Electrostatic image developing toner set, electrostatic image developer set, toner cartridge set, process cartridge, image forming apparatus, and image forming method

Abstract

To provide an electrostatic charge image development toner set capable of forming photoluminescent images with high photoluminescence and glossiness.SOLUTION: An electrostatic charge image development toner set provided herein comprises a photoluminescent toner comprising photoluminescent toner particles containing a binder resin and a photoluminescent pigment, and a colored toner comprising colored toner particles containing a binder resin and a colorant other than the photoluminescent pigment, where the binder resin contained in the photoluminescent toner particles and the binder resin contained in the colored toner particles are incompatible with each other.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a toner set for developing an electrostatic image, an electrostatic image developer set, a toner cartridge set, a process cartridge, an image forming apparatus, and an image forming method. [Background technology]

[0002] In Patent Document 1, "a toner set including a toner that forms a secondary color and a toner that does not form a secondary color is described, and the solubility parameter value (SP value: (cal / cm 3 ) 1 / 2 The toner with the largest solubility parameter (SP value: (cal / cm 3 ) 1 / 2 ) as SP(1), SP(2), and SP(3), respectively, the following equations (1) to (3); SP(1)-SP(2)<0.15 (1) 0.15≦|SP(1)-SP(3)|<1.0 (2) 0.15≦|SP(2)-SP(3)|<1.0 (3) and the third toner contains a white colorant and does not contain a crystalline resin. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 6419972 Summary of the Invention [Problem to be solved by the invention]

[0004] The object of the present invention is to provide a toner set for developing electrostatic images, which comprises a photoluminescent toner having photoluminescent toner particles containing a binder resin and a photoluminescent pigment, and a colored toner having colored toner particles containing a binder resin and a colorant other than the photoluminescent pigment, and which is capable of forming a photoluminescent image having high photoluminescence and glossiness as well as compared to a case in which the binder resin contained in the photoluminescent toner particles and the binder resin contained in the colored toner particles are compatible with each other, or the difference in solubility parameter between the binder resin contained in the photoluminescent toner particles and the binder resin contained in the colored toner particles is less than 0.5 or more than 2.0. [Means for solving the problem]

[0005] The above problems are solved by the following means: <1> a glitter toner having glitter toner particles containing a binder resin and a glitter pigment; a color toner having color toner particles containing a binder resin and a colorant other than the glittering pigment; having A toner set for developing electrostatic images, wherein the binder resin contained in the glittering toner particles and the binder resin contained in the color toner particles are incompatible with each other. <2> The binder resin contained in the glittering toner particles and the binder resin contained in the color toner particles have different solubility parameters. <1> 2. A toner set for developing electrostatic images according to claim 1 . <3> the absolute value of the difference in solubility parameter between the binder resin contained in the glitter toner particles and the binder resin contained in the color toner particles is 0.5 or more and 2.0 or less; <2> 2. A toner set for developing electrostatic images according to claim 1 . <4> One of the glittering toner particles and the colored toner particles contains an amorphous polyester resin as the binder resin, and the other contains a styrene-acrylic resin. <1> ~ <3> 10. The toner set for developing an electrostatic image according to claim 9, <5> the glittering toner particles contain the amorphous polyester resin as the binder resin, and the colored toner particles contain the styrene acrylic resin as the binder resin; <4> 2. A toner set for developing electrostatic images according to claim 1 . <6> One of the glittering toner particles and the colored toner particles contains an amorphous resin having an amorphous polyester resin segment and a styrene-acrylic resin segment as the amorphous polyester resin or the styrene-acrylic resin. <4> or <5> 2. A toner set for developing electrostatic images according to claim 1 . <7> The color toner particles have a volume average particle size of 5.5 μm to 7.5 μm. <1> ~ <6> 10. The toner set for developing an electrostatic image according to claim 9, <8> the color toner particles have a smaller volume average particle size than the glitter toner particles, and the absolute value of the difference in volume average particle size between the glitter toner particles and the color toner particles is 2.7 μm or more and 5.2 μm or less. <7> 2. A toner set for developing electrostatic images according to claim 1 . <9> The color toner has a storage modulus at 120° C. greater than that of the glitter toner. <1> ~ <8> 10. The toner set for developing an electrostatic image according to claim 9, <10> the absolute value of the difference (|Es-Ec|) between the storage modulus Es of the glitter toner at 120° C. and the storage modulus Ec of the color toner at 120° C. is 10,000 Pa or more and 20,000 Pa or less; <9> 2. A toner set for developing electrostatic images according to claim 1 . <11> the glitter toner particles and the color toner particles contain a release agent, the absolute value of the difference in solubility parameter between the release agent contained in the glitter toner particles and the binder resin contained in the colored toner particles is greater than the absolute value of the difference in solubility parameter between the release agent contained in the glitter toner particles and the binder resin contained in the glitter toner particles; <1> ~ <10> 10. The toner set for developing an electrostatic image according to claim 9, <12> a glitter toner having glitter toner particles containing a binder resin and a glitter pigment; a color toner having color toner particles containing a binder resin and a colorant other than the glittering pigment; having The toner set for developing electrostatic images, wherein the absolute value of the difference in solubility parameter between the binder resin contained in the glitter toner particles and the binder resin contained in the color toner particles is 0.5 or more and 2.0 or less. <13> The above <1> ~ <12> a first electrostatic image developer containing the glitter toner of the toner set for developing an electrostatic image according to any one of the above items; The above <1> ~ <12> a second electrostatic image developer including a color toner in the toner set for developing an electrostatic image according to any one of the above items; Electrostatic image developer set comprising: <14> The above <1> ~ <12> a first toner cartridge containing the glitter toner of the toner set for developing an electrostatic image according to any one of the above items; The above <1> ~ <12> a second toner cartridge containing the color toner of the toner set for developing an electrostatic image according to any one of the above items; having A toner cartridge set that is detachably attached to an image forming apparatus. <15> The above <13> a first developing means containing the first electrostatic image developer of the electrostatic image developer set according to claim 1; The above <13> a second developing means containing the second electrostatic image developer of the electrostatic image developer set according to claim 1; Equipped with A process cartridge that is detachably attached to an image forming apparatus. <16> The above <1> ~ <12> a first image forming means for forming a glossy image using the glossy toner of the toner set for developing an electrostatic image according to any one of the above items; The above <1> ~ <12> a second image forming means for forming a color image by the color toner of the toner set for developing an electrostatic image according to any one of the above items; a transfer means for transferring the glossy image and the color image onto a recording medium; a fixing unit for fixing the glossy image and the color image on the recording medium; An image forming apparatus comprising: <17> The above <1> ~ <12> a first image forming step of forming a glossy image using the glossy toner of the toner set for developing an electrostatic image according to any one of the above items; The above <1> ~ <12> a second image forming step of forming a color image using the color toner of the toner set for developing an electrostatic image according to any one of the above items; a transfer step of transferring the glossy image and the color image onto a recording medium; a fixing step of fixing the glossy image and the color image on the recording medium; The image forming method according to claim 1, Effect of the Invention

[0006] <1> According to the present invention, there is provided a toner set for developing electrostatic images, which comprises a photoluminescent toner having photoluminescent toner particles containing a binder resin and a photoluminescent pigment, and a colored toner having colored toner particles containing a binder resin and a colorant other than the photoluminescent pigment, and which can form a photoluminescent image that is high in both photoluminescence and glossiness as compared to a case in which the binder resin contained in the photoluminescent toner particles and the binder resin contained in the colored toner particles are compatible with each other. <2> According to the present invention, there is provided a toner set for developing electrostatic images, which can form a glossy image having high gloss and glossiness as compared to a case in which the solubility parameters of the binder resin contained in the glossy toner particles and the binder resin contained in the colored toner particles are the same. <3> According to the present invention, there is provided a toner set for developing electrostatic images, which can form a glossy image having high gloss and glossiness, as compared with a case in which the difference in absolute value of the solubility parameter between the binder resin contained in the glossy toner particles and the binder resin contained in the colored toner particles is less than 0.5 or exceeds 2.0. <4> or <6> According to the present invention, there is provided a toner set for developing electrostatic images, which can form a glossy image having high gloss and glossiness as compared to a case in which the types of binder resin contained in the glossy toner particles and the colored toner particles are the same. <5> or <6> According to the present invention, there is provided a toner set for developing electrostatic images, which can form a glossy image having high gloss and glossiness as compared with a case in which the glossy toner particles contain a styrene acrylic resin as a binder resin and the colored toner particles contain a polyester resin as a binder resin.

[0007] <7> According to the present invention, there is provided a toner set for developing electrostatic images, which can form a glossy image having high brightness and glossiness as compared with a case where the volume average particle size of the color toner particles is less than 5.5 μm or exceeds 7.5 μm. <8> According to the invention, there is provided a toner set for developing electrostatic images which can form a glossy image having high gloss as well as brilliance, as compared to a case in which the volume average particle size of color toner particles is larger than that of glossy toner particles, or the absolute value of the difference in volume average particle size between glossy toner particles and color toner particles is less than 2.7 μm or exceeds 5.2 μm. <9> According to the present invention, there is provided a toner set for developing electrostatic images that can form a glossy image having high gloss as well as glossiness, as compared with a case where a color toner has a smaller storage modulus at 120° C. than a glossy toner. <10> According to the present invention, there is provided a toner set for developing electrostatic images, which can form a glossy image having high gloss and glossiness as compared to a case where the absolute value of the difference (|Es-Ec|) between the storage modulus Es of a glossy toner at 120°C and the storage modulus Ec of a colored toner at 120°C is less than 10,000 Pa or exceeds 20,000 Pa.

[0008] <11> According to the invention, there is provided a toner set for developing electrostatic images, in which the photoluminescent toner particles and the colored toner particles contain a release agent, and which can form photoluminescent images that are high in both photoluminescence and glossiness, as compared to a case in which the absolute value of the difference in solubility parameter between the release agent contained in the photoluminescent toner particles and the binder resin contained in the colored toner particles is smaller than the absolute value of the difference in solubility parameter between the release agent contained in the photoluminescent toner particles and the binder resin contained in the photoluminescent toner particles. <12> According to the present invention, there is provided a toner set for developing electrostatic images, which comprises a photoluminescent toner having photoluminescent toner particles containing a binder resin and a photoluminescent pigment, and a colored toner having colored toner particles containing a binder resin and a colorant other than the photoluminescent pigment, and which can form a photoluminescent image that is high in both photoluminescence and glossiness as compared to a case in which the difference in solubility parameter between the binder resin contained in the photoluminescent toner particles and the binder resin contained in the colored toner particles is less than 0.5 or exceeds 2.0. <13> , <14> , <15> , <16> or <17> According to the invention, there is provided a toner cartridge set, a process cartridge, an image forming apparatus, or an image forming method including a toner set for developing electrostatic images, which comprises a photoluminescent toner having photoluminescent toner particles containing a binder resin and a photoluminescent pigment, and a colored toner having colored toner particles containing a binder resin and a colorant other than the photoluminescent pigment, and which is capable of forming a photoluminescent image having high gloss as well as photoluminescence, compared to when the binder resin contained in the photoluminescent toner particles and the binder resin contained in the colored toner particles are compatible with each other, or when the difference in solubility parameter between the binder resin contained in the photoluminescent toner particles and the binder resin contained in the colored toner particles is less than 0.5 or more than 2.0. [Brief description of the drawings]

[0009] [Figure 1] FIG. 2 is a cross-sectional view illustrating an example of a glittering toner particle according to the present embodiment. [Diagram 2] 1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to an embodiment of the present invention. [Diagram 3] FIG. 2 is a schematic diagram illustrating an example of a process cartridge according to the present embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the electrostatic image developing toner set, the toner cartridge set, the process cartridge, the image forming apparatus, and the image forming method of the present invention will be described in detail. These descriptions and examples are illustrative of embodiments and do not limit the scope of the invention. In the present specification, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range. In addition, in the present specification, the upper or lower limit of the numerical range may be replaced with a value shown in the examples.

[0011] Each component may contain multiple types of the corresponding substance. When referring to the amount of each component in a composition, if the composition contains multiple substances corresponding to each component, the amount refers to the total amount of those multiple substances present in the composition, unless otherwise specified.

[0012] <Toner set> The toner set for developing electrostatic images according to the first embodiment (hereinafter, the toner set for developing electrostatic images will also be simply referred to as the toner set) comprises a photoluminescent toner having photoluminescent toner particles containing a binder resin and a photoluminescent pigment, and a color toner having colored toner particles containing a binder resin and a colorant other than the photoluminescent pigment. The binder resin contained in the glitter toner particles and the binder resin contained in the color toner particles are incompatible with each other.

[0013] Examples of colored toners that can be included in the toner set of this embodiment (a toner set that corresponds to both the toner sets of the first and second embodiments; the same applies below) include well-known toners such as magenta toner, cyan toner, yellow toner, black toner, red toner, green toner, blue toner, orange toner, and violet toner.

[0014] In the present embodiment, the term "incompatible" means that the haze (cloudiness) H value measured by the following procedure is 20 or more and 100 or less. 1 g of each of the photoluminescent toner and color toner to be measured is weighed and added to 20 g of tetrahydrofuran. The tetrahydrofuran to which the photoluminescent toner and color toner have been added is stirred at 25° C. to dissolve the binder resin contained in the photoluminescent toner and color toner. The resulting solution is then suction filtered using filter paper [product name: qualitative filter paper (No. 2, 110 mm), manufactured by Advantec Toyo Co., Ltd.]. The mother liquid obtained by filtration is applied to an OHP film (manufactured by Kiso Kasei Sangyo Co., Ltd., product name: PPC laser OHP film) using a bar coater, and dried at 25° C. to form a coating film containing the binder resin on the OHP film (area of ​​coating film: 40 mm x 25 mm, mass of coating film: 0.008 g). Then, the OHP film on which the coating film containing the binder resin is formed is used as a measurement sample, and the haze of the measurement sample is measured using a fully automatic haze meter (TC-HIII DP type, manufactured by Tokyo Denshoku Co., Ltd.) in accordance with JIS K7136:2000 "Determination of haze of plastics - transparent materials".

[0015] The toner set according to the first embodiment, having the above-described configuration, can form a glossy image having high gloss and luster. The reason for this is presumed to be as follows.

[0016] For the purpose of creating a sense of luxury in the formation of images on publications, paper container packages, and the like, a toner set including a glitter toner containing a binder resin and a glitter pigment, and a color toner having colored toner particles containing a binder resin and a colorant other than the glitter pigment, is sometimes used to form images having a metallic color. Conventionally, when an image is formed using a toner set having a glitter toner and a color toner, the glitter and gloss of the resulting image may be reduced. For example, an image may be formed using a toner set having a glitter toner and a color toner by attaching the glitter toner and the color toner in this order onto a recording medium, and then applying pressure from above the color toner to fix the toner. The glitter pigment contained in the glitter toner has a flat shape, and is oriented along the surface of the recording medium during fixing, thereby exhibiting glitter. During fixing of the toner, among the release agents contained in the glitter toner, the release agent present between the glitter pigment and the recording medium has a long moving distance to the image surface. In addition, when the binder resin contained in the glitter toner and the binder resin contained in the color toner are compatible with each other during fixing, the release agent contained in the glitter toner must pass through not only the binder resin layer contained in the glitter toner, but also the binder resin layer contained in the color toner present in the upper layer in order to reach the image surface. Therefore, during fixing, the release agent contained in the glittering toner tends to take a long time to reach the image surface. As a result, the release agent may not reach the image surface and may be left behind in the image. When the image is irradiated with light, the light may hit the release agent present in the image, which may cause diffuse reflection. This may result in a decrease in the glittering of the resulting image.

