toner

Abstract

To provide a toner which offers superior low-temperature fixability, hot offset resistance, storage stability, and develop-ability and suppresses occurrence of gloss unevenness.SOLUTION: A toner comprising toner particles containing a binder resin is provided, the toner particles containing a compound represented by R1-[OCH2CH2]n-OH (where R1 represents a linear or branched alkyl group having 8 to 22 carbon atoms, and n represents an integer in a range of 1 to 3), and at least one polyvalent element selected from a group consisting of magnesium element, calcium element, aluminum element, boron element, and iron element, where the content of the polyvalent element in the toner is 100-5000 mass ppm, inclusive.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a toner used in a recording method using electrophotography or the like. [Background technology]

[0002] In recent years, image forming devices such as copiers and printers have become faster and more energy-efficient. To meet these demands, there is a growing demand for toners with superior low-temperature fixability. One way to improve a toner's low-temperature fixability is to lower its melting point. However, simply lowering the toner's melting point reduces the toner's storage stability. There is also a growing demand for higher image quality, and the production of clear, high-gloss images is required to meet the demand for high-quality image formation, such as photographic images. To obtain a high-gloss image, the toner must be thoroughly melted to create a smooth image surface. However, this poses the problem of hot offset.

[0003] As a method for preventing hot offset, Patent Document 1 discloses a method in which a release agent is placed near the toner surface, which is instantly exposed from the toner during fixing, thereby preventing the toner from fusing to the fixing member. Meanwhile, Patent Document 2 discloses a method in which a polyvalent metal salt compound is added to improve heat resistance and crush resistance. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 8-160660 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-218208 Summary of the Invention [Problem to be solved by the invention]

[0005] However, while the toner described in Patent Document 1 can suppress hot offset to a certain extent, there is a problem in that fusion occurs starting from the release agent while being stirred in a developing machine, and the release agent adheres to the developing member, which tends to reduce the charge amount of the toner. Furthermore, the toner described in Patent Document 2 improves crush resistance and heat resistance by adding a polyvalent metal salt compound and metal-crosslinking the binder resin, but there is a problem in that the crosslinked parts reduce gloss, causing gloss unevenness. The present disclosure provides a toner that is excellent in low-temperature fixability, hot offset resistance, storage stability, and developability, and that suppresses the occurrence of gloss unevenness. [Means for solving the problem]

[0006] The present disclosure provides a toner containing toner particles containing a binder resin, The toner particles further comprise: A compound represented by the following formula (1), at least one polyvalent element selected from the group consisting of magnesium, calcium, aluminum, boron, and iron; Contains The toner is characterized in that the content of the polyvalent element in the toner is 100 ppm by mass or more and 5000 ppm by mass or less. R 1 -[OCH2CH2] n -OH (1) In formula (1), R 1 represents a linear or branched alkyl group having 8 to 22 carbon atoms, and n is an integer of 1 to 3. [Effects of the Invention]

[0007] According to the present disclosure, it is possible to provide a toner that is excellent in low-temperature fixability, hot offset resistance, storage stability, and developability, and that suppresses the occurrence of gloss unevenness. DETAILED DESCRIPTION OF THE INVENTION

[0008] The following describes embodiments in detail, but the present disclosure is not limited to the following description. In the present disclosure, the description of a numerical range such as "XX or more and YY or less" or "XX to YY" means a numerical range including the lower and upper limits, which are the endpoints, unless otherwise specified. Furthermore, when a numerical range is described in stages, the upper and lower limits of each numerical range can be combined in any way.

[0009] The present disclosure provides a toner containing toner particles containing a binder resin, The toner particles further comprise: A compound represented by the following formula (1), at least one polyvalent element selected from the group consisting of magnesium, calcium, aluminum, boron, and iron; Contains The toner is characterized in that the content of the polyvalent element in the toner is 100 ppm by mass or more and 5000 ppm by mass or less. R 1 -[OCH2CH2] n -OH (1) In formula (1), R 1 represents a linear or branched alkyl group having 8 to 22 carbon atoms, and n is an integer of 1 to 3.

[0010] The present inventors have found that by using a toner having the above-described configuration, it is possible to provide a toner that is excellent in low-temperature fixing property, hot offset resistance, storage stability, and developability, and that suppresses the occurrence of gloss unevenness. The present inventors speculate that the reason for this is as follows.

[0011] The toner of the present disclosure contains a specific polyvalent element in an amount of 100 ppm by mass to 5,000 ppm by mass, so that even when a binder resin with a low melting point and excellent low-temperature fixability is used, ions generated from or containing the polyvalent element form a crosslinked structure with the binder resin, thereby improving storage stability, hot offset resistance, and developability. Furthermore, it is believed that the compound represented by formula (1) also forms a crosslinked structure with ions generated from or containing the polyvalent element during fixing and melting, making the crosslinked structure in the binder resin uniform and smoothing the image surface, thereby suppressing hot offset and obtaining a uniform, high-gloss image in which the occurrence of gloss unevenness in the fixed image is suppressed.

[0012] The constituent elements of the present disclosure will be described in detail below. The toner of the present disclosure contains at least one polyvalent element selected from the group consisting of magnesium, calcium, aluminum, boron, and iron in the toner particles. The content of the polyvalent element in the toner is 100 ppm by mass or more and 5000 ppm by mass or less. The content of the polyvalent element in the toner is preferably 150 ppm by mass or more and 2500 ppm by mass or less. When the content of the polyvalent element in the toner is 100 ppm by mass or more, the occurrence of gloss unevenness is suppressed, and storage stability is improved, such as blocking being less likely to occur. On the other hand, when the content of the polyvalent element in the toner is 5000 ppm by mass or less, the occurrence of gloss unevenness is suppressed, and excellent low-temperature fixability can be obtained.

[0013] The toner particles contain at least one polyvalent element selected from the group consisting of magnesium, calcium, aluminum, boron, and iron. The toner particles also contain a compound containing at least one polyvalent element selected from the group consisting of magnesium, calcium, aluminum, boron, and iron. The polyvalent element may also be used. The polyvalent element can generate ions for crosslinking during the toner manufacturing process or during fixing and fusing. Therefore, during the toner particle manufacturing process or during fixing and fusing of the toner, the toner particles preferably contain a crosslinked product of ions generated from or containing a polyvalent element and at least one selected from the group consisting of the compound represented by formula (1) and the binder resin. Among these, at least one selected from the group consisting of aluminum, boron, and iron is preferred. Boron is more preferred. Aluminum, boron, and iron have high valences, and therefore generate high ionic valences, which can increase the density of the crosslinked structure with the compound represented by formula (1) or the binder resin, thereby improving hot offset resistance and further suppressing the occurrence of uneven gloss. In particular, boron generates a small ionic radius, which reacts instantly with water under normal circumstances to form borate ions B(OH)4 - Therefore, when the polyvalent element is boron, the crosslink density becomes higher, the hot offset resistance is improved, and the occurrence of uneven gloss can be further suppressed.

[0014] The method for incorporating at least one polyvalent element selected from the group consisting of magnesium, calcium, aluminum, boron, and iron into toner particles is not particularly limited. For example, a compound containing the polyvalent element may be added during the toner particle production process. A simple example is a method in which the compound containing the polyvalent element is directly added to a toner particle composition such as a binder resin. When toner particles are produced in an aqueous medium, the compound containing the polyvalent element may be added as a pH adjuster, aggregating agent, stabilizer, or the like. From the viewpoint of easily adjusting the content of the polyvalent element in the toner, preferred examples include a method in which the compound is directly added to a toner particle composition or a method in which the compound is added as aggregating agent. Examples of the compound containing the polyvalent element include borax, aluminum chloride, polyaluminum chloride, aluminum hydroxide, aluminum sulfate, magnesium chloride, magnesium hydroxide, calcium chloride, calcium hydroxide, and polysilica iron. By using these, it is possible to easily adjust the content of the polyvalent element in the toner, the type of the polyvalent element, etc. The amount of the compound containing the polyvalent element added is preferably such that the content of the polyvalent element in the toner is 100 ppm by mass or more and 5000 ppm by mass or less, and more preferably such that the content of the polyvalent element in the toner is 150 ppm by mass or more and 2500 ppm by mass or less.

