Toner

Abstract

To provide a toner that has satisfactory storage stability while satisfying low temperature fixability, improves charge rising properties in a high temperature and high humidity environment, prevents unevenness in image density, and is excellent in developability.SOLUTION: A toner has a toner particle that contains a binder resin. The toner particle has an anionic surfactant having a monovalent aliphatic alcohol and an alkyl group. The binder resin includes a polyester resin. The monovalent aliphatic alcohol has 8-18 carbon atoms. The content ratio of the monovalent aliphatic alcohol extracted from the toner with ethanol is 30 mass ppm or more and 300 mass ppm or less in the toner. The value of the ratio (molar ratio) of the monovalent aliphatic alcohol extracted from the toner with ethanol to the anionic surfactant having the alkyl group extracted from the toner with methanol is 0.01 or more and 0.60 or less.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a toner used for developing an electrostatic latent image formed by an electrophotographic method, an electrostatic recording method, a toner jet recording method, etc. to form a toner image.

Background Art

[0002] In electrophotographic technology used in copiers, printers, facsimile receiving devices, etc., the requirements from users have become increasingly strict year by year along with the development of the devices. In recent trends, there is a strong demand for a compact design so as not to select the installation location, and also for stable image quality that is not dependent on the environment because the environments in which it is used are diverse.

[0003] From the viewpoint of compact design, for example, attempts have been made to achieve miniaturization by simplifying and streamlining fixing members such as heat rollers and films for fixing toner images onto transfer materials. In this approach, since it is necessary to enable fixing without heating the fixing member as much as possible, a toner excellent in low-temperature fixability is required, and a polyester resin excellent in low-temperature fixability is often used as the binder resin. However, polyester resin has a problem in that it is inferior to styrene-acrylic copolymer, which is also often used as the binder resin of toner, in terms of chargeability, so image defects related to charge leakage are likely to occur.

[0004] In response to the above problems, for example, Patent Document 1 discloses a black toner using a naphthalene sulfonic acid formalin condensate and an anionic surfactant having a sulfone group or a sulfate group.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, from the viewpoint of providing stable image quality independent of the environment, it has been found that when using the above toner, the charging rise in a high-humidity environment is insufficient, resulting in density unevenness in the image. In order to provide an image forming apparatus that can obtain stable image quality without depending on the usage environment while having a compact design required by the market, improvement of various toner characteristics is still required. The present disclosure provides a toner excellent in developability that satisfies low-temperature fixability, has good storability, further improves charging rise in a high-temperature and high-humidity environment, and suppresses density unevenness in the image.

Means for Solving the Problems

[0007] A toner having toner particles containing a binder resin, the toner particles have a monohydric aliphatic alcohol and an anionic surfactant having an alkyl group, the binder resin includes a polyester resin, the monohydric aliphatic alcohol has 8 to 18 carbon atoms, the content ratio of the monohydric aliphatic alcohol extracted from the toner with ethanol is 30 mass ppm or more and 300 mass ppm or less with respect to the mass of the toner, the value of the ratio (molar ratio of the monohydric aliphatic alcohol extracted from the toner with ethanol to the anionic surfactant having an alkyl group extracted from the toner with methanol) is 0.01 or more and 0.60 or less. A toner characterized by that.

Effects of the Invention

[0008] According to the present disclosure, it is possible to provide a toner excellent in developability that satisfies low-temperature fixability, has good storability, further improves charging rise in a high-temperature and high-humidity environment, and suppresses density unevenness in the image.

Brief Description of the Drawings

[0009]

Figure 1

Figure 2

Mode for Carrying Out the Invention

[0010] In the present disclosure, the description of "XX or more and YY or less" or "XX to YY" representing a numerical range means a numerical range including the lower limit and the upper limit which are the endpoints, unless otherwise specified. When the numerical ranges are described stepwise, the upper and lower limits of each numerical range can be arbitrarily combined. The "monomer unit" refers to the reacted form of the monomer substance in the polymer.

[0011] The present disclosure relates to a toner having toner particles containing a binder resin, the toner particles having a monohydric aliphatic alcohol and an anionic surfactant having an alkyl group, the binder resin including a polyester resin, the monohydric aliphatic alcohol having 8 to 18 carbon atoms, the content ratio of the monohydric aliphatic alcohol extracted from the toner with ethanol being 30 mass ppm or more and 300 mass ppm or less with respect to the mass of the toner, relates to a toner in which the value (molar ratio) of the ratio of the monohydric aliphatic alcohol extracted from the toner with ethanol to the anionic surfactant having an alkyl group extracted from the toner with methanol is 0.01 or more and 0.60 or less.

[0012] The inventors have found that the above toner can provide a toner with excellent developability that satisfies low-temperature fixability, has good storage stability, further improves charge rise in a high-humidity environment, and suppresses density unevenness of the image. Regarding the detailed mechanism, the inventors consider as follows.

[0013] In a process cartridge as shown in FIG. 1, toner is charged by rubbing against the toner carrier 14 and the regulating blade 16. In the printing area, the toner 17 is developed from the toner carrier 14 onto the electrostatic latent image carrier 10, and new toner is supplied to the toner carrier 14 through the toner supply member 15. On the other hand, in the non-printing area, the toner stays on the toner carrier 14 without being consumed. Therefore, a difference in charge amount occurs between the staying toner and the newly supplied toner, resulting in density unevenness in the image.

[0014] As described above, although toner containing a binder resin containing a polyester resin is excellent in low-temperature fixability, it is inferior in chargeability compared to toner using a styrene-acrylic copolymer as the binder resin. Especially when an anionic surfactant is used as the charge generation source, in a high-humidity environment, due to water adsorption to the anionic surfactant, charge leakage easily occurs and the charge rise of the toner decreases, so density unevenness in the image easily occurs.

