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

Abstract

The invention relates to an electrostatic charge image developing toner set, an electrostatic charge image developer set, a toner cartridge set, a process cartridge, an image forming apparatus, and an image forming method. The electrostatic charge image developing toner set includes a yellow toner containing a yellow pigment, a magenta toner containing a magenta pigment, a blue-green toner containing a blue-green pigment, and a black toner containing a black pigment; a first toner, which is a dye toner or a transparent toner, and which has a crystallization temperature T1 of from 80 DEG C to 95 DEG C (inclusive); and a second toner, which is a dye toner or a clear toner, and which has a crystallization temperature T2 of 60 DEG C or more and 75 DEG C or less.

Description

Technical Field

[0001] The present invention relates to a toner set for electrostatic charge image development, an electrostatic charge image developer set, a toner cartridge set, a processing cartridge, an image forming apparatus and an image forming method. Background Art

[0002] Japanese Patent Gazette No. 2021-127427 discloses a resin particle group comprising: fluorescent resin particles containing a fluorescent colorant; and colored resin particles containing a colored colorant, wherein the volume average particle size of the fluorescent resin particles is larger than the volume average particle size of the colored resin particles, and the average roundness of the fluorescent resin particles is greater than 0.93. A technology for using fluorescent resin particles and colored resin particles as colorants for electrostatic charge image development is also disclosed.

[0003] Japanese Patent Gazette No. 2019-056905 discloses a colorant group for use in an image forming device, the colorant group comprising: a fluorescent colorant containing a binding resin and a fluorescent agent; and a color colorant containing a binding resin and a colorant, the 60-degree gloss Gf of a solid image of the fluorescent colorant is greater than 10 and less than 25, and the difference (Gn-Gf) between the 60-degree gloss Gn of the solid image of the color colorant and the 60-degree gloss Gf of the solid image of the fluorescent colorant is greater than 10 and less than 28. Summary of the invention

[0004] The object of the present invention is to provide a colorant group for electrostatic charge image development, which can suppress both the phenomenon that the colorant is excessively melted and adheres to the fixing component when fixing the colorant image (hereinafter also referred to as "hot offset") and the phenomenon that the colorant that is insufficiently melted is transferred to the fixing component due to insufficient heat supply to the colorant when fixing the colorant image (hereinafter also referred to as "cold offset"), compared with the following situation: the colorant group for electrostatic charge image development includes a yellow toner, a magenta toner, a cyan toner, a black toner, a first toner that is a dye toner or a transparent toner, and a second toner that is a dye toner or a transparent toner, and the crystallization temperature T1 of the first toner is lower than 80°C or the crystallization temperature T2 of the second toner exceeds 75°C.

[0005] According to a first aspect of the present invention, a colorant group for developing electrostatic charge images is provided, which includes: a yellow colorant containing a yellow pigment, a magenta colorant containing a magenta pigment, a cyan colorant containing a cyan pigment, and a black colorant containing a black pigment; a first colorant, the first colorant is a dye colorant or a transparent colorant, and the crystallization temperature T1 is greater than 80°C and less than 95°C; and a second colorant, the second colorant is a dye colorant or a transparent colorant, and the crystallization temperature T2 is greater than 60°C and less than 75°C.

[0006] According to a second aspect of the present invention, in the electrostatic image developing toner set according to the first aspect, a difference between the crystallization temperature T1 and the crystallization temperature T2 is 15° C. or more.

[0007] According to a third aspect of the present invention, in the electrostatic image developing toner set according to the second aspect, a difference between the crystallization temperature T1 and the crystallization temperature T2 is 20° C. or more.

[0008] According to the fourth aspect of the present invention, in the electrostatic charge image developing colorant group of any one of the first to third aspects, when the average value of the crystallization temperature of the yellow colorant, the crystallization temperature of the magenta colorant, the crystallization temperature of the cyan colorant, and the crystallization temperature of the black colorant is set to the crystallization temperature T3, the difference between the crystallization temperature T1 and the crystallization temperature T3 is less than 5°C, and the difference between the crystallization temperature T2 and the crystallization temperature T3 is greater than 20°C.

[0009] According to a fifth aspect of the present invention, in the electrostatic image developing toner set of any one of the first to fourth aspects, the first toner includes first toner particles containing a crystalline resin and particulate matter, and the second toner includes second toner particles containing a crystalline resin.

[0010] According to a sixth aspect of the present invention, in the electrostatic image developing toner set according to the fifth aspect, the granular matter is colorless and transparent.

[0011] According to a seventh aspect of the present invention, in the electrostatic image developing toner set of the fifth or sixth aspect, the particulate matter is silica particles.

[0012] According to an eighth aspect of the present invention, in the electrostatic image developing toner set according to any one of the fifth to seventh aspects, the content of the particulate matter contained in the first toner is 1 mass % or more and 5 mass % or less.

[0013] According to the ninth aspect of the present invention, there is provided an electrostatic charge image developer group, comprising: a yellow developer, a magenta developer, a cyan developer, and a black developer, wherein the yellow developer, the magenta developer, the cyan developer, and the black developer respectively contain the yellow colorant, the magenta colorant, the cyan colorant, and the black colorant in the electrostatic charge image developing colorant group of any one of the first to eighth aspects; a first developer, wherein the first developer contains the first colorant in the electrostatic charge image developing colorant group of any one of the first to eighth aspects; and a second developer, wherein the second developer contains the second colorant in the electrostatic charge image developing colorant group of any one of the first to eighth aspects.

[0014] According to the tenth aspect of the present invention, a colorant box group is provided, which comprises: a yellow colorant box, a magenta colorant box, a cyan colorant box, and a black colorant box, the yellow colorant box, the magenta colorant box, the cyan colorant box, and the black colorant box respectively including the yellow colorant, the magenta colorant, the cyan colorant, and the black colorant in the electrostatic charge image developing colorant group of any one of the first to eighth aspects; a first colorant box, the first colorant box including the first colorant in the electrostatic charge image developing colorant group of any one of the first to eighth aspects; and a second colorant box, the second colorant box including the second colorant in the electrostatic charge image developing colorant group of any one of the first to eighth aspects, the colorant box assembly being detachable from an image forming device.

[0015] According to the eleventh aspect of the present invention, there is provided a processing box comprising: a yellow developing unit, a magenta developing unit, a cyan developing unit, and a black developing unit, wherein the yellow developing unit, the magenta developing unit, the cyan developing unit, and the black developing unit respectively include the yellow developer, the magenta developer, the cyan developer, and the black developer in the electrostatic charge image developer group of the ninth aspect; a first developing unit, wherein the first developing unit includes the first developer in the electrostatic charge image developer group of the ninth aspect; and a second developing unit, wherein the second developing unit includes the second developer in the electrostatic charge image developer group of the ninth aspect, and the processing box is installed and removed from an image forming device.

[0016] According to a twelfth aspect of the present invention, there is provided an image forming apparatus comprising: a yellow image forming unit, a magenta image forming unit, a cyan image forming unit, and a black image forming unit, wherein the yellow image forming unit, the magenta image forming unit, the cyan image forming unit, and the black image forming unit respectively form a yellow image, a magenta image, a cyan image, and a black image using the yellow toner, the magenta toner, the cyan toner, and the black toner in the electrostatic charge image developing toner group according to any one of the first to eighth aspects; and a first image forming unit, wherein the first image forming unit forms a yellow image, a magenta image, a cyan image, and a black image using the yellow toner, the magenta toner, the cyan toner, and the black toner in the electrostatic charge image developing toner group according to any one of the first to eighth aspects. On the one hand, a first image of the first colorant in the electrostatic charge image developing colorant group; a second image forming unit, which forms a second image using the second colorant in the electrostatic charge image developing colorant group of any one of the first to eighth aspects; a transfer unit, which transfers the yellow image, the magenta image, the cyan image, the black image, the first image, and the second image to a recording medium; and a fixing unit, which fixes the colorant image formed by stacking the yellow image, the magenta image, the cyan image, the black image, the first image, and the second image to the recording medium.

[0017] According to the thirteenth aspect of the present invention, in the image forming apparatus of the twelfth aspect, as for the toner image, the layer farthest from the recording medium is the first image, and the layer second farthest from the recording medium is the second image.

[0018] According to the fourteenth aspect of the present invention, there is provided an image forming method, comprising: a yellow image forming step, a magenta image forming step, a cyan image forming step, and a black image forming step, respectively forming a yellow image, a magenta image, a cyan image, and a black image using the yellow colorant, the magenta colorant, the cyan colorant, and the black colorant in the electrostatic charge image developing colorant group of any one of the first to eighth aspects; a first image forming step, forming a first image using the first colorant in the electrostatic charge image developing colorant group of any one of the first to eighth aspects; a second image forming step, forming a second image using the second colorant in the electrostatic charge image developing colorant group of any one of the first to eighth aspects; a transfer step, transferring the yellow image, the magenta image, the cyan image, the black image, the first image, and the second image to a recording medium; and a fixing step, fixing the toner image formed by stacking the yellow image, the magenta image, the cyan image, the black image, the first image, and the second image to the recording medium.

[0019] According to a fifteenth aspect of the present invention, in the image forming method of the fourteenth aspect, as for the toner image, the layer farthest from the recording medium is the first image, and the layer second farthest from the recording medium is the second image.

[0020] (Effect)

[0021] According to the first, fifth, sixth or seventh aspect, a colorant group for electrostatic charge image development is provided, which takes into account both the suppression of a phenomenon in which the colorant excessively melts and adheres to the fixing component when fixing the colorant image (hereinafter also referred to as "hot offset"), and the suppression of a phenomenon in which the colorant that is insufficiently melted is transferred to the fixing component due to insufficient heat supply to the colorant when fixing the colorant image (hereinafter also referred to as "cold offset"), compared to the following situation: the colorant group for electrostatic charge image development includes a yellow colorant, a magenta colorant, a cyan colorant, a black colorant, a first colorant that is a dye colorant or a transparent colorant, and a second colorant that is a dye colorant or a transparent colorant, and the crystallization temperature T1 of the first colorant is lower than 80°C or the crystallization temperature T2 of the second colorant exceeds 75°C.

[0022] According to the second aspect, there is provided an electrostatic image developing toner set which achieves both suppression of hot offset and suppression of cold offset compared to the case where the difference between the crystallization temperature T1 and the crystallization temperature T2 is less than 15°C.

[0023] According to the third aspect, there is provided an electrostatic image developing toner set which achieves both suppression of hot offset and suppression of cold offset compared to a case where the difference between the crystallization temperature T1 and the crystallization temperature T2 is less than 20°C.

[0024] According to the fourth aspect, a toner set for electrostatic image development is provided, which can suppress both hot offset and cold offset compared to the case where the difference between the crystallization temperature T1 and the crystallization temperature T3 is less than 5°C or the difference between the crystallization temperature T2 and the crystallization temperature T3 is less than 20°C.

[0025] According to the eighth aspect, there is provided an electrostatic image developing toner set which achieves both hot offset suppression and cold offset suppression compared to a case where the content of particulate matter contained in the first toner is less than 1 mass % or exceeds 5 mass %.

[0026] According to the ninth, tenth, eleventh, twelfth or fourteenth aspect, there is provided an electrostatic charge image developer group, a colorant box group, a processing box, an image forming device or an image forming method, which takes into account both the suppression of thermal offset and the suppression of cold offset compared to the case of applying the following electrostatic charge image developing colorant group: comprising a yellow colorant, a magenta colorant, a cyan colorant, a black colorant, a first colorant which is a dye colorant or a transparent colorant, and a second colorant which is a dye colorant or a transparent colorant, and the crystallization temperature T1 of the first colorant is lower than 80°C or the crystallization temperature T2 of the second colorant exceeds 75°C.

[0027] According to the thirteenth or fifteenth aspect, an image forming device or an image forming method is provided, which takes into account both the suppression of thermal offset and the suppression of cold offset, compared to the case of applying the following electrostatic charge image developing colorant group, even if the layer farthest from the recording medium is the first image and the layer second farthest from the recording medium is the second image: comprising a yellow colorant, a magenta colorant, a cyan colorant, a black colorant, a first colorant which is a dye colorant or a transparent colorant, and a second colorant which is a dye colorant or a transparent colorant, and the crystallization temperature T1 of the first colorant is lower than 80°C or the crystallization temperature T2 of the second colorant exceeds 75°C. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 is a schematic structural diagram showing an example of an image forming apparatus of the present invention;

[0029] Figure 2 This is a schematic structural diagram showing an example of a process cartridge that is attachable to and detachable from the image forming apparatus of the present invention. DETAILED DESCRIPTION

[0030] The following describes embodiments of the present invention. These descriptions and examples are intended to illustrate the embodiments and are not intended to limit the scope of the embodiments.

[0031] In the present invention, a numerical range expressed by "to" indicates a range including the numerical values ​​described before and after "to" as the minimum value and the maximum value, respectively.

[0032] In the numerical range of recording in stages in the present invention, the upper limit or lower limit recorded in a numerical range can also be replaced by the upper limit or lower limit of the numerical range of recording in other stages. In addition, in the numerical range of recording in the present invention, the upper limit or lower limit of this numerical range can also be replaced by the value shown in the embodiment.

[0033] In the present invention, the term "process" refers not only to an independent process but also to a process that cannot be clearly distinguished from other processes as long as the purpose of the process can be achieved.

[0034] In the present invention, when the embodiments are described with reference to the drawings, the structure of the embodiments is not limited to the structure shown in the drawings. In addition, the sizes of the components in each figure are conceptual sizes, and the relative relationship between the sizes of the components is not limited to this.

[0035] In the present invention, each component may also include a plurality of corresponding substances. In the present invention, when referring to the amount of each component in the composition, in the case where there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, it refers to the total amount of the plurality of substances present in the composition.

[0036] In the present invention, multiple types of particles corresponding to each component may be included. When multiple types of particles corresponding to each component are present in the composition, the particle size of each component refers to a value for a mixture of the multiple types of particles present in the composition unless otherwise specified.

[0037] In the present invention, “(meth)acryl” refers to an expression including both acryl and methacryl, and “(meth)acrylate” refers to an expression including both acrylate and methacrylate.

[0038] In the present invention, the main component refers to a major component. For example, the main component refers to a component that has the largest content (based on mass) relative to the total mass of a mixture of multiple components.

[0039] In the present invention, the “colorant for electrostatic charge image development” is also referred to as the “colorant”, the “colorant group for electrostatic charge image development” is also referred to as the “colorant group”, the “electrostatic charge image developer” is also referred to as the “developer”, the “electrostatic charge image developer group” is also referred to as the “developer group”, and the “carrier for electrostatic charge image development” is also referred to as the “carrier”.

[0040] [Toner set for electrostatic image development]

[0041] A colorant group according to one embodiment of the present invention includes: a yellow colorant containing a yellow pigment, a magenta colorant containing a magenta pigment, a cyan colorant containing a cyan pigment, and a black colorant containing a black pigment; a first colorant, which is a dye colorant or a transparent colorant, and has a crystallization temperature T1 of 80°C to 95°C; and a second colorant, which is a dye colorant or a transparent colorant, and has a crystallization temperature T2 of 60°C to 75°C.

[0042] In electrophotographic printing, color process printing using yellow (Y), magenta (M), cyan (C), and black (K) is the mainstream. In this color process printing, a toner set including a yellow toner containing a yellow pigment, a magenta toner containing a magenta pigment, a cyan toner containing a cyan pigment, and a black toner containing a black pigment is used.

[0043] Hereinafter, the yellow toner, the magenta toner, the cyan toner, and the black toner are collectively referred to as “YMCK toner”.

[0044] On the other hand, due to the evolution and popularization of televisions, monitors, tablet computers, smartphones, etc., it has become common to view photos, images, illustrations, etc. on beautiful and vivid displays. Photos or illustrations (for example, illustrations drawn using a PC, etc.) viewed on a display are not only wide color gamut, but also bright tones. In order to reproduce this wide color gamut and bright tones, a toner set including a dye toner containing a dye such as a fluorescent dye in addition to a YMCK toner is adopted for image formation. In addition, in order to adjust the glossiness of the image, impart adhesion, etc., a toner set also including a transparent toner is sometimes used.

[0045] The toner set of the present embodiment includes, in addition to the YMCK toners, a first toner that is a dye toner or a transparent toner, and a second toner that is a dye toner or a transparent toner.

[0046] In this embodiment, the crystallization temperature T1 of the first toner is 80° C. to 95° C., and the crystallization temperature T2 of the second toner is 60° C. to 75° C., thereby achieving both suppression of hot offset and suppression of cold offset. The reason is not clear, but is presumed as follows.

[0047] Image formation using a toner set including a YMCK toner, a first toner, and a second toner is performed, for example, as follows. Specifically, first, a yellow image, a magenta image, a cyan image, a black image, a first image, and a second image are formed using a yellow toner, a magenta toner, a cyan toner, a black toner, a first toner, and a second toner, respectively. Hereinafter, a yellow image, a magenta image, a cyan image, and a black image are collectively referred to as a "YMCK image."