[0015] The toner particles contain a compound represented by the following formula (1): (1)R 1 -[OCH2C H2] n -OH. In formula (1), R 1 represents a linear or branched alkyl group having 8 to 22 carbon atoms. 1 When R is a linear or branched alkyl group having 8 to 22 carbon atoms, the compatibility with the binder resin can be improved, the image surface can be made smooth, and the occurrence of uneven gloss of the fixed image can be suppressed. In addition, the hot offset resistance, storage stability, and charging property can be improved. 1 is preferably a linear alkyl group. 1 The number of carbon atoms in R is preferably 8 or more, more preferably 10 or more, and even more preferably 12 or more. 1 is preferably 22 or less, more preferably 14 or less. In formula (1), n ​​is an integer of 1 to 3. When n is in this range, compatibility with the binder resin is improved, and a crosslinked structure is easily formed with ions derived from or containing a polyvalent element, making the crosslinked structure in the binder resin uniform and smoothing the image surface, thereby maintaining hot offset resistance, storage stability, and charging properties, while suppressing the occurrence of uneven gloss in the fixed image. Preferably, n is 1.

[0016] The content of the compound represented by formula (1) in the toner is preferably 2 mass ppm or more and 630 mass ppm or less, more preferably 5 mass ppm or more and 500 mass ppm or less, and even more preferably 10 mass ppm or more and 400 mass ppm or less. By setting the content of the compound represented by formula (1) within the above numerical range, hot offset resistance and storage stability can be improved. While maintaining stability and charging properties, the occurrence of gloss unevenness in the fixed image can be further suppressed.

[0017] The ratio (A / B) of the number of moles A of the compound represented by formula (1) contained in the toner to the number of moles B of the polyvalent element is preferably 0.0003 or more and 0.1200 or less, more preferably 0.0010 or more and 0.1000 or less, even more preferably 0.0010 or more and 0.0200 or less, and particularly preferably 0.0015 or more and 0.0045 or less. Setting A / B to 0.0003 or more facilitates the suppression of aggregation of the polyvalent element during fixing, thereby further suppressing the occurrence of uneven gloss during fixing. Furthermore, setting A / B to 0.1200 or less facilitates the suppression of exudation of the compound represented by formula (1), further improving storage stability and charging performance. Furthermore, an appropriate crosslinking structure is formed between the compound represented by formula (1) and ions derived from or containing the polyvalent element, thereby further improving hot offset resistance.

[0018] <Binder resin> The binder resin can be any known toner resin without any particular limitation. Furthermore, from the viewpoint of forming a crosslinked structure with ions containing a polyvalent element or ions generated from the polyvalent element, it is preferable that the binder resin has a functional group such as a carboxy group, a carbonyl group, or a hydroxyl group. Specific examples include polyester resins; styrene-acrylic resins such as styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, and styrene-dimethylaminoethyl methacrylate copolymer. In addition, the binder resin preferably contains a polyester resin from the viewpoints of ease of manufacturing a resin with a low melting point and excellent low-temperature fixability, and of forming a crosslinked structure with ions containing a polyvalent element or ions derived from a polyvalent element. The polyester resin preferably contains an amorphous polyester resin. The content of the polyester resin in the binder resin, particularly the content of the amorphous polyester resin, is preferably 50% by mass or more. The upper limit of the content of the polyester resin in the binder resin is 100% by mass or less, and preferably 95% by mass or less. Polyester resins are obtained by condensation polymerization of polycarboxylic acids and polyhydric alcohols. Examples of polycarboxylic acids include aliphatic dicarboxylic acids (e.g., oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, alkenylsuccinic acid, adipic acid, and sebacic acid), alicyclic dicarboxylic acids (e.g., cyclohexanedicarboxylic acid), aromatic dicarboxylic acids (e.g., terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid), and anhydrides thereof. The polycarboxylic acids may be used in combination with dicarboxylic acids and trivalent or higher carboxylic acids having a crosslinked or branched structure. Examples of trivalent or higher carboxylic acids include trimellitic acid, pyromellitic acid, and anhydrides thereof. The polycarboxylic acids may be used alone or in combination.

[0019] Examples of polyhydric alcohols include aliphatic diols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, etc.), alicyclic diols (e.g., cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, etc.), aromatic diols (e.g., alkylene oxide adducts of bisphenol A, etc.), and heterocyclic diols (spiroglycol, isosorbide, or alkylene oxide adducts thereof, etc.). As the polyhydric alcohol, a trihydric or higher polyhydric alcohol having a crosslinked or branched structure may be used in combination with a diol. Examples of trihydric or higher polyhydric alcohols include glycerin, trimethylolpropane, and pentaerythritol. The polyhydric alcohol may be, for example, 1 Each species may be used alone or in combination of two or more species.

[0020] Furthermore, the content of the structure represented by formula (2) in the amorphous polyester resin is preferably 5.0% by mass or less. The lower limit of this content is 0.0% by mass or more, but this content is preferably 0.0% by mass. When the content of the structure represented by formula (2) in the amorphous polyester resin is 5.0% by mass or less, low-temperature fixability is easily improved. Furthermore, a crosslinked structure is easily formed between the polyester resin and ions containing a polyvalent element or ions derived from a polyvalent element, further improving hot offset resistance. [ka] (In the formula, R 2 and R 3 are each independently an ethylene group or a propylene group; x and y represent the average number of moles of alkylene oxide added, and the sum of x and y is 1 or more and 5 or less.

[0021] The content of polyester resin or amorphous polyester resin in the binder resin is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. When the content of polyester resin or amorphous polyester resin is 50% by mass or more, a crosslinked structure is easily formed between the polyester resin and ions containing a polyvalent element or ions derived from a polyvalent element, thereby further improving hot offset resistance. The weight-average molecular weight (Mw) of the polyester resin is preferably 20,000 to 300,000, more preferably 30,000 to 200,000, and even more preferably 40,000 to 100,000.

[0022] The binder resin may contain various resins to the extent that the effects of the present disclosure are not affected. Examples of such resins include the following: homopolymers of styrene and its substituted derivatives, such as polystyrene and polyvinyltoluene; styrene copolymers, such as styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, and styrene-maleic acid ester copolymer; Polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, crystalline polyester resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenolic resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, which can be used alone or in combination.

[0023] <Coloring agent> The toner particles may contain a colorant. The colorant is not particularly limited, and for example, the following known colorants may be used alone or in combination.

[0024] Examples of black colorants include carbon black and those toned to black using a yellow colorant, a magenta colorant, and a cyan colorant.

[0025] Magenta colored pigments include the following: CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48:2, 48:3, 48:4, 49, 50, 51, 52, 53, 54, 55, 57:1, 58, 60, 63, 64, 68, 81:1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; CI Pigment Violet 19; CI Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

[0026] Magenta-colored dyes include solvent dyes such as CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, and 121; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21, and 27; and CI Disperse Violet 1; and basic dyes such as CI Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, and 40; and CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28.

[0027] Cyan coloring pigments include the following: CI Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, 17; CI Vat Blue 6; CI Acid Blue 45; and copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton.

[0028] Cyan colored dyes include CI Solvent Blue 70.

[0029] Yellow coloring pigments include the following: CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; CI Vat Yellow 1, 3, 20.

[0030] Yellow coloring dyes include CI Solvent Yellow 162.

[0031] The content of the colorant is preferably 3.0% by mass to 15.0% by mass relative to the toner particles.

[0032] <Release agent> From the viewpoint of separability, the toner particles preferably contain a release agent, examples of which include hydrocarbon waxes such as low-molecular-weight polyethylene, low-molecular-weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; waxes containing fatty acid esters as the main component such as carnauba wax; and partially or completely deoxidized fatty acid esters such as deoxidized carnauba wax.