[0015] The extraction of monohydric aliphatic alcohol from the toner by ethanol indicates the presence of monohydric aliphatic alcohol near the toner surface. By making monohydric aliphatic alcohol present near the toner surface, the water molecules adsorbed to the anionic surfactant can be transferred to the more hydrophilic hydroxy group of the aliphatic alcohol. Thereby the decrease in the charging ability of the anionic surfactant due to water molecules is suppressed. Furthermore, since the hydroxy group of the aliphatic alcohol and water molecules are in a chemical equilibrium state by hydrogen bonding, the hydroxy group of the monohydric alcohol is polarized and charged. As a result, it is considered that the charge rise under a high-humidity environment is improved and density unevenness in the image is suppressed.

[0016] The monohydric aliphatic alcohol should have 8 to 18 carbon atoms. If the number of carbon atoms is less than 8, the alcohol gradually escapes from the system, making it difficult to obtain a continuous effect. If the number of carbon atoms is more than 18, the affinity with the binder resin increases, the binder resin becomes plasticized, and the storage stability is likely to decrease. Preferably, it is 10 to 16, and more preferably 12 to 14. The monohydric aliphatic alcohol may be linear or branched, but is preferably linear.

[0017] The content ratio of the monohydric aliphatic alcohol extracted from the toner with ethanol should be 30 ppm by mass or more and 300 ppm by mass or less based on the mass of the toner. If the amount of the monohydric aliphatic alcohol extracted from the toner with ethanol is less than 30 ppm by mass, it is difficult to obtain the above effects, and image density unevenness due to insufficient charge rise is likely to occur. If the amount of the aliphatic alcohol is more than 300 ppm by mass, the moisture adsorption amount of the toner increases significantly, so the hydroxy group is polarized and charge leakage is prioritized over charging, and fogging is likely to occur. Also, since the charge rise decreases, density unevenness is likely to occur. Preferably, it is 40 ppm by mass or more and 270 ppm by mass or less, more preferably 50 ppm by mass or more and 250 ppm by mass or less, and even more preferably 80 ppm by mass or more and 200 ppm by mass or less.

[0018] The value of the ratio (alcohol / surfactant, molar ratio) of the monohydric aliphatic alcohol extracted from the toner with ethanol to the anionic surfactant having an alkyl group extracted from the toner with methanol should be 0.01 or more and 0.60 or less. If the molar ratio is less than 0.01, the number of monohydric aliphatic alcohols relative to the anionic surfactant is small, so it is difficult to obtain the above effects. If it is more than 0.60, the balance between charging and leakage is disrupted and fogging is likely to occur. Preferably, it is 0.02 or more and 0.45 or less, and more preferably 0.03 or more and 0.40 or less.

[0019] Examples of the anionic surfactant having an alkyl group include sulfate ester salts, sulfonates, phosphate esters, and the like. The number of carbon atoms of the alkyl group is preferably 8 to 18, more preferably 10 to 16, and even more preferably 12 to 16. The alkyl group may be linear or branched, but is preferably linear. The anionic surfactant having an alkyl group is preferably represented by the following formula (A). R-X-SO3 - Na + ···(A) In the formula, R is an alkyl group having 8 to 18 carbon atoms (preferably 10 to 16, more preferably 12 to 16). The alkyl group may be linear or branched, but is preferably linear. X is a single bond, -O-, a phenylene group, or -(OCH2CH2) n - (where n = 2 to 10 (more preferably 2 to 6, even more preferably 2 to 4)).

[0020] The content ratio of the anionic surfactant having an alkyl group extracted from the toner with methanol is preferably 1000 ppm by mass or more and 25000 ppm by mass or less, more preferably 1500 ppm by mass or more and 10000 ppm by mass or less, based on the mass of the toner.

[0021] Among them, sulfonates are preferred, and the anionic surfactant having an alkyl group more preferably contains sodium linear alkylbenzene sulfonate. At this time, the difference between the number of carbon atoms of the alkyl group of sodium linear alkylbenzene sulfonate and the number of carbon atoms of the monohydric aliphatic alcohol is preferably 3 or less, more preferably 2 or less. The lower limit is not particularly limited, but is 0 or more. Since sodium linear alkylbenzene sulfonate and the monohydric aliphatic alcohol have alkyl groups of substantially the same chain length, the intermolecular interaction is strong, and the above effects are more easily obtained by attracting each other.

[0022] The polyester resin is preferably a polycondensate of the following polyvalent carboxylic acid and polyhydric alcohol. Examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids (such as oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, alkenyl succinic acid, adipic acid, sebacic acid, etc.), alicyclic dicarboxylic acids (such as cyclohexanedicarboxylic acid, etc.), aromatic dicarboxylic acids (such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, etc.), and anhydrides thereof.

[0023] As the polyvalent carboxylic acid, a carboxylic acid having a crosslinked structure or a branched structure with a valence of 3 or more may be used in combination with the dicarboxylic acid. Examples of the carboxylic acid having a valence of 3 or more include trimellitic acid, pyromellitic acid, and anhydrides thereof. The polyvalent carboxylic acid may be used alone or in combination of two or more.

[0024] Examples of the polyhydric alcohol include aliphatic diols (such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, etc.), alicyclic diols (such as cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, etc.), aromatic diols (such as bisphenol A or its alkylene oxide adduct, etc.), and heterocyclic diols (such as spiroglycol, isosorbide, or its alkylene oxide adduct, etc.).

[0025] As the polyhydric alcohol, a polyhydric alcohol having a crosslinked structure or a branched structure with a valence of 3 or more may be used in combination with the diol. Examples of the polyhydric alcohol having a valence of 3 or more include glycerin, trimethylolpropane, and pentaerythritol. The polyhydric alcohol may be used alone or in combination of two or more.

[0026] The polyester resin is preferably a polycondensate of an aromatic dicarboxylic acid, a carboxylic acid having a valence of 3 or more, an aliphatic diol, an aromatic diol, and a heterocyclic diol. The polyester resin preferably has a monomer unit derived from isosorbide represented by the following formula (I). The content ratio of the monomer unit represented by the formula (I) in the polyester resin is preferably 15% by mass to 40% by mass, more preferably 20% by mass to 35% by mass.

