Pigment dispersions, printed matter and toners

Abstract

To provide a pigment dispersing element that has high security and forms an image with good light resistance.SOLUTION: A pigment dispersing element contains a fluorescent agent and a binder resin. The fluorescent agent is excited by light with a wavelength of 400 nm or less. When the integrated value of light emission intensity of the fluorescent agent in an area of 400 nm or more and 700 nm or less in a light emission spectrum in excitation light with a wavelength of 250 nm or more and 290 nm or less is defined as F1, the integrated value of light emission intensity of the pigment dispersing element in an area of 400 nm or more and 700 nm or less in the light emission spectrum in excitation light with a wavelength of 250 nm or more and 290 nm or less as F2, and the ratio of the fluorescent agent contained in a solid content obtained when a change in mass when the pigment dispersing element is heated at 130°C becomes 0.3% / min or less, to the pigment dispersing element as W1 (mass%), F1, F2, and W1 satisfy the following formulas (1) and (2). Formula (1) F2×100 / W1≥F1×0.30 formula (2) 5.0≤W1≤80.0.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a pigment dispersion, a printed matter, a toner, and a method for producing a toner. [Background technology]

[0002] In recent years, the distribution of counterfeit goods has become a problem in various product forms. To combat this problem, information that cannot be recognized under visible light (invisible information) is embedded in the goods. One method for improving security using invisible information is to form an invisible image by incorporating a material that fluoresces in the visible light range when exposed to ultraviolet light into paint, ink, electrophotographic toner, etc. (Patent Document 1). However, the currently disclosed technologies for providing security are insufficient, and there is a demand for the development of more advanced technologies for providing security. Furthermore, for items that require long-term storage, there is a demand for lightfastness of the invisible image. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-144029 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to solve the above problems, that is, to provide a pigment dispersion and a toner that are capable of forming an image having high security and good light resistance. Another object of the present invention is to provide a printed matter using the pigment dispersion and a printed matter using the toner. A further object of the present invention is to provide a method for producing the toner. [Means for solving the problem]

[0005] A first aspect of the present invention is A pigment dispersion containing a fluorescent agent and a binder resin, The fluorescent agent is excited by light with a wavelength of 400 nm or less, When F1 is defined as the integral value of the emission intensity in the region of 400 nm or more and 700 nm or less of the emission spectrum of the fluorescent agent when excited by light with a wavelength of 250 nm or more and 290 nm or less, and F2 is defined as the integral value of the emission intensity in the region of 400 nm or more and 700 nm or less of the emission spectrum of the pigment dispersion when excited by light with a wavelength of 250 nm or more and 290 nm or less, and W1 (mass%) is defined as the proportion of the fluorescent agent contained in the solid content obtained when the mass change of the pigment dispersion when heated at 130°C is 0.3% / min or less, The F1, the F2, and the W1 satisfy the following formulas (1) and (2): death, F2×100 / W1≧F1×0.30 Formula (1) 5.0≦W1≦80.0 Formula (2) the binder resin in the pigment dispersion contains one or more units represented by any one of the following formulas (4) to (6), and the total content of the units represented by any one of the following formulas (4) to (6) in the total mass of the binder resin in the pigment dispersion is 70 mass% or more; [ka] [In formula (4), P 1 and P 2 represents the bond to the resin main chain, and R 1 represents a hydrogen atom or a methyl group, and n represents an integer of 0 or more and 30 or less. [ka] [In formula (5), P 3 and P 4 represents the bond to the main chain of the resin.] [ka] [In formula (6), P 5 and P 6 represents the bond to the main chain of the resin.] The pigment dispersion is characterized by the following:

[0006] A second aspect of the present invention is a printed matter characterized by using the above pigment dispersion. A third aspect of the present invention is A toner having toner particles containing a fluorescent agent that is excited by light having a wavelength of 400 nm or less, a binder resin, and a release agent, When the integral value of the emission intensity in the region of 400 nm to 700 nm of the emission spectrum of the fluorescent agent when excited by light having a wavelength of 250 nm to 290 nm is F3, the integral value of the emission intensity in the region of 400 nm to 700 nm of the emission spectrum of the toner when excited by light having a wavelength of 250 nm to 290 nm is F4, and the mass ratio of the fluorescent agent in the toner particles is W2 (mass%), the following formulas (7) and (8) are satisfied: death, F4×100 / W2≧F3×0.30 Formula (7) 5.0≦W2≦80.0 Formula (8) the binder resin in the toner particles contains one or more units represented by any one of the following formulas (4) to (6), and the total content of the units represented by any one of the following formulas (4) to (6) in the total mass of the binder resin in the toner particles is 70 mass% or more; [ka] [In formula (4), P 1 and P 2 represents the bond to the resin main chain, and R 1 represents a hydrogen atom or a methyl group, and n represents an integer of 0 or more and 30 or less. [ka] [In formula (5), P 3 and P 4 represents the bond to the main chain of the resin.] [ka] [In formula (6), P 5 and P 6 represents the bond to the main chain of the resin.] The toner is characterized by the above. A fourth aspect of the present invention is a printed matter characterized by using the above toner. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a pigment dispersion and a toner that form images having high security and good lightfastness, and also to provide a method for producing a printed matter and a toner that exhibit these effects. DETAILED DESCRIPTION OF THE INVENTION

[0010] The pigment dispersion and toner of the present invention will be specifically described. The pigment dispersion of the present invention contains a fluorescent agent and a binder resin, the fluorescent agent being excited by light with a wavelength of 400 nm or shorter, and is characterized in that F1 is the integral of the emission intensity from 400 to 700 nm in the emission spectrum of the fluorescent agent when excited by light with a wavelength of 250 to 290 nm, F2 is the integral of the emission intensity from 400 to 700 nm in the emission spectrum of the pigment dispersion when excited by light with a wavelength of 250 to 290 nm, and W1 (mass %) is the proportion of the fluorescent agent in the solid content obtained when the mass change of the pigment dispersion when heated at 130°C is 0.3% / min or less, wherein F1, F2, and W1 satisfy the following formulas (1) and (2): Note that the term "solid content" is used to exclude solvents, which may be contained in the pigment dispersion. F2×100 / W1≧F1×0.30 Formula (1) 5.0≦W1≦80.0 Formula (2)

[0011] The fluorescent agent according to the present invention is excited by light with a wavelength of 400 nm or less, i.e., ultraviolet light, and has an emission spectrum in the visible light range, so that it can form an image visible to the human eye when irradiated with ultraviolet light. Furthermore, security can be further enhanced by using light with a wavelength of 290 nm or less as excitation light, among light with a wavelength of 400 nm or less.