[0033] Further examples include the following: saturated straight-chain fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassidic acid, eleostearic acid, and parinaric acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; polyhydric alcohols such as sorbitol; palmitic acid, stearic acid, behenic acid, and montanic acid. Esters of fatty acids with alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; saturated fatty acid bisamides such as methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, and hexamethylene bisstearic acid amide; ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N,N'-dioleyl adipamide, and N,N'-dioleyl sebacic acid amide. unsaturated fatty acid amides such as m-xylene bisstearamide and N,N'-distearylisophthalamide; aromatic bisamides such as m-xylene bisstearamide and N,N'-distearylisophthalamide; fatty metal salts such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate (commonly known as metal soaps); waxes grafted onto aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; partial esters of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; and methyl ester compounds with hydroxyl groups obtained by hydrogenating vegetable oils and fats.

[0034] Among these releasing agents, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax, or fatty acid ester waxes such as carnauba wax are preferred from the viewpoint of improving low-temperature fixability and hot offset resistance. The content of the release agent is preferably 3.0% by mass to 15.0% by mass relative to the toner particles. When the content of the release agent is in this range, it is easy to efficiently exhibit hot offset resistance.

[0035] <Charge control agent> The toner particles may contain a charge control agent. There are no particular limitations on the charge control agent, and known agents can be used. In particular, charge control agents that have a high charging speed and can stably maintain a constant charge amount are preferred. The charge control agent may be added internally or externally to the toner particles.

[0036] Examples of charge control agents that control toner particles to be negatively charged include the following: Organometallic compounds and chelating compounds include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds. Other examples include aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids, and their metal salts, anhydrides, or esters, and phenol derivatives such as bisphenols. Further examples include urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, and calixarenes.

[0037] On the other hand, examples of charge control agents that control toner particles to a positive charge include the following: nigrosine and nigrosine modified with fatty acid metal salts; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts that are analogs of these, and lake pigments thereof; triphenylmethane dyes and lake pigments thereof (lacquering agents include phosphotungstic acid, phosphomolybdic acid, phosphotungstomolybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids; and resin-based charge control agents.

[0038] These charge control agents can be used alone or in combination of two or more. The content of these charge control agents in the toner particles is preferably 0.01% by mass to 10% by mass.

[0039] <External additives> Although the toner particles can be used without external additives, so-called external additives such as a fluidizing agent and a cleaning aid may be added to the toner to improve fluidity, chargeability, cleaning properties, etc. Examples of external additives include inorganic oxide fine particles such as silica fine particles, alumina fine particles, and titanium oxide fine particles, as well as inorganic titanate compound fine particles such as strontium titanate and zinc titanate. These can be used alone or in combination of two or more.

[0040] The BET specific surface area of ​​the external additive is 10m 2 / g~450m 2 / g. The BET specific surface area is determined by a low-temperature gas adsorption method using a dynamic constant pressure method in accordance with the BET multipoint method. Specifically, a specific surface area measuring device (trade name: Gemini 2375 Ver. 5.0, manufactured by Shimadzu Corporation) is used to adsorb nitrogen gas onto the surface of a sample, and measurement is performed using the BET multipoint method to determine the BET specific surface area (m 2 / g) is calculated.

[0041] The total amount of these various external additives added is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of toner particles.

[0042] <Developer> The toner can be used as a magnetic or non-magnetic one-component developer, or it can be mixed with a carrier to be used as a two-component developer. The carrier can be magnetic particles made of known materials, such as metals such as iron, ferrite, and magnetite, or alloys of these metals with metals such as aluminum and lead. Among these, ferrite particles are preferred. The carrier can also be a coated carrier in which the surfaces of magnetic particles are coated with a coating agent such as resin, or a resin-dispersed carrier in which magnetic fine powder is dispersed in a binder resin. The carrier preferably has a volume average particle size of 15 μm to 100 μm, more preferably 25 μm to 80 μm.

[0043] (Toner manufacturing method) Any method may be used to produce toner particles. For example, toner particles may be obtained by melt-kneading a toner particle composition containing a compound containing a polyvalent element, a compound represented by Formula (1), a binder resin, and, if necessary, a colorant and a release agent, followed by pulverization. Alternatively, a toner particle composition containing a compound containing a polyvalent element, a compound represented by Formula (1), and a binder resin monomer or polymer, and, if necessary, a colorant and a release agent, may be mixed in an aqueous medium to form droplets or particles containing the compound, and then polymerized or aggregated to produce toner particles. Among these production methods, a method for producing toner particles using an emulsion aggregation method will be described in detail below. The emulsion aggregation method is a method for producing toner particles by preparing a resin particle dispersion sufficiently small in size relative to the target toner particle diameter in advance and aggregating the resin fine particles in an aqueous medium. One embodiment of the toner manufacturing method (emulsion aggregation method) of the present disclosure may include a step of dispersing resin particles containing a binder resin and a compound represented by Formula (1) in an aqueous medium to prepare a resin particle dispersion, and a step of aggregating the resin particles with a compound containing at least one polyvalent element selected from the group consisting of magnesium, calcium, aluminum, boron, and iron to form aggregate particles. The method may also include a step of heating the aggregate particles to fuse them. Furthermore, the fusing step may be followed by a cooling step, a washing step, a drying step, and the like.

[0044] (Dispersion liquid preparation process) The resin particle dispersion liquid may be prepared, for example, as follows. That is, when the resin in the resin particles is a homopolymer or copolymer of a vinyl monomer (vinyl resin), the vinyl monomer is subjected to emulsion polymerization or seed polymerization in an ionic surfactant to obtain a vinyl. A dispersion can be prepared by dispersing resin particles of a homopolymer or copolymer (vinyl resin) of a vinyl monomer in an ionic surfactant. When the resin in the resin particles is a resin other than a vinyl resin, such as a polyester resin, the resin is mixed with an aqueous medium in which an ionic surfactant or a polymer electrolyte is dissolved to obtain a mixed solution. This mixed solution is then heated to above its melting point or softening point to dissolve the resin particles, and a dispersion can be prepared by dispersing the resin particles in the ionic surfactant using a disperser or agitator with strong shear force, such as a homogenizer. The dispersion method is not particularly limited, but examples include known dispersing devices such as a rotary shear homogenizer, a ball mill with media, a sand mill, and a dyno mill.

[0045] A phase inversion emulsification method may also be used to prepare the dispersion. In the phase inversion emulsification method, a binder resin and a compound represented by formula (1) are mixed with an organic solvent capable of dissolving them, heated to dissolve, and a neutralizing agent and a dispersion stabilizer are added as necessary. An aqueous solvent is then added dropwise under stirring to obtain emulsified particles, and the organic solvent in the resin dispersion is then removed to obtain resin particles. The order of adding the neutralizing agent and the dispersion stabilizer may be changed. The number-average particle size of the dispersed resin particles is typically 1.00 μm or less, and preferably 0.01 μm or more and 1.00 μm or less.

[0046] The colorant dispersion is prepared by dispersing at least a colorant in a dispersant. The number average particle size of the colorant particles is preferably 0.5 μm or less, and more preferably 0.2 μm or less.

[0047] The dispersion of the release agent is prepared by dispersing at least the release agent in a dispersant. The number average particle size of the particles of the release agent is preferably 2.0 μm or less, and more preferably 1.0 μm or less.

[0048] The combination of binder resin, colorant, and release agent is not particularly limited and can be freely selected depending on the purpose.

[0049] In addition to the binder resin dispersion, colorant dispersion, and release agent dispersion, a particle dispersion obtained by dispersing appropriately selected particles in a dispersant may be further mixed. The particles contained in the particle dispersion are not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include internal additive particles, charge control agent particles, inorganic particles, and abrasive particles. These particles may be dispersed in the binder resin dispersion or the colorant dispersion.

[0050] Examples of dispersion media contained in binder resin dispersions, colorant dispersions, release agent dispersions, particle dispersions, etc. include aqueous media containing polar surfactants. Examples of aqueous media include water such as distilled water and ion-exchanged water, and alcohols. These may be used alone or in combination of two or more. The content of the polar surfactant cannot be generally defined and can be appropriately selected depending on the purpose.

