Level 3 or higher is an acceptable level.

-Criteria-
5: There is a sparkle feeling and an optical effect, and both are in harmony.
4: There is a sparkle feeling and an optical effect, and some harmony is felt.
3: A sparkle feeling and an optical effect are felt respectively.
2: Although there is a sparkle and optical effect, it feels blurred.
1: No sparkle and optical effects.

2) Dullness at the boundary portion JIS K 5600-4-3: 1999 “General paint test method—Part 4: Visual characteristics of coating film—Section 3: Visual comparison of colors” (Natural daylight) Under the light illumination), the dullness of the boundary portion of the glitter image adjacent to the vermilion image was visually evaluated. Level 3 or higher is an acceptable level.

-Criteria-
5: Dullness is not felt at all.
4: Dullness is felt slightly.
3: Although dullness is felt, it does not become a problem.
2: Feel dull and feel uncomfortable.
1: Dullness is felt strongly.

<< Example: Examination of contents of PY74 and PR48: 1 >>
<Examples A2 to A24>
Except that the red toner particles were prepared by adjusting the amounts of the resin particle dispersion and the colorant dispersion so that the contents of PY74 and PR48: 1 are as shown in Table 2, the same as Example A1. Thus, toner particles, a toner, and a developer were prepared.

<Evaluation of Examples A1 to A24>
Using each developer set of Examples A1 to A24, the glitter and dullness of the boundary portion were evaluated in the same manner as described above. The results are shown in Table 3.

Example: Addition of other pigments
<Example A102>
A toner and a developer were prepared in the same manner as in Example A1, except that the red toner particles (A1) were changed to red toner particles (A102).
The red toner particles (A102) also use the colorant dispersion (R5) (containing PR122), and the resin particle dispersion and the colorant dispersion so that the content of each pigment is as shown in Table 4. The red toner particles (A1) were prepared in the same manner as the red toner particles (A1) except that the amount was adjusted.

<Example A103>
A toner and a developer were prepared in the same manner as in Example A1, except that the red toner particles (A1) were changed to red toner particles (A103).
Red toner particles (A103) were produced by the following production method.

-Polyester resin (1): 64.5 parts-PY74 (Hansa Yellow 5GX01 manufactured by Clariant): 0.5 parts-PR48: 1 (SimulerRed 3109 manufactured by DIC): 5 parts-Paraffin wax (HNP-9 manufactured by Nippon Seiwa Co., Ltd.) : 10 parts, silica (RX50 manufactured by Nippon Aerosil Co., Ltd.): 20 parts The above materials are kneaded with an extruder, pulverized with a surface pulverizing pulverizer, fine particles and coarse particles are classified with a wind classifier, and the volume Red toner particles (A103) having an average particle diameter of 7.5 μm were obtained.

<Example A104>
A toner and a developer were prepared in the same manner as in Example A1, except that the red toner particles (A1) were changed to red toner particles (A104).
Red toner particles (A104) were produced by the following production method.

-Polyester resin (1): 63.5 parts-PY74 (Hansa Yellow 5GX01 manufactured by Clariant): 0.5 parts-PR48: 1 (SimulerRed 3109 manufactured by DIC): 5 parts-PR122 (Chromofine Magenta 6877 manufactured by Dainichi Seika Kogyo) ): 1 part, paraffin wax (HNP-9, manufactured by Nippon Seiwa Co., Ltd.): 10 parts, silica (RX50, manufactured by Nippon Aerosil Co., Ltd.): 20 parts The above materials were kneaded with an extruder and pulverized with a surface pulverizer. Thereafter, fine particles and coarse particles were classified by a wind classifier to obtain red toner particles (A104) having a volume average particle diameter of 7.5 μm.

<Evaluation of Examples A102 to A104>
Using each developer set of Examples A102 to A104, the glitter and dullness of the boundary portion were evaluated in the same manner as described above. The results are shown in Table 4.

<< Example: Examination of contents of PY74 and PR48: 3 >>
<Examples B2 to B30>
The colorant dispersion (R1) (containing PR48: 1) is changed to the colorant dispersion (R2) (containing PR48: 3), and the resin particle dispersion and the pigment content are as shown in Table 5; Toner particles, toner, and developer were prepared in the same manner as in Example A1, except that the amount of the colorant dispersion was adjusted to prepare red toner particles.

<Evaluation of Examples B1 to B30>
Using each developer set of Examples B1 to B30, the glitter and dullness of the boundary portion were evaluated in the same manner as described above. The results are shown in Table 6.

Example: Addition of other pigments
<Example B102>
The colorant dispersion (R1) (containing PR48: 1) is changed to the colorant dispersion (R2) (containing PR48: 3), and the resin particle dispersion and the pigment content are as shown in Table 7. Toner particles, toner, and developer were prepared in the same manner as in Example A102, except that red toner particles were prepared by adjusting each amount of the colorant dispersion.