Chemical formula

[0027] The polyester resin preferably has a monomer unit represented by the following formula (1). From the viewpoint of fixing property, the content ratio of the monomer unit represented by the formula (1) in the polyester resin is preferably 5.0% by mass or less, more preferably 4.5% by mass or less. The lower limit is not particularly limited, but is preferably 1.0% by mass or more, more preferably 3.0% by mass or more.

Chemical formula

[0028] The content ratio of the polyester resin in the binder resin is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and even more preferably 80% by mass or more. The upper limit is not particularly limited, but is preferably 98% by mass or less, more preferably 95% by mass or less.

[0029] The weight average molecular weight Mw of the polyester resin is preferably from 20,000 to 300,000. More preferably, it is from 30,000 to 200,000, still more preferably from 40,000 to 100,000, and even more preferably from 40,000 to 60,000.

[0030] [Binder resin] If the binder resin contains polyester, other resins may be used in combination. For example, the following resins can be used. Homopolymers of styrene and its substituents such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene; styrene-based copolymers such as styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-acrylonitrile-indene copolymer; polyvinyl chloride, phenol resin, natural resin-modified phenol resin, natural resin-modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, amorphous polyester, crystalline polyester, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone-indene resin, petroleum resin, etc. can be used.

[0031] The binder resin preferably contains styrene acrylic resins such as styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer. For styrene acrylic resins, it is preferable to use the following styrene-based monomers and unsaturated carboxylic acid esters. The content ratio of the styrene acrylic resin in the binder resin is preferably from 2% by mass to 40% by mass, more preferably from 5% by mass to 20% by mass.

[0032] Examples of polymerizable monomers capable of forming styrene acrylic resins include styrene-based monomers such as styrene, α-methylstyrene, and divinylbenzene; unsaturated carboxylic acid esters such as methyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, t-butyl methacrylate, and 2-ethylhexyl methacrylate (for example, (meth)acrylic acid alkyl esters having 1 to 8 carbon atoms in the alkyl group); unsaturated carboxylic acids such as acrylic acid and methacrylic acid; unsaturated dicarboxylic acids such as maleic acid; unsaturated dicarboxylic acid anhydrides such as maleic anhydride; nitrile-based vinyl monomers such as acrylonitrile; halogen-containing vinyl monomers such as vinyl chloride; nitro-based vinyl monomers such as nitrostyrene; and the like. Examples include the above.

[0033] [Colorant] It is preferable that the toner particles contain a colorant. Examples of the colorant include the following. Examples of the black colorant include carbon black; examples of the black colorant toned with a yellow colorant, a magenta colorant, and a cyan colorant are also included. A pigment may be used alone as the colorant.

[0034] Examples of pigments for magenta toners include the following: C.I. 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; C.I. Pigment Violet 19; C.I. Vat Red 1, 2, 10, 13, 15, 23, 29, 35. Examples of dyes for magenta toners include the following: C.I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; C.I. Disperse Red 9; C.I. Solvent Violet 8, 13, 14, 21, 27; oil-soluble dyes such as C.I. Disperse Violet 1, C.I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; basic dyes such as C.I. Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

[0035] Examples of pigments for cyan toners include the following: C.I. Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, 17; C.I. Vat Blue 6; C.I. Acid Blue 45, and copper phthalocyanine pigments in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton. Examples of dyes for cyan toners include C.I. Solvent Blue 70. Examples of pigments for yellow toners include the following: C.I. 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; C.I. Vat Yellow 1, 3, 20. Examples of dyes for yellow toners include C.I. Solvent Yellow 162.

[0036] The content of the colorant is preferably 0.1 part by mass or more and 30.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin.

[0037] [Wax] The toner particles preferably contain wax. The wax is not particularly limited, and examples thereof include the following. 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 mainly composed of fatty acid esters such as carnauba wax; those obtained by partially or completely deoxidizing fatty acid esters such as deacidified carnauba wax.

[0038] Furthermore, the following are included: 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 Classes; Saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, melissyl alcohol; Polyhydric alcohols such as sorbitol; Fatty acids such as palmitic acid, stearic acid, behenic acid, montanic acid, and esters of fatty acids with alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, melissyl alcohol; Fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; Saturated fatty acid bisamides such as methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, hexamethylene bisstearic acid amide; Unsaturated fatty acid amides such as ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N,N'-dioleyl adipic acid amide, N,N'-dioleyl sebacic acid amide; Aromatic bisamides such as m-xylene bisstearic acid amide, N,N'-distearyl isophthalic acid amide; Fatty acid metal salts (commonly called metal soaps) such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate; Waxes grafted with vinyl monomers such as styrene and acrylic acid onto aliphatic hydrocarbon waxes; Partial esterified products of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; Methyl ester compounds having a hydroxy group obtained by hydrogenating vegetable oils and fats.

[0039] Among these waxes, from the viewpoint of improving low-temperature fixability and anti-fixing winding properties, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax and ester waxes are preferred. The content of the wax is preferably 0.5 parts by mass or more and 25.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin.

[0040] Also, from the perspective of achieving both good toner storage stability and high-temperature offset resistance, in the endothermic curve during heating measured by a differential scanning calorimeter (DSC), it is preferable that the peak temperature of the maximum endothermic peak of the wax, which exists in the temperature range of 30°C or higher and 200°C or lower, is 50°C or higher and 110°C or lower.

[0041] [Charge control agent] The toner can also contain a charge control agent as needed. Known charge control agents can be used. The charge control agent may be added internally or externally to the toner particles. The addition amount of the charge control agent is preferably 0.2 parts by mass or more and 10.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin.

[0042] [Carrier] The toner may be used as a one-component developer. In terms of obtaining a stable image over a long period, the toner may be mixed with a magnetic carrier and used as a two-component developer. As the magnetic carrier, known ones such as the following can be used. For example, iron powder with an oxidized surface, or unoxidized iron powder, or metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, rare earths, their alloy particles, oxide particles, magnetic substances such as ferrite, and a magnetic substance-dispersed resin carrier (so-called resin carrier) containing a magnetic substance and a binder resin that holds the magnetic substance in a dispersed state.