[0048] Then, by transferring each image onto a recording medium, a toner image formed by stacking six layers of images is obtained, and then the toner image formed by stacking six layers of images is fixed onto the recording medium. At this time, in the toner image on the recording medium, for example, the first image and the second image are stacked on the side farther from the recording medium than the YMCK image.

[0049] As described above, in image formation using a toner set including a first toner and a second toner in addition to YMCK toners, a toner image formed by stacking six layers of images formed by the toners is fixed to a recording medium through a fixing process. Therefore, compared with image formation using a toner set consisting of only YMCK toners, more heat is required to fix the toner image to the recording medium in the fixing process, and the fixing temperature becomes higher.

[0050] When a toner image formed by stacking six layers of images is fixed to a recording medium at a high fixing temperature, for example, when the crystallization temperatures of both the first toner and the second toner are low, thermal offset is likely to occur. Specifically, when the first image and the second image stacked on the YMCK image and present on the fixing component side have low viscosity and are difficult to solidify, they are subjected to the load caused by the fixing component. At this time, since the toner image formed by stacking six layers of images is thicker, the load caused by the fixing component becomes larger, and therefore, the melted toner is likely to adhere to the fixing component. In particular, when forming an image on a thin recording medium such as thin paper, the above-mentioned thermal offset is likely to become noticeable.

[0051] On the other hand, for example, when the crystallization temperatures of both the first toner and the second toner are high, cold offset is likely to occur because the heat supply is insufficient for the heat required for melting the toner image. In particular, when forming an image on a thick recording medium such as thick paper, the cold offset is likely to become noticeable.

[0052] In contrast, in the present embodiment, the crystallization temperature T1 of the first toner is 80° C. or higher and 95° C. or lower, and the crystallization temperature T2 of the second toner is 60° C. or higher and 75° C. or lower. Therefore, compared with the case where the crystallization temperature T1 is lower than 80° C., the thermal offset that is likely to occur when the crystallization temperatures of both the first toner and the second toner are low is suppressed. In addition, compared with the case where the crystallization temperature T2 exceeds 75° C., the cold offset that is likely to occur when the crystallization temperatures of both the first toner and the second toner are high is suppressed. As a result, it is presumed that both the thermal offset and the cold offset are suppressed.

[0053] In addition, when forming an image using a toner set consisting of only YMCK toners and a second toner, the above-mentioned thermal offset is less likely to occur. The reason is unclear, but it is presumed that the second image adjoining the YMCK image is difficult to separate from the YMCK image due to the adhesion of the YMCK image.

[0054] In addition, when only the second toner is used for image formation, the above-mentioned thermal offset is unlikely to occur. The reason is unclear, but it is presumed that the second image in contact with the recording medium penetrates into the recording medium to obtain an anchoring effect, making it difficult to peel off from the recording medium.

[0055] The toner set of the present invention only needs to include at least a YMCK toner, a first toner, and a second toner, and may also include a toner other than the six toners (hereinafter, also referred to as other toners). As other toners, for example, pigment toners other than YMCK toners, i.e., toners containing toner particles as follows: containing a pigment as a main component of a colorant, and the content of the dye relative to the total mass of the colorant is less than 10% by mass.

[0056] <Crystallization temperature>

[0057] The crystallization temperature of the toner is determined by differential scanning calorimetry. Specifically, the toner to be measured is placed in a differential scanning calorimeter (DSC-50) manufactured by Shimadzu Corporation with an automatic tangent processing system, and liquid nitrogen is added as a cooling medium. The toner is heated from 20°C to 150°C at a heating rate of 10°C / min, and the relationship between temperature (°C) and heat (mW) is determined. Next, the exothermic peak temperature of the cooling spectrum when the toner is cooled to 0°C at a cooling rate of -10°C / min is set as the crystallization temperature of the toner. In the case of multiple exothermic peaks, the largest peak is regarded as the crystallization temperature.

[0058] The crystallization temperature T1 of the first toner is 80° C. to 95° C., preferably 80° C. to 90° C., and more preferably 85° C. to 90° C. from the viewpoint of suppressing both hot offset and cold offset.

[0059] The crystallization temperature T2 of the second toner is 60° C. to 75° C., preferably 60° C. to 70° C., and more preferably 65° C. to 70° C. from the viewpoint of suppressing both hot offset and cold offset.

[0060] As a combination of the first colorant and the second colorant whose crystallization temperature T1 and the crystallization temperature T2 are respectively within the above range, for example, a combination of a first colorant including first colorant particles containing a crystalline resin and particulate matter and a second colorant including second colorant particles containing a crystalline resin can be cited. The first colorant and the second colorant preferably also contain a release agent, respectively. That is, the combination of the first colorant and the second colorant whose crystallization temperature T1 and the crystallization temperature T2 are respectively within the above range is preferably a combination of a first colorant including first colorant particles containing a crystalline resin, a release agent, and particulate matter and a second colorant including second colorant particles containing a crystalline resin and a release agent. In addition, the second colorant particles preferably do not substantially contain particulate matter, that is, the content of the particulate matter relative to the entire second colorant particles is less than 1% by mass.

[0061] It is believed that since the first toner particles contain a crystalline resin and granular materials, the granular materials are used as crystal nuclei to promote the crystallization of the crystalline resin, thereby controlling the crystallization temperature T1 within the above range. It is believed that, particularly when the first toner particles contain a crystalline resin, a release agent, and granular materials, the granular materials are used as crystal nuclei to promote the crystallization of the crystalline resin and the release agent, and the crystallization temperature T1 is controlled within the above range.

[0062] In addition, it is considered that the second toner particles contain a crystalline resin and substantially do not contain particulate matter, so that the material that becomes the crystal nucleus does not exist, and the crystallization of the crystalline resin is not promoted, thereby controlling the crystallization temperature T2 within the above range. The same is true for the case where the second toner particles contain a crystalline resin and a release agent and substantially do not contain particulate matter. The material that becomes the crystal nucleus does not exist, and the crystallization of the crystalline resin and the release agent is not promoted, thereby controlling the crystallization temperature T2 within the above range.

[0063] In addition, the details of the crystalline resin and the granular material will be described later.

[0064] From the viewpoint of suppressing both hot and cold offsets, the difference between the crystallization temperature T1 and the crystallization temperature T2 is preferably 15° C. or more, more preferably 20° C. or more, and even more preferably 25° C. or more. The upper limit of the difference between the crystallization temperature T1 and the crystallization temperature T2 is not particularly limited, and an example thereof is 35° C.

[0065] In the toner group in which the difference between the crystallization temperature T1 and the crystallization temperature T2 is equal to or greater than the above lower limit, the crystallization temperature T1 is high and the crystallization temperature T2 is low. Therefore, compared with the case where both the crystallization temperature T1 and the crystallization temperature T2 are low, the hot offset is suppressed, and compared with the case where both the crystallization temperature T1 and the crystallization temperature T2 are high, the cold offset is suppressed. As a result, both the hot offset and the cold offset are suppressed.

[0066] The average value of the crystallization temperature of the yellow colorant, the crystallization temperature of the magenta colorant, the crystallization temperature of the cyan colorant, and the crystallization temperature of the black colorant, i.e., the crystallization temperature T3, is not particularly limited, and may be, for example, 80°C or higher and 95°C or lower, preferably 80°C or higher and 90°C or lower, and more preferably 85°C or higher and 90°C or lower.

[0067] The difference between the crystallization temperature T1 and the crystallization temperature T3 is, for example, 10° C. or less, and is preferably 5° C. or less, more preferably 3° C. or less from the viewpoint of achieving both suppression of hot offset and suppression of cold offset.

[0068] The difference between the crystallization temperature T2 and the crystallization temperature T3 is, for example, 12° C. or more, preferably 20° C. or more, and more preferably 25° C. or more from the viewpoint of suppressing both the thermal offset and the cold offset. The upper limit of the difference between the crystallization temperature T2 and the crystallization temperature T3 is not particularly limited, and is, for example, 35° C.

[0069] From the viewpoint of taking into account both the suppression of thermal offset and the suppression of cold offset, it is preferred that the difference between the crystallization temperature T1 and the crystallization temperature T3 is 10°C or less, and the difference between the crystallization temperature T2 and the crystallization temperature T3 is 12°C or more. It is more preferred that the difference between the crystallization temperature T1 and the crystallization temperature T3 is 5°C or less, and the difference between the crystallization temperature T2 and the crystallization temperature T3 is 20°C or more. It is further preferred that the difference between the crystallization temperature T1 and the crystallization temperature T3 is 3°C or less, and the difference between the crystallization temperature T2 and the crystallization temperature T3 is 25°C or more.

[0070] Next, details of each toner included in an example of the toner set according to the present embodiment will be described.

[0071] <YMCK toner>

[0072] There is no particular limitation on the YMCK toners, as long as they are yellow toners containing yellow pigments, magenta toners containing magenta pigments, cyan toners containing cyan pigments, and black toners containing black pigments. YMCK toners are all toners containing toner particles, the toner particles contain pigments as the main component of the colorant, and the content of the dye relative to the total mass of the colorant is less than 10% by mass. YMCK toners use conventionally known yellow toners, magenta toners, cyan toners, and black toners.

[0073] The specific structure of the YMCK toner can be, for example, the same structure as the first toner and the second toner described below except that pigments of various colors are used as colorants.

[0074] <First toner and second toner>

[0075] The first toner and the second toner are not particularly limited as long as they are dye toners or transparent toners and have a crystallization temperature within the above range.

[0076] Dye toner is a toner containing a dye. Dye toner includes toner particles containing a dye, i.e., dye toner particles. Dye toner particles may also contain colorants other than dyes. In the case where the dye toner particles contain colorants other than dyes, the dye toner particles are toner particles in which the content of the dye relative to the total mass of the colorant is 10% by mass or more. As dye toners, for example, fluorescent toners, i.e., toners containing toner particles containing a fluorescent dye as a dye, may be cited. As fluorescent toners, fluorescent green toners, fluorescent pink toners, fluorescent red toners, fluorescent orange toners, fluorescent yellow toners, fluorescent blue toners, fluorescent violet toners, etc. may be cited. Fluorescent toners may also be invisible fluorescent toners that are usually colorless and emit light by irradiation with ultraviolet rays.

[0077] The transparent toner is a toner that does not substantially contain a colorant, that is, a toner in which the content of the colorant relative to the entire toner is less than 1% by mass.

[0078] In the present embodiment, both the first toner and the second toner may be dye toners, the first toner may be a dye toner and the second toner may be a transparent toner, or the first toner may be a transparent toner and the second toner may be a dye toner.

[0079] When both the first colorant and the second colorant are dye colorants, it is preferred that the first colorant and the second colorant are colorants of different colors. Examples of the combination of the first colorant and the second colorant of different colors include a combination of a fluorescent green colorant and a fluorescent pink colorant, a combination of a green colorant and a pink colorant, a combination of a fluorescent green colorant and a fluorescent orange colorant, a combination of a green colorant and an orange colorant, and a combination of a fluorescent yellow colorant and a fluorescent pink colorant.

[0080] When both the first colorant and the second colorant are dye colorants, from the viewpoint of obtaining a wide color gamut, the difference in hue angle between the first colorant and the second colorant is preferably greater than 120 degrees and less than 180 degrees, more preferably greater than 135 degrees and less than 180 degrees, further preferably greater than 145 degrees and less than 180 degrees, and particularly preferably greater than 160 degrees and less than 180 degrees.

[0081] The difference in chroma between the first toner and the second toner is preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less. The difference in chroma between the first toner and the second toner may be 0 or 10 or more.

[0082] The difference in brightness between the first toner and the second toner is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The difference in brightness between the first toner and the second toner may be 0 or 3 or more.

[0083] The hue angle, chroma, and brightness of the toner were measured by the following method.

[0084] The toner to be measured was placed in Revoriá Press PC1120 manufactured by Fujifilm Business Innovation Co., Ltd. Using this device, only the toner to be measured was used at a toner loading of 4.0 g / m 2 A solid image (4.0 cm×2.5 cm) was formed on OS coated paper (127 gsm) A4 as a recording medium under the conditions of a fixing temperature of 180°C.

[0085] Hue angle (h), chroma (C * ) and brightness (L * ), the solid image on the recording medium obtained by the above method was randomly measured ten times using eXact Advanced (aperture 4 mm: manufactured by X-Rite Corporation), and the color gamut of the solid image of the average value was set as the color reproduction measurement value (L * 、a * and b * ). According to the obtained color reproduction measurement value (L * 、a *and b * ) to find the brightness (L * ), hue angle (h) and chroma (C * ) is calculated according to the following formula.

[0086] Chroma (C * )=((a * ) 2 +(b * ) 2 )) 1 / 2

[0087] Hue angle (h) = tan -1 (b * / a * )

[0088] Next, the first toner and the second toner will be described in detail.

[0089] The first toner is configured to include first toner particles and, if necessary, an external additive.

[0090] The second toner is configured to include second toner particles and, if necessary, an external additive.

[0091] (Toner particles)

[0092] The first toner particles and the second toner particles are each configured to contain, for example, a binder resin, and, if necessary, a colorant, a release agent, and other additives.

[0093] From the viewpoint of easily controlling the crystallization temperature T1 and the crystallization temperature T2 within the above range, the first toner particles and the second toner particles preferably contain a crystalline resin. The crystalline resin is contained in the toner particles as a component of a binder resin constituting the toner particles, for example. From the viewpoint of easily controlling the crystallization temperature T1 and the crystallization temperature T2 within the above range, the first toner particles and the second toner particles more preferably contain a crystalline resin and a release agent, respectively.

[0094] In addition, from the viewpoint of easily controlling the crystallization temperature T1 within the above range, the first toner particles preferably contain particulate matter. When the particulate matter is a pigment described later, the particulate matter is contained in the toner particles as a component of a colorant contained in the toner particles as required. In addition, when the particulate matter is an inorganic particle described later, the particulate matter is contained in the toner particles as a component of other additives contained in the toner particles as required.

[0095] Next, each component constituting the toner particles will be described.

[0096] -Bonding resin-

[0097] Examples of the binder resin include vinyl resins composed of homopolymers of monomers such as styrenes (e.g., styrene, p-chlorostyrene, α-methylstyrene, etc.), (meth)acrylates (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.), olefins (e.g., ethylene, propylene, butadiene, etc.), or copolymers formed by combining two or more of these monomers.

[0098] Examples of the binder resin include non-vinyl resins such as epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, and modified rosins, mixtures thereof with the vinyl resins, and graft polymers obtained by polymerizing vinyl monomers in the presence of the non-vinyl resins.

[0099] These binder resins may be used alone or in combination of two or more.

[0100] As described above, the first toner particles and the second toner particles preferably contain a crystalline resin as a component of the binder resin.

[0101] Furthermore, the first toner particles and the second toner particles more preferably contain a crystalline resin and a non-crystalline resin as the binder resin.

[0102] The "crystallinity" of a resin refers to the presence of a clear endothermic peak in differential scanning calorimetry (DSC) rather than a step-like change in endothermic value, and specifically, the half width of the endothermic peak when measured at a heating rate of 10 (°C / min) is within 10°C.

[0103] On the other hand, "amorphous" of a resin means when the half width exceeds 10°C, when a step-like change in endothermic value is shown, or when no clear endothermic peak is observed.

[0104] --Crystalline resin--

[0105] Examples of the crystalline resin include known crystalline resins such as crystalline polyester resins and crystalline vinyl resins (e.g., polyalkylene resins, long-chain alkyl (meth) acrylate resins, etc.). Among them, from the viewpoint of mechanical strength and low-temperature fixing property of the toner, the crystalline resin is preferably a crystalline polyester resin.

[0106] Crystalline polyester resin

[0107] Examples of the crystalline polyester resin include polycondensates of polycarboxylic acids and polyols. In addition, as the crystalline polyester resin, a commercially available product may be used, and a synthetic crystalline polyester resin may also be used.

[0108] Here, in order to easily form a crystal structure, the crystalline polyester resin is more preferably a polycondensate using a polymerizable monomer having a straight-chain aliphatic group rather than a polycondensate using a polymerizable monomer having an aromatic group.

[0109] Examples of the polycarboxylic acid 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, and naphthalene-2,6-dicarboxylic acid); and acid anhydrides thereof or lower (e.g., having a carbon number of 1 or more and 5 or less) alkyl esters thereof.

[0110] The polycarboxylic acid may be used together with the dicarboxylic acid, and a trivalent or higher carboxylic acid having a cross-linked structure or a branched structure. 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, or their lower (e.g., carbon number 1 to 5) alkyl esters.

[0111] As the polycarboxylic acid, a dicarboxylic acid having a sulfonic acid group or a dicarboxylic acid having an ethylenic double bond may be used in combination with these dicarboxylic acids.

[0112] The polyvalent carboxylic acid may be used alone or in combination of two or more.

[0113] Examples of the polyol include aliphatic diols (e.g., linear aliphatic diols having a main chain portion having carbon atoms of 7 or more and 20 or less). Examples of the aliphatic diols include ethylene glycol, 1,3-propylene glycol, 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 them, preferred aliphatic diols include 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol.