[0012] In image formation, a binder resin is often blended when fixing a colorant (dye or pigment) on a medium. Common binder resins often have absorption in the wavelength range of 250 nm to 290 nm, and when an image is irradiated with excitation light in this wavelength range, the excitation light is absorbed by the binder resin, resulting in a decrease in luminous efficiency. When the pigment dispersion of the present invention satisfies the above formula (1), it is possible to reduce the decrease in luminous efficiency even when irradiated with excitation light in the wavelength range of 250 nm to 290 nm, thereby improving visibility when irradiated with ultraviolet light.

[0013] Furthermore, the pigment dispersion of the present invention is characterized by satisfying the above formula (2). When W1 is 5.0 or more, visibility can be improved. Furthermore, when W1 is 80.0 or less, image graininess can be reduced, thereby achieving invisibility when irradiated with visible light. It is preferable that W1 further satisfies the following formula (3). 30.0≦W1≦70.0 Formula (3)

[0014] The pigment dispersion of the present invention was applied to the media in an amount of 0.3 mg / cm 2 It is preferable that the maximum light absorptance (Rmax1) in the wavelength region of 400 nm or more and 700 nm or less in the image of the solid content formed in step 1 is 10% or less.

[0015] When the above conditions are satisfied, the invisibility of the image is improved. The light absorption rate in the wavelength range of 400 nm to 700 nm can be controlled by changing the particle size of the fluorescent agent, the proportion W1 of the fluorescent agent contained in the solid content, or the spectrum of the binder resin in the wavelength range of 400 nm to 700 nm.

[0016] The pigment dispersion of the present invention has an emission wavelength spectrum when irradiated with excitation light in the wavelength range of 250 nm to 290 nm and in the wavelength range of 315 nm to 400 nm. * a * b *When the color coordinates converted to the color system are G1 and G2, respectively, the difference ΔE1 between the color coordinates of G1 and G2 is preferably 20.0 or more. The image emits two colors at two different excitation wavelengths of ultraviolet light (dual excitation, two-color emission), improving the security of the image. When ΔE1 is 20.0 or more, the two-color emission is easily recognized, improving security. A more preferable range for ΔE1 is 30.0 or more. ΔE1 can also be changed by changing the type of fluorescent agent, the metal contained in the fluorescent agent, or the manufacturing conditions of the fluorescent agent.

[0017] The pigment dispersion may be solvent-free or may contain various solvents as required. The solvent used in the pigment dispersion is not particularly limited as long as it is an organic solvent in which the binder resin can be dissolved. Specific examples of the organic solvent include ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and isobutyl acetate, cyclic saturated hydrocarbons such as cyclohexane and cycloheptane, cyclic ethers such as tetrahydrofuran, and aromatic hydrocarbons such as toluene and xylene. These organic solvents may be used alone or in combination of two or more.

[0018] The pigment dispersion can be produced by any known method, for example, by mixing a fluorescent agent, a binder resin, and, if necessary, a solvent using a dispersing machine such as a bead mill, a roll mill, or a media-less dispersing machine.

[0019] The fluorescent agent according to the present invention will be described in detail below. The fluorescent agent according to the present invention is not particularly limited as long as it is excited by light having a wavelength of 400 nm or less and has an emission spectrum when excited by light having a wavelength of 250 nm or more and 290 nm or less.

[0020] The fluorescent agent is preferably in the form of a pigment in the pigment dispersion or toner, and when it is in the form of a pigment, the light resistance of the formed image is improved. The pigment in the present invention is in a state of being present as particles in the pigment dispersion or toner. The state of being present as particles can be confirmed by observing the cross section of the image film or toner obtained from the pigment dispersion using an SEM or TEM.

[0021] The following fluorescent agents can be used: Fluorescent dyes such as thiophene-based, β-quinophthalone-based, coumarin-based, bisstyrylbenzene-based, and oxazole-based dyes, europium-based complex compounds, and inorganic compounds such as calcium fluoride, calcium tungstate, barium silicate, calcium phosphate, and calcium zinc phosphate, and alkaline earth metal tungstates, arsenates, silicates, and phosphates can be used. The above inorganic compounds may contain other metal elements as needed.

[0022] Among these, the fluorescent agent is preferably an inorganic compound containing a lanthanoid element and having calcium fluoride as a main component, since the use of an inorganic compound containing a lanthanoid element and having calcium fluoride as a main component can provide good light resistance.

[0023] In the present invention, in order to enhance the security of the image, it is preferable that the image emits light in two different colors at two different excitation wavelengths of ultraviolet light (dual excitation, two-color emission). When the fluorescent agent according to the present invention is an inorganic compound containing calcium fluoride containing a lanthanoid element as a main component, dual excitation, two-color emission is easily exhibited, which facilitates improved security. Among the lanthanoid elements, it is particularly preferable that the fluorescent agent contains Eu (europium).

[0024] In a cross-sectional observation image of an image film or toner obtained using the pigment dispersion, the fluorescent agent preferably has a 500 nm or less 500% particle diameter based on the number of particles. When the 50% particle diameter based on the number of particles is 500 nm or less, the graininess of the image is reduced, and therefore invisibility is likely to be improved. The 50% particle diameter based on the number of particles is more preferably 400 nm or less, and even more preferably 300 nm or less. The particle diameter of the fluorescent agent can be controlled by the pigment dispersion conditions, etc. Furthermore, from the viewpoint of improving lightfastness, the particle diameter of the fluorescent agent is preferably 50 nm or more.

[0025] Next, the binder resin according to the present invention will be described in detail. The binder resin according to the present invention contains one or more units selected from the units represented by any one of the following formulas (4) to (6), and it is preferable that the total content of the units represented by any one of the formulas (4) to (6) in the total mass of the binder resin is 70 mass % or more.

[0026] [ka] [P in formula (4) 1 and P 2 , represents the bond to the main chain skeleton of the resin, R1 represents a hydrogen atom or a methyl group, and n represents an integer of 0 to 30.

[0027] [ka] [P in formula (5) 3 , P 4 represents the bond to the main chain of the resin.]

[0028] [ka] [P in formula (6) 5 , P 6 represents the bond to the main chain of the resin.]

[0029] When the above requirements are satisfied, the absorption of ultraviolet excitation light by the binder resin can be reduced, thereby improving visibility when irradiated with ultraviolet light. When the binder resin has formula (4) and n in formula (4) is 16 or more and 30 or less, the structure of formula (4) is easily crystallized, which is preferable because it improves light resistance.