[0043] When the toner is mixed with a magnetic carrier and used as a two-component developer, the carrier mixing ratio at that time, as the toner concentration in the two-component developer, is preferably 2% by mass or more and 15% by mass or less, more preferably 4% by mass or more and 13% by mass or less.

[0044] (Method for manufacturing toner) The method for manufacturing toner particles is not particularly limited as long as it is a known manufacturing method such as an emulsion aggregation method, a pulverization method, or a dissolution suspension method. Among these, it is preferable to obtain toner particles by the emulsion aggregation method. .

[0045] Specifically, when manufacturing toner particles by the emulsion aggregation method, a step of preparing a resin particle dispersion in which resin particles serving as a binder resin are dispersed using an anionic surfactant having an alkyl group, and in the resin particle dispersion, a monohydric aliphatic alcohol, an anionic surfactant having an alkyl group, and, if necessary, a coloring agent, wax, and other particle dispersions are mixed, and the resin particles are aggregated to form aggregated particles; and heating the aggregated particle dispersion in which the aggregated particles are dispersed to fuse and unite the aggregated particles to form toner particles. Through these steps, toner particles are manufactured. In the following description, a method for obtaining toner particles containing a coloring agent and wax will be described, but other additives other than the coloring agent and wax may also be used.

[0046] - Step of preparing resin particle dispersion - Prepare a resin particle dispersion in which resin particles serving as a binder resin are dispersed, a coloring agent particle dispersion in which coloring agent particles are dispersed, and a wax particle dispersion in which wax particles are dispersed. Here, the resin particle dispersion is prepared by dispersing resin particles in a dispersion medium using a surfactant. Examples of the dispersion medium used for the resin particle dispersion include aqueous media. Examples of the aqueous medium include water such as distilled water and ion-exchanged water. These may be used in combination.

[0047] As the surfactant, an anionic surfactant having an alkyl group as described above can be used to incorporate an anionic surfactant into the toner. In addition to the anionic surfactant, other cationic surfactants such as amine salt type and quaternary ammonium salt type; and non-ionic surfactants such as polyethylene glycol type, alkylphenol ethylene oxide adduct type, and polyhydric alcohol type may be used in combination. When manufacturing the resin particle dispersion, it is preferable to manufacture the resin particle dispersion by polymerizing a polymerizable monomer that forms a binder resin in an aqueous medium to which an anionic surfactant having an alkyl group is added.

[0048] In a resin particle dispersion, as a method for dispersing resin particles in a dispersion medium, for example, general dispersion methods such as a rotary shear type homogenizer, a ball mill having media, a sand mill, a dyno mill, etc. can be mentioned. Further, depending on the type of resin particles, for example, the resin particles may be dispersed in the resin particle dispersion using a phase inversion emulsification method.

[0049] As the volume average particle diameter of the resin particles dispersed in the resin particle dispersion, for example, 0.01 μm or more and 1 μm or less is preferable, 0.08 μm or more and 0.8 μm or less is more preferable, and 0.1 μm or more and 0.6 μm or less is even more preferable. As the content of the resin particles contained in the resin particle dispersion, for example, 5 mass% or more and 50 mass% or less is preferable, and 10 mass% or more and 40 mass% or less is more preferable. In the same manner as the resin particle dispersion, a colorant particle dispersion, a wax particle dispersion, etc. are also prepared.

[0050] -Agglomerated Particle Formation Step- Next, a resin particle dispersion, a monohydric aliphatic alcohol, an anionic surfactant having an alkyl group, and, if necessary, a colorant particle dispersion, a wax particle dispersion, etc. are mixed. In the mixed dispersion, the resin particles (and colorant particles and wax particles) are hetero-aggregated to form agglomerated particles containing the resin particles (and colorant particles and wax particles) having a diameter close to the diameter of the target toner particles.

[0051] Specifically, for example, while adding a flocculant to the mixed dispersion, adjusting the pH of the mixed dispersion to acidic (for example, pH is 2 or more and 5 or less), and adding a dispersion stabilizer if necessary, then heating to the temperature of the glass transition temperature of the resin particles (specifically, for example, the glass transition temperature of the resin particles - 30 °C or more, the glass transition temperature of the resin particles - 10 °C or less), and aggregating the particles dispersed in the mixed dispersion to form agglomerated particles.

[0052] Examples of the flocculant include inorganic metal salts and divalent or higher metal complexes. An additive that forms a complex or a similar bond with the metal ions of the flocculant may be used if necessary. As this additive, a chelating agent is preferably used.

[0053] Examples of the inorganic metal salts include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and inorganic metal salt polymers such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide.

[0054] As the chelating agent, a water-soluble chelating agent may be used. Examples of the chelating agent include oxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid, iminodiacid (IDA), nitrilotriacetic acid (NTA), and ethylenediaminetetraacetic acid (EDTA).

[0055] -Fusion and unification step- The aggregated particle dispersion in which the aggregated particles are dispersed is heated to a temperature equal to or higher than the glass transition temperature of the resin particles (a temperature 10 °C to 30 °C higher than the glass transition temperature of the resin particles) to fuse and unify the aggregated particles and form toner particles. After the completion of the fusion and unification step, the toner particles formed in the solution are dried through known washing steps, solid-liquid separation steps, and drying steps to obtain toner particles in a dried state.

[0056] In the washing step, substitution washing with ion-exchanged water makes it easier to control the molar ratio of the monovalent aliphatic alcohol to the anionic surfactant within the above range. In addition, although there are no particular restrictions on the solid-liquid separation step, suction filtration, pressure filtration, etc. are preferably performed from the viewpoint of productivity. Also, although there are no particular restrictions on the drying method in the drying step, freeze drying, flash jet drying, fluidized drying, vibration type fluidized drying, etc. are preferably performed from the viewpoint of productivity. The obtained toner particles may be used as toner as they are. If necessary, an external additive may be added to and mixed with the toner particles to obtain a toner. The mixing is preferably performed using, for example, a V blender, a Henschel mixer, a Lodige mixer, etc. Further, if necessary, coarse particles of the toner may be removed using a vibrating classifier, an air classifier, etc.