[0114] The polyol may be used together with the diol and a trivalent or higher alcohol having a cross-linked structure or a branched structure. Examples of the trivalent or higher alcohol include glycerol, trimethylolethane, trimethylolpropane, and pentaerythritol.

[0115] The polyols may be used alone or in combination of two or more.

[0116] Here, the polyol preferably contains an aliphatic diol in an amount of 80 mol % or more, and more preferably 90 mol % or more.

[0117] The weight average molecular weight (Mw) of the crystalline polyester resin is preferably 6,000 or more and 35,000 or less.

[0118] In addition, the weight average molecular weight is measured by gel permeation chromatography (GPC). The molecular weight measurement based on GPC uses Tosoh GPC HLC-8120GPC as a measuring device, Tosoh column TSKgel SuperHM-M (15cm), and THF solvent. The weight average molecular weight is calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample based on the measurement results.

[0119] The crystalline polyester resin can be obtained by a known production method, for example, similarly to the non-crystalline polyester described below.

[0120] ·Melting temperature of crystalline resin

[0121] From the viewpoint of controlling the crystallization temperature T1 within the above range, the melting temperature of the crystalline resin contained in the first toner particles is preferably 50°C to 100°C, more preferably 55°C to 90°C, and further preferably 60°C to 85°C.

[0122] From the viewpoint of controlling the crystallization temperature T2 within the above range, the melting temperature of the crystalline resin contained in the second toner particles is preferably 50°C to 100°C, more preferably 55°C to 90°C, and further preferably 60°C to 85°C.

[0123] The melting temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC) according to the “melting peak temperature” described in the method for determining the melting temperature in JIS K7121-1987 “Methods for determining transition temperatures of plastics”.

[0124] ·Crystalline resin content

[0125] From the viewpoint of controlling the crystallization temperature T1 within the above range, the content of the crystalline resin contained in the first colorant particles is preferably greater than 1 mass % and less than 20 mass %, more preferably greater than 3 mass % and less than 15 mass %, and further preferably greater than 6 mass % and less than 10 mass %, relative to the first colorant particles as a whole.

[0126] From the viewpoint of controlling the crystallization temperature T2 within the said range, the content of the crystalline resin contained in the second colorant particles is preferably greater than 1 mass % and less than 20 mass %, more preferably greater than 3 mass % and less than 15 mass %, and further preferably greater than 6 mass % and less than 10 mass %, relative to the second colorant particles as a whole.

[0127] From the viewpoint of controlling the crystallization temperature T1 within the said range, the content of the crystalline resin contained in the first colorant particles is preferably greater than 2 mass % and less than 40 mass %, more preferably greater than 2 mass % and less than 20 mass %, and further preferably greater than 5 mass % and less than 15 mass %, relative to the total binding resin contained in the first colorant particles.

[0128] From the viewpoint of controlling the crystallization temperature T2 within the said range, the content of the crystalline resin contained in the second colorant particles is preferably greater than 2 mass % and less than 40 mass %, more preferably greater than 2 mass % and less than 20 mass %, and further preferably greater than 5 mass % and less than 15 mass %, relative to the total binding resin contained in the second colorant particles.

[0129] --Amorphous resin--

[0130] Examples of the amorphous resin include known amorphous resins such as amorphous polyester resins, amorphous vinyl resins (e.g., styrene acrylate resins, etc.), epoxy resins, polycarbonate resins, and polyurethane resins. Among them, amorphous polyester resins and amorphous vinyl resins (particularly styrene acrylate resins) are preferred, and amorphous polyester resins are more preferred.

[0131] Amorphous polyester resin

[0132] Examples of the non-crystalline polyester resin include polycondensates of polycarboxylic acids and polyols. In addition, as the non-crystalline polyester resin, a commercially available product may be used, and a synthetic non-crystalline polyester resin may also be used.

[0133] Examples of the polycarboxylic acid 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, naphthalene dicarboxylic acid, etc.), their anhydrides, or their lower (e.g., carbon number of 1 to 5) alkyl esters. Among them, the polycarboxylic acid is preferably, for example, an aromatic dicarboxylic acid.

[0134] The polycarboxylic acid may be used together with the dicarboxylic acid to form a cross-linked or branched trivalent or higher carboxylic acid. Examples of the trivalent or higher carboxylic acid include trimellitic acid, pyromellitic acid, their anhydrides, or their lower (e.g., carbon number 1 to 5) alkyl esters.

[0135] The polyvalent carboxylic acid may be used alone or in combination of two or more.

[0136] Examples of the polyol 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 them, the polyol is preferably, for example, an aromatic diol or an alicyclic diol, and more preferably an aromatic diol.

[0137] As the polyol, a trivalent or higher polyol having a cross-linked structure or a branched structure may be used together with a diol. Examples of the trivalent or higher polyol include glycerol, trimethylolpropane, and pentaerythritol.

[0138] The polyols may be used alone or in combination of two or more.

[0139] 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.

[0140] The glass transition temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC), more specifically, by the "extrapolated glass transition start temperature" described in the method for determining the glass transition temperature in JIS K 7121-1987 "Methods for determining transition temperatures of plastics".

[0141] 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.

[0142] The number average molecular weight (Mn) of the amorphous polyester resin is preferably 2,000 or more and 100,000 or less.

[0143] 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.

[0144] In addition, the weight average molecular weight and the number average molecular weight are measured by gel permeation chromatography (GPC). The molecular weight measurement based on GPC uses GPC HLC-8120GPC manufactured by Tosoh as a measuring device, a column TSKgel SuperHM-M (15 cm) manufactured by Tosoh, and THF solvent. The weight average molecular weight and the number average molecular weight are calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample based on the measurement results.

[0145] The amorphous polyester resin is obtained by a known production method, specifically, for example, by setting the polymerization temperature to 180° C. to 230° C., reducing the pressure in the reaction system as required, and reacting while removing water and alcohol generated during condensation.

[0146] In addition, when the monomer of the raw material is insoluble or incompatible at the reaction temperature, a high boiling point solvent may be added as a cosolvent to dissolve it. In this case, the polycondensation reaction is carried out while the cosolvent is removed by distillation. In the case of the presence of monomers with poor mutual solubility, it is preferred to condense the monomers with poor mutual solubility and the acid or alcohol to be polycondensed with the monomers before polycondensation with the main component.

[0147] --Content of Binder Resin-

[0148] The content of the binder resin is, for example, preferably 40% by mass or more and 95% by mass or less, more preferably 50% by mass or more and 90% by mass or less, and further preferably 60% by mass or more and 85% by mass or less, based on the entire toner particles.

[0149] - Granular matter -

[0150] The particulate matter is not particularly limited as long as it is composed of a component other than a resin, and examples thereof include pigments and inorganic particles.

[0151] Examples of the pigment include known pigments used as colorants, and specific examples include aggregation-induced emission colorants and non-fluorescent pigments described below.

[0152] Examples of the inorganic particles include metal oxide particles such as silicon dioxide, titanium oxide, zinc oxide, and tin oxide; metal compound particles such as barium sulfate, aluminum borate, and potassium titanate; and metal particles such as gold, silver, and copper.

[0153] The granular materials may be used alone or in combination of two or more.

[0154] When the granular material is an inorganic particle, the granular material is preferably colorless and transparent from the viewpoint of facilitating the control of the color of the toner while controlling the crystallization temperature. Here, the granular material is colorless and transparent means that the brightness (L * ) is more than 95%, chromaticity (a * ) is -5 or more and 5 or less, chromaticity (b * ) is -5 or more and 5 or less, and the haze value is 5% or less.

[0155] Specifically, a spectrophotometer SE7700 (Nippon Denshoku Industries Co., Ltd.) was used to place a powder sample of a granular substance in a cuvette and measure the brightness (L * ), chromaticity (a * ) and chromaticity (b * ).

[0156] On the other hand, the haze value was measured using a haze meter HZ-V3 (Suga Test Instruments Co., Ltd.). In the measurement of the haze value, first, 5 g of the granular material and 50 g of acetone were added to 95 g of a general-purpose polyester resin and mixed using a paint stirrer. Next, a film-like sample was prepared on a glass plate using a bar coater (manufactured by Daiichi Rika Co., Ltd.) to a thickness of 10 μm, and the dried sample was measured.

[0157] Examples of the colorless and transparent particulate matter include silicon dioxide, nano-sized titanium oxide (eg, titanium oxide having a volume average particle size of 100 nm or less), and nano-sized zinc oxide (eg, zinc oxide having a volume average particle size of 100 nm or less).

[0158] When the particulate matter is a pigment, the volume average particle size of the particulate matter is, for example, 10 nm to 150 nm, preferably 50 nm to 150 nm, and more preferably 80 nm to 130 nm from the viewpoint of dispersibility.

[0159] When the particulate matter is an inorganic particle, the volume average particle size of the particulate matter is preferably 10 nm to 150 nm, more preferably 10 nm to 100 nm, and even more preferably 10 nm to 50 nm, from the viewpoint of transparency.

[0160] Regarding the volume average particle size of the granular material, the particle size distribution obtained by measurement using a laser diffraction particle size distribution measuring apparatus (e.g., LA-700 manufactured by Horiba, Ltd.) is used, and the cumulative distribution of the volume is plotted from the small particle size side for the divided particle size range (channel), and the particle size that is 50% cumulatively relative to all particles is measured as the volume average particle size D50v.

[0161] From the viewpoint of controlling the crystallization temperature T1 within the above range, the content of the granular matter contained in the first colorant particles is preferably 0.5% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 8% by mass or less, and further preferably 2% by mass or more and 6% by mass or less, relative to the entire first colorant particles. In addition, when the first colorant particles contain a plurality of granular matters, the content of the granular matter refers to the total content of the plurality of granular matters.

[0162] -Colorants-

[0163] As described above, the dye toner particles contain a dye as a main component of a colorant, and may contain a colorant other than the dye as necessary. The dye toner particles may contain only one colorant, or may contain two or more colorants.

[0164] As dyes, fluorescent dyes, non-fluorescent dyes, etc. can be cited. Fluorescent dyes refer to dyes that emit light by light energy from the outside, and non-fluorescent dyes refer to dyes that do not emit light by light energy from the outside. Generally speaking, fluorescent dyes develop colors by reflecting light and emitting light, and non-fluorescent dyes develop colors only by reflecting light.

[0165] As colorants other than dyes, there are aggregation-induced emission colorants, non-fluorescent pigments, etc. Aggregation-induced emission colorants are colorants that have the property of emitting fluorescence when a molecule alone does not emit fluorescence but when many molecules are aggregated in a crystalline state (aggregated state), i.e., aggregation-induced emission (AIE), and non-fluorescent pigments are pigments that emit light without light energy from the outside.

[0166] --Fluorescent dyes--

[0167] Examples of fluorescent dyes include: naphthalimides; cationic or non-cationic coumarins; xanthenodiquinolizine (e.g., sulforhodamine); azaxanthene; naphtholactam; azlactone; oxazines; thiazines; dioxazines; and single or mixed monocationic or polycationic fluorescent dyes of azo, azomethine or methine type.

[0168] As the fluorescent dye, for example, a fluorescent dye having a cationic group can be mentioned as a preferable fluorescent dye.

[0169] As the cationic group, from the viewpoint of fluorescence intensity, an onium group is preferred, an ammonium group, an imine group, or a pyridyl group is more preferred, and a quaternary ammonium group is particularly preferred.

[0170] The fluorescent dye may have only one cationic group or may have two or more cationic groups. However, from the viewpoint of fluorescence intensity, it preferably has one or more and four or less cationic groups, more preferably one or two cationic groups, and particularly preferably only one cationic group.

[0171] Specific examples of the fluorescent dye include CI Basic Red 1 (Rhodamine 6G), CI Basic Red 1:1, CI Basic Red 2, CI Basic Red 12, CI Basic Red 13, CI Basic Red 14, CI Basic Red 15, CI Basic Red 36, CI Basic Violet 7, CI Basic Violet 10 (Rhodamine B), CI Basic Violet 11 (Rhodamine 3B), CI Basic Violet 11:1 (Rhodamine A), CI Basic Violet 15, CI Basic Violet 16, CI Basic Violet 27, CI Basic Yellow 1, CI Basic Yellow 2, CI Basic Yellow 9, CI Basic Yellow 24, and CI Basic Yellow 4. 0, CI Basic Orange 15, CI Basic Orange 22, CI Basic Blue 1, CI Basic Blue 3, CI Basic Blue 7, CI Basic Blue 9, CI Basic Blue 45, CI Basic Green 1, CI Acid Yellow 3, CI Acid Yellow 7, CI Acid Yellow 73, CI Acid Yellow 87, CI Acid Yellow 184, CI Acid Yellow 245, CI Acid Yellow 250, CI Acid Red 51, CI Acid Red 52, CI Acid Red 57, CI Acid Red 77, CI Acid Red 87, CI Acid Red 89, CI Acid Red 92, CI Acid Blue 9, CI Acid Black 2, CI Solvent Yellow 43, CI Solvent Yellow 44, CI Solvent Yellow 85, CI Solvent Yellow 98, CI Solvent Yellow 116, CI Solvent Yellow 131, CI Solvent Yellow 145, CI Solvent Yellow 160:1, CI Solvent Yellow 172, CI Solvent Yellow 185, CI Solvent Yellow 195, CI Solvent Yellow 196, CI Solvent Orange 63, CI Solvent Orange 112, CI Solvent Red 49, CI Solvent Red 149, CI Solvent Red 175, CI Solvent Red 196, CI Solvent Red 197, CI Solvent Blue 5, CI Solvent Green 5, CI Solvent Green 7, CI Direct Yellow 27, CI Direct Yellow 85, CI Direct Yellow 96, Direct Orange 8, CI Direct Red 2, CI Direct Red 9, CI Direct Blue 22, CI Direct Blue 199, CI Direct Green 6, CI Disperse Yellow 11, CI Disperse Yellow 82, CI Disperse Yellow 139, CI Disperse Yellow 184, CI Disperse Yellow 186, CI Disperse Yellow 199, CI Disperse Yellow 202, CI Disperse Yellow 232, CI Disperse Orange 11, CI Disperse Orange 32, CI Disperse Red 58, CI Disperse Red 274, CI Disperse Red 277, CI Disperse Red 303, CI Disperse Blue 7, CI Reactive Yellow 78, CI Vat Red 41, etc.

[0172] The fluorescent dye also includes a fluorescent dye dispersed in a resin to form a pigment (pigmented fluorescent dye).

[0173] Examples of the pigmented fluorescent dye include resin particles obtained by dispersing the above-mentioned various fluorescent dyes in resins such as melamine resins, alkyd resins, vinyl chloride resins, acrylic resins, polyester resins, amino resins, and formaldehyde condensation resins.

[0174] As pigmented fluorescent dyes, for example, powdered fluorescent pigments manufactured by Sinloihi Co., Ltd. (SX-100 series, SX-200 series, SX-300 series, NEZ-100 series, etc. of Sinloihi Color), fluorescent pigments manufactured by DayGlo Co., Ltd. (T series, GT series, ZQ series, GPL series, etc.), fluorescent pigments manufactured by Nippon Fluorescent Chemical Co., Ltd. (NKV-S series, NKW-3200E series, etc.), etc.

[0175] In addition, fluorescent dyes also include fluorescent whitening agents.

[0176] Examples of the fluorescent brightener include benzoxazole derivatives, benzothiazole derivatives, benzimidazole derivatives, stilbene derivatives, coumarin derivatives, biphenyl derivatives, naphthalimide derivatives, benzidine derivatives, etc. Specifically, fluorescent brightener 184, fluorescent brightener 393, etc. are included.

[0177] --Non-fluorescent dyes--

[0178] The non-fluorescent dye is not limited in color as long as it is a dye that does not have fluorescence, and examples thereof include non-fluorescent green dye, non-fluorescent red dye, non-fluorescent yellow dye, non-fluorescent pink dye, non-fluorescent orange dye, and non-fluorescent violet dye.

[0179] --Aggregation-induced emission pigments--

[0180] As the aggregation-induced emission colorant, any colorant having the above-mentioned properties can be used without particular limitation.

[0181] Specific examples of the aggregation-induced emission colorant include CI Pigment Yellow 101, a boron difluoride derivative of CI Pigment Yellow 101, and 1,2,3,4-Tetrachloro-11H-isoindolo[2,1-a]benzimidazole-11-one.

[0182] Among them, as the aggregation-induced emission colorant, CI Pigment Yellow 101 is preferred from the viewpoint of chroma and fluorescence intensity.

[0183] Furthermore, 1,2,3,4-Tetrachloro-11H-isoindolo[2,1-a]benzimidazole-11-one can be obtained by obtaining Radglo VSF-0-05 manufactured by Radiant Color Co., Ltd.

[0184] --Non-fluorescent pigments--

[0185] The non-fluorescent pigment is not limited in color as long as it is a pigment that does not have fluorescence, and examples thereof include non-fluorescent green pigments, non-fluorescent red pigments, non-fluorescent yellow pigments, non-fluorescent pink pigments, non-fluorescent orange pigments, and non-fluorescent violet pigments.