[0017] In the toner set according to the first embodiment, the binder resin contained in the glitter toner particles and the binder resin contained in the color toner particles are incompatible. Therefore, when forming an image using a toner set having a glitter toner and a color toner, for example, by attaching the glitter toner and the color toner in this order onto a recording medium and then applying pressure from above the color toner to fix the toner, an interface is likely to be generated between the glitter toner and the color toner during fixing. Therefore, the release agent contained in the glitter toner is likely to move to the image surface through the interface. Then, even the release agent present between the glitter pigment and the recording medium among the release agents contained in the glitter toner is likely to move to the image surface. Therefore, the amount of release agent left behind in the image is reduced, and the glitter of the obtained image is likely to be high. In addition, it is preferable that an image including a metallic color also has a glossy feel in order to enhance a sense of luxury. As described above, an image formed using the toner set according to the first embodiment is likely to have a reduced amount of release agent remaining in the image. This tends to increase the amount of release agent present on the image surface, and the gloss of the image tends to be high.

[0018] From the above, it is presumed that the toner set according to the first embodiment, due to the above-mentioned composition, can form a glossy image that is high in both glossiness and gloss.

[0019] The toner set according to the second embodiment has a glitter toner having glitter toner particles containing a binder resin and a glitter pigment, and a color toner having color toner particles containing a binder resin and a colorant other than the glitter pigment. The difference in solubility parameter between the binder resin contained in the glitter toner particles and the binder resin contained in the color toner particles is 0.3 or more and 1.5 or less.

[0020] In this embodiment, the "solubility parameter (SP value)" is a value calculated by the Fedor method. Specifically, the solubility parameter (SP value) is calculated by the following formula, for example, in accordance with the description in Polym. Eng. Sci., vol. 14, p. 147 (1974). Formula: SP value = √(Ev / v) = √(ΣΔei / ΣΔvi) (Wherein, Ev: evaporation energy (cal / mol), v: molar volume (cm 3 / mol), Δei: evaporation energy of each atom or atomic group, Δvi: molar volume of each atom or atomic group) The solubility parameter (SP value) is expressed in units of (cal / cm 3 ) 1 / 2 However, following convention, the units are omitted and the value is expressed as dimensionless.

[0021] The toner set according to the first embodiment, having the above-described configuration, can form a glossy image having high gloss and luster. The reason for this is presumed to be as follows.

[0022] By setting the difference in solubility parameter between the binder resin contained in the glitter toner particles and the binder resin contained in the color toner particles to a range of 0.5 to 2.0, the binder resin contained in the glitter toner particles and the binder resin contained in the color toner particles are likely to be incompatible. Therefore, when an image is formed using a toner set having a glitter toner and a color toner, for example, by attaching the glitter toner and the color toner in this order onto a recording medium and then applying pressure from above the color toner to fix the toner, an interface is likely to occur between the glitter toner and the color toner during fixing. Therefore, for the same reason as the toner set according to the first embodiment described above, the surface smoothness of the obtained image is likely to be improved, and the glossiness of the image is likely to be increased.

[0023] Therefore, it is presumed that the toner set according to the second embodiment, due to the above-mentioned composition, can form a glittery image that is high in both glitter and gloss.

[0024] Hereinafter, a toner set that corresponds to both the toner set according to the first and second embodiments (hereinafter also referred to as the "toner set according to the present embodiment") will be described in detail. However, an example of the toner set of the present invention may be a toner set that corresponds to either one of the toner sets according to the first and second embodiments.

[0025] (Photoluminescent toner) The glitter toner of this embodiment that constitutes the toner set of this embodiment will be described below. Specifically, when a solid image is formed with the glittering toner according to the present embodiment, the ratio (X / Y) of the reflectance X at a light-receiving angle of +30° to the reflectance Y at a light-receiving angle of -30°, measured when the image is irradiated with incident light at an incident angle of -45° using a goniophotometer, is preferably 2 or more and 100 or less.

[0026] A ratio (X / Y) of 2 or more indicates that the light is reflected more to the side opposite the incident side (positive angle side) than to the side where the light is incident (negative angle side), meaning that diffuse reflection of the incident light is suppressed. When diffuse reflection occurs, where incident light is reflected in various directions, the color appears dull when the reflected light is visually inspected. Therefore, when the ratio (X / Y) is less than 2, the gloss cannot be confirmed even when the reflected light is visually inspected, and the brilliance may be poor. On the other hand, if the ratio (X / Y) exceeds 100, the viewing angle at which the reflected light can be seen becomes too narrow, and the specular reflected light component is large, which may make the image appear black depending on the viewing angle.

[0027] From the viewpoints of glitter and toner manufacturability, the ratio (X / Y) is more preferably 4 or more and 50 or less, further preferably 6 or more and 20 or less, and particularly preferably 8 or more and 15 or less.

[0028] <Measurement of the ratio (X / Y) using a goniophotometer> First, the angle of incidence and the angle of reception will be described. In this embodiment, when measuring with a goniophotometer, the angle of incidence is set to -45°. This is because the measurement sensitivity is high for images with a wide range of glossiness. The reason why the light-receiving angles are set to -30° and +30° is that these have the highest measurement sensitivity for evaluating images with a glittering feel and images without a glittering feel.

[0029] Next, the method for measuring the ratio (X / Y) will be described. The image to be measured (glossy image) is irradiated with light at an incident angle of -45° using a GC5000L spectrophotometer manufactured by Nippon Denshoku Industries Co., Ltd., and the reflectance X at an acceptance angle of +30° and the reflectance Y at an acceptance angle of -30° are measured. The reflectance X and reflectance Y are measured at 20 nm intervals for light with wavelengths ranging from 400 nm to 700 nm, and the average reflectance at each wavelength is calculated. The ratio (X / Y) is calculated from these measurement results.

[0030] In order to satisfy the above-mentioned ratio (X / Y), the toner according to this embodiment preferably satisfies the following requirements (1) and (2). (1) The average equivalent circle diameter D is longer than the average maximum thickness C of the glittering toner particles. (2) When a cross section of a glossy toner particle in the thickness direction is observed, the proportion of glossy pigments in which the angle between the long axis direction of the glossy toner particle in the cross section and the long axis direction of the glossy pigment is in the range of -30° to +30° is 60% or more of all the glossy pigments observed.

[0031] If the glittering toner particles are flat with a circular equivalent diameter longer than their thickness (see Figure 1), then in the fixing step of image formation, the pressure applied during fixing causes the flat glittering toner particles to line up so that their flat surfaces face the recording medium surface. In Figure 1, 2 indicates the glittering toner particles, 4 indicates the glittering pigment, and L indicates the thickness of the glittering toner particles. Therefore, among the flat (scaly) glittering pigments contained in the glittering toner particles, those that satisfy the requirement in (2) above, that "the angle between the long axis direction of the toner in the cross section and the long axis direction of the glittering pigment is in the range of -30° to +30°," are considered to be aligned so that the side with the largest area faces the recording medium surface. When light is irradiated onto the image thus formed, the proportion of the glittering pigment that diffusely reflects the incident light is suppressed, and it is considered that the aforementioned range of the ratio (X / Y) is achieved.

[0032] The glossy toner according to this embodiment will be described in detail below.

[0033] The glittering toner particles contained in the glittering toner according to this embodiment contain a glittering pigment and a binder resin. The glittering toner particles according to this embodiment may contain other components as necessary. -Brilliant toner particles- Average maximum thickness C and average equivalent circle diameter D of glittering toner particles The glittering toner particles are flat and preferably have an average equivalent circular diameter D longer than the average maximum thickness C. The ratio (C / D) of the average maximum thickness C to the average equivalent circular diameter D is more preferably in the range of 0.001 to 0.700, even more preferably in the range of 0.100 to 0.600, and particularly preferably in the range of 0.300 to 0.450. By making the ratio (C / D) 0.001 or more, the strength of the glittering toner particles is ensured, breakage due to stress during image formation is suppressed, and a decrease in charge due to exposure of the pigment, which results in fogging, is suppressed. On the other hand, by making the ratio 0.700 or less, excellent glittering properties are obtained.

[0034] The average maximum thickness C and the average equivalent circle diameter D are measured by the following method. The glittering toner particles are placed on a smooth surface and dispersed evenly by applying vibration. For 1000 glittering toner particles, the maximum thickness C and the equivalent circle diameter D of the glittering toner particle as viewed from above are measured at 1000 times magnification using a color laser microscope "VK-9700" (manufactured by Keyence Corporation), and the arithmetic average value is calculated.

[0035] The angle between the long axis direction of the cross section of the glittering toner particle and the long axis direction of the glittering pigment When a cross section of a glittering toner particle in the thickness direction is observed, the proportion (by number) of glittering pigments in which the angle between the long axis direction of the glittering toner particle in the cross section and the long axis direction of the glittering pigment is in the range of -30° to +30° is preferably 60% or more of all glittering pigments observed.Moreover, this proportion is more preferably 70% to 95%, and particularly preferably 80% to 90%. When the above ratio is 60% or more, excellent brilliance can be obtained.

[0036] Here, a method for observing the cross section of a glittering toner particle will be described. The glittering toner particles are embedded in a bisphenol A liquid epoxy resin and a hardener, and then a cutting sample is prepared. The cutting sample is then cut at -100°C using a cutting machine with a diamond knife, for example, an ultramicrotome (UltracutUCT, manufactured by Leica), to prepare a sample for observation. The observation sample is observed, for example, with an ultra-high resolution field emission scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation) at a magnification where 1 to 10 glittering toner particles are visible in one field of view. Specifically, the cross section of a glossy toner particle (cross section along the thickness direction of the glossy toner particle) is observed, and for 100 observed glossy toner particles, the number of glossy pigments for which the angle between the long axis direction in the cross section of the glossy toner particle and the long axis direction of the glossy pigment is in the range of -30° to +30° is counted using image analysis software such as the image analysis software (Win ROOF) manufactured by Mitani Shoji Co., Ltd., or an output sample of the observed image and a protractor, and the percentage is calculated.

[0037] The volume average particle size of the glittering toner particles is preferably 3 μm or more and 30 μm or less, and more preferably 5 μm or more and 20 μm or less.

[0038] The various average particle sizes and particle size distribution indexes of the glittering toner particles are measured using a Coulter Multisizer II (manufactured by Beckman Coulter, Inc.), and the electrolyte is measured using an ISOTON-II (manufactured by Beckman Coulter, Inc.). For the measurement, 0.5 mg to 50 mg of the measurement sample is added to 2 ml of a 5% aqueous solution of a surfactant (preferably sodium alkylbenzene sulfonate) as a dispersant, and this is then added to 100 ml to 150 ml of the electrolyte. The electrolyte with the sample suspended in it is dispersed for 1 minute using an ultrasonic disperser, and the particle size distribution of particles with diameters in the range of 2 μm to 60 μm is measured using a Coulter Multisizer II with an aperture diameter of 100 μm. The number of particles sampled is 50,000. Based on the measured particle size distribution, cumulative distributions of volume and number are drawn for each divided particle size range (channel) from the smallest diameter side, and the particle size at 16% of the cumulative size is defined as the volume particle size D16v, the number particle size D16p, the particle size at 50% of the cumulative size as the volume average particle size D50v, the cumulative number average particle size D50p, and the particle size at 84% of the cumulative size as the volume particle size D84v and number particle size D84p. Using these, the volumetric particle size distribution index (GSDv) is (D84v / D16v) 1 / 2 The number size distribution index (GSDp) is (D84p / D16p) 1 / 2 It is calculated as:

[0039] The ratio (aspect ratio) of the average length in the major axis direction to the average length in the thickness direction of the glittering toner particles is preferably 1.5 or more and 15 or less, more preferably 2 or more and 10 or less, and even more preferably 3 or more and 8 or less. The average length in the thickness direction and the average length in the major axis direction of the glittering toner particles are calculated by placing the glittering toner particles on a smooth surface and dispersing them evenly by applying vibration. For 1,000 glittering toner particles, the maximum thickness and the major axis length of the glittering toner particles as viewed from above are measured at 1,000 times magnification using a color laser microscope "VK-9700" (manufactured by Keyence Corporation), and the arithmetic average value is calculated.

[0040] The components constituting the glittering toner according to this embodiment will be described below.

[0041] -Binding resin- Examples of the binder resin include vinyl resins made of homopolymers of monomers such as styrenes (e.g., styrene, parachlorostyrene, α-methylstyrene, etc.), (meth)acrylic acid esters (e.g., methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, etc.), ethylenically unsaturated nitriles (e.g., acrylonitrile, methacrylonitrile, etc.), vinyl ethers (e.g., vinyl methyl ether, vinyl isobutyl ether, etc.), vinyl ketones (vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone, etc.), and olefins (e.g., ethylene, propylene, butadiene, etc.), or copolymers of two or more of these monomers. Examples of the binder resin include non-vinyl resins such as epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, and modified rosin, mixtures of these with the vinyl resins, and graft polymers obtained by polymerizing vinyl monomers in the coexistence of these. Among these, styrene-acrylic resin or polyester resin is preferably used. These binder resins may be used alone or in combination of two or more.

[0042] Styrene acrylic resin The styrene-acrylic resin may be a copolymer obtained by copolymerizing at least a styrene and a (meth)acrylic acid ester. The styrene-acrylic resin may be a copolymer obtained by polymerizing other monomers in addition to the styrene and the (meth)acrylic acid ester. In addition, the term "(meth)acrylic" and the like include both "acrylic" and "methacrylic", etc.

[0043] The styrenes are monomers having a styrene skeleton, and specifically include styrene, vinylnaphthalene, alkyl-substituted styrenes such as α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, and pn-dodecylstyrene, aryl-substituted styrenes such as p-phenylstyrene, alkoxy-substituted styrenes such as p-methoxystyrene, halogen-substituted styrenes such as p-chlorostyrene and 3,4-dichlorostyrene, nitro-substituted styrenes such as m-nitrostyrene, o-nitrostyrene, and p-nitrostyrene, 4-fluorostyrene, 2,5-difluorostyrene, and fluorine-substituted styrenes. Among these, styrenes are preferably styrene, p-ethylstyrene, and pn-butylstyrene. These styrenes may be used alone or in combination of two or more.

[0044] The (meth)acrylic acid esters are monomers having a structure in which (meth)acrylic acid is esterified. Specific examples of the (meth)acrylic acid esters include n-methyl (meth)acrylate, n-ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, n-lauryl (meth)acrylate, n-tetradecyl (meth)acrylate, ... p) (meth)acrylic acid alkyl esters such as n-hexadecyl acrylate, n-octadecyl (meth)acrylate, isopropyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, isopentyl (meth)acrylate, amyl (meth)acrylate, neopentyl (meth)acrylate, isohexyl (meth)acrylate, isoheptyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate; (Meth)acrylic acid carboxy-substituted alkyl esters such as β-carboxyethyl (meth)acrylate; (meth)acrylic acid hydroxy-substituted alkyl esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; (Meth)acrylic acid alkoxy-substituted alkyl esters such as 2-methoxyethyl (meth)acrylate; etc.