[0057] Hereinafter, the measurement methods for various physical properties will be described.

[0058] ​ <Identification and Quantification of Anionic Surfactants Extracted with Methanol in Toner> Precisely weigh 1 g of toner, add 10 g of methanol, and subject it to treatment for 20 minutes in an ultrasonic cleaner maintained at a water temperature of 30°C ± 2°C. After filtration, extract the surfactant into methanol. Analyze the content ratio of the surfactant using 10.0 μl of this methanol solution with high-performance liquid chromatography (Hitachi High-Performance Liquid Chromatograph LaChrom Elite (L-2000 series), manufactured by Hitachi High-Technologies Corporation). The column is GL Sciences InertSil Ph (5μ) Φ4.6×250 mm is used, and the column is maintained at a temperature of 50°C ± 1°C in a column oven. As the mobile phase, a mixed solvent of 0.1% by volume phosphoric acid / acetonitrile ((volume ratio) 0.1% by volume phosphoric acid / acetonitrile = 80 / 20) is fractionated at a flow rate of 1.0 ml / min to detect the surfactant. A UV detector is used as the detector, and the amount of surfactant is quantified using a calibration curve prepared in advance from the absorbance at a wavelength of 224 nm.

[0059] The structure of the anionic surfactant is analyzed and the structure is determined using the above extract with an FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.) 1 1H-NMR 400 MHz, CDCl3, room temperature (25°C)]( 13 13C-NMR, etc. are also used in combination).

[0060] <Identification and Quantification of Monohydric Aliphatic Alcohols Extracted with Ethanol in Toner> (Preparation of Extraction Sample) Add 2 g of toner and 18 g of ethanol, homogenize by hand shaking, and then irradiate with ultrasonic waves for 5 minutes. Then, leave it standing in a constant-temperature bath at 60°C for one day and night, and further leave it standing at room temperature for 3 days. Collect the supernatant of the sample after standing and filter it with a PTFE syringe filter (pore size 250 nm), and use the filtrate as the extraction sample.

[0061] (GC / MS Analysis) The GC / MS apparatus is GC TRACE―1310 (Thermo Scientifi For the detector, use the single quadrupole mass spectrometer MS ISQ LT (manufactured by Thermo Scientific), and for the autosampler, use the TRIPLUS RSH (manufactured by Thermo Scientific). The measurement is carried out under the conditions shown below. Sample volume: 1 μL (liquid injection) Column: HP5-MS (manufactured by Agilent Technologies) Length: 30 m, inner diameter 0.25 mm, film thickness 0.25 μm Split ratio: 10 Split flow: 15 mL / min Inlet temperature: 250 °C Flow rate of helium gas in the column: 1.5 mL / min MS ionization: EI Column temperature condition: Hold at 40 °C for 3 min, then raise the temperature to 300 °C at a rate of 10 °C / min and hold for 10 min. Ion source temperature: 250 °C Mass Range: m / z 45 - 1000 Carrier line temperature: 250 °C

[0062] <Calibration curve preparation> Prepare calibration curve samples so that the concentration (mass basis) of monohydric aliphatic alcohols in the ethanol solution is 10 ppm, 50 ppm, 100 ppm, and 250 ppm. Measure these samples under the above conditions, and prepare a calibration curve from the peak area values of the monohydric aliphatic alcohols. Use the obtained calibration curve to analyze the above extraction sample and calculate the content ratio of monohydric aliphatic alcohols in the toner extracted with ethanol.

[0063] The structure of the monohydric aliphatic alcohol is analyzed and determined using the above extraction sample with the FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.) 1 H-NMR 400 MHz, CDCl3, room temperature (25 °C) 13 C-NMR, etc. are also used in combination. Based on the content ratio of monohydric aliphatic alcohol in the toner extracted with ethanol obtained by the above method and the content ratio measured by the method described in <Identification and Quantification of Anionic Surfactant in Toner>, calculate the molar ratio of monohydric aliphatic alcohol to anionic surfactant.

[0064] <Identification and Quantification of Binder Resin> For the identification of the composition and ratio of the binder resin, thermogravimetric gas chromatography mass spectrometer (hereinafter also referred to as "pyrolysis GC / MS") and NMR are used. Pyrolysis GC / MS is used for the analysis of the types of constituent compounds of the binder resin. Using toner as a sample, the types of constituent compounds are identified by analyzing the mass spectrum of the components of the decomposition products of the binder resin generated when the toner is pyrolyzed at 550 °C to 700 °C. The specific measurement conditions are as follows. [Measurement Conditions of Pyrolysis GC / MS] Pyrolysis apparatus: JPS-700 (JEOL Ltd.) Decomposition temperature: 590 °C GC / MS apparatus: Focus GC / ISQ (Thermo Fisher) Column: HP-5MS, length 60 m, inner diameter 0.25 mm, film thickness 0.25 μm Inlet temperature: 200 °C Flow pressure: 100 kPa Split: 50 mL / min MS ionization: EI Ion source temperature: 200 °C Mass Range: 45 - 650

[0065] Subsequently, the abundance ratio of the identified constituent compounds of the resin is 1 Measured and calculated by 1H-NMR. Structure determination is performed using an FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.) 1 [1H-NMR 400 MHz, CDCl3, room temperature (25 °C)] From the integral values of the obtained spectra, the mol ratio of each monomer component is determined, and based on this, the composition ratio (mass %) is calculated.