[0186] Examples of the non-fluorescent pigment include carbon black, chrome yellow, Hansa yellow, benzidine yellow, threne yellow, quinoline yellow, pigment yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brilliant carmine 3B, brilliant carmine 6B, DuPont oil soluble red, pyrazolone red, lithotripsy scarlet, rhodamine B lake, lake red C, pigment red, pigment orange, rose Bengal, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, pigment blue, phthalocyanine green, malachite green oxalate, titanium oxide, zinc oxide, calcium carbonate, basic lead carbonate, zinc sulfide-barium sulfate mixture, zinc sulfide, silica, and aluminum oxide.

[0187] --Content of colorant--

[0188] The content of the colorant is, for example, preferably 0.5% by mass or more and 30% by mass or less, and more preferably 1% by mass or more and 15% by mass or less, based on the entire toner particles.

[0189] -Release agent-

[0190] Examples of the release agent include hydrocarbon waxes such as microcrystalline wax, natural waxes such as carnauba wax, rice wax, and candelilla wax, synthetic or mineral / petroleum waxes such as montan wax, and ester waxes such as fatty acid esters and montanic acid esters. The release agent is not limited thereto.

[0191] From the viewpoint of controlling the crystallization temperature T1 within the above range, the melting temperature of the release agent contained in the first toner particles is preferably 50°C to 110°C, more preferably 60°C to 100°C, and further preferably 70°C to 100°C.

[0192] From the viewpoint of controlling the crystallization temperature T2 within the above range, the melting temperature of the release agent contained in the second toner particles is preferably 50°C to 110°C, more preferably 60°C to 100°C, and further preferably 70°C to 100°C.

[0193] The melting temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC) according to the “melting peak temperature” described in the method for determining the melting temperature in JIS K 7121-1987 “Methods for determining transition temperatures of plastics”.

[0194] The content of the release agent is, for example, preferably 1% by mass or more and 20% by mass or less, and more preferably 5% by mass or more and 15% by mass or less, based on the entire toner particles.

[0195] -Other additives-

[0196] Examples of other additives include known additives such as magnetic materials, charge control agents, and inorganic particles. These additives are contained in toner particles as internal additives.

[0197] -Characteristics of toner particles, etc.-

[0198] The toner particles may be toner particles of a single-layer structure, or may be toner particles of a so-called core-shell structure consisting of a core portion (core particle) and a coating layer (shell layer) that covers the core portion.

[0199] Here, the toner particles of the core-shell structure preferably include, for example, a core portion including a binder resin and, if necessary, other additives such as a colorant and a release agent, and a coating layer including a binder resin.

[0200] The volume average particle size (D50v) of the toner particles is preferably 2 μm or more and 10 μm or less, and more preferably 4 μm or more and 8 μm or less.

[0201] In addition, various average particle diameters and various particle size distribution indices of toner particles were measured using Coulter Multisizer II (manufactured by Beckman Coulter) and ISOTON-II (manufactured by Beckman Coulter) as an electrolyte.

[0202] When measuring, 0.5 mg to 50 mg of the sample to be measured is added to 2 ml of a 5% aqueous solution of a surfactant (preferably sodium alkylbenzene sulfonate) as a dispersant, and then added to 100 ml to 150 ml of the electrolyte.

[0203] The electrolyte in which the sample was suspended was dispersed for 1 minute using an ultrasonic disperser, and the particle size distribution of particles with a particle size ranging from 2 μm to 60 μm was measured using a Coulter Multisizer II with an aperture of 100 μm. The number of particles sampled was 50,000.

[0204] The particle size range (channel) divided based on the measured particle size distribution is plotted with respect to the cumulative distribution of volume and number from the small diameter side, and the particle size that will become 16% of the cumulative is defined as the volume particle size D16v and the number average particle size D16p, the particle size that will become 50% of the cumulative is defined as the volume average particle size D50v and the cumulative number average particle size D50p, and the particle size that will become 84% of the cumulative is defined as the volume particle size D84v and the number average particle size D84p.

[0205] Using these particle sizes, (D84v / D16v) 1 / 2 Calculate the volume particle size distribution index (GSDv) from (D84p / D16p) 1 / 2 Calculate the number average particle size distribution index (GSDp).

[0206] The average circularity of the 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.

[0207] The average circularity of the toner particles is obtained by (circle equivalent circumference) / (circumference) [(circumference of a circle having the same projected area as the particle image) / (circumference of the particle projected image)]. Specifically, it is a value measured by the following method.

[0208] First, the toner particles to be measured were collected by suction to form a flat flow, and the particle image was captured as a still image by instantaneous stroboscopic light emission. The average circularity was calculated using a flow-type particle image analyzer (FPIA-3000 manufactured by Sysmex) for image analysis of the particle image. The number of samples for calculating the average circularity was set to 3500.

[0209] When the toner has an external additive, the toner (developer) to be measured is dispersed in water containing a surfactant and then subjected to ultrasonic treatment to obtain toner particles from which the external additive has been removed.

[0210] (External Additives)

[0211] Examples of the external additive include inorganic particles. Examples of the inorganic particles include SiO2, TiO2, Al2O3, CuO, ZnO, SnO2, CeO2, Fe2O3, MgO, BaO, CaO, K2O, Na2O, ZrO2, CaO·SiO2, K2O·(TiO2)n , Al2O3·2SiO2, CaCO3, MgCO3, BaSO4, MgSO4, etc.

[0212] The surface of the inorganic particles as an external additive is preferably subjected to a hydrophobic treatment. The hydrophobic treatment is performed, for example, by immersing the inorganic particles in a hydrophobic treatment agent. The hydrophobic treatment agent is not particularly limited, and for example, a silane coupling agent, silicone oil, a titanate coupling agent, an aluminum coupling agent, etc. can be cited. These can be used alone or in combination of two or more.

[0213] The amount of the hydrophobizing agent is usually, for example, 1 part by mass or more and 10 parts by mass or less relative to 100 parts by mass of the inorganic particles.

[0214] Examples of the external additives include resin particles (polystyrene, polymethyl methacrylate (PMMA), melamine resin and other resin particles), detergent active agents (for example, metal salts of higher fatty acids represented by zinc stearate, and particles of fluorine-based high molecular weight bodies).

[0215] The amount of the external additive added is, for example, preferably 0.01% by mass or more and 5% by mass or less, and more preferably 0.01% by mass or more and 2.0% by mass or less, based on the toner particles.

[0216] (Method for producing toner)

[0217] Next, a method for producing the toner according to the present embodiment will be described.

[0218] The toner according to the present embodiment is obtained by manufacturing toner particles and then adding the external additive to the toner particles.

[0219] Toner particles can be produced by any of dry methods (eg, kneading and pulverization methods) and wet methods (eg, aggregation and coalescence methods, suspension polymerization methods, and dissolution and suspension methods). The method for producing toner particles is not particularly limited to these methods, and a known method can be used.

[0220] Among them, it is preferable to obtain the toner particles by an aggregation and coalescence method.

[0221] Specifically, for example, when toner particles are produced by an aggregation and coalescence method, the toner particles are produced through the following steps:

[0222] A process for preparing a resin particle dispersion in which resin particles serving as a binding resin are dispersed (resin particle dispersion preparation process); a process for aggregating resin particles (other particles as needed) in the resin particle dispersion (in a dispersion after other particle dispersions are mixed as needed) to form aggregated particles (aggregated particle formation process); and a process for heating the aggregated particle dispersion in which the aggregated particles are dispersed to fuse / agglomerate the aggregated particles to form colorant particles (fusion / agglomeration process).

[0223] The details of each process are described below.

[0224] In the following description, a method for obtaining toner particles containing a colorant and a release agent is described, but the colorant and the release agent are used as necessary. Of course, other additives besides the colorant and the release agent may also be used.

[0225] -Resin particle dispersion preparation step-

[0226] First, together with a resin particle dispersion in which resin particles serving as a binder resin are dispersed, for example, a colorant particle dispersion in which colorant particles are dispersed and a release agent particle dispersion in which release agent particles are dispersed are prepared.

[0227] Here, the resin particle dispersion is prepared by, for example, dispersing the resin particles in a dispersion medium using a surfactant.

[0228] Examples of the dispersion medium used for the resin particle dispersion include aqueous media.

[0229] Examples of the aqueous medium include water such as distilled water and deionized water, and alcohols, etc. These may be used alone or in combination of two or more.

[0230] As surfactants, for example, anionic surfactants such as sulfate ester salts, sulfonates, phosphates, and soaps; cationic surfactants such as amine salts and quaternary ammonium salts; nonionic surfactants such as polyethylene glycols, alkylphenol ethylene oxide adducts, and polyols, etc. can be cited. Among them, anionic surfactants and cationic surfactants can be cited in particular. Nonionic surfactants can also be used in combination with anionic surfactants or cationic surfactants.

[0231] The surfactant may be used alone or in combination of two or more.

[0232] In the resin particle dispersion, as a method for dispersing the resin particles in the dispersion medium, for example, a general dispersion method such as a rotary shearing homogenizer, a ball mill with a medium, a sand mill, and a Dyno mill can be cited. In addition, depending on the type of the resin particles, for example, the resin particles can be dispersed in the resin particle dispersion using a phase inversion emulsification method.

[0233] In addition, the phase inversion emulsification method refers to the following method: the resin to be dispersed is dissolved in a hydrophobic organic solvent that can dissolve the resin, a base is added to the organic continuous phase (O phase) for neutralization, and then an aqueous medium (W phase) is added, thereby converting the resin from W / O to O / W (so-called phase inversion) and becoming a discontinuous phase, thereby dispersing the resin in the aqueous medium in the form of particles.

[0234] The volume average particle size of the resin particles dispersed in the resin particle dispersion is, for example, preferably 0.01 μm or more and 1 μm or less, more preferably 0.08 μm or more and 0.8 μm or less, and further preferably 0.1 μm or more and 0.6 μm or less.

[0235] In addition, for the volume average particle size of the resin particles, the particle size distribution obtained by the measurement of the laser diffraction particle size distribution measuring device (for example, LA-700 manufactured by Horiba, Ltd.) is used, and the cumulative distribution of the volume is plotted from the small particle size side for the divided particle size range (channel), and the particle size that becomes 50% cumulatively with respect to all particles is measured as the volume average particle size D50v. In addition, the volume average particle size of the particles in other dispersions is also measured in the same manner.

[0236] The content of the resin particles in the resin particle dispersion is, for example, preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 40% by mass or less.

[0237] In addition, in the same manner as the resin particle dispersion, for example, a colorant particle dispersion and a release agent particle dispersion are also prepared. That is, the volume average particle size of the particles in the resin particle dispersion, the dispersion medium, the dispersion method, and the content of the particles are the same for the colorant particles dispersed in the colorant particle dispersion and the release agent particles dispersed in the release agent particle dispersion.

[0238] - Aggregate particle formation process -

[0239] Next, the colorant particle dispersion and the release agent particle dispersion are mixed together with the resin particle dispersion.

[0240] Then, the resin particles, the colorant particles, and the releasing agent particles are heterogeneously aggregated in the mixed dispersion to form aggregated particles having a diameter close to the target toner particle diameter and including the resin particles, the colorant particles, and the releasing agent particles.

[0241] Specifically, for example, an aggregating agent is added to the mixed dispersion, and the pH of the mixed dispersion is adjusted to be acidic (for example, a pH of 2 or more and 5 or less), a dispersion stabilizer is added as needed, and then the mixture is heated to a temperature of the glass transition temperature of the resin particles (specifically, for example, a glass transition temperature of the resin particles of not less than -30°C and not more than -10°C), so that the particles dispersed in the mixed dispersion are aggregated to form aggregated particles.

[0242] In the aggregated particle formation step, for example, the above-mentioned aggregating agent may be added at room temperature (e.g., 25° C.) while the mixed dispersion is stirred with a rotary shearing homogenizer, the pH of the mixed dispersion is adjusted to be acidic (e.g., pH is greater than 2 and less than 5), and the above-mentioned heating may be performed after adding a dispersion stabilizer as needed.

[0243] As the aggregating agent, for example, a surfactant having a polarity opposite to that of the surfactant used as a dispersant added to the mixed dispersion, an inorganic metal salt, a divalent or higher metal complex can be cited. In particular, when a metal complex is used as an aggregating agent, the amount of the surfactant used is reduced and the charging characteristics are improved.

[0244] If necessary, an additive that forms a complex or similar bond with the metal ion of the aggregating agent may be used. As such an additive, a chelating agent is preferably used.

[0245] Examples of the inorganic metal salt include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate; and inorganic metal salt polymers such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide.

[0246] As the chelating agent, a water-soluble chelating agent can be used. Examples of the chelating agent include hydroxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid, iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), and ethylenediaminetetraacetic acid (EDTA).

[0247] The amount of the chelating agent added is, for example, preferably 0.01 parts by mass or more and 5.0 parts by mass or less, and more preferably 0.1 parts by mass or more and less than 3.0 parts by mass, relative to 100 parts by mass of the resin particles.

[0248] -Fusion / Agglomeration Process-

[0249] Next, the aggregated particle dispersion containing the aggregated particles is heated to, for example, a temperature higher than the glass transition temperature of the resin particles (eg, a temperature 10 to 30° C. higher than the glass transition temperature of the resin particles) to fuse / agglomerate the aggregated particles to form toner particles.

[0250] Through the above steps, toner particles are obtained.

[0251] In addition, the colorant particles can also be manufactured through the following steps: after obtaining an aggregated particle dispersion in which aggregated particles are dispersed, further mixing the aggregated particle dispersion and a resin particle dispersion in which resin particles are dispersed, so that the resin particles are aggregated in a manner that further adheres to the surface of the aggregated particles to form second aggregated particles; and heating the second aggregated particle dispersion in which the second aggregated particles are dispersed to allow the second aggregated particles to fuse / agglomerate to form colorant particles with a core-shell structure.

[0252] Here, after the fusion / aggregation step is completed, the toner particles formed in the solution are subjected to a known washing step, a solid-liquid separation step, and a drying step to obtain dry toner particles.

[0253] From the viewpoint of chargeability, the washing process preferably fully performs displacement washing using deionized water. In addition, the solid-liquid separation process is not particularly limited, but from the viewpoint of productivity, it is preferably performed by suction filtration, pressure filtration, etc. In addition, the method of the drying process is not particularly limited, but from the viewpoint of productivity, it is preferably performed by freeze drying, air flow drying, fluidized drying, vibration type fluidized drying, etc.

[0254] Then, the toner of the present embodiment is produced by, for example, adding an external additive to the obtained dry toner particles and mixing them. The mixing is preferably performed by, for example, a V-type mixer, a Henschel mixer, a Lödige mixer, etc. Furthermore, if necessary, a vibration sieving machine, a wind sieving machine, etc. may be used to remove coarse particles of the toner.

[0255] [Electrostatic image developer set]

[0256] An electrostatic charge image developer group according to one embodiment of the present invention comprises: a yellow developer, a magenta developer, a cyan developer, and a black developer, each of which contains the yellow colorant, the magenta colorant, the cyan colorant, and the black colorant in the colorant group of the present invention; a first developer, which contains the first colorant in the colorant group of the present invention; and a second developer, which contains the second colorant in the colorant group of the present invention.

[0257] Hereinafter, the yellow developer, the magenta developer, the cyan developer, and the black developer are collectively referred to as “YMCK developer”.

[0258] Each electrostatic image developer may be a single-component developer containing a toner, or a two-component developer in which a toner and a carrier are mixed.

[0259] The carrier is not particularly limited, and known carriers may be mentioned. Examples of the carrier include a coated carrier obtained by coating the surface of a core material composed of magnetic powder with a coating resin, a magnetic powder dispersed carrier obtained by dispersing / blending magnetic powder in a matrix resin, and a resin impregnated carrier obtained by impregnating porous magnetic powder with a resin.

[0260] Furthermore, the magnetic powder dispersed carrier and the resin impregnated carrier may be a carrier in which the constituent particles of the carrier are used as a core material and the core material is coated with a coating resin.

[0261] Examples of the magnetic powder include magnetic metals such as iron, nickel, and cobalt, and magnetic oxides such as ferrite and magnetite.

[0262] 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-acrylate copolymer, straight-chain silicone resin containing an organic siloxane bond or a modified product thereof, fluororesin, polyester, polycarbonate, phenol resin, epoxy resin, and the like.

[0263] Furthermore, other additives such as conductive particles may be contained in the coating resin and the matrix resin.

[0264] 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.

[0265] Here, in order to coat the surface of the core material with coating resin, a coating layer obtained by dissolving the coating resin and various additives added as required in a suitable solvent can be enumerated to coat with a solution etc. As solvent, there is no particular restriction, and it can be selected considering the coating resin used, coating suitability etc.

[0266] Specific resin coating methods include an immersion method in which the core material is immersed in a coating layer forming solution, a spray method in which the coating layer forming solution is sprayed onto the surface of the core material, a fluidized bed method in which the coating layer forming solution is sprayed while the core material is suspended by flowing air, and a kneading coating method in which the core material of the carrier and the coating layer forming solution are mixed in a kneading coater and the solvent is removed.