[0045] Among these (meth)acrylic acid esters, (meth)acrylic acid esters having an alkyl group having 2 to 14 carbon atoms (preferably 2 to 10 carbon atoms, more preferably 3 to 8 carbon atoms) are preferred. These (meth)acrylic acid esters may be used alone or in combination of two or more kinds.

[0046] Examples of other monomers include (meth)acrylic acid, ethylenically unsaturated nitriles (acrylonitrile, methacrylonitrile, etc.), vinyl ethers (vinyl methyl ether, vinyl isobutyl ether, etc.), vinyl ketones (vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone, etc.), divinyls (divinyl adipate, etc.), olefins (ethylene, propylene, butadiene, etc.), thiols (dodecanethiol, etc.), dicarboxylic acids (decanediol acrylate, etc.), and the like.

[0047] In the styrene-acrylic resin, the proportion of styrenes in the total polymer components is 60% by mass or more, preferably 65% ​​by mass or more and 90% by mass or less, and more preferably 70% by mass or more and 85% by mass or less. On the other hand, the proportion of (meth)acrylic acid esters in the total polymer components is preferably from 10% by mass to 40% by mass, and more preferably from 10% by mass to 35% by mass.

[0048] The glass transition temperature (Tg) of the styrene-acrylic resin is preferably 45°C or higher and 80°C or lower, and more preferably 45°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, from the "extrapolated glass transition onset temperature" described in JIS K 7121 1987 "Method for measuring transition temperature of plastics."

[0049] The weight average molecular weight (Mw) of the styrene-acrylic resin is preferably 5,000 or more and 700,000 or less, and more preferably 7,000 or more and 300,000 or less. 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 styrene-acrylic resin is preferably 1.0 or more and 100 or less, and more preferably 1.2 or more and 50 or less. The weight average molecular weight and number average molecular weight are measured by gel permeation chromatography (GPC). The molecular weight measurement by GPC is performed using a Tosoh GPC HLC-8120GPC as the measuring device, a Tosoh TSKgel SuperHM-M (15 cm) column, and THF solvent. The weight average molecular weight and number average molecular weight are calculated from the measurement results using a molecular weight calibration curve created with a monodisperse polystyrene standard sample.

[0050] Polyester resin The polyester resin may be, for example, a known amorphous polyester resin. The polyester resin may be used in combination with a crystalline polyester resin together with the amorphous polyester resin. However, the content of the crystalline polyester resin is preferably in the range of 2% by mass to 40% by mass (preferably 2% by mass to 20% by mass) based on the total binder resin.

[0051] The "crystalline" nature of a resin refers to the presence of a clear endothermic peak rather than a stepwise change in the amount of endothermic heat in differential scanning calorimetry (DSC); specifically, the half-width of the endothermic peak is within 10°C when measured at a heating rate of 10 (°C / min). On the other hand, the term "amorphous" for a resin refers to a half-width exceeding 10° C., a stepwise change in endothermic heat quantity, or no clear endothermic peak being observed.

[0052] Amorphous polyester resin The amorphous polyester resin may be, for example, a condensation polymer of a polyvalent carboxylic acid and a polyhydric alcohol. The amorphous polyester resin may be a commercially available product or a synthesized product.

[0053] Examples of polyvalent carboxylic acids include aliphatic dicarboxylic acids (e.g., oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, alkenylsuccinic acid, adipic acid, sebacic acid, etc.), alicyclic dicarboxylic acids (e.g., cyclohexanedicarboxylic acid, etc.), aromatic dicarboxylic acids (e.g., terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, etc.), anhydrides thereof, and lower alkyl esters thereof (e.g., having 1 to 5 carbon atoms). Among these, aromatic dicarboxylic acids are preferable as polyvalent carboxylic acids. The polyvalent carboxylic acid may be a trivalent or higher carboxylic acid having a crosslinked or branched structure in combination with a dicarboxylic acid. Examples of the trivalent or higher carboxylic acid include trimellitic acid, pyromellitic acid, anhydrides thereof, and lower (e.g., carbon number 1 to 5) alkyl esters thereof. The polyvalent carboxylic acids may be used alone or in combination of two or more kinds.

[0054] Examples of polyhydric alcohols include aliphatic diols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, etc.), alicyclic diols (e.g., cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, etc.), and aromatic diols (e.g., ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, etc.). Among these, examples of polyhydric alcohols include aromatic diols and alicyclic diols, and more preferably aromatic diols. As the polyhydric alcohol, a polyhydric alcohol having a crosslinked or branched structure of three or more may be used in combination with the diol. Examples of the polyhydric alcohol having a trihydric or higher valence include glycerin, trimethylolpropane, and pentaerythritol. The polyhydric alcohols may be used alone or in combination of two or more kinds.

[0055] The glass transition temperature (Tg) of the amorphous polyester resin is preferably 50°C or higher and 80°C or lower, and more preferably 50°C or higher and 65°C or lower. The glass transition temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC), more specifically, from the "extrapolated glass transition onset temperature" described in the method for determining glass transition temperature in JIS K 7121-1987 "Method for measuring transition temperature of plastics."

[0056] The weight average molecular weight (Mw) of the amorphous polyester resin is preferably 5,000 or more and 1,000,000 or less, and more preferably 7,000 or more and 500,000 or less. The number average molecular weight (Mn) of the amorphous polyester resin is preferably 2,000 or more and 100,000 or less. The molecular weight distribution Mw / Mn of the amorphous polyester resin is preferably 1.5 or more and 100 or less, and more preferably 2 or more and 60 or less. The weight average molecular weight and number average molecular weight are measured by gel permeation chromatography (GPC). The molecular weight measurement by GPC is performed using a Tosoh GPC HLC-8120GPC as the measuring device, a Tosoh TSKgel SuperHM-M (15 cm) column, and THF solvent. The weight average molecular weight and number average molecular weight are calculated from the measurement results using a molecular weight calibration curve created with a monodisperse polystyrene standard sample.

[0057] The amorphous polyester resin can be obtained by a known manufacturing method, for example, by carrying out the reaction while removing water and alcohol generated during condensation by setting the polymerization temperature to 180° C. or higher and 230° C. or lower, and reducing the pressure in the reaction system as necessary. If the raw material monomer is not soluble or compatible at the reaction temperature, a high boiling point solvent may be added as a solubilizing agent to dissolve it. In this case, the polycondensation reaction is carried out while distilling off the solubilizing agent. If a monomer with poor compatibility is present, it is recommended that the monomer with poor compatibility is condensed in advance with the acid or alcohol to be polycondensed, and then polycondensed with the main component.

[0058] Crystalline polyester resin The crystalline polyester resin may be, for example, a polycondensate of a polyvalent carboxylic acid and a polyhydric alcohol. The crystalline polyester resin may be a commercially available product or a synthesized product. Here, the crystalline polyester resin is preferably a polycondensate using a polymerizable monomer having a linear aliphatic group rather than a polymerizable monomer having an aromatic group, since the crystalline polyester resin can easily form a crystalline structure.

[0059] Examples of polyvalent carboxylic acids include aliphatic dicarboxylic acids (e.g., oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, etc.), aromatic dicarboxylic acids (e.g., dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, etc.), anhydrides thereof, and lower alkyl esters thereof (e.g., having 1 to 5 carbon atoms). The polyvalent carboxylic acid may be a trivalent or higher carboxylic acid having a crosslinked or branched structure in combination with a dicarboxylic acid. Examples of the trivalent carboxylic acid include aromatic carboxylic acids (e.g., 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, etc.), their anhydrides, and their lower alkyl esters (e.g., carbon number 1 to 5). As the polyvalent carboxylic acid, a dicarboxylic acid having a sulfonic acid group and a dicarboxylic acid having an ethylenic double bond may be used in combination with these dicarboxylic acids. The polyvalent carboxylic acids may be used alone or in combination of two or more kinds.

[0060] Examples of polyhydric alcohols include aliphatic diols (for example, straight-chain aliphatic diols having 7 to 20 carbon atoms in the main chain). Examples of aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, and 1,14-eicosanedecanediol. Among these, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol are preferred as aliphatic diols. The polyhydric alcohol may be a trihydric or higher alcohol having a crosslinked or branched structure in combination with the diol. Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol. The polyhydric alcohols may be used alone or in combination of two or more kinds.

[0061] Here, the polyhydric alcohol has an aliphatic diol content of 80 mol % or more, preferably 90 mol % or more.

[0062] The melting temperature of the crystalline polyester resin is preferably 50°C or higher and 100°C or lower, more preferably 55°C or higher and 90°C or lower, and even more preferably 60°C or higher and 85°C or lower. The melting temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC) based on the "melting peak temperature" described in the method for determining melting temperature in JIS K7121-1987 "Method for measuring transition temperature of plastics."

[0063] The weight average molecular weight (Mw) of the crystalline polyester resin is preferably 6,000 or more and 35,000 or less.

[0064] The crystalline polyester resin can be obtained by a known manufacturing method, for example, in the same manner as the amorphous polyester.

[0065] Amorphous resin having an amorphous polyester resin segment and a styrene-acrylic resin segment (hereinafter also referred to as "hybrid amorphous resin") The hybrid amorphous resin is an amorphous resin in which an amorphous polyester resin segment and a styrene-acrylic resin segment are chemically bonded to each other. Examples of the hybrid amorphous resin include a resin having a main chain made of a polyester resin and a side chain made of a styrene-acrylic resin chemically bonded to the main chain; a resin having a main chain made of a styrene-acrylic resin and a side chain made of a polyester resin chemically bonded to the main chain; a resin having a main chain formed by chemically bonding a polyester resin and a styrene-acrylic resin; a resin having a main chain formed by chemically bonding a polyester resin and a styrene-acrylic resin, and at least one of a side chain made of a polyester resin chemically bonded to the main chain and a side chain made of a styrene-acrylic resin chemically bonded to the main chain; and the like.

[0066] The amorphous polyester resin and the styrene-acrylic resin in each segment are as described above, and therefore the description will be omitted.

[0067] The total amount of the polyester resin segment and the styrene-acrylic resin segment in the entire hybrid amorphous resin is preferably 80 mass% or more, more preferably 90 mass% or more, even more preferably 95 mass% or more, and even more preferably 100 mass%.

[0068] In the hybrid amorphous resin, the proportion of the styrene-acrylic resin segment in the total amount of the polyester resin segment and the styrene-acrylic resin segment is preferably 20% by mass or more and 60% by mass or less, more preferably 25% by mass or more and 55% by mass or less, and even more preferably 30% by mass or more and 50% by mass or less.

[0069] The hybrid amorphous resin is preferably produced by any one of the following methods (i) to (iii). (i) After preparing a polyester resin segment by condensation polymerization of a polyhydric alcohol and a polycarboxylic acid, a monomer constituting a styrene-acrylic resin segment is addition-polymerized. (ii) A styrene-acrylic resin segment is prepared by addition polymerization of an addition-polymerizable monomer, and then a polyhydric alcohol and a polycarboxylic acid are condensation-polymerized. (iii) Polycondensation of a polyhydric alcohol and a polycarboxylic acid and addition polymerization of an addition-polymerizable monomer are carried out in parallel.

[0070] The content of the binder resin is, for example, preferably from 40% by mass to 95% by mass, more preferably from 50% by mass to 90% by mass, and even more preferably from 60% by mass to 85% by mass, based on the total amount of the glittering toner particles.

[0071] -Photoluminescent pigments- Examples of the luster pigment include pigments (luster pigments) that can impart a sense of luster such as metallic luster.Specific examples of the luster pigment include metal powders such as aluminum (metal of aluminum alone), brass, bronze, nickel, stainless steel, and zinc; mica coated with titanium oxide, yellow iron oxide, and the like; coated flaky inorganic crystal substrates such as barium sulfate, layered silicate, and layered aluminum silicate; single crystal plate-like titanium oxide; basic carbonate; acid oxychloride bismuth; natural guanine; flaky glass powder; and metal-deposited flaky glass powder, and there is no particular limit to the luster pigments.

[0072] Among the bright pigments, metal powders are preferred, particularly from the viewpoint of specular reflection intensity, and among these, aluminum is most preferred.

[0073] The shape of the bright pigment according to this embodiment is flat (scaly) in order to provide high brightness in a fixed image. The flat bright pigment will be described below. The average length in the major axis direction of the flat bright pigment is preferably from 1 μm to 30 μm, more preferably from 3 μm to 20 μm, and even more preferably from 5 μm to 15 μm. The ratio (aspect ratio) of the average length in the major axis direction to the average length in the thickness direction of the shiny pigment is preferably 5 or more and 200 or less, more preferably 10 or more and 100 or less, and even more preferably 30 or more and 70 or less.

[0074] The average length and aspect ratio of each of the brilliant pigments are measured by the following method: Using a scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation), photographs of pigment particles are taken at a measurable magnification (300 to 100,000 times), and in a state in which the obtained images of the pigment particles are two-dimensionalized, the length in the major axis direction and the length in the thickness direction of each particle are measured, and the average length in the major axis direction and the aspect ratio of the brilliant pigment are calculated.

[0075] The volume average particle size of the bright pigment is preferably from 1.0 μm to 20.0 μm, and more preferably from 2.0 μm to 15.0 μm. When the volume average particle size of the glittering pigment is 1.0 μm or more, the resulting image has excellent glittering properties. If the volume average particle size of the bright pigment is 20.0 μm or less, the resulting toner has excellent charging characteristics and transfer unevenness is suppressed.

[0076] The volume average particle size of the bright pigment is measured as follows. Based on the particle size distribution measured with a measuring device such as Multisizer II (manufactured by Coulter), a cumulative distribution is drawn for each volume of divided particle size ranges (channels) from the smallest diameter side, and the particle size at which the cumulative 50% is reached is the volume average particle size. The volume average particle size of the glittering pigment in the toner particles after production is measured by mixing and stirring the toner with a solvent that is capable of dissolving only the toner resin but not the glittering pigment, and after the toner resin has sufficiently dissolved in the solvent, the glittering pigment is subjected to solid-liquid separation and the volume average particle size is measured using a particle size distribution measuring device similar to that described above.

[0077] The content of the glittering pigment relative to the total mass of the glittering toner particles is preferably from 1% by mass to 70% by mass, more preferably from 5% by mass to 50% by mass, and even more preferably from 5% by mass to 40% by mass.

[0078] The glitter toner in this embodiment may contain a colorant and a release agent.

[0079] -Coloring agent- As the colorant, the same colorant as that used in the colored toner described later is used.

[0080] When the glitter toner contains a colorant, the content of the colorant is, for example, preferably from 0% by mass to 20% by mass, and more preferably from 3.0% by mass to 15% by mass, based on the total glitter toner particles.

[0081] -Release agent- Examples of the release agent include hydrocarbon waxes, natural waxes such as carnauba wax, rice wax, and candelilla wax, synthetic or mineral / petroleum waxes such as montan wax, and ester waxes such as fatty acid esters and montan acid esters. The release agent is not limited to these.