[0066] [Method for Measuring 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, dissolve the binder resin in tetrahydrofuran (THF) over 24 hours at room temperature. Then, filter the resulting solution through a solvent-resistant membrane filter "Micron Disc" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. Note that the sample solution is adjusted so that the concentration of components soluble in THF is about 0.8 mass%. Using this sample solution, measure under the following conditions. Apparatus: HLC8120 GPC (Detector: RI) (manufactured by Tosoh Corporation) Column: Seven columns of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK) Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 ml / min Oven temperature: 40.0 °C Sample injection volume: 0.10 ml

[0067] When calculating the molecular weight of the sample, use the molecular weight calibration curve prepared using a standard polystyrene resin (for example, product 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).

[0068] [Method for Measuring Weight-Average Particle Size (D4) of Toner Particles] The weight average particle size (D4) of the toner particles is measured and calculated using a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube, and the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.) for setting measurement conditions and analyzing measurement data. The measurement is carried out with an effective number of measurement channels of 25,000 channels, and the measurement data is analyzed and calculated. The electrolytic aqueous solution used for the measurement is prepared by dissolving special grade sodium chloride in ion-exchanged water so that the concentration is about 1% by mass. For example, "ISOTON II" (manufactured by Beckman Coulter, Inc.) can be used.

[0069] Before performing the measurement and analysis, the settings of the dedicated software are made as follows. In the "Change Screen of Standard Measurement Method (SOM)" of the dedicated software, set the total count of the control mode to 50,000 particles, the number of measurements to 1 time, and the Kd value to the value obtained using "Standard Particle 10.0 μm" (manufactured by Beckman Coulter, Inc.). By pressing the measurement button for the threshold / noise level, the threshold and noise level are automatically set. Also, set the current to 1,600 μA, the gain to 2, the electrolyte to ISOTON II, and check the flash of the aperture tube after the measurement. In the "Conversion Setting Screen from Pulse to Particle Size" of the dedicated software, set the bin interval 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. (1) Pour about 200 mL of the electrolytic aqueous solution into a 250 mL round-bottom glass beaker dedicated to Multisizer 3, set it on the sample stand, and stir with a stirrer rod counterclockwise at 24 revolutions per second. Then, use the "Flash of Aperture Tube" function of the dedicated software to remove dirt and bubbles in the aperture tube.

[0070] (1) Place about 200 mL of the electrolytic aqueous solution in a 250 mL round-bottom glass beaker dedicated to Multisizer 3, set it on the sample stand, and stir with a stirrer rod counterclockwise at 24 revolutions per second. Then, use the "Flash of Aperture Tube" function of the dedicated software to remove dirt and bubbles in the aperture tube. (2) Put about 30 mL of the electrolytic aqueous solution into a 100 mL flat-bottomed beaker made of glass, and add about 0.3 mL of the following diluent as a dispersant thereto. · Diluent: A diluent obtained by diluting "Contaminon N" (a neutral detergent for precision measuring instrument cleaning with a pH of 7, composed of a nonionic surfactant, an anionic surfactant, and an organic builder, a 10% by mass aqueous solution manufactured by Wako Pure Chemical Industries, Ltd.) three times by mass with ion-exchanged water (3) Put a predetermined amount of ion-exchanged water into the water tank of the following ultrasonic disperser that incorporates two oscillators with an oscillation frequency of 50 kHz and a 180-degree phase shift, and an electrical output of 120 W, and add about 2 mL of the Contaminon N to this water tank. · Ultrasonic disperser: "Ultrasonic Dispersion System Tetora150" (manufactured by Nikkaki Bios Co., Ltd.) (4) Set the beaker of (2) in the beaker fixing hole of the ultrasonic disperser and operate the ultrasonic disperser. Then, adjust the height position of the beaker so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized. (5) While irradiating the electrolytic aqueous solution in the beaker of (4) with ultrasonic waves, add about 10 mg of toner little by little to the electrolytic aqueous solution and disperse it. Then, continue the ultrasonic dispersion treatment for another 60 seconds. In ultrasonic dispersion, appropriately adjust so that the water temperature in the water tank is 15°C or higher and 40°C or lower. (6) Drop the electrolytic aqueous solution of (5) in which the toner is dispersed into the round-bottomed beaker of (1) installed in the sample stand using a pipette, and adjust so that the measured concentration becomes about 5%. Then, perform the measurement until the number of measured particles reaches 50,000. (7) Analyze the measurement data using the dedicated software attached to the device to calculate the weight average particle diameter (D4). Note that when set to graph / volume% in the dedicated software, the "average diameter" on the analysis / volume statistical value (arithmetic mean) screen is the weight average particle diameter (D4).

Example

[0071] Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited by the following examples. Note that, unless otherwise specified, the amounts in the examples and comparative examples are all based on mass.

[0072] (Production of Polyester Resin 1) Into a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet tube, dehydrating tube, and decompression device, 100.0 parts of terephthalic acid, 3.3 parts of trimellitic anhydride, 17.1 parts of ethylene glycol, 48.4 parts of isosorbide, and 7.0 parts of bisphenol A ethylene oxide 5-mol adduct were added, and the mixture was heated to 130 °C with stirring.

[0073] After adding 0.3 part of titanium(IV) isopropoxide as an esterification catalyst to 100 parts of the total amount of the above monomer components, the temperature was raised to 235 °C over 1 hour under a nitrogen gas stream and reacted for 3 hours. Then, while reducing the pressure inside the reaction vessel to 10.0 mmHg, the reaction was continued until the desired molecular weight was obtained to obtain Polyester Resin 1. The reaction was terminated when the required molecular weight was reached to obtain Polyester Resin 1. The weight-average molecular weight Mw of Polyester Resin 1 was 50,000. The reaction was terminated when the required molecular weight was reached to obtain Polyester Resin 1. The weight-average molecular weight Mw of Polyester Resin 1 was 50,000.