[0030] The type of resin that can be used as the binder resin is not particularly limited, but examples include polyester, vinyl resin, polyurethane, polyurea, polycarbonate, phenol resin, polyolefin, and epoxy resin.

[0031] As a method for introducing the unit represented by formula (4) into a polymer, there is a method for polymerizing the acrylic monomer shown below. Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, n-dodecyl acrylate, tetradecyl acrylate, n-stearyl acrylate, n-behenyl acrylate, nonadecyl acrylate, eicosyl acrylate, heneicosanyl acrylate, ceryl acrylate, octacosanyl acrylate, myricyl acrylate, methyl methacrylate, ethyl Methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, n-dodecyl methacrylate, tetradecyl methacrylate, n-stearyl methacrylate, n-behenyl methacrylate, nonadecyl methacrylate, eicosyl methacrylate, heneicosanyl methacrylate, ceryl methacrylate, octacosanyl methacrylate, and myricyl acrylate.

[0032] If necessary, it can also be copolymerized with other monomers having an ethylenically unsaturated bond. Examples of copolymerizable monomers include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, maleic acid, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, vinyl acetate, and 2-hydroxyethyl methacrylate.

[0033] To introduce the unit represented by formula (5) into a polymer, polylactic acid can be used as part or all of the binder resin. One method for synthesizing polylactic acid is to subject L-lactide, a cyclic dimer of lactic acid, to ring-opening polymerization using an initiator in the presence of a catalyst.

[0034] The unit represented by formula (6) can be introduced into a polymer by polycondensation of isosorbide with a polycondensable monomer. Specific examples of the polycarboxylic acid include oxalic acid, glutaric acid, succinic acid, maleic acid, adipic acid, β-methyladipic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-dicarboxylic acid, hexahydroterephthalic acid, malonic acid, pimelic acid, phthalic acid, isophthalic acid, terephthalic acid, tetracarboxylic ... Examples of suitable polycarboxylic acids include chlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediglycolic acid, p-phenylenediglycolic acid, o-phenylenediglycolic acid, diphenylacetic acid, diphenyl-p,p'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracenedicarboxylic acid, cyclohexanedicarboxylic acid, etc. Examples of suitable polycarboxylic acids other than dicarboxylic acids include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid.

[0035] If necessary, the composition may contain a polyhydric alcohol other than isosorbide. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, and dipentaerythritol. Examples of suitable bisphenol A include ethanol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, isosorbide, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adduct, and hydrogenated bisphenol A propylene oxide adduct.

[0036] The binder resin according to the present invention preferably has low absorption of ultraviolet light. One method for reducing absorption of ultraviolet light is to reduce the amount of units having aromatic rings in the binder resin.

[0037] Examples of the unit having an aromatic ring include styrene and its derivatives such as those exemplified above for the monomer, phthalic acid and its derivatives such as those exemplified above, bisphenol A, and various adducts of bisphenol A. The content of these units having an aromatic ring is preferably 10.0% by mass or less, and more preferably 5.0% by mass or less, of the binder resin.

[0038] Next, the toner of the present invention will be described in detail. The toner of the present invention has toner particles containing a fluorescent agent that is excited by light with a wavelength of 400 nm or less, a binder resin, and a release agent, and is characterized in that, when F3 is the integral of the emission intensity from 400 nm to 700 nm in the emission spectrum of the fluorescent agent when exposed to excitation light with a wavelength of 250 nm to 290 nm, F4 is the integral of the emission intensity from 400 nm to 700 nm in the emission spectrum of the toner when exposed to excitation light with a wavelength of 250 nm to 290 nm, and W2 (mass%) is the mass proportion of the fluorescent agent in the toner particles, the following formulas (7) and (8) are satisfied: F4×100 / W2≧F3×0.30 Formula (7) 5.0≦W2≦80.0 Formula (8)

[0039] It is believed that visibility upon irradiation with ultraviolet light can be improved for the same reasons as those described above in connection with the pigment dispersion. It is more preferable that W2 satisfies the following formula (9). 30.0≦W2≦70.0 Formula (9)

[0040] The toner of the present invention is used to form an image on a medium with a coverage of 0.3 / cm 2 It is preferable that the maximum light absorptance (Rmax2) in the wavelength region of 400 nm or more and 700 nm or less is 10% or less. For the same reasons as those described above in the description of the pigment dispersion, invisibility is likely to be improved.

[0041] The toner of the present invention has an emission wavelength spectrum of L when irradiated with excitation light having a wavelength of 250 nm to 290 nm and a wavelength of 315 to 400 nm. * a * b * When the color coordinates converted into the color system are G3 and G4, respectively, the difference ΔE2 between the color coordinates of G3 and G4 is preferably 20.0 or more. When ΔE2 is 20.0 or more, it is easy to recognize the two-color emission from the two wavelengths, and security can be improved. A more preferable range for ΔE2 is 30.0 or more.

[0042] The toner of the present invention can be produced by a conventionally known method. For example, a suspension polymerization method is used in which a polymerizable monomer composition containing a polymerizable monomer for obtaining a binder resin, a fluorescent agent, and a release agent is suspended and granulated in an aqueous medium, and the polymerizable monomer in the polymerizable monomer composition is polymerized; a kneading and pulverization method is used which includes a step of melting and kneading various toner constituent materials containing a binder resin, a fluorescent agent, and a release agent to obtain a kneaded mixture, a step of pulverizing the kneaded mixture, and a step of classifying the mixture; an emulsion aggregation method is used in which a composition containing a binder resin, a dispersion obtained by emulsifying and dispersing a fluorescent agent, and a dispersion of a release agent are mixed, aggregated, and heat-fused to obtain toner particles; an emulsion polymerization and aggregation method is used in which a dispersion obtained by emulsion-polymerizing a polymerizable monomer for a binder resin is mixed with a composition containing a dispersion obtained by emulsifying and dispersing a fluorescent agent and a dispersion of a release agent, and then aggregated and heat-fused to obtain toner particles; and a solution suspension method is used in which an organic solvent dispersion containing a binder resin, a fluorescent agent, and a release agent in an organic solvent is suspended in an aqueous medium and granulated.

[0043] The binder resin preferably has a THF-insoluble content of 20% by mass or less, and in ultraviolet-visible light absorption spectroscopy (UV-vis), the integral value of the absorption intensity of a tetrahydrofuran (THF)-soluble content solution from 250 nm to 290 nm (AInt250nm-290nm) is 20 or less. When the THF-insoluble content of the binder resin is 20.0% by mass or less relative to the total mass of the binder resin and the absorption intensity of the THF-soluble content is 20 or less, visibility upon irradiation with ultraviolet light is likely to be improved.