[0051] Examples of polar surfactants include anionic surfactants such as sulfate ester salts, sulfonates, phosphate esters, and soaps; and cationic surfactants such as amine salts and quaternary ammonium salts. Specific examples of anionic surfactants include sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium alkylnaphthalenesulfonate, and sodium dialkylsulfosuccinate. Specific examples of cationic surfactants include alkylbenzenedimethylammonium chloride, alkyltrimethylammonium chloride, and distearylammonium chloride. These surfactants may be used alone or in combination of two or more. These polar surfactants can also be used in combination with nonpolar surfactants. Nonpolar surfactants include, for example, polyethylene glycols, alkylphenol ethylene oxide adducts, and Examples include nonionic surfactants such as polyhydric alcohol surfactants.

[0052] The content of the colorant particles is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the binder resin in the aggregated particle dispersion formed in the aggregation step described below. The content of the release agent particles is about 0.5 to 25 parts by mass, and preferably 5 to 20 parts by mass, relative to 100 parts by mass of the binder resin in the aggregated particle dispersion formed in the aggregation step.

[0053] Furthermore, in order to control the chargeability of the toner obtained in more detail, charge control particles and binder resin particles may be added after the formation of aggregated particles. Note that the particle sizes of resin particles in the binder resin dispersion, colorant particles in the colorant dispersion, release agent particles in the release agent dispersion, particles in the particle dispersion, etc. may be measured using a laser diffraction / scattering particle size distribution analyzer LA-920 manufactured by Horiba, Ltd.

[0054] (Agglutination process) The aggregation process for forming aggregated particles is a process for forming aggregated particles containing binder resin particles, colorant particles, and release agent particles in an aqueous medium containing binder resin particles, colorant particles, and release agent particles. The aggregated particles can be formed in the aqueous medium by, for example, adding and mixing an aggregating agent, pH adjuster, stabilizer, etc. to the aqueous medium, and then applying appropriate temperature, mechanical power, etc. Here, a compound containing the above-mentioned polyvalent element is preferably used as the aggregating agent.

[0055] Examples of pH adjusters include alkalis such as ammonia and sodium hydroxide, and acids such as nitric acid and citric acid. Examples of flocculants include monovalent metal salts such as sodium and potassium, divalent metal salts such as calcium and magnesium, trivalent metal salts such as iron and aluminum, and alcohols such as methanol, ethanol, and propanol.

[0056] The stabilizer may be a polar surfactant itself or an aqueous medium containing the same. For example, when the polar surfactant contained in each particle dispersion is anionic, a cationic stabilizer may be selected.

[0057] The addition and mixing of the aggregating agent and the like is preferably carried out at a temperature equal to or lower than the glass transition temperature of the resin contained in the aqueous medium. Mixing under these temperature conditions allows for stable aggregation. Mixing can be carried out using, for example, a known mixing device, homogenizer, mixer, or the like. In the aggregation step, a binder resin particle dispersion containing second binder resin particles can be used to attach the second binder resin particles to the surfaces of the aggregated particles, forming a coating layer (shell layer), thereby obtaining aggregated particles having a core / shell structure in which a shell layer is formed on the surfaces of the core aggregated particles. The second binder resin particles used in this case may be the same as or different from the binder resin particles that constitute the core aggregated particles. The aggregation step may be repeated in multiple stages.

[0058] (fusion process) The fusion process is a process in which the resulting aggregated particles are heated and fused. Prior to the fusion process, a pH adjuster, a polar surfactant, a non-polar surfactant, etc. may be added as needed to prevent fusion between toner particles. The heating temperature may be between the glass transition temperature of the resin contained in the aggregated particles (if two or more types of resin are used, the glass transition temperature of the resin with the highest glass transition temperature) and the decomposition temperature of the resin. Therefore, the heating temperature differs depending on the type of resin in the binder resin particles and cannot be generally defined, but is generally between the glass transition temperature of the resin contained in the aggregated particles and 140°C. Heating can be performed using a known heating device or tool.

[0059] The fusion time is short if the heating temperature is high, and long if the heating temperature is low. In other words, the fusion time cannot be generally determined because it depends on the heating temperature, but it is generally between 30 minutes and 10 hours.

[0060] The toner particles obtained through the above steps can be separated into solid and liquid by a known method, and the toner particles can be recovered, and then washed, dried, etc. under appropriate conditions.

[0061] (External addition process) The obtained toner particles can be used as they are, but external additives may be added as needed to make the toner, in order to adjust the chargeability, fluidity, storage stability, etc. of the toner. The agitator used for the external addition treatment is not particularly limited as long as it is a stirring device that can adhere external additives to the surface of the toner particles. For example, the external addition treatment can be performed using a mixing and stirring device such as a double cone mixer, a V-type mixer, a drum mixer, a super mixer, a Henschel mixer, a Nauta mixer, a Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.), or a Nobilta (manufactured by Hosokawa Micron Corporation).

[0062] The methods for measuring various physical properties of the toner, toner particles, and raw materials are described below. <Identification and quantification of binder resin> To identify the constituent composition and ratio of the binder resin, a pyrolysis gas chromatography mass spectrometer (hereinafter also referred to as "pyrolysis GC / MS") and NMR are used. Pyrolysis GC / MS is used to analyze the types of constituent compounds of the resin. The types of constituent compounds are identified by analyzing the mass spectrum of the components of the resin decomposition products that are produced when the resin is pyrolyzed at 550°C to 700°C. The specific measurement conditions are as follows:

[0063] <Measurement conditions for pyrolysis GC / MS> Pyrolysis device: JPS-700 (Japan Analysis Industry) Decomposition temperature: 590℃ GC / MS equipment: Focus GC / ISQ (Thermo Fisher) Column: HP-5MS, length 60 m, inner diameter 0.25 mm, film thickness 0.25 μm Inlet temperature: 200℃ Flow pressure: 100kPa Split: 50mL / min MS ionization: EI Ion source temperature: 200℃ Mass Range 45-650

[0064] Next, the abundance ratio of the constituent compounds of the identified resin is 1The structure was determined using a FT NMR system JNM-EX400 (manufactured by JEOL Ltd.) [ 1 H-NMR 400 MHz, CDCl3, room temperature (25 °C)].

[0065] < 1 H-NMR measurement conditions Measurement frequency: 400MHz Pulse condition: 5.0 μs Frequency range: 10500Hz Number of times accumulated: 1024 Measurement temperature: 25℃ Sample: 50 mg of the sample to be measured was placed in a sample tube with an inner diameter of 5 mm, and heavy chloroform was used as the solvent. Form (CDCl3) is added and dissolved in a constant temperature bath at 40°C.

[0066] The molar ratio of each monomer component is determined from the integral value of the obtained spectrum, and the composition ratio (mass %) is calculated based on this.

[0067] <Method for measuring the weight average molecular weight (Mw) of binder resin> The weight-average molecular weight (Mw) of the binder resin is measured by gel permeation chromatography (GPC) as follows. First, the binder resin is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. The resulting solution is then filtered through a solvent-resistant membrane filter "Myshoridisc" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of components soluble in THF is approximately 0.8 mass%. Measurements are performed using this sample solution under the following conditions.

[0068] Apparatus: HLC8120 GPC (detector: RI) (Tosoh Corporation) Column: Shodex KF-801, 802, 803, 804, 805, 806, 807 (7 columns, manufactured by Showa Denko Co., Ltd.) Eluent: tetrahydrofuran (THF) Flow rate: 1.0ml / min Oven temperature: 40.0℃ Sample injection volume: 0.10 ml

[0069] To calculate the molecular weight of a sample, a molecular weight calibration curve prepared using standard polystyrene resins (trade names: "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation) is used.

