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

Abstract

To provide an electrostatic charge image developing toner set which produces images whose color shifts over time in a high-temperature, high-humidity environment is prevented.SOLUTION: An electrostatic charge image developing toner is provided, comprising a toner A comprising toner particles A containing an aluminum pigment, a toner B comprising toner particles B containing a phthalocyanine dye, and a toner C comprising toner particles C containing a pyrazolotriazole dye.SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[0002] Patent Document 1 discloses a toner set that includes a glitter toner containing a glitter pigment and a color toner containing a colorant, in which the heat absorption amount of the glitter toner is 1.2 to 5 times the heat absorption amount of the color toner.

[0003] Patent Document 2 discloses a full-color toner kit for forming a full-color image from at least yellow toner, magenta toner, cyan toner, and black toner, characterized in that the yellow toner contains a specific yellow pigment, the magenta toner contains a dye represented by a specific chemical formula and a metal compound represented by a specific general formula, and the cyan toner contains silicon phthalocyanine represented by a specific general formula. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-126199 [Patent Document 2] Japanese Patent Application Laid-Open No. 2010-002897 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present disclosure is to provide a toner set for developing electrostatic images that can produce images in which color variation over time under high temperature and high humidity conditions is suppressed compared to when a pigment is used instead of a phthalocyanine dye or when a pigment is used instead of a pyrazolotriazole dye. [Means for solving the problem]

[0006] Specific means for solving the above problems include the following aspects. <1> Toner A containing toner particles A containing an aluminum pigment; Toner B containing toner particles B containing a phthalocyanine dye; Toner C containing toner particles C containing a pyrazolotriazole dye; A toner set for developing electrostatic images comprising: <2> The phthalocyanine dye contains a phthalocyanine compound represented by the following formula (I): <1> 10. The toner set for developing electrostatic images according to claim 19.

[0007] [ka]

[0008] In the formula (I), M represents a silicon atom, a germanium atom, or a tin atom; Ra1 to Ra4 each independently represent an electron-withdrawing group; na1 to na4 each independently represent an integer of 0 to 4; and Z1 and Z2 each independently represent a hydroxy group, an aryloxy group having 6 to 18 carbon atoms, an alkoxy group having 1 to 22 carbon atoms, or a group represented by the following formula (II):

[0009] [ka]

[0010] In the formula (II), R3 to R5 each independently represent an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. <3> The pyrazolotriazole dye contains a pyrazolotriazole compound represented by the following formula (III): <1> or <2> 10. The toner set for developing electrostatic images according to claim 19.

[0011] [ka]

[0012] In formula (III), Rx1 and Rx2 each independently represent an alkyl group which may have a substituent; Lx represents a hydrogen atom or an alkyl group which may have a substituent; Gx1 represents an alkyl group having 2 or more carbon atoms; Gx2 represents an aryl group or an alkyl group which may have a substituent; Gx3 represents a hydrogen atom, a halogen atom, Gx4-CO-NH-, or Gx5-N(Gx6)-CO-; Gx4 represents an aryl group or an alkyl group which may have a substituent; Gx5 and Gx6 each independently represent a hydrogen atom or an alkyl group which may have a substituent; and Qx1 to Qx5 each independently represent a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent. <4> The content of the aluminum pigment relative to the toner particles A is C A The content of the phthalocyanine dye relative to the toner particles B is C B and the pyrazolotriazole dye for the toner particles C is C C When (C B +C C ) / C A The value of is between 0.40 and 2.00. <1> ~ <3> 10. The toner set for developing electrostatic images according to claim 9, wherein the toner set is a toner for developing electrostatic images. <5> Said (C B +C C ) / C A The value of is between 1.00 and 2.00, <4> 10. The toner set for developing electrostatic images according to claim 19. <6> The volume average particle diameter of the toner particles A is D A , the volume average particle diameter of the toner particles B is D B , the volume average particle diameter of the toner particles C is D C When D B / D A The value of is 0.30 or more and 1.00 or less, and D C / D A The value of is between 0.30 and 1.00, <1> ~ <5> 10. The toner set for developing electrostatic images according to claim 9, wherein the toner set is a toner for developing electrostatic images. <7> The above DB / D A The value of is 0.40 or more and 0.80 or less, and the D C / D A The value of is between 0.40 and 0.80. <6> 10. The toner set for developing electrostatic images according to claim 19. <8> the toner particles A, the toner particles B, and the toner particles C contain a crystalline resin; <1> ~ <7> 10. The toner set for developing electrostatic images according to claim 9. <9> The content of the crystalline resin contained in the toner particles A is E A The content of the crystalline resin contained in the toner particles B is E B The content of the crystalline resin contained in the toner particles C is E C When E A <E B And E A <E C That is, <8> 10. The toner set for developing electrostatic images according to claim 19. <10> E B / E A The value of is greater than 1.00 and less than or equal to 2.00, and E C / E A is greater than 1.00 and less than or equal to 2.00, <9> 10. The toner set for developing electrostatic images according to claim 19.

[0013] <11> <1> ~ <10> a developer A containing the toner A in the toner set for developing electrostatic images according to any one of the above items; <1> ~ <10> Developer B containing the toner B of the toner set for developing electrostatic images according to any one of the above items; <1> ~ <10> a developer C containing the toner C of the toner set for developing electrostatic images according to any one of the above items; Electrostatic image developer set comprising: <12> <1> ~ <10> a toner cartridge A containing the toner A in the toner set for developing electrostatic images according to any one of the above items; <1> ~ <10> a toner cartridge B containing the toner B of the toner set for developing electrostatic images according to any one of the above items; <1> ~ <10> a toner cartridge C containing the toner C of the toner set for developing electrostatic images according to any one of the above items; and A toner cartridge set that is detachably attached to an image forming apparatus. <13> <11> a developing means A containing the developer A of the electrostatic image developer set described in <11> a developing means B containing the developer B of the electrostatic image developer set described in <11> a developing means C containing the developer C of the electrostatic image developer set described in Equipped with A process cartridge is detachably mounted in an image forming apparatus. <14> <1> ~ <10> an image forming means A for forming an image A using the toner A in the toner set for developing an electrostatic image according to any one of the above items; <1> ~ <10> an image forming means B for forming an image B using the toner B of the toner set for developing an electrostatic image according to any one of the above items; <1> ~ <10> an image forming means C for forming an image C using the toner C in the toner set for developing an electrostatic image according to any one of the above items; a transfer means for transferring the image A, the image B, and the image C onto a recording medium; a fixing unit for fixing a toner image, in which the image A, the image B, and the image C are stacked, onto the recording medium; An image forming apparatus comprising: <15> <1> ~ <10> an image forming step A in which an image A is formed using the toner A in the toner set for developing electrostatic images according to any one of the above items; <1> ~ <10> an image forming step B for forming an image B using the toner B of the toner set for developing an electrostatic image according to any one of the above items; <1> ~ <10> an image forming step C of forming an image C using the toner C of the toner set for developing an electrostatic image according to any one of the above items; a transfer step of transferring the image A, the image B, and the image C onto a recording medium; a fixing step of fixing a toner image formed by stacking the image A, the image B, and the image C on the recording medium; An image forming method comprising: [Effects of the Invention]

[0014] <1> or <3> According to the invention, there is provided a toner set for developing electrostatic images that can produce images in which color variation over time under high temperature and high humidity conditions is suppressed compared to when a pigment is used instead of a phthalocyanine dye or when a pigment is used instead of a pyrazolotriazole dye. <2> According to the invention, there is provided a toner set for developing electrostatic images, which can produce images in which color change over time under high temperature and high humidity conditions is suppressed compared to when the phthalocyanine dye is a compound represented by formula (I) in which M in formula (I) is copper. <4> According to the invention, (C B +C C ) / C A The present invention provides a toner set for developing electrostatic images that can provide images that suppress color variation over time under high temperature and high humidity conditions and improve metallic appearance, as compared with when the value is less than 0.40 or more than 2.00. <5> According to the invention, (C B +C C ) / C A In comparison with a case where the value is less than 1.00, an electrostatic image developing toner set is provided which can obtain an image in which color variation over time under high temperature and high humidity conditions is suppressed. <6> According to the invention, D B / D A The value of is less than 0.30 or more than 1.00, or D C / D A In comparison with a case where the value is less than 0.30 or more than 1.00, an electrostatic image developing toner set is provided which can obtain an image in which color variation over time under high temperature and high humidity conditions is suppressed and metallic feel is improved. <7> According to the invention, D B / D A The value of is less than 0.40 or more than 0.80, or D C / D AThe present invention provides a toner set for developing electrostatic images that can provide images that suppress color variation over time under high temperature and high humidity conditions and improve metallic appearance, as compared with when the value is less than 0.40 or more than 0.80. <8> According to the invention, there is provided a toner set for developing electrostatic images that can produce images in which color variation over time under high temperature and high humidity conditions is suppressed compared to when toner particles A, toner particles B, or toner particles C do not contain a crystalline resin. <9> According to the invention, E A ≧E B or E A ≧E C The present invention provides a toner set for developing electrostatic images that is less susceptible to color variations over time under high temperature and high humidity conditions than in other cases. <10> According to the invention, E B / E A The value of is 1.00 or less or exceeds 2.00, or E C / E A In comparison with a toner set having a value of 1.00 or less or exceeding 2.00, the toner set for developing electrostatic images is provided in which color fluctuation over time under high temperature and high humidity conditions is suppressed.

[0015] <11> , <12> , <13> , <14> , or <15> According to the invention, there is provided an electrostatic image developer set, a toner cartridge set, a process cartridge, an image forming apparatus, or an image forming method that can produce images in which color variation over time under high temperature and high humidity conditions is suppressed compared to when a toner set for developing electrostatic images using a pigment instead of a phthalocyanine dye or a toner set for developing electrostatic images using a pigment instead of a pyrazolotriazole dye is used. [Brief explanation of the drawings]

[0016] [Figure 1] 1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to the present disclosure. [Figure 2] 1 is a schematic configuration diagram illustrating an example of a process cartridge according to the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0017]

[0023] The following describes embodiments of the present disclosure. These descriptions and examples are intended to illustrate the embodiments and are not intended to limit the scope of the embodiments.

[0018] In the present disclosure, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples.

[0019] In the present disclosure, the term "step" includes not only an independent step but also a step that cannot be clearly distinguished from other steps as long as the purpose of the step is achieved.

[0020] When embodiments of the present disclosure are described with reference to the drawings, the configuration of the embodiment is not limited to the configuration shown in the drawings. Furthermore, the sizes of the components in each drawing are conceptual, and the relative size relationships between the components are not limited to these.

[0021] In the present disclosure, each component may contain multiple corresponding substances. When referring to the amount of each component in a composition in the present disclosure, if multiple substances corresponding to each component are present in the composition, the total amount of the multiple substances present in the composition is meant unless otherwise specified. In the present disclosure, the composition may contain multiple types of particles corresponding to each component. When multiple types of particles corresponding to each component are present in the composition, the particle size of each component means the value for a mixture of the multiple types of particles present in the composition, unless otherwise specified.

[0022] In this disclosure, "(meth)acrylic" is an expression that includes both acrylic and methacrylic, and "(meth)acrylate" is an expression that includes both acrylate and methacrylate. This is an expression that sounds similar to the above.

[0023] In this disclosure, "toner for developing electrostatic images" will also be referred to as "toner," "toner set for developing electrostatic images" will also be referred to as "toner set," "electrostatic image developer" will also be referred to as "developer," "electrostatic image developer set" will also be referred to as "developer set," and "carrier for developing electrostatic images" will also be referred to as "carrier."

[0024] [Electrostatic image developing toner set] A toner set according to one embodiment of the present disclosure includes toner A including toner particles A containing an aluminum pigment, toner B including toner particles B containing a phthalocyanine dye, and toner C including toner particles C containing a pyrazolotriazole dye.

[0025] In electrophotographic printing, in order to reproduce a wide range of colors, images are formed by combining toners of special colors such as gold, silver, white, colorless, red, fluorescent pink, and fluorescent green in addition to yellow (Y), magenta (M), cyan (C), and black (K). In particular, for the purpose of creating a sense of luxury in image formation for publications, paper container packages, etc., metallic color images are sometimes formed using a toner set that includes a glitter toner such as a silver toner and a colored toner such as a magenta toner or a cyan toner.

[0026] However, when an image formed using a toner set containing a glitter toner that uses an aluminum pigment as the glitter pigment is stored under high temperature and humidity conditions (for example, in an environment with a temperature of 30°C and a humidity of 80%), the color of the image may change over time. In particular, in blue metallic images formed using a toner set that combines a glitter toner containing glitter toner particles containing an aluminum pigment with a cyan toner and a magenta toner having low brightness, color variations in the image over time are easily noticeable.

[0027] The color variation of the image is thought to be due to corrosion of the aluminum pigment contained in the image. Aluminum is a metal that is relatively resistant to corrosion because it forms an oxide film on its surface, but when a person touches the image, for example, chloride ions adhere to the surface of the image, and these chloride ions facilitate corrosion of the aluminum pigment. As the corrosion of the aluminum pigment progresses, the image becomes whiter, and it is thought that this is the cause of the color variation.

[0028] In contrast, the toner set of this embodiment includes toner A containing toner particles A containing an aluminum pigment, toner B containing toner particles B containing a phthalocyanine dye, and toner C containing toner particles C containing a pyrazolotriazole dye. The toner set of this embodiment, having the above-described configuration, suppresses color variation in images over time under high-temperature and high-humidity conditions. While the reason for this is unclear, it is presumed that the phthalocyanine dye contained in toner particles B and the pyrazolotriazole dye contained in toner particles C capture chloride ions, thereby slowing the progression of corrosion of the aluminum pigment in the image.

[0029] The toner set according to the present disclosure may contain at least Toner A, Toner B, and Toner C, and may also contain toners other than the above three types of toners (hereinafter also referred to as other toners). Examples of other toners include clear toner, yellow toner, black toner, red toner, fluorescent pink toner, and fluorescent green toner.

[0030] <Pigment and dye content> The content of aluminum pigment in toner particles A is C A The content of the phthalocyanine dye relative to the toner particles B is C B , the pyrazolotriazole dye for toner particles C is C C Then, (C B +C C ) / C A The value of is preferably 0.40 or more and 2.00 or less.B +C C ) / C A When the value of is within the above range, both the suppression of color variation of the image over time under high temperature and high humidity conditions and the improvement of the metallic appearance of the image can be achieved. Specifically, (C B +C C ) / C A When the value of is equal to or greater than the lower limit, the amount of aluminum pigment contained in the image is not too large, making color variation due to corrosion of the aluminum pigment less visible, and the amount of phthalocyanine dye and pyrazolotriazole dye contained in the image is not too small, making it easier to obtain the effect of these dyes in inhibiting the progression of corrosion of the aluminum pigment.It is presumed that this inhibits color variation of the image over time under high temperature and high humidity conditions. Also, (C B +C C ) / C A It is presumed that when the value of is equal to or less than the upper limit, a decrease in the brightness of the image caused by an excessive amount of the phthalocyanine dye and the pyrazolotriazole dye is suppressed, and the metallic feel of the image is improved. (C B +C C ) / C A From the above viewpoint, the value of is preferably 0.40 or more and 2.00 or less, more preferably 1.00 or more and 2.00 or less, and even more preferably 1.50 or more and 2.00 or less.

[0031] Aluminum pigment content C relative to toner particle A A is, for example, from 11% by mass to 28% by mass, and from the viewpoint of simultaneously suppressing color variation in an image over time under high temperature and high humidity conditions and improving the metallic feel of the image, it is preferably from 16% by mass to 28% by mass, more preferably from 17% by mass to 27% by mass, and even more preferably from 17.5% by mass to 26% by mass. Phthalocyanine dye content C relative to toner particles B Bis, for example, from 3.5% by mass to 25% by mass, and from the viewpoint of simultaneously suppressing color variation in an image over time under high temperature and high humidity conditions and improving the metallic feel of the image, it is preferably from 5.5% by mass to 25% by mass, more preferably from 8.0% by mass to 20% by mass, and particularly preferably from 10% by mass to 15% by mass. Content C of pyrazolotriazole dye relative to toner particles C C From the viewpoint of simultaneously suppressing color variation in an image over time under high temperature and high humidity conditions and improving the metallic feel of the image, the content is preferably 3.0% by mass or more and 25% by mass or less, more preferably 5.0% by mass or more and 20% by mass or less, and particularly preferably 10% by mass or more and 15% by mass or less. C C / C B The value of is not particularly limited, and may be, for example, 0.1 or more and 2.1 or less. From the viewpoint of good color balance, it is preferably 0.2 or more and 1.5 or less, and more preferably 0.3 or more and 1.1 or less.

[0032] <Volume average particle size of toner particles> The volume average particle size of toner particles A is D A , the volume average particle size of toner particles B is D B , the volume average particle size of toner particles C is D C When D B / D A The value of is 0.30 or more and 1.00 or less, and D C / D A It is preferable that the value of is 0.30 or more and 1.00 or less. B / D A The value of D C / D A When the values ​​of are within the above ranges, both the suppression of color variation of the image over time under high temperature and high humidity conditions and the improvement of the metallic appearance of the image can be achieved. Specifically, D B / D A The value of D C / D AWhen the values ​​of are equal to or greater than the respective lower limits, the aluminum pigment in the image is easily coated with toner particles B and toner particles C. This makes it easier to obtain the effect of inhibiting the progress of corrosion of the aluminum pigment by the phthalocyanine dye contained in toner particles B and the pyrazolotriazole dye contained in toner particles C, and is presumed to suppress color variation of the image over time under high temperature and high humidity conditions. Also, D B / D A The value of D C / D A When the values ​​of are each equal to or less than the above upper limit values, it is presumed that a decrease in image brightness due to toner particles B and toner particles C excessively covering the aluminum pigment in the image is suppressed, and the metallic feel of the image is improved. From the above perspective, D B / D A The value of is 0.40 or more and 0.80 or less and D C / D A It is more preferable that the value of is 0.40 or more and 0.80 or less, and D B / D A The value of is 0.50 or more and 0.70 or less and D C / D A It is more preferable that the value is 0.50 or more and 0.70 or less.

[0033] Volume average particle size D of toner particles A A From the viewpoint of simultaneously suppressing color variation in an image over time under high temperature and high humidity conditions and improving the metallic feel of the image, the thickness is preferably 3 μm or more and 30 μm or less, more preferably 5 μm or more and 20 μm or less, and even more preferably 7 μm or more and 15 μm or less. Volume average particle size D of toner particles B B From the viewpoint of simultaneously suppressing color variation of an image over time under high temperature and high humidity conditions and improving the metallic feel of the image, the thickness is preferably 2 μm or more and 15 μm or less, more preferably 3 μm or more and 10 μm or less, and even more preferably 4 μm or more and 9 μm or less. Volume average particle size D of toner particles C CFrom the viewpoint of simultaneously suppressing color variation of an image over time under high temperature and high humidity conditions and improving the metallic feel of the image, the thickness is preferably 2 μm or more and 15 μm or less, more preferably 3 μm or more and 10 μm or less, and even more preferably 4 μm or more and 9 μm or less. D C / D B The value of is not particularly limited, and may be, for example, 0.5 or more and 2.0 or less. From the viewpoint of image quality stability, it is preferably 0.6 or more and 1.5 or less, and more preferably 0.7 or more and 1.3 or less.

[0034] The volume average particle size of the toner particles is measured using a Coulter Multisizer II (manufactured by Beckman Coulter), and the electrolyte is measured using an ISOTON-II (manufactured by Beckman Coulter). For the measurement, 0.5 mg to 50 mg of the sample to be measured is added to 2 ml of a 5 mass % aqueous solution of a surfactant (preferably sodium alkylbenzene sulfonate) as a dispersant, and this is then added to 100 ml to 150 ml of the electrolyte. The electrolyte solution containing the suspended sample is dispersed for 1 minute using an ultrasonic disperser, and the particle size distribution of particles with a particle size range of 2 μm to 60 μm is measured using a Coulter Multisizer II with an aperture diameter of 100 μm. The number of particles sampled is 50,000. Based on the particle size distribution measured, cumulative distributions of volume and number are drawn for each divided particle size range (channel) from the smallest diameter side, and the particle size at which the cumulative 50% is reached is defined as the volume average particle size D50v.

[0035] <Crystalline resin> It is preferable that toner particles A, toner particles B, and toner particles C each contain a crystalline resin. When toner particles A, toner particles B, and toner particles C each contain a crystalline resin, color fluctuations in images over time under high temperature and high humidity conditions are suppressed. The reason for this is not clear, but it is presumed that when a crystalline resin is contained, grain boundaries are formed by domains of the crystalline resin during the image formation process, reducing the mobility of chloride ions and further suppressing the progression of corrosion of the aluminum pigment.

[0036] The content of the crystalline resin contained in the toner particles A is E A The content of the crystalline resin contained in the toner particles B is E B The content of the crystalline resin contained in the toner particles C is E C When E A <E B And E A <E C It is preferable that E A <E B And E A <E C By doing so, the color variation of the image over time under high temperature and high humidity conditions is further suppressed. Although the reason for this is not clear, it is thought that the relatively large amount of crystalline resin contained in toner particles B and C causes the grain boundary area of ​​the crystalline resin domains in toner particles B and C to become relatively large. Furthermore, it is speculated that the relatively large grain boundary area of ​​the crystalline resin domains in toner particles B and C reduces the mobility of chloride ions within toner particles B and C, further suppressing the progress of corrosion of the aluminum pigment.

[0037] From the above perspective, E B / E A The value of is greater than 1.00 and less than or equal to 2.00 and E C / E A It is preferable that the value of E is more than 1.00 and not more than 2.00. B / E A The value of E C / E A It is presumed that the value of E is greater than the lower limit, and therefore the grain boundary area of ​​the crystalline resin domains in toner particles B and C is relatively large, as described above, and therefore the corrosion of the aluminum pigment is suppressed. B / E A The value of E C / E A When the value is equal to or less than the upper limit, the content of the crystalline resin in the toner particles A is not too low relatively, and the mobility of chloride ions within the toner particles A is also reduced, which is presumably why the progress of corrosion of the aluminum pigment is suppressed. From the above perspective, EB / E A The value of is greater than 1.00 and less than or equal to 1.62 and E C / E A It is more preferable that the value of E is more than 1.00 and not more than 1.62. B / E A The value of is greater than 1.00 and less than or equal to 1.56 and E C / E A It is more preferable that the value is greater than 1.00 and not greater than 1.56.

[0038] Content E of crystalline resin contained in toner particles A A is, for example, 2% by mass or more and 11% by mass or less, and from the viewpoint of improving image fixability, it is preferably 2% by mass or more and 10% by mass or less, more preferably 3% by mass or more and 9% by mass or less, and even more preferably 4% by mass or more and 8% by mass or less. Content E of crystalline resin contained in toner particles B B From the viewpoint of ensuring a crystalline resin domain that reduces the mobility of chloride ions, the content is preferably 2% by mass or more and 15% by mass or less, and more preferably 3% by mass or more and 14% by mass or less. Content E of crystalline resin contained in toner particles C C From the viewpoint of ensuring a crystalline resin domain suitable for reducing the mobility of chloride ions, the content is preferably 2% by mass or more and 15% by mass or less, and more preferably 3% by mass or more and 14% by mass or less. E C / E B The value of is not particularly limited, and may be, for example, 0.7 or more and 1.3 or less, and from the viewpoint of good transferability, is preferably 0.8 or more and 1.2 or less, and more preferably 0.9 or more and 1.1 or less. The crystalline resin will be described in detail later.

[0039] Hereinafter, each toner included in an example of the toner set according to this embodiment will be described in detail.

[0040] <Toner A> Toner A is composed of toner particles A containing an aluminum pigment and, if necessary, an external additive. Toner A is a glitter toner containing glitter toner particles containing an aluminum pigment as a glitter pigment.

[0041] When a solid image is formed using the glitter toner, the ratio (X / Y) of the reflectance X at a light-receiving angle of +30° to the reflectance Y at a light-receiving angle of -30° measured when the image is irradiated with incident light at an incident angle of -45° using a goniophotometer is preferably 2 or more and 100 or less.

[0042] A ratio (X / Y) of 2 or more indicates that the incident light is reflected more in the direction opposite to the incident side (positive angle side) than in the direction of the incident side (negative angle side), meaning that diffuse reflection of the incident light is suppressed. When diffuse reflection occurs, where incident light is reflected in various directions, the color appears dull when the reflected light is visually inspected. Therefore, if the ratio (X / Y) is less than 2, the gloss cannot be confirmed even when the reflected light is visually inspected, and the brilliance may be poor. On the other hand, if the ratio (X / Y) exceeds 100, the viewing angle at which reflected light can be seen becomes too narrow, and the specular reflection component is large, which may cause the image to appear black depending on the viewing angle.

[0043] From the viewpoint of brightness and toner manufacturability, the ratio (X / Y) is more preferably 4 or more and 50 or less, even more preferably 6 or more and 20 or less, and particularly preferably 8 or more and 15 or less.

[0044] <Measurement of the ratio (X / Y) using a goniophotometer> First, the angle of incidence and the angle of acceptance will be described. In this embodiment, when measuring using a goniophotometer, the angle of incidence is set to -45° because this provides high measurement sensitivity for images with a wide range of gloss levels. The reason why the light-receiving angles are set to -30° and +30° is that these provide the highest measurement sensitivity for evaluating images with a glittery feel and images without a glittery feel.

[0045] Next, the method for measuring the ratio (X / Y) will be explained. The image to be measured (glossy image) is irradiated with light at an incident angle of -45° using a GC5000L spectral variable goniochromator manufactured by Nippon Denshoku Industries Co., Ltd., as a variable goniophotometer, and the reflectance X at an acceptance angle of +30° and the reflectance Y at an acceptance angle of -30° are measured. The reflectance X and reflectance Y are measured at 20 nm intervals for light with wavelengths ranging from 400 nm to 700 nm, and the average reflectance values ​​at each wavelength are used. The ratio (X / Y) is calculated from these measurement results.

[0046] From the viewpoint of satisfying the above-mentioned ratio (X / Y), it is preferable that the glitter toner satisfy the following requirements (1) and (2). (1) The average equivalent circle diameter D is longer than the average maximum thickness C of the glitter toner particles. (2) When a cross section of a lustrous toner particle in the thickness direction is observed, the proportion of lustrous pigments in which the angle between the long axis direction of the lustrous toner particle in the cross section and the long axis direction of the lustrous pigment is in the range of −30° to +30° is 60% or more of all the lustrous pigments observed.

[0047] When the glitter toner particles are flat with a circular equivalent diameter longer than their thickness, it is thought that in the fixing process of image formation, the pressure applied during fixing causes the flat glitter toner particles to align with their flat surfaces facing the surface of the recording medium. Therefore, among the flat (scale-like) luster pigments contained in these luster toner particles, those that satisfy the requirement (2) above, "the angle between the long axis direction of the toner cross section and the long axis direction of the luster pigment is in the range of -30° to +30°," are thought to be aligned so that the side with the largest area faces the recording medium surface. When light is irradiated onto an image formed in this way, the proportion of the luster pigment that diffusely reflects the incident light is suppressed, and the aforementioned range of the ratio (X / Y) is thought to be achieved.

[0048] (Toner particles A) The toner particles A contain, for example, an aluminum pigment which is a glitter pigment, a binder resin, and, if necessary, a release agent and other components. As described above, the toner particles A preferably contain a crystalline resin from the viewpoint of further suppressing color variation of images over time under high temperature and high humidity conditions. The crystalline resin is contained in the toner particles A, for example, as one component of the binder resin that constitutes the toner particles A.

[0049] -Average maximum thickness C and average equivalent circle diameter D of toner particles A- The toner particles A are preferably flat and have an average circular diameter D longer than their average maximum thickness C. The ratio (C / D) of the average maximum thickness C to the average circular diameter D is more preferably in the range of 0.001 to 0.700, even more preferably in the range of 0.100 to 0.600, and particularly preferably in the range of 0.300 to 0.450. By making the ratio (C / D) 0.001 or more, the strength of the toner particles A is ensured, breakage due to stress during image formation is suppressed, and a decrease in charge due to exposure of the pigment and the resulting fogging are suppressed.On the other hand, by making the ratio 0.700 or less, excellent brilliance is obtained.

[0050] The average maximum thickness C and the average equivalent circle diameter D of the glitter toner particles are measured by the following method. The glitter toner particles are placed on a smooth surface and vibrated to disperse evenly. For 1,000 glitter toner particles, the maximum thickness C and the equivalent circle diameter D of the glitter toner particle as viewed from above are measured at 1,000x magnification using a color laser microscope "VK-9700" (manufactured by Keyence Corporation), and the arithmetic mean value of these is calculated.

[0051] The angle between the long axis direction of the cross section of toner particle A and the long axis direction of the bright pigment When a cross section of toner particle A in the thickness direction is observed, the proportion (by number) of bright pigment particles for which the angle between the long axis direction of the toner particle A in the cross section and the long axis direction of the bright pigment is in the range of -30° to +30° is preferably 60% or more of all the bright pigment particles observed.Moreover, this proportion is more preferably 70% to 95%, and particularly preferably 80% to 90%. When the above ratio is 60% or more, excellent brilliance can be obtained.

[0052] Here, a method for observing the cross section of the glitter toner particles will be described. The glittering toner particles are embedded in a bisphenol A liquid epoxy resin and a curing agent, and then a cutting sample is prepared. The cutting sample is then cut at -100°C using a cutting machine with a diamond knife, such as an ultramicrotome (Ultracut UCT, manufactured by Leica), to prepare a sample for observation. The observation sample is then observed using, for example, an ultra-high resolution field emission scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation) at a magnification such that approximately 1 to 10 glittering toner particles are visible in one field of view. Specifically, the cross section of a glitter toner particle (cross section along the thickness direction of the glitter toner particle) is observed, and for 100 glitter toner particles observed, the number of glitter pigment particles for which the angle between the long axis direction in the cross section of the glitter toner particle and the long axis direction of the glitter pigment is in the range of -30° to +30° is counted using image analysis software such as the image analysis software (Win ROOF) manufactured by Mitani Shoji Co., Ltd., or an output sample of the observed image and a protractor, and the percentage is calculated.

[0053] Aspect ratio of toner particle A The ratio (aspect ratio) of the average length in the major axis direction to the average length in the thickness direction of the toner particles A, which is taken as 1, is preferably 1.5 or more and 15 or less, more preferably 2 or more and 10 or less, and even more preferably 3 or more and 8 or less. The average length in the thickness direction and the average length in the major axis direction of the glitter toner particles are calculated by placing the glitter toner particles on a smooth surface and vibrating them to disperse them evenly. For 1,000 glitter toner particles, the maximum thickness and the major axis length of the glitter toner particles as viewed from above are measured at 1,000x magnification using a color laser microscope "VK-9700" (manufactured by Keyence Corporation), and the arithmetic mean value of these is calculated.

[0054] Average circularity of toner particles A The average circularity of the toner particles A is preferably 0.94 or more, and more preferably 0.95 or more, from the viewpoint of suppressing color variation of images over time under high temperature and high humidity conditions. The upper limit of the average circularity of the toner particles A is not particularly limited, and may be, for example, 0.99. The average circularity of toner particles is calculated by (circular equivalent perimeter) / (perimeter) [(perimeter of a circle having the same projected area as the particle image) / (perimeter of the particle projected image)]. Specifically, this value is measured by the following method. First, the toner particles to be measured are sucked and collected, forming a flat flow, and a still image of the particles is captured by instantaneously activating a strobe light, and the particle image is analyzed using a flow-type particle image analyzer (FPIA-3000 manufactured by Sysmex Corporation).The number of samples to be sampled when calculating the average circularity is 3,500. When the toner contains an external additive, the toner particles to be measured are dispersed in water containing a surfactant, and then ultrasonically treated to obtain toner particles from which the external additive has been removed.

[0055] The components constituting the toner particles A will be described below.

[0056] -Binder resin- Examples of binder resins include homopolymers of monomers such as styrenes (e.g., styrene, parachlorostyrene, α-methylstyrene, etc.), (meth)acrylic acid esters (e.g., methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, etc.), ethylenically unsaturated nitriles (e.g., acrylonitrile, methacrylonitrile, etc.), vinyl ethers (e.g., vinyl methyl ether, vinyl isobutyl ether, etc.), vinyl ketones (vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone, etc.), and olefins (e.g., ethylene, propylene, butadiene, etc.), and vinyl resins made of copolymers of two or more of these monomers. Examples of the binder resin include non-vinyl resins such as epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, and modified rosin, mixtures of these with the vinyl resins, and graft polymers obtained by polymerizing vinyl monomers in the presence of these. Among these, styrene acrylic resin or polyester resin is preferably used. These binder resins may be used alone or in combination of two or more.

[0057] As described above, the toner particles A preferably contain a crystalline resin as one component of the binder resin, and more preferably contain a crystalline resin and an amorphous resin as the binder resin.

[0058] The "crystalline" nature of a resin refers to the presence of a clear endothermic peak rather than a stepwise change in endothermic heat in differential scanning calorimetry (DSC). Specifically, this refers to the half-width of the endothermic peak being within 10°C when measured at a heating rate of 10°C / min. On the other hand, the term "amorphous" for a resin means that the half-width exceeds 10°C, that the endothermic amount exhibits a stepwise change, or that no clear endothermic peak is observed.

[0059] --Crystalline resin-- 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 these, crystalline polyester resins are preferred as the crystalline resin in terms of the mechanical strength and low-temperature fixability of the toner.

[0060] Crystalline polyester resin The crystalline polyester resin may be, for example, a polycondensate of a polycarboxylic acid and a polyhydric alcohol. Note that, as the crystalline polyester resin, a commercially available product or a synthesized product may be used. Here, the crystalline polyester resin is preferably a polycondensate using a polymerizable monomer having a linear aliphatic group rather than a polymerizable monomer having an aromatic group, since it easily forms a crystalline structure.

[0061] Examples of polycarboxylic acids include aliphatic dicarboxylic acids (e.g., oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, etc.), aromatic dicarboxylic acids (e.g., dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalene-2,6-dicarboxylic acid), anhydrides thereof, and lower alkyl esters thereof (e.g., having 1 to 5 carbon atoms). The polycarboxylic acid may be a tricarboxylic or higher carboxylic acid having a crosslinked or branched structure in combination with a dicarboxylic acid. Examples of the tricarboxylic acid include aromatic carboxylic acids (e.g., 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, etc.), anhydrides thereof, and lower alkyl esters thereof (e.g., having 1 to 5 carbon atoms). As the polycarboxylic acid, a dicarboxylic acid having a sulfonic acid group and a dicarboxylic acid having an ethylenic double bond may be used in combination with these dicarboxylic acids. The polycarboxylic acids may be used alone or in combination of two or more.

[0062] Examples of polyhydric alcohols include aliphatic diols (for example, straight-chain aliphatic diols having 7 to 20 carbon atoms in the main chain). Examples of aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, and 1,14-eicosanedecanediol. Among these, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol are preferred as aliphatic diols. The polyhydric alcohol may be a trihydric or higher alcohol having a crosslinked or branched structure, such as glycerin, trimethylolethane, trimethylolpropane, or pentaerythritol, in combination with the diol. The polyhydric alcohols may be used alone or in combination of two or more.

[0063] Here, the polyhydric alcohol has an aliphatic diol content of 80 mol % or more, preferably 90 mol % or more.

[0064] The melting temperature of the crystalline polyester resin is preferably 50°C or higher and 100°C or lower, more preferably 55°C or higher and 90°C or lower, and even more preferably 60°C or higher and 85°C or lower. The melting temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC) using the "melting peak temperature" described in the method for determining the melting temperature in JIS K7121-1987 "Method for measuring transition temperatures of plastics."

[0065] The weight average molecular weight (Mw) of the crystalline polyester resin is preferably 6,000 or more and 35,000 or less. The weight-average molecular weight is measured by gel permeation chromatography (GPC). Molecular weight measurements by GPC are performed using a Tosoh GPC HLC-8120GPC measuring device, a Tosoh TSKgel SuperHM-M (15 cm) column, and THF solvent. The weight-average molecular weight is calculated from the measurement results using a molecular weight calibration curve created with monodisperse polystyrene standard samples.

[0066] The crystalline polyester resin can be obtained by a known manufacturing method, for example, in the same manner as the amorphous polyester described below.

[0067] --Amorphous resin-- Examples of amorphous resins include known amorphous resins such as amorphous polyester resins, amorphous vinyl resins (e.g., styrene-acrylic resins), epoxy resins, polycarbonate resins, polyurethane resins, etc. Among these, amorphous polyester resins and amorphous vinyl resins (particularly styrene-acrylic resins) are preferred, and amorphous polyester resins are more preferred.

[0068] Styrene acrylic resin Examples of styrene-acrylic resins include copolymers obtained by copolymerizing at least styrenes and (meth)acrylic esters. The styrene-acrylic resin may also be a copolymer obtained by polymerizing other monomers in addition to styrenes and (meth)acrylic esters. The term "(meth)acrylic" includes both "acrylic" and "methacrylic".

[0069] Styrenes are monomers having a styrene skeleton, and specific examples thereof include styrene, vinylnaphthalene, alkyl-substituted styrenes such as α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, and pn-dodecylstyrene, aryl-substituted styrenes such as p-phenylstyrene, alkoxy-substituted styrenes such as p-methoxystyrene, halogen-substituted styrenes such as p-chlorostyrene and 3,4-dichlorostyrene, nitro-substituted styrenes such as m-nitrostyrene, o-nitrostyrene, and p-nitrostyrene, and fluorine-substituted styrenes such as 4-fluorostyrene and 2,5-difluorostyrene. Among these, preferred styrenes include styrene, p-ethylstyrene, and pn-butylstyrene. These styrenes may be used alone or in combination of two or more.

[0070] The (meth)acrylic acid esters are monomers having a structure in which (meth)acrylic acid is esterified, and specific examples of the (meth)acrylic acid esters include n-methyl (meth)acrylate, n-ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, n-lauryl (meth)acrylate, n-tetradecyl (meth)acrylate, and p) (meth)acrylic acid alkyl esters such as n-hexadecyl acrylate, n-octadecyl (meth)acrylate, isopropyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, isopentyl (meth)acrylate, amyl (meth)acrylate, neopentyl (meth)acrylate, isohexyl (meth)acrylate, isoheptyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate; (Meth)acrylic acid carboxy-substituted alkyl esters such as β-carboxyethyl (meth)acrylate; hydroxy-substituted alkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; (meth)acrylic acid alkoxy-substituted alkyl esters such as 2-methoxyethyl (meth)acrylate; etc.

[0071] Among these (meth)acrylic acid esters, (meth)acrylic acid esters having an alkyl group with 2 to 14 carbon atoms (preferably 2 to 10 carbon atoms, more preferably 3 to 8 carbon atoms) are preferred. These (meth)acrylic acid esters may be used alone or in combination of two or more.

[0072] Examples of other monomers include (meth)acrylic acid, ethylenically unsaturated nitriles (acrylonitrile, methacrylonitrile, etc.), vinyl ethers (vinyl methyl ether, vinyl isobutyl ether, etc.), vinyl ketones (vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone, etc.), divinyls (divinyl adipate, etc.), olefins (ethylene, propylene, butadiene, etc.), thiols (dodecanethiol, etc.), and dicarboxylic acids (decanediol acrylate, etc.).

[0073] In the styrene-acrylic resin, the proportion of styrenes in all polymer components is 60% by mass or more, preferably 65% ​​by mass or more and 90% by mass or less, and more preferably 70% by mass or more and 85% by mass or less. On the other hand, the proportion of (meth)acrylic acid esters in all polymer components is preferably 10% by mass or more and 40% by mass or less, and more preferably 10% by mass or more and 35% by mass or less.

[0074] The glass transition temperature (Tg) of the styrene acrylic resin is preferably 45°C or higher and 115°C or lower, and more preferably 45°C or higher and 105°C or lower. The glass transition temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC), and more specifically, is determined from the "extrapolated glass transition onset temperature" described in JIS K 7121 1987 "Method for measuring transition temperatures of plastics."

[0075] The weight average molecular weight (Mw) of the styrene acrylic resin is preferably 5,000 or more and 700,000 or less, and more preferably 7,000 or more and 300,000 or less. The number average molecular weight (Mn) of the styrene acrylic resin is preferably 2,000 or more and 100,000 or less. The molecular weight distribution Mw / Mn of the styrene acrylic resin is preferably 1.0 or more and 100 or less, and more preferably 1.2 or more and 50 or less. The weight-average molecular weight and number-average molecular weight are measured by gel permeation chromatography (GPC). Molecular weight measurements by GPC are performed using a Tosoh GPC HLC-8120GPC measuring device and a Tosoh TSKgel SuperHM-M (15 cm) column in THF solvent. The weight-average molecular weight and number-average molecular weight are calculated from the measurement results using a molecular weight calibration curve prepared with monodisperse polystyrene standard samples.

[0076] Amorphous polyester resin Examples of the amorphous polyester resin include a condensation polymer of a polycarboxylic acid and a polyhydric alcohol. Note that, as the amorphous polyester resin, a commercially available product or a synthesized product may be used.

[0077] Examples of polycarboxylic acids include aliphatic dicarboxylic acids (such as oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, alkenylsuccinic acid, adipic acid, and sebacic acid), alicyclic dicarboxylic acids (such as cyclohexanedicarboxylic acid), aromatic dicarboxylic acids (such as terephthalic acid, isophthalic acid, orthophthalic acid, and naphthalenedicarboxylic acid), anhydrides thereof, and lower alkyl esters thereof (e.g., having 1 to 5 carbon atoms). Among these, aromatic dicarboxylic acids are preferred as polycarboxylic acids. The polycarboxylic acid may be a trivalent or higher carboxylic acid having a crosslinked or branched structure in combination with a dicarboxylic acid. Examples of the trivalent or higher carboxylic acid include trimellitic acid, pyromellitic acid, anhydrides thereof, and lower alkyl esters thereof (e.g., having 1 to 5 carbon atoms). The polycarboxylic acids may be used alone or in combination of two or more.

[0078] Examples of polyhydric alcohols include aliphatic diols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, etc.), alicyclic diols (e.g., cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, etc.), and aromatic diols (e.g., ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, etc.). Among these, preferred polyhydric alcohols are aromatic diols and alicyclic diols, and more preferred are aromatic diols. As the polyhydric alcohol, a trihydric or higher polyhydric alcohol having a crosslinked or branched structure may be used in combination with the diol. Examples of trihydric or higher polyhydric alcohols include glycerin, trimethylolpropane, and pentaerythritol. The polyhydric alcohols may be used alone or in combination of two or more.

[0079] The glass transition temperature (Tg) of the amorphous polyester resin is preferably 50°C or higher and 120°C or lower, and more preferably 50°C or higher and 110°C or lower. The glass transition temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC), more specifically, from the "extrapolated glass transition onset temperature" described in JIS K 7121-1987 "Method for measuring transition temperatures of plastics."

[0080] The weight average molecular weight (Mw) of the amorphous polyester resin is preferably 5,000 or more and 1,000,000 or less, and more preferably 7,000 or more and 500,000 or less. The number average molecular weight (Mn) of the amorphous polyester resin is preferably 2,000 or more and 100,000 or less. The molecular weight distribution Mw / Mn of the amorphous polyester resin is preferably 1.5 or more and 100 or less, and more preferably 2 or more and 60 or less. The weight-average molecular weight and number-average molecular weight are measured by gel permeation chromatography (GPC). Molecular weight measurements by GPC are performed using a Tosoh GPC HLC-8120GPC measuring device and a Tosoh TSKgel SuperHM-M (15 cm) column in THF solvent. The weight-average molecular weight and number-average molecular weight are calculated from the measurement results using a molecular weight calibration curve prepared with monodisperse polystyrene standard samples.

[0081] The amorphous polyester resin can be obtained by a known manufacturing method, for example, by carrying out the reaction at a polymerization temperature of 180°C or higher and 230°C or lower, reducing the pressure in the reaction system as necessary, and removing water and alcohol generated during the condensation. If the raw material monomer is not soluble or compatible at the reaction temperature, a high-boiling solvent may be added as a solubilizer to dissolve it. In this case, the polycondensation reaction is carried out while distilling off the solubilizer. If a monomer with poor compatibility is present, it is advisable to first condense the poorly compatible monomer with the acid or alcohol to be polycondensed, and then polycondense the monomer with the main component.

[0082] Amorphous resins having an amorphous polyester resin segment and a styrene-acrylic resin segment (hereinafter also referred to as "hybrid amorphous resins") The hybrid amorphous resin is an amorphous resin in which an amorphous polyester resin segment and a styrene-acrylic resin segment are chemically bonded. Examples of hybrid amorphous resins include resins having a main chain made of polyester resin and a side chain made of styrene-acrylic resin chemically bonded to the main chain; resins having a main chain made of styrene-acrylic resin and a side chain made of polyester resin chemically bonded to the main chain; resins having a main chain made of polyester resin and styrene-acrylic resin chemically bonded to the main chain; and resins having a main chain made of polyester resin and styrene-acrylic resin chemically bonded to the main chain, and at least one side chain made of polyester resin chemically bonded to the main chain and a side chain made of styrene-acrylic resin chemically bonded to the main chain.

[0083] The amorphous polyester resin and styrene-acrylic resin in each segment are as described above, and therefore further explanation is omitted.

[0084] The total amount of the polyester resin segment and the styrene-acrylic resin segment in the entire hybrid amorphous resin is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably 100% by mass.

[0085] In the hybrid amorphous resin, the proportion of the styrene-acrylic resin segment in the total amount of the polyester resin segment and the styrene-acrylic resin segment is preferably 20% by mass or more and 60% by mass or less, more preferably 25% by mass or more and 55% by mass or less, and even more preferably 30% by mass or more and 50% by mass or less.

[0086] The hybrid amorphous resin is preferably produced by any one of the following methods (i) to (iii). (i) After preparing a polyester resin segment by condensation polymerization of a polyhydric alcohol and a polycarboxylic acid, a monomer constituting a styrene-acrylic resin segment is subjected to addition polymerization. (ii) After preparing a styrene-acrylic resin segment by addition polymerization of an addition-polymerizable monomer, polyhydric alcohol and polycarboxylic acid are condensation-polymerized. (iii) Polycondensation of a polyhydric alcohol and a polycarboxylic acid and addition polymerization of an addition-polymerizable monomer are carried out in parallel.

[0087] The content of the binder resin is, for example, preferably 40% by mass to 95% by mass, more preferably 50% by mass to 90% by mass, and even more preferably 60% by mass to 85% by mass, based on the total mass of the toner particles A.

[0088] -Brilliant pigments- Examples of the luster pigment include pigments that can impart a sense of luster such as metallic luster (luster pigments). Toner particles A contain at least an aluminum pigment as a luster pigment. Examples of the aluminum pigment include a metal pigment of aluminum alone. Toner particles A may further contain other luster pigments. The proportion of the aluminum pigment relative to the total luster pigment is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. Other luster pigments include, for example, powders of metals other than aluminum, such as brass, bronze, nickel, stainless steel, and zinc; mica coated with titanium oxide, yellow iron oxide, and the like; flaky inorganic crystalline substrates coated with barium sulfate, layered silicates, layered aluminum silicates, and the like; single-crystal plate-like titanium oxide; basic carbonates; bismuth acid oxychloride; natural guanine; flaky glass powder; and metal-deposited flaky glass powder, and there are no particular limitations on these pigments as long as they have luster.

[0089] The shape of the bright pigment is preferably flat (scale-like) from the viewpoint of providing high brightness in a fixed image. The flat bright pigment will be described below. The average length in the major axis direction of the flat bright pigment is preferably 1 μm or more and 30 μm or less, more preferably 3 μm or more and 20 μm or less, and even more preferably 5 μm or more and 15 μm or less. The ratio (aspect ratio) of the average length in the major axis direction to the average length in the thickness direction of the luster pigment, which is taken as 1, is preferably 5 or more and 200 or less, more preferably 10 or more and 100 or less, and even more preferably 30 or more and 70 or less.

[0090] The average length and aspect ratio of each of the bright pigments are measured by the following method: Using a scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation), photographs of pigment particles are taken at a measurable magnification (300 to 100,000 times), and the resulting images of the pigment particles are converted into two-dimensional images, and the lengths of each particle in the major axis direction and thickness direction are measured to calculate the average length of the bright pigment in the major axis direction and the aspect ratio.

[0091] The volume average particle size of the bright pigment is preferably 1.0 μm or more and 20.0 μm or less, and more preferably 2.0 μm or more and 15.0 μm or less. When the volume average particle size of the bright pigment is 1.0 μm or more, the brightness of the resulting image is excellent. If the volume average particle size of the bright pigment is 20.0 μm or less, the resulting toner has excellent charging characteristics and transfer unevenness is suppressed.

[0092] The volume average particle size of the bright pigment is measured as follows. Based on the particle size distribution measured with a measuring instrument such as Multisizer II (manufactured by Coulter), a cumulative distribution of the volume is drawn for each divided particle size range (channel) from the smallest diameter side, and the particle size at which the cumulative 50% is reached is taken as the volume-average particle size. The volume average particle size of the glitter pigment in the toner particles after production is measured by mixing and stirring the toner with a solvent that is capable of dissolving only the toner resin but not the glitter pigment, and after the toner resin has sufficiently dissolved in the solvent, the glitter pigment is subjected to solid-liquid separation, and the volume average particle size is measured using the same particle size distribution measuring device as above.

[0093] The content of the bright pigment relative to the total mass of toner particles A is preferably 1% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 50% by mass or less, and even more preferably 5% by mass or more and 40% by mass or less.

[0094] -Colorants other than photoluminescent pigments- The toner particles A may contain a colorant other than the luster pigment, if necessary. As colorants other than the luster pigment, colorants similar to those used in general color toners such as Toner B and Toner C described below are used.

[0095] The content of colorants other than the luster pigment is preferably 30% by mass or less, and more preferably 25% by mass or less, based on the total amount of toner particles A, from the viewpoint of reproducing images with a wide color gamut.

[0096] -Mold release agent- Examples of release agents include hydrocarbon waxes, natural waxes such as carnauba wax, rice wax, and candelilla wax, synthetic or mineral / petroleum waxes such as montan wax, and ester waxes such as fatty acid esters and montanic acid esters, but are not limited thereto.

[0097] The melting temperature of the release agent is preferably 50°C or higher and 110°C or lower, and more preferably 60°C or higher and 100°C or lower. The melting temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC) by using the "melting peak temperature" as described in the method for determining the melting temperature in JIS K 7121-1987 "Method for measuring transition temperatures of plastics."

[0098] 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 total amount of the toner particles A.

[0099] -Other additives- Examples of other additives include well-known additives such as magnetic materials, charge control agents, inorganic powders, etc. These additives are contained in the toner particles A as internal additives.

[0100] -Characteristics of toner particles A- The toner particles A may be toner particles having a single layer structure, or may be toner particles having a so-called core-shell structure composed of a core (core particle) and a coating layer (shell layer) that coats the core. Here, the toner particles having a core-shell structure may preferably be composed of a core containing a binder resin, an aluminum pigment, and, if necessary, other additives such as a release agent, and a coating layer containing the binder resin.

[0101] (external additives) Toner A may contain an external additive. Examples of external additives include inorganic particles, such as SiO2, TiO2, Al2O3, CuO, ZnO, SnO2, CeO2, Fe2O3, MgO, BaO, CaO, K2O, Na2O, ZrO2, CaO·SiO2, and K2O·(TiO2). n , Al2O3·2SiO2, CaCO3, MgCO3, BaSO4, MgSO4, etc.

[0102] The surfaces of inorganic particles as external additives are preferably subjected to a hydrophobic treatment. The hydrophobic treatment is carried out, for example, by immersing the inorganic particles in a hydrophobic treatment agent. The hydrophobic treatment agent is not particularly limited, and examples thereof include silane coupling agents, silicone oils, titanate coupling agents, and aluminum coupling agents. These may be used alone or in combination of two or more. The amount of the hydrophobic treatment agent is usually, for example, 1 part by mass or more and 10 parts by mass or less per 100 parts by mass of the inorganic particles.

[0103] Examples of external additives include resin particles (resin particles such as polystyrene, polymethyl methacrylate (PMMA), and melamine resin), cleaning agents (for example, metal salts of higher fatty acids such as zinc stearate, and particles of fluorine-based polymers).

[0104] The amount of the external additive added is, for example, preferably 0.01% by mass to 5% by mass, more preferably 0.01% by mass to 2.0% by mass, based on the total mass of the toner particles A.

[0105] <Toner B and Toner C> Toner B is configured to contain toner particles B containing a phthalocyanine dye and, if necessary, an external additive. Toner B can be a cyan toner containing cyan toner particles containing a phthalocyanine dye, which is a cyan dye, as a colorant. Toner C is composed of toner particles C containing a pyrazolotriazole dye and, if necessary, an external additive. Toner C is, for example, a magenta toner containing magenta toner particles containing a pyrazolotriazole dye, which is a magenta dye, as a colorant.

[0106] (Toner particles B and toner particles C) The toner particles B contain, for example, a phthalocyanine dye which is a cyan dye, a binder resin, and, if necessary, a release agent and other components. As described above, the toner particles B preferably contain a crystalline resin from the viewpoint of further suppressing color variation of images over time under high temperature and high humidity conditions. The crystalline resin is contained in the toner particles B, for example, as one component of the binder resin constituting the toner particles B. The toner particles C contain, for example, a pyrazolotriazole dye which is a magenta dye, a binder resin, and, if necessary, a release agent and other components. As described above, the toner particles C preferably contain a crystalline resin from the viewpoint of further suppressing color variation of images over time under high temperature and high humidity conditions. The crystalline resin is contained in the toner particles C, for example, as one component of the binder resin that constitutes the toner particles C. The components constituting the toner particles B and C will be described below.

[0107] -Binder resin- As the binder resin, the same binder resins as those used in the toner particles A are used. As described above, toner particles B and toner particles C each preferably contain a crystalline resin as one component of the binder resin. Furthermore, toner particles B and toner particles C each more preferably contain a crystalline resin and an amorphous resin as the binder resin. When the toner particles B and the toner particles C contain a crystalline resin, the crystalline resin is preferably a crystalline polyester resin. When toner particles B and toner particles C contain an amorphous resin, the amorphous resin is preferably an amorphous polyester resin or an amorphous vinyl resin, respectively, more preferably an amorphous polyester resin or a styrene-acrylic resin, and even more preferably an amorphous polyester resin.

[0108] When toner particles A, toner particles B, and toner particles C all contain a crystalline resin, it is preferable that the crystalline resin contained in each of toner particles A, toner particles B, and toner particles C all contain a crystalline polyester resin. When toner particles A, toner particles B, and toner particles C all contain an amorphous resin, the combination of the amorphous resins contained in toner particles A, toner particles B, and toner particles C is not particularly limited. When the amorphous resin contained in toner particle A is referred to as amorphous resin A, the amorphous resin contained in toner particle B is referred to as amorphous resin B, and the amorphous resin contained in toner particle C is referred to as amorphous resin C, amorphous resin A, amorphous resin B, and amorphous resin C may all contain amorphous polyester resins, amorphous resin A, amorphous resin B, and amorphous resin C may all contain styrene-acrylic resins, amorphous resin A may contain styrene-acrylic resin and amorphous resin B and amorphous resin C may contain amorphous polyester resins, or amorphous resin A may contain amorphous polyester resin and amorphous resin B and amorphous resin C may contain styrene-acrylic resin.

[0109] 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 even more preferably 60% by mass or more and 85% by mass or less, based on the total amount of toner particles B or toner particles C.

[0110] -Phthalocyanine dyes- Phthalocyanine dyes are dyes that are compounds having a phthalocyanine skeleton. The phthalocyanine dye preferably contains a phthalocyanine compound represented by the following formula (I): When the phthalocyanine dye contains the phthalocyanine compound represented by formula (I), color variation of images over time under high temperature and high humidity conditions is suppressed compared to, for example, when the phthalocyanine dye is a compound represented by formula (I) in which M in formula (I) is copper. The reason for this is not clear, but it is presumed that, compared to copper phthalocyanine compounds, the phthalocyanine compound represented by formula (I) can be dispersed in a nearly uniform state in the toner, thereby further enhancing the chloride ion capturing effect.

[0111] [ka]

[0112] In the formula (I), M represents a silicon atom, a germanium atom, or a tin atom; Ra1 to Ra4 each independently represent an electron-withdrawing group; na1 to na4 each independently represent an integer of 0 to 4; and Z1 and Z2 each independently represent a hydroxy group, an aryloxy group having 6 to 18 carbon atoms, an alkoxy group having 1 to 22 carbon atoms, or a group represented by the following formula (II):

[0113] [ka]

[0114] In the formula (II), R3 to R5 each independently represent an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.

[0115] The phthalocyanine compound represented by formula (I) has axial ligands (Z1 and Z2) with a bulky structure. The presence of such bulky axial ligands facilitates more uniform dispersion of the phthalocyanine compound in toner particles and fixed images, further enhancing the color development of the cyan toner. Furthermore, even in superimposed images with other color toners, the bulky phthalocyanine compound is less likely to move, making it less likely for the cyan toner and other color toners to mix. This makes it possible to suppress color turbidity and achieve excellent color development.

[0116] In the formula (I), M represents a silicon atom (Si), a germanium atom (Ge), or a tin atom (Sn). From the viewpoint of suppressing color mixing with other color toners due to the bulky structure and from the viewpoint of excellent color development properties of the compound itself, M is preferably a silicon atom (Si).

[0117] In the formula (I), Ra1 to Ra4 (Ra1, Ra2, Ra3, and Ra4) are each independently an electron-withdrawing group. Examples of the electron-withdrawing group include a chlorine group (-Cl), a monochlorodihalogenomethyl group (-CClX2), a trifluoromethyl group (-CF3), and a nitro group (-NO2). In the monochlorodihalogeno group (-CClX2), "X" represents a halogen atom.

[0118] In the formula (I), na1 to na4 (na1, na2, na3, and na4) each independently represent an integer of 0 to 4. When na1 to na4 are integers of 0 to 4, the desired color gamut can be covered as a colorant.

[0119] In the formula (I), Z1 and Z2 are each independently a hydroxy group, an aryloxy group having 6 to 18 carbon atoms, an alkoxy group having 1 to 22 carbon atoms, or a group represented by the formula (II).

[0120] Examples of the aryloxy group having 6 to 18 carbon atoms include a phenoxy group, an o-tolyloxy group, an m-tolyloxy group, a p-tolyloxy group, a 2,3-xylyloxy group, a 2,4-xylyloxy group, a 2,5-xylyloxy group, a 2,6-xylyloxy group, a 3,4-xylyloxy group, a 3,5-xylyloxy group, a 2,3,4-trimethylphenoxy group, a 2,3,5-trimethylphenoxy group, a 2,3,6-trimethylphenoxy group, a 2,4,6-trimethylphenoxy group, a 3,4,5-trimethylphenoxy group, a 2,3,4,5-tetramethylphenoxy group, and a 2,3,4,6 n-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, isobutylphenoxy group, n-pentylphenoxy group, neopentylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-dodecylphenoxy group, n-tetradecylphenoxy group, naphthyloxy group, anthracenyloxy group, and the like.

[0121] Examples of the alkoxy group having 1 to 22 carbon atoms include linear, branched, and cyclic alkoxy groups such as methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, t-butyloxy, n-pentyloxy, neopentyloxy, n-hexyloxy, isohexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-octadecyloxy, n-eicosyloxy, n-docosyloxy, 2-ethylhexyloxy, 3-ethylheptyloxy, 3-ethyldecyloxy, 2-hexyldecyloxy, cyclopentyloxy, cyclohexyloxy, and cycloheptyloxy.

[0122] From the viewpoint of suppressing color mixing with other color toners due to the bulky structure and from the viewpoint of excellent color development properties of the compound itself, Z1 and Z2 are preferably groups represented by the formula (II) above.

[0123] Examples of the alkyl group having 1 to 6 carbon atoms used in R3 to R5 in the formula (II) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, a neopentyl group, and an n-hexyl group.

[0124] Examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, an o-, m-, or p-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, a mesityl group, a naphthyl group, an anthryl group, a phenanthryl group, a triphenylenyl group, a tetracenyl group, a chrysenyl group, a pyrenyl group, a pentacenyl group, and a picenyl group.

[0125] Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a t-butyloxy group, an n-pentyloxy group, a neopentyloxy group, an n-hexyloxy group, and an isohexyloxy group.

[0126] Preferred examples of the phthalocyanine compound represented by the formula (I) are shown in the following Table 1. In Table 1, "-" indicates that the compound does not have the corresponding substituent.

[0127] [Table 1]

[0128] The phthalocyanine compounds represented by the formula (I) may be used singly or in combination of two or more.

[0129] The phthalocyanine compound represented by the formula (I) may be a commercially available product or a synthetic product. As the synthesis method, a known method may be used. For example, the method described in JP-A-2011-99047 may be adopted.

[0130] -Pyrazolotriazole-based dye- The pyrazolotriazole-based dye is a dye that is a compound having a pyrazolotriazole skeleton. The pyrazolotriazole-based dye preferably contains a pyrazolotriazole-based compound represented by the following formula (III).

[0131] [Chemical formula]

[0132] In formula (III), Rx1 and Rx2 each independently represent an alkyl group which may have a substituent, Lx represents a hydrogen atom or an alkyl group which may have a substituent, Gx1 represents an alkyl group having 2 or more carbon atoms, Gx2 represents an aryl group or an alkyl group which may have a substituent, Gx3 represents a hydrogen atom, a halogen atom, Gx4-CO-NH-, or Gx5-N(Gx6)-CO-, Gx4 represents an aryl group or an alkyl group which may have a substituent, Gx5 and Gx6 each independently represent a hydrogen atom or an alkyl group which may have a substituent, and Qx1 to Qx5 each independently represent a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent.

[0133] [[Rx1 and Rx2]] Rx1 and Rx2 are each independently an alkyl group which may have a substituent, and it is preferably an alkyl group. Here, the alkyl group which may have a substituent includes not only an alkyl group (a substituent consisting only of an alkyl group) but also a substituent formed by substituting one or more atoms constituting the alkyl group with a substituent other than an alkyl group (for example, an alkenyl group).

[0134] The alkyl group may be any of a linear alkyl group, a branched alkyl group, and a cycloalkyl group, but is preferably a linear alkyl group or a branched alkyl group.

[0135] Examples of the straight-chain alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group, a tridecyl group, a tetradecyl group, and a pentadecyl group.

[0136] Examples of branched alkyl groups include an isopropyl group, an isobutyl group, a tert-butyl group, an amyl group, and an isoamyl group.

[0137] Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a 4-tert-butyl-cyclohexyl group.

[0138] The total number of carbon atoms contained in the alkyl group represented by Rx1 and the alkyl group represented by Rx2 is preferably 8 or more, more preferably 12 or more, and even more preferably 16 or more.

[0139] Examples of the substituent in the alkyl group that may have a substituent include an alkenyl group, an alkynyl group, an aryl group, an aliphatic heterocyclic group, an aromatic heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, a phosphoryl group, a sulfamoyl group, an acyl group, an acyloxy group, an amido group, a carbamoyl group, a ureido group, a sulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, or an amino group. That is, Rx1 and Rx2 may each independently be configured by substituting one or more atoms constituting the alkyl group with any of these substituents. The number of substituents substituting one or more atoms constituting the alkyl group is not limited to one and may be two or more.

[0140] The alkenyl group is, for example, a vinyl group or an allyl group. The alkynyl group is, for example, an ethynyl group or a propargyl group.

[0141] The aryl group is, for example, a phenyl group or a naphthyl group. Examples of the aliphatic heterocyclic group include a pyrrolidyl group, an imidazolidyl group, a morpholyl group, and an oxazolidyl group.

[0142] Examples of the aromatic heterocyclic group include a furyl group, a thienyl group, a pyridyl group, a pyridazyl group, a pyrimidyl group, a pyrazyl group, a triazyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, a benzimidazolyl group, a benzoxazolyl group, a quinazolyl group, and a phthalazyl group.

[0143] Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, and a dodecyloxy group.

[0144] Examples of the cycloalkoxy group include a cyclopentyloxy group and a cyclohexyloxy group.

[0145] The aryloxy group is, for example, a phenoxy group or a naphthyloxy group. Examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, a pentylthio group, a hexylthio group, an octylthio group, and a dodecylthio group.

[0146] The cycloalkylthio group includes, for example, a cyclopentylthio group or a cyclohexylthio group.

[0147] The arylthio group includes, for example, a phenylthio group or a naphthylthio group. Examples of the alkoxycarbonyl group include a methyloxycarbonyl group, an ethyloxycarbonyl group, a butyloxycarbonyl group, an octyloxycarbonyl group, and a dodecyloxycarbonyl group.

[0148] The aryloxycarbonyl group includes, for example, a phenyloxycarbonyl group or a naphthyloxycarbonyl group.

[0149] The phosphoryl group may be a methoxyphosphoryl group or a diphenylphosphoryl group. Examples of the sulfamoyl group include an aminosulfonyl group, a methylaminosulfonyl group, a dimethylaminosulfonyl group, a butylaminosulfonyl group, a hexylaminosulfonyl group, a cyclohexylaminosulfonyl group, an octylaminosulfonyl group, a dodecylaminosulfonyl group, a phenylaminosulfonyl group, a naphthylaminosulfonyl group, and a 2-pyridylaminosulfonyl group.

[0150] Examples of the acyl group include an acetyl group, an ethylcarbonyl group, a propylcarbonyl group, a pentylcarbonyl group, a cyclohexylcarbonyl group, an octylcarbonyl group, a 2-ethylhexylcarbonyl group, a dodecylcarbonyl group, a phenylcarbonyl group, a naphthylcarbonyl group, and a pyridylcarbonyl group.

[0151] Examples of the acyloxy group include an acetyloxy group, an ethylcarbonyloxy group, a butylcarbonyloxy group, an octylcarbonyloxy group, a dodecylcarbonyloxy group, and a phenylcarbonyloxy group.

[0152] Examples of the amide group include a methylcarbonylamino group, an ethylcarbonylamino group, a dimethylcarbonylamino group, a propylcarbonylamino group, a pentylcarbonylamino group, a cyclohexylcarbonylamino group, a 2-ethylhexylcarbonylamino group, an octylcarbonylamino group, a dodecylcarbonylamino group, a phenylcarbonylamino group, and a naphthylcarbonylamino group.

[0153] Examples of the carbamoyl group include an aminocarbonyl group, a methylaminocarbonyl group, a dimethylaminocarbonyl group, a propylaminocarbonyl group, a pentylaminocarbonyl group, a cyclohexylaminocarbonyl group, an octylaminocarbonyl group, a 2-ethylhexylaminocarbonyl group, a dodecylaminocarbonyl group, a phenylaminocarbonyl group, a naphthylaminocarbonyl group, and a 2-pyridylaminocarbonyl group.

[0154] Examples of the ureido group include a methylureido group, an ethylureido group, a pentylureido group, a cyclohexylureido group, an octylureido group, a dodecylureido group, a phenylureido group, a naphthylureido group, and a 2-pyridylaminoureido group.

[0155] Examples of the sulfinyl group include a methylsulfinyl group, an ethylsulfinyl group, a butylsulfinyl group, a cyclohexylsulfinyl group, a 2-ethylhexylsulfinyl group, a dodecylsulfinyl group, a phenylsulfinyl group, a naphthylsulfinyl group, and a 2-pyridylsulfinyl group.

[0156] Examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a cyclohexylsulfonyl group, a 2-ethylhexylsulfonyl group, and a dodecylsulfonyl group.

[0157] Examples of the arylsulfonyl group include a phenylsulfonyl group, a naphthylsulfonyl group, and a 2-pyridylsulfonyl group.

[0158] Examples of the amino group include an amino group, an ethylamino group, a dimethylamino group, a butylamino group, a dibutylamino group, a cyclopentylamino group, a 2-ethylhexylamino group, a dodecylamino group, an anilino group, a naphthylamino group, and a 2-pyridylamino group.

[0159] In addition to the above-mentioned substituents, the substituent in the alkyl group which may have a substituent may be, for example, an azo group such as a phenylazo group, an alkylsulfonyloxy group such as a methanesulfonyloxy group, a cyano group, a nitro group, a halogen atom (for example, a fluorine atom, a chlorine atom, or a bromine atom; the same applies hereinafter), or a hydroxyl group.

[0160] The substituent in the alkyl group which may have a substituent may be any of the substituents described above, but is preferably an alkoxy group, an aryl group, a cycloalkoxy group, a halogen atom, or a hydroxyl group.

[0161] The substituent in the alkyl group which may have a substituent may have a substituent other than the aforementioned substituent bonded thereto.

[0162] < <lx>> Lx may be a hydrogen atom or an alkyl group which may have a substituent, but is preferably a hydrogen atom. When Lx is an alkyl group which may have a substituent, Lx may be any of the substituents represented by Rx1 and Rx2, and is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group.

[0163] < <gx1>> Gx1 is an alkyl group having two or more carbon atoms. The alkyl group may be any of a linear alkyl group, a branched alkyl group, and a cycloalkyl group, but is preferably a branched alkyl group, more preferably a tertiary alkyl group, and further preferably a tert-butyl group.

[0164] Examples of the straight-chain alkyl group include an ethyl group, a propyl group, an n-butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group, a tridecyl group, a tetradecyl group, and a pentadecyl group.

[0165] Examples of branched alkyl groups include an isopropyl group, an isobutyl group, a tert-butyl group, an amyl group, and an isoamyl group.

[0166] Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a 4-tert-butyl-cyclohexyl group.

[0167] < <gx2>> Gx2 may be an aryl group or an alkyl group which may have a substituent. Here, the aryl group is, for example, a phenyl group or a naphthyl group. The alkyl group which may have a substituent is any of the substituents represented by Rx1 and Rx2. Among these, Gx2 is preferably an alkyl group, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably a methyl group or an ethyl group.

[0168] < <gx3>> Gx3 is any one of a hydrogen atom, a halogen atom, Gx4-CO-NH-, and Gx5-N(Gx6)-CO-, and among these, a hydrogen atom is preferred.

[0169] < <gx4>> Gx4 may be an aryl group or an alkyl group which may have a substituent. Here, the aryl group is, for example, a phenyl group or a naphthyl group, etc. Further, the alkyl group which may have a substituent is any of the substituents represented by the above Rx1 and Rx2, and it is preferably an alkyl group represented by the above Rx1 and Rx2.

[0170] <<Gx5 and Gx6>> Gx5 and Gx6 are each independently may be a hydrogen atom or an alkyl group which may have a substituent. Here, the alkyl group which may have a substituent is any of the substituents represented by the above Rx1 and Rx2, and it is preferably an alkyl group represented by the above Rx1 and Rx2.

[0171] <<Qx1~Qx5>> Qx1~Qx5 are each independently may be a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent. Here, the alkyl group which may have a substituent is any of the substituents represented by the above Rx1 and Rx2. Preferably, Qx1~Qx5 are each independently any of a hydrogen atom, an alkyl group, a halogen atom, and an alkoxy group. More preferably, any of Qx1~Qx5 is a hydrogen atom.

[0172] Specific examples of the pyrazolotriazole compound represented by the above formula (III) include, in addition to (I-1)~(I-23) shown below, in the following (I-1)~(I-8), (I-11)~(I-16), (I-18), and (I-20)~(I-23), compounds in which Gx1 in the formula (III) is a triethylmethyl group, but it is needless to say that it is not limited to the specific examples shown below.

[0173]

Chemical formula

[0174] [ka]

[0175] [ka]

[0176] [ka]

[0177] The pyrazolotriazole compounds represented by the formula (III) may be used singly or in combination of two or more.

[0178] -Other colorants- The toner particles B may further contain a colorant other than the phthalocyanine dye. The ratio of the phthalocyanine dye to the total colorants contained in the toner particles B is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. The toner particles C may further contain a colorant other than the pyrazolotriazole dye. The ratio of the pyrazolotriazole dye to the total colorants contained in the toner particles C is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more.

[0179] Of the other colorants, known dyes may be used, and examples thereof include various dyes such as acridine-based, xanthene-based, azo-based, benzoquinone-based, azine-based, anthraquinone-based, thioindigo-based, dioxazine-based, thiazine-based, azomethine-based, indigo-based, aniline black-based, polymethine-based, triphenylmethane-based, diphenylmethane-based, and thiazole-based dyes. Other colorants include pigments in addition to dyes. In this embodiment, a "pigment" is a colorant whose solubility in 100 g of water at 23°C and in 100 g of cyclohexanone at 23°C is less than 0.1 g, and a "dye" is a colorant whose solubility in 100 g of water at 23°C or in 100 g of cyclohexanone at 23°C is 0.1 g or more.

[0180] -Acetylacetone metal compounds- From the viewpoints of transparency and suppression of discoloration under high temperature and high humidity conditions, it is preferable that the toner particles B and C each further contain an acetylacetonate metal compound. In particular, in toner particle C, it is estimated that the pyrazolotriazole dye and the acetylacetone metal compound partially form a complex within the toner particle, which acts as a nucleating agent during cooling after toner fixation, inhibits migration to the surface, and provides superior fading inhibition and transparency under high temperature and high humidity conditions.

[0181] The acetylacetone metal compound is not particularly limited, but from the viewpoint of the color transfer suppression property and transparency of the obtained image, an acetylacetone metal compound having an electron-withdrawing group is preferred, an acetylacetone copper, nickel or cobalt compound having an electron-withdrawing group is more preferred, and a compound represented by the following formula (IV) is particularly preferred.

[0182] [ka]

[0183] In formula (IV), R1 and R2 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aliphatic heterocyclic group, an aromatic heterocyclic group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a sulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a cyano group, a trifluoroalkyl group, or a nitro group, at least one of R1 and R2 is an electron-withdrawing group, R3 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aliphatic heterocyclic group, or an aromatic heterocyclic group, R2 and R3 may be bonded to each other to form a ring, and X represents a metal atom of any one of copper, nickel, or cobalt.

[0184] In the compound represented by formula (IV), the total number of carbon atoms in one molecule of the acetylacetone ligand is preferably 25 or less.

[0185] <<R1 and R2>> R1 and R2 are each independently any one of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aliphatic heterocyclic group, an aromatic heterocyclic group, a haloalkyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, an acyl group, an acyloxy group, an amide group, a carbamoyl group, a ureido group, a sulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and an amino group. Although the combination of R1 and R2 is not particularly limited, either one of R1 and R2 is an electron-withdrawing group.

[0186] The alkyl group may be any of a straight-chain alkyl group, a branched alkyl group, and a cycloalkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, an octyl group, a dodecyl group, a tridecyl group, a tetradecyl group, or a pentadecyl group.

[0187] The alkenyl group is, for example, a vinyl group or an allyl group. The alkynyl group is, for example, an ethynyl group or a propargyl group.

[0188] The aryl group is, for example, a phenyl group or a naphthyl group. Examples of the aliphatic heterocyclic group include a pyrrolidyl group, an imidazolidyl group, a morpholyl group, and an oxazolidyl group.

[0189] Examples of the aromatic heterocyclic group include a furyl group, a thienyl group, a pyridyl group, a pyridazyl group, a pyrimidyl group, a pyrazyl group, a triazyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, a benzimidazolyl group, a benzoxazolyl group, a quinazolyl group, and a phthalazyl group.

[0190] The halogen alkyl group may be a monohalogen alkyl group, a dihalogen alkyl group, or a trihalogen alkyl group. The halogen may be fluorine, chlorine, bromine, or iodine. The alkyl group is not particularly limited and may be a methyl group, an ethyl group, a propyl group, or the like.

[0191] Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, and a dodecyloxy group.

[0192] Examples of the cycloalkoxy group include a cyclopentyloxy group and a cyclohexyloxy group.

[0193] The aryloxy group is, for example, a phenoxy group or a naphthyloxy group. Examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, a pentylthio group, a hexylthio group, an octylthio group, and a dodecylthio group.

[0194] Examples of the cycloalkylthio group include a cyclopentylthio group and a cyclohexylthio group.

[0195] The arylthio group includes, for example, a phenylthio group or a naphthylthio group. The alkoxycarbonyl group may be, for example, a methyloxycarbonyl group, an ethyloxycarbonyl group, a butyloxycarbonyl group, an octyloxycarbonyl group, or a dodecyloxycarbonyl group. Examples include an alkoxycarbonyl group.

[0196] The aryloxycarbonyl group includes, for example, a phenyloxycarbonyl group or a naphthyloxycarbonyl group.

[0197] Examples of the sulfamoyl group include an aminosulfonyl group, a methylaminosulfonyl group, a dimethylaminosulfonyl group, a butylaminosulfonyl group, a hexylaminosulfonyl group, a cyclohexylaminosulfonyl group, an octylaminosulfonyl group, a dodecylaminosulfonyl group, a phenylaminosulfonyl group, a naphthylaminosulfonyl group, and a 2-pyridylaminosulfonyl group.

[0198] Examples of the acyl group include an acetyl group, an ethylcarbonyl group, a propylcarbonyl group, a pentylcarbonyl group, a cyclohexylcarbonyl group, an octylcarbonyl group, a 2-ethylhexylcarbonyl group, a dodecylcarbonyl group, a phenylcarbonyl group, a naphthylcarbonyl group, and a pyridylcarbonyl group.

[0199] Examples of the acyloxy group include an acetyloxy group, an ethylcarbonyloxy group, a butylcarbonyloxy group, an octylcarbonyloxy group, a dodecylcarbonyloxy group, and a phenylcarbonyloxy group.

[0200] Examples of the amide group include a methylcarbonylamino group, an ethylcarbonylamino group, a dimethylcarbonylamino group, a propylcarbonylamino group, a pentylcarbonylamino group, a cyclohexylcarbonylamino group, a 2-ethylhexylcarbonylamino group, an octylcarbonylamino group, a dodecylcarbonylamino group, a phenylcarbonylamino group, and a naphthylcarbonylamino group.

[0201] Examples of the carbamoyl group include an aminocarbonyl group, a methylaminocarbonyl group, a dimethylaminocarbonyl group, a propylaminocarbonyl group, a pentylaminocarbonyl group, a cyclohexylaminocarbonyl group, an octylaminocarbonyl group, a 2-ethylhexylaminocarbonyl group, a dodecylaminocarbonyl group, a phenylaminocarbonyl group, a naphthylaminocarbonyl group, and a 2-pyridylaminocarbonyl group.

[0202] Examples of the ureido group include a methylureido group, an ethylureido group, a pentylureido group, a cyclohexylureido group, an octylureido group, a dodecylureido group, a phenylureido group, a naphthylureido group, and a 2-pyridylaminoureido group.

[0203] Examples of the sulfinyl group include a methylsulfinyl group, an ethylsulfinyl group, a butylsulfinyl group, a cyclohexylsulfinyl group, a 2-ethylhexylsulfinyl group, a dodecylsulfinyl group, a phenylsulfinyl group, a naphthylsulfinyl group, and a 2-pyridylsulfinyl group.

[0204] Examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a cyclohexylsulfonyl group, a 2-ethylhexylsulfonyl group, and a dodecylsulfonyl group.

[0205] Examples of the arylsulfonyl group include a phenylsulfonyl group, a naphthylsulfonyl group, and a 2-pyridylsulfonyl group.

[0206] Examples of the amino group include a methylamino group, an ethylamino group, a dimethylamino group, a butylamino group, a cyclopentylamino group, a 2-ethylhexylamino group, a dodecylamino group, Examples include an anilino group, a naphthylamino group, and a 2-pyridylamino group.

[0207] Furthermore, R1 and R2 may each independently represent a cyano group, a nitro group, a halogen atom, or the like, in addition to the above-mentioned substituents.

[0208] Among the above substituents, R1 and R2 are preferably each independently an alkyl group, a trifluoroalkyl group, an aryl group, an aliphatic heterocyclic group, an aromatic heterocyclic group, an alkoxy group, a sulfamoyl group, a ureido group, an amino group, an amido group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, a cyano group, or a halogen atom. R1 and R2 are more preferably each independently an alkyl group, a trifluoroalkyl group, a cyano group, an alkoxy group, an amido group, or a halogen atom, and even more preferably a trifluoroalkyl group, a cyano group, or an alkoxy group.

[0209] R1 and R2 may each independently represent the above-mentioned substituent to which another substituent is bonded. The substituent bonded to the above-mentioned substituent may be the same as the above-mentioned substituent or may be a different substituent from the above-mentioned substituent.

[0210] < <r3>> R3 is any one of an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aliphatic heterocyclic group, an aromatic heterocyclic group, and the ether group shown below. When R3 is an alkyl group, an alkenyl group, an alkynyl group, or an ether group, it preferably has 3 or more carbon atoms. Specific examples of the alkyl group, the alkenyl group, the alkynyl group, the aryl group, and the heterocyclic group may be any one of the specific examples represented by R1 and R2.

[0211] < <x>> X is, for example, any one of a metal atom of copper, nickel, and cobalt, and is preferably copper.

[0212] Specific examples of the compound represented by formula (IV) include (II-1) to (II-85) shown below, but needless to say, the compound is not limited to these specific examples. The structural formula shown below is one of the resonance structures that the example compound can adopt. In the formula, the distinction between the covalent bond shown by a solid line and the coordinate bond shown by a dashed line is merely a formal distinction and does not represent an absolute distinction.

[0213] [ka]

[0214] [ka]

[0215] [ka]

[0216] [ka]

[0217] [ka]

[0218] [ka]

[0219] [ka]

[0220] The toner particles may contain only one type of acetylacetonate metal compound, or two or more types of acetylacetonate metal compounds. From the viewpoint of suppressing fading under high temperature and high humidity conditions and transparency, the content of the acetylacetone metal compound is preferably from 0.5% by mass to 30% by mass, more preferably from 1% by mass to 25% by mass, and particularly preferably from 2% by mass to 20% by mass, relative to the total mass of the toner particles. The content ratio of the acetylacetone metal compound to the pyrazolotriazole dye in the toner particles C (acetylacetone metal compound content / pyrazolotriazole dye content) is preferably 1 or more and 10 or less, more preferably 1.2 or more and 5 or less, and particularly preferably 1.5 or more and 3 or less, from the viewpoints of anti-fading properties and transparency under high temperature and high humidity conditions.

[0221] -Mold release agent- As the release agent, those exemplified as the release agents used in the toner particles A can be used, and the preferred embodiments are also the same.

[0222] -Other additives- As the other additives, the same additives as those used in the toner particles A are used.

[0223] -Characteristics of toner particles B and C- Toner particles B and toner particles C may each be toner particles having a single layer structure, or toner particles having a so-called core-shell structure consisting of a core particle and a coating layer (shell layer) that covers the core. Here, the toner particles having a core-shell structure may preferably be composed of a core containing a binder resin, a colorant, and optionally other additives such as a release agent, and a coating layer containing the binder resin.

[0224] The average circularity of toner particles B and toner particles C is preferably 0.94 or more and 1.00 or less, more preferably 0.95 or more and 0.98 or less, from the viewpoint of suppressing color variation of images over time under high temperature and high humidity conditions.

[0225] (external additives) Toner B and toner C may each contain an external additive. The external additives used may be those listed as external additives used in the glitter toner, and the preferred embodiments are also the same.

[0226] <Toner manufacturing method> Toner A, toner B, and toner C (hereinafter, collectively referred to as "toner") may be produced by producing toner particles A, toner particles B, and toner particles C (hereinafter, collectively referred to as "toner particles"), respectively, and then adding an external additive to the toner particles. The method for producing toner particles is not particularly limited, and they can be produced by known dry methods such as kneading and pulverization, or wet methods such as emulsion aggregation, dissolution suspension, and suspension polymerization. The kneading and grinding method involves mixing various materials including colorants, then melting and kneading the materials using a kneader, extruder, etc., and then roughly grinding the resulting molten mixture, which is then pulverized using a jet mill, etc., and then using an air classifier to obtain toner particles of the desired particle size. Among these methods, the emulsion aggregation method is preferred because it is easy to control the shape and particle size of toner particles and has a wide range of control over the toner particle structure, such as a core-shell structure. The method for producing toner particles by the emulsion aggregation method will be described in detail below.

[0227] The emulsion aggregation method of this embodiment includes an emulsification step of emulsifying the raw materials constituting the toner particles to form resin particles (emulsified particles), etc., an aggregation step of forming aggregates of the resin particles, and a fusion step of fusing the aggregates.

[0228] (emulsification process) Resin particle dispersions can be prepared by a general polymerization method, such as emulsion polymerization, suspension polymerization, or dispersion polymerization. Alternatively, a solution of a water-based medium and a binder resin can be emulsified by applying shear force using a disperser. Heating can be used to reduce the viscosity of the resin component and form particles. A dispersant can also be used to stabilize the dispersed resin particles. Furthermore, if the resin is oil-based and dissolves in a solvent with relatively low solubility in water, the resin can be dissolved in the solvent and dispersed in water together with a dispersant and a polymer electrolyte. The solvent can then be evaporated by heating or reducing the pressure to prepare a resin particle dispersion.

[0229] Examples of aqueous media include water such as distilled water and ion-exchanged water; alcohols; and the like, with water being preferred. Examples of dispersants used in the emulsification step include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, sodium polyacrylate, and sodium polymethacrylate; anionic surfactants such as sodium dodecylbenzenesulfonate, sodium octadecyl sulfate, sodium oleate, sodium laurate, and potassium stearate; cationic surfactants such as laurylamine acetate, stearylamine acetate, and lauryltrimethylammonium chloride; zwitterionic surfactants such as lauryldimethylamine oxide; and nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, and polyoxyethylene alkylamines; and inorganic salts such as tricalcium phosphate, aluminum hydroxide, calcium sulfate, calcium carbonate, and barium carbonate.

[0230] Examples of dispersing machines used to prepare the emulsion include homogenizers, homomixers, pressure kneaders, extruders, and media dispersers. The average particle size (volume average particle size) of the resin particles is preferably 1.0 μm or less, more preferably 60 nm or more and 300 nm or less, and even more preferably 150 nm or more and 250 nm or less. If the size is 60 nm or more, the resin particles tend to become unstable in the dispersion, which may lead to aggregation of the resin particles. If the size is 1.0 μm or less, the particle size distribution of the toner may become narrow.

[0231] To prepare the release agent dispersion, the release agent is dispersed in water together with an ionic surfactant and a polymer electrolyte such as a polymer acid or a polymer base, and then the dispersion is heated to a temperature above the melting temperature of the release agent and dispersed using a homogenizer or pressure-discharge disperser that applies strong shear force. This process yields the release agent dispersion. During the dispersion process, an inorganic compound such as polyaluminum chloride may be added to the dispersion. Examples of suitable inorganic compounds include polyaluminum chloride, aluminum sulfate, highly basic polyaluminum chloride (BAC), polyaluminum hydroxide, and aluminum chloride. Among these, polyaluminum chloride and aluminum sulfate are preferred. While the release agent dispersion is used in emulsion aggregation, it may also be used when producing toner by suspension polymerization.

[0232] By the dispersion treatment, a release agent dispersion liquid containing release agent particles having a volume average particle size of 1 μm or less is obtained. The volume average particle size of the release agent particles is more preferably 100 nm or more and 500 nm or less. If the volume average particle size is 100 nm or more, the release agent component is generally more easily incorporated into the toner, although this is affected by the properties of the binder resin used. If the volume average particle size is 500 nm or less, the release agent is better dispersed in the toner.

[0233] The colorant dispersion can be prepared by any known dispersing method, including, for example, a rotary shear homogenizer, a ball mill with media, a sand mill, a Dyno Mill, an Ultimizer, and other common dispersing means, without any particular limitation. The colorant is dispersed in water together with an ionic surfactant and a polymer electrolyte such as a polymer acid or a polymer base. When the colorant is a luster pigment, the luster pigment and binder resin may be dispersed or dissolved in a solvent, mixed, and then dispersed in water by phase inversion emulsification or shear emulsification, thereby preparing a dispersion of the luster pigment coated with the binder resin.

[0234] (Agglutination process) In the aggregation process, a resin particle dispersion, a colorant dispersion, a release agent dispersion, etc. are mixed to form a mixture, which is then heated at a temperature below the glass transition temperature of the resin particles to aggregate them and form aggregated particles. The formation of aggregated particles is often achieved by adjusting the pH of the mixture to an acidic value while stirring. The pH is preferably in the range of 2 to 7, and the use of an aggregating agent is also effective in this case.

[0235] Suitable flocculants include surfactants with polarity opposite to that of the surfactant used in the dispersant, inorganic metal salts, and divalent or higher metal complexes. In particular, metal complexes are particularly desirable because they can reduce the amount of surfactant used and improve charging properties.

[0236] As the inorganic metal salt, aluminum salts and polymers thereof are particularly suitable. To obtain a narrower particle size distribution, inorganic metal salts with a valence of divalent rather than monovalent, trivalent rather than divalent, or tetravalent rather than trivalent are more suitable, and even if the valence is the same, polymerized inorganic metal salt polymers are more suitable. In this embodiment, it is desirable to use a polymer of a tetravalent inorganic metal salt containing aluminum in order to obtain a narrow particle size distribution.

[0237] Furthermore, when the aggregated particles reach the desired particle size, a resin particle dispersion may be added (coating step) to produce a toner in which the surfaces of the core aggregated particles are coated with resin. In this case, the release agent and colorant are less likely to be exposed on the toner surface, which is desirable from the viewpoint of chargeability and developability. When adding the resin dispersion, an aggregating agent may be added or the pH may be adjusted before the addition.

[0238] (fusion process) In the fusion step, the aggregation is stopped by increasing the pH of the suspension of aggregated particles to a range of 3 to 9 under stirring conditions similar to those in the aggregation step, and the aggregated particles are fused by heating at a temperature equal to or higher than the glass transition temperature of the resin. Furthermore, if the core aggregated particles are coated with the resin, the resin also fuses and coats the core aggregated particles. The heating time is sufficient to achieve fusion, and may be from 0.5 to 10 hours.

[0239] After the fusion, the mixture is cooled to obtain fused particles. Crystallization may be promoted by slowing the cooling rate near the glass transition temperature of the resin (within a range of glass transition temperature ±10°C), i.e., by slow cooling. The fused particles obtained by the fusion are subjected to a solid-liquid separation step such as filtration, and if necessary, a washing step and a drying step to form toner particles.

[0240] To the obtained toner particles, inorganic oxides such as silica, titania, and aluminum oxide are added and attached as external additives for the purposes of charge adjustment, imparting fluidity, imparting charge exchangeability, etc. This can be done using, for example, a V-type blender, a Henschel mixer, a Lödige mixer, etc., and the addition may be carried out in stages. The amount of external additive added is preferably in the range of 0.1 to 5 parts by mass, more preferably 0.3 to 2 parts by mass, per 100 parts by mass of toner particles. Furthermore, if necessary, coarse particles of the toner may be removed after external addition using an ultrasonic sieving machine, a vibration sieving machine, a wind sieving machine or the like.

[0241] In addition to the inorganic oxides and the like described above, other components (particles) such as a charge control agent, organic particles, lubricants, and abrasives may be added as external additives.

[0242] The charge control agent is not particularly limited, but a colorless or light-colored one is preferably used. Examples include quaternary ammonium salt compounds, nigrosine compounds, complexes of aluminum, iron, chromium, etc., and triphenylmethane pigments.

[0243] Examples of organic particles include particles of vinyl resin, polyester resin, silicone resin, etc., which are usually used as external additives on the toner surface. These organic particles are used as flow aids, cleaning aids, etc. Examples of the lubricant include fatty acid amides such as ethylene bisstearic acid amide and oleic acid amide, and fatty acid metal salts such as zinc stearate and calcium stearate. Examples of the abrasive include the above-mentioned silica, alumina, and cerium oxide.

[0244] Next, the method for producing toner particles by the solution suspension method will be described in detail. The solution suspension method is a method in which a liquid obtained by dissolving or dispersing materials containing a binder resin, a colorant, and other components such as a release agent, which is used as needed, in a solvent in which the binder resin is soluble is granulated in an aqueous medium containing an inorganic dispersant, and then the solvent is removed to obtain toner particles. Other components used in the solution suspension method include various components such as internal additives, charge control agents, inorganic powders (inorganic particles), and organic particles, in addition to release agents.

[0245] In this embodiment, the binder resin, the colorant, and other components used as needed are dissolved or dispersed in a solvent capable of dissolving the binder resin. Whether or not a binder resin is soluble depends on the constituent components, molecular chain length, degree of three-dimensionality, etc. of the binder resin, and therefore cannot be stated in general terms. However, generally, hydrocarbons such as toluene, xylene, hexane, etc.; halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, dichloroethylene, etc.; alcohols or ethers such as ethanol, butanol, benzyl alcohol ethyl ether, benzyl alcohol isopropyl ether, tetrahydrofuran, tetrahydropyran, etc.; esters such as methyl acetate, ethyl acetate, butyl acetate, isopropyl acetate, etc.; ketones or acetals such as acetone, methyl ethyl ketone, diisobutyl ketone, dimethyl oxide, diacetone alcohol, cyclohexanone, methylcyclohexanone, etc. are used.

[0246] These solvents dissolve the binder resin, but do not necessarily dissolve the colorant and other components, as long as they can be dispersed in the binder resin solution. There is no limitation on the amount of solvent used, provided that the viscosity allows granulation in an aqueous medium. A ratio of the material (including the binder resin, colorant, and other components) to the solvent (the latter) of 10 / 90 to 50 / 50 (mass ratio of the former / the latter) is preferred in terms of ease of granulation and the final yield of toner particles.

[0247] A liquid (toner mother liquid) of binder resin, colorant, and other components dissolved or dispersed in a solvent is granulated to a predetermined particle size in an aqueous medium containing an inorganic dispersant. Water is primarily used as the aqueous medium. The mixing ratio of the aqueous medium to the toner mother liquid is preferably 90 / 10 to 50 / 50 (by weight). The inorganic dispersant is preferably selected from tricalcium phosphate, hydroxyapatite, calcium carbonate, titanium oxide and silica powder. The amount of inorganic dispersant used is determined depending on the particle size of the particles to be granulated, but it is generally preferable to use it in the range of 0.1% by mass to 15% by mass of the toner mother liquid. If it is 0.1% by mass or more, granulation is easily carried out, and if it is 15% by mass or less, unnecessary fine particles are less likely to be generated and the desired particles are easily obtained in high yield.

[0248] In order to improve granulation from the toner mother liquid, an auxiliary agent may be further added to the aqueous medium containing the inorganic dispersant. The auxiliary agent may be any of known cationic, anionic, and nonionic surfactants, and anionic surfactants are particularly preferred. Examples of such surfactants include sodium alkylbenzene sulfonate, sodium α-olefin sulfonate, and sodium alkyl sulfonate. These surfactants are used in an amount of 1×10 based on the toner mother liquid. -4 It is preferably used in the range of 0.1% by mass or more and 0.1% by mass or less.

[0249] Granulation from the toner mother liquid in an aqueous medium containing an inorganic dispersant is preferably carried out under shear. In this case, it is desirable that the average particle size of the granules be 20 μm or less, and it is particularly desirable that the granules be 3 μm or more and 15 μm or less. There are various types of dispersers equipped with a shearing mechanism, among which a homogenizer is preferred. By using a homogenizer, substances that are incompatible with each other (in this embodiment, an aqueous medium containing an inorganic dispersant and a toner mother liquid) can be passed through the gap between a casing and a rotating rotor, and the substance that is incompatible with a certain liquid can be dispersed in particulate form in the liquid. Specific examples of homogenizers include TK homomixer, line flow homomixer, auto homomixer (all manufactured by Tokushu Kika Kogyo Co., Ltd.), Silverson homogenizer (manufactured by Silverson), and Polytron homogenizer (manufactured by Kinematica AG). The stirring conditions using a homogenizer are preferably a rotor blade peripheral speed of 2 m / s or more, as a peripheral speed of 2 m / s or more tends to result in good particle formation.

[0250] After granulation as described above, the solvent is removed. The solvent may be removed at room temperature (25°C) and atmospheric pressure, but because removal takes a long time, it is preferably carried out at a temperature lower than the boiling point of the solvent and within a range of a difference of 80°C from the boiling point. The pressure may be atmospheric pressure or reduced pressure, but when reduced pressure is applied, it is preferably 20 mmHg or more and 150 mmHg or less.

[0251] After the solvent is removed, the toner particles are preferably washed with hydrochloric acid or the like. This removes the inorganic dispersant remaining on the surface of the toner particles, restoring the toner particles to their original composition and improving their properties. Then, the mixture is dehydrated and dried to obtain powder toner particles.

[0252] The toner is then produced by, for example, adding an external additive to the obtained dry toner particles and mixing them. The mixing can be carried out using, for example, a V blender, a Henschel mixer, a Loedige mixer, etc. Furthermore, if necessary, coarse particles may be removed from the toner using a vibrating sieve, an air sieve, etc.

[0253] [Electrostatic image developer set] An electrostatic image developer set according to one embodiment of the present disclosure includes developer A containing toner A from the toner set according to the present disclosure, developer B containing toner B from the toner set according to the present disclosure, and developer C containing toner C from the toner set according to the present disclosure. Each electrostatic image developer may be a one-component developer containing only toner, or may be a two-component developer containing a mixture of toner and carrier.

[0254] The carrier is not particularly limited, and examples thereof include known carriers, such as coated carriers in which the surface of a core material made of magnetic powder is coated with a coating resin, magnetic powder dispersion carriers in which magnetic powder is dispersed and blended in a matrix resin, and resin-impregnated carriers in which porous magnetic powder is impregnated with a resin. The magnetic powder dispersion type carrier and the resin impregnated type carrier may be a carrier in which the constituent particles of the carrier are used as a core material and are coated with a coating resin.

[0255] Examples of magnetic powder include magnetic metals such as iron, nickel, and cobalt, and magnetic oxides such as ferrite and magnetite.

[0256] Examples of coating resins and matrix resins include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic acid ester copolymer, straight silicone resins containing organosiloxane bonds or modified products thereof, fluororesins, polyesters, polycarbonates, phenolic resins, and epoxy resins. The coating resin and the matrix resin may contain other additives such as conductive particles. Examples of 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.

[0257] Here, the method of coating the surface of the core material with a coating resin includes a method of coating with a solution for forming a coating layer in which the coating resin and, if necessary, various additives are dissolved in an appropriate solvent. The solvent is not particularly limited and may be selected taking into consideration the coating resin to be used, its applicability, etc. Specific resin coating methods include an immersion method in which the core material is immersed in a solution for forming a coating layer, a spray method in which the solution for forming a coating layer is sprayed onto the surface of the core material, a fluidized bed method in which the solution for forming a coating layer is sprayed onto the core material while it is suspended in flowing air, and a kneader coater method in which the core material of the carrier and the solution for forming a coating layer are mixed in a kneader coater and the solvent is removed.

[0258] In the two-component developer, the mixing ratio (mass ratio) of toner to carrier is preferably toner:carrier=1:100 to 30:100, and more preferably 3:100 to 20:100.

[0259] [Image forming device / image forming method] An image forming apparatus / image forming method according to the present disclosure will be described. An image forming apparatus according to one embodiment of the present disclosure includes an image forming means A that forms image A using toner A from the toner set according to the present disclosure, an image forming means B that forms image B using toner B from the toner set according to the present disclosure, an image forming means C that forms image C using toner C from the toner set according to the present disclosure, a transfer means that transfers image A, image B, and image C onto a recording medium, and a fixing means that fixes the toner image formed by stacking image A, image B, and image C onto the recording medium.

[0260] The image forming apparatus according to the present disclosure may be configured to include, as image forming means A, image forming means B, and image forming means C, each image forming means having an image carrier, a charging means for charging the surface of the image carrier, an electrostatic image forming means for forming an electrostatic image on the surface of the charged image carrier, and a developing means for developing the electrostatic image formed on the surface of the image carrier with an electrostatic image developer into a toner image.

[0261] In addition, the image forming apparatus according to the present disclosure may be in a form having an image carrier, a charging means for charging the surface of the image carrier, an electrostatic image forming means for forming an electrostatic image on the surface of the charged image carrier, and developing means A, B, and C as image forming means A, B, and C for developing the electrostatic image formed on the surface of the image carrier with an electrostatic image developer into a toner image.

[0262] In the image forming apparatus according to the present disclosure, an image forming method (the image forming method according to the present disclosure) is carried out, which includes an image forming process A in which image A is formed using toner A from the toner set according to the present disclosure, an image forming process B in which image B is formed using toner B from the toner set according to the present disclosure, an image forming process C in which image C is formed using toner C from the toner set according to the present disclosure, a transfer process in which image A, image B, and image C are transferred onto a recording medium, and a fixing process in which a toner image formed by stacking image A, image B, and image C is fixed onto the recording medium.

[0263] The image forming apparatus according to the present disclosure may be a known image forming apparatus such as a direct transfer type apparatus that transfers a toner image formed on the surface of an image carrier directly to a recording medium; an intermediate transfer type apparatus that primarily transfers a toner image formed on the surface of an image carrier to the surface of an intermediate transfer medium, and then secondarily transfers the toner image transferred to the surface of the intermediate transfer medium to the surface of a recording medium; an apparatus equipped with a cleaning means that cleans the surface of the image carrier after the transfer of the toner image but before charging; or an apparatus equipped with a discharging means that irradiates the surface of the image carrier with discharging light to discharge it after the transfer of the toner image but before charging. In the case of an intermediate transfer type device, the transfer means is configured to have, for example, an intermediate transfer body onto whose surface a toner image is transferred, a primary transfer means which primarily transfers the toner image formed on the surface of the image carrier onto the surface of the intermediate transfer body, and a secondary transfer means which secondarily transfers the toner image transferred onto the surface of the intermediate transfer body onto the surface of the recording medium.

[0264] An example of an image forming apparatus according to the present disclosure will be described below, but the present disclosure is not limited to this. In the following description, the main parts shown in the drawings will be described, and other parts will be omitted. In the following description, an example of a toner set according to the present disclosure will be described, with toner A referred to as "silver toner," toner B referred to as "cyan toner," and toner C referred to as "magenta toner."

[0265] FIG. 1 is a schematic diagram showing the configuration of an image forming apparatus according to this embodiment, and is a diagram showing a five-tandem type and intermediate transfer type image forming apparatus. The image forming apparatus shown in FIG. 1 includes first through fifth electrophotographic image forming units 150Y, 150M, 150C, 150K, and 150B (image forming means) that output images in the colors yellow (Y), magenta (M), cyan (C), black (K), and silver (B) based on color-separated image data. These image forming units (hereinafter sometimes simply referred to as "units") 150Y, 150M, 150C, 150K, and 150B are arranged side by side horizontally spaced a predetermined distance apart from one another. These units 150Y, 150M, 150C, 150K, and 150B may be process cartridges that are detachably attached to the image forming apparatus.

[0266] An intermediate transfer belt (an example of an intermediate transfer body) 133 extends below each of the units 150Y, 150M, 150C, 150K, and 150B. The intermediate transfer belt 133 is wound around a drive roll 113, a support roll 112, and an opposing roll 114, which are in contact with the inner surface of the intermediate transfer belt 133, and runs in a direction from the first unit 150Y to the fifth unit 150B (the direction of arrow B in FIG. 1). An intermediate transfer body cleaning device 116 is provided on the image bearing surface side of the intermediate transfer belt 133, facing the drive roll 113. Furthermore, a voltage application device 160 is provided upstream of the intermediate transfer body cleaning device 116 in the rotation direction of the intermediate transfer belt 133, which generates a potential difference between the drive roll 113 and the intermediate transfer belt 133, thereby generating an electric field between the intermediate transfer belt 133 and the drive roll 113. The developing devices (examples of developing means) 120Y, 120M, 120C, 120K, and 120B of each unit 150Y, 150M, 150C, 150K, and 150B are supplied with yellow, magenta, cyan, black, and silver toner contained in toner cartridges 140Y, 140M, 140C, 140K, and 140B, respectively.

[0267] The first to fifth units 150Y, 150M, 150C, 150K, and 150B have the same configuration, operation, and function, so here we will explain the first unit 150Y, which forms a yellow image and is arranged upstream in the direction of travel of the intermediate transfer belt, as a representative.

[0268] The first unit 150Y has a photoconductor 111Y that acts as an image carrier. Around the photoconductor 111Y, there are arranged in this order: a charging roll (an example of a charging means) 118Y that charges the surface of the photoconductor 111Y to a predetermined potential; an exposure device (an example of an electrostatic image forming means) 119Y that exposes the charged surface to a laser beam based on a color-separated image signal to form an electrostatic image; a developing device (an example of a developing means) 120Y that supplies toner to the electrostatic image to develop it; a primary transfer roll (an example of a primary transfer means) 117Y that transfers the developed toner image onto the intermediate transfer belt 133; and a photoconductor cleaning device (an example of a cleaning means) 115Y that removes toner remaining on the surface of the photoconductor 111Y after the primary transfer. The primary transfer roll 117Y is disposed inside the intermediate transfer belt 133 and is provided at a position facing the photosensitive member 111Y. A bias power supply (not shown) that applies a primary transfer bias is connected to the primary transfer rolls 117Y, 117M, 117C, 117K, and 117B of each unit. Each bias power supply changes the value of the transfer bias applied to each primary transfer roll under the control of a control unit (not shown).

[0269] The operation of forming a yellow image in first unit 150Y will be described below. First, prior to operation, the surface of the photosensitive member 111Y is charged to a potential of −600V to −800V by the charging roll 118Y. The photoconductor 111Y has conductivity (for example, a volume resistivity of 1×10 at 20° C. -6 The photosensitive layer is formed by laminating a photosensitive layer on a substrate with a resistivity of Ωcm or less. This photosensitive layer normally has a high resistance (the resistance of ordinary resins), but when irradiated with a laser beam, the resistivity of the irradiated portion changes. Therefore, the charged surface of the photosensitive element 111Y is irradiated with a laser beam from the exposure device 119Y in accordance with image data for yellow sent from a control unit (not shown). As a result, an electrostatic charge image of a yellow image pattern is formed on the surface of the photosensitive element 111Y.

[0270] An electrostatic image is an image formed on the surface of the photosensitive element 111Y by charging it; it is a so-called negative latent image formed when the resistivity of the irradiated portion of the photosensitive layer is reduced by the laser beam from the exposure device 119Y, causing the charged charges on the surface of the photosensitive element 111Y to flow, while the charges remain in the portions not irradiated by the laser beam. The electrostatic image formed on the photoconductor 111Y rotates to a predetermined development position as the photoconductor 111Y travels in the direction of arrow A. At this development position, the electrostatic image on the photoconductor 111Y is developed into a visualized toner image by the developing device 120Y.

[0271] The developing device 120Y contains an electrostatic image developer containing, for example, at least yellow toner and a carrier. The yellow toner is frictionally charged by being stirred inside the developing device 120Y, and is held on a developer roll (an example of a developer holder) with a charge of the same polarity (negative polarity) as the charge on the photoconductor 111Y. As the surface of the photoconductor 111Y passes through the developing device 120Y, the yellow toner electrostatically adheres to the discharged latent image portion on the surface of the photoconductor 111Y, and the latent image is developed with the yellow toner. The photoconductor 111Y on which the yellow toner image has been formed continues to travel at a predetermined speed, and the toner image developed on the photoconductor 111Y is transported to a predetermined primary transfer position.

[0272] When the yellow toner image on the photoconductor 111Y is transported to the primary transfer position, a primary transfer bias is applied to the primary transfer roll 117Y, and an electrostatic force from the photoconductor 111Y toward the primary transfer roll 117Y acts on the toner image, causing the toner image on the photoconductor 111Y to be transferred onto the intermediate transfer belt 133. The transfer bias applied at this time has a (+) polarity opposite to the (-) polarity of the toner, and is controlled to, for example, +10 μA by a control unit (not shown) in the first unit 150Y. On the other hand, the toner remaining on the photoconductor 111Y is removed and collected by the photoconductor cleaning device 115Y.

[0273] The primary transfer biases applied to the primary transfer rolls 117M, 117C, 117K, and 117B of the second unit 150M and subsequent units are also controlled in accordance with the first unit. In this way, the intermediate transfer belt 133 onto which the yellow toner image has been transferred by the first unit 150Y is conveyed sequentially through the second to fifth units 150M, 150C, 150K, and 150B, and the toner images of each color are superimposed and transferred.

[0274] The intermediate transfer belt 133 onto which the five-color toner images have been multiplex-transferred through the first to fifth units reaches a secondary transfer section made up of the intermediate transfer belt 133, an opposing roll 114 in contact with the inner surface of the intermediate transfer belt, and a secondary transfer roll (an example of a secondary transfer means) 134 arranged on the image bearing surface side of the intermediate transfer belt 133. Meanwhile, recording paper (an example of a recording medium) P is fed via a supply mechanism into the gap between the secondary transfer roll 134 and the intermediate transfer belt 133 at a predetermined timing, and a secondary transfer bias is applied to the opposing roll 114. The transfer bias applied at this time has a negative polarity, the same as the negative polarity of the toner. Electrostatic force from the intermediate transfer belt 133 toward the recording paper P acts on the toner image, and the toner image on the intermediate transfer belt 133 is transferred onto the recording paper P. The secondary transfer bias at this time is determined according to resistance detected by resistance detection means (not shown) that detects resistance in the secondary transfer section, and is voltage-controlled.

[0275] Thereafter, the recording paper P is sent to a pressure contact portion (nip portion) of a pair of fixing rolls in a fixing device (an example of fixing means) 135, where the toner image is fixed onto the recording paper P, forming a fixed image.

[0276] Examples of the recording paper P onto which the toner image is transferred include plain paper used in electrophotographic copiers, printers, etc. In addition to the recording paper P, examples of the recording medium include overhead projector sheets and the like. To further improve the smoothness of the image surface after fixing, it is preferable that the surface of the recording paper P is also smooth. For example, coated paper in which the surface of plain paper is coated with resin or the like, or art paper for printing, etc., is preferably used.

[0277] The recording paper P on which the color image has been fixed is conveyed toward the discharge section, and the series of color image forming operations is completed.

[0278] 1 is an image forming apparatus having a configuration in which toner cartridges 140Y, 140M, 140C, 140K, and 140B are detachably attached, and developing devices 120Y, 120M, 120C, 120K, and 120B are connected to toner cartridges corresponding to the respective developing devices (colors) via toner supply pipes (not shown). When the toner stored in a toner cartridge runs low, the toner cartridge is replaced.

[0279] <Process cartridge / toner cartridge set> The process cartridge according to the present disclosure will be described. The process cartridge according to the present disclosure is a process cartridge that is detachably attached to an image forming apparatus and includes developing means A that contains developer A from the electrostatic image developer set according to the present disclosure, developing means B that contains developer B from the electrostatic image developer set according to the present disclosure, and developing means C that contains developer C from the electrostatic image developer set according to the present disclosure.

[0280] The process cartridge according to the present disclosure is not limited to the above configuration, but may also be configured to include a developing device and, as necessary, at least one other means selected from an image carrier, a charging means, an electrostatic image forming means, and a transfer means.

[0281] An example of a process cartridge according to the present disclosure will be described below, but the present disclosure is not limited to this example. Note that only the main parts shown in the drawings will be described, and descriptions of other parts will be omitted.

[0282] FIG. 2 is a schematic diagram showing the configuration of the process cartridge according to the present embodiment. The process cartridge 200 shown in FIG. 2 is configured to integrally combine and hold a photosensitive member 207 (an example of an image carrier), a charging roll 208 (an example of a charging means) provided around the photosensitive member 207, a developing device 211 (an example of a developing means), and a photosensitive member cleaning device 213 (an example of a cleaning means), which are combined and held together by a housing 217 provided with, for example, mounting rails 216 and an opening 218 for exposure, to form a cartridge. In FIG. 2, 209 denotes an exposure device (an example of an electrostatic image forming means), 212 denotes a primary transfer roll (an example of a primary transfer means), 220 denotes an intermediate transfer belt (an example of an intermediate transfer body), 222 denotes a drive roll (an example of an intermediate transfer body de-electrification means) that also serves as an intermediate transfer belt de-electrification means, 224 denotes a support roll, 226 denotes a secondary transfer roll (an example of a secondary transfer means), 228 denotes a fixing device (an example of a fixing means), and 300 denotes recording paper (an example of a recording medium).

[0283] Next, a toner cartridge set according to the present disclosure will be described. The toner cartridge set according to the present disclosure has toner cartridge A containing toner A from the toner set according to the present disclosure, toner cartridge B containing toner B from the toner set according to the present disclosure, and toner cartridge C containing toner C from the toner set according to the present disclosure, and is a toner cartridge set that can be attached to and detached from an image forming device. Each toner cartridge contains replenishment toner to be supplied to each developing means provided in the image forming apparatus. [Example]

[0284] Hereinafter, the embodiments of the present invention will be described in detail with reference to examples, but the embodiments of the present invention are not limited to these examples. In the following description, unless otherwise specified, "parts" and "%" are by mass. All syntheses, processing, preparations, etc. were carried out at room temperature (25°C ± 3°C) unless otherwise noted.

[0285] [Preparation of resin dispersion] <Amorphous polyester resin dispersion 1> (Synthesis of amorphous polyester resin 1) Dimethyl adipate: 74 parts Dimethyl terephthalate: 192 parts Bisphenol A ethylene oxide adduct: 216 parts Ethylene glycol: 38 parts Tetrabutoxytitanate (catalyst): 0.037 parts, The above components were placed in a heated and dried two-necked flask, nitrogen gas was introduced into the vessel to maintain an inert atmosphere, and the temperature was raised while stirring. A polycondensation co-reaction was then carried out at 160°C for 7 hours, after which the pressure was gradually reduced to 10 Torr while the temperature was raised to 220°C and maintained for 4 hours. The pressure was then returned to normal, 9 parts of trimellitic anhydride was added, and the pressure was again gradually reduced to 10 Torr and maintained at 220°C for 1 hour to synthesize amorphous polyester resin 1. The glass transition temperature of amorphous polyester resin 1 was 105°C, and the weight average molecular weight Mw was 40,000.

[0286] (Preparation of amorphous polyester resin dispersion 1) Amorphous polyester resin 1:160 parts Ethyl acetate: 233 parts Sodium hydroxide solution (0.3N): 0.1 parts The above components were placed in a 1000 ml separable flask, heated to 70°C, and stirred with a Three-One Motor (manufactured by Shinto Scientific Co., Ltd.) to prepare a resin mixture. While further stirring this resin mixture, 373 parts of ion-exchanged water was gradually added, followed by phase inversion emulsification and desolvation to obtain amorphous polyester resin dispersion 1 (solid concentration: 30% by mass). The volume average particle size D50v of the resin particles in this dispersion was 170 nm.

[0287] <Crystalline polyester resin dispersion 2> (Synthesis of crystalline polyester resin) 1,10-decanedicarboxylic acid: 50 mol% 1,9-nonanediol: 50 mol% The above monomer components were placed in a reaction vessel equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube. The atmosphere in the reaction vessel was replaced with dry nitrogen gas, and then 0.25 parts of titanium tetrabutoxide (reagent) per 100 parts of the monomer components was added. After stirring and reacting for 3 hours at 170°C under a nitrogen gas stream, the temperature was further increased to 210°C over 1 hour, the pressure in the reaction vessel was reduced to 3 kPa, and the mixture was stirred and reacted under reduced pressure for 13 hours to obtain crystalline polyester resin 2. The melting temperature of crystalline polyester resin 2 was 70°C and the weight-average molecular weight Mw was 23,000.

[0288] (Preparation of Crystalline Polyester Resin Dispersion 2) 300 parts of the crystalline polyester resin, 160 parts of methyl ethyl ketone (solvent), and 100 parts of isopropyl alcohol (solvent) were placed in a jacketed 3-liter reaction vessel (Tokyo Rikakiki Co., Ltd.: BJ-30N) equipped with a condenser, a thermometer, a water dropping device, and an anchor blade, and the resin was dissolved by stirring and mixing at 100 rpm while maintaining the temperature at 70°C in a water-circulating thermostatic bath. Thereafter, the stirring speed was increased to 150 rpm, the water circulation type thermostatic bath was set to 66°C, and 17 parts of 10% aqueous ammonia (reagent) was added over 10 minutes, followed by adding a total of 900 parts of ion-exchanged water maintained at 66°C dropwise at a rate of 7 parts / min to cause phase inversion and obtain an emulsion. Immediately, 800 parts of the resulting emulsion and 700 parts of ion-exchanged water were placed in a 2-liter recovery flask and placed in an evaporator (Tokyo Rikakiki Co., Ltd.) equipped with a vacuum control unit via a trap bulb. While rotating the recovery flask, the pressure was increased to 7 kPa while taking care to prevent bumping, and the solvent was removed. When the amount of recovered solvent reached 1,100 parts, the pressure was returned to normal, and the recovery flask was cooled with water to obtain a dispersion. The resulting dispersion had no solvent odor. The volume-average particle size D50v of the resin particles in this dispersion was 130 nm. Subsequently, ion-exchanged water was added to adjust the solids concentration to 20% by mass, and this was designated as crystalline polyester resin dispersion 2.

[0289] <Styrene acrylic resin dispersion 3> Styrene: 320 parts by weight n-Butyl acrylate: 80 parts by weight Acrylic acid: 12 parts by weight 10-Dodecanethiol: 2 parts by mass The above components were mixed and dissolved in a flask and emulsified in 550 parts by weight of a nonionic surfactant (Nonipol 400, manufactured by Sanyo Chemical Industries, Ltd.) and an anionic surfactant (Neogen SC, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) dissolved in 550 parts by weight of ion-exchanged water. While slowly mixing for 10 minutes, 50 parts by weight of ion-exchanged water containing 4 parts by weight of ammonium persulfate was added. After nitrogen substitution, the contents of the flask were heated in an oil bath with stirring until the temperature reached 70°C, and emulsion polymerization was continued for 5 hours. The solids concentration was then adjusted to 30% by weight, yielding a styrene-acrylic resin dispersion 3 containing dispersed resin particles of styrene-acrylic resin 3 with a glass transition temperature of 103°C and a weight-average molecular weight of 35,000. The volume average particle size D50v of the resin particles in this dispersion was 170 nm.

[0290] [Preparation of colorant dispersion] <Glitter pigment dispersion 1> Aluminum pigment (Showa Aluminum Powder Co., Ltd., 2173EA 6 μm): 100 parts Anionic surfactant (Dai-ichi Kogyo Seiyaku Co., Ltd., Neogen R): 1.5 parts Ion-exchanged water: 400 parts The solvent was removed from the aluminum pigment paste, and the pigment was mechanically ground and classified to 5.2 μm using a Star Mill (LMZ, manufactured by Ashizawa Finetech Co., Ltd.). The pigment was then mixed with the surfactant and ion-exchanged water and dispersed for approximately one hour using a Cavitron emulsifier / disperser (CR1010, manufactured by Pacific Machinery Works Co., Ltd.) to prepare a bright pigment dispersion liquid 1 containing dispersed bright pigment particles (aluminum pigment) (solids concentration: 20% by mass). The pigment dispersion diameter, i.e., the volume average particle diameter of the bright pigment, was 5.2 μm.

[0291] <Phthalocyanine dye particle dispersion 2> Phthalocyanine dye c1: 15.8 parts Acetylacetone Metal Compound II-34: 34.2 parts Anionic surfactant (Dai-ichi Kogyo Seiyaku Co., Ltd., Neogen RK): 5 parts Ion-exchanged water: 193 parts The above components were mixed and treated for 10 minutes at 240 MPa using an Ultimizer (manufactured by Sugino Machine Co., Ltd.) to prepare phthalocyanine dye particle dispersion 2 (dye concentration: 20% by mass).

[0292] The phthalocyanine dye c1 and the acetylacetone metal compound II-34 are the compounds shown below.

[0293] [ka]

[0294] [ka]

[0295] <Phthalocyanine dye particle dispersion 3> Phthalocyanine dye particle dispersion liquid 3 was obtained in the same manner as phthalocyanine dye particle dispersion liquid 2, except that the phthalocyanine dye c1 was changed to a compound in which the Si atom of the phthalocyanine dye c1 was replaced with a Cu atom.

[0296] <Phthalocyanine dye particle dispersion 4> Phthalocyanine dye particle dispersion liquid 4 was obtained in the same manner as phthalocyanine dye particle dispersion liquid 2, except that the phthalocyanine dye c1 was changed to a compound in which the Si atom of the phthalocyanine dye c1 was replaced with an Sn atom.

[0297] <Pyrazolotriazole dye particle dispersion 5> Pyrazolotriazole dye particle dispersion 5 was obtained in the same manner as phthalocyanine dye particle dispersion 2, except that the phthalocyanine dye c1 was changed to pyrazolotriazole dye I-3. The pyrazolotriazole dye I-3 is the compound shown below.

[0298] [ka]

[0299] <Pyrazolotriazole dye particle dispersion 6> Pyrazolotriazole dye particle dispersion 6 was obtained in the same manner as phthalocyanine dye particle dispersion 2, except that phthalocyanine dye c1 was changed to a compound in which the t-butyl group of pyrazolotriazole dye I-3 was replaced with a triethylmethyl group.

[0300] <Cyan pigment dispersion 7> CI Pigment Blue 15:3 (copper phthalocyanine) (manufactured by Dainichi Seika Chemicals): 50 parts Ionic surfactant Neogen RK (Dai-ichi Kogyo Seiyaku): 5 parts Ion-exchanged water: 192.9 parts The above components were mixed and treated with an Ultimizer (manufactured by Sugino Machine Co., Ltd.) at 240 MPa for 10 minutes to obtain Cyan Pigment Dispersion Liquid 7. The solid content concentration was 20% by mass.

[0301] <Magenta pigment dispersion 8> Magenta pigment dispersion 8 was obtained in the same manner as cyan pigment dispersion 7, except that the cyan pigment CI Pigment Blue 15:3 was changed to a magenta pigment CI Pigment RED 122 (manufactured by Dainichiseika Chemicals).

[0302] [Preparation of release agent dispersion] <Release agent dispersion> Carnauba wax (Toa Kasei Co., Ltd., RC-160): 50 parts Anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK): 1.0 part Ion-exchanged water: 200 parts The above ingredients were mixed and heated to 95°C, and dispersed using a homogenizer (Ultra Turrax T50, manufactured by IKA). After that, a dispersion treatment was carried out for 360 minutes using a Manton-Gaulin high-pressure homogenizer (Gaulin), to prepare a release agent dispersion liquid (solid content concentration: 20% by mass) in which release agent particles with a volume average particle size of 0.23 μm were dispersed.

[0303] [Production of Toner A] <Toner A1> Brilliant pigment dispersion 1:145 parts Crystalline polyester resin dispersion 2:52 parts Styrene acrylic resin dispersion 3:280 parts Release agent dispersion: 75 parts The above ingredients were placed in a 2 L cylindrical stainless steel container and dispersed and mixed for 10 minutes using a homogenizer (Ultra Turrax T50, manufactured by IKA) at 4000 rpm while applying shear force. Next, 1.75 parts of a 10% aqueous solution of polyaluminum chloride in nitric acid was gradually added dropwise as a flocculant, and the homogenizer was rotated at 5000 rpm for 15 minutes to disperse and mix the ingredients to obtain a raw material dispersion. The dispersion was then transferred to a polymerization kettle equipped with a stirrer using a four-paddle stirrer and a thermometer, the stirring speed was set to 1000 rpm, and heating was started using a mantle heater to promote the growth of aggregated particles at 54°C. The pH of the dispersion was controlled to a range of 2.2 to 3.5 using 0.3 mol / L nitric acid or 1 mol / L aqueous sodium hydroxide solution. The pH was maintained within this range for approximately 2 hours to form aggregated particles. In other words, the aggregation time before the additional addition was 2 hours.

[0304] Next, 3:70 parts of styrene-acrylic resin dispersion was added to adhere styrene-acrylic resin particles to the surface of the aggregated particles. The temperature was further increased to 56°C, and the aggregated particles were adjusted while checking the particle size and morphology using an optical microscope and a Multisizer II. Subsequently, 3.25 parts of a chelating agent (HIDS, manufactured by Nippon Shokubai Co., Ltd.) was added, and the pH was adjusted to 7.8 using a 5% aqueous sodium hydroxide solution and maintained for 15 minutes. The pH was then increased to 8.0 to fuse the aggregated particles, and the temperature was then increased to 67.5°C. After confirming that the aggregated particles had fused using an optical microscope, the pH was lowered to 6.0 while maintaining the temperature at 67.5°C. After 1 hour, heating was stopped and the mixture was cooled at a rate of 1.0°C / min. The mixture was then sieved through a 40 μm mesh, washed repeatedly with water, and dried in a vacuum dryer to obtain toner particles A1. 100 parts of the obtained toner particles A1 were mixed with 1.5 parts of fumed silica (R972, manufactured by Nippon Aerosil Co., Ltd.) in a Henschel mixer at a peripheral speed of 30 m / s for 2 minutes to obtain toner A1.

[0305] <Toner A7> Toner particles A7 and toner A7 were obtained in the same manner as toner particles A1 and toner A1, respectively, except that the amount of lustrous pigment dispersion 1 added was changed from 145 parts to 109 parts, and the amount of styrene acrylic resin dispersion 3 added as the raw material dispersion was changed from 280 parts to 304 parts.

[0306] <Toner A9> Toner particles A9 and toner A9 were obtained in the same manner as toner particles A1 and toner A1, respectively, except that the amount of lustrous pigment dispersion 1 added was changed from 145 parts to 162 parts, and the amount of styrene acrylic resin dispersion 3 added as a raw material dispersion was changed from 280 parts to 268 parts.

[0307] <Toner A10> Toner particles A10 and toner A10 were obtained in the same manner as toner particles A1 and toner A1, respectively, except that the amount of lustrous pigment dispersion 1 added was changed from 145 parts to 93 parts, and the amount of styrene acrylic resin dispersion 3 added as a raw material dispersion was changed from 280 parts to 315 parts.

[0308] <Toner A11> Toner particles A11 and toner A11 were obtained in the same manner as toner particles A1 and toner A1, respectively, except that the amount of lustrous pigment dispersion 1 added was changed from 145 parts to 173 parts, and the amount of styrene acrylic resin dispersion 3 added as a raw material dispersion was changed from 280 parts to 261 parts.

[0309] <Toner A12> Toner particles A12 and toner A12 were obtained in the same manner as toner particles A1 and toner A1, respectively, except that the aggregation time before the additional addition was changed from 2 hours to 3 hours.

[0310] <Toner A13> Toner particles A13 and toner A13 were obtained in the same manner as toner particles A1 and toner A1, respectively, except that the aggregation time before the additional addition was changed from 2 hours to 2.5 hours.

[0311] <Toner A14> Toner particles A14 and toner A14 were obtained in the same manner as toner particles A1 and toner A1, respectively, except that the aggregation time before the additional addition was changed from 2 hours to 1.5 hours.

[0312] <Toner A17> Toner particles A17 and toner A17 were obtained in the same manner as toner particles A1 and toner A1, except that the aggregation time before the additional addition was changed from 2 hours to 1 hour.

[0313] <Toner A19> Toner particles A19 and toner A19 were obtained in the same manner as toner particles A1 and toner A1, respectively, except that crystalline polyester resin dispersion 2 was not added and the initial amount of styrene acrylic resin dispersion 3 added was changed from 280 parts to 315 parts.

[0314] <Toner A20> Toner particles A20 and toner A20 were obtained in the same manner as toner particles A1 and toner A1, respectively, except that the amount of crystalline polyester resin dispersion 2 added was changed from 52 parts to 49 parts and the amount of initial styrene acrylic resin dispersion 3 added was changed from 280 parts to 282 parts.

[0315] <Toner A21> Toner particles A21 and toner A21 were obtained in the same manner as toner particles A1 and toner A1, respectively, except that the amount of crystalline polyester resin dispersion 2 added was changed from 52 parts to 35 parts and the amount of initial styrene acrylic resin dispersion 3 added was changed from 280 parts to 291 parts.

[0316] <Toner A23> Toner particles A23 and toner A23 were obtained in the same manner as toner particles A1 and toner A1, respectively, except that the 280 parts of styrene acrylic resin dispersion 3 added initially was changed to 280 parts of amorphous polyester resin dispersion 1, and the 70 parts of styrene acrylic resin dispersion 3 added later was changed to 70 parts of amorphous polyester resin dispersion 1.

[0317] Content C of aluminum pigment in the obtained toner particles A1, A7, A9 to A14, A17, A19 to A21, and A23 A , volume average particle size D A , crystalline resin content E A The average circularity, ratio (C / D), and aspect ratio are shown in Table 2.

[0318] [Table 2]

[0319] [Production of Toner B] <Toner B1> ·Phthalocyanine dye particle dispersion 2:113 parts Amorphous polyester resin dispersion 1:320 parts Crystalline polyester resin dispersion 2:56 parts Release agent dispersion: 75 parts The above ingredients were placed in a 2 L cylindrical stainless steel container and dispersed and mixed for 10 minutes using a homogenizer (Ultra Turrax T50, manufactured by IKA) at 4000 rpm while applying shear force. Next, 1.75 parts of a 10% aqueous solution of polyaluminum chloride in nitric acid was gradually added dropwise as a flocculant, and the homogenizer was rotated at 5000 rpm for 15 minutes to disperse and mix the ingredients to obtain a raw material dispersion. The raw material dispersion was then transferred to a polymerization kettle equipped with a stirrer using a four-paddle stirrer and a thermometer, the stirring speed was set to 600 rpm, and heating was started using a mantle heater to promote the growth of aggregated particles at 50°C. The pH of the dispersion was controlled to a range of 2.2 to 3.5 using 0.3 mol / L nitric acid or 1 mol / L aqueous sodium hydroxide. The pH was maintained within this range for about 1.5 hours to form aggregated particles. In other words, the aggregation time before the additional addition was 1.5 hours. Next, 1:70 parts of the amorphous polyester resin dispersion was added to adhere the amorphous polyester resin particles to the surface of the aggregated particles. The temperature was then raised to 52°C, and the aggregated particles were adjusted while checking the particle size and morphology using an optical microscope and a Multisizer II. Then, 2.25 parts of a chelating agent (HIDS, manufactured by Nippon Shokubai Co., Ltd.) was added, and the pH was adjusted to 7.8 using a 5% by weight aqueous solution of sodium hydroxide and maintained for 15 minutes. The pH was then raised to 8.0 to fuse the aggregated particles, and the temperature was then raised to 67.5°C. After confirming that the aggregated particles had fused using an optical microscope, the pH was lowered to 6.0 while maintaining the temperature at 67.5°C. After 1 hour, heating was stopped and the mixture was cooled at a rate of 1.0°C / min. The toner particles were then sieved through a 20 μm mesh, washed repeatedly with water, and dried in a vacuum dryer to obtain toner particles B1. 100 parts of the obtained toner particles B1 were mixed with 1.5 parts of fumed silica (R972, manufactured by Nippon Aerosil Co., Ltd.) in a Henschel mixer at a peripheral speed of 30 m / s for 2 minutes to obtain toner B1.

[0320] <Toner B2> Toner particles B2 and toner B2 were obtained in the same manner as toner particles B1 and toner B1, except that 113 parts of phthalocyanine dye particle dispersion 2 was changed to 113 parts of phthalocyanine dye particle dispersion 4, respectively.

[0321] <Toner B4> Toner particles B4 and toner B4 were obtained in the same manner as toner particles B1 and toner B1, except that 113 parts of phthalocyanine dye particle dispersion 2 was changed to 113 parts of phthalocyanine dye particle dispersion 3, respectively.

[0322] <Toner B5> Toner particles B5 and toner B5 were obtained in the same manner as toner particles B1 and toner B1, respectively, except that the amount of phthalocyanine dye particle dispersion 2 added was changed from 113 parts to 30 parts, and the amount of amorphous polyester resin dispersion 1 added as a raw material dispersion was changed from 320 parts to 375 parts.

[0323] <Toner B6> Toner particles B6 and toner B6 were obtained in the same manner as toner particles B1 and toner B1, respectively, except that the amount of phthalocyanine dye particle dispersion 2 added was changed from 113 parts to 75 parts, and the amount of amorphous polyester resin dispersion 1 added as the raw material dispersion was changed from 320 parts to 345 parts.

[0324] <Toner B8> Toner particles B8 and toner B8 were obtained in the same manner as toner particles B1 and toner B1, respectively, except that the amount of phthalocyanine dye particle dispersion 2 added was changed from 113 parts to 84 parts, and the amount of amorphous polyester resin dispersion 1 added as a raw material dispersion was changed from 320 parts to 399 parts.

[0325] <Toner B9> Toner particles B9 and toner B9 were obtained in the same manner as toner particles B1 and toner B1, respectively, except that the amount of phthalocyanine dye particle dispersion 2 added was changed from 113 parts to 70 parts, and the amount of amorphous polyester resin dispersion 1 added as a raw material dispersion was changed from 320 parts to 349 parts.

[0326] <Toner B10> Toner particles B10 and toner B10 were obtained in the same manner as toner particles B1 and toner B1, respectively, except that the amount of phthalocyanine dye particle dispersion 2 added was changed from 113 parts to 150 parts, and the amount of amorphous polyester resin dispersion 1 added as a raw material dispersion was changed from 320 parts to 295 parts.

[0327] <Toner B11> Toner particles B11 and toner B11 were obtained in the same manner as toner particles B1 and toner B1, respectively, except that the amount of phthalocyanine dye particle dispersion 2 added was changed from 113 parts to 35 parts, and the amount of amorphous polyester resin dispersion 1 added as a raw material dispersion was changed from 320 parts to 372 parts.

[0328] <Toner B12> Toner particles B12 and toner B12 were obtained in the same manner as toner particles B1 and toner B1, except that the aggregation time before the additional addition was changed from 1.5 hours to 1.2 hours.

[0329] <Toner B15> Toner particles B15 and toner B15 were obtained in the same manner as toner particles B1 and toner B1, except that the aggregation time before the additional addition was changed from 1.5 hours to 1.8 hours.

[0330] <Toner B16> Toner particles B16 and toner B16 were obtained in the same manner as toner particles B1 and toner B1, except that the aggregation time before the additional addition was changed from 1.5 hours to 0.5 hours.

[0331] <Toner B18> Toner particles B18 and toner B18 were obtained in the same manner as toner particles B1 and toner B1, except that the aggregation time before the additional addition was changed from 1.5 hours to 2.5 hours.

[0332] <Toner B19> Toner particles B19 and toner B19 were obtained in the same manner as toner particles B1 and toner B1, respectively, except that crystalline polyester resin dispersion 2 was not added and the initial amount of amorphous polyester resin dispersion 1 added was changed from 320 parts to 357 parts.

[0333] <Toner B20> Toner particles B20 and toner B20 were obtained in the same manner as toner particles B1 and toner B1, respectively, except that the amount of crystalline polyester resin dispersion 2 added was changed from 56 parts to 50 parts and the amount of initial amorphous polyester resin dispersion 1 added was changed from 320 parts to 324 parts.

[0334] <Toner B21> Toner particles B21 and toner B21 were obtained in the same manner as toner particles B1 and toner B1, respectively, except that the amount of crystalline polyester resin dispersion 2 added was changed from 56 parts to 82 parts and the amount of initial amorphous polyester resin dispersion 1 added was changed from 320 parts to 303 parts.

[0335] <Toner B22> Toner particles B22 and toner B22 were obtained in the same manner as toner particles B1 and toner B1, except that the 320 parts of amorphous polyester resin dispersion 1 added initially was changed to 320 parts of styrene acrylic resin dispersion 3, the 70 parts of amorphous polyester resin dispersion 1 added additionally was changed to 70 parts of styrene acrylic resin dispersion 3, and the aggregation time before the additional addition was changed to 50°C until the aggregated particles had grown to 5.2 μm.

[0336] Content C of phthalocyanine dye in the obtained toner particles B1 to B2, B4 to B6, B8 to B12, B15 to B16, and B18 to B22 B , volume average particle size D B , crystalline resin content E B , and average circularity are shown in Table 3.

[0337] [Table 3]

[0338] <Toner B25> Toner particles B25 and toner B25 were obtained in the same manner as toner particles B1 and toner B1, respectively, except that 80 parts of phthalocyanine dye particle dispersion 2 was changed to 124 parts of cyan pigment dispersion 7. The cyan pigment content of toner particles B25 was 13.4 mass%, the volume average particle size was 5.8 μm, the crystalline resin content was 6.7 mass%, and the average circularity was 0.96.

[0339] [Production of Toner C] <Toner C1> Toner particles C1 and toner C1 were obtained in the same manner as toner particles B1 and toner B1, except that 113 parts of phthalocyanine dye particle dispersion 2 was replaced with 113 parts of pyrazolotriazole dye particle dispersion 5, respectively.

[0340] <Toner C3> Toner particles C3 and toner C3 were obtained in the same manner as toner particles B1 and toner B1, except that 113 parts of phthalocyanine dye particle dispersion 2 was replaced with 113 parts of pyrazolotriazole dye particle dispersion 6, respectively.

[0341] <Toner C5> Toner particles C5 and toner C5 were obtained in the same manner as toner particles C1 and toner C1, respectively, except that the amount of pyrazolotriazole dye particle dispersion 5 added was changed from 113 parts to 30 parts, and the amount of amorphous polyester resin dispersion 1 added as a raw material dispersion was changed from 320 parts to 375 parts.

[0342] <Toner C6> Toner particles C6 and toner C6 were obtained in the same manner as toner particles C1 and toner C1, respectively, except that the amount of pyrazolotriazole dye particle dispersion 5 added was changed from 113 parts to 75 parts, and the amount of amorphous polyester resin dispersion 1 added as the raw material dispersion was changed from 320 parts to 345 parts.

[0343] <Toner C8> Toner particles C8 and toner C8 were obtained in the same manner as toner particles C1 and toner C1, respectively, except that the amount of pyrazolotriazole dye particle dispersion 5 added was changed from 113 parts to 169 parts, and the amount of amorphous polyester resin dispersion 1 added as a raw material dispersion was changed from 320 parts to 283 parts.

[0344] <Toner C9> Toner particles C9 and toner C9 were obtained in the same manner as toner particles C1 and toner C1, respectively, except that the amount of pyrazolotriazole dye particle dispersion 5 added was changed from 113 parts to 70 parts and the amount of amorphous polyester resin dispersion 1 added as the raw material dispersion was changed from 320 parts to 349 parts.

[0345] <Toner C10> Toner particles C10 and toner C10 were obtained in the same manner as toner particles C1 and toner C1, respectively, except that the amount of pyrazolotriazole dye particle dispersion 5 added was changed from 113 parts to 150 parts and the amount of amorphous polyester resin dispersion 1 added as the raw material dispersion was changed from 320 parts to 295 parts.

[0346] <Toner C11> Toner particles C11 and toner C11 were obtained in the same manner as toner particles C1 and toner C1, respectively, except that the amount of pyrazolotriazole dye particle dispersion 5 added was changed from 113 parts to 35 parts, and the amount of amorphous polyester resin dispersion 1 added as a raw material dispersion was changed from 320 parts to 372 parts.

[0347] <Toner C12> Toner particles C12 and toner C12 were obtained in the same manner as toner particles C1 and toner C1, except that the aggregation time before the additional addition was changed from 1.5 hours to 1.2 hours.

[0348] <Toner C15> Toner particles C15 and toner C15 were obtained in the same manner as toner particles C1 and toner C1, except that the aggregation time before the additional addition was changed from 1.5 hours to 1.8 hours.

[0349] <Toner C16> Toner particles C16 and toner C16 were obtained in the same manner as toner particles C1 and toner C1, except that the aggregation time before the additional addition was changed from 1.5 hours to 0.5 hours.

[0350] <Toner C18> Toner particles C18 and toner C18 were obtained in the same manner as toner particles C1 and toner C1, except that the aggregation time before the additional addition was changed from 1.5 hours to 2.5 hours.

[0351] <Toner C19> Toner particles C19 and toner C19 were obtained in the same manner as toner particles C1 and toner C1, respectively, except that crystalline polyester resin dispersion 2 was not added and the initial amount of amorphous polyester resin dispersion 1 added was changed from 320 parts to 357 parts.

[0352] <Toner C20> Toner particles C20 and toner C20 were obtained in the same manner as toner particles C1 and toner C1, respectively, except that the amount of crystalline polyester resin dispersion 2 added was changed from 56 parts to 50 parts and the amount of initial amorphous polyester resin dispersion 1 added was changed from 320 parts to 324 parts.

[0353] <Toner C21> Toner particles C12 and toner C12 were obtained in the same manner as toner particles C1 and toner C1, respectively, except that the amount of crystalline polyester resin dispersion 2 added was changed from 56 parts to 87 parts and the amount of initial amorphous polyester resin dispersion 1 added was changed from 320 parts to 303 parts.

[0354] <Toner C22> Toner particles C22 and toner C22 were obtained in the same manner as toner particles C1 and toner C1, respectively, except that the 320 parts of amorphous polyester resin dispersion 1 added initially was changed to 320 parts of styrene acrylic resin dispersion 3, and the 70 parts of amorphous polyester resin dispersion 1 added later was changed to 70 parts of styrene acrylic resin dispersion 3.

[0355] Content C of pyrazolotriazole dye in the obtained toner particles C1, C3, C5 to C6, C8 to C12, C15 to C16, and C18 to C22 C , volume average particle size D C , crystalline resin content E C , and average circularity are shown in Table 4.

[0356] [Table 4]

[0357] <Toner C26> Toner particles C26 and toner C26 were obtained in the same manner as toner particles C1 and toner C1, respectively, except that 113 parts of pyrazolotriazole dye particle dispersion 5 was replaced with 113 parts of magenta pigment dispersion 8. The magenta pigment content in toner particles C26 was 13.4 mass%, the volume average particle size was 5.8 μm, the crystalline resin content was 6.7 mass%, and the average circularity was 0.96.

[0358] [Carrier manufacturing] Ferrite particles (volume average particle size: 35 μm): 100 parts Toluene: 14 parts Perfluorooctylethyl acrylate-methyl methacrylate copolymer (critical surface tension: 24 dyn / cm, copolymerization ratio 2:8, weight average molecular weight 77,000): 1.6 parts Carbon black (product name: VXC-72, manufactured by Cabot Corporation, volume resistivity: 100 Ω cm or less): 0.12 parts Cross-linked melamine resin particles (average particle size: 0.3 μm, insoluble in toluene): 0.3 parts First, carbon black diluted with toluene was added to a perfluorooctyl ethyl acrylate-methyl methacrylate copolymer and dispersed using a sand mill. Next, the above components except for the ferrite particles were dispersed with a stirrer for 10 minutes to prepare a coating layer forming liquid. Next, this coating layer forming liquid and the ferrite particles were placed in a vacuum degassing kneader and stirred at 60°C for 30 minutes, after which the pressure was reduced and the toluene was distilled off to form a resin coating layer, thereby obtaining a carrier.

[0359] [Preparation of developer] For each toner, 36 parts of the toner and 414 parts of the carrier were placed in a V blender and stirred for 20 minutes, and then sieved through a 212 μm sieve to prepare a developer.

[0360] [Examples 1 to 27, Comparative Examples 1 and 2] Toner A (developer A), toner B (developer B), and toner C (developer C) shown in Tables 5 and 6 below were combined to obtain a toner set. In the obtained toner set (C B +C C ) / C A The value of D B / D A The value of D C / D A The value of E B / E A The value of and E C / E A The values ​​of the cyan pigment and the color pigment content of the toner particles B16 are also shown in Tables 5 and 6. In Comparative Example 1, the cyan pigment content of the toner particles B16 was B In Comparative Example 2, the content of the magenta pigment in the toner particles C17 is C C It was calculated as:

[0361] [evaluation] <Image forming device> In the image forming apparatus shown in FIG. 1, developer A containing toner A shown in Tables 5 and 6 was supplied to developing device 120B of fifth image forming unit 150B, developer B containing toner B shown in Tables 5 and 6 was supplied to developing device 120C of third image forming unit 150C, and developer C containing toner C shown in Tables 5 and 6 was supplied to developing device 120M of second image forming unit 150M, and image formation was performed.

[0362] <Evaluation of brilliance (metallic finish)> Coated paper (OK topcoat + paper, surface roughness Rz = 1.98 μm, manufactured by Oji Paper Co., Ltd.) was used as the recording medium, and the toner A amount was 5 g / m at a fixing temperature of 180 °C (pressure roll temperature 100 °C). 2 , Toner B loading amount is 3 g / m 2 , and the amount of toner C is 3 g / m 2 A solid image (blue metallic image) of 1000 nm was formed. The images were printed 100 times in succession, and the 100th print was used for the subsequent evaluation. Using a three-dimensional spectral goniochromator DDS5000 (manufactured by Nippon Denshoku Industries Co., Ltd.), light was irradiated from a direction tilted 45° relative to the normal to the surface of the solid image, and the lightness index L*45° was measured by receiving the light from the normal to the surface of the solid image, the lightness index L*15° was measured by receiving the light from a direction tilted -30° relative to the normal to the surface of the solid image, and the lightness index L*110° was measured by receiving the light from a direction tilted -65° relative to the normal to the surface of the solid image. The flop index (FI) was then calculated by substituting each lightness index into the following formula. Based on the obtained values, the brilliance was evaluated according to the following criteria. The results are shown in Tables 5 and 6. Formula: FI=2.69×{(L*15°)-(L*110°)1.11} / (L*45°)0.86 (Evaluation criteria) A: Flop index value is 12.5 or more B: Flop index value is 10.0 or more and less than 12.5 C: Flop index value is 5.0 or more but less than 10.0, practical usable level D: Flop index value is 0 or greater but less than 5.0

[0363] <Evaluation of color variation> The 100th print produced in the above glitter evaluation was stored for 60 days under high temperature and high humidity conditions (temperature 30°C, humidity 80%). After the above storage procedure, the print was subjected to the same measurements as in the glitter evaluation above to calculate the flop index (FI) and determine the difference between the flop index values ​​before and after the storage procedure. Based on the obtained values, color variation was evaluated according to the following criteria. The results are shown in Tables 5 and 6. (Evaluation criteria) A: Flop index difference is less than 0.25 B: Flop index difference is 0.25 or more but less than 0.5 C: Flop index difference is 0.5 or more but less than 0.75 D: Flop index difference is 0.75 or more

[0364] [Table 5]

[0365] [Table 6]

[0366] From the results shown in Tables 5 and 6, it can be seen that the toner set of this example suppresses color fluctuation of images over time under high temperature and high humidity conditions, compared to the toner set of the comparative example.

[0367] Preferred aspects of the present disclosure will be described below. (((1))) Toner A containing toner particles A containing an aluminum pigment; Toner B containing toner particles B containing a phthalocyanine dye; Toner C containing toner particles C containing a pyrazolotriazole dye; A toner set for developing electrostatic images comprising: (((2))) The toner set for developing electrostatic images according to (((1))), wherein the phthalocyanine dye contains a phthalocyanine compound represented by the following formula (I):

[0368] [ka]

[0369] In the formula (I), M represents a silicon atom, a germanium atom, or a tin atom; Ra1 to Ra4 each independently represent an electron-withdrawing group; na1 to na4 each independently represent an integer of 0 to 4; and Z1 and Z2 each independently represent a hydroxy group, an aryloxy group having 6 to 18 carbon atoms, an alkoxy group having 1 to 22 carbon atoms, or a group represented by the following formula (II):

[0370] [ka]

[0371] In the formula (II), R3 to R5 each independently represent an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. (((3))) The toner set for developing electrostatic images according to (((1))) or (((2))), wherein the pyrazolotriazole dye contains a pyrazolotriazole compound represented by the following formula (III):

[0372] [ka]

[0373] In formula (III), Rx1 and Rx2 each independently represent an alkyl group which may have a substituent; Lx represents a hydrogen atom or an alkyl group which may have a substituent; Gx1 represents an alkyl group having 2 or more carbon atoms; Gx2 represents an aryl group or an alkyl group which may have a substituent; Gx3 represents a hydrogen atom, a halogen atom, Gx4-CO-NH-, or Gx5-N(Gx6)-CO-; Gx4 represents an aryl group or an alkyl group which may have a substituent; Gx5 and Gx6 each independently represent a hydrogen atom or an alkyl group which may have a substituent; and Qx1 to Qx5 each independently represent a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent. (((4))) The content of the aluminum pigment relative to the toner particles A is C A The content of the phthalocyanine dye relative to the toner particles B is C B The pyrazolotriazole dye for the toner particles C is C Then, (C B +C C ) / C A The toner set for developing electrostatic images according to any one of (((1))) to (((3))), wherein the value of is 0.40 or more and 2.00 or less. (((5))) Above (C B +C C ) / C A The toner set for developing electrostatic images according to (((4))), wherein the value of is 1.00 or more and 2.00 or less. (((6))) The volume average particle diameter of the toner particles A is D A , the volume average particle diameter of the toner particles B is D B , the volume average particle diameter of the toner particles C is D C When D B / D A The value of is 0.30 or more and 1.00 or less, and D C / D A The toner set for developing electrostatic images according to any one of (((1))) to (((5))), wherein the value of is 0.30 or more and 1.00 or less. (((7))) D B / D A The value of is 0.40 or more and 0.80 or less, and the D C / D A The toner set for developing electrostatic images according to (((6))), wherein the value of is 0.40 or more and 0.80 or less. (((8))) The toner set for developing electrostatic images according to any one of (((1))) to (((7))), wherein the toner particles A, the toner particles B, and the toner particles C contain a crystalline resin. (((9))) The content of the crystalline resin contained in the toner particles A is E A The content of the crystalline resin contained in the toner particles B is E B The content of the crystalline resin contained in the toner particles C is E C When E A <E B And E A <E C The toner set for developing electrostatic images according to (((8))), (((10))) E B / E A The value of is greater than 1.00 and less than or equal to 2.00, and E C / E A The toner set for developing electrostatic images according to (((9))), wherein the value of is more than 1.00 and not more than 2.00.

[0374] (((11))) A developer A containing the toner A in the toner set for developing electrostatic images according to any one of (((1))) to (((10))), and a developer B containing the toner B of the toner set for developing electrostatic images according to any one of (((1))) to (((10))); a developer C containing the toner C in the toner set for developing electrostatic images according to any one of (((1))) to (((10))); Electrostatic image developer set comprising: (((12))) A toner cartridge A containing the toner A in the toner set for developing electrostatic images according to any one of (((1))) to (((10))), and a toner cartridge B containing the toner B in the toner set for developing electrostatic images according to any one of (((1))) to (((10))); a toner cartridge C containing the toner C in the toner set for developing electrostatic images according to any one of (((1))) to (((10))); and A toner cartridge set that is detachably attached to an image forming apparatus. (((13))) A developing means A containing the developer A of the electrostatic image developer set described in (((11))), a developing means B containing the developer B of the electrostatic image developer set described in (((11))); a developing means C containing the developer C of the electrostatic image developer set described in (((11))); Equipped with A process cartridge is detachably mounted in an image forming apparatus. (((14))) An image forming means A for forming an image A using the toner A in the toner set for developing an electrostatic image according to any one of (((1))) to (((10))); an image forming means B for forming an image B using the toner B in the toner set for developing electrostatic images according to any one of (((1))) to (((10))); an image forming means C for forming an image C using the toner C in the toner set for developing electrostatic images according to any one of (((1))) to (((10))); a transfer means for transferring the image A, the image B, and the image C onto a recording medium; a fixing unit for fixing a toner image, in which the image A, the image B, and the image C are stacked, onto the recording medium; An image forming apparatus comprising: (((15))) An image forming step A in which an image A is formed using the toner A in the toner set for developing electrostatic images according to any one of ((1))) to (((10))); an image forming step B in which an image B is formed using the toner B of the toner set for developing electrostatic images according to any one of (((1))) to (((10))); an image forming step C of forming an image C using the toner C of the toner set for developing electrostatic images according to any one of (((1))) to (((10))); a transfer step of transferring the image A, the image B, and the image C onto a recording medium; a fixing step of fixing a toner image formed by stacking the image A, the image B, and the image C on the recording medium; An image forming method comprising:

[0375] According to the invention related to (((1))) or (((3))), there is provided a toner set for developing electrostatic images that can produce images in which color variation over time under high temperature and high humidity conditions is suppressed compared to when a pigment is used instead of a phthalocyanine dye or when a pigment is used instead of a pyrazolotriazole dye. According to the invention related to (((2))), there is provided a toner set for developing electrostatic images which can produce images in which color change over time under high temperature and high humidity conditions is suppressed compared to when the phthalocyanine dye is a compound represented by formula (I) in which M in formula (I) is copper. According to the invention (((4))), (C B +C C ) / C A The present invention provides a toner set for developing electrostatic images that can provide images that suppress color variation over time under high temperature and high humidity conditions and improve metallic appearance, as compared with when the value is less than 0.40 or more than 2.00. According to the invention (((5))), (C B +C C ) / C A In comparison with a case where the value is less than 1.00, an electrostatic image developing toner set is provided which can obtain an image in which color variation over time under high temperature and high humidity conditions is suppressed. According to the invention (((6))), D B / D A The value of is less than 0.30 or more than 1.00, or D C / D A In comparison with a case where the value is less than 0.30 or more than 1.00, an electrostatic image developing toner set is provided which can obtain an image in which color variation over time under high temperature and high humidity conditions is suppressed and metallic feel is improved. According to the invention (((7))), D B / D A The value of is less than 0.40 or more than 0.80, or D C / D A The present invention provides a toner set for developing electrostatic images that can provide images that suppress color variation over time under high temperature and high humidity conditions and improve metallic appearance, as compared with when the value is less than 0.40 or more than 0.80. According to the invention related to (((8))), there is provided a toner set for developing electrostatic images that can produce images in which color variation over time under high temperature and high humidity conditions is suppressed compared to when toner particles A, toner particles B, or toner particles C do not contain a crystalline resin. According to the invention (((9))), E A ≧E B or E A ≧E C The present invention provides a toner set for developing electrostatic images that can produce images in which color variation over time under high temperature and high humidity conditions is suppressed compared to other cases. According to the invention (((10))), E B / E A The value of is 1.00 or less or exceeds 2.00, or E C / E A In comparison with a case where the value is 1.00 or less or exceeds 2.00, an image in which color variation over time under high temperature and high humidity conditions is suppressed is provided.

[0376] According to the inventions pertaining to (((11))), (((12))), (((13))), (((14))), or (((15))), there are provided an electrostatic image developer set, a toner cartridge set, a process cartridge, an image forming apparatus, or an image forming method which can produce images in which color variation over time under high temperature and high humidity conditions is suppressed compared to when an electrostatic image developing toner set using a pigment instead of a phthalocyanine dye or an electrostatic image developing toner set using a pigment instead of a pyrazolotriazole dye is used. [Explanation of symbols]

[0377] 111Y, 111M, 111C, 111K, 111B, 207 Photoconductor 112, 224 Support roll 113, 222 Drive roll 114 Opposing Roll 115Y, 115M, 115C, 115K, 115B Photoconductor Cleaning Device 116 Intermediate transfer body cleaning device 117Y, 117M, 117C, 117K, 117B, 212 Primary transfer roll 118Y, 118M, 118C, 118K, 118B, 208 charging roll 119Y, 119M, 119C, 119K, 119B, 209 Exposure equipment 120Y, 120M, 120C, 120K, 120B, 211 developing device 133, 220 Intermediate transfer belt 134, 226 Secondary transfer roll 135, 228 Fixing device 140Y, 140M, 140C, 140K, 140B Toner Cartridges 150Y, 150M, 150C, 150K, 150B Image forming unit 200 Process Cartridge 213 Photoconductor cleaning device 216 Mounting Rail 217 Case 218 Opening 300, P recording paper< / x> < / lx>

Claims

1. Toner A including toner particles A containing an aluminum pigment; Toner B containing toner particles B containing a phthalocyanine dye; a toner C containing toner particles C containing a pyrazolotriazole dye; A toner set for developing electrostatic images comprising:

2. 2. The toner set for developing electrostatic images according to claim 1, wherein the phthalocyanine dye comprises a phthalocyanine compound represented by the following formula (I): 【Chemical 1】 In the formula (I), M represents a silicon atom, a germanium atom, or a tin atom; １ ~Ra ４ each independently represents an electron-withdrawing group; na1 to na4 each independently represent an integer of 0 to 4; Z １ and Z ２ each independently represents a hydroxy group, an aryloxy group having 6 to 18 carbon atoms, an alkoxy group having 1 to 22 carbon atoms, or a group represented by the following formula (II): 【Chemistry 2】 In the formula (II), R ３ ~R ５ each independently represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.

3. 2. The toner set for developing electrostatic images according to claim 1, wherein the pyrazolotriazole dye comprises a pyrazolotriazole compound represented by the following formula (III): 【Chemistry 3】 In formula (III), Rx １ and Rx ２ each independently represents an alkyl group which may have a substituent, Lx represents a hydrogen atom or an alkyl group which may have a substituent, Gx １ represents an alkyl group having two or more carbon atoms, and Gx ２ represents an aryl group or an alkyl group which may have a substituent; Gx ３ is a hydrogen atom, a halogen atom, Gx ４ —CO—NH—, or Gx ５ -N(Gx ６ )-CO-, Gx ４ represents an aryl group or an alkyl group which may have a substituent; Gx ５ and Gx ６ each independently represents a hydrogen atom or an alkyl group which may have a substituent; Qx １ ~Qx ５ each independently represents a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent.

4. The content of the aluminum pigment relative to the toner particles A is C Ａ The content of the phthalocyanine dye relative to the toner particles B is C Ｂ The pyrazolotriazole dye for the toner particles C is Ｃ When this is done, (C Ｂ +C Ｃ ) / C Ａ 2. The toner set for developing electrostatic images according to claim 1, wherein the value of is 0.40 or more and 2.00 or less.

5. Said (C Ｂ +C Ｃ ) / C Ａ 5. The toner set for developing electrostatic images according to claim 4, wherein the value of is 1.00 or more and 2.00 or less.

6. The volume average particle diameter of the toner particles A is D Ａ , the volume average particle diameter of the toner particles B is D Ｂ , the volume average particle diameter of the toner particles C is D Ｃ When this is done, D Ｂ / D Ａ The value of is 0.30 or more and 1.00 or less, and D Ｃ / D Ａ 2. The toner set for developing electrostatic images according to claim 1, wherein the value of is 0.30 or more and 1.00 or less.

7. The above D Ｂ / D Ａ The value of is 0.40 or more and 0.80 or less, and the D Ｃ / D Ａ 7. The toner set for developing electrostatic images according to claim 6, wherein the value of is 0.40 or more and 0.80 or less.

8. 2. The toner set for developing electrostatic images according to claim 1, wherein the toner particles A, the toner particles B, and the toner particles C contain a crystalline resin.

9. The content of the crystalline resin contained in the toner particles A is E Ａ The content of the crystalline resin contained in the toner particles B is E Ｂ The content of the crystalline resin contained in the toner particles C is E Ｃ When this is done, E Ａ <E Ｂ And E Ａ <E Ｃ 9. The toner set for developing electrostatic images according to claim 8, wherein

10. E Ｂ / E Ａ The value of is more than 1.00 and less than 2.00, and E Ｃ / E Ａ 10. The toner set for developing electrostatic images according to claim 9, wherein the value of is more than 1.00 and not more than 2.

00.

11. Developer A containing the toner A of the toner set for developing electrostatic images according to any one of claims 1 to 10; Developer B containing the toner B of the toner set for developing electrostatic images according to any one of claims 1 to 10; a developer C containing the toner C of the toner set for developing electrostatic images according to any one of claims 1 to 10; Electrostatic image developer set comprising:

12. a toner cartridge A containing the toner A of the toner set for developing electrostatic images according to any one of claims 1 to 10; a toner cartridge B containing the toner B of the toner set for developing electrostatic images according to any one of claims 1 to 10; a toner cartridge C containing the toner C of the toner set for developing electrostatic images according to any one of claims 1 to 10; and A toner cartridge set that is detachably attached to an image forming apparatus.

13. a developing means A containing the developer A of the electrostatic image developer set according to claim 11; a developing means B containing the developer B of the electrostatic image developer set according to claim 11; a developing means C containing the developer C of the electrostatic image developer set according to claim 11; Equipped with A process cartridge is detachably mounted in an image forming apparatus.

14. an image forming means A for forming an image A using the toner A of the toner set for developing an electrostatic image according to any one of claims 1 to 10; an image forming means B for forming an image B using the toner B of the toner set for developing an electrostatic image according to any one of claims 1 to 10; an image forming means C for forming an image C using the toner C of the toner set for developing an electrostatic image according to any one of claims 1 to 10; a transfer means for transferring the image A, the image B, and the image C onto a recording medium; a fixing unit for fixing a toner image, in which the image A, the image B, and the image C are stacked, onto the recording medium; An image forming apparatus comprising:

15. an image forming step A for forming an image A using the toner A of the toner set for developing electrostatic images according to any one of claims 1 to 10; an image forming step B for forming an image B using the toner B of the toner set for developing an electrostatic image according to any one of claims 1 to 10; an image forming step C of forming an image C using the toner C of the toner set for developing an electrostatic image according to any one of claims 1 to 10; a transfer step of transferring the image A, the image B, and the image C onto a recording medium; a fixing step of fixing a toner image formed by stacking the image A, the image B, and the image C on the recording medium; An image forming method comprising:

Images