[0044] In the present invention, an external additive may be added to the toner particles to improve the image quality of the toner. As the external additive, an inorganic fine powder such as silica fine powder, titanium oxide fine powder, or aluminum oxide fine powder can be used. The amount of the inorganic fine powder added is preferably 0.5% by mass or more and 5.0% by mass or less, based on the mass of the toner.

[0045] The toner of the present invention is characterized by containing a releasing agent. Examples of the releasing agent that can be used include aliphatic hydrocarbon waxes, oxides of aliphatic hydrocarbon waxes, block copolymers of aliphatic hydrocarbon waxes, waxes mainly composed of fatty acid esters, and those obtained by partially or completely deoxidizing fatty acid esters such as deacidified carnauba wax, partial esterified products of fatty acids and polyhydric alcohols, methyl ester compounds having hydroxyl groups obtained by hydrogenating vegetable oils, Fischer-Tropsch waxes, and the like. The content of the releasing agent in the toner particles is preferably 1.50% by mass or more and 20.0% by mass or less based on the toner mass.

[0046] Hereinafter, the measurement methods for each physical property related to the pigment dispersion and the toner will be described. <Measurement Method of Emission Spectrum and Calculation Method of F1 to F4> When the pigment dispersion contains water and an organic solvent, a solid content sample heated until the mass change at 130 °C becomes 0.3% / min or less was collected and filled into a quartz glass cell. The fluorescent agent and the toner were directly filled into a quartz glass cell. The prepared samples were measured using the following apparatus and conditions. Measuring apparatus: Quantaurus-τ (manufactured by Hamamatsu Photonics K.K.) Excitation wavelength: 280 nm Fluorescence wavelength: 400 nm to 700 nm Step width: 2 nm Integration: 2 times Repetition frequency: 10 MHz F1 to F4 were calculated from the measured spectrum.

[0047] <Measurement Method of Rmax1 and Rmax2> Using A4 paper "High White Paper GF-C081" (manufactured by Canon Inc.) as a recording material, a 1 cm × 10 cm rectangular unfixed image with a toner loading of 0.30 mg / cm 2 was formed. This unfixed image was left standing in a natural convection constant temperature dryer set at 110 °C for 3 minutes to fix the toner on the paper, and a sample image (fixed image) was obtained. The above sample image was subjected to spectroscopic analysis measurement in the wavelength range of 400 nm to 700 nm using the following photometer, and the maximum light absorptance (Rmax2) of the toner in the range of 400 nm to 700 nm was calculated. An ultraviolet-visible-near-infrared spectrophotometer "UV-3600" (Shimadzu Corporation) equipped with an integrating sphere accessory "ISR-240A" (Shimadzu Corporation) was used.

[0048] Spectroscopic analysis of a sheet of paper (paper on which no image is formed) is also performed as a blank. The value obtained by subtracting the measured value (light absorptance (%)) of the sheet of paper alone from the measured value (light absorptance (%)) of the sample image is used as the light absorptance (%) for evaluating the toner in the present invention. Note that the toner amount of an unfixed image formed on the paper is precisely 0.30 mg / cm. 2 If this is not the case, the absorption rate was calculated as follows. Toner loading: 0.27 to 0.30 mg / cm 2 An unfixed image was formed in the range of 0.30 to 0.33 mg / cm 2 and fixed on paper by the above method to obtain a first sample image. 2 An unfixed image was formed in the range of 1 to 3 mm, and then fixed on paper by the above method to prepare a second sample image. Spectroscopic analysis measurements were then performed on each of the first and second sample images. The value obtained by subtracting the measured value (light absorptance (%)) of the paper alone from the measured value (light absorptance (%)) of the first sample image was taken as the first light absorptance (%). Similarly, the value obtained by subtracting the measurement value (light absorptance (%)) of the paper alone from the measurement value (light absorptance (%)) of the second sample image was taken as the second light absorptance (%). The absorptance (%) of the first light and the absorptance (%) of the second light were plotted on an xy plane with the toner amount on the horizontal axis and the light absorptance on the vertical axis. These two points were then connected by a straight line to obtain a value of 0.30 mg / cm. 2 The equivalent value is a toner load of 0.30 mg / cm 2 was taken as the light absorption rate of the image.

[0049] The pigment dispersion was applied to the lower half of the super art paper in the longitudinal direction using a wire bar, with the amount of pigment applied after drying being 0.30 mg / cm. 2 The model number of the wire bar was adjusted so that the image obtained was 0.30 mg / cm. The spectroscopic analysis was carried out in the same manner as in the evaluation of the toner described above. 2 The light absorption rate was calculated from the image, and the maximum light absorption rate (Rmax1) in the region of 400 nm to 700 nm in the pigment was obtained.

[0050] <Calculation method for ΔE1 and ΔE2> The spectrum of the pigment dispersion or toner was obtained in the same manner as in the above emission spectrum measurement method, except that the excitation wavelength was changed to 365 nm and the step width was changed to 10 nm. The obtained emission spectrum was then measured in accordance with CIE1976. * a * b * Each of the resulting L * a * b * From the coordinate system, ΔE1 for the pigment dispersion and ΔE2 for the toner were calculated.

[0051] <Method for calculating the average particle size of fluorescent agent in pigment dispersion or toner> When the pigment dispersion contained water and an organic solvent, a solid sample was collected in the same manner as in the above-mentioned method for measuring the emission spectrum. Cross sections of solid samples or toner particles were prepared using a JEOL Ltd. cross-section polisher (product name: SM-09010). Specifically, a piece of carbon double-sided adhesive sheet was attached to a silicon wafer, a Mo mesh (diameter: 3 mm, thickness: 30 μm) was fixed, and the solid sample or toner particles were attached to the surface. Platinum was then vapor-deposited onto the surface, and the cross-section of the solid sample or toner particles was then prepared using the cross-section polisher under conditions of an accelerating voltage of 4 kV and a processing time of 3 hours. The cross sections of the obtained solid samples or toner particles were observed using a scanning electron microscope (SEM) ("S-4800" manufactured by Hitachi High-Technologies). The observation conditions were adjusted to maximize visualization depending on the sample. Images of five fields were measured at a magnification of 30.0 K, and the long side lengths of all particles were measured. From these data, the frequency in each data section (10 nm interval) was calculated, and a cumulative distribution was created to calculate the 50% particle size on a number basis.