[0070] <Method for measuring weight average particle diameter (D4) and number average particle diameter (D1) of toner particles> The weight-average particle size (D4) of the toner particles is measured with an effective number of 25,000 measurement channels using a precision particle size distribution measuring device equipped with a 100 μm aperture tube and using the narrow-pore electrical resistance method, "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.), and the accompanying dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.), for setting measurement conditions and analyzing measurement data, and the weight-average particle size (D4) is calculated by analyzing the measurement data. The aqueous electrolyte solution used for the measurement is prepared by dissolving special-grade sodium chloride in ion-exchanged water to a concentration of approximately 1% by mass, such as "ISOTON II" (manufactured by Beckman Coulter, Inc.). Before performing the measurement and analysis, the dedicated software must be set up as follows:

[0071] In the dedicated software's "Change Standard Measurement Method (SOM) screen," set the total count in control mode to 50,000 particles, the number of measurements to 1, and the Kd value to the value obtained using a "Standard Particle 10.0 μm" (Beckman Coulter, Inc.). Press the threshold / noise level measurement button to automatically set the threshold and noise level. Also, set the current to 1,600 μA, the gain to 2, the electrolyte solution to ISOTON II, and check the "Flush aperture tube after measurement" box. In the dedicated software's "Pulse to particle size conversion setting screen," set the bin spacing to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm or more and 60 μm or less. The specific measurement method is as follows.

[0072] (1) Pour approximately 200 mL of the electrolyte solution into a 250 mL round-bottom glass beaker made specifically for the Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 revolutions per second. Then, use the "aperture tube flush" function of the dedicated software to remove any dirt and air bubbles from inside the aperture tube. (2) Approximately 30 mL of the above aqueous electrolyte solution is placed in a 100 mL flat-bottom glass beaker, and approximately 0.3 mL of the following dilution solution is added as a dispersant. Diluted solution: "Contaminon N" (a 10% aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) diluted 3 times by mass with ion-exchanged water. (3) A predetermined amount of ion-exchanged water is placed in the water tank of the ultrasonic disperser described below, "Ultrasonic Dispersion System Tetora150" (manufactured by Nikkaki Bios Co., Ltd.), which has two built-in oscillators with an oscillation frequency of 50 kHz and a phase shift of 180 degrees and an electrical output of 120 W, and approximately 2 mL of the diluted solution is added to this water tank. (4) Set the beaker (2) in the beaker fixing hole of the ultrasonic disperser, operate the ultrasonic disperser, and adjust the height of the beaker so that the resonance state of the liquid surface of the electrolytic solution in the beaker is maximized. (5) With the electrolytic aqueous solution in the beaker of (4) irradiated with ultrasonic waves, about 10 mg of toner (particles) is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion treatment is continued for another 60 seconds. In ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted so that it is 15°C or higher and 40°C or lower. (6) Using a pipette, the electrolytic aqueous solution of (5) in which the toner (particles) is dispersed is dropped into the round-bottom beaker of (1) installed in the sample stand, and adjusted so that the measured concentration becomes about 5%. Then, the measurement is carried out until the measured number of particles reaches 50,000. (7) The measurement data is analyzed with the dedicated software attached to the device to calculate the weight average particle size (D4). When set to graph / volume% in the dedicated software, the "arithmetic diameter" on the analysis / volume statistical value (arithmetic mean) screen is the weight average particle size (D4), and when set to graph / number% in the dedicated software, the "arithmetic mean diameter" on the analysis / number statistical value (arithmetic mean) screen is the number average particle size (D1).

[0073] <Method for Identifying and Measuring the Content of the Compound Represented by Formula (1) in Toner> <Preparation of Extraction Sample> Add 2 g of toner and 18 g of ethanol to the sample tube, homogenize by hand shaking, and then irradiate with ultrasonic waves for 5 minutes. Then, let it stand in a constant temperature bath at 60°C for one day and night, and further let it stand at room temperature for 3 days. Collect the supernatant of the sample after standing and filter it through a PTFE syringe filter (pore size 250 nm), and use the filtrate as the extraction sample.

[0074] <GC / MS Analysis> The GC / MS device is GC TRACE―1310 (manufactured by Thermo Scientifi c), the detector is a single quadrupole analyzer MS ISQ LT (manufactured by Thermo Scientific), and the autosampler is TRIPLUS RSH (manufactured by Thermo Scientific). The measurement is carried out under the conditions shown below.

[0075] Sample volume: 1 μL (liquid injection) Column: HP5-MS (Agilent Technologies) Length: 30m, inner diameter: 0.25mm, film thickness: 0.25μm Split ratio: 10 Split flow: 15mL / min MS ionization: EI Column temperature conditions: 40°C, held for 3 minutes, then increased to 300°C at 10°C / min and held for 10 minutes. Ion source temperature: 250°C Mass Range: m / z 45-1000 Conveyor line temperature: 250℃

[0076] <Creating a calibration curve> The concentration of the compound represented by formula (1) in the ethanol solution is 10 ppm, 50 ppm Samples for creating a calibration curve are prepared so that the concentrations are m, 100 ppm, and 250 ppm. These samples are measured under the above conditions, and a calibration curve is created from the area values ​​of the peaks derived from the compound represented by formula (1).

[0077] The sample was analyzed by FT NMR using a JNM-EX400 (manufactured by JEOL Ltd.) 1 H-NMR 400MHz, CDCl3, room temperature (25℃)]( 13 The structure of the compound represented by formula (1) is determined by analyzing the compound using a method such as C-NMR (also used in combination with C-NMR). Based on the information obtained by the above method, the compound represented by formula (1) is identified and its content is measured.

[0078] <Method for measuring the content of polyvalent elements in toner> The content of polyvalent elements in toner is measured using fluorescent X-rays and determined using a calibration curve method. Fluorescent X-ray measurements of polyvalent elements conform to JIS K 0119-1969, specifically as follows: The measurement equipment used was a wavelength dispersive X-ray fluorescence analyzer "Axios" (manufactured by PANalytical) and the accompanying software "SuperQ" for setting measurement conditions and analyzing measurement data. ver.4.0F" (PANalytical) is used. Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, and the measurement diameter (collimator mask diameter) is 27 mm. Light elements are detected using a proportional counter (PC), and heavy elements are detected using a scintillation counter (SC).

[0079] [Creating a calibration curve for boron element] As pellets for creating a calibration curve for determining the content of polyvalent elements in toner, binder [trade name: Spectro Blend, components: C 81.0, O 2.9, H 13.5, N 2.6 (mass%), chemical formula: C 19 H 38 0.10 parts by mass of borax [Na2(B4O5(OH)4)·8H2O] was added to 100 parts by mass of POWDER (44 μm, manufactured by Rigaku Corporation) and thoroughly mixed using a coffee mill. Four grams of the mixture was placed in a dedicated aluminum ring press and flattened. A tablet press "BRE-32" (Maekawa Testing Machinery Manufacturing Co., Ltd.) was used to pressurize the mixture at 20 MPa for 60 seconds to produce pellets with a thickness of 2 mm and a diameter of 39 mm. Similarly, pellets containing 0.50, 1.00, 5.00, and 10.00 parts borax were prepared. The count rate (unit: cps) of the B-Kα ray observed at a diffraction angle (2θ) of 41.75° using PET as a spectroscopic crystal was measured. The accelerating voltage and current of the X-ray generator were 32 kV and 125 mA, respectively, and the measurement time was 10 seconds. A linear calibration curve is obtained by plotting the obtained X-ray count rate on the vertical axis and the boron concentration calculated from the amount of borax added in each calibration curve sample on the horizontal axis.

[0080] [Quantitative determination of boron element in toner] To quantify the boron element content in the toner, 4g of toner is placed in a special press aluminum ring and pelletized in the same way as the sample for creating the calibration curve. The molded toner pellets are measured under the same conditions as the calibration curve sample, and the boron element content (ppm by mass) in the toner is determined from the calibration curve that has been created. The number of moles is also calculated from the content in the toner.

[0081] [Creating a calibration curve for aluminum elements and quantifying aluminum elements in toner] A calibration sample is prepared by substituting aluminum hydroxide (Al(OH)3) for borax, and the count rate (unit: cps) of the Al-Kα ray observed at a diffraction angle (2θ) of 144.8° when PET is used as the analyzing crystal is measured with the acceleration voltage and current of the X-ray generator set to 32 kV and 125 mA, and the measurement time set to 10 seconds, to obtain a calibration curve with a linear correlation to the concentration of added aluminum element. The determination of aluminum content in toner is carried out in the same manner as the determination of boron element. A sample is prepared and measured under the same conditions as the calibration curve sample, and the aluminum content (ppm by mass) in the toner is determined from the aluminum element calibration curve. The number of moles is also calculated from the aluminum content relative to the toner.