[0082] The melting temperature of the release agent is preferably 50°C or higher and 110°C or lower, and more preferably 60°C or higher and 100°C or lower. The melting temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC) based on the "melting peak temperature" described in the method for determining melting temperature in JIS K 7121-1987 "Method for measuring transition temperature of plastics."

[0083] The content of the release agent is, for example, preferably from 1% by mass to 20% by mass, and more preferably from 5% by mass to 15% by mass, based on the total amount of the glittering toner particles.

[0084] -Other additives- Examples of other additives include well-known additives such as magnetic materials, charge control agents, inorganic powders, etc. These additives are contained in the glittering toner particles as internal additives.

[0085] -External additives- The glittering toner may contain an external additive. Examples of the external additive include inorganic particles, such as SiO2, TiO2, Al2O3, CuO, ZnO, SnO2, CeO2, Fe2O3, MgO, BaO, CaO, K2O, Na2O, ZrO2, CaO·SiO2, K2O·(TiO2)n, Al2O3·2SiO2, CaCO3, MgCO3, BaSO4, and MgSO4.

[0086] The surface of the inorganic particles as an external additive may be subjected to a hydrophobic treatment. The hydrophobic treatment may be performed, for example, by immersing the inorganic particles in a hydrophobic treatment agent. The hydrophobic treatment agent is not particularly limited, and examples thereof include silane coupling agents, silicone oils, titanate coupling agents, and aluminum coupling agents. These may be used alone or in combination of two or more. The amount of the hydrophobizing agent is usually, for example, 1 part by mass or more and 10 parts by mass or less per 100 parts by mass of the inorganic particles.

[0087] Examples of external additives include resin particles (resin particles such as polystyrene, polymethyl methacrylate (PMMA), and melamine resin), cleaning agents (for example, metal salts of higher fatty acids such as zinc stearate, and fluorine-based polymer particles).

[0088] The amount of the external additive is, for example, preferably from 0.01% by mass to 5% by mass, more preferably from 0.01% by mass to 2.0% by mass, based on the total mass of the glitter toner particles.

[0089] (Color toner) Next, components constituting the color toner according to this embodiment will be described. The color toner according to the present embodiment contains color toner particles that contain a binder resin and a colorant other than the above-mentioned glittering pigment.

[0090] -Binding resin- As the binder resin, those listed as binder resins used in glittering toners can be used.

[0091] The content of the binder resin is, for example, preferably from 40% by mass to 95% by mass, more preferably from 50% by mass to 90% by mass, and even more preferably from 60% by mass to 85% by mass, based on the total amount of the color toner particles.

[0092] -Coloring agent- Examples of colorants include carbon black, chrome yellow, Hansa Yellow, benzidine yellow, threne yellow, quinoline yellow, pigment yellow, permanent orange GTR, pyrazolone orange, Balkan orange, watch young red, permanent red, brilliant carmine 3B, brilliant carmine 6B, DuPont oil red, pyrazolone red, lithol red, rhodamine B lake, lake red C, pigment red, rose bengal, aniline blue, ultramarine blue, and tetrahydrofuran. Examples of the dyes include various pigments such as phosphorus blue, chalcoil blue, methylene blue chloride, phthalocyanine blue, pigment blue, phthalocyanine green, and malachite green oxalate, and various dyes such as acridine-based, xanthene-based, azo-based, benzoquinone-based, azine-based, anthraquinone-based, thioindigo-based, dioxazine-based, thiazine-based, azomethine-based, indigo-based, phthalocyanine-based, aniline black-based, polymethine-based, triphenylmethane-based, diphenylmethane-based, and thiazole-based dyes. The colorant may be used alone or in combination of two or more kinds.

[0093] The colorant may be surface-treated as necessary, or may be used in combination with a dispersant. In addition, a plurality of types of colorants may be used in combination.

[0094] The content of the colorant is, for example, preferably from 1% by mass to 30% by mass, and more preferably from 3% by mass to 15% by mass, based on the total amount of the color toner particles.

[0095] -Release agent- The colored toner particles may include a release agent. The external additive used has the same meaning as the release agent used in the glittering toner particles, and the preferred embodiments are also the same.

[0096] -Other additives- The color toner particles may contain a binder resin, a colorant other than the photoluminescent pigment, and other additives other than the release agent. The other additives are the same as those used in the glittering toner particles.

[0097] -Characteristics of colored toner particles- The color toner particles may be toner particles having a single layer structure, or may be toner particles having a so-called core-shell structure composed of a core particle and a coating layer (shell layer) that coats the core. Here, the toner particles having a core-shell structure may be composed of, for example, a core containing a binder resin and, if necessary, other additives such as a colorant and a release agent, and a coating layer containing the binder resin.

[0098] The volume average particle size (D50v) of the color toner particles is preferably from 5.5 μm to 7.5 μm, more preferably from 5.8 μm to 7.2 μm, and even more preferably from 6.0 μm to 7.0 μm. By setting the volume average particle size of the color toner particles within the above numerical range, the pressure applied to the glitter toner during fixing is likely to be improved. This promotes the exudation of the release agent from the glitter toner. This makes it easier to reduce the amount of release agent left behind in the image, and makes it easier to suppress offset during fixing. It is presumed that this makes it possible to form a glitter image that is higher in gloss as well as glitter.

[0099] The various average particle sizes and particle size distribution indexes of the color toner particles are measured by the same methods as those of the glitter toner particles.

[0100] The average circularity of the color toner particles is preferably 0.94 or more and 1.00 or less, and more preferably 0.95 or more and 0.98 or less.

[0101] The average circularity of color toner particles is calculated by (circular equivalent perimeter) / (perimeter) [(perimeter of a circle having the same projected area as the particle image) / (perimeter of the particle projected image)]. Specifically, it is a value measured by the following method. First, the colored toner particles to be measured are sucked and collected, flattened, and a still image of the particles is captured by instantaneous strobe light emission, and the particle image is analyzed by a flow-type particle image analyzer (FPIA-3000 manufactured by Sysmex Corporation). The number of samples to be taken in order to calculate the average circularity is 3,500. In addition, when the color toner contains an external additive, the color toner (developer) to be measured is dispersed in water containing a surfactant, and then ultrasonic treatment is performed to obtain color toner particles from which the external additive has been removed.

[0102] (External additives) The color toner may contain an external additive. The external additives used are the same as those used in the glitter toner, and the preferred embodiments are also the same.

[0103] <Relationship between glitter toner and color toner> (Aspects of binder resin) In the toner set according to this embodiment, the binder resin contained in the glitter toner particles and the binder resin contained in the color toner particles are incompatible with each other.

[0104] It is preferable that the binder resin contained in the glitter toner particles and the binder resin contained in the color toner particles have different solubility parameters. By making the solubility parameters of the binder resin contained in the glitter toner particles and the binder resin contained in the color toner particles different from each other, the compatibility of the two binder resins is likely to be reduced. Therefore, an interface is more likely to be formed between the glitter toner and the color toner when the toner is fixed. This makes it easier for the release agent to seep out to the image surface, and it is presumed that a glitter image with higher glitter and gloss can be formed.

[0105] The difference in absolute value of the solubility parameter between the binder resin contained in the glitter toner particles and the binder resin contained in the colored toner particles is 0.5 or more and 2.0 or less, preferably 0.6 or more and 1.8 or less, more preferably 0.7 or more and 1.6 or less, and even more preferably 0.8 or more and 1.4 or less.

[0106] By setting the difference in solubility parameter between the binder resin contained in the glitter toner particles and the binder resin contained in the color toner particles within the above numerical range, the compatibility of the two binder resins is likely to be further reduced. Therefore, an interface is more likely to be formed between the glitter toner and the color toner when the toner is fixed. This makes it easier for the release agent to seep out to the image surface, and it is presumed that a glitter image with higher glitter and gloss can be formed.

[0107] It is preferable that one of the glittering toner particles and the colored toner particles contains an amorphous polyester resin as a binder resin, and the other contains a styrene-acrylic resin. By combining the types of binder resins contained in the glitter toner particles and the color toner particles as described above, the difference in solubility parameters of the two binder resins is likely to become large. Therefore, the compatibility of the two binder resins is likely to be further reduced, and an interface is likely to be formed between the glitter toner and the color toner when the toner is fixed. In addition, the difference in solubility parameters of the two binder resins and the release agent is likely to be large, and the compatibility of the binder resin and the release agent is likely to be reduced. As a result, it is assumed that the release agent is more likely to seep out to the image surface, and a glitter image with higher glitter and gloss can be formed.

[0108] It is preferable that the glittering toner particles contain an amorphous polyester resin as a binder resin, and the colored toner particles contain a styrene-acrylic resin as a binder resin. By using the above-mentioned combination of binder resins contained in the glitter toner particles and the color toner particles, it is possible to form a glitter image having higher glitter and gloss. The reason for this is presumed to be as follows. Styrene acrylic resins tend to have higher hardness than amorphous polyester resins. Therefore, when a glitter toner and a color toner are applied to a recording medium in this order, the pressure applied to the glitter toner during fixing tends to increase. This promotes the exudation of the release agent from the glitter toner. Therefore, the amount of release agent left in the image tends to decrease, and offset during fixing is more easily suppressed. It is presumed that this allows the formation of a glitter image that has higher glossiness as well as glitteriness.

[0109] It is preferable that one of the glittering toner particles and the colored toner particles contains, as the amorphous polyester resin or the styrene-acrylic resin, an amorphous resin having an amorphous polyester resin segment and a styrene-acrylic resin segment (hybrid amorphous resin). When either the glitter toner particles or the color toner particles contain a hybrid amorphous resin, the glitter and glossiness tend to be further increased. The reason for this is presumed to be as follows. During thermal fixing, it acts mainly as a plasticizer for the binder resin and functions as a fixing aid that contributes to low-temperature fixing properties. The toner melt viscosity is reduced, making the surface smoother and improving gloss. The increased gloss also improves the orientation of the glittering pigment, which is presumably improving glittering properties.

[0110] (Storage modulus) It is preferable that the storage modulus at 120° C. of the color toner is greater than that of the glitter toner. By setting the storage modulus relationship between the glitter toner and the color toner as described above, it is easy to improve both the glitter and the gloss. The reason for this is presumed to be as follows. When the storage modulus of the color toner at 120°C is greater than that of the glossy toner, the color toner tends to have a higher hardness than the glossy toner. Therefore, when the glossy toner and the color toner are attached to a recording medium in this order, the pressure applied to the glossy toner during fixing tends to increase. This promotes the exudation of the release agent from the glossy toner. Therefore, the amount of release agent left in the image tends to decrease, and offset during fixing is more easily suppressed. It is presumed that this makes it possible to form a glossy image that has higher glossiness as well as glossiness.

[0111] The absolute value of the difference (|Es-Ec|) between the storage modulus Es of the glossy toner at 120°C and the storage modulus Ec of the colored toner at 120°C is preferably 10,000 Pa or more and 20,000 Pa or less, more preferably 12,000 Pa or more and 18,000 Pa or less, and even more preferably 13,000 Pa or more and 16,000 Pa or less. By setting the storage modulus of the glitter toner and the color toner within the above-mentioned range, the glitter and the glossiness tend to be further improved. The reason for this is presumed to be as follows. By setting the storage modulus of the glossy toner and the color toner within the above-mentioned numerical range, when the glossy toner and the color toner are adhered to a recording medium in this order, the pressure applied to the glossy toner during fixing is more likely to be improved. Therefore, the exudation of the release agent from the glossy toner is more promoted. Therefore, the amount of release agent left behind in the image is more likely to be reduced, and offset during fixing is more likely to be suppressed. It is presumed that this makes it possible to form a glossy image with even higher glossiness and glossiness.

[0112] (Relationship between solubility parameters of binder resin and release agent) It is preferable that the glossy toner particles and the colored toner particles contain a release agent, and that the absolute value of the difference in solubility parameter between the release agent contained in the glossy toner particles and the binder resin contained in the colored toner particles is greater than the absolute value of the difference in solubility parameter between the release agent contained in the glossy toner particles and the binder resin contained in the colored toner particles.

[0113] By setting the relationship between the solubility parameters of the binder resin and the release agent as described above, it is easy to improve the luster as well as the brightness. The reason for this is presumed to be as follows. When the absolute value of the difference in solubility parameter between the release agent contained in the glitter toner particles and the binder resin contained in the colored toner particles is larger than the absolute value of the difference in solubility parameter between the release agent contained in the glitter toner particles and the binder resin contained in the glitter toner particles, the compatibility between the release agent contained in the glitter toner particles and the binder resin contained in the colored toner particles decreases. Then, when the toner is fixed, the release agent contained in the glitter toner particles is more likely to pass through the colored toner layer. Therefore, when the toner is fixed, the release agent contained in the glitter toner particles is more likely to move to the image surface. Therefore, it is presumed that the glossiness is likely to be increased as well as the glitteriness.

[0114] (Toner particle size difference) It is preferable that the volume average particle size of the color toner particles is smaller than that of the glitter toner particles, and the absolute value of the difference in volume average particle size between the glitter toner particles and the color toner particles is 2.7 μm or more and 5.2 μm or less.

[0115] The absolute value of the difference in volume average particle size between the glitter toner particles and the color toner particles is more preferably 3.0 μm or more and 4.9 μm or less, and further preferably 3.3 μm or more and 4.6 μm or less.

[0116] By setting the volume average particle size relationship between the glossy toner particles and the color toner particles as described above, the pressure applied to the glossy toner during toner fixing is more likely to be improved, which is believed to result in the formation of a glossy image with higher gloss and glossiness.

[0117] <Toner manufacturing method> The glossy toner and colored toner (hereinafter, collectively referred to as "toner") of this embodiment may be prepared by producing glossy toner particles or colored toner particles (hereinafter, collectively referred to as "toner particles"), and then adding an external additive to the toner particles. The method for producing the toner particles is not particularly limited, and the toner particles can be produced by a known dry method such as a kneading and pulverizing method, or a wet method such as an emulsion aggregation method, a dissolution suspension method, or a suspension polymerization method. In the kneading and grinding method, the colorants and other materials are mixed together, then the materials are melted and kneaded using a kneader or extruder, etc., the resulting molten mixture is coarsely ground, then pulverized using a jet mill, etc., and the toner particles of the desired particle size are obtained using an air classifier. Among these methods, the emulsion aggregation method is preferred because it is easy to control the shape and particle size of the toner particles and also has a wide range of control over the toner particle structure, such as a core-shell structure. The method for producing toner particles by the emulsion aggregation method will be described in detail below.

[0118] The emulsion aggregation method of this embodiment includes an emulsification step of emulsifying the raw materials constituting the toner particles to form resin particles (emulsion particles) and the like, an aggregation step of forming aggregates of the resin particles, and a fusion step of fusing the aggregates.

[0119] (emulsification process) The resin particle dispersion may be prepared by a general polymerization method, such as emulsion polymerization, suspension polymerization, or dispersion polymerization, or by emulsifying a solution of a water-based medium and a binder resin by applying shear force with a disperser. In this case, the resin may be heated to reduce the viscosity of the resin component to form particles. A dispersant may be used to stabilize the dispersed resin particles. Furthermore, if the resin is oil-based and dissolves in a solvent with a relatively low solubility in water, the resin is dissolved in the solvent and dispersed in water together with a dispersant and a polymer electrolyte, and then the solvent is evaporated by heating or reducing pressure to prepare a resin particle dispersion.