[0267] The mixing ratio (mass ratio) of the toner and the carrier in the two-component developer is preferably toner:carrier=1:100 to 30:100, more preferably 3:100 to 20:100.

[0268] [Image Forming Apparatus / Image Forming Method]

[0269] The image forming apparatus and image forming method of the present invention will be described.

[0270] An image forming apparatus according to one embodiment of the present invention comprises: a yellow image forming unit, a magenta image forming unit, a cyan image forming unit, and a black image forming unit, which respectively form a yellow image, a magenta image, a cyan image, and a black image using a yellow toner, a magenta toner, a cyan toner, and a black toner in a toner set of the present invention; a first image forming unit, which forms a first image using a first toner in the toner set of the present invention; a second image forming unit, which forms a second image using a second toner in the toner set of the present invention; a transfer unit, which transfers the yellow image, the magenta image, the cyan image, the black image, the first image, and the second image to a recording medium; and a fixing unit, which fixes a toner image formed by stacking the yellow image, the magenta image, the cyan image, the black image, the first image, and the second image to the recording medium.

[0271] In the toner image, the first image and the second image may be stacked in contact. In this embodiment, since the crystallization temperature T1 and the crystallization temperature T2 are respectively within the above ranges, even if the first image and the second image are stacked in contact, both the suppression of hot offset and the suppression of cold offset are achieved.

[0272] In the colorant image, one of the layer farthest from the recording medium and the layer second farthest from the recording medium may be the first image, and the other may be the second image. That is, the first colorant and the second colorant contained in the colorant set of the present invention may be colorants used to form two layers on the side of the colorant image farthest from the recording medium (that is, the side farther from the recording medium than the image formed by the YMCK toner). In this embodiment, since the crystallization temperature T1 and the crystallization temperature T2 are respectively within the range, even if the first image and the second image are the two layers on the side of the colorant image farthest from the recording medium, both the suppression of hot offset and the suppression of cold offset are achieved.

[0273] In the colorant image, the layer farthest from the recording medium may be the first image, and the layer second farthest from the recording medium may be the second image. That is, the first toner contained in the toner set of the present invention may be a toner for forming the layer farthest from the recording medium in the toner image, and the second toner may be a toner for forming the layer second farthest from the recording medium. In the present embodiment, since the crystallization temperature T1 and the crystallization temperature T2 are respectively within the above ranges, even if the first image is the layer farthest from the recording medium and the second image is the layer second farthest from the recording medium, both the suppression of hot offset and the suppression of cold offset are achieved.

[0274] The image forming device of the present invention can also be in the following form: it has a yellow image forming unit, a magenta image forming unit, a cyan image forming unit, a black image forming unit, a first image forming unit, and a second image forming unit as each image forming unit, and each of the above-mentioned image forming units has an image retaining body, a charging unit for charging the surface of the image retaining body, an electrostatic charge image forming unit for forming an electrostatic charge image on the surface of the charged image retaining body, and a developing unit for developing the electrostatic charge image formed on the surface of the image retaining body into a colorant image by an electrostatic charge image developer.

[0275] In addition, the image forming device of the present invention can also be in the following form: it has an image retaining body; a charging unit for charging the surface of the image retaining body; an electrostatic charge image forming unit for forming an electrostatic charge image on the surface of the charged image retaining body; and a yellow developing unit, a magenta developing unit, a cyan developing unit, a black developing unit, a first developing unit, and a second developing unit for developing the electrostatic charge image formed on the surface of the image retaining body into a colorant image using an electrostatic charge image developer, wherein the yellow image forming unit, the magenta image forming unit, the cyan image forming unit, the black image forming unit, the first image forming unit, and the second image forming unit respectively serve as the yellow image forming unit, the magenta image forming unit, the cyan image forming unit, the black image forming unit, the first image forming unit, and the second image forming unit.

[0276] In the image forming apparatus of the present invention, an image forming method (image forming method of the present invention) is implemented, and the image forming method comprises: a yellow image forming step, a magenta image forming step, a cyan image forming step, and a black image forming step, respectively forming a yellow image, a magenta image, a cyan image, and a black image using the yellow toner, the magenta toner, the cyan toner, and the black toner in the toner group of the present invention, respectively; a first image forming step, forming a first image using the first toner in the toner group of the present invention; a second image forming step, forming a second image using the second toner in the toner group of the present invention; a transfer step, transferring the yellow image, the magenta image, the cyan image, the black image, the first image, and the second image to a recording medium; and a fixing step, fixing the toner image formed by stacking the yellow image, the magenta image, the cyan image, the black image, the first image, and the second image to the recording medium.

[0277] The image forming apparatus of the present invention is applied to: a direct transfer apparatus for directly transferring a colorant image formed on the surface of an image retaining body onto a recording medium; an intermediate transfer apparatus for primarily transferring a colorant image formed on the surface of an image retaining body onto the surface of an intermediate transfer body, and secondarily transferring the colorant image transferred to the surface of the intermediate transfer body onto the surface of a recording medium; an apparatus having a cleaning unit for cleaning the surface of an image retaining body before charging after the transfer of the colorant image; an apparatus having a de-staticizing unit for de-staticizing the surface of an image retaining body by irradiating de-staticizing light onto the surface of the image retaining body before charging after the transfer of the colorant image, and other well-known image forming apparatuses.

[0278] In the case of an intermediate transfer type device, the transfer unit, for example, has a structure comprising an intermediate transfer body for transferring a colorant image to a surface, a primary transfer unit for transferring a colorant image formed on the surface of an image retaining body to the surface of the intermediate transfer body for the first time, and a secondary transfer unit for secondary transferring the colorant image transferred to the surface of the intermediate transfer body to the surface of a recording medium.

[0279] An example of the image forming apparatus of the present invention is shown below, but the present invention is not limited thereto. In the following description, the main parts shown in the drawings are described, and the description of the others is omitted.

[0280] In the following description, as an example of the image forming apparatus of the present invention, a six-tandem image forming apparatus in which six image forming units are arranged will be described. However, the tandem image forming apparatus is not limited thereto.

[0281] Figure 1 1 is a schematic diagram showing the structure of the image forming apparatus of the present invention, and is a diagram showing an image forming apparatus of a six-column system and an intermediate transfer system.

[0282] Figure 1 The image forming apparatus shown in the figure includes a first image forming unit 10G (an example of a first image forming unit), a second image forming unit 10P (an example of a second image forming unit), a yellow image forming unit 10Y (an example of a yellow image forming unit), a magenta image forming unit 10M (an example of a magenta image forming unit), a cyan image forming unit 10C (an example of a cyan image forming unit), and a black image forming unit 10K (an example of a black image forming unit). Each image forming unit is an image forming unit of an electrophotographic method, and outputs images of green (G), pink (P), yellow (Y), magenta (M), cyan (C), and black (K) based on color-separated image data. These image forming units (hereinafter, sometimes simply referred to as "units") 10G, 10P, 10Y, 10M, 10C, 10K are arranged in parallel with each other at a predetermined distance in the horizontal direction. These units 10G, 10P, 10Y, 10M, 10C, 10K may also be process cartridges that are attached to and detached from the image forming apparatus.

[0283] exist Figure 1 In the example, pink (P) and green (G) are used, but are not limited thereto.

[0284] Below each unit 10G, 10P, 10Y, 10M, 10C, 10K, an intermediate transfer belt (an example of an intermediate transfer body) 20 is extended to pass through each unit. The intermediate transfer belt 20 is wound around a driving roller 22, a supporting roller 23, and a counter roller 24 that are in contact with the inner surface of the intermediate transfer belt 20, and travels in the direction from the second unit 10P to the first unit 10G. An intermediate transfer body cleaning device 21 is provided on the image holding surface side of the intermediate transfer belt 20, which is opposite to the driving roller 22.

[0285] Fluorescent green, fluorescent pink, yellow, magenta, cyan, and black colorants contained in colorant boxes 8G, 8P, 8Y, 8M, 8C, and 8K are respectively supplied to the developing devices (an example of developing units) 4G, 4P, 4Y, 4M, 4C, and 4K of each unit 10G, 10P, 10Y, 10M, 10C, and 10K.

[0286] The units 10G, 10P, 10Y, 10M, 10C, and 10K have the same structure and operation, and therefore the unit 10G that forms a green image will be described as a representative.

[0287] The unit 10G has a photosensitive body 1G that functions as an image holder. Around the photosensitive body 1G, there are arranged in order: a charging roller (an example of a charging unit) 2G that charges the surface of the photosensitive body 1G to a preset potential; an exposure device (an example of an electrostatic image forming unit) 3G that forms an electrostatic image by exposing the charged surface to a laser beam based on a color-resolved image signal; a developing device (an example of a developing unit) 4G that supplies toner to the electrostatic image and develops the electrostatic image; a primary transfer roller (an example of a primary transfer unit) 5G that transfers the developed toner image to the intermediate transfer belt 20; and a photosensitive body cleaning device (an example of a cleaning unit) 6G that removes the toner remaining on the surface of the photosensitive body 1G after the primary transfer.

[0288] The primary transfer roller 5G is arranged inside the intermediate transfer belt 20 and is provided at a position opposite to the photosensitive body 1G. A bias power supply (not shown) for applying a primary transfer bias is connected to each of the primary transfer rollers 5G, 5P, 5Y, 5M, 5C, and 5K of each unit. Each bias power supply is controlled by a control unit (not shown) to change the value of the transfer bias applied to each primary transfer roller.

[0289] Next, the operation of forming a green image in the unit 10G will be described.

[0290] First, before operation, the surface of the photoreceptor 1G is charged to a potential of -600 V to -800 V by the charging roller 2G.

[0291] The photoreceptor 1G is conductive (e.g., a volume resistivity of 1×10 -6 The photosensitive layer is formed by laminating a photosensitive layer on a substrate with a resistance of 100 Ω·cm or less. The photosensitive layer is usually high in resistance (resistance of a general resin), but has a property that when irradiated with a laser beam, the resistivity of the portion irradiated with the laser beam changes. Therefore, according to the green image data sent from the control unit (not shown), the laser beam is irradiated from the exposure device 3G to the surface of the charged photoreceptor 1G. As a result, an electrostatic charge image of a green image pattern is formed on the surface of the photoreceptor 1G.

[0292] The electrostatic charge image refers to an image formed on the surface of the photoreceptor 1G by charging, and is a so-called negative latent image formed as follows: the resistivity of the irradiated portion of the photosensitive layer is reduced by the laser beam from the exposure device 3G, and the charge on the surface of the photoreceptor 1G is lost, while on the other hand, the charge of the portion not irradiated by the laser beam remains.

[0293] The electrostatic charge image formed on the photoreceptor 1G rotates to a preset development position as the photoreceptor 1G travels. Then, at the development position, the electrostatic charge image on the photoreceptor 1G is developed into a toner image by the developing device 4G and visualized.

[0294] In the developing device 4G, for example, an electrostatic charge image developer including at least a fluorescent green colorant and a carrier is stored. The fluorescent green colorant is stirred inside the developing device 4G to be triboelectrically charged, and has a charge of the same polarity (negative polarity) as the charge carried by the photoreceptor 1G and is retained on the developer roller (an example of a developer retainer). Then, the surface of the photoreceptor 1G passes through the developing device 4G, whereby the fluorescent green colorant is electrostatically attached to the latent image portion on the surface of the photoreceptor 1G that has been de-charged, and the latent image is developed by the fluorescent green colorant. The photoreceptor 1G on which the fluorescent green colorant image is formed continues to move at a preset speed, and the toner image developed on the photoreceptor 1G is conveyed to a preset primary transfer position.

[0295] When the fluorescent green toner image on the photoreceptor 1G is conveyed to the primary transfer position, a primary transfer bias is applied to the primary transfer roller 5G, and an electrostatic force from the photoreceptor 1G toward the primary transfer roller 5G acts on the toner image, and the toner image on the photoreceptor 1G is transferred to the intermediate transfer belt 20. The transfer bias applied at this time is a (+) polarity opposite to the polarity (-) of the toner, and is controlled to, for example, +10 μA by a control section (not shown) in the first unit 10G.

[0296] The photoreceptor 1G, after transferring the toner image to the intermediate transfer belt 20, continues to rotate and comes into contact with a cleaning blade provided in the photoreceptor cleaning device 6G. The toner remaining on the photoreceptor 1G is removed and recovered by the photoreceptor cleaning device 6G.

[0297] The intermediate transfer belt 20 is sequentially conveyed through the units 10G, 10P, 10Y, 10M, 10C, and 10K, and toner images of respective colors are overlapped and multi-transferred.

[0298] The intermediate transfer belt 20 to which the six-color toner images are multi-transferred by each unit arrives at the secondary transfer section composed of the intermediate transfer belt 20, the counter roller 24 in contact with the inner surface of the intermediate transfer belt, and the secondary transfer roller (an example of the secondary transfer unit) 26 arranged on the image holding surface side of the intermediate transfer belt 20. On the other hand, the recording paper (an example of the recording medium) P is supplied to the gap between the secondary transfer roller 26 and the intermediate transfer belt 20 at a preset timing via a supply mechanism, and a secondary transfer bias is applied to the counter roller 24. At this time, the applied transfer bias has the same polarity (-) as the polarity (-) of the toner, and the electrostatic force from the intermediate transfer belt 20 toward the recording paper P acts on the toner image, and the toner image on the intermediate transfer belt 20 is transferred to the recording paper P. The secondary transfer bias at this time is determined based on the resistance detected by the resistance detection unit (not shown) that detects the resistance of the secondary transfer section, and is voltage-controlled.

[0299] After transferring the toner image onto the recording paper P, the intermediate transfer belt 20 continues to travel and contacts a cleaning blade provided in the intermediate transfer body cleaning device 21. The toner remaining on the intermediate transfer belt 20 is removed and recovered by the intermediate transfer body cleaning device 21.

[0300] The recording paper P to which the toner image is transferred is fed to a pressure-contact portion (nip portion) of a pair of fixing rollers in a fixing device (an example of a fixing unit) 28 , and the toner image is fixed to the recording paper P to form a fixed image.

[0301] Examples of the recording paper P to which the toner image is transferred include plain paper used in electrophotographic copy machines, printers, and the like. Examples of the recording medium include OHP sheets and the like in addition to the recording paper P.

[0302] In order to further improve the smoothness of the image surface after fixing, the surface of the recording paper P is preferably smooth, and for example, coated paper obtained by coating the surface of ordinary paper with a resin or the like, coated paper for printing, or the like is preferably used.

[0303] The recording paper P on which the color image has been fixed is conveyed toward the discharge portion, and a series of color image forming operations are completed.

[0304] <Process Cartridge / Toner Cartridge Set>

[0305] The process cartridge of the present invention will be described.

[0306] The processing box of the present invention is the following processing box, which comprises: a yellow developing unit, a magenta developing unit, a cyan developing unit, and a black developing unit, which respectively include the yellow developer, the magenta developer, the cyan developer, and the black developer in the electrostatic charge image developer group of the present invention; a first developing unit, which includes the first developer in the electrostatic charge image developer group of the present invention; and a second developing unit, which includes the second developer in the electrostatic charge image developer group of the present invention, and the processing box is installed and removed from the image forming device.

[0307] The process cartridge of the present invention is not limited to the above structure, but may be provided with a developing device and at least one of other units selected from an image holding member, a charging unit, an electrostatic charge image forming unit, and a transfer unit as required.

[0308] An example of the process cartridge of the present invention is shown below, but the present invention is not limited thereto. In addition, the main parts shown in the drawings are described, and the description of the others is omitted.

[0309] Figure 2 It is a schematic structural diagram showing a process cartridge of the present invention.

[0310] Figure 2The processing box 200 shown is constructed, for example, by installing a rail 116 and a frame 117 having an opening 118 for exposure, so that a photosensitive body 107 (an example of an image retaining body), a charging roller 108 (an example of a charging unit) provided around the photosensitive body 107, a developing device 111 (an example of a developing unit), and a photosensitive body cleaning device 113 (an example of a cleaning unit) are integrally combined and retained to form a box.

[0311] Figure 2 109 denotes an exposure device (an example of an electrostatic charge image forming unit), 112 denotes a transfer device (an example of a transfer unit), 115 denotes a fixing device (an example of a fixing unit), and 300 denotes recording paper (an example of a recording medium).

[0312] Next, the toner cartridge of the present invention will be described.

[0313] The colorant box group of the present invention is the following colorant box group, comprising: a yellow colorant box, a magenta colorant box, a cyan colorant box, and a black colorant box, which respectively include the yellow colorant, the magenta colorant, the cyan colorant, and the black colorant in the colorant group of the present invention; a first colorant box, which includes the first colorant in the colorant group of the present invention; and a second colorant box, which includes the second colorant in the colorant group of the present invention, and the colorant box assembly is detachable from the image forming device.

[0314] Each toner cartridge stores toner for supply to each developing unit provided in the image forming apparatus.