[0082] [Creating a calibration curve for magnesium element and quantifying magnesium element in toner] A calibration sample is prepared by substituting magnesium hydroxide (Mg(OH)2) for borax, and the acceleration voltage and current of the X-ray generator are set to 32 kV, 125 mA, and the measurement time is 50 seconds. When PET is used as the analyzing crystal, the count rate (unit: cps) of the Mg-Kα ray observed at a diffraction angle (2θ) = 22.93° is measured, and a calibration curve is obtained as a first-order correlation to the magnesium element addition concentration. To quantify the magnesium content in the toner, a toner sample is prepared in the same manner as for quantifying boron element, and measurements are carried out under the same conditions as for the calibration curve sample. The magnesium content in the toner (ppm by mass) is then determined from the magnesium element calibration curve. The number of moles is then calculated from the content relative to the toner.

[0083] [Creating a calibration curve for calcium element and quantifying calcium element in toner] A calibration sample is prepared by substituting calcium hydroxide (Ca(OH)2) for borax, and the acceleration voltage and current of the X-ray generator are set to 32 kV, 125 mA, and the measurement time is 10 seconds. When PET is used as the analyzing crystal, the count rate (unit: cps) of the Ca-Kα ray observed at a diffraction angle (2θ) = 113.0° is measured, and a calibration curve is obtained in linear correlation with the calcium element addition concentration. To quantify the calcium content in toner, a toner sample is prepared in the same manner as for quantifying boron element, and measurements are carried out under the same conditions as for the calibration curve sample. The calcium content (ppm by mass) in the toner is then determined from the calcium element calibration curve. The number of moles is then calculated from the content relative to the toner.

[0084] [Creating a calibration curve for iron elements and quantifying iron elements in toner] A calibration sample is prepared by substituting iron oxide (Fe2O3) for borax, and the count rate (unit: cps) of the Fe-Kα ray observed at a diffraction angle (2θ) of 57.48° when PET is used as the analyzing crystal is measured with the acceleration voltage and current of the X-ray generator set to 60 kV and 66 mA, and the measurement time set to 10 seconds, to obtain a calibration curve with a linear correlation to the concentration of added iron element. To quantify the iron content in the toner, a toner sample is prepared in the same manner as for quantifying boron element, and measurements are carried out under the same conditions as for the calibration curve sample. The iron content (ppm by mass) in the toner is then determined from the iron content in the toner. The number of moles is then calculated from the iron content relative to the toner.

[0085] <Ratio (A / B) of the number of moles A of the compound represented by formula (1) to the number of moles B of the polyvalent element> The number of moles A is calculated from the content of the compound represented by formula (1) in the identified toner, and the number of moles B of the polyvalent element is calculated from the content of the polyvalent element in the identified toner, thereby calculating the ratio (A / B) of the number of moles A of the compound represented by formula (1) to the number of moles of the polyvalent element.

[0086] <Separation of binder resin from toner> The binder resin in the toner particles can be extracted, for example, by extracting it using tetrahydrofuran (THF) and separating it using a solvent gradient elution method. The preparation method is shown below. Weigh out 10.0 g of toner particles, place them in a cylindrical filter paper (Toyo Roshi No. 84), and place them in a Soxhlet extractor. Extract for 20 hours using 200 mL of THF as the solvent, and the solid obtained by removing the solvent from the extract is the THF-soluble fraction. The THF-soluble fraction contains the binder resin. Repeat this process multiple times to obtain the required amount of THF-soluble fraction.

[0087] The solvent gradient elution method was performed using a gradient preparative HPLC (Shimadzu LC-20AP high-pressure gradient preparative system, Waters SunFire 50mm preparative column). A column (φ250mm) is used. The column temperature is 30°C, the flow rate is 50mL / min, and the mobile phase uses acetonitrile as a poor solvent and THF as a good solvent. 0.02g of the THF soluble matter obtained by extraction is dissolved in 1.5mL of THF to prepare the sample for separation. The mobile phase starts with a composition of 100% acetonitrile, and 5 minutes after sample injection, the proportion of THF is increased by 4% per minute until the mobile phase composition becomes 100% THF over 25 minutes. The components can be separated by drying the obtained fractions, which allows the binder resin to be obtained. Which fraction components are the binder resin will be explained later. 13 This can be determined by C-NMR (solid state) measurement. The required amount of binder resin can be obtained by repeating solvent gradient elution as necessary. The ratio of the mass of the obtained binder resin to the mass of the toner particles used to extract the binder resin is defined as the binder resin content (mass %) in the toner particles.

[0088] <Confirmation of the structure of the binder resin separated from the toner, and measurement of the content of the structure represented by formula (2) in the binder resin in the toner particles> The content of the structure represented by formula (2) in the binder resin is 13 This can be confirmed by known analytical methods such as C-NMR (solid state) measurement.

[0089] (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

[0090] The peaks obtained by the above measurement are separated according to the type of monomer unit in the binder resin, and each is identified. In addition, the structure of the monomer represented by formula (2) is identified, and the content is calculated from the integral ratio of the peaks. [Example]

[0091] The present disclosure will be specifically described below with reference to examples, but the present disclosure is not limited to these examples. "Parts" of each material in the examples and comparative examples are all by mass unless otherwise specified.

[0092] (Production of polyester resin 1) The following components were added to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube, a dehydration tube, and a pressure reducing device, and heated to a temperature of 130°C with stirring. Terephthalic acid: 100.0 parts Trimellitic anhydride: 3.3 parts Ethylene glycol: 17.1 parts Isosorbide: 48.4 parts Bisphenol A ethylene oxide 5 mole adduct: 7.0 parts

[0093] Titanium (IV) isopropoxide was added as an esterification catalyst in an amount of 0.3% based on the total amount of the monomer components added to the reaction vessel, and the temperature was raised to 235°C over 1 hour under a nitrogen gas flow, and the reaction was carried out for 3 hours. Thereafter, the pressure inside the reaction vessel was reduced to 10.0 mmHg. The reaction was continued while stirring until the desired molecular weight was reached, thereby obtaining polyester resin 1. The reaction was terminated when the desired molecular weight was reached, thereby obtaining polyester resin 1. The weight average molecular weight (Mw) of polyester resin 1 was 50,000. The proportion of the structural unit represented by formula (2) in polyester resin 1 was 4.0 mass%.

[0094] (Production of polyester resin 2) Fumaric acid: 100.0 parts Trimellitic anhydride: 4.4 parts Bisphenol A ethylene oxide 5 mole adduct: 37.9 parts Bisphenol A propylene oxide 5 mole adduct: 36.3 parts Polyester resin 2 was obtained in the same manner as polyester resin 1, except that the monomer components added to the reactor were the above components. The weight average molecular weight (Mw) of the obtained polyester resin 2 was 44,000. The proportion of the structural unit represented by formula (2) in polyester resin 2 was 45.6 mass%.

[0095] (Production of styrene acrylic resin dispersion 1) Styrene: 78 parts n-Butyl acrylate: 22 parts Anionic surfactant (sodium dodecylbenzenesulfonate): 3 parts Ethylene glycol monododecyl ether: 0.0021 parts Ion-exchanged water: 80 parts The above ingredients were placed in a container, and a monomer emulsion A was prepared using a homogenizer.

[0096] Ion-exchanged water: 200 parts Anionic surfactant (sodium dodecylbenzenesulfonate): 0.5 parts The above components were charged into a polymerization reaction vessel, a reflux condenser was attached, and the contents were slowly stirred while injecting nitrogen, and the polymerization flask was heated to 75°C in a water bath and maintained at that temperature.

[0097] 10 parts of the monomer emulsion A was added dropwise to the polymerization reaction vessel over 10 minutes using a metering pump. Then, 1.05 parts of ammonium persulfate was dissolved in 20 parts of ion-exchanged water. The resulting mixture was added dropwise to the polymerization flask over 10 minutes using a metering pump. Stirring was continued for 1 hour under this condition. The remaining monomer emulsion A was then added dropwise over 2 hours using a metering pump. After all the monomer emulsion A had been added, stirring was continued for another 3 hours, and then ion-exchanged water was added to adjust the solids concentration to 25.0%, thereby obtaining styrene acrylic resin dispersion 1.