[0120] Examples of the aqueous medium include water such as distilled water and ion-exchanged water; alcohols; and the like, with water being preferred. Examples of dispersants used in the emulsification step include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, sodium polyacrylate, and sodium polymethacrylate; anionic surfactants such as sodium dodecylbenzenesulfonate, sodium octadecyl sulfate, sodium oleate, sodium laurate, and potassium stearate; cationic surfactants such as laurylamine acetate, stearylamine acetate, and lauryl trimethylammonium chloride; amphoteric surfactants such as lauryl dimethylamine oxide; and nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, and polyoxyethylene alkyl amines; and inorganic salts such as tricalcium phosphate, aluminum hydroxide, calcium sulfate, calcium carbonate, and barium carbonate.

[0121] Examples of dispersing machines used to prepare the emulsion include homogenizers, homomixers, pressure kneaders, extruders, and media dispersing machines. The size of the resin particles is preferably an average particle size (volume average particle size) of 1.0 μm or less, more preferably 60 nm to 300 nm, and even more preferably 150 nm to 250 nm. If the size is 60 nm or more, the resin particles tend to become unstable in the dispersion liquid, and may easily aggregate. If the size is 1.0 μm or less, the particle size distribution of the toner may become narrow.

[0122] In preparing the release agent dispersion, the release agent is dispersed in water together with an ionic surfactant, a polymer electrolyte such as a polymer acid or a polymer base, and then heated to a temperature equal to or higher than the melting temperature of the release agent, and a dispersion treatment is performed using a homogenizer or a pressure discharge type disperser to which a strong shear force is applied. Through such treatment, the release agent dispersion is obtained. During the dispersion treatment, an inorganic compound such as polyaluminum chloride may be added to the dispersion. Examples of desirable inorganic compounds include polyaluminum chloride, aluminum sulfate, highly basic polyaluminum chloride (BAC), polyaluminum hydroxide, and aluminum chloride. Among these, polyaluminum chloride, aluminum sulfate, and the like are desirable. The release agent dispersion is used in the emulsion aggregation method, but the release agent dispersion may also be used when producing a toner by the suspension polymerization method.

[0123] By the dispersion treatment, a release agent dispersion liquid containing release agent particles having a volume average particle size of 1 μm or less is obtained. The volume average particle size of the release agent particles is more preferably 100 nm or more and 500 nm or less. When the volume average particle size is 100 nm or more, the releasing agent component is generally more easily incorporated into the toner, although this is influenced by the properties of the binder resin used. Also, when the volume average particle size is 500 nm or less, the releasing agent is better dispersed in the toner.

[0124] The colorant dispersion and the luster pigment dispersion can be prepared by using a known dispersion method, and is not limited to any particular method, such as a rotary shear homogenizer, a ball mill having a media, a sand mill, a dyno mill, an ultimizer, etc. The colorant is dispersed in water together with an ionic surfactant and a polymer electrolyte such as a polymer acid or a polymer base. Alternatively, a dispersion of a bright pigment coated with a binder resin may be prepared by dispersing or dissolving the bright pigment and the binder resin in a solvent, mixing them, and dispersing them in water by phase inversion emulsification or shear emulsification.

[0125] (agglomeration process) In the aggregation step, a resin particle dispersion, a colorant dispersion, a luster pigment dispersion, and a release agent dispersion are mixed to form a mixed liquid, which is then heated at a temperature below the glass transition temperature of the resin particles to aggregate and form aggregated particles. The formation of aggregated particles is often achieved by making the pH of the mixed liquid acidic while stirring. The pH is preferably in the range of 2 to 7, and it is also effective to use an aggregating agent in this case. By adjusting the amount of dispersion of resin particles containing a crystalline resin used in the aggregation process when producing a glossy toner and when producing a colored toner, the value of endothermic heat QA / endothermic heat QB is adjusted, and the toner set of this embodiment is obtained.

[0126] As the flocculant, a surfactant having a polarity opposite to that of the surfactant used in the dispersant, an inorganic metal salt, or a divalent or higher metal complex is preferably used. In particular, when a metal complex is used, the amount of the surfactant used can be reduced and the charging characteristics are improved, which is particularly desirable.

[0127] As the inorganic metal salt, particularly, aluminum salts and polymers thereof are suitable. In order to obtain a narrower particle size distribution, inorganic metal salts having a valence of divalent rather than monovalent, trivalent rather than divalent, and tetravalent rather than trivalent are more suitable, and even if the valence is the same, polymerized inorganic metal salt polymers are more suitable. In this embodiment, it is desirable to use a polymer of a tetravalent inorganic metal salt including aluminum in order to obtain a narrow particle size distribution.

[0128] In addition, when the aggregated particles reach a desired particle size, a resin particle dispersion liquid may be added (coating step) to produce a toner having a configuration in which the surfaces of the core aggregated particles are coated with a resin. In this case, the release agent, colorant, and glittering pigment are less likely to be exposed on the toner surface, which is a desirable configuration from the viewpoint of charging properties and developability. When adding, an aggregating agent may be added or the pH may be adjusted before adding.

[0129] (fusion process) In the fusion step, the pH of the suspension of the aggregated particles is raised to a range of 3 to 9 under stirring conditions similar to those in the aggregation step to stop the progress of aggregation, and the aggregated particles are fused by heating at a temperature equal to or higher than the glass transition temperature of the resin. When the particles are coated with the resin, the resin also fuses and coats the core aggregated particles. The heating time may be long enough to fuse the particles, and may be about 0.5 to 10 hours.

[0130] After the fusion, the mixture is cooled to obtain fused particles. In the cooling process, the cooling rate may be slowed down near the glass transition temperature of the resin (within the range of glass transition temperature ±10°C), which is called slow cooling, to promote crystallization. The fused particles obtained by the fusion are subjected to a solid-liquid separation step such as filtration, and if necessary, a washing step and a drying step to form toner particles.

[0131] To the obtained toner particles, inorganic oxides such as silica, titania, and aluminum oxide are added and attached as external additives for the purpose of charge adjustment, imparting fluidity, imparting charge exchangeability, etc. This can be done, for example, by using a V-type blender, a Henschel mixer, a Loedige mixer, etc., and the attachment may be performed in separate steps. The amount of the external additive added is preferably in the range of 0.1 parts by mass to 5 parts by mass, more preferably in the range of 0.3 parts by mass to 2 parts by mass, based on 100 parts by mass of the toner particles. Furthermore, if necessary, coarse particles of the toner may be removed after the external addition using an ultrasonic sieve, a vibration sieve, a wind sieve or the like.

[0132] In addition to the above-mentioned inorganic oxides, other components (particles) such as a charge control agent, organic particles, a lubricant, and an abrasive may be added as external additives.

[0133] The charge control agent is not particularly limited, but it is preferable to use a colorless or light-colored one. Examples of the charge control agent include quaternary ammonium salt compounds, nigrosine compounds, complexes of aluminum, iron, chromium, etc., and triphenylmethane pigments.

[0134] Examples of the organic particles include particles that are usually used as external additives on the toner surface, such as vinyl resins, polyester resins, silicone resins, etc. These inorganic particles and organic particles are used as flow aids, cleaning aids, etc. Examples of the lubricant include fatty acid amides such as ethylene bisstearic acid amide and oleic acid amide, and fatty acid metal salts such as zinc stearate and calcium stearate. Examples of the abrasive include the above-mentioned silica, alumina, and cerium oxide.

[0135] Next, the method for producing toner particles by the solution suspension method will be described in detail. The solution suspension method is a method in which a liquid obtained by dissolving or dispersing materials including a binder resin, a luster pigment, a colored pigment, and other components such as a release agent that is used as necessary in a solvent in which the binder resin is soluble is granulated in an aqueous medium containing an inorganic dispersant, and then the solvent is removed to obtain toner particles. Other components used in the solution suspension method include various components such as internal additives, charge control agents, inorganic powders (inorganic particles), and organic particles, in addition to the release agent.

[0136] In this embodiment, the binder resin, the luster pigment, the colored pigment, and other components used as necessary are dissolved or dispersed in a solvent capable of dissolving the binder resin. Whether or not a binder resin is soluble depends on the constituent components, molecular chain length, degree of three-dimensionality, etc. of the binder resin, and therefore cannot be stated in general terms. Generally, however, hydrocarbons such as toluene, xylene, hexane, etc.; halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, dichloroethylene, etc.; alcohols or ethers such as ethanol, butanol, benzyl alcohol ethyl ether, benzyl alcohol isopropyl ether, tetrahydrofuran, tetrahydropyran, etc.; esters such as methyl acetate, ethyl acetate, butyl acetate, isopropyl acetate, etc.; ketones or acetals such as acetone, methyl ethyl ketone, diisobutyl ketone, dimethyl oxide, diacetone alcohol, cyclohexanone, methylcyclohexanone, etc. are used.

[0137] These solvents dissolve the binder resin, but do not necessarily dissolve the glittering pigment, colored pigment, and other components, as long as they can be dispersed in the binder resin solution. There is no limit to the amount of solvent used, so long as the viscosity allows granulation in an aqueous medium. A ratio of the binder resin, the photoluminescent pigment, and other components (the former) to the solvent (the latter) of 10 / 90 to 50 / 50 (the former / latter mass ratio) is preferred in terms of ease of granulation and the final yield of toner particles.

[0138] The liquid (toner mother liquid) of the binder resin, the luster pigment, the color pigment, and other components dissolved or dispersed in the solvent is granulated to a predetermined particle size in an aqueous medium containing an inorganic dispersant. Water is mainly used as the aqueous medium. The mixing ratio of the aqueous medium and the toner mother liquid is preferably aqueous medium / toner mother liquid=90 / 10 to 50 / 50 (mass ratio). The inorganic dispersing agent is preferably selected from tricalcium phosphate, hydroxyapatite, calcium carbonate, titanium oxide and silica powder. The amount of inorganic dispersant used is determined according to the particle size of the particles to be granulated, but it is generally preferable to use it in the range of 0.1% by mass to 15% by mass based on the toner mother liquid. If it is 0.1% by mass or more, granulation is easily performed, and if it is 15% by mass or less, unnecessary fine particles are unlikely to be generated, and the desired particles are easily obtained in high yield.

[0139] In order to improve granulation from the toner mother liquid, an auxiliary may be further added to the aqueous medium containing the inorganic dispersant. The auxiliary agent may be any of known cationic, anionic and nonionic surfactants, and anionic surfactants are particularly preferred. For example, sodium alkylbenzenesulfonate, sodium α-olefinsulfonate, sodium alkylsulfonate, etc. may be used in an amount of 1×10 to the toner mother liquid. -4 It is preferably used in the range of 0.1% by mass or more and 0.2% by mass or less.

[0140] Granulation from the toner mother liquid in an aqueous medium containing an inorganic dispersant is preferably carried out under shear. In this case, it is desirable to granulate the material so that the average particle size is 20 μm or less, and it is particularly desirable to granulate the material so that the average particle size is 3 μm or more and 15 μm or less. There are various types of dispersing machines equipped with a shearing mechanism, among which a homogenizer is preferred. By using a homogenizer, substances that are incompatible with each other (in this embodiment, an aqueous medium containing an inorganic dispersant and a toner mother liquid) can be passed through the gap between a casing and a rotating rotor, and the substance that is incompatible with a certain liquid can be dispersed in particulate form in the liquid. Specific examples of homogenizers include TK homomixer, line flow homomixer, auto homomixer (all manufactured by Tokushu Kika Kogyo Co., Ltd.), Silverson homogenizer (manufactured by Silverson), and Polytron homogenizer (manufactured by Kinematica AG). The stirring conditions using a homogenizer are preferably a rotor blade peripheral speed of 2 m / sec or more, which tends to result in good particle formation.

[0141] After granulation as described above, the solvent is removed. The removal of the solvent may be carried out at room temperature (25° C.) and normal pressure, but since it takes a long time to remove the solvent, it is preferable to carry out the removal at a temperature lower than the boiling point of the solvent and within a range of a difference of 80° C. from the boiling point. The pressure may be normal pressure or reduced pressure, but when reducing pressure, it is preferable to carry out the removal at a pressure of 20 mmHg or more and 150 mmHg or less.

[0142] After the solvent is removed, the toner particles are preferably washed with hydrochloric acid or the like. This removes the inorganic dispersant remaining on the surface of the toner particles, and the toner particles are restored to their original composition, thereby improving their characteristics. Then, the mixture is dehydrated and dried to obtain powder toner particles.

[0143] The toner according to the present embodiment is produced, for example, by adding an external additive to the obtained toner particles in a dry state and mixing them. The mixing may be performed, for example, by using a V blender, a Henschel mixer, a Loedige mixer, etc. Furthermore, if necessary, coarse particles of the toner may be removed using a vibration sieve, an air sieve, etc.

[0144] <Electrostatic image developer set> The electrostatic image developer set according to this embodiment has a first electrostatic image developer containing a gloss toner from the toner set according to this embodiment, and a second electrostatic image developer containing a color toner from the toner set according to this embodiment. Each electrostatic image developer may be a one-component developer containing only toner, or may be a two-component developer containing a mixture of the toner and a carrier.

[0145] The carrier is not particularly limited, and may be any known carrier, such as a coated carrier in which the surface of a core material made of magnetic powder is coated with a coating resin, a magnetic powder dispersion type carrier in which magnetic powder is dispersed and mixed in a matrix resin, or a resin impregnated type carrier in which porous magnetic powder is impregnated with a resin. The magnetic powder dispersion type carrier and the resin impregnated type carrier may be a carrier in which the constituent particles of the carrier are used as a core material and are coated with a coating resin.

[0146] Examples of the magnetic powder include magnetic metals such as iron, nickel, and cobalt, and magnetic oxides such as ferrite and magnetite.

[0147] Examples of the coating resin and matrix resin include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic acid copolymer, straight silicone resin containing an organosiloxane bond or a modified product thereof, fluororesin, polyester, polycarbonate, phenolic resin, and epoxy resin. The coating resin and the matrix resin may contain other additives such as conductive particles. Examples of the conductive particles include particles of metals such as gold, silver, and copper, carbon black, titanium oxide, zinc oxide, tin oxide, barium sulfate, aluminum borate, and potassium titanate.

[0148] Here, in order to coat the surface of the core material with a coating resin, a method of coating with a coating layer forming solution in which the coating resin and, if necessary, various additives are dissolved in an appropriate solvent can be mentioned. The solvent is not particularly limited and may be selected taking into consideration the coating resin to be used, the suitability for application, etc. Specific resin coating methods include an immersion method in which the core material is immersed in a solution for forming a coating layer, a spray method in which the solution for forming a coating layer is sprayed onto the surface of the core material, a fluidized bed method in which the solution for forming a coating layer is sprayed onto the core material while it is suspended in flowing air, and a kneader coater method in which the core material of a carrier and the solution for forming a coating layer are mixed in a kneader coater and the solvent is removed.