[0074] (Preparation of Polyester Resin Particle Dispersion 1) · Polyester Resin 1: 100 parts · Methyl ethyl ketone: 60 parts · Isopropyl alcohol: 10 parts Into a reaction vessel equipped with a stirrer, the above components were added and dissolved at 60 °C. After confirming the dissolution and cooling the reaction vessel to 35 °C, 3.5 parts of a 10% aqueous ammonia solution was added. Then, 300 parts of ion-exchanged water was added dropwise into the reaction vessel over 3 hours to prepare a polyester resin particle dispersion. Next, methyl ethyl ketone and isopropyl alcohol were removed with an evaporator to obtain Polyester Resin Particle Dispersion 1.

[0075] (Synthesis of Polyester Resin 2) · Fumaric acid: 100.0 parts · 4.4 parts of trimellitic anhydride · Bisphenol A ethylene oxide 5 mol adduct: 37.9 parts · Bisphenol A propylene oxide 5 mol adduct: 36.3 parts A polyester resin 2 was obtained in the same manner as polyester resin 1, except that the monomer components were the above monomers. The weight average molecular weight Mw of the obtained polyester resin 2 was 44000.

[0076] (Preparation of polyester resin particle dispersion 2) A polyester resin particle dispersion 2 was prepared in the same manner as polyester resin particle dispersion 1, except that the polyester resin used was polyester resin 2.

[0077] (Preparation of styrene-acrylic resin particle dispersion) · Styrene: 126 parts · n-Butyl acrylate: 14 parts · Anionic surfactant (sodium dodecylbenzenesulfonate): 4 parts · Ion-exchanged water: 59.2 parts The above components were put into a container and emulsified using a homogenizer to prepare a monomer emulsion A.

[0078] · Ion-exchanged water: 133 parts · Anionic surfactant (sodium dodecylbenzenesulfonate): 0.6 part On the other hand, the above components were put into a polymerization reaction vessel, a reflux pipe was installed, and while injecting nitrogen, it was slowly stirred, and the polymerization flask was heated to 75 °C with a water bath and held. 10 parts of the above monomer emulsion A was dropped into this container using a metering pump over 10 minutes.

[0079] Next, 1.05 parts of ammonium persulfate was dissolved in 10 parts of ion-exchanged water, and the solution was dropped into a polymerization flask using a metering pump over 10 minutes. Stirring was continued for 1 hour in this state. Further, the remaining monomer emulsion A was dropped using a metering pump over 2 hours. After all additions were completed, stirring was continued for another 3 hours to obtain a styrene-acrylic resin particle dispersion.

[0080] (Preparation of Wax Particle Dispersion) · Hydrocarbon wax (manufactured by Nippon Seiro Co., Ltd., trade 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 wax was dissolved at an internal liquid temperature of 120°C using a pressure discharge type homogenizer (manufactured by Gorin Co., Gorin homogenizer), followed by dispersion treatment at a dispersion pressure of 5 MPa for 120 minutes and then at 40 MPa for 360 minutes, and then cooled to obtain a wax particle dispersion. The volume average particle diameter D50v of the particles in this wax particle dispersion was 220 nm. Thereafter, ion-exchanged water was added to adjust the solid content concentration to 20.0%.

[0081] (Preparation of Black Colorant Dispersion) · Carbon black (manufactured by Cabot Japan Ltd., REGAL330): 200 parts · Anionic surfactant (sodium dodecylbenzenesulfonate): 13 parts · Ion-exchanged water: 750 parts When all the above components were put into a stainless steel container with a size such that the liquid level height became 1 / 3 of the container height, the above components were put in and stirred using a stirrer until there was no undissolved pigment, and defoamed. After defoaming, it was dispersed at 5,000 rpm for 10 minutes using a homogenizer (manufactured by IKA Co., Ultra Turrax T50), and then stirred with a stirrer for 1 day and night to defoam. After defoaming, it was dispersed again at 6,000 rpm for 10 minutes using a homogenizer, and then stirred with a stirrer for 1 day and night to defoam. Subsequently, it was dispersed at a pressure of 240 MPa using a high-pressure impact disperser, Altimizer (manufactured by Sugino Machine Ltd., HJP30006). The dispersion was carried out for the equivalent of 25 passes, calculated from the total charged amount and the processing capacity of the apparatus. The obtained dispersion was left standing for 72 hours to remove the precipitate, and ion-exchanged water was added to adjust the solid content concentration to 15%, obtaining a black colorant dispersion. The volume average particle size D50v of the particles in this colorant dispersion was 110 nm.

[0082] <Manufacture of Toner 1> (Manufacture of Toner Particles 1) · 450.0 parts of polyester resin particle dispersion 1 · 50.0 parts of styrene-acrylic resin particle dispersion · 50.0 parts of black colorant (Black) dispersion · 50.0 parts of wax particle dispersion · 5.0 parts of sodium dodecylbenzenesulfonate · 0.4 part of dodecyl alcohol A polyester resin particle dispersion, a styrene-acrylic resin particle dispersion, a wax particle dispersion, and sodium dodecylbenzenesulfonate were charged into a reactor (1-liter flask with baffles and anchor blades) and mixed uniformly. On the other hand, the black colorant dispersion was uniformly mixed in a 500 mL beaker, and this was gradually added to the reactor while stirring to obtain a mixed dispersion. While stirring the obtained mixed dispersion, an aqueous aluminum sulfate solution was dropped as 0.5 part by solid content to form aggregated particles.

[0083] After the dropping was completed, the inside of the system was purged with nitrogen and held at 50 °C for 1 hour and then at 55 °C for 1 hour. Then, the temperature was raised and held at 90 °C for 30 minutes. Then, after cooling to 63 °C, it was held for 3 hours to form fused particles. After the predetermined time ended, it was cooled at a cooling rate of 0.5 °C per minute until it reached 40 °C. After cooling, it was filtered, washed with water, and dried to obtain toner particles 1 with a weight average particle size (D4) of 6.5 μm.

[0084] (Manufacture of Toner 1) To 100 parts of the toner particles 1 obtained above, 1.5 parts of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) was added, and using a Mitsui Henschel mixer (manufactured by Mitsui Miike Chemical Machinery Co., Ltd.) it was mixed. Thereafter, it was sieved with a vibrating sieve having an aperture of 45 μm to prepare Toner 1. The physical properties etc. of the obtained Toner 1 are shown in Table 1.