<Example B103>
PR48: 1 (Dyclicer Red 3109) is changed to PR48: 3 (Fuji Red 5R763 from Fuji Dye Co., Ltd.), and the resin and colorant amounts are adjusted so that the pigment content is as shown in Table 7. Toner particles, toner and developer were prepared in the same manner as in Example A103 except that toner particles were prepared.

<Example B104>
PR48: 1 (Dyclicer Red 3109) is changed to PR48: 3 (Fuji Red 5R763 from Fuji Dye Co., Ltd.), and the resin and colorant amounts are adjusted so that the pigment content is as shown in Table 7. Toner particles, toner and developer were prepared in the same manner as in Example A104 except that toner particles were prepared.

<Evaluation of Examples B102 to B104>
Using each developer set of Examples B102 to B104, the glitter and dullness of the boundary portion were evaluated in the same manner as described above. The results are shown in Table 7.

<< Example: Examination of contents of PY74 and PR57: 1 >>
<Examples C2 to C56>
The colorant dispersion (R1) (containing PR48: 1) is changed to the colorant dispersion (R3) (containing PR57: 1), and the resin particle dispersion and the pigment content are as shown in Table 8. Toner particles, toner, and developer were prepared in the same manner as in Example A1, except that the amount of the colorant dispersion was adjusted to prepare red toner particles.

<Evaluation of Examples C1 to C56>
Using each developer set of Examples C1 to C56, the glitter and dullness of the boundary portion were evaluated in the same manner as described above. The results are shown in Table 9.

Example: Addition of other pigments
<Example C102>
The colorant dispersion (R1) (containing PR48: 1) is changed to the colorant dispersion (R3) (containing PR57: 1), and the resin particle dispersion and the pigment content are as shown in Table 10. Toner particles, toner, and developer were prepared in the same manner as in Example A102, except that red toner particles were prepared by adjusting each amount of the colorant dispersion.

<Example C103>
Change PR48: 1 (Dyclicer Red 3109) to PR57: 1 (Fuji Carmine 6BNo. 50 from Fuji Dye Co., Ltd.) and adjust the amount of resin and colorant so that the pigment content is as shown in Table 10. Then, toner particles, toner and developer were prepared in the same manner as in Example A103 except that red toner particles were prepared.

<Example C104>
Change PR48: 1 (Dyclicer Red 3109) to PR57: 1 (Fuji Carmine 6BNo. 50 from Fuji Dye Co., Ltd.) and adjust the amount of resin and colorant so that the pigment content is as shown in Table 10. Then, toner particles, toner and developer were prepared in the same manner as in Example A104 except that red toner particles were prepared.

<Evaluation of Examples C102 to C104>
Using each developer set of Examples C102 to C104, the glitter and dullness of the boundary portion were evaluated in the same manner as described above. The results are shown in Table 10.

Example: Examination of PY74 and PR184 content
<Examples D2 to D48>
The colorant dispersion (R1) (containing PR48: 1) was changed to the colorant dispersion (R4) (containing PR184), and the resin particle dispersion and colorant were changed so that the pigment content was as shown in Table 11. Toner particles, toner, and developer were prepared in the same manner as in Example A1, except that red toner particles were prepared by adjusting each amount of the dispersion.

<Evaluation of Examples D1 to D48>
Using each developer set of Examples D1 to D48, the glitter and dullness of the boundary portion were evaluated in the same manner as described above. The results are shown in Table 12.

Example: Addition of other pigments
<Example D102>
The colorant dispersion (R1) (containing PR48: 1) was changed to the colorant dispersion (R4) (containing PR184), and the resin particle dispersion and colorant were changed so that the pigment content was as shown in Table 13. Toner particles, toner, and developer were prepared in the same manner as in Example A102, except that red toner particles were prepared by adjusting each amount of the dispersion.

<Example D103>
Change PR48: 1 (DIC Red, Symreder 3109) to PR 184 (Clariant Toner Magenta F8B), adjust the amount of resin and colorant as shown in Table 13, and adjust the amount of red toner particles. Except for the production, toner particles, toner and developer were produced in the same manner as in Example A103.

<Example D104>
Change PR48: 1 (DIC Red, Symreder 3109) to PR 184 (Clariant Toner Magenta F8B), adjust the amount of resin and colorant as shown in Table 13, and adjust the amount of red toner particles. Except for the production, toner particles, toner and developer were produced in the same manner as in Example A104.

<Evaluation of Examples D102 to D104>
Using each developer set of Examples D102 to D104, the glitter and dullness of the boundary portion were evaluated in the same manner as described above. The results are shown in Table 13.