[0149] In the two-component developer, the mixture ratio (mass ratio) of the toner and the carrier is preferably toner:carrier=1:100 to 30:100, and more preferably 3:100 to 20:100.

[0150] <Image forming device / image forming method> An image forming apparatus / image forming method according to this embodiment will be described. The image forming apparatus according to this embodiment includes a first image forming means for forming a glossy image using a glossy toner in the toner set according to this embodiment, a second image forming means for forming a colored image using a colored toner in the toner set according to this embodiment, a transfer means for transferring the glossy image and the colored image onto a recording medium, and a fixing means for fixing the glossy image and the colored image onto the recording medium. The image forming apparatus according to the present embodiment may be in a form including, as first and second image forming means, image forming means each having an image carrier, a charging means for charging the surface of the image carrier, an electrostatic image forming means for forming an electrostatic image on the charged surface of the image carrier, and a developing means for developing the electrostatic image formed on the surface of the image carrier by an electrostatic image developer into a toner image. In addition, the image forming apparatus according to the present embodiment may have a configuration including an image carrier, a charging means for charging the surface of the image carrier, an electrostatic image forming means for forming an electrostatic image on the charged surface of the image carrier, and first and second developing means as first and second image forming means for developing the electrostatic image formed on the surface of the image carrier by an electrostatic image developer into a toner image.

[0151] In the image forming apparatus according to this embodiment, an image forming method (image forming method according to this embodiment) is carried out, which includes a first image forming process of forming a glossy image using a glossy toner from the toner set according to this embodiment, a second image forming process of forming a colored image using a colored toner from the toner set according to this embodiment, a transfer process of transferring the glossy image and the colored image onto a recording medium, and a fixing process of fixing the glossy image and the colored image onto the recording medium.

[0152] The image forming apparatus according to this embodiment may be any of known image forming apparatuses, such as a direct transfer type apparatus that transfers a toner image (in this embodiment, a glossy image or a colored image) formed on the surface of an image holder directly to a recording medium; an intermediate transfer type apparatus that performs primary transfer of a toner image formed on the surface of an image holder to the surface of an intermediate transfer body, and then performs secondary transfer of the toner image transferred to the surface of the intermediate transfer body to the surface of a recording medium; an apparatus equipped with a cleaning means that cleans the surface of the image holder before charging after the transfer of the toner image; and an apparatus equipped with a discharging means that irradiates the surface of the image holder with discharging light to discharge it before charging after the transfer of the toner image. In the case of an intermediate transfer type device, the transfer means has, for example, an intermediate transfer body onto whose surface a toner image is transferred, a primary transfer means which primarily transfers the toner image formed on the surface of the image carrier onto the surface of the intermediate transfer body, and a secondary transfer means which secondarily transfers the toner image transferred onto the surface of the intermediate transfer body onto the surface of a recording medium.

[0153] An example of an image forming apparatus according to the present embodiment will be described below, but the present invention is not limited to this. In the following description, the main parts shown in the drawings will be described, and the description of the rest will be omitted. In the following description, an example of a toner set according to the present embodiment will be described with the glitter toner referred to as "silver toner."

[0154] FIG. 2 is a schematic diagram showing the configuration of an image forming apparatus according to the present embodiment, and shows a five-unit tandem type and intermediate transfer type image forming apparatus. The image forming apparatus shown in Fig. 2 includes first to fifth image forming units 150Y, 150M, 150C, 150K, and 150B (image forming means) of an electrophotographic type that output images of each color of yellow (Y), magenta (M), cyan (C), black (K), and silver (B) based on color-separated image data. These image forming units (hereinafter sometimes simply referred to as "units") 150Y, 150M, 150C, 150K, and 150B are arranged in parallel at a predetermined distance from each other in the horizontal direction. These units 150Y, 150M, 150C, 150K, and 150B may be process cartridges that are detachably attached to the image forming apparatus.

[0155] Below each of the units 150Y, 150M, 150C, 150K, and 150B, an intermediate transfer belt (an example of an intermediate transfer body) 133 is provided extending through each unit. The intermediate transfer belt 133 is provided by being wound around a driving roll 113, a support roll 112, and an opposing roll 114 that are in contact with the inner surface of the intermediate transfer belt 133, and is configured to run in a direction from the first unit 150Y toward the fifth unit 150B (the direction of the arrow B in FIG. 2). An intermediate transfer body cleaning device 116 is provided on the image carrying surface side of the intermediate transfer belt 133, facing the driving roll 113. In addition, a voltage application device 160 is provided on the upstream side of the intermediate transfer body cleaning device 116 in the rotation direction of the intermediate transfer belt 133, which generates an electric field between the intermediate transfer belt 133 and the support roll 113 by generating a potential difference between the intermediate transfer belt 133 and the intermediate transfer body cleaning device 116. The developing devices (examples of developing means) 120Y, 120M, 120C, 120K, and 120B of each unit 150Y, 150M, 150C, 150K, and 150B are supplied with yellow, magenta, cyan, black, and silver toner contained in toner cartridges 140Y, 140M, 140C, 140K, and 140B, respectively.

[0156] Since the first to fifth units 150Y, 150M, 150C, 150K, and 150B have the same configuration, operation, and function, the following description will focus on the first unit 150Y, which forms a yellow image and is disposed upstream in the direction of travel of the intermediate transfer belt.

[0157] The first unit 150Y has a photoconductor 111Y that acts as an image carrier. Around the photoconductor 111Y, a charging roll (an example of a charging means) 118Y that charges the surface of the photoconductor 111Y to a predetermined potential, an exposure device (an example of an electrostatic image forming means) 119Y that exposes the charged surface to a laser beam based on a color-separated image signal to form an electrostatic image, a developing device (an example of a developing means) 120Y that supplies toner to the electrostatic image to develop it, a primary transfer roll (an example of a primary transfer means) 117Y that transfers the developed toner image onto the intermediate transfer belt 133, and a photoconductor cleaning device (an example of a cleaning means) 115Y that removes toner remaining on the surface of the photoconductor 111Y after the primary transfer are arranged in this order. The primary transfer roll 117Y is disposed inside the intermediate transfer belt 133, and is provided at a position facing the photoconductor 111Y. A bias power supply (not shown) that applies a primary transfer bias is connected to the primary transfer rolls 117Y, 117M, 117C, 117K, and 117B of each unit. Each bias power supply changes the value of the transfer bias applied to each primary transfer roll under the control of a control unit (not shown).

[0158] Hereinafter, the operation of forming a yellow image in first unit 150Y will be described. First, prior to operation, the surface of the photoconductor 111Y is charged to a potential of −600V to −800V by the charging roll 118Y. The photoconductor 111Y has a conductivity (for example, a volume resistivity of 1×10 at 20° C. -6 The photosensitive layer is formed by laminating a photosensitive layer on a substrate having a resistivity of Ωcm or less. This photosensitive layer is usually highly resistive (the resistance of ordinary resins), but when irradiated with a laser beam, the resistivity of the portion irradiated with the laser beam changes. Therefore, a laser beam is irradiated from an exposure device 119Y onto the charged surface of the photosensitive member 111Y in accordance with image data for yellow sent from a control unit (not shown). As a result, an electrostatic charge image of a yellow image pattern is formed on the surface of the photosensitive member 111Y.

[0159] An electrostatic image is an image formed on the surface of the photoconductor 111Y by electrostatic charging. The laser beam from the exposure device 119Y reduces the resistivity of the irradiated parts of the photosensitive layer, causing the charged charges on the surface of the photoconductor 111Y to flow, while the charges remain in the parts not irradiated by the laser beam. This is a so-called negative latent image. The electrostatic image formed on the photoconductor 111Y rotates to a predetermined developing position as the photoconductor 111Y travels. At this developing position, the electrostatic image on the photoconductor 111Y is developed into a toner image by the developing device 120Y and made visible.

[0160] The developing device 120Y contains an electrostatic image developer including at least yellow toner and a carrier, for example. The yellow toner is triboelectrically charged by being stirred inside the developing device 120Y, and is held on a developer roll (an example of a developer holder) with a charge of the same polarity (negative polarity) as the charge on the photoconductor 111Y. As the surface of the photoconductor 111Y passes through the developing device 120Y, the yellow toner electrostatically adheres to the discharged latent image portion on the surface of the photoconductor 111Y, and the latent image is developed with the yellow toner. The photoconductor 111Y on which the yellow toner image has been formed continues to travel at a predetermined speed, and the toner image developed on the photoconductor 111Y is transported to a predetermined primary transfer position.

[0161] When the yellow toner image on the photoconductor 111Y is transported to the primary transfer position, a primary transfer bias is applied to the primary transfer roll 117Y, and an electrostatic force from the photoconductor 111Y toward the primary transfer roll 117Y acts on the toner image, and the toner image on the photoconductor 111Y is transferred onto the intermediate transfer belt 133. 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 a control unit (not shown) in the first unit 150Y. On the other hand, the toner remaining on the photoconductor 111Y is removed and collected by the photoconductor cleaning device 115Y.

[0162] The primary transfer bias applied to the primary transfer rolls 117M, 117C, 117K, and 117B of the second unit 150M and subsequent units is also controlled in accordance with the first unit. In this manner, the intermediate transfer belt 133 onto which the yellow toner image has been transferred by the first unit 150Y is conveyed successively through the second to fifth units 150M, 150C, 150K, and 150B, where the toner images of each color are transferred and superimposed.

[0163] The intermediate transfer belt 133 onto which the five color toner images have been transferred in multiple layers through the first to fifth units reaches a secondary transfer section that is composed of the intermediate transfer belt 133, the opposing roll 114 that contacts the inner surface of the intermediate transfer belt, and a secondary transfer roll (an example of a secondary transfer means) 134 arranged on the image carrying surface side of the intermediate transfer belt 133. Meanwhile, a recording paper (an example of a recording medium) P is fed at a predetermined timing into the gap between the secondary transfer roll 134 and the intermediate transfer belt 133 via a supply mechanism, and a secondary transfer bias is applied to the opposing roll 114. The transfer bias applied at this time has a (-) polarity that is the same as the (-) polarity of the toner, and an electrostatic force from the intermediate transfer belt 133 toward the recording paper P acts on the toner image, and the toner image on the intermediate transfer belt 133 is transferred onto the recording paper P. The secondary transfer bias at this time is determined according to the resistance detected by a resistance detection means (not shown) that detects the resistance of the secondary transfer section, and is voltage controlled.

[0164] Thereafter, the recording paper P is sent to a pressure contact portion (nip portion) of a pair of fixing rolls in a fixing device (one example of a fixing means) 135, where the toner image is fixed onto the recording paper P, forming a fixed image.

[0165] The recording paper P onto which the toner image is transferred can be, for example, plain paper used in electrophotographic copying machines, printers, etc. In addition to the recording paper P, other examples of the recording medium include overhead projector sheets and the like. 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 ordinary paper is coated with a resin or the like, art paper for printing, etc. are preferably used.

[0166] After the color image has been fixed, the recording paper P is conveyed toward the discharge section, and the series of color image forming operations is completed.

[0167] 2 is an image forming apparatus having a configuration in which toner cartridges 140Y, 140M, 140C, 140K, and 140B are detachably attached, and developing devices 120Y, 120M, 120C, 120K, and 120B are connected to toner cartridges corresponding to the respective developing devices (colors) by toner supply pipes (not shown). When the toner contained in a toner cartridge becomes low, the toner cartridge is replaced.

[0168] <Process cartridge / toner cartridge set> The process cartridge according to this embodiment will be described. The process cartridge according to this embodiment is a process cartridge that is detachably attached to an image forming apparatus and includes a first developing means that contains a first electrostatic image developer of the electrostatic image developer set according to this embodiment, and a second developing means that contains the second electrostatic image developer of the electrostatic image developer set according to this embodiment.

[0169] In addition, the process cartridge according to this embodiment is not limited to the above configuration, and may be configured to include a developing device and, as necessary, at least one other means selected from an image carrier, a charging means, an electrostatic image forming means, and a transfer means.

[0170] An example of a process cartridge according to the present embodiment will be described below, but the present invention is not limited to this example. Note that only the main parts shown in the drawings will be described, and descriptions of the rest will be omitted.

[0171] FIG. 3 is a schematic diagram showing the process cartridge according to the present embodiment. The process cartridge 200 shown in FIG. 3 is configured by, for example, a housing 217 having a mounting rail 216 and an opening 218 for exposure, and integrally combining and holding a photoconductor 207 (an example of an image carrier), a charging roll 208 (an example of a charging means) provided around the photoconductor 207, a developing device 211 (an example of a developing means), and a photoconductor cleaning device 213 (an example of a cleaning means), which are formed into a cartridge. In FIG. 3, reference numeral 209 denotes an exposure device (an example of an electrostatic image forming means), 212 denotes a primary transfer roll (an example of a primary transfer means), 220 denotes an intermediate transfer belt (an example of an intermediate transfer body), 222 denotes a drive roll (an example of an intermediate transfer body discharging means) also serving as an intermediate transfer belt discharging means, 224 denotes a support roll, 226 denotes a secondary transfer roll (an example of a secondary transfer means), 228 denotes a fixing device (an example of a fixing means), and 300 denotes a recording paper (an example of a recording medium).

[0172] Next, the toner cartridge set according to this embodiment will be described. The toner cartridge set of this embodiment has a first toner cartridge that contains a glossy toner from the toner set of this embodiment, and a second toner cartridge that contains a colored toner from the toner set of this embodiment, and is a toner cartridge set that is detachably attached to an image forming device. Each toner cartridge contains replenishment toner to be supplied to each developing means provided in the image forming apparatus. EXAMPLES

[0173] Examples will be described below, but the present invention is not limited to these examples. In the following description, unless otherwise specified, all "parts" and "%" are based on mass.

[0174] <Preparation of various resin dispersions> (Preparation procedure for amorphous polyester resin dispersion 1) -Synthesis of amorphous polyester resin 1- Dimethyl adipate: 74 parts Dimethyl terephthalate: 192 parts Bisphenol A ethylene oxide adduct: 216 parts Ethylene glycol: 38 parts Tetrabutoxytitanate (catalyst): 0.037 parts, The above components were placed in a heated and dried two-necked flask, nitrogen gas was introduced into the vessel to maintain an inert atmosphere, and the temperature was raised while stirring, after which a polycondensation reaction was carried out at 160°C for 7 hours, after which the pressure was gradually reduced to 10 Torr while the temperature was raised to 220°C and maintained for 4 hours. The pressure was once returned to normal, 9 parts of trimellitic anhydride was added, the pressure was gradually reduced again to 10 Torr, and the mixture was maintained at 220°C for 1 hour to synthesize amorphous polyester resin 1.

[0175] -Preparation of amorphous polyester resin dispersion 1- Amorphous polyester resin 1:160 parts Ethyl acetate: 233 parts Sodium hydroxide solution (0.3N): 0.1 part The above components were placed in a 1000 ml separable flask, heated to 70° C., and stirred with a Three-One Motor (manufactured by Shinto Scientific Co., Ltd.) to prepare a resin mixture. While further stirring this resin mixture, 373 parts of ion-exchanged water was gradually added to cause phase inversion emulsification and desolvation to obtain amorphous polyester resin dispersion 1 (solid concentration: 30%).