[0315] Figure 1 The image forming apparatus shown is an image forming apparatus having a structure for attaching and detaching toner cartridges 8G, 8P, 8Y, 8M, 8C, and 8K, and the developing devices 4G, 4P, 4Y, 4M, 4C, and 4K are connected to the toner cartridges corresponding to the respective colors by toner supply pipes not shown. In addition, when the toner stored in the toner cartridge becomes less, the toner cartridge is replaced. An example of the toner cartridge set of the present invention is toner cartridges 8G, 8P, 8Y, 8M, 8C, and 8K, which store the toner set of the present invention. The toner cartridges 8G, 8P, 8Y, 8M, 8C, and 8K store the toners of fluorescent green, fluorescent pink, yellow, magenta, cyan, and black, respectively.

[0316] [Example]

[0317] The embodiments of the present invention are described in detail below by way of examples, but the embodiments of the present invention are not limited to these examples.

[0318] In the following description, "parts" and "%" are based on mass unless otherwise specified.

[0319] Unless otherwise specified, synthesis, treatment, production, etc. were carried out at room temperature (25° C.±3° C.).

[0320] [Manufacturing of Fluorescent Green Toner 1 and Developer 1]

[0321] <Synthesis of Crystalline Resin Particle Dispersion (1)>

[0322] 1,10-Dodecanedioic acid: 50 mol%

[0323] 1,9-nonanediol: 50 mol%

[0324] The monomer components were placed in a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen inlet tube, and the reaction vessel was replaced with dry nitrogen. Then, 0.25 parts of tetrabutoxide (titanium tetrabutoxide) (reagent) was added to 100 parts of the monomer components. After stirring and reacting at 170°C for 3 hours under a nitrogen flow, the temperature was further raised to 210°C over 1 hour, and the pressure in the reaction vessel was reduced to 3 kPa. The reaction was stirred and reacted for 13 hours under reduced pressure to obtain a crystalline polyester resin (1).

[0325] The obtained crystalline polyester resin (1) had a melting temperature of 73.6° C. based on DSC, a mass average molecular weight Mw of 25,000 based on GPC, a number average molecular weight Mn of 10,500, and an acid value AV of 10.1 mgKOH / g.

[0326] In a jacketed reactor (BJ-30N manufactured by Tokyo Rikaki Co., Ltd.) equipped with a condenser, a thermometer, a water dripping device and an anchor wing, 300 parts of the crystalline polyester resin (1), 160 parts of methyl ethyl ketone (solvent) and 100 parts of isopropyl alcohol (solvent) were placed, and the resin was dissolved while being stirred and mixed at 100 rpm while being maintained at 70° C. in a water circulation thermostatic bath.

[0327] After that, the stirring speed was set to 150 rpm, the water circulation thermostatic bath was set to 66°C, and after adding 17 parts of 10% by mass ammonia water (reagent) over 10 minutes, a total of 900 parts of deionized water maintained at 66°C was dripped at a rate of 7 parts / min to achieve phase inversion and obtain an emulsion.

[0328] Immediately put 800 parts of the obtained emulsion and 700 parts of deionized water into an eggplant-shaped bottle, and install it on an evaporator equipped with a vacuum control unit (Tokyo Rika Instruments Co., Ltd.) via a splash-proof ball. While rotating the eggplant-shaped bottle, heat it in a 60°C hot water bath, paying attention to violent boiling, and at the same time reduce the pressure to 7 kPa to remove the solvent. When the amount of solvent recovered reaches 1,100 parts, return to normal pressure, cool the eggplant-shaped bottle with water, and obtain a dispersion. There is no solvent smell in the obtained dispersion. The volume average particle size of the resin particles in the dispersion is 130 nm. Thereafter, deionized water is added to adjust the solid content concentration to 20% by mass to prepare a crystalline resin particle dispersion (1).

[0329] <Preparation of amorphous resin particle dispersion (1)>

[0330] Terephthalic acid: 30 mol parts

[0331] Fumaric acid: 70 mol parts

[0332] Bisphenol A ethylene oxide adduct: 5 mol parts

[0333] Bisphenol A propylene oxide adduct: 95 mol parts

[0334] The above materials were prepared in a flask equipped with a stirring device, a nitrogen introduction tube, a temperature sensor, and a distillation column, and the temperature was raised to 220°C over 1 hour. 1 part of tetraethoxytitanium was added to 100 parts of the above materials. While distilling off the generated water, the temperature was raised to 230°C over 30 minutes. After the dehydration condensation reaction was continued at the temperature for 1 hour, the reactant was cooled. Thus, an amorphous polyester resin (1) having a weight average molecular weight of 18,000 and a glass transition temperature of 60°C was obtained.

[0335] In a container equipped with a temperature control unit and a nitrogen replacement unit, 40 parts of ethyl acetate and 25 parts of 2-butanol were added to prepare a mixed solvent, and 100 parts of amorphous polyester resin (1) was slowly added to dissolve it, and a 10% by mass ammonia aqueous solution (equivalent to 3 times the amount of the acid value of the resin in terms of molar ratio) was added thereto and stirred for 30 minutes. Next, the container was replaced with dry nitrogen, the temperature was maintained at 40°C, and 400 parts of deionized water were dropped at a rate of 2 parts / minute while stirring the mixed liquid. After the dropwise addition was completed, the temperature was returned to room temperature (20°C to 25°C), and dry nitrogen was bubbled for 48 hours while stirring, thereby obtaining a resin particle dispersion in which ethyl acetate and 2-butanol were reduced to less than 1,000 ppm. Deionized water was added to the resin particle dispersion to adjust the solid content to 20% by mass, thereby obtaining an amorphous resin particle dispersion (1).

[0336] <Preparation of Colorant Particle Dispersion (1)>

[0337] · Fluorescent dye Solvent Green 5 (C.I. Solvent Green 5, manufactured by BASF, Oracet F Yellow 084, emission peak 520 nm): 2 parts

[0338] · Amorphous polyester resin (weight-average molecular weight 13,000, glass transition temperature 62 °C): 100 parts

[0339] The above materials are heated and mixed, and the dye is incorporated into the resin. The mixture is rolled and cooled to below 30 °C. The obtained mixture is coarsely pulverized to less than 1 mm using a hammer mill, and then finely pulverized using an air jet mill (AFG, Hosokawa Micron Corporation). The particles obtained by fine pulverization, 30 parts of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK) (solid content 20%), and 200 parts of deionized water are mixed and pulverized to a volume-average particle size of 200 nm using a continuous Key sand mill (KMC-3, manufactured by Inoue Manufacturing Co., Ltd.). The solid content is adjusted to 20% by mass to obtain a colorant particle dispersion (1).

[0340] <Preparation of Colorant Particle Dispersion (2)>

[0341] · Non-fluorescent pigment PG36 (C.I. Pigment Green 36, manufactured by Toyo Color Co., Ltd., LIONOL GREEN 8624, volume-average particle size: 120 nm): 70 parts

[0342] · Anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK): 30 parts (solid content concentration 20%)

[0343] · Deionized water: 200 parts

[0344] The above components are mixed and pulverized to 95 nm using a continuous Key sand mill (KMC-3), and the solid content is adjusted to 20% by mass to obtain a colorant particle dispersion (2).

[0345] <Preparation of Release Agent Particle Dispersion (1)>

[0346] · Microcrystalline wax (manufactured by Nippon Seiro Co., Ltd., HiMic-1090, melting temperature: 87 °C): 100 parts

[0347] · Anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK): 1 part

[0348] · Deionized water: 350 parts

[0349] The above materials are mixed and heated to 100°C, dispersed using a homogenizer (IKA, trade name ULTRA-TURRAXT50), and then dispersed using a Manton-Gaulin high-pressure homogenizer (Gaulin) to obtain a release agent particle dispersion (1) (solid content: 20% by mass) in which release agent particles with a volume average particle size of 200 nm are dispersed.

[0350] <Production of fluorescent green toner particles (1)>

[0351] Crystalline resin particle dispersion (1): 35 parts

[0352] Amorphous resin particle dispersion (1): 100 parts

[0353] Colorant particle dispersion (1): 125 parts

[0354] Colorant particle dispersion (2): 17 parts

[0355] Release agent particle dispersion (1): 40 parts

[0356] Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd.: Neogen RK, 20%): 10 parts

[0357] The above materials were placed in a round stainless steel flask, 0.1N (= mol / L) nitric acid was added to adjust the pH to 3.5, and then 30 parts of a nitric acid aqueous solution with a polyaluminum chloride concentration of 10% by mass was added. Then, a homogenizer (manufactured by IKA, trade name ULTRA-TURRAX T50) was used to disperse the mixture at a liquid temperature of 30°C, and then the mixture was heated to 45°C in a heating oil bath and maintained for 30 minutes. After that, 100 parts of amorphous resin particle dispersion (1) was added and maintained for 1 hour, and 0.1N sodium hydroxide aqueous solution was added to adjust the pH to 8.5, and then the mixture was heated to 84°C and maintained for 2.5 hours. Then, the mixture was cooled to 20°C at a rate of 20°C / min, and the solid component was filtered and separated, and then the solid component was fully washed with deionized water and dried to obtain fluorescent green toner particles (1). The volume average particle size of the fluorescent green toner particles (1) was 5.8 μm, and the content of the granular matter relative to the entire fluorescent green toner particles (1) was 4% by mass.

[0358] <Toner production>

[0359] 1.5 parts by mass of hydrophobic silica (RY50 manufactured by Nippon Aerosil Co., Ltd.) and 1.0 parts by mass of hydrophobic titanium dioxide (T805 manufactured by Nippon Aerosil Co., Ltd.) were mixed with 100 parts by mass of the obtained fluorescent green toner particles (1) using a sample mill at 10,000 rpm (revolutions per minute) for 30 seconds. Thereafter, the mixture was sieved using a vibrating sieve having a mesh size of 45 μm to prepare fluorescent green toner 1. The volume average particle size of the obtained fluorescent green toner 1 was 5.8 μm.

[0360] <Preparation of carrier 1>

[0361] Ferrite particles (average particle size 35 μm): 100 parts

[0362] Toluene: 14 parts

[0363] Polymethyl methacrylate (PMMA, weight average molecular weight 75,000): 5 parts

[0364] Carbon black: 0.2 parts (VXC-72, manufactured by Cabot Corporation, volume resistivity: 100 Ω·cm or less)

[0365] The above materials except the ferrite particles were dispersed in a sand mill to prepare a dispersion, and the dispersion was placed in a vacuum degassing kneader together with the ferrite particles, and dried under reduced pressure while stirring, thereby obtaining a carrier 1.

[0366] <Production of electrostatic image developer>

[0367] 8 parts of fluorescent green toner 1 and 92 parts of carrier 1 were mixed by a V-type mixer to prepare developer 1 (electrostatic charge image developer).

[0368] [Manufacturing of Fluorescent Green Toner 2 and Developer 2]

[0369] <Preparation of Release Agent Particle Dispersion (2)>

[0370] Polyethylene wax (Acculin 600 manufactured by Nippon Seira Co., Ltd., melting temperature: 94°C): 100 parts

[0371] Anionic surfactant (Neogen RK, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 1 part

[0372] Deionized water: 350 parts

[0373] The above materials are mixed and heated to 100°C, dispersed using a homogenizer (IKA, trade name ULTRA-TURRAXT50), and then dispersed using a Manton-Gaulin high-pressure homogenizer (Gaulin) to obtain a release agent particle dispersion (2) (solid content of 20% by mass) in which release agent particles with a volume average particle size of 200 nm are dispersed.

[0374] <Production of fluorescent green toner particles (2)>

[0375] Fluorescent green toner particles (2) were obtained in the same manner as the fluorescent green toner particles (1) except that the release agent particle dispersion (1) was replaced with the release agent particle dispersion (2). The volume average particle size of the fluorescent green toner particles (2) was 5.9 μm, and the content of the granular matter relative to the total fluorescent green toner particles (2) was 4% by mass.

[0376] <Manufacturing of toner and developer>

[0377] A fluorescent green toner 2 and a developer 2 were obtained in the same manner as the fluorescent green toner 1 and the developer 1 except that the fluorescent green toner particles ( 2 ) were used instead of the fluorescent green toner particles ( 1 ).

[0378] [Manufacturing of Fluorescent Green Toner 3 and Developer 3]

[0379] <Preparation of Release Agent Particle Dispersion (3)>

[0380] Microcrystalline wax (manufactured by Nippon Seira Co., Ltd., HiMic-1070, melting temperature: 80°C): 100 parts

[0381] Anionic surfactant (Neogen RK, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 1 part

[0382] Deionized water: 350 parts

[0383] The above materials are mixed and heated to 100°C, dispersed using a homogenizer (IKA, trade name ULTRA-TURRAXT50), and then dispersed using a Manton-Gaulin high-pressure homogenizer (Gaulin) to obtain a release agent particle dispersion (3) (solid content of 20% by mass) in which release agent particles with a volume average particle size of 200 nm are dispersed.

[0384] <Production of fluorescent green toner particles (3)>

[0385] Except for changing the release agent particle dispersion (1) to the release agent particle dispersion (3), the same operations as those for the fluorescent green toner particles (1) were performed to obtain the fluorescent green toner particles (3). The volume average particle diameter of the fluorescent green toner particles (3) is 5.9 μm, and the content of the granular matter relative to the whole of the fluorescent green toner particles (3) is 4% by mass.

[0386] <Production of Toner and Developer>

[0387] Except for using the fluorescent green toner particles (3) instead of the fluorescent green toner particles (1), the same operations as those for the fluorescent green toner 1 and the developer 1 were performed to obtain the fluorescent green toner 3 and the developer 3.

[0388] [Manufacture of Fluorescent Green Toner 4 and Developer 4]

[0389] <Production of Colorant Particle Dispersion (3)>

[0390] · Fluorescent dye Solvent Green 3 (C.I. Solvent Green 3 (OPLAS GREEN 533 manufactured by BASF Corporation)): 2 parts

[0391] · Amorphous polyester resin (weight average molecular weight 13,000, glass transition temperature 62°C): 100 parts

[0392] The above materials were heated and mixed to mix the dye into the resin. The kneaded product was rolled and cooled to 30°C or lower. The obtained kneaded product was roughly pulverized to 1 mm or less using a hammer mill and finely pulverized using an air jet mill (AFG, Hosokawa Micron Corporation). The particles obtained by the fine pulverization, 30 parts (solid content 20%) of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK), and 200 parts of deionized water were mixed and pulverized to a volume average particle diameter of 200 nm using a continuous Key sand mill (KMC-3, Inoue Manufacturing Co., Ltd.). The solid content amount was adjusted to 20% by mass to obtain the colorant particle dispersion (3).

[0393] <Production of Fluorescent Green Toner Particles (4)>

[0394] · Crystalline resin particle dispersion (1): 35 parts

[0395] · Amorphous resin particle dispersion (1): 100 parts

[0396] · Colorant particle dispersion (1): 100 parts

[0397] · Colorant particle dispersion (3): 42 parts

[0398] Release agent particle dispersion (1): 40 parts

[0399] Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd.: Neogen RK, 20%): 10 parts

[0400] The above materials were placed in a round stainless steel flask, 0.1N (= mol / L) nitric acid was added to adjust the pH to 3.5, and then 30 parts of a nitric acid aqueous solution with a polyaluminum chloride concentration of 10% by mass was added. Then, a homogenizer (manufactured by IKA, trade name ULTRA-TURRAX T50) was used to disperse the mixture at a liquid temperature of 30°C, and then the mixture was heated to 45°C in a heating oil bath and maintained for 30 minutes. After that, 100 parts of amorphous resin particle dispersion (1) was added and maintained for 1 hour, and a 0.1N sodium hydroxide aqueous solution was added to adjust the pH to 8.5, and then the mixture was heated to 84°C and maintained for 2.5 hours. Then, the mixture was cooled to 20°C at a rate of 20°C / min, and the solid component was filtered and separated, and then the solid component was fully washed with deionized water and dried to obtain fluorescent green toner particles (4). The volume average particle size of the fluorescent green toner particles (4) was 5.7 μm, and the content of the granular matter relative to the entire fluorescent green toner particles (4) was 0% by mass.

[0401] <Manufacturing of toner and developer>

[0402] Fluorescent green toner 4 and developer 4 were obtained in the same manner as fluorescent green toner 1 and developer 1 except that fluorescent green toner particles ( 4 ) were used instead of fluorescent green toner particles ( 1 ).

[0403] [Manufacturing of Fluorescent Pink Toner 5 and Developer 5]

[0404] <Preparation of Colorant Particle Dispersion (4)>

[0405] Fluorescent dye Basic Red 1:1 (CI Basic Red 1:1 (Basonyl Red 485 manufactured by BASF): 2 parts

[0406] Amorphous polyester resin (weight average molecular weight 13,000, glass transition temperature 62°C): 100 parts

[0407] Heat and mix the above materials, and mix a dye into the resin. Roll the kneaded mixture and cool it to 30°C or lower. Coarsely crush the obtained kneaded mixture to 1 mm or less using a hammer mill, and finely crush it using an air jet mill (AFG, Hosokawa Micron Corporation). Mix the particles obtained by fine crushing, 30 parts (solid content 20%) of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK), and 200 parts of deionized water, and crush them to a volume average particle size of 200 nm using a continuous Key sand mill (KMC-3, Inoue Manufacturing Co., Ltd.). Adjust the solid content to 20% by mass to obtain a colored particle dispersion (4).

[0408] <Preparation of Colored Particle Dispersion (5)>

[0409] · Fluorescent dye Basic Violet 11:1 (C.I. Basic Violet 11:1 (Neeliglow Basic Violet 11:1 manufactured by NEELIKON): 2 parts

[0410] · Amorphous polyester resin (weight average molecular weight 13,000, glass transition temperature 62°C): 100 parts

[0411] Heat and mix the above materials, and mix a dye into the resin. Roll the kneaded mixture and cool it to 30°C or lower. Coarsely crush the obtained kneaded mixture to 1 mm or less using a hammer mill, and finely crush it using an air jet mill (AFG, Hosokawa Micron Corporation). Mix the particles obtained by fine crushing, 30 parts (solid content 20%) of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK), and 200 parts of deionized water, and crush them to a volume average particle size of 200 nm using a continuous Key sand mill (KMC-3, Inoue Manufacturing Co., Ltd.). Adjust the solid content to 20% by mass to obtain a colored particle dispersion (5).

[0412] <Preparation of Fluorescent Pink Toner Particles (5)>

[0413] · Crystalline resin particle dispersion (1): 35 parts

[0414] · Amorphous resin particle dispersion (1): 100 parts

[0415] · Colored particle dispersion (4): 71 parts

[0416] · Colored particle dispersion (5): 71 parts

[0417] · Release agent particle dispersion (1): 40 parts

[0418] Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd.: Neogen RK, 20%): 10 parts

[0419] The above materials were placed in a round stainless steel flask, 0.1N (= mol / L) nitric acid was added to adjust the pH to 3.5, and then 30 parts of a nitric acid aqueous solution with a polyaluminum chloride concentration of 10% by mass was added. Then, the mixture was dispersed at a liquid temperature of 30°C using a homogenizer (manufactured by IKA, trade name ULTRA-TURRAX T50), and then heated to 45°C in a heating oil bath and maintained for 30 minutes. Thereafter, 100 parts of amorphous resin particle dispersion (1) was added and maintained for 1 hour, and 0.1N sodium hydroxide aqueous solution was added to adjust the pH to 8.5, and then heated to 84°C and maintained for 2.5 hours. Then, the mixture was cooled to 20°C at a rate of 20°C / min, and the solid content was filtered and separated, and then fully washed with deionized water and dried to obtain fluorescent pink toner particles (5). The volume average particle size of the fluorescent pink toner particles (5) was 5.7 μm, and the content of the granular matter relative to the entire fluorescent pink toner particles (5) was 0% by mass.

[0420] <Manufacturing of toner and developer>

[0421] A fluorescent pink toner 5 and a developer 5 were obtained in the same manner as the fluorescent green toner 1 and the developer 1 except that the fluorescent pink toner particles ( 5 ) were used instead of the fluorescent green toner particles ( 1 ).

[0422] [Manufacturing of Fluorescent Pink Toner 6 and Developer 6]

[0423] <Synthesis of Crystalline Resin Particle Dispersion (2)>

[0424] 1,10-Dodecanedioic acid: 50 mol%

[0425] 1,2-nonanediol: 50 mol%

[0426] The monomer components were placed in a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen inlet tube, and the reaction vessel was replaced with dry nitrogen. Then, 0.25 parts of tetrabutoxytitanium (reagent) were added to 100 parts of the monomer components. After stirring and reacting at 170° C. for 3 hours under a nitrogen flow, the temperature was further raised to 210° C. over 1 hour, and the pressure in the reaction vessel was reduced to 3 kPa. The reaction was stirred and reacted for 13 hours under reduced pressure to obtain a crystalline polyester resin (2).

[0427] The obtained crystalline polyester resin (2) had a melting temperature of 85.3° C. based on DSC, a mass average molecular weight Mw of 24,000 based on GPC, a number average molecular weight Mn of 10,800, and an acid value AV of 11.1 mgKOH / g.

[0428] In a jacketed reactor (BJ-30N manufactured by Tokyo Rikaki Co., Ltd.) equipped with a condenser, a thermometer, a water dripping device and an anchor wing, 300 parts of the crystalline polyester resin (1), 160 parts of methyl ethyl ketone (solvent) and 100 parts of isopropyl alcohol (solvent) were placed, and the resin was dissolved while being stirred and mixed at 100 rpm while being maintained at 70° C. in a water circulation thermostatic bath.

[0429] After that, the stirring speed was set to 150 rpm, the water circulation thermostatic bath was set to 66°C, and after adding 17 parts of 10% by mass ammonia water (reagent) over 10 minutes, a total of 900 parts of deionized water maintained at 66°C was dripped at a rate of 7 parts / minute to achieve phase inversion and obtain an emulsion.

[0430] Immediately put 800 parts of the obtained emulsion and 700 parts of deionized water into an eggplant-shaped bottle, and install it in an evaporator equipped with a vacuum control unit (Tokyo Rika Instruments Co., Ltd.) via a splash-proof ball. While rotating the eggplant-shaped bottle, heat it in a 60°C hot water bath, paying attention to violent boiling, and at the same time reduce the pressure to 7 kPa to remove the solvent. When the amount of solvent recovered reaches 1,100 parts, return to normal pressure, cool the eggplant-shaped bottle with water, and obtain a dispersion. There is no solvent smell in the obtained dispersion. The volume average particle size of the resin particles in the dispersion is 130 nm. Thereafter, deionized water is added to adjust the solid content concentration to 20% by mass to prepare a crystalline resin particle dispersion (2).

[0431] <Production of fluorescent pink toner particles (6)>

[0432] Fluorescent pink toner particles (6) were obtained in the same manner as the fluorescent pink toner particles (5) except that the crystalline resin particle dispersion (1) was replaced by the crystalline resin particle dispersion (2). The volume average particle size of the fluorescent pink toner particles (6) was 5.9 μm, and the content of the granular matter relative to the total amount of the fluorescent pink toner particles (6) was 0% by mass.

[0433] <Manufacturing of toner and developer>

[0434] A fluorescent pink toner 6 and a developer 6 were obtained in the same manner as for the fluorescent pink toner 5 and the developer 5 except that the fluorescent pink toner particles ( 6 ) were used instead of the fluorescent pink toner particles ( 5 ).

[0435] [Manufacturing of Fluorescent Pink Toner 7 and Developer 7]

[0436] <Preparation of Release Agent Particle Dispersion (4)>

[0437] Paraffin wax (Nippon Seira Co., Ltd., Parafin Wax-140, melting temperature: 61°C): 100 parts

[0438] Anionic surfactant (Neogen RK, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 1 part

[0439] Deionized water: 350 parts

[0440] The above materials are mixed and heated to 100°C, dispersed using a homogenizer (IKA, trade name ULTRA-TURRAXT50), and then dispersed using a Manton-Gaulin high-pressure homogenizer (Gaulin) to obtain a release agent particle dispersion (4) (solid content of 20% by mass) in which release agent particles with a volume average particle size of 200 nm are dispersed.

[0441] <Production of fluorescent pink toner particles (7)>

[0442] Fluorescent pink toner particles (7) were obtained in the same manner as the fluorescent pink toner particles (5) except that the release agent particle dispersion (1) was replaced with the release agent particle dispersion (4). The volume average particle size of the fluorescent pink toner particles (7) was 5.8 μm, and the content of the granular matter relative to the total amount of the fluorescent pink toner particles (7) was 0% by mass.

[0443] <Manufacturing of toner and developer>

[0444] Fluorescent pink toner 7 and developer 7 were obtained in the same manner as fluorescent pink toner 5 and developer 5 except that fluorescent pink toner particles ( 7 ) were used instead of fluorescent pink toner particles ( 5 ).

[0445] [Manufacturing of Fluorescent Pink Toner 8 and Developer 8]

[0446] <Preparation of Colorant Particle Dispersion (6)>

[0447] Non-fluorescent pigment PR122 (CI Pigment Red 122 (FASTOGEN SUPER MAGENTA R manufactured by DIC Corporation), volume average particle size: 100 nm): 70 parts

[0448] Anionic surfactant (Neogen RK, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 30 parts

[0449] Deionized water: 200 parts

[0450] The above components were mixed and pulverized to 90 nm using a continuous Key sand mill (KMC-3), and the solid content was adjusted to 20% by mass to obtain a colorant particle dispersion (6).

[0451] <Production of fluorescent pink toner particles (8)>

[0452] Crystalline resin particle dispersion (1): 35 parts

[0453] Amorphous resin particle dispersion (1): 100 parts

[0454] Colorant particle dispersion (4): 125 parts

[0455] Colorant particle dispersion (6): 17 parts

[0456] Release agent particle dispersion (1): 40 parts

[0457] Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd.: Neogen RK, 20%): 10 parts

[0458] The above materials were placed in a round stainless steel flask, 0.1N (= mol / L) nitric acid was added to adjust the pH to 3.5, and then 30 parts of a nitric acid aqueous solution with a polyaluminum chloride concentration of 10% by mass was added. Then, the mixture was dispersed at a liquid temperature of 30°C using a homogenizer (manufactured by IKA, trade name ULTRA-TURRAX T50), and then heated to 45°C in a heating oil bath and maintained for 30 minutes. Thereafter, 100 parts of amorphous resin particle dispersion (1) was added and maintained for 1 hour, and 0.1N sodium hydroxide aqueous solution was added to adjust the pH to 8.5, and then heated to 84°C and maintained for 2.5 hours. Then, the mixture was cooled to 20°C at a rate of 20°C / min, and the solid content was filtered and separated, and then fully washed with deionized water and dried to obtain fluorescent pink toner particles (8). The volume average particle size of the fluorescent pink toner particles (8) was 5.7 μm, and the content of the granular matter relative to the entire fluorescent pink toner particles (8) was 4% by mass.

[0459] <Manufacturing of toner and developer>

[0460] Fluorescent pink toner 8 and developer 8 were obtained in the same manner as fluorescent pink toner 5 and developer 5 except that fluorescent pink toner particles ( 8 ) were used instead of fluorescent pink toner particles ( 5 ).

[0461] [Manufacturing of Transparent Toner 9 and Developer 9]

[0462] <Preparation of Inorganic Particle Dispersion (1)>

[0463] Silica particles (manufactured by Shin-Etsu Silicone, trade name: X-24-9404, volume average particle size: 50 nm): 70 parts

[0464] Anionic surfactant (Neogen RK, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 30 parts

[0465] Deionized water: 200 parts

[0466] The above materials were mixed and dispersed for 10 minutes using a homogenizer (ULTRA-TURRAX T50 manufactured by IKA Corporation), and deionized water was added so that the solid content in the dispersion became 20% by mass to obtain an inorganic particle dispersion (1) having a volume average particle diameter of 50 nm.

[0467] <Production of Transparent Toner Particles (9)>

[0468] Crystalline resin particle dispersion (1): 35 parts

[0469] Amorphous resin particle dispersion (1): 225 parts

[0470] Inorganic particle dispersion (1): 17 parts

[0471] Release agent particle dispersion (1): 40 parts

[0472] Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd.: Neogen RK, 20%): 10 parts

[0473] The above materials were placed in a round stainless steel flask, 0.1N (= mol / L) nitric acid was added to adjust the pH to 3.5, and then 30 parts of a nitric acid aqueous solution with a polyaluminum chloride concentration of 10% by mass was added. Then, the mixture was dispersed at a liquid temperature of 30°C using a homogenizer (manufactured by IKA, trade name ULTRA-TURRAX T50), and then heated to 45°C in a heating oil bath and maintained for 30 minutes. Thereafter, 100 parts of amorphous resin particle dispersion (1) was added and maintained for 1 hour, and 0.1N sodium hydroxide aqueous solution was added to adjust the pH to 8.5, and then heated to 84°C and maintained for 2.5 hours. Then, the mixture was cooled to 20°C at a rate of 20°C / min, and the solid content was separated by filtration, fully washed with deionized water, and dried to obtain transparent toner particles (9). The volume average particle size of the transparent toner particles (9) was 5.7 μm, and the content of the granular matter relative to the entire transparent toner particles (9) was 4% by mass.

[0474] <Manufacturing of toner and developer>

[0475] Transparent toner 9 and developer 9 were obtained in the same manner as fluorescent green toner 1 and developer 1 except that transparent toner particles ( 9 ) were used instead of fluorescent green toner particles ( 1 ).

[0476] [Manufacturing of Transparent Toner 10 and Developer 10]

[0477] Transparent toner particles (10) were obtained in the same manner as transparent toner particles (9) except that the inorganic particle dispersion (1) was not used. The volume average particle size of the transparent toner particles (10) was 5.8 μm, and the content of the particulate matter relative to the entire transparent toner particles (10) was 0% by mass.

[0478] A transparent toner 10 and a developer 10 were obtained in the same manner as for the transparent toner 9 and the developer 9 except that the transparent toner particles ( 10 ) were used instead of the transparent toner particles ( 9 ).

[0479] <Preparation of Release Agent Particle Dispersion (5)>

[0480] Microcrystalline wax (manufactured by Nippon Seira Co., Ltd., FT95, melting temperature: 98°C): 100 parts

[0481] Anionic surfactant (Neogen RK, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 1 part

[0482] Deionized water: 350 parts

[0483] The above materials are mixed and heated to 100°C, dispersed using a homogenizer (IKA, trade name ULTRA-TURRAXT50), and then dispersed using a Manton-Gaulin high-pressure homogenizer (Gaulin) to obtain a release agent particle dispersion (5) (solid content of 20% by mass) in which release agent particles with a volume average particle size of 200 nm are dispersed.

[0484] <Preparation of Release Agent Particle Dispersion (6)>

[0485] Microcrystalline wax (Nippon Seiro Co., Ltd., Paraffin Wax-130, melting temperature: 56°C): 100 parts

[0486] Anionic surfactant (Neogen RK, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 1 part

[0487] Deionized water: 350 parts

[0488] The above materials are mixed and heated to 100°C, dispersed using a homogenizer (IKA, trade name ULTRA-TURRAXT50), and then dispersed using a Manton-Gaulin high-pressure homogenizer (Gaulin) to obtain a release agent particle dispersion (6) (solid content of 20% by mass) in which release agent particles with a volume average particle size of 200 nm are dispersed.

[0489] <Production of fluorescent green toner particles (5)>

[0490] Fluorescent green toner particles (5) were obtained in the same manner as the fluorescent green toner particles (2) except that the release agent particle dispersion (2) was replaced with the release agent particle dispersion (5). The volume average particle size of the fluorescent green toner particles (5) was 5.9 μm, and the content of the granular matter relative to the total fluorescent green toner particles (5) was 4% by mass.

[0491] <Manufacturing of toner and developer>

[0492] Fluorescent green toner 5 and developer 11 were obtained in the same manner as fluorescent green toner 2 and developer 2 except that fluorescent green toner particles ( 5 ) were used instead of fluorescent green toner particles ( 2 ).

[0493] <Production of fluorescent green toner particles (6)>

[0494] Fluorescent green toner particles (6) were obtained in the same manner as the fluorescent green toner particles (2) except that the release agent particle dispersion (2) was replaced with the release agent particle dispersion (6). The volume average particle size of the fluorescent green toner particles (6) was 5.9 μm, and the content of the granular matter relative to the total fluorescent green toner particles (6) was 4% by mass.

[0495] <Manufacturing of toner and developer>

[0496] Fluorescent green toner 6 and developer 12 were obtained in the same manner as fluorescent green toner 2 and developer 2 except that fluorescent green toner particles ( 6 ) were used instead of fluorescent green toner particles ( 2 ).

[0497] [Example 1 to Example 8, Comparative Example 1 to Comparative Example 4]

[0498] The toners and developers obtained as described above were combined as shown in Table 1 to obtain a toner set.

[0499] Furthermore, commercially available toners of various colors are used as the YMCK toners.

[0500] For each colorant, the crystallization temperature T1, crystallization temperature T2, crystallization temperature T3, the difference between the crystallization temperature T1 and the crystallization temperature T2 ("T1-T2(℃)" in the table), the difference between the crystallization temperature T1 and the crystallization temperature T3 ("|T3-T1|(℃)" in the table), and the difference between the crystallization temperature T2 and the crystallization temperature T3 ("|T3-T2|(℃)" in the table) calculated by the above method are shown in Table 1.

[0501] [evaluate]

[0502] <Image forming device>

[0503] exist Figure 1 In the image forming apparatus shown, the developer A shown in Table 1 is supplied to the developing device 4G of the first image forming unit 10G, the developer B shown in Table 1 is supplied to the developing device 4P of the second image forming unit 10P, the developing device 4Y of the yellow image forming unit 10Y, the developing device 4M of the magenta image forming unit 10M, the developing device 4C of the cyan image forming unit 10C, and the developing device 4K of the black image forming unit 10K are supplied with YMCK developers, and the fixing device 28 is modified to be able to change the fixing temperature, and image formation is performed. The processing speed is 534 mm / sec.