40 Yellow toner layer 41 Yellow toner particle 50 Magenta toner layer 51 Magenta toner particle 60 Bright toner layer 61 Bright toner particle 62 Bright pigment 70 Superposed toner image 80 Fixed image 90 Recording medium

10Y, 10M, 10R, 10C, 10K, 10G Image forming unit 1Y, 1M, 1R, 1C, 1K, 1G Photoconductor (an example of an image carrier)
2Y, 2M, 2R, 2C, 2K, 2G charging roll (an example of charging means)
3Y, 3M, 3R, 3C, 3K, 3G exposure apparatus (an example of electrostatic charge image forming means)
4Y, 4M, 4R, 4C, 4K, 4G developing device (an example of developing means)
5Y, 5M, 5R, 5C, 5K, 5G primary transfer roll (an example of primary transfer means)
6Y, 6M, 6R, 6C, 6K, 6G Photoconductor cleaning device (an example of cleaning means)
8Y, 8M, 8R, 8C, 8K, 8G Toner cartridge 20 Intermediate transfer belt (an example of an intermediate transfer member)
21 Intermediate transfer member cleaning device 22 Drive roll 23 Support roll 24 Opposing roll 26 Secondary transfer roll (an example of secondary transfer means)
28 Fixing device (an example of fixing means)
P Recording paper (an example of a recording medium)

107 photoconductor (an example of an image carrier)
108 Charging roll (an example of charging means)
109 Exposure apparatus (an example of electrostatic charge image forming means)
111 Developing device (an example of developing means)
112 Transfer device (an example of transfer means)
113 photoconductor cleaning device (an example of cleaning means)
115 Fixing device (an example of fixing means)
116 Mounting rail 117 Housing 118 Opening 200 for exposure Process cartridge 300 Recording paper (an example of a recording medium)

Claims (10)

A glitter toner containing a glitter pigment;
A red toner containing a colorant and having a color difference ΔE of 30 or less from PANTONE 199C in the color system when forming a solid image; and CIE1976L ^* a ^* b ^*
A toner set for developing electrostatic images. The red toner is
C. I. Pigment Yellow 74,
C. I. PigmentRed 48: 1, C.I. I. Pigment Red 48: 3, C.I. I. PigmentRed 57: 1 and C.I. I. At least one selected from the group consisting of PigmentRed 184;
The toner set for developing electrostatic images according to claim 1, comprising: The red toner is
C. as a yellow colorant I. Contains only Pigment Yellow 74,
C. as a red colorant I. PigmentRed 48: 1, C.I. I. Pigment Red 48: 3, C.I. I. Pigment Red 57: 1 or C.I. I. Containing only one of PigmentRed 184,
The toner set for developing electrostatic images according to claim 1 or 2. A first electrostatic charge image developer comprising a glitter toner containing a glitter pigment;
A second electrostatic charge image developer containing a red toner that contains a colorant and has a color difference ΔE of 30 or less from PANTONE 199C in the color system when forming a solid image, and CIE1976L ^* a ^* b ^*
An electrostatic charge image developer set. The red toner is
C. I. Pigment Yellow 74,
C. I. PigmentRed 48: 1, C.I. I. Pigment Red 48: 3, C.I. I. PigmentRed 57: 1 and C.I. I. At least one selected from the group consisting of PigmentRed 184;
The electrostatic charge image developer set according to claim 4, comprising: The red toner is
C. as a yellow colorant I. Contains only Pigment Yellow 74,
C. as a red colorant I. PigmentRed 48: 1, C.I. I. Pigment Red 48: 3, C.I. I. Pigment Red 57: 1 or C.I. I. Containing only one of PigmentRed 184,
The electrostatic charge image developer set according to claim 4 or 5. While using the electrostatic image developing toner set according to any one of claims 1 to 3,
A first toner cartridge that contains the glitter toner and is attached to and detached from the image forming apparatus;
A second toner cartridge that contains the red toner and is attached to and detached from the image forming apparatus;
Including toner cartridge set. While using the electrostatic charge image developer set of any one of Claims 4-6,
An image forming apparatus comprising: a developing unit that contains the first electrostatic charge image developer, and that develops the electrostatic charge image formed on the surface of the image carrier as a toner image with the first electrostatic charge image developer; A first process cartridge to be attached to and detached from,
An image forming apparatus comprising: a developing unit that accommodates the second electrostatic charge image developer and develops the electrostatic charge image formed on the surface of the image carrier as a toner image with the second electrostatic charge image developer. A second process cartridge to be attached to and detached from,
Including process cartridge set. While using the electrostatic charge image developer set of any one of Claims 4-6,
An image carrier,
Charging means for charging the surface of the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
First developing means for accommodating the first electrostatic charge image developer, and developing the electrostatic image formed on the surface of the image carrier as a toner image by the first electrostatic charge image developer;
A second developing unit that contains the second electrostatic charge image developer and develops the electrostatic image formed on the surface of the image carrier as a toner image by the second electrostatic charge image developer;
Transfer means for transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
Fixing means for fixing the toner image transferred to the surface of the recording medium;
An image forming apparatus comprising: While using the electrostatic charge image developer set of any one of Claims 4-6,
A charging step for charging the surface of the image carrier;
An electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged image carrier;
A first developing step of developing the electrostatic image formed on the surface of the image carrier as a toner image with the first electrostatic image developer;
A second developing step of developing the electrostatic image formed on the surface of the image carrier as a toner image with the second electrostatic image developer;
A transfer step of transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
A fixing step of fixing the toner image transferred to the surface of the recording medium;
An image forming method comprising: