Resin particles

Abstract

The present invention relates to a resin particle comprising a fluorescent colorant and a coloring pigment, wherein the hue angle of the resin particle is different from the hue angle of the fluorescent colorant, and when the fluorescence peak wavelength in the spectral reflectance of the fluorescent colorant is A (nm), the integrated value of the spectral reflectance (%) of the coloring pigment in the wavelength range of A (nm) ± 30nm is 2,500 or more.

Description

Technical Field

[0001] The present invention relates to resin particles. Background Art

[0002] Methods of visualizing image information via electrostatic images, such as electrophotography, are currently used in various fields.

[0003] In the past, in electronic photography, the following method is usually used: various mechanisms are used to form an electrostatic latent image on a photoreceptor or an electrostatic recording body, and electrostatically detecting (anti-charge) particles called toners are attached to the electrostatic latent image to develop the electrostatic latent image (toner image), transfer it to the surface of the transfer body, and fix it by heating, etc., and visualization is achieved through such multiple steps.

[0004] In addition, as a conventional toner, the toner described in Patent Document 1 is well known.

[0005] Japanese Patent Application Laid-Open No. 2017-3818 discloses a toner containing a binder resin and a colorant, wherein the colorant contains a coloring pigment and a fluorescent dye, and the mass-based contents of the coloring pigment and the fluorescent dye in the toner are W and W, respectively. G , W F When the above W G and the above W F Satisfies the following formula (1),

[0006] W G ×0.5>W F >W G ×0.025 (1)

[0007] Assume that the absorption peak wavelength of the above coloring pigment is P G , let the peak wavelength of the fluorescent dye be P F When the above P G and the above P F The following formula (2) is satisfied.

[0008] P G <P F (2) Summary of the invention

[0009] Technical problem to be solved by the invention

[0010] The technical problem to be solved by the present invention is to provide a resin particle, the fluorescence intensity of the obtained image is higher than the following situation, wherein: the resin particle contains a fluorescent colorant and a coloring pigment, the hue angle of the resin particle is different from the hue angle of the above-mentioned fluorescent colorant, and when the fluorescence peak wavelength in the spectral reflectance of the above-mentioned fluorescent colorant is A (nm), the integrated value of the spectral reflectance (%) of the above-mentioned coloring pigment in the wavelength range of A (nm) ± 30nm is less than 2,500.

[0011] Means for solving technical problems

[0012] According to a first aspect of the present invention, there is provided a resin particle comprising a fluorescent colorant and a coloring pigment, wherein the hue angle of the resin particle is different from the hue angle of the fluorescent colorant, and when the fluorescence peak wavelength in the spectral reflectance of the fluorescent colorant is A (nm), the integrated value of the spectral reflectance (%) of the coloring pigment in the wavelength range of A (nm) ± 30nm is 2,500 or more.

[0013] According to the second aspect of the present invention, a color difference ΔE between the resin particles and the fluorescent colorant is 3 or more.

[0014] According to a third aspect of the present invention, a difference between a hue angle of the resin particles and a hue angle of the fluorescent colorant is 1 (°) or more.

[0015] According to a fourth aspect of the present invention, the fluorescent colorant includes at least one compound having a xanthene structure; and the coloring pigment is a compound having a quinacridone structure.

[0016] According to the fifth aspect of the present invention, a color difference ΔE between the resin pellet and the color sample DIC584B is 10 or less.

[0017] According to the sixth aspect of the present invention, a color difference ΔE between the resin pellet and the color sample DIC584 is 10 or less.

[0018] According to the seventh aspect of the present invention, the content of the fluorescent colorant is 0.1% to 3.5% by mass relative to the total mass of the resin particles, and the content of the coloring pigment is 0.05% to 1.5% by mass relative to the total mass of the resin particles.

[0019] According to an eighth aspect of the present invention, the fluorescent colorant includes at least one compound having a heterocyclic structure formed of a benzimidazole skeleton and a coumarin skeleton, and the coloring pigment is a compound having an azo structure or a benzimidazolone structure.

[0020] According to the ninth aspect of the present invention, a color difference ΔE between the resin pellet and the color sample DIC590 is 10 or less.

[0021] According to a tenth aspect of the present invention, a color difference ΔE between the resin pellet and a color sample PANTONE 803C is 10 or less.

[0022] According to the 11th aspect of the present invention, the content of the fluorescent colorant is 0.1 mass % to 3.5 mass % based on the total mass of the resin particles, and the content of the coloring pigment is 0.05 mass % to 1.5 mass % based on the total mass of the resin particles.

[0023] According to a twelfth aspect of the present invention, the fluorescent colorant is a compound having a triarylmethane structure, and the coloring pigment is a compound having a phthalocyanine structure.

[0024] According to the thirteenth aspect of the present invention, a color difference ΔE between the resin pellet and the color sample DIC591 is 10 or less.

[0025] According to a fourteenth aspect of the present invention, a color difference ΔE between the resin pellets and a color sample PANTONE 802C is 10 or less.

[0026] According to the fifteenth aspect of the present invention, the content of the fluorescent colorant is 0.1% to 3.5% by mass, and the content of the coloring pigment is 0.05% to 1.5% by mass, based on the total mass of the resin particles.

[0027] According to the 16th embodiment of the present invention, the fluorescent colorant is a compound having a heterocyclic structure formed by a benzimidazole skeleton and a coumarin skeleton, a compound having an acridine structure or a compound having a methine structure, and the coloring pigment is a compound having an azo structure, a naphthamide structure or an anthraquinone structure.

[0028] According to the seventeenth aspect of the present invention, a color difference ΔE between the resin pellets and a color sample PANTONE 804C is 10 or less.

[0029] According to the eighteenth aspect of the present invention, a color difference ΔE between the resin pellet and the color sample DIC587 is 10 or less.

[0030] According to the 19th aspect of the present invention, a color difference ΔE between the resin pellet and the color sample DIC588 is 10 or less.

[0031] Effects of the Invention

[0032] According to the above-mentioned embodiment 1, 4, 5, 6, 8, 9, 10, 12, 13, 14, 16, 17, 18 or 19, a resin particle is provided, and the fluorescence intensity of an image obtained by the resin particle of the embodiment is high compared with the case where the resin particle contains a fluorescent colorant and a coloring pigment, the hue angle of the resin particle is different from the hue angle of the above-mentioned fluorescent colorant, and when the fluorescence peak wavelength in the spectral reflectance of the above-mentioned fluorescent colorant is A (nm), the integrated value of the spectral reflectance (%) of the above-mentioned coloring pigment in the wavelength range of A (nm) ± 30nm is less than 2,500.

[0033] According to the second aspect, there is provided a resin particle, wherein the target color reproducibility and fluorescence intensity of an image obtained using the resin particle are further improved compared to a case where the color difference ΔE between the resin particle and the fluorescent colorant is less than 3.

[0034] According to the third aspect, there is provided a resin particle, wherein the color reproducibility and fluorescence intensity of an image obtained using the resin particle are further improved compared to a case where the difference between the hue angle of the resin particle and the hue angle of the fluorescent colorant is less than 1 (°).

[0035] According to the above-mentioned seventh embodiment, a resin particle is provided, in which the target color reproducibility and fluorescence intensity of the image obtained by using the resin particles of this embodiment are further improved compared with the case where the content of the above-mentioned fluorescent colorant is less than 0.1 mass% or greater than 3.5 mass% relative to the total mass of the above-mentioned resin particles, or the content of the above-mentioned coloring pigment is less than 0.05 mass% or greater than 1.5 mass% relative to the total mass of the above-mentioned resin particles.

[0036] According to the above-mentioned 11th scheme, a resin particle is provided, and the target color reproducibility and fluorescence intensity of the image obtained by using the resin particles of the scheme are further improved compared with the case where the content of the above-mentioned fluorescent colorant is less than 0.1 mass% or greater than 3.5 mass% relative to the total mass of the above-mentioned resin particles, or the content of the above-mentioned coloring pigment is less than 0.05 mass% or greater than 1.5 mass% relative to the total mass of the above-mentioned resin particles.

[0037] According to the above-mentioned 15th scheme, a resin particle is provided, and the target color reproducibility and fluorescence intensity of the image obtained by using the resin particles of this scheme are further improved compared with the case where the content of the above-mentioned fluorescent colorant is less than 0.1 mass% or greater than 3.5 mass% relative to the total mass of the above-mentioned resin particles, or the content of the above-mentioned coloring pigment is less than 0.05 mass% or greater than 1.5 mass% relative to the total mass of the above-mentioned resin particles. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 2 is a diagram schematically showing the structure of the image forming apparatus according to the present embodiment.

[0039] Figure 2 It is a schematic structural diagram showing the process cartridge of this embodiment. DETAILED DESCRIPTION

[0040] In the present specification, when referring to the amount of each component in a composition, if two or more substances corresponding to each component exist in the composition, unless otherwise stated, it means the total amount of the two or more substances present in the composition.

[0041] In the present specification, “toner for developing an electrostatic image” is also simply referred to as “toner”, and “developer for developing an electrostatic image” is also simply referred to as “developer”.

[0042] Next, an embodiment as an example of the present invention will be described.

[0043] <Resin Pellets>

[0044] The resin particles of this embodiment contain a fluorescent colorant and a coloring pigment, the hue angle of the resin particles is different from the hue angle of the above-mentioned fluorescent colorant, and the fluorescence peak wavelength in the spectral reflectance of the above-mentioned fluorescent colorant is assumed to be A (nm), and the integrated value of the spectral reflectance (%) of the above-mentioned coloring pigment in the wavelength range of A (nm) ± 30 (nm) is greater than 2,500.

[0045] In recent years, various companies have launched printers for commercial printing, publishing, paper packaging and other fields, as well as models that use spot color toners as an attraction. Regarding fluorescent colors, there are known colors with very strong fluorescent feeling, such as PANTONE's Neons Guide, and light fluorescent colors, such as DIC Color Guide of DIC Corporation and COLORFINDER of Toyo Ink Co., Ltd. However, when trying to reproduce fluorescent colors using toners whose hues are adjusted by containing fluorescent colorants and pigments, the fluorescence intensity may decrease.

[0046] In addition, the present inventors conducted detailed studies and found that, in conventional resin particles containing a fluorescent colorant and a coloring pigment, absorption of the coloring pigment inhibits fluorescence generated by the fluorescent colorant, thereby reducing fluorescence intensity.

[0047] The resin particles of the present embodiment have the above-described structure, and the fluorescence intensity of the obtained image is high. The reason for this is not clear, but is presumed to be the following.

[0048] The resin particles contain a fluorescent colorant and a coloring pigment, the hue angle of the resin particles is different from the hue angle of the fluorescent colorant, and the integrated value of the spectral reflectance (%) of the coloring pigment in the wavelength range of A (nm) ± 30 (nm) is 2,500 or more, which does not hinder the fluorescence generated by the fluorescent colorant, suppresses the reduction of the fluorescence intensity due to the coloring pigment, and the color reproducibility and fluorescence intensity of the obtained image are high. In addition, in order to suppress the reduction of the fluorescence intensity due to the coloring pigment, it is effective to add a combination of a specific fluorescent colorant and a coloring pigment at a specific concentration.

[0049] The resin particles according to this embodiment will be described in detail below.

[0050] The hue angle of the resin particles is measured by the following method.

[0051] In an environmental room at a temperature of 25° C. and a humidity of 60% RH, the main body, developer, and toner cartridge of DocuCentreColor 400CP manufactured by Fuji Xerox Corporation were cleaned by fully removing the previously installed developer and toner, and then resin pellets were added to the toner cartridge.

[0052] Next, the developer toner amount of a monochrome 100% image on OS coated paper manufactured by Fuji Xerox Co., Ltd. was adjusted to 4.5 g / m 2 , an image consisting of only resin particles with a size of 5 cm × 5 cm was produced, and the resulting image density (L * ), red(a * ) and blue (b * The image density was measured using X-Rite 939 (manufactured by X-Rite, with a hole of 4 mm), and the image surface was randomly measured 10 times, and the image density was calculated by averaging.

[0053] From the obtained a * and b * Calculate the hue angle (=tan(b * / a * )).

[0054] The hue angle of the fluorescent colorant was calculated by removing the colorant (coloring pigment, etc.) other than the fluorescent colorant from the resin particles to prepare a sample, and the hue angle was calculated by the same method as the above-mentioned resin particles.

[0055] In the resin particles of the present embodiment, assuming that the fluorescence peak wavelength in the spectral reflectance of the above-mentioned fluorescent colorant is A (nm), the integrated value of the spectral reflectance (%) of the above-mentioned coloring pigment in the wavelength range of A (nm) ± 30 (nm) is 2,500 or more. From the perspective of fluorescence intensity and color reproducibility, the integrated value is preferably 2,800 or more, more preferably 2,900 or more, and particularly preferably 3,000 or more.

[0056] For example, if the fluorescence peak wavelength A is 600 nm, the wavelength range is 570 nm to 630 nm.

[0057] In addition, the unit of the above-mentioned integrated value is wavelength (nm)×spectral reflectance (%)=nm, but this description is omitted.

[0058] The spectral reflectance of the resin particles is measured by the following method.

[0059] In an environmental room at a temperature of 25° C. and a humidity of 60% RH, the main body, developer, and toner cartridge of DocuCentreColor 400CP manufactured by Fuji Xerox Corporation were cleaned by fully removing the previously installed developer and toner, and then resin pellets were added to the toner cartridge.

[0060] Next, the developer toner amount of a monochrome 100% image on OS coated paper manufactured by Fuji Xerox Co., Ltd. was adjusted to 4.5 g / m 2 , make an image of size 5cm×5cm consisting only of resin particles, use X-Rite939 (manufactured by X-Rite, hole 4mm), measure the spectral reflectance in the visible light region at 10 random locations within the image surface, average them, and calculate the spectral reflectance of the resin particles.

[0061] The spectral reflectance of the fluorescent colorant is calculated by removing colorants (coloring pigments, etc.) other than the fluorescent colorant from the resin particles to prepare a sample, and the spectral reflectance of the fluorescent colorant is calculated by the same method as the spectral reflectance of the resin particles described above.

[0062] The spectral reflectance of the coloring pigment is calculated by the same method as the spectral reflectance of the resin particles described above by removing coloring agents (fluorescent coloring agents, etc.) other than the coloring pigment from the resin particles to prepare a sample.

[0063] The resin particles contain a binder resin, a fluorescent colorant, a coloring pigment, and, if necessary, a release agent and other additives, and preferably contain a binder resin, a fluorescent colorant, a coloring pigment, and a release agent.

[0064] -Fluorescent colorant-

[0065] The fluorescent colorant may be any colorant that exhibits fluorescence, and is preferably a colorant that exhibits fluorescence in the visible light region (wavelength 380 nm to 760 nm). In addition, the light that excites the fluorescent colorant is not particularly limited, but preferably includes at least visible light or ultraviolet light, and more preferably includes at least visible light.

[0066] Furthermore, the fluorescent colorant may be a fluorescent pigment or a fluorescent dye, and is preferably a fluorescent dye.

[0067] It should be noted that, in the present embodiment, "pigment" refers to a colorant whose solubility in 100 g of water at 23°C and in 100 g of cyclohexanone at 23°C are both less than 0.1 g, and "dye" refers to 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.

[0068] In addition, the color of the fluorescent colorant is not particularly limited and may be appropriately selected as desired.

[0069] Examples of the fluorescent colorant include a fluorescent pink colorant, a fluorescent red colorant, a fluorescent orange colorant, a fluorescent yellow colorant, and a fluorescent green colorant.

[0070] From the perspective of fluorescence visual intensity and target color reproducibility, the fluorescent colorant preferably has a fluorescence peak wavelength in spectral reflectance of 380 nm to 760 nm, preferably in a region separated from the absorption wavelength of the target color.

[0071] For example, when it is desired to exhibit fluorescent pink color, it is more preferable to have the fluorescence peak wavelength in the range of 560 nm to 700 nm, and particularly preferably in the range of 580 nm to 680 nm.

[0072] In view of the fluorescence visual intensity, the spectral reflectance of the fluorescent colorant at the fluorescence peak wavelength is preferably 100% or more, more preferably 105% or more, and particularly preferably 110% or more.

[0073] As the fluorescent colorant, a known fluorescent colorant can be used, and specific examples thereof include Basic Red 1 (Rhodamine 6GCP), Basic Red 1:1 (Rhodamine 6GCP-N), Basic Red 2, Basic Red 12, Basic Red 13, Basic Red 14, Basic Red 15, Basic Red 36, Basic Violet 7, Basic Violet 10 (Rhodamine B), Basic Violet 11 (Rhodamine 3B), Basic Violet 11:1 (Rhodamine A), Basic Violet 15, Basic Violet 16, Basic Violet 27, Basic Violet 49, CI Pigment Yellow 101, Basic Yellow 1, Basic Yellow 2, Basic Yellow 9, Basic Yellow 24, Basic Yellow 40, Basic Orange 15, Basic Orange 22, Basic Blue 1, Basic Blue 3, Basic Blue 7, Basic Blue 9, Basic Blue 45, Basic Green 1, Acid Yellow 3, Acid Yellow 7, Acid Yellow 73, Acid Yellow 87, Acid Yellow 184, Acid Yellow 245, Acid Yellow 250, Acid Red 51, Acid Red 52, Acid Red 57, Acid Red 77, Acid Red 87, Acid Red 8 9, Acid Red 92, Acid Blue 9, Acid Black 2, Solvent Yellow 43, Solvent Yellow 44, Solvent Yellow 85, Solvent Yellow 98, Solvent Yellow 116, Solvent Yellow 131, Solvent Yellow 145, Solvent Yellow 160:1, Solvent Yellow 172, Solvent Yellow 185, Solvent Yellow 195, Solvent Yellow 196, Solvent Orange 63, Solvent Orange 112, Solvent Red 49, Solvent Red 149, Solvent Red 175, Solvent Red 196, Solvent Red 197, Solvent Blue 5, Solvent Green 5, Solvent Green 7, Direct Yellow 27, Direct Yellow 85, Direct Yellow 96, Direct Orange 8, Direct Red 2, Direct Red 9, Direct Blue 22, Direct Blue 199, Direct Green 6, Disperse Yellow 11, Disperse Yellow 82, Disperse Yellow 139, Disperse Yellow 184, Disperse Yellow 186, Disperse Yellow 199, Disperse Yellow 202, Disperse Yellow 232, Disperse Orange 11, Disperse Orange 32, Disperse Red 58, Disperse Red 274, Disperse Red 277, Disperse Red 303, Disperse Blue 7, Reaction Yellow 78, Vat Red 41, etc.

[0074] Among them, from the aspect of fluorescence intensity, at least one fluorescent colorant selected from the group consisting of Basic Red 1 (Rhodamine 6GCP), Basic Red 1:1 (Rhodamine 6GCP-N), Basic Red 2, Basic Red 12, Basic Red 13, Basic Red 14, Basic Red 15, Basic Red 36, Basic Violet 7, Basic Violet 10 (Rhodamine B), Basic Violet 11 (Rhodamine 3B), Basic Violet 11:1 (Rhodamine A), Basic Violet 15, Basic Violet 16, Basic Violet 27, Basic Yellow 24, Basic Yellow 40, Basic Orange 15, Basic Orange 22, and Basic Green 1 is preferred.

[0075] In addition, as a fluorescent colorant, from the aspects of fluorescence intensity and target color reproducibility, it is preferred to include a compound having a xanthene structure, a heterocyclic structure formed by a benzimidazole skeleton and a coumarin skeleton, a triarylmethane structure, an acridine structure, and a methine structure, and it is more preferred to include a fluorescent colorant having a xanthene structure.

[0076] In addition, the xanthene structure is preferably a compound having a rhodamine structure, a fluorescein structure, or an eosin structure, and is particularly preferably a compound having a rhodamine structure.

[0077] The resin particles may contain a single fluorescent colorant or a combination of two or more fluorescent colorants.

[0078] The content of the fluorescent colorant is preferably 0.01% by mass to 20% by mass, more preferably 0.1% by mass to 3.5% by mass, and particularly preferably 0.2% by mass to 2.0% by mass, based on the entire resin particles, from the viewpoint of fluorescence intensity.

[0079] -Coloring Pigments-

[0080] The coloring pigment may be any coloring pigment other than the above-mentioned fluorescent coloring agent, and a known coloring pigment may be used.

[0081] The coloring pigment is preferably a coloring pigment that does not exhibit fluorescence in the visible light region.

[0082] Specific examples of the coloring pigment include CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 14, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 38, CI Pigment Red 41, CI Pigment Red 42, CI Pigment Red 43, CI Pigment Red 44, CI Pigment Red 45, CI Pigment Red 46, CI Pigment Red 47, CI Pigment Red 48, CI Pigment Red 49, CI Pigment Red 50, CI Pigment Red 51, CI Pigment Red 52, CI Pigment Red 53, CI Pigment Red 54, CI Pigment Red 55, CI Pigment Red 56, CI Pigment Red 57, CI Pigment Red 58, CI Pigment Red 59, CI Pigment Red 60, CI Pigment Red 61, CI Pigment Red 62, CI Pigment Red 63, CI Pigment Red 64, CI Pigment Red 65 CI Pigment Red 48, CI Pigment Red 48:1, CI Pigment Red 48:2, CI Pigment Red 48:3, CI Pigment Red 48:4, CI Pigment Red 49, CI Pigment Red 52, CI Pigment Red 53:1, CI Pigment Red 54, CI Pigment Red 57:1, CI Pigment Red 58, CI Pigment Red 60:1, CI Pigment Red 63, CI Pigment Red 64:1, CI Pigment Red 68, CI Pigment Red 81:1, CI Pigment Red 81:4, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 89, CI Pigment Red 112, CI Pigment Red 114, CI Pigment Red 1 22, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 166, CI Pigment Red 170, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 184, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 210, CI Pigment Red 213, CI Pigment Red 220, CI CI Pigment Red 221, CI Pigment Red 238, CI Pigment Red 242, CI Pigment Red 245, CI Pigment Red 253, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 256, CI Pigment Red 258, CI Pigment Red 264, CI Pigment Red 266, CI Pigment Red 269, CI Pigment Red 282, etc., CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 32, etc., CI Pigment Blue 15:6, CI Pigment Blue 60, etc., CI Pigment Orange 13, CI Pigment Orange 16, CI Pigment Orange 38, CI Pigment Orange 43, CI Pigment Orange 62, etc., CIPigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 17, CI Pigment Yellow 74, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 155, CI Pigment Yellow 180, CI Pigment Yellow 185, etc., CI Pigment Green 7, CI Pigment Green 36, etc., Red Iron Oxide, Cadmium Red, Red Lead, Mercuric Sulfide, Permanent Red 4R, Lisol Red, Pyrazolone Red, Wotting Red, Calcium Salt, Titanium Oxide, Color Lake Red D, Brilliant Carmine 6B, Aeolian Lake, Rhodamine Lake B, Alizarin Lake, Brilliant Carmine 3B, Carbon Black, Chrome Yellow, Hansa Yellow, Benzidine Yellow, Vat Yellow, Quinoline Yellow, Pigment Yellow, Permanent Orange GTR, Pyrazolone Orange, Sulfur Resistant Orange, Brilliant Carmine 3B, Brilliant Carmine 6B, DuPont Oil Red, Lake Red C, Aniline Blue, Ultramarine Blue, Oil-soluble Blue, Methylene Blue Chloride, Phthalocyanine Blue, Pigment Blue, Phthalocyanine Green, Malachite Green Oxalate and other pigments.

[0083] The coloring pigment may be contained alone or in combination of two or more.

[0084] In addition, from the viewpoint of fluorescence intensity and target color reproducibility, it is preferable to use a coloring pigment that does not have an absorption wavelength near the fluorescence peak wavelength of the fluorescent coloring agent.

[0085] The coloring pigment may be a coloring agent that has been subjected to surface treatment as required, or may be used in combination with a dispersant. In addition, two or more coloring agents may be used in combination.

[0086] The content of the coloring pigment is preferably 0.005% by mass to 10% by mass, more preferably 0.05% by mass to 1.5% by mass, and particularly preferably 0.05% by mass to 1.2% by mass, based on the entire resin particles, from the perspective of fluorescence intensity and target color reproducibility.

[0087] From the viewpoint of fluorescence intensity and target color reproducibility, the ratio of the content WA of the fluorescent colorant to the content WB of the coloring pigment in the resin particles (WB / WA) is preferably 0.001 to 10, more preferably 0.005 to 5, particularly preferably 0.01 to 1.5.

[0088] <<The case of fluorescent pink resin particles>>

[0089] In the case where the resin particles of the present embodiment are fluorescent pink resin particles, in the resin particles of the present embodiment, from the aspects of fluorescence intensity and target color reproducibility, the fluorescent colorant more preferably has a fluorescence peak wavelength in the spectral reflectivity of not less than 560 nm and not more than 700 nm, and further preferably has a fluorescence peak wavelength in the spectral reflectivity of not less than 580 nm and not more than 680 nm.

[0090] In addition, when the resin particles of this embodiment are fluorescent pink resin particles, in the resin particles of this embodiment, from the aspects of fluorescence intensity and target color reproducibility, the above-mentioned coloring pigment preferably includes at least one magenta pigment, preferably a magenta pigment with little absorption in the wavelength region of the fluorescence peak wavelength A (nm) ± 30 (nm) of the above-mentioned fluorescent colorant.

[0091] Among them, in the resin particles of the present embodiment, it is more preferable that the fluorescent colorant is a compound having a xanthene structure and the coloring pigment is a compound having a quinacridone structure from the viewpoint of fluorescence intensity and target color reproducibility.

[0092] The compound having a xanthene structure is preferably a compound having a rhodamine structure, a fluorescein structure or an eosin structure, and more preferably a compound having a rhodamine structure, from the viewpoint of fluorescence intensity and target color reproducibility.

[0093] In addition, examples of the above-mentioned compounds having a xanthene structure include Basic Red 1 (Rhodamine 6GCP), Basic Red 1:1 (Rhodamine 6GCP-N), Basic Violet 10 (Rhodamine B), Basic Violet 11 (Rhodamine 3B), Basic Violet 11:1 (Rhodamine A), Acid Red 51, Acid Red 52, Acid Red 87, Acid Red 92, Solvent Red 49, etc.

[0094] As the above-mentioned compound having a quinacridone structure, from the aspects of fluorescence intensity and target color reproducibility, it is preferably at least one compound selected from the group consisting of CI Pigment Red 122, CI Pigment Red 202, CI Pigment Red 207, CI Pigment Red 209, CI Pigment Red 238 and CI Pigment Violet 19, more preferably at least one compound selected from the group consisting of CI Pigment Red 122, CI Pigment Red 238 and CI Pigment Violet 19, and further preferably at least two compounds selected from the group consisting of CI Pigment Red 122, CI Pigment Red 238 and CI Pigment Violet 19.

[0095] In addition, when the resin particles of the present embodiment are fluorescent pink resin particles, from the perspective of target color reproducibility, it is preferred that the color difference ΔE between the resin particles and the color sample DIC584B is 10 or less, the color difference ΔE between the resin particles and the color sample DIC584 is 10 or less, or the color difference ΔE between the resin particles and the color sample PANTONE806C is 10 or less, more preferably the color difference ΔE between the resin particles and the color sample DIC584B is 10 or less, or the color difference ΔE between the resin particles and the color sample DIC584 is 10 or less, and particularly preferably the color difference ΔE between the resin particles and the color sample DIC584B is 10 or less. In addition, the ΔE is preferably 5 or less. It should be noted that the lower limit of ΔE is 0.

[0096] It should be noted that the color sample DIC584B and the like are color samples in the DIC Color Guide of the above-mentioned DIC Corporation, and the color sample PANTONE806C and the like are color samples in the Neons Guide of the above-mentioned PANTONE company.

[0097] ΔE is measured by the following method.

[0098] In an environmental room at a temperature of 25° C. and a humidity of 60% RH, the main body, developer, and toner cartridge of DocuCentreColor 400CP manufactured by Fuji Xerox Corporation were cleaned by fully removing the previously installed developer and toner, and then resin pellets were added to the toner cartridge.

[0099] Next, the developer toner amount of a monochrome 100% image on OS coated paper manufactured by Fuji Xerox Co., Ltd. was adjusted to 4.5 g / m 2 , an image consisting of only resin particles with a size of 5 cm × 5 cm was produced, and the resulting image density (L * a ), red(a * a ) and blue (b * a The image density was measured using X-Rite 939 (manufactured by X-Rite, with a hole of 4 mm), and the image surface was randomly measured 10 times, and the average was taken to calculate the image density.

[0100] In addition, the L of the target color sample is calculated in the same way as the above-mentioned image measurement method. * b 、a * b and b * b .

[0101] According to the obtained resin particles and color samples L * 、a * and b * Calculate the color difference ΔE=√{(L * b -L * a ) 2 +(a * b -a * a ) 2 +(b * b -b * a ) 2}).

[0102] Furthermore, when the resin particles of the present embodiment are fluorescent pink resin particles, from the aspects of fluorescence intensity and target color reproducibility, it is preferred that the content of the fluorescent colorant is 0.01% by mass to 20% by mass, and the content of the coloring pigment is 0.005% by mass to 10% by mass, relative to the total mass of the resin particles. It is more preferred that the content of the fluorescent colorant is 0.1% by mass to 3.5% by mass, and the content of the coloring pigment is 0.05% by mass to 1.5% by mass, relative to the total mass of the resin particles. It is particularly preferred that the content of the fluorescent colorant is 0.2% by mass to 2.0% by mass, and the content of the coloring pigment is 0.05% by mass to 1.2% by mass, relative to the total mass of the resin particles.

[0103] <<Case of Fluorescent Yellow Resin Pellets>>

[0104] When the resin particles of the present embodiment are fluorescent yellow resin particles, examples of the fluorescent colorant include CI Pigment Yellow 101, Basic Yellow 1, Basic Yellow 2, Basic Yellow 9, Basic Yellow 24, Basic Yellow 40, Solvent Yellow 43, Solvent Yellow 44, Solvent Yellow 85, Solvent Yellow 98, Solvent Yellow 116, Solvent Yellow 131, Solvent Yellow 145, Solvent Yellow 160:1, Solvent Yellow 172, Solvent Yellow 185, Solvent Yellow 195, Solvent Yellow 196, Direct Yellow 27, Direct Yellow 85, Direct Yellow 96, Disperse Yellow 11, Disperse Yellow 82, Disperse Yellow 139, Disperse Yellow 184, Disperse Yellow 186, Disperse Yellow 199, Disperse Yellow 202, Disperse Yellow 232, and Reaction Yellow 78.

[0105] Furthermore, when the resin particles of the present embodiment are fluorescent yellow resin particles, in the resin particles of the present embodiment, the coloring pigment is preferably a yellow pigment from the viewpoint of fluorescence intensity and target color reproducibility.

[0106] Among them, in the resin particles of this embodiment, from the aspects of fluorescence intensity and target color reproducibility, it is more preferred that the fluorescent colorant is a compound having a heterocyclic structure formed by a benzimidazole skeleton and a coumarin skeleton, and the coloring pigment is a compound having an azo structure or a benzimidazolone structure.

[0107] Examples of the compound having a heterocyclic structure formed of a benzimidazole skeleton and a coumarin skeleton include CI Basic Yellow 40 and the like.

[0108] Examples of the compound having an azo structure include monoazo pigments such as CI Pigment Yellow 74, CI Pigment Yellow 1, 2, 3, 5, 6, 49, 65, 73, 75, 97, 98, 111, 116, and 130; disazo condensation pigments such as CI Pigment Yellow 93, CI Pigment Yellow 94, 95, 128, and 166; and disazo pigments such as CI Pigment Yellow 12, 13, 14, 17, 55, 63, 81, 83, 87, 90, 106, 113, 114, 121, 124, 126, 127, 136, 152, 170, 171, 172, 174, 176, and 188.

[0109] Examples of the compound having a benzimidazolone structure include CI Pigment Yellow 180 and the like.

[0110] In addition, when the resin particles of the present embodiment are fluorescent yellow resin particles, from the perspective of color tone and color reproducibility, the color difference ΔE between the resin particles and the color sample DIC589 is preferably 10 or less, the color difference ΔE between the resin particles and the color sample DIC590 is preferably 10 or less, or the color difference ΔE between the resin particles and the color sample PANTONE 803C is preferably 10 or less, more preferably the color difference ΔE between the resin particles and the color sample DIC589 is preferably 10 or less, or the color difference ΔE between the resin particles and the color sample DIC590 is preferably 10 or less, and particularly preferably the color difference ΔE between the resin particles and the color sample DIC590 is preferably 10 or less. In addition, the ΔE is preferably 5 or less.

[0111] Furthermore, when the resin particles of the present embodiment are fluorescent yellow resin particles, from the aspects of fluorescence intensity and target color reproducibility, it is preferred that the content of the fluorescent colorant is 0.01% by mass to 20% by mass, and the content of the coloring pigment is 0.005% by mass to 10% by mass, relative to the total mass of the resin particles. It is more preferred that the content of the fluorescent colorant is 0.1% by mass to 3.5% by mass, and the content of the coloring pigment is 0.05% by mass to 1.5% by mass, relative to the total mass of the resin particles. It is particularly preferred that the content of the fluorescent colorant is 0.2% by mass to 2.0% by mass, and the content of the coloring pigment is 0.05% by mass to 1.2% by mass, relative to the total mass of the resin particles.

[0112] <<The case of fluorescent green resin particles>>

[0113] When the resin particles of this embodiment are fluorescent green resin particles, in the resin particles of this embodiment, the coloring pigment is preferably at least one coloring pigment selected from the group consisting of green pigments, cyan pigments, and yellow pigments from the aspects of fluorescence intensity and target color reproducibility.

[0114] Among them, in the resin particles of the present embodiment, it is more preferable that the fluorescent colorant is a compound having a triarylmethane structure and the coloring pigment is a compound having a phthalocyanine structure from the viewpoint of fluorescence intensity and target color reproducibility.

[0115] Examples of the compound having a triarylmethane structure include Basic Blue 1, Basic Blue 7, Basic Green 1, and the like.

[0116] Examples of the compound having a phthalocyanine structure include CI Pigment Green 7, CI Pigment Green 36, CI Pigment Blue 15:1, and CI Pigment Blue 15:3.

[0117] In addition, when the resin particles of the present embodiment are fluorescent green resin particles, from the perspective of target color reproducibility, the color difference ΔE between the resin particles and the color sample DIC591 is preferably 10 or less, or the color difference ΔE between the resin particles and the color sample PANTONE 802C is preferably 10 or less. In addition, the ΔE is preferably 5 or less.

[0118] In addition, when the resin particles of the present embodiment are fluorescent green resin particles, from the aspects of fluorescence intensity and target color reproducibility, it is preferred that the content of the fluorescent colorant is 0.01% by mass to 20% by mass relative to the total mass of the resin particles, and the content of the coloring pigment is 0.005% by mass to 10% by mass relative to the total mass of the resin particles. It is more preferred that the content of the fluorescent colorant is 0.1% by mass to 3.5% by mass relative to the total mass of the resin particles, and the content of the coloring pigment is 0.05% by mass to 1.5% by mass relative to the total mass of the resin particles. It is particularly preferred that the content of the fluorescent colorant is 0.2% by mass to 2.0% by mass relative to the total mass of the resin particles, and the content of the coloring pigment is 0.05% by mass to 1.2% by mass relative to the total mass of the resin particles.

[0119] <<The case of fluorescent red resin particles>>

[0120] When the resin particles of this embodiment are fluorescent red resin particles, in the resin particles of this embodiment, from the aspects of fluorescence intensity and target color reproducibility, the above-mentioned coloring pigment is preferably at least one coloring pigment selected from the group consisting of magenta pigments and red pigments, and more preferably a red pigment.

[0121] Among them, in the resin particles of this embodiment, from the aspects of fluorescence intensity and target color reproducibility, it is preferred that the above-mentioned fluorescent colorant is a compound having a xanthene structure, and the above-mentioned coloring pigment is a compound having a quinacridone structure, a naphthamide structure or a diketopyrrolopyrrole structure, and it is more preferred that the above-mentioned colorant is a compound having a quinacridone structure or a naphthamide structure.

[0122] The compound having a xanthene structure is preferably a compound having a rhodamine structure, a fluorescein structure or an eosin structure, and more preferably a compound having a rhodamine structure, from the viewpoint of fluorescence intensity and target color reproducibility.

[0123] As the above-mentioned compound having a quinacridone structure, from the aspects of fluorescence intensity and target color reproducibility, it is preferably at least one compound selected from the group consisting of CI Pigment Red 122, CI Pigment Red 202, CI Pigment Red 207, CI Pigment Red 209, CI Pigment Red 238 and CI Pigment Violet 19, and more preferably at least one compound selected from the group consisting of CI Pigment Red 122, CI Pigment Red 238 and CI Pigment Violet 19.

[0124] Examples of the compound having a naphthamide structure include CI Pigment Red 112, CI Pigment Red 150, CI Pigment Red 160, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 188, and CI Pigment Red 213.

[0125] Examples of the compound having a diketopyrrolopyrrole structure include CI Pigment Red 254, CI Pigment Red 255, and CI Pigment Red 264.

[0126] In addition, when the resin particles of the present embodiment are fluorescent red resin particles, from the perspective of color tone and color reproducibility, the color difference ΔE between the resin particles and the color sample DIC585 is preferably 10 or less, the color difference ΔE between the resin particles and the color sample DIC586 is preferably 10 or less, or the color difference ΔE between the resin particles and the color sample PANTONE805C is preferably 10 or less. In addition, the ΔE is preferably 5 or less.

[0127] In addition, when the resin particles of the present embodiment are fluorescent red resin particles, from the aspects of fluorescence intensity and target color reproducibility, it is preferred that the content of the fluorescent colorant is 0.01% by mass to 20% by mass relative to the total mass of the resin particles, and the content of the coloring pigment is 0.005% by mass to 10% by mass relative to the total mass of the resin particles. It is more preferred that the content of the fluorescent colorant is 0.1% by mass to 3.5% by mass relative to the total mass of the resin particles, and the content of the coloring pigment is 0.05% by mass to 1.5% by mass relative to the total mass of the resin particles. It is particularly preferred that the content of the fluorescent colorant is 0.2% by mass to 2.0% by mass relative to the total mass of the resin particles, and the content of the coloring pigment is 0.05% by mass to 1.2% by mass relative to the total mass of the resin particles.

[0128] <<The case of fluorescent orange resin particles>>

[0129] When the resin particles of this embodiment are fluorescent orange resin particles, in the resin particles of this embodiment, from the aspects of fluorescence intensity and color reproducibility, the above-mentioned coloring pigment is preferably at least one coloring pigment selected from the group consisting of orange pigment, magenta pigment and yellow pigment, and is more preferably an orange pigment.

[0130] Among them, in the resin particles of this embodiment, from the aspects of fluorescence intensity and color reproducibility, it is preferred that the fluorescent colorant is a compound having a heterocyclic structure formed by a benzimidazole skeleton and a coumarin skeleton, and the coloring pigment is a compound having an azo structure, a naphthamide structure or anthraquinone structure.

[0131] Examples of the compound having an acridine structure include CI Basic Orange 15 and the like.

[0132] Examples of the compound having a methine structure include CI Basic Orange 22 and the like.

[0133] Examples of the compound having an anthraquinone structure include Solvent Orange 63 and Disperse Orange 11.

[0134] Examples of the compound having a naphthamide structure include CI Pigment Orange 24 and CI Pigment Orange 38.

[0135] In addition, when the resin particles of the present embodiment are fluorescent orange resin particles, from the perspective of color tone and color reproducibility, the color difference ΔE between the resin particles and the color sample DIC587 is preferably 10 or less, the color difference ΔE between the resin particles and the color sample DIC588 is preferably 10 or less, or the color difference ΔE between the resin particles and the color sample PANTONE 804C is preferably 10 or less, and the color difference ΔE between the resin particles and the color sample DIC587 is more preferably 10 or less, or the color difference ΔE between the resin particles and the color sample DIC588 is preferably 10 or less. In addition, the ΔE is preferably 5 or less.

[0136] In addition, when the resin particles of the present embodiment are fluorescent orange resin particles, from the aspects of fluorescence intensity and target color reproducibility, it is preferred that the content of the fluorescent colorant is 0.01% by mass to 20% by mass relative to the total mass of the resin particles, and the content of the coloring pigment is 0.005% by mass to 10% by mass relative to the total mass of the resin particles. It is more preferred that the content of the fluorescent colorant is 0.1% by mass to 3.5% by mass relative to the total mass of the resin particles, and the content of the coloring pigment is 0.05% by mass to 1.5% by mass relative to the total mass of the resin particles. It is particularly preferred that the content of the fluorescent colorant is 0.2% by mass to 2.0% by mass relative to the total mass of the resin particles, and the content of the coloring pigment is 0.05% by mass to 1.2% by mass relative to the total mass of the resin particles.

[0137] <<The case of fluorescent purple resin particles>>

[0138] In the case where the resin particles of the present embodiment are fluorescent purple (violet) resin particles, in the resin particles of the present embodiment, from the aspects of fluorescence intensity and hue, the coloring pigment is preferably at least one coloring pigment selected from the group consisting of a purple pigment (violet pigment), a magenta pigment, and a cyan pigment, and more preferably at least one coloring pigment selected from the group consisting of a purple pigment and a magenta pigment.

[0139] Among them, in the resin particles of this embodiment, from the aspects of fluorescence intensity and color tone, it is preferred that the above-mentioned fluorescent colorant is a compound having a xanthene structure or a methine structure, and the above-mentioned coloring pigment is a compound having any one of a quinacridone structure, a naphthamide structure, a dioxazine structure, a benzimidazolone structure, an anthraquinone structure, and a phthalocyanine structure. It is more preferred that the above-mentioned fluorescent colorant is a compound having a xanthene structure, and the above-mentioned coloring pigment is a compound having a quinacridone structure.

[0140] As the compound having a xanthene structure, from the viewpoint of fluorescence intensity and color tone, a compound having a rhodamine structure, a fluorescein structure or an eosin structure is preferred, and a compound having a rhodamine structure is more preferred.

[0141] Examples of the compound having a xanthene structure include Basic Violet 10 (Rhodamine B), Basic Violet 11 (Rhodamine 3B), and Basic Violet 11:1 (Rhodamine A).

[0142] The compound having a quinacridone structure is preferably at least one compound selected from the group consisting of CI Violet 19 and CI Pigment Violet 42 from the viewpoint of fluorescence intensity and target color reproducibility.

[0143] The compound having a naphthamide structure is preferably at least one compound selected from the group consisting of CI Violet 13, CI Violet 17, CI Violet 25, and CI Pigment Violet 50 from the viewpoint of fluorescence intensity and target color reproducibility.

[0144] Examples of the compound having a phthalocyanine structure include CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, and CI Pigment Blue 16.

[0145] Moreover, as another violet pigment, CI Pigment Violet 23, CI Pigment Violet 37, etc. are mentioned, for example.

[0146] When the resin particles of the present embodiment are fluorescent violet resin particles, the color difference ΔE between the resin particles and the color sample PANTONE 807C is preferably 10 or less, more preferably 5 or less, from the viewpoint of color tone and color reproducibility.

[0147] In addition, when the resin particles of the present embodiment are fluorescent purple resin particles, from the aspects of fluorescence intensity and target color reproducibility, it is preferred that the content of the fluorescent colorant is 0.01% by mass to 20% by mass relative to the total mass of the resin particles, and the content of the coloring pigment is 0.005% by mass to 10% by mass relative to the total mass of the resin particles. It is more preferred that the content of the fluorescent colorant is 0.1% by mass to 3.5% by mass relative to the total mass of the resin particles, and the content of the coloring pigment is 0.05% by mass to 1.5% by mass relative to the total mass of the resin particles. It is particularly preferred that the content of the fluorescent colorant is 0.2% by mass to 2.0% by mass relative to the total mass of the resin particles, and the content of the coloring pigment is 0.05% by mass to 1.2% by mass relative to the total mass of the resin particles.

[0148] <<The case of fluorescent water-colored resin particles>>

[0149] When the resin particles of this embodiment are fluorescent water-colored (light blue) resin particles, in the resin particles of this embodiment, from the aspects of fluorescence intensity and hue, the above-mentioned coloring pigment is preferably at least one coloring pigment selected from the group consisting of a cyan pigment, a blue pigment and a white pigment.

[0150] Among them, in the resin particles of the present embodiment, it is preferred that the fluorescent colorant is a compound having a triarylmethane structure, and the coloring pigment is a compound having a phthalocyanine structure or titanium oxide from the viewpoint of fluorescence intensity and color tone.

[0151] Examples of the compound having a triarylmethane structure include Basic Blue 1, Basic Blue 7, Acid Blue 9, and Solvent Blue 5.

[0152] Examples of the compound having a phthalocyanine structure include CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, and CI Pigment Blue 16.

[0153] When the resin particles of the present embodiment are fluorescent water-colored resin particles, the color difference ΔE between the resin particles and the color sample PANTONE 801C is preferably 10 or less, more preferably 5 or less, from the perspective of color tone and color reproducibility.

[0154] In addition, when the resin particles of this embodiment are fluorescent water-colored resin particles, from the aspects of fluorescence intensity and target color reproducibility, it is preferred that the content of the fluorescent colorant is 0.01 mass % to 20 mass % relative to the total mass of the resin particles, and the content of the coloring pigment is 0.005 mass % to 10 mass % relative to the total mass of the resin particles. It is more preferred that the content of the fluorescent colorant is 0.1 mass % to 3.5 mass % relative to the total mass of the resin particles, and the content of the coloring pigment is 0.05 mass % to 1.5 mass % relative to the total mass of the resin particles. It is particularly preferred that the content of the fluorescent colorant is 0.2 mass % to 2.0 mass % relative to the total mass of the resin particles, and the content of the coloring pigment is 0.05 mass % to 1.2 mass % relative to the total mass of the resin particles.

[0155] - Adhesive resin -

[0156] Examples of the adhesive resin include vinyl resins formed by homopolymers of the following monomers or copolymers of two or more of these monomers: styrenes (e.g., styrene, p-chlorostyrene, α-methylstyrene, etc.), (meth)acrylates (e.g., methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, etc.), ethylenically unsaturated nitriles (e.g., acrylonitrile, methacrylonitrile, etc.), vinyl ethers (e.g., vinyl methyl ether, vinyl isobutyl ether, etc.), vinyl ketones (e.g., vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone, etc.), olefins (e.g., ethylene, propylene, butadiene, etc.), and the like.

[0157] Examples of the adhesive resin include non-vinyl resins such as epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, and modified rosins, mixtures of these resins with the above-mentioned vinyl resins, or graft polymers obtained by polymerizing vinyl monomers in the coexistence of these resins.

[0158] Among them, styrene-acrylic acid copolymer or polyester resin is suitable, and polyester resin is more suitable.

[0159] These adhesive resins may be used alone or in combination of two or more.

[0160] Examples of the binder resin include non-crystalline (also referred to as “amorphous”) resins and crystalline resins.

[0161] From the viewpoint of suppressing density unevenness in the obtained image, the binder resin preferably contains a crystalline resin, and more preferably contains an amorphous resin and a crystalline resin.

[0162] The content of the crystalline resin is preferably 2 mass % to 40 mass %, more preferably 2 mass % to 20 mass %, particularly preferably 3 mass % to 15 mass %, based on the total mass of the binder resin.

[0163] It should be noted that the "crystallinity" of a resin means that there is no step-like change in endothermic value in differential scanning calorimetry (DSC) and that there is a clear endothermic peak. Specifically, it means that the half-width of the endothermic peak when measured at a heating rate of 10 (°C / min) is within 10°C.

[0164] On the other hand, the "amorphous" nature of a resin means that the half-peak width is larger than 10°C, the endothermic quantity changes stepwise, or no clear endothermic peak is observed.

[0165] <<Polyester resin>>

[0166] Examples of the polyester resin include known polyester resins.

[0167] Amorphous polyester resin

[0168] Examples of the amorphous polyester resin include polycondensates of polycarboxylic acids and polyols. As the amorphous polyester resin, a commercially available product or a synthetic product may be used.

[0169] Examples of the polycarboxylic acid include aliphatic dicarboxylic acids (e.g., oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, alkenyl succinic acid, adipic acid, sebacic acid, etc.), alicyclic dicarboxylic acids (e.g., cyclohexane dicarboxylic acid, etc.), aromatic dicarboxylic acids (e.g., terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, etc.), and anhydrides thereof or lower (e.g., carbon number 1 to 5) alkyl esters thereof. Among these, aromatic dicarboxylic acids are preferred as the polycarboxylic acid.

[0170] Among the polycarboxylic acids, dicarboxylic acids and trivalent or higher carboxylic acids having a crosslinked structure or a branched structure may be used in combination. Examples of the trivalent or higher carboxylic acids include trimellitic acid, pyromellitic acid, their anhydrides, or their lower (e.g., carbon number 1 to 5) alkyl esters.

[0171] The polyvalent carboxylic acid may be used alone or in combination of two or more.

[0172] Examples of the polyol include aliphatic diols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, etc.), alicyclic diols (e.g., cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, etc.), and aromatic diols (e.g., ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, etc.). Among these, the polyol is preferably an aromatic diol or an alicyclic diol, and more preferably an aromatic diol.

[0173] As the polyol, a diol may be used in combination with a trivalent or higher polyol having a cross-linked structure or a branched structure. Examples of the trivalent or higher polyol include glycerin, trimethylolpropane, and pentaerythritol.

[0174] The polyols may be used alone or in combination of two or more.

[0175] The glass transition temperature (Tg) of the amorphous polyester resin is preferably 50°C to 80°C, and more preferably 50°C to 65°C.

[0176] The glass transition temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC), more specifically, by the "extrapolated glass transition start temperature" described in the method for measuring glass transition temperature of JIS K7121:1987 "Method for measuring transition temperature of plastics".

[0177] The weight average molecular weight (Mw) of the amorphous polyester resin is preferably 5,000 to 1,000,000, and more preferably 7,000 to 500,000.

[0178] The number average molecular weight (Mn) of the amorphous polyester resin is preferably 2,000 to 100,000.

[0179] 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.

[0180] It should be noted that the weight average molecular weight and the number average molecular weight are measured by gel permeation chromatography (GPC). In the molecular weight measurement using GPC, GPC HLC-8120GPC manufactured by Tosoh Corporation is used as a measuring device, and a column TSKgel SuperHM-M (15 cm) manufactured by Tosoh Corporation is used, and the measurement is performed using THF solvent. The weight average molecular weight and the number average molecular weight are calculated based on the measurement results using a molecular weight calibration curve made from a monodisperse polystyrene standard sample.

[0181] The amorphous polyester resin is obtained by a known production method. Specifically, for example, the amorphous polyester resin is obtained by setting the polymerization temperature to 180° C. to 230° C., reducing the pressure in the reaction system as necessary, and reacting while removing water or alcohol generated during condensation.

[0182] It should be noted that when the raw material monomer is insoluble or incompatible at the reaction temperature, a high boiling point solvent can be added as a dissolving aid to dissolve it. In this case, the polycondensation reaction is carried out while the dissolving aid is distilled off. In the case of a monomer with poor compatibility, the monomer with poor compatibility can be condensed in advance with an acid or alcohol to be polycondensed with the monomer, and then polycondensed with the main component.

[0183] Crystalline polyester resin

[0184] Examples of the crystalline polyester resin include polycondensates of polycarboxylic acids and polyols. As the crystalline polyester resin, a commercially available product may be used, or a synthetic product may be used.

[0185] Here, in order to make the crystalline polyester resin easily form a crystal structure, the crystalline polyester is preferably obtained by using a polycondensate obtained by using a polymerizable monomer having a linear aliphatic group rather than a polycondensate obtained by using a polymerizable monomer having an aromatic group.

[0186] Examples of the polycarboxylic acid include aliphatic dicarboxylic acids (e.g., oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, etc.), aromatic dicarboxylic acids (e.g., dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalene-2,6-dicarboxylic acid, etc.), their anhydrides, or their lower (e.g., carbon number 1 to 5) alkyl esters.

[0187] Among the polycarboxylic acids, dicarboxylic acids and trivalent or higher carboxylic acids having a cross-linked structure or a branched structure may be used in combination. Examples of trivalent carboxylic acids include aromatic carboxylic acids (e.g., 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, etc.), their anhydrides, or their lower (e.g., carbon number 1 to 5) alkyl esters.

[0188] As the polycarboxylic acid, these dicarboxylic acids may be used in combination with a dicarboxylic acid having a sulfonic acid group or a dicarboxylic acid having an ethylenic double bond.

[0189] The polyvalent carboxylic acid may be used alone or in combination of two or more.

[0190] Examples of the polyol include aliphatic diols (e.g., linear aliphatic diols having a main chain portion having carbon atoms of 7 or more and 20 or less). Examples of the aliphatic diols include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, and 1,14-eicosandiol. Among these, preferred aliphatic diols include 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol.

[0191] Among the polyols, diols may be used in combination with trivalent or higher alcohols having a cross-linked structure or a branched structure. Examples of the trivalent or higher alcohols include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.

[0192] The polyols may be used alone or in combination of two or more.

[0193] Here, the content of the aliphatic diol in the polyol is preferably 80 mol % or more, and preferably 90 mol % or more.

[0194] The melting temperature of the crystalline polyester resin is preferably 50°C to 100°C, more preferably 55°C to 90°C, and even more preferably 60°C to 85°C.

[0195] The melting temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC) according to the “melting peak temperature” described in the method for measuring melting temperature in JIS K7121:1987 “Method for measuring transition temperatures of plastics”.

[0196] The weight average molecular weight (Mw) of the crystalline polyester resin is preferably 6,000 or more and 35,000 or less.

[0197] The crystalline polyester resin can be obtained, for example, by a known production method similar to the amorphous polyester.

[0198] From the aspect of the friction resistance of the image, the weight average molecular weight (Mw) of the adhesive resin is preferably 5,000 to 1,000,000, more preferably 7,000 to 500,000, and particularly preferably 25,000 to 60,000. The number average molecular weight (Mn) of the adhesive resin is preferably 2,000 to 100,000. The molecular weight distribution Mw / Mn of the adhesive resin is preferably 1.5 to 100, more preferably 2 to 60.

[0199] The weight average molecular weight and number average molecular weight of the binder resin are measured by gel permeation chromatography (GPC). In the molecular weight measurement using GPC, a GPC HLC-8120GPC manufactured by Tosoh Corporation is used as a measuring device, a column TSKgel SuperHM-M (15 cm) manufactured by Tosoh Corporation is used, and the measurement is performed using tetrahydrofuran (THF) solvent. The weight average molecular weight and number average molecular weight are calculated based on the measurement results using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample.

[0200] The content of the binder resin is preferably 40% by mass to 95% by mass, more preferably 50% by mass to 95% by mass, and even more preferably 60% by mass to 90% by mass, based on the entire resin particles.

[0201] -Release agent-

[0202] Examples of the release agent include hydrocarbon waxes, natural waxes such as carnauba wax, rice wax, and candelilla wax, synthetic waxes such as montan wax, or mineral and petroleum waxes, and ester waxes such as fatty acid esters and montanic acid esters. The release agent is not limited thereto.

[0203] The melting temperature of the release agent is preferably 50°C to 110°C, more preferably 60°C to 100°C.

[0204] The melting temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC) according to the “melting peak temperature” described in the method for measuring melting temperature in JIS K7121-1987 “Methods for measuring transition temperatures of plastics”.

[0205] The content of the release agent is preferably 1% by mass to 20% by mass, and more preferably 5% by mass to 15% by mass, based on the entire resin pellet.

[0206] -Other additives-

[0207] Examples of other additives include known additives such as magnetic materials, charge control agents, and inorganic powders. These additives may be contained in the resin particles as internal additives.

[0208] -Resin Pellets Characteristics, etc.-

[0209] The resin particles may be single-layer resin particles or so-called core / shell resin particles (core / shell type particles) composed of a core (core particle) and a coating layer (shell layer) covering the core. The core / shell resin particles may be composed of, for example, a core containing a binder resin, a fluorescent colorant, a coloring pigment, and, if necessary, a release agent, and the coating layer containing a binder resin.

[0210] The volume average particle size (D 50v ), preferably 2 μm or more and 10 μm or less, more preferably 4 μm or more and 8 μm or less.

[0211] The volume average particle size of the resin particles was measured using Coulter Multisizer II (manufactured by Beckman Coulter), and the electrolyte was measured using ISOTON-II (manufactured by Beckman Coulter).

[0212] In the measurement, 0.5 mg to 50 mg of the measurement sample is added to 2 ml of a 5 mass % aqueous solution of a surfactant (preferably sodium alkylbenzene sulfonate) as a dispersant, and then added to 100 ml to 150 ml of the electrolyte.

[0213] The electrolyte in which the sample was suspended was dispersed by an ultrasonic disperser for 1 minute, and the particle sizes of particles ranging from 2 μm to 60 μm were measured by Coulter Multisizer II using an aperture of 100 μm. The number of particles sampled was 50,000.

[0214] The measured particle diameters were plotted as a cumulative distribution based on volume from the smaller diameter side, and the particle diameter at the cumulative 50% point was defined as the volume average particle diameter D 50v .

[0215] The average circularity of the resin particles in the present embodiment is not particularly limited, but is preferably 0.91 to 0.98, more preferably 0.94 to 0.98, and even more preferably 0.95 to 0.97, from the viewpoint of improving the cleanability of the image holding member.

[0216] The roundness of the resin particles in this embodiment refers to (the circumference of a circle having the same area as the particle projection image) ÷ (the circumference of the particle projection image), and the average roundness of the resin particles refers to the roundness of 50% of the points accumulated from the small roundness side in the distribution of roundness. The average roundness of the resin particles is obtained by analyzing at least 3,000 resin particles using a flow particle image analyzer.

[0217] The average circularity of the resin particles can be controlled by adjusting the stirring speed of the dispersion, the temperature of the dispersion, or the retention time in the fusion / coalescence step, for example, when the resin particles are produced by the aggregation and coalescence method.

[0218] (External Additives)

[0219] When the resin particles are used as a toner for electrostatic image development described later, the resin particles may contain an external additive as necessary.

[0220] The resin particles may be resin particles without an external additive, or may be particles in which an external additive is added to the resin particles.

[0221] Examples of the external additive include inorganic particles. Examples of the inorganic particles include SiO2, TiO2, Al2O3, CuO, ZnO, SnO2, CeO2, Fe2O3, MgO, BaO, CaO, K2O, Na2O, ZrO2, CaO·SiO2, K2O·(TiO2) n , Al2O3·2SiO2, CaCO3, MgCO3, BaSO4, MgSO4, etc.

[0222] The surface of the inorganic particles as an external additive can also be subjected to a hydrophobic treatment. The hydrophobic treatment is carried out by, for example, immersing the inorganic particles in a hydrophobic treatment agent. The hydrophobic treatment agent is not particularly limited, and for example, a silane coupling agent, silicone oil, a titanate coupling agent, an aluminum coupling agent, etc. can be cited. These treatment agents can be used alone or in combination of two or more.

[0223] The amount of the hydrophobizing agent is, for example, preferably 1 part by mass or more and 10 parts by mass or less relative to 100 parts by mass of the inorganic particles.

[0224] Examples of the external additives include resin particles (polystyrene, polymethyl methacrylate (PMMA), melamine resin and other resin particles), detergent active agents (metal salts of higher fatty acids such as zinc stearate, and particles of fluorine-based high molecular weight bodies).

[0225] The amount of the external additive added is, for example, preferably from 0.01% by mass to 10% by mass, and more preferably from 0.01% by mass to 6% by mass, based on the resin particles.

[0226] <Application of resin pellets>

[0227] The resin particles of the present embodiment are suitably used as resin particles for image formation, and more suitably used as a toner for electrostatic image development.

[0228] In addition, the resin particles of this embodiment are also suitable for use as powder coatings. They can also be used to apply them to the surface to be coated, and then heat (baking) to form a coating film formed by solidifying the powder to produce a coated product. In this case, coating and heating (baking) can be performed simultaneously.

[0229] The powder can be applied by a known coating method such as spray coating, electrostatic powder coating, friction charging powder coating, fluidization dipping, etc. The thickness of the powder coating film is preferably 30 μm or more and 50 μm or less, for example.

[0230] The heating temperature (calcining temperature) is, for example, preferably 90° C. to 250° C., more preferably 100° C. to 220° C., and further preferably 120° C. to 200° C. The heating time (calcining time) is adjusted by the heating temperature (calcining temperature).

[0231] The object to which the powder is applied is not particularly limited, and examples thereof include various metal parts, ceramic parts, resin parts, etc. These object objects may be unformed products before being formed into various articles such as plate-shaped products and linear products, or may be formed products for electronic parts, road vehicles, and interior and exterior decorative materials for buildings. In addition, the object objects may be articles on which the surface to be coated has been previously subjected to a surface treatment such as primer treatment, plating treatment, or electrodeposition coating.

[0232] Furthermore, the resin particles of the present embodiment can also be suitably used as resin particles for toner displays in fields other than coating.

[0233] Toner displays are well known in which charged resin particles are dispersed in a medium (mostly air) and the resin particles are moved under the action of an electric field to display an image. The resin particles of this embodiment can also be used in this method without any problem. For example, resin particles are placed in a cell sandwiched between two transparent electrodes, and a voltage is applied to move the resin particles to display an image.

[0234] [Method for producing resin pellets]

[0235] Next, the method for producing the resin pellets according to the present embodiment will be described.

[0236] The resin pellets of the present embodiment may have an external additive added thereto after the resin pellets are produced.

[0237] The resin particles can be produced by any of dry methods (e.g., kneading and pulverization methods) and wet methods (e.g., aggregation and merging methods (aggregation-aggregation methods), suspension polymerization methods, and dissolution suspension methods). These methods are not particularly limited, and known methods can be used. Among these, it is preferable to obtain the resin particles by the aggregation and merging method.

[0238] Examples of the agglomeration method include the method described in Japanese Patent Application Laid-Open No. 2010-97101 and Japanese Patent Application Laid-Open No. 2006-154641.

[0239] Examples of the kneading and pulverizing method include the method described in Japanese Patent Application Laid-Open No. 2000-267338.

[0240] As the dissolution suspension method, there can be mentioned the method described in Japanese Patent Application Laid-Open No. 2000-258950.

[0241] In addition, specifically, for example, in the case of manufacturing resin particles by an agglomeration and merging method, the resin particles are manufactured through the following steps: a step of preparing a resin particle dispersion in which resin particles serving as a binding resin are dispersed (resin particle dispersion preparation step); a step of agglomerating resin particles (and other particles if necessary) in the resin particle dispersion (in a dispersion after mixing other particle dispersions if necessary) to form agglomerated particles (agglomerated particle formation step); and a step of heating the agglomerated particle dispersion in which the agglomerated particles are dispersed to fuse / merge (fusion / unity) the agglomerated particles to form resin particles (fusion / merging step).

[0242] The details of each step are described below.

[0243] In the following description, a method for obtaining resin particles containing a colorant and a release agent is described, but the release agent is an additive used as needed. Of course, other additives besides the release agent may also be used.

[0244] In the following description, as the colorant, at least one colorant selected from the group consisting of the fluorescent colorant and the color pigment can be cited. In addition, as the colorant particle dispersion, both a fluorescent colorant particle dispersion and a color pigment particle dispersion can be used, and a dispersion containing both fluorescent colorant particles and color pigment particles can also be used.

[0245] - Resin particle dispersion preparation step -

[0246] A resin particle dispersion in which resin particles as a binding resin are dispersed is prepared, and at the same time, a colorant particle dispersion in which colorant particles are dispersed and, for example, a release agent particle dispersion in which release agent particles are dispersed are prepared.

[0247] The resin particle dispersion is prepared, for example, by dispersing the resin particles in a dispersion medium using a surfactant.

[0248] Examples of the dispersion medium used for the resin particle dispersion include aqueous media.

[0249] Examples of the aqueous medium include water such as distilled water and ion-exchanged water, alcohols, etc. These media may be used alone or in combination of two or more.

[0250] Examples of surfactants include anionic surfactants such as sulfate ester salts, sulfonates, phosphates, and soaps; cationic surfactants such as amine salts and quaternary ammonium salts; nonionic surfactants such as polyethylene glycols, alkylphenol ethylene oxide adducts, and polyols; and the like. Among these, anionic surfactants and cationic surfactants can be particularly mentioned. Nonionic surfactants can also be used in combination with anionic surfactants or cationic surfactants.

[0251] Among them, a nonionic surfactant is preferably used, and a nonionic surfactant is preferably used in combination with an anionic surfactant or a cationic surfactant.

[0252] In addition, as described above, in the method for producing resin particles, when a fluorescent colorant having an anionic group and a binder resin having a cationic group are used, it is preferred to use a surfactant having a cationic group from the aspects of fluorescence intensity and the granularity of the image. On the other hand, in the method for producing resin particles, when a fluorescent colorant having a cationic group and a binder resin having an anionic group are used, it is preferred to use a surfactant having an anionic group from the aspects of fluorescence intensity and the granularity of the image.

[0253] The surfactant may be used alone or in combination of two or more.

[0254] In the resin particle dispersion, as a method for dispersing the resin particles in the dispersion medium, for example, a common dispersion method using a rotary shearing homogenizer or a ball mill, sand mill, bead mill, etc. with a medium can be cited. In addition, depending on the type of resin particles, the resin particles can also be dispersed in the dispersion medium using a phase inversion emulsification method. The phase inversion emulsification method is a method in which the resin to be dispersed is dissolved in a hydrophobic organic solvent that can dissolve the resin, a base is added to the organic continuous phase (O phase) for neutralization, and then an aqueous medium (W phase) is added to thereby invert the phase from W / O to O / W, so that the resin is dispersed in the aqueous medium in a particle form.

[0255] The volume average particle size of the resin particles dispersed in the resin particle dispersion is, for example, preferably 0.01 μm or more and 1 μm or less, more preferably 0.03 μm or more and 0.8 μm or less, and further preferably 0.05 μm or more and 0.6 μm or less.

[0256] The volume average particle size of the resin particles is determined by using a particle size distribution obtained by measurement using a laser diffraction particle size distribution measuring device (e.g., LA-700 manufactured by Horiba, Ltd.). For the divided particle size range (segment), a cumulative distribution is plotted for volume from the small particle size side, and the particle size at the cumulative 50% point relative to all particles is measured, which is taken as the volume average particle size D50v. The volume average particle size of particles in other dispersions is measured in the same manner.

[0257] The content of the resin particles contained in the resin particle dispersion is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 40% by mass or less.

[0258] In the following description, unless otherwise specified, the resin particles are resin particles to which a fluorescent colorant is chemically bonded or resin particles to which a fluorescent colorant is molecularly dispersed.

[0259] A colorant particle dispersion and a release agent particle dispersion are prepared in the same manner as the resin particle dispersion. That is, the volume average particle size of the particles in the resin particle dispersion, the dispersion medium, the dispersion method, and the content of the particles are the same for the colorant particles dispersed in the colorant particle dispersion and the release agent particles dispersed in the release agent particle dispersion.

[0260] - Agglomerated Particle Formation Step-

[0261] Next, the resin particle dispersion, the colorant particle dispersion, and the release agent particle dispersion are mixed.

[0262] Then, the resin particles, the colorant particles, and the release agent particles are heterogeneously aggregated in the mixed dispersion to form aggregated particles containing the resin particles, the colorant particles, and the release agent particles and having a diameter close to that of the target resin particles.

[0263] Specifically, for example, a coagulant is added to the mixed dispersion, and the pH of the mixed dispersion is adjusted to acidity (for example, pH 2 to 5), a dispersion stabilizer is added as needed, and then heated to a temperature close to the glass transition temperature of the resin particles (specifically, for example, the glass transition temperature of the resin particles is -30°C to the glass transition temperature of -10°C), so that the particles dispersed in the mixed dispersion are agglomerated to form agglomerated particles.

[0264] In the aggregated particle forming step, for example, a coagulant may be added at room temperature (e.g., 25° C.) while the mixed dispersion is stirred using a rotary shearing homogenizer, the pH of the mixed dispersion is adjusted to acidic (e.g., pH 2 to 5), a dispersion stabilizer may be added as needed, and then the mixture may be heated.

[0265] Examples of the coagulant include surfactants having opposite polarity to the surfactant contained in the mixed dispersion, inorganic metal salts, and divalent or higher metal complexes. When a metal complex is used as the coagulant, the amount of surfactant used is reduced and the charging characteristics are improved.

[0266] If necessary, an additive that forms a complex or similar bond with the metal ion of the coagulant may be used together with the coagulant. As the additive, a chelating agent is preferably used.

[0267] Examples of the inorganic metal salt include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate; inorganic metal salt polymers such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide; and the like.

[0268] As the chelating agent, a water-soluble chelating agent can be used. Examples of the chelating agent include hydroxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid; aminocarboxylic acids such as iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), and ethylenediaminetetraacetic acid (EDTA); and the like.

[0269] The amount of the coagulant added is preferably 0.01 parts by mass or more and 5.0 parts by mass or less, and more preferably 0.1 parts by mass or more and less than 3.0 parts by mass, relative to 100 parts by mass of the resin particles.

[0270] - Fusion / Merge Steps-

[0271] Next, the agglomerated particle dispersion in which the agglomerated particles are dispersed is heated to, for example, a temperature above the glass transition temperature of the resin particles (for example, a temperature 30°C to 50°C higher than the glass transition temperature of the resin particles) and to a temperature above the melting point of the release agent to fuse / merge the agglomerated particles to form resin particles.

[0272] In the fusion / combination step, the resin and the release agent are in a fused state at a temperature above the glass transition temperature of the resin particles and above the melting temperature of the release agent. Thereafter, the resin particles are cooled to obtain resin particles.

[0273] As a method for adjusting the aspect ratio of the release agent in the resin particles, the aspect ratio can be adjusted by maintaining the temperature near the solidification point of the release agent for a certain period of time during cooling to allow crystal growth, or by using two or more release agents with different melting points to promote crystal growth during cooling.

[0274] After the above steps, resin particles are obtained.

[0275] After obtaining a dispersion of agglomerated particles in which agglomerated particles are dispersed, resin particles can be manufactured by the following steps: further mixing the above-mentioned dispersion of agglomerated particles with a resin particle dispersion in which resin particles are dispersed, and agglomerating the resin particles in a manner that further adheres to the surface of the agglomerated particles to form second agglomerated particles; and heating the second dispersion of agglomerated particles in which the second agglomerated particles are dispersed to fuse / merge the second agglomerated particles to form resin particles with a core / shell structure.

[0276] After the fusion / merging step is completed, the resin particles formed in the solution are subjected to a known washing step, a solid-liquid separation step, and a drying step to obtain resin particles in a dry state. Regarding the washing step, from the perspective of charging performance, replacement washing using ion exchange water can be fully implemented. Regarding the solid-liquid separation step, from the perspective of productivity, suction filtration, pressure filtration, etc. can be implemented. Regarding the drying step, from the perspective of productivity, freeze drying, airflow drying, fluidized bed drying, vibration fluidized bed drying, etc. can be implemented.

[0277] Then, when the resin particles of this embodiment are used as a toner for electrostatic image development, the toner is produced by adding an external additive to the obtained dry resin particles and mixing them. The mixing can be performed using, for example, a V-type blender, a Henschel mixer, a Loedige mixer, or the like.

[0278] Furthermore, coarse particles of the resin particles may be removed using a vibration classifier, a wind classifier, or the like, as necessary.

[0279] <Electrostatic Image Developer>

[0280] When the resin particles of the present embodiment are used as an electrostatic image developer, a one-component developer containing only the resin particles of the present embodiment may be used, or a two-component developer in which the resin particles and a carrier are mixed may be used.

[0281] The carrier is not particularly limited, and known carriers can be cited. Examples of the carrier include: a coated carrier in which a core material formed of magnetic powder is coated with a resin; a magnetic powder dispersion carrier in which magnetic powder is dispersed and mixed in a matrix resin; a resin impregnated carrier in which porous magnetic powder is impregnated with a resin; and the like. The magnetic powder dispersion carrier and the resin impregnated carrier may also be a carrier in which the constituent particles of the carrier are used as a core material and the surface is coated with a resin.

[0282] Examples of the magnetic powder include magnetic metals such as iron, nickel, and cobalt; and magnetic oxides such as ferrite and magnetite.

[0283] Examples of the coating resin and base resin include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylate copolymer, pure silicone resin or modified products thereof containing organic siloxane bonds, fluororesins, polyesters, polycarbonates, phenolic resins, epoxy resins, etc. The coating resin and base resin may contain additives such as conductive particles. Examples of the conductive particles include particles of metals such as gold, silver, and copper, carbon black, titanium oxide, zinc oxide, tin oxide, barium sulfate, aluminum borate, and potassium titanate.

[0284] Among them, from the viewpoint of suppressing density unevenness in the obtained image, a carrier whose surface is coated with a resin including a silicone resin is preferred, and a carrier whose surface is coated with a silicone resin is more preferred.

[0285] When the surface of the core material is coated with a resin, a coating layer forming solution prepared by dissolving the coating resin and various additives (used as needed) in an appropriate solvent can be used. The solvent is not particularly limited and can be selected in consideration of the type of resin used, coating suitability, etc. Specific resin coating methods include: an immersion method, in which the core material is immersed in the coating layer forming solution; a spray method, in which the coating layer forming solution is sprayed onto the surface of the core material; a fluidized bed method, in which the coating layer forming solution is sprayed while the core material is suspended by flowing air; a kneading coater method, in which the core material of the carrier is mixed with the coating layer forming solution in a kneading coater and then the solvent is removed; and the like.

[0286] The mixing ratio (mass ratio) of the resin particles (toner for electrostatic image development) and the carrier in the two-component developer is preferably resin particles (toner for electrostatic image development):carrier=1:100 to 30:100, more preferably 3:100 to 20:100.

[0287] <Image Forming Apparatus, Image Forming Method>

[0288] An image forming apparatus and an image forming method in the case of using the resin particles of the present embodiment as a toner for electrostatic image development will be described.

[0289] The image forming device includes: an image holder; a charging mechanism for charging the surface of the image holder; an electrostatic image forming mechanism for forming an electrostatic image on the charged surface of the image holder; a developing mechanism for storing an electrostatic image developer and developing the electrostatic image formed on the surface of the image holder into a toner image using the electrostatic image developer; a transfer mechanism for transferring the toner image formed on the surface of the image holder to the surface of a recording medium; and a fixing mechanism for fixing the toner image transferred to the surface of the recording medium. As the electrostatic image developer, an electrostatic image developer containing the resin particles of the present embodiment is used.

[0290] An image forming method having the following steps is implemented in an image forming device: a charging step of charging the surface of an image retaining body; an electrostatic image forming step of forming an electrostatic image on the charged surface of the image retaining body; a developing step of developing the electrostatic image formed on the surface of the image retaining body into a toner image using an electrostatic image developer containing resin particles of the present embodiment; a transferring step of transferring the toner image formed on the surface of the image retaining body to the surface of a recording medium; and a fixing step of fixing the toner image transferred to the surface of the recording medium.

[0291] As an image forming device, the following well-known image forming devices can be applied: a device using a direct transfer method for directly transferring a toner image formed on the surface of an image holder to a recording medium; a device using an intermediate transfer method for transferring a toner image formed on the surface of an image holder to the surface of an intermediate transfer body for the first time, and transferring the toner image transferred to the surface of the intermediate transfer body to the surface of a recording medium for a second time; a device having a cleaning mechanism for cleaning the surface of the image holder after the transfer of the toner image and before charging; a device having a de-staticizing mechanism for de-staticizing the surface of the image holder by irradiating de-staticizing light to the surface of the image holder after the transfer of the toner image and before charging; and the like.

[0292] When the image forming device is an intermediate transfer device, the transfer mechanism used is, for example, a structure having the following components: an intermediate transfer body that transfers the toner image to a surface; a primary transfer mechanism that transfers the toner image formed on the surface of the image retaining body to the surface of the intermediate transfer body for the first time; and a secondary transfer mechanism that transfers the toner image transferred to the surface of the intermediate transfer body to the surface of the recording medium for the second time.

[0293] In the image forming apparatus, for example, the part including the developing mechanism may be a cartridge structure (processing box) that is detachable from the image forming apparatus. As the processing box, for example, a processing box having a developing mechanism storing an electrostatic image developer including the resin particles of this embodiment is suitable.

[0294] An example of an image forming apparatus is described below, but the present invention is not limited thereto. In the following description, the main parts shown in the drawings are described, and other descriptions are omitted.

[0295] Figure 1 1 is a diagram schematically showing the structure of an image forming apparatus used in this embodiment.

[0296] Figure 1 The image forming apparatus shown in the figure is provided with first to fourth image forming units 10Y, 10M, 10C, 10K (image forming mechanism) of the electrophotographic method for outputting images of yellow (Y), magenta (M), cyan (C), and black (K) colors based on color separation image data. These image forming units (hereinafter also referred to as "units") 10Y, 10M, 10C, 10K are arranged in parallel with each other at a predetermined distance in the horizontal direction. These units 10Y, 10M, 10C, 10K may be process cartridges that are attachable to and detachable from the image forming apparatus.

[0297] Above each unit 10Y, 10M, 10C, 10K, an intermediate transfer belt (an example of an intermediate transfer body) 20 is extended through each unit. The intermediate transfer belt 20 is wound around a driving roller 22 and a supporting roller 24 that are in contact with the inner surface of the intermediate transfer belt 20, and is caused to run in a direction from the first unit 10Y to the fourth unit 10K. The supporting roller 24 is applied with a force in a direction away from the driving roller 22 by a spring (not shown) or the like, and tension is applied to the intermediate transfer belt 20 wound around the two. An intermediate transfer belt cleaning device 30 is provided on the image holding surface side of the intermediate transfer belt 20, which is opposed to the driving roller 22.

[0298] Yellow, magenta, cyan and black toners stored in toner cartridges 8Y, 8M, 8C and 8K are supplied to developing devices (an example of developing mechanisms) 4Y, 4M, 4C and 4K of the respective units 10Y, 10M, 10C and 10K.

[0299] The first to fourth units 10Y, 10M, 10C, and 10K have the same configuration and operation, and therefore the first unit 10Y disposed on the upstream side in the running direction of the intermediate transfer belt and forming a yellow image will be described as a representative.

[0300] The first unit 10Y has a photoreceptor 1Y that functions as an image holder. The following are arranged in order around the photoreceptor 1Y: a charging roller (an example of a charging mechanism) 2Y that charges the surface of the photoreceptor 1Y to a preset potential; an exposure device (an example of an electrostatic image forming mechanism) 3 that forms an electrostatic image by exposing the charged surface using a laser beam 3Y based on a color separation image signal; a developing device (an example of a developing mechanism) 4Y that supplies the charged toner to the electrostatic image to develop the electrostatic image; a primary transfer roller (an example of a primary transfer mechanism) 5Y that transfers the developed toner image to the intermediate transfer belt 20; and a photoreceptor cleaning device (an example of an image holder cleaning mechanism) 6Y that removes the toner remaining on the surface of the photoreceptor 1Y after the primary transfer.

[0301] The primary transfer roller 5Y is arranged inside the intermediate transfer belt 20 and is provided at a position facing the photosensitive body 1Y. The primary transfer rollers 5Y, 5M, 5C, and 5K of each unit are connected to bias power supplies (not shown) for applying primary transfer bias. Each bias power supply changes the value of the transfer bias applied to each primary transfer roller under the control of a control unit (not shown).

[0302] Next, the operation of forming a yellow image in the first unit 10Y will be described.

[0303] First, before the operation, the surface of the photoreceptor 1Y is charged to a potential of -600 V to -800 V by the charging roller 2Y.

[0304] The photoreceptor 1Y has a conductivity (e.g., a volume resistivity of 1×10 -6 The photosensitive layer is formed by laminating a photosensitive layer on a substrate with a resistance of 100 Ωcm or less. The photosensitive layer generally has a high resistance (resistance of a common resin), but has a property that the resistivity of the portion irradiated with the laser beam changes when the laser beam is irradiated. Therefore, according to the yellow image data sent from the control unit (not shown), the laser beam 3Y is irradiated from the exposure device 3 to the charged surface of the photoreceptor 1Y. As a result, an electrostatic image of a yellow image pattern is formed on the surface of the photoreceptor 1Y.

[0305] The electrostatic image is an image formed on the surface of the photoreceptor 1Y by charging, which is a so-called negative latent image. The negative latent image is formed as follows: the resistivity of the irradiated portion of the photosensitive layer is reduced by using the laser beam 3Y, so that the charged charge on the surface of the photoreceptor 1Y flows; on the other hand, the charge of the portion not irradiated with the laser beam 3Y remains, thereby forming the negative latent image.

[0306] The electrostatic image formed on the photoreceptor 1Y rotates to a preset development position as the photoreceptor 1Y runs. At the development position, the electrostatic image on the photoreceptor 1Y is developed into a toner image by the developing device 4Y and visualized.

[0307] The developing device 4Y stores an electrostatic image developer containing, for example, at least a yellow toner and a carrier. The yellow toner is frictionally charged by being stirred inside the developing device 4Y, and has a charge of the same polarity (negative polarity) as the charge charged on the photoreceptor 1Y, and is held on the developer roller (an example of a developer holding member). After that, the surface of the photoreceptor 1Y passes through the developing device 4Y, whereby the yellow toner is electrostatically attached to the latent image portion on the surface of the photoreceptor 1Y that has been de-charged, and the latent image is developed using the yellow toner. The photoreceptor 1Y formed with the yellow toner image continues to run at a preset speed, and the toner image developed on the photoreceptor 1Y is conveyed to a preset primary transfer position.

[0308] When the yellow toner image on the photoreceptor 1Y is transferred to the primary transfer position, a primary transfer bias is applied to the primary transfer roller 5Y, and the electrostatic force from the photoreceptor 1Y toward the primary transfer roller 5Y acts on the toner image, and the toner image on the photoreceptor 1Y is transferred to the intermediate transfer belt 20. The transfer bias applied at this time has a polarity (+) opposite to the polarity (-) of the toner, and is controlled to, for example, +10 μA by a control unit (not shown) in the first unit 10Y. The toner remaining on the photoreceptor 1Y is removed and recovered by the photoreceptor cleaning device 6Y.

[0309] The primary transfer bias applied to the primary transfer rollers 5M, 5C, and 5K after the second unit 10M is also controlled in accordance with the first unit.

[0310] In this way, the intermediate transfer belt 20 to which the yellow toner image has been transferred by the first unit 10Y is sequentially transported through the second to fourth units 10M, 10C, and 10K, and the toner images of the respective colors are multiply transferred in a superimposed manner.

[0311] The intermediate transfer belt 20 to which the four-color toner image has been multi-transferred by the first to fourth units arrives at the secondary transfer section, which is composed of the intermediate transfer belt 20, the support roller 24 in contact with the inner surface of the intermediate transfer belt, and the secondary transfer roller (an example of the secondary transfer mechanism) 26 arranged on the image holding surface side of the intermediate transfer belt 20. On the other hand, the recording paper (an example of the recording medium) P is fed to the gap between the secondary transfer roller 26 and the intermediate transfer belt 20 by the feeding member at a preset timing, and a secondary transfer bias is applied to the support roller 24. The transfer bias applied at this time has the same (-) polarity as the polarity (-) of the toner, and the electrostatic force from the intermediate transfer belt 20 to the recording paper P acts on the toner image, so that the toner image on the intermediate transfer belt 20 is transferred to the recording paper P. The secondary transfer bias at this time is determined based on the resistance detected by the resistance detection mechanism (not shown) that detects the resistance of the secondary transfer section, and the voltage is controlled.

[0312] The recording paper P to which the toner image has been transferred is fed to the pressure contact portion (nipping portion) of a pair of fixing rollers in the fixing device (an example of a fixing mechanism) 28, and the toner image is fixed on the recording paper P to form a fixed image. The recording paper P to which the color image has been fixed is fed to the discharge portion, and a series of color image forming operations are completed.

[0313] As the recording paper P to which the toner image is transferred, for example, ordinary paper used in electrophotographic copiers, printers, etc. can be cited. As the recording medium, in addition to the recording paper P, OHP transparent films can also be cited. In order to further improve the smoothness of the image surface after fixing, it is preferred that the surface of the recording paper P is also smooth, for example, coated paper obtained by coating the surface of ordinary paper with a resin, art paper for printing, etc. can be used.

[0314] <Process Cartridge, Toner Cartridge>

[0315] The processing box in the case of using the resin particles of this embodiment as an electrostatic image developer is a processing box that is loaded and unloaded in an image forming device, and has a developing mechanism that stores the electrostatic image developer containing the resin particles of this embodiment, and uses the electrostatic image developer to develop the electrostatic image formed on the surface of the image retaining body into a toner image.

[0316] The process cartridge may be provided with a developing mechanism and, if necessary, at least one of other mechanisms selected from, for example, an image holding member, a charging mechanism, an electrostatic image forming mechanism, and a transfer mechanism.

[0317] An example of the process cartridge is shown below, but the present invention is not limited thereto. In the following description, the main parts shown in the drawings are described, and the other descriptions are omitted.

[0318] Figure 2 This is a schematic structural diagram showing an example of a process cartridge used in this embodiment.

[0319] Figure 2 The processing box 200 shown is constructed by, for example, integrally combining and retaining a photosensitive body 107 (an example of an image holding body) and a charging roller 108 (an example of a charging mechanism) provided around the photosensitive body 107, a developing device 111 (an example of a developing mechanism), and a photosensitive body cleaning device 113 (an example of a cleaning mechanism) through a shell 117 having a mounting guide 116 and an opening 118 for exposure to form an ink cartridge.

[0320] Figure 2In the figure, 109 denotes an exposure device (an example of an electrostatic image forming mechanism), 112 denotes a transfer device (an example of a transfer mechanism), 115 denotes a fixing device (an example of a fixing mechanism), and 300 denotes recording paper (an example of a recording medium).

[0321] Next, the toner cartridge will be described.

[0322] The toner cartridge is a toner cartridge that stores the resin particles of the present embodiment as a toner for electrostatic image development and is loaded and unloaded in an image forming apparatus. The toner cartridge stores replenishment toner to be supplied to a developing mechanism provided in the image forming apparatus.

[0323] Figure 1 The image forming apparatus shown is an image forming apparatus having a structure of attaching and detaching toner cartridges 8Y, 8M, 8C, and 8K, and the developing devices 4Y, 4M, 4C, and 4K are connected to the toner cartridges corresponding to the respective colors by toner supply pipes not shown in the figure. In addition, when the toner stored in the toner cartridge is insufficient, the toner cartridge is replaced.

[0324] Example

[0325] The following is an explanation of examples of the present invention, but the present invention is not limited to the following examples. It should be noted that in the following description, "parts" and "%" are all based on mass unless otherwise specified.

[0326] (Example 1: Aggregation and merging method)

[0327] <Preparation of Fluorescent Colorant Particle Dispersion (1)>

[0328] Fluorescent colorant (basic red 1): 70 parts

[0329] Anionic surfactant (manufactured by Daiichi Kogyo Chemical Co., Ltd., NEOGEN RK): 30 parts

[0330] Ion exchange water: 200 parts

[0331] The above materials were mixed and dispersed for 10 minutes using a homogenizer (ULTRA-TURRAX T50 manufactured by IKA Co.), and ion exchanged water was added so that the solid content in the dispersion became 20% by mass to obtain a fluorescent colorant particle dispersion (1) in which colorant particles having a volume average particle size of 140 nm were dispersed.

[0332] <Preparation of Colored Pigment Particle Dispersion Liquid (1)>

[0333] Coloring pigment (CI Pigment Violet 19): 70 parts

[0334] Anionic surfactant (manufactured by Daiichi Kogyo Chemical Co., Ltd., NEOGEN RK): 30 parts

[0335] Ion exchange water: 200 parts

[0336] The above materials were mixed and dispersed for 10 minutes using a homogenizer (ULTRA-TURRAX T50 manufactured by IKA Co.), and ion exchange water was added to adjust the solid content of the dispersion to 20% by mass to obtain a color pigment particle dispersion (1) in which colorant particles having a volume average particle size of 140 nm were dispersed.

[0337] <Preparation of Resin Particle Dispersion (1)>

[0338] ·Terephthalic acid: 30 mol parts

[0339] Fumaric acid: 70 mol

[0340] Bisphenol A ethylene oxide adduct: 5 mol

[0341] Bisphenol A propylene oxide adduct: 95 mol

[0342] The above materials were placed in a flask equipped with a stirring device, a nitrogen inlet pipe, a temperature sensor and a distillation tower, and the temperature was raised to 220°C in 1 hour. 1 part of titanium tetraethoxide was added to 100 parts of the above materials. The temperature was raised to 230°C in 30 minutes while distilling off the generated water. After the dehydration condensation reaction was continued at this temperature for 1 hour, the reactant was cooled. In this way, a polyester resin with a weight average molecular weight of 18,000 and a glass transition temperature of 60°C was obtained.

[0343] 40 parts of ethyl acetate and 25 parts of 2-butanol were added to a container equipped with a temperature control mechanism and a nitrogen replacement mechanism to prepare a mixed solvent, and 100 parts of a polyester resin was slowly added to dissolve it, and a 10% by mass ammonia aqueous solution (equivalent to 3 times the amount of the acid value of the resin in terms of molar ratio) was added thereto and stirred for 30 minutes. Then, the container was replaced with dry nitrogen, the temperature was maintained at 40°C, and 400 parts of ion exchange water was added dropwise at a rate of 2 parts / minute while stirring the mixed solution. After the addition was completed, the temperature was returned to room temperature (20°C to 25°C), and dry nitrogen was bubbled for 48 hours while stirring, thereby obtaining a resin particle dispersion in which ethyl acetate and 2-butanol were reduced to less than 1,000 ppm. Ion exchange water was added to the above resin particle dispersion to adjust the solid content to 20% by mass, thereby obtaining a resin particle dispersion (1).

[0344] <Preparation of Release Agent Particle Dispersion (1)>

[0345] Solid paraffin wax (HNP-9 manufactured by Nippon Seira Co., Ltd.): 100 parts

[0346] Anionic surfactant (Neogen RK, manufactured by Daiichi Kogyo Chemical Co., Ltd.): 1 part

[0347] Ion exchange water: 350 parts

[0348] The above materials were mixed, heated to 100°C, dispersed using a homogenizer (IKA, trade name ULTRA-TURRAX T50), and then dispersed using a Manton Gaulin high-pressure homogenizer (Gaulin) to obtain a release agent particle dispersion (1) (solid content 20% by mass) in which release agent particles with a volume average particle size of 200 nm were dispersed.

[0349] <Preparation of Toner Particles (1)>

[0350] Resin particle dispersion (1): 60.8 parts

[0351] Fluorescent colorant particle dispersion (1): 0.9 parts

[0352] Coloring pigment particle dispersion (1): 0.9 parts

[0353] Release agent particle dispersion (1): 6 parts

[0354] Anionic surfactant (Daiichi Kogyo Chemical Co., Ltd.: NEOGEN RK, 20%): 1 part

[0355] The above materials were placed in a round stainless steel flask, 0.1N (= mol / L) nitric acid was added to adjust the pH to 3.5, and then 30 parts of a nitric acid aqueous solution with a polyaluminium chloride concentration of 10% by mass was added. Next, a homogeniser (manufactured by IKA, trade name ULTRA-TURRAX T50) was used to disperse the mixture at a liquid temperature of 30°C, and then the mixture was heated to 45°C in a heating oil bath and maintained for 30 minutes. Thereafter, 30.4 parts of a resin particle dispersion (1) was added, and the mixture was maintained for 1 hour, and a 0.1N sodium hydroxide aqueous solution was added to adjust the pH to 8.5, and then the mixture was heated to 84°C and maintained for 2.5 hours. Next, the mixture was cooled to 20°C at a rate of 20°C / min, the solid content was filtered out, and the mixture was fully washed with ion exchange water and dried to obtain toner particles (1). The volume average particle size of the toner particles (1) was 7 μm.

[0356] <Preparation of Carrier 1>

[0357] Ferrite particles (average particle size 35 μm): 100 parts

[0358] Toluene: 14 parts

[0359] Polymethyl methacrylate (PMMA, weight average molecular weight 75,000): 5 parts

[0360] Carbon black: 0.2 parts (VXC-72, manufactured by Cabot Corporation, volume resistivity: 100 Ωcm or less)

[0361] The above materials except the ferrite particles are dispersed in a sand mill to prepare a dispersion, and the dispersion is charged into a vacuum degassing kneader together with the ferrite particles, and dried under reduced pressure while stirring, thereby obtaining a carrier 1.