[0176] (Preparation procedure for amorphous polyester resin dispersion 2) Amorphous polyester resin dispersion 2 was prepared in the same manner as in the synthesis of amorphous polyester resin 1, except that 38 parts of propylene glycol was added instead of 38 parts of ethylene glycol.

[0177] (Preparation procedure for amorphous polyester resin dispersion 3) Amorphous polyester resin dispersion 3 was prepared in the same manner as in the synthesis of amorphous polyester resin 1, except that 55 parts of propylene glycol was added instead of 38 parts of ethylene glycol.

[0178] (Preparation procedure of amorphous polyester resin dispersion 4) -Synthesis of amorphous polyester resin 4- Dimethyl adipate: 104 parts Dimethyl terephthalate: 257 parts Bisphenol A ethylene oxide adduct: 108 parts Ethylene glycol: 38 parts Tetrabutoxytitanate (catalyst): 0.037 parts, The above components were placed in a heated and dried two-necked flask, nitrogen gas was introduced into the vessel to maintain an inert atmosphere, and the temperature was raised while stirring, after which a polycondensation reaction was carried out at 160°C for 7 hours, after which the pressure was gradually reduced to 10 Torr while the temperature was raised to 220°C and maintained for 4 hours. The pressure was once returned to normal pressure, 9 parts of trimellitic anhydride was added, the pressure was gradually reduced again to 10 Torr, and the mixture was maintained at 220°C for 1 hour to synthesize amorphous polyester resin 4.

[0179] -Preparation of amorphous polyester resin dispersion 4- Amorphous polyester resin dispersion 4 was prepared in the same manner as in the preparation of amorphous polyester resin dispersion 1, except that 160 parts of amorphous polyester resin 4 was added instead of 160 parts of amorphous polyester resin 1 in the preparation of amorphous polyester resin dispersion 1.

[0180] (Preparation procedure for amorphous polyester resin dispersion 5) -Synthesis of amorphous polyester resin 5- Dimethyl adipate: 116 parts Dimethyl terephthalate: 272 parts Bisphenol A ethylene oxide adduct: 82 parts Ethylene glycol: 38 parts Tetrabutoxytitanate (catalyst): 0.037 parts, The above components were placed in a heated and dried two-necked flask, nitrogen gas was introduced into the vessel to maintain an inert atmosphere, and the temperature was raised while stirring, after which a co-condensation polymerization reaction was carried out at 160°C for 7 hours, after which the pressure was gradually reduced to 10 Torr while the temperature was raised to 220°C and maintained for 4 hours. The pressure was once returned to normal pressure, 9 parts of trimellitic anhydride was added, the pressure was gradually reduced again to 10 Torr, and the mixture was maintained at 220°C for 1 hour to synthesize amorphous polyester resin 5.

[0181] -Preparation of amorphous polyester resin dispersion 5- Amorphous polyester resin dispersion 5 was prepared in the same manner as in the preparation of amorphous polyester resin dispersion 1, except that 160 parts of amorphous polyester resin 5 was added instead of 160 parts of amorphous polyester resin 1 in the preparation of amorphous polyester resin dispersion 1.

[0182] (Preparation procedure for crystalline polyester resin dispersion 1) -Synthesis of crystalline polyester resin- 1,10-decanedicarboxylic acid: 50 mol% 1,9-nonanediol: 50 mol% The monomer components were placed in a reaction vessel equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas inlet tube, and the inside of the reaction vessel was replaced with dry nitrogen gas, after which 0.25 parts of titanium tetrabutoxide (reagent) was added per 100 parts of the monomer components. After stirring and reacting for 3 hours at 170°C under a nitrogen gas stream, the temperature was further raised to 210°C over 1 hour, the pressure inside the reaction vessel was reduced to 3 kPa, and stirring and reacting were continued under reduced pressure for 13 hours to obtain a crystalline polyester resin.

[0183] -Preparation of crystalline polyester resin dispersion- 300 parts of the crystalline polyester resin, 160 parts of methyl ethyl ketone (solvent), and 100 parts of isopropyl alcohol (solvent) were placed in a jacketed 3-liter reaction tank (Tokyo Rikakiki Co., Ltd.: BJ-30N) equipped with a condenser, a thermometer, a water dropping device, and an anchor blade, and the resin was dissolved by stirring and mixing at 100 rpm while maintaining the temperature at 70°C in a water-circulating thermostatic bath. Thereafter, the stirring speed was changed to 150 rpm, the water circulation type thermostatic bath was set to 66°C, and 17 parts of 10% ammonia water (reagent) was added over 10 minutes, after which a total of 900 parts of ion-exchanged water kept at 66°C was dropped at a rate of 7 parts / min to cause phase inversion and obtain an emulsion. Immediately, 800 parts of the obtained emulsion and 700 parts of ion-exchanged water were placed in a 2-liter eggplant flask and set in an evaporator (Tokyo Rikakiki Co., Ltd.) equipped with a vacuum control unit via a trap bulb. The eggplant flask was rotated and heated in a hot water bath at 60°C, and the pressure was reduced to 7 kPa while paying attention to bumping to remove the solvent. When the amount of solvent recovered reached 1100 parts, the pressure was returned to normal pressure, and the eggplant flask was water-cooled to obtain a dispersion. The obtained dispersion had no solvent odor. The volume average particle size D50v of the resin particles in this dispersion was 130 nm. After that, ion-exchanged water was added to adjust the solid content concentration to 20 mass%, and this was used as a crystalline polyester resin dispersion.

[0184] (Preparation of styrene acrylic resin particle dispersion 1) Styrene: 320 parts by weight n-Butyl acrylate: 80 parts by weight Acrylic acid: 12 parts by weight 10-Dodecanethiol: 2 parts by weight The above ingredients were mixed and dissolved, and then added to a non-ionic surfactant (Nonipol 400, Yokasei Co., Ltd.) and 6 parts by mass of anionic surfactant (Neogen SC, Daiichi Kogyo Seiyaku Co., Ltd. 10 parts by weight of 1,2-dichlorophenyl ether (10 parts by weight) was dissolved in 550 parts by weight of ion-exchanged water, and the solution was emulsified and dispersed in a flask. Then, slowly mix for 10 minutes and add 4 parts by mass of ammonium persulfate dissolved in the ion exchange solution. After nitrogen replacement, the inside of the flask was stirred while adding 50 parts by mass of ammonium nitrate. The container was heated in an oil bath until the temperature reached 70° C., and emulsion polymerization was continued for 5 hours. Thereafter, the solid content was adjusted to 30%, thereby obtaining a resin dispersion in which styrene-acrylic resin particles were dispersed.

[0185] (Preparation of styrene acrylic resin dispersion 2) Styrene acrylic resin dispersion 2 (solid concentration: 30%) was obtained in the same manner as in the preparation of styrene acrylic resin dispersion 1, except that the amount of 10-dodecanethiol added was changed from 2 parts by mass to 1 part by mass in the preparation of styrene acrylic resin dispersion 1.

[0186] (Preparation of styrene acrylic resin dispersion 3) Styrene acrylic resin dispersion 3 (solid concentration: 30%) was obtained in the same manner as in the preparation of styrene acrylic resin dispersion 1, except that the amount of 10-dodecanethiol added was changed from 2 parts by mass to 0.5 parts by mass.

[0187] (Preparation of hybrid resin (amorphous resin having amorphous polyester resin segment and styrene acrylic resin segment) particle dispersion (SPE1)) The inside of a four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 5,670 parts of polyoxypropylene (2.2)-2,2-bis (4-hydroxyphenyl) propane, 585 parts of polyoxyethylene (2.0)-2,2-bis (4-hydroxyphenyl) propane, 2,450 parts of terephthalic acid, and 44 parts of di(2-ethylhexanoate) tin (II) were added, and the mixture was heated to 235°C under a nitrogen atmosphere while stirring, and maintained for 5 hours, after which the pressure in the flask was further reduced and maintained at 8.0 kPa for 1 hour. After returning to atmospheric pressure, the mixture was cooled to 190°C, 42 parts of fumaric acid and 207 parts of trimellitic acid were added, and the mixture was maintained at a temperature of 190°C for 2 hours, and then heated to 210°C over 2 hours. The pressure in the flask was further reduced and maintained at 8.0 kPa for 4 hours to obtain an amorphous polyester resin A (polyester segment). Next, 800 parts of amorphous polyester resin A was added to a four-neck flask equipped with a cooling tube, a stirrer, and a thermocouple, and the mixture was stirred at a stirring speed of 200 rpm under a nitrogen atmosphere. After that, 40 parts of styrene, 142 parts of ethyl acrylate, 16 parts of acrylic acid, 2 parts of 1,10-decanediol diacrylate, and 1000 parts of toluene were added as addition polymerizable monomers, and mixed for another 30 minutes. Furthermore, 6 parts of polyoxyethylene alkyl ether (nonionic surfactant, trade name: Emulgen 430, manufactured by Kao Corporation), 40 parts of a 15% aqueous sodium dodecylbenzenesulfonate solution (anionic surfactant, trade name: Neopelex G-15, manufactured by Kao Corporation) and 233 parts of 5% potassium hydroxide were added, and the mixture was heated to 95°C with stirring to melt, and mixed at 95°C for 2 hours to obtain a resin mixture solution. Next, while stirring the resin mixture solution, 1,145 parts of deionized water was added dropwise at a rate of 6 parts / min to obtain an emulsion. Next, the obtained emulsion was cooled to 25°C, passed through a 200-mesh wire screen, and deionized water was added to adjust the solid content to 30%, thereby obtaining a hybrid resin particle dispersion (SPE1). The content of styrene-derived structural units in the synthesized hybrid resin was 4 mass % relative to the total mass of the hybrid resin.

[0188] <Preparation procedure for colorant dispersion> (Preparation of glitter pigment dispersion 1) Aluminum pigment (Showa Aluminum Powder Co., Ltd., 2173EA 6μm): 100 parts Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R): 1.5 parts Ion-exchanged water: 400 parts The solvent was removed from the aluminum pigment paste, and the pigment was mechanically ground and classified to 5.2 μm using a Star Mill (LMZ, manufactured by Ashizawa Finetech Co., Ltd.). The pigment was then mixed with the above-mentioned activator and ion-exchanged water, and dispersed for about 1 hour using an emulsifying disperser Cavitron (CR1010, manufactured by Pacific Machinery Co., Ltd.) to prepare a brilliant pigment dispersion 1 in which brilliant pigment particles (aluminum pigment) were dispersed (solid concentration: 20% by mass). The pigment dispersion diameter was 5.2 μm.

[0189] (Preparation of Cyan Colorant Dispersion) CI Pigment Blue 15:3 (copper phthalocyanine) (manufactured by Dainichi Seika Chemicals): 50 parts Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku): 5 parts Ion-exchanged water: 192.9 parts The above components were mixed and treated for 10 minutes at 240 MPa with an Ultimizer (manufactured by Sugino Machine Co., Ltd.) to obtain a cyan colorant dispersion liquid. The solid content concentration was 20 mass %.

[0190] <Preparation procedure for release agent dispersion> (Preparation of release agent dispersion) Carnauba wax (Toa Kasei Co., Ltd., RC-160): 50 parts Anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK): 1.0 part -Ion-exchanged water: 200 parts The above ingredients were mixed and heated to 95°C, and dispersed using a homogenizer (Ultra Turrax T50, manufactured by IKA Corporation). After that, a dispersion treatment was carried out for 360 minutes using a Manton-Gaulin high pressure homogenizer (Gaulin Corporation) to prepare a release agent dispersion liquid (solid content concentration: 20% by mass) in which release agent particles having a volume average particle size of 0.23 μm were dispersed.

[0191] <Production procedure for glitter toner> (Production of Glittering Toner 1) Luminous pigment dispersion 1:150 parts Styrene acrylic resin particle dispersion 1:280 parts Crystalline polyester resin dispersion: 70.0 parts Release agent dispersion: 75 parts The above ingredients were placed in a 2L cylindrical stainless steel container and dispersed and mixed for 10 minutes while applying shear force at 4000 rpm using a homogenizer (IKA Ultra Turrax T50). Next, 1.75 parts of a 10% aqueous nitric acid solution of polyaluminum chloride as a flocculant was gradually added dropwise, and the homogenizer was rotated at 5000 rpm to disperse and mix for 15 minutes to obtain a raw material dispersion. The dispersion was then transferred to a polymerization kettle equipped with a stirrer using four paddle stirrers and a thermometer, and the stirring speed was set to 1000 rpm and heating was started with a mantle heater to promote the growth of aggregated particles at 54°C. The pH of the dispersion was controlled in the range of 2.2 to 3.5 using 0.3 mol / L nitric acid and 1 mol / L aqueous sodium hydroxide solution. The pH was maintained in the above range for about 2 hours to form aggregated particles. Next, 1:70 parts of the styrene-acrylic resin particle dispersion liquid was added, and the styrene-acrylic resin particles were attached to the surface of the aggregated particles. The temperature was further increased to 56°C, and the aggregated particles were adjusted while checking the particle size and shape with an optical microscope and a Multisizer II. Thereafter, 3.25 parts of a chelating agent (HIDS, manufactured by Nippon Shokubai Co., Ltd.) was added, and then the pH was adjusted to 7.8 using a 5% aqueous sodium hydroxide solution and maintained for 15 minutes. Thereafter, the pH was increased to 8.0 in order to fuse the aggregated particles, and the temperature was increased to 67.5°C. After confirming that the aggregated particles had fused with an optical microscope, the pH was lowered to 6.0 while maintaining the temperature at 67.5°C, and heating was stopped after 1 hour, and the mixture was cooled at a temperature drop rate of 1.0°C / min. Thereafter, the mixture was sieved through a 40 μm mesh, repeatedly washed with water, and then dried in a vacuum dryer to obtain toner particles. The volume average particle size of the obtained toner particles was 10.2 μm. 100 parts of the obtained toner particles were mixed with 1.5 parts of colloidal silica (R972, manufactured by Nippon Aerosil Co., Ltd.) for 2 minutes at a peripheral speed of 30 m / s in a Henschel mixer to obtain glittering toner 1.

[0192] (Production of Glittering Toner 2) Glittering toner 2 was obtained in the same manner as glittering toner 1, except that the resin dispersion used in the production of toner particles was changed from styrene acrylic resin particle dispersion 1 to an amorphous polyester resin dispersion.

[0193] (Production of Glittering Toner 3) A glossy toner 3 was obtained in the same manner as for the glossy toner 2, except that the amorphous polyester resin dispersion 1 was changed to the amorphous polyester resin dispersion 4.

[0194] (Production of Glittering Toner 4) Glittering toner 4 was obtained in the same manner as for glittering toner 2, except that amorphous polyester resin dispersion 1 was changed to amorphous polyester resin dispersion 5.

[0195] (Production of Glittering Toner 5) Glittering toner 5 was obtained in the same manner as for glittering toner 2, except that the particle diameter of the toner particles was adjusted to the values ​​shown in Table 1.

[0196] (Production of Glittering Toner 6) Glittering toner 6 was obtained in the same manner as for glittering toner 2, except that the particle diameter of the toner particles was set to the value shown in Table 1.