[0504] <Evaluation of thermal offset>

[0505] Use thin high-quality paper (npi high-quality paper, 52g / m 2 , Nippon Paper Industries, Ltd.) as the recording medium, with a toner loading of 20 g / m 2 The unfixed image is formed by laminating six colors of a solid image of 50 mm×50 mm with an image density of 100%.

[0506] The unfixed image was fixed at a fixing temperature of 5° C. from 170° C. to 230° C., and the presence or absence of thermal offset was visually confirmed. The lowest temperature at which thermal offset occurred was evaluated as the thermal offset occurrence temperature. The evaluation criteria were as follows. The results are shown in Table 1.

[0507] A: The thermal offset occurrence temperature is 230°C or higher.

[0508] B: The thermal offset occurrence temperature is 210°C or higher and lower than 230°C.

[0509] C: The thermal offset occurrence temperature is 190°C or higher and lower than 210°C.

[0510] D: The thermal offset occurrence temperature is lower than 190°C.

[0511] <Evaluation of cold offset>

[0512] Use thick coated paper (Aurora coated paper, 209g / m 2 , Nippon Paper Industries, Ltd.) as the recording medium, with a toner loading of 20 g / m 2 The unfixed image is formed by laminating six colors of a solid image of 50 mm×50 mm with an image density of 100%.

[0513] The unfixed image was fixed at a fixing temperature of 5°C from 150°C to 200°C, and the presence or absence of cold offset was visually confirmed. The lowest temperature at which cold offset occurred was evaluated as the cold offset occurrence temperature. The evaluation criteria were as follows. The results are shown in Table 1.

[0514] A: The cold offset occurrence temperature is 150°C or lower.

[0515] B: The cold offset generation temperature exceeds 150°C and is 160°C or less. C: The cold offset generation temperature exceeds 160°C and is 170°C or less. D: The cold offset generation temperature exceeds 170°C.

[0516] [Table 1]

[0517]

[0518] As can be seen from the results shown in Table 1, according to the toner set of this embodiment, both the suppression of hot offset and the suppression of cold offset can be achieved.

[0519] (Note) (((1)))

[0521] A toner set for electrostatic charge image development, comprising:

[0522] A yellow toner containing a yellow pigment, a magenta toner containing a magenta pigment, a cyan toner containing a cyan pigment, and a black toner containing a black pigment;

[0523] a first toner, the first toner being a dye toner or a transparent toner, and having a crystallization temperature T1 of 80° C. or more and 95° C. or less; and

[0524] The second toner is a dye toner or a transparent toner, and has a crystallization temperature T2 of 60° C. or more and 75° C. or less. (((2)))

[0526] The electrostatic image developing toner set according to (((1))), wherein:

[0527] The difference between the crystallization temperature T1 and the crystallization temperature T2 is 15° C. or more. (((3)))

[0529] The electrostatic image developing toner set according to (((2))), wherein:

[0530] The difference between the crystallization temperature T1 and the crystallization temperature T2 is 20° C. or more. (((4)))

[0532] The electrostatic charge image developing toner set according to any one of (((1))) to (((3))), wherein

[0533] When the average value of the crystallization temperature of the yellow toner, the crystallization temperature of the magenta toner, the crystallization temperature of the cyan toner, and the crystallization temperature of the black toner is defined as the crystallization temperature T3,

[0534] The difference between the crystallization temperature T1 and the crystallization temperature T3 is 5° C. or less, and the difference between the crystallization temperature T2 and the crystallization temperature T3 is 20° C. or more. (((5)))

[0536] The electrostatic charge image developing toner set according to any one of (((1))) to (((4))), wherein

[0537] The first toner includes first toner particles containing a crystalline resin and a particulate matter.

[0538] The second toner includes second toner particles containing a crystalline resin. (((6)))

[0540] The electrostatic image developing toner set according to (((5))), wherein:

[0541] The granules are colorless and transparent. (((7)))

[0543] The electrostatic charge image developing toner set according to (((5))) or (((6))), wherein:

[0544] The granular materials are silicon dioxide particles. (((8)))

[0546] The electrostatic charge image developing toner set according to any one of (((5))) to (((7))), wherein:

[0547] The content of the particulate matter contained in the first toner is 1 mass % or more and 5 mass % or less. (((9)))

[0549] An electrostatic charge image developer set comprising:

[0550] a yellow developer, a magenta developer, a cyan developer, and a black developer, wherein the yellow developer, the magenta developer, the cyan developer, and the black developer each contain the yellow toner, the magenta toner, the cyan toner, and the black toner in the electrostatic charge image developing toner set described in any one of (((1))) to (((8)));

[0551] a first developer including the first toner in the electrostatic charge image developing toner set described in any one of (((1))) to (((8))); and

[0552] A second developer comprising the second toner in the electrostatic charge image developing toner set described in any one of (((1))) to (((8))). (((10)))

[0554] A toner cartridge set comprising:

[0555] a yellow toner cartridge, a magenta toner cartridge, a cyan toner cartridge, and a black toner cartridge, wherein the yellow toner cartridge, the magenta toner cartridge, the cyan toner cartridge, and the black toner cartridge each contain the yellow toner, the magenta toner, the cyan toner, and the black toner of the electrostatic charge image developing toner set described in any one of (((1))) to (((8)));

[0556] a first toner cartridge including the first toner in the electrostatic charge image developing toner set described in any one of (((1))) to (((8))); and

[0557] a second toner cartridge, the second toner cartridge comprising the second toner in the electrostatic charge image developing toner set described in any one of (((1))) to (((8))),

[0558] The toner cartridge is assembled and detached from the image forming device. (((11)))

[0560] A processing box, comprising:

[0561] a yellow developing unit, a magenta developing unit, a cyan developing unit, and a black developing unit, wherein the yellow developing unit, the magenta developing unit, the cyan developing unit, and the black developing unit each include the yellow developer, the magenta developer, the cyan developer, and the black developer of the electrostatic charge image developer group described in (((9)));

[0562] a first developing unit, the first developing unit comprising the first developer in the electrostatic charge image developer group described in (((9))); and

[0563] a second developing unit, the second developing unit comprising the second developer in the electrostatic charge image developer group described in (((9))),

[0564] The process cartridge is attachable to and detachable from the image forming apparatus. (((12)))

[0566] An image forming device comprising:

[0567] a yellow image forming unit, a magenta image forming unit, a cyan image forming unit, and a black image forming unit, wherein the yellow image forming unit, the magenta image forming unit, the cyan image forming unit, and the black image forming unit respectively form a yellow image, a magenta image, a cyan image, and a black image using the yellow toner, the magenta toner, the cyan toner, and the black toner in the electrostatic charge image developing toner set described in any one of (((1))) to (((8)));

[0568] a first image forming unit that forms a first image using the first toner in the electrostatic charge image developing toner set described in any one of (((1))) to (((8)));

[0569] a second image forming unit that forms a second image using the second toner in the electrostatic charge image developing toner set described in any one of (((1))) to (((8)));

[0570] a transfer unit that transfers the yellow image, the magenta image, the cyan image, the black image, the first image, and the second image onto a recording medium; and

[0571] A fixing unit fixes a toner image formed by stacking the yellow image, the magenta image, the cyan image, the black image, the first image, and the second image onto the recording medium. (((13)))

[0573] An image forming apparatus according to (((12))), wherein:

[0574] With respect to the toner images, the layer farthest from the recording medium is the first image, and the layer second farthest from the recording medium is the second image. (((14)))

[0576] An image forming method, comprising:

[0577] a yellow image forming step, a magenta image forming step, a cyan image forming step, and a black image forming step, respectively forming a yellow image, a magenta image, a cyan image, and a black image using the yellow toner, the magenta toner, the cyan toner, and the black toner in the electrostatic charge image developing toner set described in any one of (((1))) to (((8)));

[0578] a first image forming step of forming a first image using the first toner in the electrostatic charge image developing toner set described in any one of (((1))) to (((8)));

[0579] a second image forming step of forming a second image using the second toner in the electrostatic charge image developing toner set described in any one of (((1))) to (((8)));

[0580] a transfer step of transferring the yellow image, the magenta image, the cyan image, the black image, the first image, and the second image onto a recording medium; and

[0581] The fixing step fixes a toner image formed by stacking the yellow image, the magenta image, the cyan image, the black image, the first image, and the second image onto the recording medium. (((15)))

[0583] The image forming method according to (((14))), wherein:

[0584] With respect to the toner images, the layer farthest from the recording medium is the first image, and the layer second farthest from the recording medium is the second image.

[0585] According to (((1))), (((5))), (((6))) or (((7))), a colorant group for electrostatic charge image development is provided, which takes into account both the suppression of a phenomenon in which the colorant excessively melts and adheres to a fixing component when fixing a colorant image (hereinafter also referred to as "hot offset") and the suppression of a phenomenon in which the colorant that is insufficiently melted is transferred to the fixing component due to insufficient heat supply to the colorant when fixing the colorant image (hereinafter also referred to as "cold offset"), compared to the following situation: the colorant group for electrostatic charge image development includes a yellow colorant, a magenta colorant, a cyan colorant, a black colorant, a first colorant that is a dye colorant or a transparent colorant, and a second colorant that is a dye colorant or a transparent colorant, and the crystallization temperature T1 of the first colorant is lower than 80°C or the crystallization temperature T2 of the second colorant exceeds 75°C.

[0586] According to (((2))), there is provided a toner set for electrostatic image development which achieves both suppression of hot offset and suppression of cold offset compared to a case where the difference between the crystallization temperature T1 and the crystallization temperature T2 is less than 15°C.

[0587] According to (((3))), there is provided a toner set for electrostatic image development which achieves both suppression of hot offset and suppression of cold offset compared to a case where the difference between the crystallization temperature T1 and the crystallization temperature T2 is less than 20°C.

[0588] According to (((4))), a toner group for electrostatic image development is provided, which takes into account both the suppression of hot offset and the suppression of cold offset compared to the case where the difference between the crystallization temperature T1 and the crystallization temperature T3 is less than 5°C or the difference between the crystallization temperature T2 and the crystallization temperature T3 is less than 20°C.

[0589] According to (((8))), there is provided a toner set for electrostatic image development which achieves both suppression of hot offset and suppression of cold offset compared to a case where the content of particulate matter contained in the first toner is less than 1 mass % or exceeds 5 mass %.

[0590] According to (((9))), (((10))), (((11))), (((12))) or (((14))), there is provided an electrostatic charge image developer group, a colorant box group, a processing box, an image forming device or an image forming method, which takes into account both the suppression of hot offset and the suppression of cold offset compared to the case where the following electrostatic charge image developing colorant group is used: comprising a yellow colorant, a magenta colorant, a cyan colorant, a black colorant, a first colorant which is a dye colorant or a transparent colorant, and a second colorant which is a dye colorant or a transparent colorant, and the crystallization temperature T1 of the first colorant is lower than 80°C or the crystallization temperature T2 of the second colorant exceeds 75°C.

[0591] According to (((13))) or (((15))), an image forming device or an image forming method is provided, which takes into account both the suppression of thermal offset and the suppression of cold offset, compared to the case of applying the following electrostatic charge image developing colorant group, even if the layer farthest from the recording medium is the first image and the layer second farthest from the recording medium is the second image: comprising a yellow colorant, a magenta colorant, a cyan colorant, a black colorant, a first colorant which is a dye colorant or a transparent colorant, and a second colorant which is a dye colorant or a transparent colorant, and the crystallization temperature T1 of the first colorant is lower than 80°C or the crystallization temperature T2 of the second colorant exceeds 75°C.

Claims

1. A toner set for electrostatic image development, characterized in that: include: A yellow toner containing a yellow pigment, a magenta toner containing a magenta pigment, a cyan toner containing a cyan pigment, and a black toner containing a black pigment; a first toner, the first toner being a dye toner or a transparent toner, and having a crystallization temperature T1 of 80° C. or more and 95° C. or less; and The second toner is a dye toner or a transparent toner, and has a crystallization temperature T2 of 60° C. or more and 75° C. or less.

2. The electrostatic image developing toner set according to claim 1, wherein: The difference between the crystallization temperature T1 and the crystallization temperature T2 is 15° C. or more.

3. The electrostatic charge image developing toner set according to claim 2, wherein: The difference between the crystallization temperature T1 and the crystallization temperature T2 is 20° C. or more.

4. The electrostatic charge image developing toner set according to any one of claims 1 to 3, wherein When the average value of the crystallization temperature of the yellow toner, the crystallization temperature of the magenta toner, the crystallization temperature of the cyan toner, and the crystallization temperature of the black toner is defined as the crystallization temperature T3, The difference between the crystallization temperature T1 and the crystallization temperature T3 is 5° C. or less, and the difference between the crystallization temperature T2 and the crystallization temperature T3 is 20° C. or more.

5. The electrostatic image developing toner set according to any one of claims 1 to 4, wherein The first toner includes first toner particles containing a crystalline resin and a particulate matter. The second toner includes second toner particles containing a crystalline resin.

6. The electrostatic image developing toner set according to claim 5, wherein: The granules are colorless and transparent.

7. The electrostatic charge image developing toner set according to claim 5 or 6, wherein: The granular materials are silicon dioxide particles.

8. The electrostatic image developing toner set according to any one of claims 5 to 7, wherein: The content of the particulate matter contained in the first toner is 1 mass % or more and 5 mass % or less.

9. An electrostatic charge image developer set, characterized in that: have: A yellow developer, a magenta developer, a cyan developer, and a black developer, wherein the yellow developer, the magenta developer, the cyan developer, and the black developer each contain the yellow toner, the magenta toner, the cyan toner, and the black toner in the electrostatic charge image developing toner set according to any one of claims 1 to 8; a first developer, the first developer comprising the first toner in the electrostatic charge image developing toner set according to any one of claims 1 to 8; as well as A second developer comprising the second toner in the electrostatic charge image developing toner set according to any one of claims 1 to 8.

10. A toner cartridge set, characterized in that: have: A yellow toner cartridge, a magenta toner cartridge, a cyan toner cartridge, and a black toner cartridge, wherein the yellow toner cartridge, the magenta toner cartridge, the cyan toner cartridge, and the black toner cartridge each contain the yellow toner, the magenta toner, the cyan toner, and the black toner of the electrostatic charge image developing toner set according to any one of claims 1 to 8; a first toner cartridge comprising the first toner in the electrostatic charge image developing toner set according to any one of claims 1 to 8; as well as a second toner cartridge, the second toner cartridge comprising the second toner in the electrostatic charge image developing toner set according to any one of claims 1 to 8, The toner cartridge is assembled and detached from the image forming device.

11. A processing box, characterized in that: have: a yellow developing unit, a magenta developing unit, a cyan developing unit, and a black developing unit, wherein the yellow developing unit, the magenta developing unit, the cyan developing unit, and the black developing unit respectively comprise the yellow developer, the magenta developer, the cyan developer, and the black developer of the electrostatic charge image developer set according to claim 9; a first developing unit, the first developing unit comprising the first developer in the electrostatic charge image developer set according to claim 9; as well as a second developing unit, the second developing unit comprising the second developer in the electrostatic charge image developer set according to claim 9, The process cartridge is attachable to and detachable from the image forming apparatus.

12. An image forming device, characterized in that: have: a yellow image forming unit, a magenta image forming unit, a cyan image forming unit, and a black image forming unit, each of which forms a yellow image, a magenta image, a cyan image, and a black image using the yellow toner, the magenta toner, the cyan toner, and the black toner in the electrostatic charge image developing toner set according to any one of claims 1 to 8, respectively; a first image forming unit that forms a first image using the first toner in the electrostatic charge image developing toner set according to any one of claims 1 to 8; a second image forming unit that forms a second image using the second toner in the electrostatic charge image developing toner set according to any one of claims 1 to 8; a transfer unit that transfers the yellow image, the magenta image, the cyan image, the black image, the first image, and the second image onto a recording medium; as well as A fixing unit fixes a toner image formed by stacking the yellow image, the magenta image, the cyan image, the black image, the first image, and the second image onto the recording medium.

13. The image forming apparatus according to claim 12, wherein: With respect to the toner images, the layer farthest from the recording medium is the first image, and the layer second farthest from the recording medium is the second image.

14. An image forming method, characterized in that: have: a yellow image forming step, a magenta image forming step, a cyan image forming step, and a black image forming step, respectively forming a yellow image, a magenta image, a cyan image, and a black image using the yellow toner, the magenta toner, the cyan toner, and the black toner in the electrostatic charge image developing toner set according to any one of claims 1 to 8; a first image forming step of forming a first image using the first toner in the electrostatic charge image developing toner set according to any one of claims 1 to 8; a second image forming step of forming a second image using the second toner in the electrostatic charge image developing toner set according to any one of claims 1 to 8; a transfer step of transferring the yellow image, the magenta image, the cyan image, the black image, the first image, and the second image onto a recording medium; as well as The fixing step fixes a toner image formed by stacking the yellow image, the magenta image, the cyan image, the black image, the first image, and the second image onto the recording medium.

15. The image forming method according to claim 14, wherein: With respect to the toner images, the layer farthest from the recording medium is the first image, and the layer second farthest from the recording medium is the second image.

Images