[0362] <Preparation of Toner>

[0363] With respect to 100 parts by mass of the obtained toner particles (1), 1.5 parts by mass of hydrophobic silica (RY50 manufactured by NIPPON AEROSIL Co., Ltd.) and 1.0 parts by mass of hydrophobic titanium oxide (T805 manufactured by NIPPON AEROSIL Co., Ltd.) were mixed and blended using a sample mill at 10,000 rpm (revolutions / minute) for 30 seconds. Thereafter, the mixture was sieved using a vibrating sieve having a mesh size of 45 μm to prepare a toner 1 (toner for electrostatic image development). The volume average particle size of the obtained toner 1 was 7 μm.

[0364] <Production of Electrostatic Image Developer>

[0365] 8 parts of Toner 1 and 92 parts of Carrier 1 were mixed by a V-blender to prepare Developer 1 (electrostatic image developer).

[0366] (Example 2: Mixing and pulverizing method)

[0367] Linear polyester resin (linear amorphous polyester resin obtained from terephthalic acid / bisphenol A / ethylene oxide adduct / cyclohexanedimethanol: Tg=62°C, Mn=4,000, Mw=35,000, acid value=12 mgKOH / g, hydroxyl value=25 mgKOH / g): 88.1 parts

[0368] · Fluorescent colorant pigment (basic red 1): 1.00 part

[0369] Coloring pigment (CI Pigment Violet 19): 0.90 parts

[0370] Wax A (stearyl behenate, endothermic onset temperature: 47°C, melt viscosity at 120°C: 50 mPa·s): 5 parts

[0371] Copolymer petroleum resin (A) (C5 petroleum fraction (isoprene) / C5 petroleum fraction (piperylene) / isopropenyltoluene = monomer weight ratio (1.5 / 1.5 / 97), softening point: 125°C): 5 parts

[0372] The mixture was kneaded by an extruder, crushed by a surface crushing mill, and then classified into fine particles and coarse particles by a wind classifier to obtain a volume average particle size D 50 =8.0μm toner particles.

[0373] <Preparation of Toner>

[0374] To 100 parts of the obtained toner particles, 1.0 part of negatively chargeable silica having an average particle size of 40 nm and 0.5 part of negatively chargeable titanium dioxide having an average particle size of 15 nm were added to prepare Toner 2 (external addition toner).

[0375] <Production of Electrostatic Image Developer>

[0376] Next, 100 parts of a carrier (the carrier is a ferrite having a particle size of 50 μm coated with a styrene-methacrylate copolymer) is added to 6 parts of the toner 2 and mixed to prepare a developer 2 (electrostatic image developer).

[0377] (Examples 3 to 38 and Comparative Examples 1 to 6)

[0378] The electrostatic image developing toner and electrostatic image developer were prepared in the same manner as in Example 1 or Example 2, except that the type of fluorescent colorant, the type of coloring pigment, their contents (adjusted by the amount of dispersion used when preparing the toner), and the type of binding resin were changed as described in Tables 1 to 3.

[0379] (Example 39: Styrene acrylic acid-EA method)

[0380] <Preparation of Styrene Acrylic Resin Particle Dispersion>

[0381] Styrene: 308 parts

[0382] n-Butyl acrylate: 100 parts

[0383] Acrylic acid: 4 parts

[0384] · Dodecanethiol: 6 parts

[0385] Propylene glycol diacrylate: 1.5 parts

[0386] The above components were mixed, and the dissolved mixture was added to an aqueous solution obtained by dissolving 4 parts of anionic surfactant (manufactured by Daiichi Kogyo Yaku Co., Ltd.: NEOGEN SC) in 550 parts of ion exchange water. After emulsification in a flask, the mixture was mixed for 10 minutes, and an aqueous solution obtained by dissolving 6 parts of ammonium persulfate in 100 parts of ion exchange water was added thereto. After nitrogen substitution, the flask was stirred while heating the contents in an oil bath until the contents reached 75°C, and the mixture was kept at this temperature for 5 hours to continue emulsion polymerization. In this way, a resin particle dispersion (39) using a styrene acrylic resin was obtained in which resin particles having an average particle size of 195 nm and a weight average molecular weight (Mw) of 34,000 were dispersed (resin particle concentration: 20%). It should be noted that the glass transition temperature of the styrene acrylic resin is 52°C.

[0387] <Preparation of Toner Particles (39)>

[0388] Resin particle dispersion (39): 60.8 parts

[0389] Fluorescent colorant particle dispersion (39): 0.9 parts

[0390] Coloring pigment particle dispersion (39): 0.9 parts

[0391] Release agent particle dispersion (39): 6 parts

[0392] Anionic surfactant (Daiichi Kogyo Chemical Co., Ltd.: NEOGEN RK, 20%): 1 part

[0393] The above materials were placed in a round stainless steel flask, 0.1N (= mol / L) nitric acid was added to adjust the pH to 3.5, and then 30 parts of a nitric acid aqueous solution with a polyaluminium chloride concentration of 10% by mass was added. Next, a homogeniser (manufactured by IKA, trade name ULTRA-TURRAX T50) was used to disperse the mixture at a liquid temperature of 30°C, and then the mixture was heated to 45°C in a heating oil bath and maintained for 30 minutes. Thereafter, 30.4 parts of a resin particle dispersion (39) was added, and the mixture was maintained for 1 hour, and 0.1N (= 0.1 mol / L) sodium hydroxide aqueous solution was added to adjust the pH to 8.5, and then the mixture was heated to 84°C and maintained for 2.5 hours. Next, the mixture was cooled to 20°C at a rate of 20°C / min, the solid content was filtered out, and the mixture was fully washed with ion exchange water and dried to obtain toner particles (39). The volume average particle size of the toner particles (39) was 8 μm.

[0394] A toner for developing an electrostatic image and a developer for developing an electrostatic image were prepared in the same manner as in Example 1 except that the toner particles (39) were used instead of the toner particles (1).

[0395] The following evaluations were performed using the obtained electrostatic image developing toners or electrostatic image developers of Examples 1 to 39 and Comparative Examples 1 to 6. The evaluation results are summarized in Tables 1 to 3.

[0396] <Evaluation method>

[0397] -Spectral reflectance (fluorescence intensity) evaluation-

[0398] The spectral reflectance of the toner is measured by the following method.

[0399] In an environmental room at a temperature of 25° C. and a humidity of 60% RH, the main body, developer, and toner cartridge of DocuCentreColor 400CP manufactured by Fuji Xerox Corporation were cleaned by fully removing the previously installed developer and toner, and then toner was added to the toner cartridge.

[0400] Next, the developer toner amount of a monochrome 100% image on OS coated paper manufactured by Fuji Xerox Co., Ltd. was adjusted to 4.5 g / m 2 , make an image of size 5cm×5cm consisting only of toner, use X-Rite939 (manufactured by X-Rite, hole 4mm) to measure the spectral reflectance in the visible light region at 10 random locations within the image surface, average the results, and calculate the spectral reflectance.

[0401] The spectral reflectance of the fluorescent colorant was measured and calculated by the same method as above in the toner production method in each of the Examples and Comparative Examples, using a material except for the coloring pigment to produce the toner.

[0402] The spectral reflectance of the coloring pigment was measured and calculated by the same method as above in the toner production method in each of the Examples and Comparative Examples, using a material except for the fluorescent colorant to produce the toner.

[0403] -Color gamut evaluation-

[0404] In an environmental room with a temperature of 25°C and a humidity of 60% RH, the main body, developer, and toner box of DocuCentreColor 400CP manufactured by Fuji Xerox Co., Ltd. are thoroughly cleaned by removing the previously installed developer and toner, and then the prepared developer is added to the developer and the replenishing toner is added to each toner box.

[0405] Next, the developer toner amount of a monochrome 100% image on OS coated paper manufactured by Fuji Xerox Co., Ltd. was adjusted to 4.5 g / m 2 , an image consisting of only toner and having a size of 5 cm × 5 cm was produced, and the resulting image density (L * ), red(a* ) and blue (b * ). In the measurement, X-Rite939 (hole 4mm) was used, and the image surface was randomly measured 10 times, and the average was calculated to calculate L * 、a * and b * , and further calculates ΔE with respect to a target color sample in PANTONE's Neons Guide or a target color sample in DIC Corporation's DIC Color Guide.

[0406]

[0407]

[0408]

[0409]

[0410]

[0411] The “difference in hue angle” in Tables 1 to 3 indicates the difference between the hue angle of the resin particles (toner for electrostatic image development) and the hue angle of the fluorescent colorant.

[0412] In addition, the details of the fluorescent coloring agents and coloring pigments described in Tables 1 to 3 other than the above are as follows.

[0413] Xanthene skeleton compound A: Basic Red 1

[0414] Quinacridone skeleton compound A: CI Pigment Violet 19

[0415] Xanthene skeleton compound B: Basic violet 11:1

[0416] Quinacridone skeleton compound B: CI Pigment Red 122

[0417] Azo skeleton compound A: CI Pigment Yellow 74

[0418] Compound A having a heterocyclic structure formed by a benzimidazole skeleton and a coumarin skeleton: Basic Yellow 40

[0419] Benzimidazolone skeleton compound A: CI Pigment Yellow 180

[0420] Triarylmethane skeleton compound A: Basic Blue 7

[0421] Phthalocyanine skeleton compound A: CI pigment blue 15:3

[0422] Azo skeleton compound B: CI Pigment Yellow 174

[0423] Naphthamide skeleton compound A: CI Pigment Orange 38

[0424] The results shown in Tables 1 to 3 indicate that the resin particles (toner for electrostatic image development) of this example have a higher fluorescence intensity than the resin particles (toner for electrostatic image development) of the comparative example.

[0425] Furthermore, as can be seen from the results shown in Tables 1 to 3, the resin particles (toner for electrostatic image development) of this example are close to the target color and are also excellent in color reproducibility.

[0426] (Example 40)

[0427] -Production of coated products-

[0428] The resin particles of Example 1 were applied to a 10 cm × 10 cm square test plate of a zinc phosphate treated steel plate using a corona gun manufactured by Asahi Suntec Co., Ltd. by sliding the corona gun up, down, left, and right from a distance of 30 cm from the front surface so that the coating thickness was 30 μm or more and 50 μm or less, and then baked at 150° C. for 5 minutes to produce a coated product.

[0429] In the produced coated product, the powder adhered to the coated product (zinc phosphate treated steel sheet), and it was confirmed that the coating was performed.

Claims

1. A toner resin particle, wherein: The toner resin particles contain a resin, a fluorescent colorant and a coloring pigment, The hue angle of the toner resin particles is different from the hue angle of the fluorescent colorant. When the fluorescence peak wavelength in the spectral reflectance of the fluorescent colorant is A (nm), the integrated value of the spectral reflectance (%) of the coloring pigment in the wavelength range of A (nm) ± 30nm is 2,500 or more, The content of the fluorescent colorant is 0.1% by mass or more and 3.5% by mass or less based on the total mass of the toner resin particles. The content of the coloring pigment is 0.05 mass % or more and 1.5 mass % or less based on the total mass of the toner resin particles. The fluorescent colorant comprises at least one compound having a xanthene structure, and the coloring pigment comprises a compound having a quinacridone structure, wherein the compound having a xanthene structure is a compound having a rhodamine structure, a fluorescein structure or an eosin structure, The above resin includes a styrene-acrylic acid copolymer or a polyester resin.

2. The toner resin particles according to claim 1, wherein The color difference ΔE between the toner resin particles and the fluorescent colorant is 3 or more.

3. The toner resin particles according to claim 2, wherein The difference between the hue angle of the toner resin particles and the hue angle of the fluorescent colorant is 1 (°) or more.

4. The toner resin particles according to claim 1, wherein The color difference ΔE between the toner resin particles and the color sample DIC584B is 10 or less.

5. The toner resin particles according to claim 1, wherein The color difference ΔE between the toner resin particles and the color sample DIC584 is 10 or less.

6. The toner resin particles according to any one of claims 1 to 3, wherein The fluorescent colorant further comprises at least one compound having a heterocyclic structure formed by a benzimidazole skeleton and a coumarin skeleton, The above-mentioned coloring pigments also include compounds having an azo structure or a benzimidazolone structure.

7. The toner resin particles according to claim 6, wherein The color difference ΔE between the toner resin particles and the color sample DIC590 is 10 or less.

8. The toner resin particles according to claim 6, wherein The color difference ΔE between the toner resin particles and the color sample PANTONE 803C is 10 or less.

9. The toner resin particles according to any one of claims 1 to 3, wherein The fluorescent colorant further comprises a compound having a triarylmethane structure, The above-mentioned coloring pigments also include compounds having a phthalocyanine structure.

10. The toner resin particles according to claim 9, wherein The color difference ΔE between the toner resin particles and the color sample DIC591 is 10 or less.

11. The toner resin particles according to claim 9, wherein The color difference ΔE between the toner resin particles and the color sample PANTONE 802C is 10 or less.

12. The toner resin particles according to any one of claims 1 to 3, wherein The fluorescent colorant further includes a compound having a heterocyclic structure formed by a benzimidazole skeleton and a coumarin skeleton, a compound having an acridine structure, or a compound having a methine structure. The coloring pigments mentioned above also include compounds having an azo structure, a naphthamide structure or anthraquinone structure.

13. The toner resin particles according to claim 12, wherein The color difference ΔE between the toner resin particles and the color sample PANTONE 804C is 10 or less.

14. The toner resin particles according to claim 12, wherein The color difference ΔE between the toner resin particles and the color sample DIC587 is 10 or less.

15. The toner resin particles according to claim 12, wherein The color difference ΔE between the toner resin particles and the color sample DIC588 is 10 or less.

Images