[0197] (Production of Glitter Toner 7) Glittering toner 7 was obtained in the same manner as for glittering toner 2, except that the particle diameter of the toner particles was set to the value shown in Table 1.

[0198] (Production of Glittering Toner 8) Glittering toner 8 was obtained in the same manner as for glittering toner 2, except that the particle diameter of the toner particles was adjusted to the values ​​shown in Table 1.

[0199] (Production of Glitter Toner 9) Glittering toner 9 was obtained in the same manner as for glittering toner 2, except that the amount of the crystalline polyester resin dispersion added was changed from 70 parts by mass to 10 parts by mass.

[0200] (Production of Glittering Toner 10) Glittering toner 10 was obtained in the same manner as for glittering toner 2, except that the amount of the crystalline polyester resin dispersion added was changed from 70 parts by mass to 20 parts by mass.

[0201] <Color toner manufacturing procedure> (Manufacturing of Cyantoner 1) Cyan colorant dispersion: 37.5 parts Amorphous polyester resin dispersion: 330 parts Crystalline polyester resin dispersion: 37.5 parts Release agent dispersion: 75 parts The above ingredients were placed in a 2L cylindrical stainless steel container and dispersed and mixed for 10 minutes while applying shear force at 4000 rpm using a homogenizer (IKA Ultra Turrax T50). Next, 1.75 parts of a 10% aqueous nitric acid solution of polyaluminum chloride as a flocculant was gradually added dropwise, and the homogenizer was rotated at 5000 rpm to disperse and mix for 15 minutes to obtain a raw material dispersion. Thereafter, the raw material dispersion was transferred to a polymerization kettle equipped with a stirrer using a four-paddle stirrer blade and a thermometer, and the stirring speed was set to 600 rpm and heating was started with a mantle heater to promote the growth of aggregated particles at 50° C. At this time, the pH of the dispersion was controlled in the range of 2.2 to 3.5 using 0.3 mol / L nitric acid and 1 mol / L aqueous sodium hydroxide solution. The pH was maintained in the above range for about 2 hours to form aggregated particles. Next, 70 parts of the amorphous polyester resin dispersion liquid was added, and the amorphous polyester resin particles were attached to the surface of the aggregated particles. The temperature was further increased to 52°C, and the aggregated particles were adjusted while checking the particle size and shape with an optical microscope and a Multisizer II. Thereafter, 2.25 parts of a chelating agent (HIDS, manufactured by Nippon Shokubai Co., Ltd.) was added, and then the pH was adjusted to 7.8 using a 5% by mass aqueous solution of sodium hydroxide, and maintained for 15 minutes. Thereafter, the pH was increased to 8.0 in order to fuse the aggregated particles, and the temperature was increased to 67.5°C. After confirming that the aggregated particles had fused with an optical microscope, the pH was lowered to 6.0 while maintaining the temperature at 67.5°C, and heating was stopped after 1 hour, and the mixture was cooled at a temperature drop rate of 1.0°C / min. Thereafter, the mixture was sieved through a 20 μm mesh, repeatedly washed with water, and then dried in a vacuum dryer to obtain toner particles. The volume average particle size of the obtained toner particles was 6.4 μm. 100 parts of the obtained toner particles were mixed with 1.5 parts of colloidal silica (R972, manufactured by Nippon Aerosil Co., Ltd.) for 2 minutes at a peripheral speed of 30 m / s in a Henschel mixer to obtain Cyan Toner 1.

[0202] (Manufacturing of Cyantoner 2) Cyan toner 2 was obtained in the same manner as Cyan toner 1, except that the resin dispersion liquid used in the production of toner particles was changed to styrene acrylic resin particle dispersion liquid 1. Here, in the production of Cyan Toner 2, the resin particle dispersion added when the raw materials were charged was 1,367.5 parts of styrene-acrylic resin particle dispersion, instead of 330 parts of amorphous polyester resin dispersion and 37.5 parts of crystalline polyester resin dispersion added in the production of Cyan Toner 1.

[0203] (Manufacturing of Cyantoner 3) Cyan toner 3 was obtained in the same manner as in Cyan toner 1, except that the amorphous polyester resin dispersion 1 was changed to the amorphous polyester resin dispersion 2.

[0204] (Manufacturing of Cyantoner 4) Cyan toner 4 was obtained in the same manner as in Cyan toner 1, except that the amorphous polyester resin dispersion 1 was changed to the amorphous polyester resin dispersion 3.

[0205] (Manufacturing of Cyantoner 5) Cyan toner 5 was obtained in the same manner as in the production of Cyan toner 2, except that the styrene-acrylic resin particle dispersion 1 in the production of Cyan toner 2 was changed to a hybrid resin particle dispersion (SPE1).

[0206] (Manufacturing of Cyantoner 6) Cyan toner 6 was obtained in the same manner as in Cyan toner 2, except that the particle diameter of the toner particles was set to the value shown in Table 1.

[0207] (Manufacturing of Cyantoner 7) Cyan toner 7 was obtained in the same manner as in Cyan toner 2, except that the particle diameter of the toner particles was adjusted to the value shown in Table 1.

[0208] (Manufacturing of Cyantoner 8) Cyan toner 8 was obtained in the same manner as in Cyan toner 2, except that the particle diameter of the toner particles was set to the value shown in Table 1.

[0209] (Manufacturing of Cyantoner 9) Cyan toner 9 was obtained in the same manner as in Cyan toner 2, except that the particle diameter of the toner particles was adjusted to the value shown in Table 1.

[0210] (Manufacturing of Cyantoner 10) Cyan toner 10 was obtained in the same manner as in Cyan toner 2, except that styrene-acrylic resin dispersion 1 was changed to styrene-acrylic resin dispersion 2.

[0211] (Manufacturing of Cyantoner 11) Cyan toner 11 was obtained in the same manner as in Cyan toner 2, except that styrene-acrylic resin dispersion 1 was changed to styrene-acrylic resin dispersion 3.

[0212] <Carrier manufacturing> Ferrite particles (volume average particle size: 35 μm): 100 parts Toluene: 14 parts Perfluorooctylethyl acrylate-methyl methacrylate copolymer (critical surface tension: 24 dyn / cm, copolymerization ratio 2:8, weight average molecular weight 77000): 1.6 parts Carbon black (product name: VXC-72, manufactured by Cabot Corporation, volume resistivity: 100 Ω cm or less): 0.12 parts Crosslinked melamine resin particles (average particle size: 0.3 μm, insoluble in toluene): 0.3 parts First, carbon black was diluted with toluene and added to perfluorooctylethyl acrylate-methyl methacrylate copolymer, and dispersed with a sand mill. Next, the above-mentioned components other than ferrite particles were dispersed in the mixture with a stirrer for 10 minutes to prepare a coating layer forming liquid. Next, the coating layer forming liquid and ferrite particles were placed in a vacuum degassing kneader, stirred at a temperature of 60°C for 30 minutes, and then the pressure was reduced to remove the toluene, forming a resin coating layer and obtaining a carrier.

[0213] <Preparation of developer> For each glitter toner and each cyan toner, 36 parts of toner and 414 parts of carrier were placed in a V blender and stirred for 20 minutes, and then sieved through a 212 μm sieve to prepare a developer.

[0214] <Examples 1 to 18 and Comparative Examples 1 to 3> The glitter toner (glitter developer) and color toner (color developer) shown in Table 1 below were combined to obtain a toner set.

[0215] -Evaluation of brilliance- The developer was filled into the developing unit of Fuji Xerox Color 1000 Press, and the glitter toner was applied to coated paper (OK topcoat + paper, surface roughness Rz = 1.98 μm, Oji Paper Co., Ltd.) at a fixing temperature of 180°C (pressure roll temperature 100°C) with a glitter toner load of 5 g / m. 2 And the color toner amount is 3 g / m2 A solid image (a metallic image portion having color) of 1000 nm was formed. 100 images were printed in succession, and the 100th print was used for the subsequent evaluations. The glitter toner and color toner contained in the developer used in each of the Examples and Comparative Examples are shown in Table 1. In addition, in Table 3, the value in the column for the amount of crystalline resin indicates the content of the crystalline resin relative to the total mass of the toner particles. Using a three-dimensional spectroscopic variable angle color difference meter DDS5000 (manufactured by Nippon Denshoku Industries Co., Ltd.), light was irradiated from a direction inclined at 45° relative to the vertical direction of the surface of the solid image, and the lightness index L*45° was obtained by receiving the light in the vertical direction of the surface of the solid image, the lightness index L*15° was obtained by receiving the light in a direction inclined at -30° relative to the vertical direction of the surface of the solid image, and the lightness index L*110° was obtained by receiving the light in a direction inclined at -65° relative to the vertical direction of the surface of the solid image. Then, the flop index value (FI) was calculated by substituting each lightness index into the following formula. Based on the obtained values, the glitter was evaluated according to the following criteria. Formula: FI=2.69×{(L*15°)-(L*110°)1.11} / (L*45°)0.86 (Evaluation Criteria) A(◎): Flop index value is 12.5 or more B(○): Flop index value is 10.0 or more and less than 12.5 C(△): Flop index value is 5.0 or more and less than 10.0, practical usable level D(×): Flop index value is 0 or more and less than 5.0

[0216] -Gross evaluation- In the above glitter evaluation, the gloss (gloss) of the metallic image part having color output on the coated paper was measured using a gloss meter Micro Gloss 60° (manufactured by BYK-Gardner) under the condition of an incident light angle to the image of 60 degrees. The gloss was measured at five points: both ends 1 cm from the leading edge of the image, the center of the image, and both ends 1 cm from the trailing edge of the image. The average gloss value obtained from the measurements at these five points was calculated, and the gloss was evaluated based on the following evaluation criteria. (Evaluation Criteria) A(◎): Gross average value is 60 or more B(○): Average gross value is 50 or more and less than 60 C (△): Average gloss value is between 40 and 50, practical usable level D(×): Average gross value is 30 or more and less than 40

[0217] [Table 1]

[0218] The abbreviations in the table are explained below. <Resin type> Amorphous PE: Amorphous polyester resin Crystalline PE: Crystalline polyester resin <Other> Toner particle size: The volume average particle size of the glitter toner particles or colored toner particles. SP value A: Solubility parameter of the binder resin contained in the glittering toner particles SP value B: Solubility parameter of binder resin contained in colored toner particles SP value difference |SP value A - SP value B|: Absolute value of the difference in solubility parameter between the binder resin contained in the glitter toner particles and the binder resin contained in the colored toner particles

[0219] From the above results, it is apparent that the toner set of this embodiment can form a glittery image having high glitter and gloss. [Explanation of symbols]

[0220] 2. Photoluminescent toner particles 4. Luminous pigments 111Y, 111M, 111C, 111K, 111B, 207 Photoconductor 113, 222 Driving roll 112, 224 Support roll 114 Opposing Roll 115Y, 115M, 115C, 115K, 115B Cleaning device 116 Intermediate transfer body cleaning device 117Y, 117M, 117C, 117K, 117B, 212 Primary transfer roll 118Y, 118M, 118C, 118K, 118B, 208 Charging Roll 119Y, 119M, 119C, 119K, 119B, 209 Exposure equipment 120Y, 120M, 120C, 120K, 120B, 211 developing device 133 Intermediate transfer belt 134, 226 Secondary transfer roll 135, 228 Fixing device 140Y, 140M, 140C, 140K, 140B toner cartridges 150Y, 150M, 150C, 150K, 150B Image forming unit 200 Process Cartridge 213 Photoconductor cleaning device 216 Mounting Rail 217 Cabinet 218 Opening 300, P Recording Paper

Claims

1. a glitter toner having glitter toner particles containing a binder resin and a glitter pigment; a color toner having color toner particles containing a binder resin and a colorant other than the glittering pigment; having the binder resin contained in the glittering toner particles and the binder resin contained in the color toner particles are incompatible with each other, the glittering toner particles contain an amorphous polyester resin as the binder resin, The toner set for developing electrostatic images, wherein the color toner particles contain, as the binder resin, an amorphous resin having an amorphous polyester resin segment and a styrene-acrylic resin segment.

2. 2. The toner set for developing electrostatic images according to claim 1, wherein the binder resin contained in said glittering toner particles and the binder resin contained in said color toner particles have different solubility parameters.

3. 3. The toner set for developing electrostatic images according to claim 2, wherein an absolute value of a difference in solubility parameter between the binder resin contained in said glittering toner particles and the binder resin contained in said color toner particles is 0.5 or more and 2.0 or less.

4. 4. The toner set for developing electrostatic images according to claim 1, wherein the color toner particles have a volume average particle size of 5.5 μm or more and 7.5 μm or less.

5. the color toner particles have a smaller volume average particle size than the glitter toner particles, 5. The toner set for developing electrostatic images according to claim 4, wherein the absolute value of the difference in volume average particle size between the glitter toner particles and the color toner particles is 2.7 μm or more and 5.2 μm or less.

6. 6. The toner set for developing an electrostatic image according to claim 1, wherein the color toner has a storage modulus at 120° C. greater than that of the glittering toner.

7. 7. The toner set for developing electrostatic images according to claim 6, wherein an absolute value of a difference (|Es-Ec|) between a storage modulus Es of the glitter toner at 120° C. and a storage modulus Ec of the color toner at 120° C. is 10,000 Pa or more and 20,000 Pa or less.

8. the glitter toner particles and the color toner particles contain a release agent, The toner set for developing electrostatic images according to any one of claims 1 to 7, wherein an absolute value of a difference in solubility parameter between the release agent contained in the glitter toner particles and the binder resin contained in the colored toner particles is larger than an absolute value of a difference in solubility parameter between the release agent contained in the glitter toner particles and the binder resin contained in the glitter toner particles.

9. A first electrostatic image developer containing the glitter toner of the toner set for developing an electrostatic image according to any one of claims 1 to 8; A second electrostatic image developer containing a color toner of the toner set for developing an electrostatic image according to any one of claims 1 to 8; Electrostatic image developer set comprising:

10. A first toner cartridge containing the glitter toner of the toner set for developing an electrostatic image according to any one of claims 1 to 8; a second toner cartridge containing the color toner of the toner set for developing an electrostatic image according to any one of claims 1 to 8; having A toner cartridge set that is detachably attached to an image forming apparatus.

11. a first developing unit containing the first electrostatic image developer of the electrostatic image developer set according to claim 9; a second developing unit containing the second electrostatic image developer of the electrostatic image developer set according to claim 9; Equipped with A process cartridge that is detachably attached to an image forming apparatus.

12. A first image forming means for forming a glossy image using the glossy toner of the toner set for developing an electrostatic image according to any one of claims 1 to 8; A second image forming means for forming a color image by the color toner of the toner set for developing an electrostatic image according to any one of claims 1 to 8; a transfer means for transferring the glossy image and the color image onto a recording medium; a fixing unit for fixing the glossy image and the color image on the recording medium; An image forming apparatus comprising:

13. A first image forming step of forming a glossy image using the glossy toner of the toner set for developing electrostatic images according to any one of claims 1 to 8; A second image forming step of forming a color image using the color toners of the toner set for developing electrostatic images according to any one of claims 1 to 8; a transfer step of transferring the glossy image and the color image onto a recording medium; a fixing step of fixing the glossy image and the color image on the recording medium; The image forming method according to claim 1,

Images