[0052] <Method for measuring toner particles and toner weight average particle size (D4)> The toner particles and the weight average particle diameter (D4) of the toner were measured using a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.). The measurement was carried out under the following conditions. Effective number of measurement channels: 25,000 channels Total number of control motors: 50,000 Aperture: 100 μm Current: 1600μA Gain: 2 The Kd value was measured using a "Standard Particle 10.0 μm" (Beckman Coulter). The measurement data was analyzed using the dedicated software provided with the device to calculate the weight-average particle size (D4). Note that when the dedicated software was set to Graph / Volume %, the "Average Diameter" on the "Analysis / Volume Statistics (Arithmetic Mean)" screen was the weight-average particle size (D4).

[0053] <Method for measuring the amount of THF insoluble content of binder resin> 1 g of binder resin was precisely weighed and placed in a cylindrical filter paper, and subjected to Soxhlet extraction with 200 ml of tetrahydrofuran (THF) for 20 hours. The cylindrical filter paper was then removed and vacuum dried at 40°C for 20 hours, and the mass of the residue was measured. The amount of tetrahydrofuran (THF) insoluble content of the binder resin was calculated using the following formula. Amount of THF insoluble matter = Residue mass / Mass of binder resin before Soxhlet extraction × 100 (mass%)

[0054] <Contents of units of formulae (4) to (6) in binder resin> The binder resin was separated using the solvent gradient method described below. The solvent gradient elution method uses a gradient preparative HPLC (Shimadzu LC-20AP high-pressure gradient preparative system, Waters SunFire preparative column 50 mm φ 250 mm) with a column temperature of 30 °C, a flow rate of 50 mL / min, and a mobile phase of acetonitrile as a poor solvent and THF as a good solvent. As in the measurement of the insoluble matter above, 0.02 g of the THF-soluble matter obtained by extraction was dissolved in 1.5 mL of THF to prepare the sample for separation. The mobile phase started with a composition of 100% acetonitrile, and 5 minutes after sample injection, the THF ratio was increased by 4% per minute until the mobile phase composition reached 100% THF over 25 minutes. The components could be separated by drying the resulting fractions. This allowed the separation of the bound components. The separated components are treated under the following conditions: 1 H-NMR, 13 This can be determined by C-NMR measurement.

[0055] (Measurement conditions for nuclear magnetic resonance spectroscopy (1H-NMR)) Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL) Measurement frequency: 400MHz Pulse condition: 5.0 μs Frequency range: 10500Hz Accumulation count: 64 times Solvent: A deuterated solvent that dissolves the resin is used appropriately.

[0056] ( 13 C-NMR (solid state) measurement conditions Equipment: JEOL RESONANCE JNM-ECX500II Sample tube: 3.2 mm diameter Sample amount: 150 mg Measurement temperature: room temperature Pulse mode: CP / MAS Measurement nuclear frequency: 123.25MHz ( 13 C) Reference substance: Adamantane (external standard: 29.5ppm) Sample rotation speed: 20kHz Contact time: 2ms Delay time: 2 seconds Number of times accumulated: 1024 Solvent: A deuterated solvent that dissolves the resin is used appropriately.

[0057] (Pyrolysis GCMS measurement conditions) Measuring device: Pyrolysis GCMS device Pyrolysis equipment: Curie point pyrolyzer JPS700 (Japan Analytical Industry Co., Ltd.) Pyrofoil: F590 (Curie point 590°C) GCMS FocusGC / ISQ (Thermo Fisher Scientific) Carrier gas: He gas (purity 99.99995%) Column: HP-5MS (30 m, inner diameter 0.25 mm, film thickness 0.25 μm) Injection port temperature: 280°C, MS transfer temperature: 280°C, ion current temperature: 250°C Oven temperature: Start at 50°C, hold for 3 minutes, then increase to 300°C at 10°C / min and hold for 30 minutes. Helium flow rate: 1.2 mL / min constant flow control, split ratio: 20 MS ion source: EI, MS detection range (m / z): 25-800 Library:NIST Under the above measurement conditions, 0.5 mg of resin and 5 μL of a methylation reagent (10% tetramethylammonium hydroxide in methanol) are added to Pyrofoil and analyzed.

[0058] <Method for measuring ultraviolet absorption of tetrahydrofuran (THF) soluble matter> The THF-soluble portion extracted by the above-mentioned method for measuring the THF-insoluble portion of the binder resin was dried to obtain a solid THF-soluble portion. 0.05 g of the obtained soluble portion was dissolved in 2 g of THF and placed in a quartz cell. Ultraviolet absorption measurement was performed using the following equipment and conditions. Measuring device: UV-3100PC (Shimadzu Corporation) Slit width: 5.0 mm Scan Speed: Slow Sampling pitch: 1 nm Scan wavelength: 250nm~400nm The integrated value of the absorbance in the range of 250 nm to 290 nm of the obtained spectrum was calculated. [Example]

[0059] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, the "parts" of each material in the examples and comparative examples are all based on mass.

[0060] <Production example of fluorescent agent 1> Materials were placed in a glass container (manufactured by TGK) at the mixing ratio shown below, and dispersed for 10 hours using a disperser (Disperser DAS H 200-K manufactured by LAU). Fluobright+ red / blue type (Canon Optron) 5 parts by weight ·RO water 50 parts by mass Glass beads (Φ0.991~1.397mm) 30 parts by weight After dispersion, the glass beads were filtered off using a mesh, and the fluorescent agent dispersion was separated using a centrifuge to collect the precipitate. The collected precipitate was then dried in a vacuum. The emission spectrum of the obtained fluorescent agent 1 was measured, and F1 was calculated.

[0061] <Production Examples of Fluorescent Agents 2 to 6> Fluorescent agents 2 to 6 were produced in the same manner as in the production example of fluorescent agent 1, except that the materials and dispersion time were changed as shown in Table 1. Emission spectra of the obtained fluorescent agents were measured, and F1 was calculated.

[0062] [Table 1]

[0063] <Manufacturing example of resin P1> Behenyl acrylate 80.0 parts by mass Methacrylonitrile 19.0 parts by mass Styrene 1.0 parts by mass Toluene 50.0 parts by mass The above materials were mixed and heated to 70°C, and then 1.0 parts by mass of t-butyl peroxypivalate was added as a polymerization initiator while stirring. The temperature was then maintained at 70°C, and polymerization was carried out for 5 hours. The temperature was then raised to 85°C and maintained at this temperature for 2 hours. After cooling, the mixture was reprecipitated in methanol, filtered, and dried to obtain Resin P1.