[0098] (Production of styrene acrylic resin dispersion 2) Styrene: 126 parts n-Butyl acrylate: 14 parts Anionic surfactant (sodium dodecylbenzenesulfonate): 4 parts Ion-exchanged water: 59.2 parts The above ingredients were placed in a container, and a monomer emulsion B was prepared using a homogenizer.

[0099] Ion-exchanged water: 133 parts Anionic surfactant (sodium dodecylbenzenesulfonate): 0.6 parts The above components were charged into a polymerization reaction vessel, a reflux condenser was installed, and the mixture was slowly stirred while injecting nitrogen. The polymerization flask was heated to 75°C in a water bath and maintained at this temperature. 10 parts of the above monomer emulsion B was added dropwise to the polymerization reaction vessel over 10 minutes using a metering pump. Next, 1.05 parts of ammonium persulfate was dissolved in 10 parts of ion-exchanged water, and the polymerization flask was heated to 75°C in a water bath and maintained at this temperature. The mixture was added dropwise to the flask over 10 minutes using a metering pump. Stirring was continued for 1 hour under this condition. The remaining monomer emulsion B was then added dropwise over 2 hours using a metering pump. After the stirring was completed, stirring was continued for another 3 hours, and then ion-exchanged water was added to adjust the solid concentration to 40.0%, thereby obtaining a styrene acrylic resin dispersion liquid 2.

[0100] (Preparation of Polyester Resin Dispersion 1) Polyester resin 1: 100 parts Methyl ethyl ketone: 60 parts Isopropyl alcohol: 10 parts Ethylene glycol monododecyl ether: 0.0021 parts The above components were placed in a reaction vessel equipped with a stirrer and dissolved at 60°C. After confirming dissolution, the reaction vessel was cooled to 35°C, and 3.5 parts of a 10% aqueous ammonia solution was added. Next, 300 parts of ion-exchanged water was added dropwise to the reaction vessel over 3 hours to prepare a polyester resin dispersion. Next, methyl ethyl ketone and isopropyl alcohol were removed using an evaporator. Thereafter, ion-exchanged water was added to adjust the solids concentration to 25.0%, and polyester resin dispersion 1 was obtained.

[0101] (Preparation of Polyester Resin Dispersions 2 to 18) Polyester resin dispersions 2 to 18 were obtained in the same manner as in the preparation of polyester resin dispersion 1, except that the types and amounts of the polyester resin and compound represented by formula (1) used were changed as shown in Table 1.

[0102] [Table 1]

[0103] In the table, R of the compound represented by formula (1) 1 and n are R in the compound represented by formula (1), 1 and n are shown.

[0104] (Preparation of release agent dispersion) Hydrocarbon wax (manufactured by Nippon Seiro Co., Ltd., product name: FNP0090, melting temperature Tw = 90.2°C): 270 parts Anionic surfactant (sodium dodecylbenzenesulfonate): 10.5 parts Ion-exchanged water: 700 parts The above components were mixed and the release agent was dissolved in a pressure discharge homogenizer (Gaulin Homogenizer, manufactured by Gaulin Co., Ltd.) at an internal liquid temperature of 120°C. The mixture was then dispersed at a dispersion pressure of 5 MPa for 120 minutes, then at 40 MPa for 360 minutes, and cooled to obtain a release agent dispersion. The particle size distribution of this release agent dispersion was measured using a particle size measuring device (LA-950, manufactured by Horiba, Ltd.), and the volume average particle size of the release agent particles contained therein was found to be 220 nm. Ion-exchange water was then added to adjust the solids concentration to 20.0%.

[0105] (Preparation of Colorant Dispersion 1) CI Pigment Red 122: 200 parts Anionic surfactant (sodium dodecylbenzenesulfonate): 13 parts Ion-exchanged water: 750 parts 280 parts of ion-exchanged water and 13 parts of anionic surfactant (sodium dodecylbenzenesulfonate) were added to a stainless steel container large enough that the liquid level would be 1 / 3 of the container's height when all of the above ingredients were added. After the surfactant was thoroughly dissolved, 200 parts of CI Pigment Red 122 was added and the mixture was stirred using a stirrer until no unwetted pigment remained. 470 parts of ion-exchanged water was then added and the mixture was further stirred to thoroughly degass. After degassing, the mixture was dispersed at 5,000 rpm for 10 minutes using a homogenizer (IKA Ultra Turrax T50) and then stirred overnight with a stirrer for degassing. After degassing, the mixture was again dispersed at 6,000 rpm for 10 minutes using a homogenizer, and then further degassed by stirring overnight with a stirrer. The mixture was then dispersed at a pressure of 240 MPa using a high-pressure impact disperser, Ultimizer (Sugino Machine Corporation, HJP30006). The dispersion was carried out for 25 passes, calculated based on the total amount charged and the processing capacity of the equipment. The resulting dispersion was left to stand for 72 hours to remove precipitates, and ion-exchanged water was added to adjust the solids concentration to 15%, yielding Colorant Dispersion 1. The volume average particle size of the particles in this colorant dispersion was 110 nm.

[0106] (Preparation of Colorant Dispersion 2) Except for changing the colorant used to CI Pigment Blue 15:3, Colorant Dispersion Liquid 2 was obtained in the same manner as in Colorant Dispersion Liquid 1. The volume average particle size of the particles in this colorant dispersion liquid was 90 nm.

[0107] (Preparation of Colorant Dispersion 3) Colorant dispersion 3 was obtained in the same manner as in the preparation of colorant dispersion 1, except that the colorant used was changed to CI Pigment Yellow 180. The volume average particle size of the particles in this colorant dispersion was 120 nm.

[0108] (Preparation of Colorant Dispersion 4) Except for changing the colorant used to carbon black, colorant dispersion 4 was obtained in the same manner as in the preparation of colorant dispersion 1. The volume average particle size of the particles in this colorant dispersion was 50 nm.

[0109] <Production of Toner 1> (Production of Toner Particles 1) Polyester resin dispersion 1 450 parts Styrene acrylic resin dispersion 2 50 parts Colorant dispersion 1 65 parts Release agent dispersion 70 parts A reactor (1-liter flask, baffled anchor blade) was charged with polyester resin dispersion 1, styrene-acrylic resin dispersion 2, and release agent dispersion and mixed uniformly. Meanwhile, colorant dispersion 1 was mixed uniformly in a 500 mL beaker, and this was gradually added to the reactor while stirring to obtain a mixed dispersion. While stirring the resulting mixed dispersion, 8.0 parts of a 5% by mass aqueous borax solution was added dropwise to form aggregated particles. After the dropwise addition was completed, the system was purged with nitrogen and the mixture was maintained at 50°C for 1 hour and then at 55°C for 1 hour. The temperature was then increased and maintained at 90°C for 30 minutes. The temperature was then lowered to 63°C and maintained at this temperature for 3 hours to form fused particles. After the specified time had passed, the mixture was cooled to 40°C at a rate of 0.5°C per minute, and after cooling, the mixture was filtered, washed with water, and dried to obtain toner particles 1 having a weight average particle size (D4) of 6.5 μm.

[0110] (Toner 1 production) To 100 parts of the toner particles 1 obtained above, 1.5 parts of hydrophobic silica (RY50, manufactured by Nippon Aerosil Co., Ltd.) was added and mixed using a Mitsui Henschel mixer (manufactured by Mitsui Miike Chemical Engineering Co., Ltd.). The mixture was then sieved using a vibrating sieve with 45 μm openings to obtain toner 1. The physical properties of the obtained toner 1 are shown in Table 2.

[0111] <Production of Toners 2 to 29> Toners 2 to 29 were obtained by the same production method as Toner 1, except that the types and amounts of polyester resin dispersion, styrene acrylic resin dispersion, colorant dispersion, and flocculant added were changed as shown in Table 2.