[0064] <Production examples of resin P2, resins P4 to P7, and resin P10> Resins P2, P4 to P7, and P10 were produced in the same manner as in the production example for resin P1, except that the types and amounts of monomers were changed as shown in Table 2.

[0065] [Table 2] In the table, BEA represents n-behenyl acrylate, St represents styrene, MAN represents methacrylonitrile, MMA represents methyl methacrylate, tBA represents tert-butyl acrylate, and nBA represents n-butyl acrylate.

[0066] <Resin P3> Polylactic acid (10361D) manufactured by NatureWorks was used as the resin P3.

[0067] <Manufacturing example of resin P8> In an autoclave equipped with a pressure reducing device, a water separator, a nitrogen gas introducing device, a temperature measuring device, and a stirring device, Terephthalic acid 29.9 parts by mass Bisphenol A-propylene oxide 2 mole adduct 40.0 parts by mass Isosorbide 10.0 parts by mass Ethylene glycol 4.5 parts by mass Tetrabutoxytitanate 0.125 parts by mass The above monomers and catalyst were charged, and the reaction was carried out under a nitrogen atmosphere at normal pressure at 200° C. for 5 hours to obtain resin P8.

[0068] <Manufacturing example of resin P9> Resin P9 was produced in the same manner as in the production example for Resin P8, except that the monomers and catalyst were changed as follows. Bisphenol A-propylene oxide 2 mole adduct 71.3 parts by mass Terephthalic acid 14.0 parts by mass Isophthalic acid 14.0 parts by mass Tetrabutoxytitanate 0.1 parts by mass Trimellitic acid 0.90 parts by mass

[0069] <Production example of pigment dispersion 1> ·Resin P1 40.0 parts by mass Fluorescent agent 1 60.0 parts by mass The above raw materials were charged into a kneader-type mixer and heated without pressure while mixing. The mixture was further heated and melt-kneaded at 90 to 100°C for 15 minutes. Then, 100 parts by mass of toluene was added, and the mixture was kneaded at 60°C for 1 hour to obtain Pigment Dispersion 1. The obtained Pigment Dispersion 1 was heated to 130°C, and the fluorescence spectrum of a solid sample heated until the mass change upon heating at 130°C was 0.3% / min or less was measured, and F2 was calculated. The obtained fluorescence spectrum is L * a * b * Converting to color coordinates, at 365 nm excitation, L *= 4.8, a * =40.5, b * = -58.5 and at 280 nm excitation, L * =16.9, a * =34.6, b * = -19.9. From this value, ΔE1 was calculated to be 40.8. The 50% particle size based on the number distribution of the obtained solid sample was measured from a cross-sectional SEM image and was found to be 160 nm. The physical properties of the obtained pigment dispersion 1 are shown in Table 4.

[0070] <Production Examples of Pigment Dispersions 2 to 17 and Comparative Pigment Dispersions 1 to 4> Pigment Dispersions 2 to 17 and Comparative Pigment Dispersions 1 to 4 were produced in the same manner as in the Production Example of Pigment Dispersion 1, except that the fluorescent agent and binder resin were changed as shown in Table 3. The physical properties of the obtained Pigment Dispersions 2 to 17 and Comparative Pigment Dispersions 1 to 4 are shown in Table 4.

[0071] <Production Example of Comparative Pigment Dispersion 5> 90.0 parts by mass of Resin P1, 10.0 parts by mass of diethyl 2,5-dihydroxyterephthalate, and 100 parts by mass of toluene were dissolved at 80° C. to obtain Comparative Pigment Dispersion 5. The physical properties of the obtained Comparative Pigment Dispersion 5 are shown in Table 4.

[0072] [Table 3]

[0073] [Table 4]

[0074] <Production Example of Toner Particle 1> Fluorescent agent 1 60.0 parts by mass ·Resin P1 34.5 parts by mass Paraffin wax (DSC endothermic peak temperature: 80°C) 4.0 parts by mass The raw materials shown in the above recipe were mixed in a Henschel mixer (FM-75, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 20 s. -1After mixing for 5 minutes, the mixture was kneaded in a twin-screw kneader (PCM-30, manufactured by Ikegai Corporation) set at a temperature of 125°C. The resulting kneaded mixture was cooled and coarsely pulverized to 1 mm or less using a hammer mill to obtain a coarsely pulverized product. The coarsely pulverized product was then finely pulverized using a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.). Further, classification was carried out using a rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) to obtain toner particles 1.

[0075] <Production Examples of Toner Particles 2 to 17 and Comparative Toners 1 to 4> Toner particles 2 to 17 and comparative toners 1 to 4 were obtained in the same manner as in the production example of toner particle 1, except that the materials were changed as shown in Table 5.

[0076] [Table 5]

[0077] <Production Example of Comparative Toner Particles 5> 10.0 parts by mass of diethyl 2,5-dihydroxyterephthalate ·Resin P1 79.5 parts by mass Paraffin wax (DSC endothermic peak temperature: 80°C) 9.0 parts by mass Toluene 20.0 parts by mass The raw materials shown in the above recipe were mixed in a Henschel mixer (FM-75, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 20 s. -1 After mixing for 5 minutes, the mixture was kneaded in a twin-screw kneader (PCM-30, manufactured by Ikegai Corporation) set at 80°C. The temperature was then raised to 140°C and kneaded again. The resulting kneaded mixture was cooled and coarsely pulverized to 1 mm or less using a hammer mill to obtain a coarsely pulverized product. The coarsely pulverized product was then finely pulverized using a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.). Further classification was performed using a rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) to obtain comparative toner particles 5.

[0078] <Production Example of Toner Particle 18> 390.0 parts by mass of ion-exchanged water and 14.0 parts by mass of sodium phosphate (12-hydrate) were added to a reaction vessel, and the mixture was kept at 65 ° C for 1 hour while purging with nitrogen. Next, using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), an aqueous calcium chloride solution prepared by dissolving 9.2 parts by mass of calcium chloride (dihydrate) in 10.0 parts by mass of ion-exchanged water was added all at once while stirring at 12,000 rpm, to prepare an aqueous medium containing a dispersion stabilizer. Furthermore, hydrochloric acid was added to the aqueous medium, and the pH was adjusted to 6.0, to obtain aqueous medium 1. Next, the following materials were mixed: Fluorescent agent 1 60.0 parts by mass Behenyl acrylate 27.6 parts by mass Styrene 0.34 parts by mass Methacrylonitrile 6.56 parts by mass Wax (Fischer-Tropsch wax, melting point: 78°C) 4.0 parts by mass ·Resin P8 1.0 parts by mass The mixture was kept at 65° C. and uniformly dissolved and dispersed using a TK homomixer at 500 rpm to prepare a polymerizable monomer composition 1. While maintaining the temperature of the aqueous medium 1 at 70°C and the rotation speed of the stirrer at 12,000 rpm, the polymerizable monomer composition 1 was charged into the aqueous medium 1, and 9.0 parts by mass of t-butyl peroxypivalate was added as a polymerization initiator. Granulation was continued for 10 minutes while maintaining the stirring speed at 12,000 rpm. The stirring device was changed to a stirrer equipped with a propeller stirring blade, and polymerization was carried out for 5 hours while stirring at 150 rpm and maintaining the temperature at 70°C. The temperature was then raised to 85°C and maintained at this temperature for 2 hours, after which the mixture was cooled to room temperature to obtain toner particle dispersion liquid 18. Hydrochloric acid was added to the obtained toner particle dispersion 18 to adjust the pH to 1.4 or less, and the dispersion stabilizer was dissolved therein. The mixture was then filtered, washed, and dried to obtain toner particles 18.

[0079] <Toner 1 manufacturing example> The toner particles obtained had a BET value of 200 m 2 / g and 1.5 parts of hydrophobic silica fine particles having a number average particle size of primary particles of 8 nm were mixed in a Henschel mixer (manufactured by Mitsui Miike Chemical Engineering Co., Ltd.) to obtain Toner 1. The fluorescence spectrum of the obtained toner was measured, and F4 was calculated. The obtained fluorescence spectrum is L * a * b * Converting to color coordinates, at 365 nm excitation, L * = 4.7, a * =41.0, b * = -58.5 and at 280 nm excitation, L * =16.9, a * =34.6, b * =-19.9. From this value, ΔE2 was calculated to be 40.9. The number-average 50% particle diameter of the obtained solid sample was measured from a cross-sectional SEM image and was found to be 160 nm. The physical properties of the obtained toner 1 are shown in Table 6.

[0080] <Production Examples of Toners 2 to 18 and Comparative Toners 1 to 5> Toners 2 to 18 and Comparative Examples 1 to 5 were produced in the same manner as in the production example of Toner 1 using the obtained Toner Particles 1 to 18 and Comparative Toner Particles 1 to 5, respectively. Table 6 shows the physical properties of the obtained toners 2 to 18 and comparative toners 1 to 5.

[0081] [Table 6]

[0082] <Examples 1 to 35> Evaluations were carried out using Pigment Dispersions 1 to 17 for Examples 1 to 17, respectively, and Toners 1 to 18 for Examples 18 to 35, respectively. The evaluation methods and results are shown below. The evaluation results are shown in Table 7.

[0083] <Comparative Examples 1 to 10> Pigment dispersions 1 to 5 were used for Comparative Examples 1 to 5, and comparative toners 1 to 5 were used for Comparative Examples 6 to 10. The evaluations were carried out in the same manner as in Examples 1 to 35. The evaluation results are shown in Table 7.

[0084] <Visibility evaluation when irradiated with ultraviolet light> For the evaluation of the pigment dispersion, Super Art Paper [SA Kinto + 180 kg, manufactured by Oji Paper Co., Ltd.] cut into 80 mm x 160 mm was used. The pigment dispersion was coated on the lower half of the Super Art Paper in the longitudinal direction using a wire bar, so that coated and uncoated areas were formed within the same paper. When coating, the coverage after drying was 0.3 mg / cm. 2 The wire bar size was adjusted so that the printed matter was 250-290 nm. Two sheets were prepared. After the coating film dried, the printed matter was irradiated with ultraviolet light in the wavelength range of 250-290 nm using an ultraviolet light irradiation device (ENF260-CJ). The areas of the paper where a coating film was formed (image areas) and areas where no coating film was formed (non-image areas) were compared visually, and the discrimination was ranked according to the following criteria. A: The image area can be identified even when the distance to the paper is 100 cm or more. B: The image area cannot be distinguished at a distance of 100 cm from the paper, but can be distinguished at a distance of 30 cm. C: The image area cannot be distinguished when the paper is 30 cm away, but when checked at a distance of 10 cm, the image area can be distinguished. D: The image area cannot be identified even when viewed from a distance of 10 cm. To evaluate the toner, a color laser printer (HP Color LaserJet 3525dn, manufactured by HP) was prepared and modified so that the amount of toner applied could be changed. The toner was removed from the cyan cartridge and replaced with the toner to be evaluated. Next, a medium (GF-C081, basis weight 81.4 g / m) was used. 2 ) and the toner was applied to the surface of the substrate with a toner amount (0.3 mg / cm 2 ) and printed a fixed image in the form of a 50 mm x 50 mm square image pattern in the center of the paper. The printed image was compared with the image area and non-image area and ranked in the same manner as in the evaluation of the pigment dispersions described above.

[0085] <Evaluation of recognizability when irradiated with two wavelengths (two-color recognizability)> The same evaluation as the above-mentioned evaluation of visibility when irradiated with ultraviolet light was also carried out when irradiated with ultraviolet light of 315 nm to 400 nm, and the evaluation was carried out visually with the image at a distance of 100 cm. A: Even if the UV wavelength is switched for the same image, two colors can be recognized. B: If you line up the images illuminated with each wavelength side by side, you can recognize them as two colors. C: If you line up the images illuminated with each wavelength side by side, you can see the slight difference in color. D: Unable to recognize color differences

[0086] <Invisibility Evaluation> For the pigment dispersion and the toner, image formation was carried out in the same manner as in the evaluation of visibility when irradiated with ultraviolet light. Under normal indoor lighting, the image area and non-image area were compared and the following criteria were used for discrimination. A: When the paper is placed 10cm away, the image area cannot be distinguished. B: The image is discernible when the paper is 10 cm away, but is indistinguishable when the paper is 30 cm away. C: The image is discernible when the paper is 30 cm away, but is indistinguishable when the paper is 100 cm away. D: The image area is discernible even when the paper is 100 cm away.