[0112] [Table 2]

[0113] In the table, ppm of contained elements indicates the content (ppm) of polyvalent elements in the toner. (A / B ) represents the ratio (A / B) of the number of moles A of the compound represented by formula (1) contained in the toner to the number of moles B of the polyvalent element. 1 and n are each represented by the formula R in the compound represented by (1) 1 and n. ppm in formula (1) represents the content (ppm) of the compound represented by formula (1) in the toner. Polysilica iron (PSI-100) represents polysilica iron (manufactured by Nankai Chemical Co., Ltd., product name: PSI-100).

[0114] [Examples 1 to 23, Comparative Examples 1 to 6] The evaluation methods for each of Toners 1 to 29 are described below. The evaluation results are listed in Table 3. A modified, commercially available color laser printer [HP LaserJet Enterprise Color m553dn] was used for the evaluation. The color laser printer was modified so that it could operate with only one process cartridge installed. It was also modified so that the fuser temperature could be adjusted as desired. Furthermore, the toner was removed from the magenta toner cartridge and refilled with 150 g of Toners 1 to 20 and 24 to 29, respectively. The toner was also removed from the cyan cartridge and refilled with 150 g of Toner 21. The toner was also removed from the yellow cartridge and refilled with 150 g of Toner 22. The toner was also removed from the black cartridge and refilled with 150 g of Toner 23. The refilled toner cartridges were installed in the printer's stations, and dummy cartridges were installed in the other stations, and the following image output test was performed.

[0115] <Evaluation of gloss unevenness> XEROX4200 paper (XEROX 75g / m 2Nine 30mm x 30mm solid patch images were printed on a sheet of paper, and the paper was run at a heating unit temperature setting of 170°C and a process speed of 300mm / sec. From the perspective of gloss unevenness, the difference between the maximum and minimum gloss values ​​of the nine points on the image when one sheet was run was evaluated. A Nippon Denshoku Industries PG-3D (incident angle θ = 75°) gloss meter was used, and black glass with a gloss value of 96.9 was used as the standard surface. The difference between the maximum and minimum gloss values ​​(gloss difference) was evaluated using the following four ranks. A: Gross difference is less than 5 B: Gross difference is 5 or more but less than 10 C: Gross difference is 10 or more and less than 15 D: Gross difference is 15 or more

[0116] <Low temperature fixability> XEROX4200 paper (XEROX 75g / m 2 ) The tip has a toner carrying capacity of 0.5 mg / cm 2 A band-shaped unfixed image is formed under normal temperature and humidity conditions (temperature 23°C, relative humidity The humidity was set to 60%), the process speed was set to 250 mm / s, and the initial temperature was set to 100° C., and the set temperature was gradually increased by 5° C. at each temperature, while fixing the unfixed image at each temperature.

[0117] The evaluation criteria for low-temperature fixability are as follows: The low-temperature fixation starting point is the lowest temperature at which low-temperature offset (a phenomenon in which part of the toner adheres to the fixing device) is not observed. Evaluation was made into the following four ranks according to the degree of fixability. A: Low temperature fixing start point is less than 140°C B: Low temperature fixing start point is 140℃ or higher and less than 150℃ C: Low temperature fixing start point is 150℃ or higher but less than 160℃ D: Low temperature fixing start point is 160°C or higher

[0118] <Hot offset resistance> The fixing temperature was increased, and the highest temperature at which the offset phenomenon did not occur visually was taken as the high-temperature offset-free temperature, which was used as an index of offset resistance. The degree of offset resistance was evaluated into the following four ranks. A: High temperature offset free temperature is 190℃ or higher B: High temperature offset free temperature is 180℃ or more and less than 190℃ C: High temperature offset free temperature is 170℃ or more and less than 180℃ D: High temperature offset free temperature is less than 170℃

[0119] <Blocking resistance (storage stability)> 10 g of the toner after the external additive treatment was placed in a plastic cup and left to stand for 3 days in an environment of 53° C., and the degree of the toner was evaluated into the following 4 ranks. A: It easily collapses when tilted. B: There are lumps, but they break down easily when shaken C: It crumbles easily when tilted, but there are clumps that do not break apart. D: It won't collapse even if tilted.

[0120] <Evaluation of fog durability under high temperature and humidity conditions (developability)> Fog was evaluated under a high temperature and high humidity environment (30°C / 80%RH). XEROX 4200 paper (75 g / m, manufactured by XEROX Corporation) was used as the evaluation paper. 2 ) was used. Under a high temperature and high humidity environment, intermittent durability printing was performed on 15,000 sheets, in which two E character images with a printing rate of 1% were printed every four seconds. After that, a solid white image was printed and evaluated. Measurements were performed using a reflection densitometer (Reflectometer Model TC-6DS, manufactured by Tokyo Denshoku Co., Ltd.), with the worst reflection density value of the white background being Ds, the average reflection density of the transfer material before image formation being Dr, and Dr - Ds being the fog value. The smaller the fog value, the better the level of fog. Evaluation was performed using the following four ranks according to the degree of fog. A: Less than 0.5% B: 0.5% or more and less than 1.5% C: 1.5% or more and less than 3.0% D: 3.0% or more

[0121] [Table 3]

Claims

1. A toner containing toner particles containing a binder resin, The toner particles further comprise: A compound represented by the following formula (1), at least one polyvalent element selected from the group consisting of magnesium, calcium, aluminum, boron, and iron; Contains the content of the polyvalent element in the toner is 100 ppm by mass or more and 5000 ppm by mass or less, The toner, wherein the ratio (A / B) of the number of moles A of the compound represented by formula (1) contained in the toner to the number of moles B of the polyvalent element is 0.0010 or more and 0.1000 or less. R １ -[[H ２ CH ２ ] ｎ -OH (1) [In formula (1), R １ represents a linear or branched alkyl group having 8 to 22 carbon atoms, and n represents is an integer from 1 to 3.

2. A toner containing toner particles containing a binder resin, The toner particles further comprise: A compound represented by the following formula (1), at least one polyvalent element selected from the group consisting of aluminum, boron, and iron; Contains The toner has a content of the polyvalent element in the toner of 100 ppm by mass or more and 5000 ppm by mass or less. R 1 -[OCH 2 CH 2 ] n -OH (1) In formula (1), R 1 represents a linear or branched alkyl group having 8 to 22 carbon atoms, and n represents is an integer from 1 to 3.

3. A toner containing toner particles containing a binder resin, The toner particles further comprise: A compound represented by the following formula (1), at least one polyvalent element selected from the group consisting of magnesium, calcium, aluminum, boron, and iron; Contains the binder resin contains a polyester resin, the polyester resin is an amorphous polyester resin, the content of the amorphous polyester resin in the binder resin is 50% by mass or more, the content of the structure represented by formula (2) in the amorphous polyester resin is 5.0 mass% or less, The toner has a content of the polyvalent element in the toner of 100 ppm by mass or more and 5000 ppm by mass or less. R 1 -[OCH 2 CH 2 ] n -OH (1) In formula (1), R 1 represents a linear or branched alkyl group having 8 to 22 carbon atoms, and n represents is an integer from 1 to 3. (In the formula, R 2 and R 3 each independently represent an ethylene group or a propylene group. x and y represent the average number of moles of alkylene oxide added, and the sum of x and y is 1 or more and 5 or less.)

4. 4. The toner according to claim 1, wherein the content of the compound represented by formula (1) in the toner is 5 ppm by mass or more and 500 ppm by mass or less.

5. 5. The toner according to claim 1, wherein a ratio (A / B) of the number of moles A of the compound represented by formula (1) contained in the toner to the number of moles B of the polyvalent element is 0.0010 or more and 0.0200 or less.

6. In the formula (1), R １ 6. The toner according to claim 1, wherein is a linear alkyl group having 12 to 22 carbon atoms.

7. 7. The toner according to claim 1, wherein n is 1 in formula (1).

8. 8. The toner according to claim 1, wherein the polyvalent element is boron.

9. The toner according to any one of claims 1 to 8, comprising a crosslinked product of an ion containing the polyvalent element or an ion generated from the polyvalent element and at least one selected from the group consisting of the compound represented by formula (1) and the binder resin.

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