[0087] <Evaluation of light resistance> The same image as that used for the visibility evaluation was formed, and the L * a * b * The color coordinates were set to the initial values. After that, the image was irradiated with light at an intensity of 80,000 (lux) in a Super Fluorescent Light Fade Meter FL (manufactured by Suga Test Instruments) for 180 hours in a room temperature and humidity environment (23°C / 60%RH). After that, the spectrum was measured again when irradiated with ultraviolet light, and the L * a * b * Color coordinate conversion was performed to determine the color difference (ΔE3) from the initial value. The results were ranked according to the following criteria: A: ΔE3 is 3.0 or less B: ΔE3 is greater than 3.0 and less than 6.0 C: ΔE3 is greater than 6.0 and less than 9.0 D: ΔE3 is greater than 9.0

[0088] [Table 7]

Claims

1. A pigment dispersion containing a fluorescent agent and a binder resin, the fluorescent agent is excited by light with a wavelength of 400 nm or less, When F1 is defined as the integral value of the emission intensity in the region of 400 nm or more and 700 nm or less of the emission spectrum of the fluorescent agent when excited by light having a wavelength of 250 nm or more and 290 nm or less, F2 is defined as the integral value of the emission intensity in the region of 400 nm or more and 700 nm or less of the emission spectrum of the pigment dispersion when excited by light having a wavelength of 250 nm or more and 290 nm or less, and W1 (mass%) is defined as the proportion of the fluorescent agent contained in the solid content obtained when the mass change of the pigment dispersion when heated at 130°C becomes 0.3% / min or less, The F1, the F2, and the W1 satisfy the following formulas (1) and (2), F2×100 / W1≧F1×0.30 Formula (1) 5.0≦W1≦80.0 Formula (2) the binder resin in the pigment dispersion contains one or more units represented by any one of the following formulas (4) to (6), and the total content of the units represented by any one of the following formulas (4) to (6) in the total mass of the binder resin in the pigment dispersion is 70 mass% or more; 【Chemistry 1】 [In formula (4), P 1 and P 2 represent bonding sites to the main chain skeleton of the resin, R 1 represents a hydrogen atom or a methyl group, and n represents an integer of 0 to 30.] 【Chemistry 2】 [In formula (5), P 3 and P 4 represent bonding sites to the main chain skeleton of the resin.] 【Transformation 3】 [In formula (6), P 5 and P 6 represent bonding sites to the main chain skeleton of the resin.] A pigment dispersion characterized by:

2. The pigment dispersion was applied to the media in an amount of 0.3 mg / cm ２ 2. The pigment dispersion according to claim 1, wherein the image of the solid content formed in step 1 has a maximum light absorptance (Rmax1) in the wavelength region of 400 nm or more and 700 nm or less of 10% or less.

3. 3. The pigment dispersion according to claim 1, wherein the fluorescent agent is an inorganic compound containing a lanthanoid element and containing calcium fluoride as a main component.

4. 4. The pigment dispersion according to claim 1, wherein a 50% particle diameter based on the number of the fluorescent agent is 500 nm or less in a cross-sectional image of a solid content of the pigment dispersion observed with a scanning electron microscope (SEM).

5. The pigment dispersion according to any one of claims 1 to 4, wherein W1 (mass%) satisfies the following formula (3): 30.0≦W1≦70.0 Formula (3)

6. The pigment dispersion according to any one of claims 1 to 5, wherein the binder resin in the pigment dispersion contains a unit represented by formula (4), and n in formula (4) is 16 or more and 30 or less.

7. The pigment dispersion according to any one of claims 1 to 6, wherein when the emission wavelength spectra of the pigment dispersion when irradiated with excitation light having a wavelength of 250 nm or more and 290 nm or less and a wavelength of 315 nm or more and 400 nm or less are converted into the L*a*b* color system, the color coordinates are designated as G1 and G2, respectively, and a difference ΔE1 between the color coordinates G1 and G2 is 20.0 or more.

8. A printed matter having an image formed on a medium using the pigment dispersion according to any one of claims 1 to 7.

9. A toner having toner particles containing a fluorescent agent that is excited by light having a wavelength of 400 nm or less, a binder resin, and a release agent, When the integral value of the emission intensity in the region of 400 nm or more and 700 nm or less of the emission spectrum of the fluorescent agent when excited by light having a wavelength of 250 nm or more and 290 nm or less is taken as F3, the integral value of the emission intensity in the region of 400 nm or more and 700 nm or less of the emission spectrum of the toner when excited by light having a wavelength of 250 nm or more and 290 nm or less is taken as F4, and the mass proportion of the fluorescent agent in the toner particles is taken as W2 (mass%), the following formulas (7) and (8) are satisfied: F4×100 / W2≧F3×0.30 Formula (7) 5.0≦W2≦80.0 Formula (8) the binder resin in the toner particles contains one or more units represented by any one of the following formulas (4) to (6), and the total content of the units represented by any one of the following formulas (4) to (6) in the total mass of the binder resin in the toner particles is 70 mass % or more; 【Chemistry 4】 [In formula (4), P 1 and P 2 represent bonding sites to the main chain skeleton of the resin, R 1 represents a hydrogen atom or a methyl group, and n represents an integer of 0 to 30.] 【Transformation 5】 [In formula (5), P 3 and P 4 represent bonding sites to the main chain skeleton of the resin.] 【Transformation 6】 [In formula (6), P 5 and P 6 represent bonding sites to the main chain skeleton of the resin.] A toner characterized by:

10. The amount of the toner applied to the image formed on the medium is 0.3 mg / cm ２ 10. The toner according to claim 9, wherein the maximum light absorptance (Rmax2) in the wavelength region of 400 nm or more and 700 nm or less is 10% or less.

11. 11. The toner according to claim 9, wherein the fluorescent agent is an inorganic compound containing a lanthanoid element and containing calcium fluoride as a main component.

12. A toner according to any one of claims 9 to 11, wherein in a cross-sectional image of the toner particles observed with a scanning electron microscope (SEM), the 50% particle diameter based on the number of the fluorescent agent is 500 nm or less.

13. The toner according to any one of claims 9 to 12, wherein W2 satisfies the following formula (9): 30.0≦W2≦70.0 Formula (9)

14. The toner according to any one of claims 9 to 13, wherein the binder resin in the toner particles contains a unit represented by formula (4), and n in formula (4) is 16 or more and 30 or less.

15. The toner according to any one of claims 9 to 14, wherein when the toner is irradiated with excitation light having a wavelength of 250 nm or more and 290 nm or less and a wavelength of 315 nm or more and 400 nm or less, and the color coordinates obtained by converting the emission wavelength spectrum of the toner into the L*a*b* color system are set to G3 and G4, respectively, a difference ΔE2 between the color coordinates G3 and G4 is 20.0 or more.

16. A printed matter having an image formed on a medium using the toner according to any one of claims 9 to 15.

Images