[0085] <Manufacture of Toners 2 to 22> Toners 2 to 22 were obtained by the same manufacturing method as Toner 1, except that the types and amounts of the polyester resin particle dispersion, styrene-acrylic resin particle dispersion, anionic surfactant, and monohydric aliphatic alcohol were changed so as to have the physical properties shown in Table 1 for the obtained toner. The amount of the anionic surfactant was adjusted by the addition amount of the anionic surfactant when mixing the respective dispersions in the manufacture of the toner particles.

[0086] <Reference Example> A reference example toner was prepared by tracing the example of JP-A-2005-107089 (black toner Bk6). When the amount of monohydric aliphatic alcohol by the headspace method disclosed in JP-A-2005-107089 was measured for the reference example toner, octyl alcohol derived from the hydrolysis of n-octyl-3-mercaptopropionate as a chain transfer agent was detected at 300 ppm, but it was 10 ppm when measured by the ethanol extraction method of the present disclosure.

[0087]

Table 1-1

[0088]

Table 1-2

[0089] <Image evaluation> The image evaluation was carried out by partially modifying a commercially available color laser printer HP LaserJet Enterprise Color M553dn. By this modification, it was made to operate even when only a single-color process cartridge was installed. Also, the temperature of the fuser was modified so that it could be changed to an arbitrary temperature. The toner contained in the process cartridge for black toner installed in this color laser printer was removed, the inside was cleaned with an air blower, and then each toner (350 g) was introduced into the process cartridge. The process cartridge with the replaced toner was installed in the color laser printer, and the following image evaluation was carried out. The specific image evaluation items are as follows.

[0090] 〔Density unevenness〕 The evaluation was carried out before endurance printing (initial) and after the following endurance printing. In a high-temperature and high-humidity environment (temperature 32°C / humidity 85%RH), after printing 30,000 images with an initial and 0.5% printing rate with a horizontal line, the image shown in Figure 2 was printed, and the difference in image density between the printed part and the solid part downstream of the non-printed part was evaluated. For measuring the image density, "Macbeth Reflection Densitometer RD918" (manufactured by Macbeth) was used to measure the relative density with respect to the printed-out image of the white background part with a manuscript density of 0.00. The transfer material used was ordinary paper of LETTER size (XEROX 4200, manufactured by XEROX, 75 g / m 2 ). (Evaluation criteria) A: Difference in image density less than 0.05 B: Difference in image density 0.05 or more and less than 0.10 C: Difference in image density is 0.10 or more and less than 0.20 D: Difference in image density is 0.20 or more

[0091] 〔Fogging〕 Under high temperature and high humidity environment (temperature 32 °C / humidity 85% RH), after printing out 30,000 images with a printing rate of 0.5% marked by a horizontal line, the reflectance (%) of the first (initial) durable printed image and the non-image part after durable printing was measured with a "REFLECTOMETER MODEL TC-6DS" (manufactured by Tokyo Denshoku Co., Ltd.). The obtained reflectance was evaluated using the value (fogging value) (%) obtained by subtracting the reflectance (%) of the unused printout paper (standard paper) measured in the same manner. The smaller the value, the more the image fogging is suppressed. The evaluation was carried out in the glossy paper mode using plain paper (HP Brochure Paper 200g / m 2 , Glossy, manufactured by HP, 200g / m 2 ) (Evaluation criteria) A: Fogging value is less than 0.5% B: Fogging value is 0.5% or more and less than 1.5% C: Fogging value is 1.5% or more and less than 3.0% D: Fogging value is 3.0% or more

[0092] 〔Fixing property〕 A solid image (toner loading amount: 0.9mg / cm 2 ) was printed on the transfer material while changing the fixing temperature, and it was evaluated according to the following criteria based on the lowest temperature at which no offset occurred. The fixing temperature is the value measured using a non-contact thermometer on the surface of the fixing roller. The transfer material used was plain paper of LETTER size (XEROX 4200, manufactured by XEROX, 75g / m 2 ) (Evaluation criteria) A: No offset at 140 °C B: Offset occurs at 140 °C or more and less than 150 °C C: Offset occurs at 150 °C or more and less than 160 °C D: Offset occurs at 160 °C

[0093] 〔Blocking (storage stability)〕 5 g of each toner was placed in a 50 mL resin cup and left for 3 days at a temperature of 60°C and a humidity of 10% RH, and the presence or absence of agglomerates was examined and evaluated according to the following criteria. (Evaluation Criteria) A: No agglomerates were generated. B: Slight agglomerates were generated and collapsed when gently pressed with a finger. C: Agglomerates were generated and did not collapse even when gently pressed with a finger. D: Completely agglomerated.

[0094] 〔Examples 1 to 16〕 In Examples 1 to 16, the above evaluation was performed using Toners 1 to 16 as toners, respectively. The evaluation results are shown in Table 2.

[0095] 〔Comparative Examples 1 to 6〕 In Comparative Examples 1 to 6, the above evaluation was performed using Toners 17 to 22 as toners, respectively. The evaluation results are shown in Table 2.

[0096]

Table 2

Explanation of Symbols

[0097] 10: Electrostatic latent image carrier, 11: Charging roller, 14: Toner carrier, 15: Toner supply member, 16: Regulation blade, 17: Toner, 13: Toner container, 25: Stirring section

Claims

1. A toner having toner particles containing a binder resin, wherein the toner particles have a monohydric aliphatic alcohol and an anionic surfactant having an alkyl group, the binder resin includes a polyester resin, the monohydric aliphatic alcohol has 8 to 18 carbon atoms, the content ratio of the monohydric aliphatic alcohol extracted from the toner with ethanol is 30 ppm by mass or more and 300 ppm by mass or less in the toner, and a value (molar ratio) of a ratio of the monohydric aliphatic alcohol extracted from the toner with ethanol to the anionic surfactant having an alkyl group extracted from the toner with methanol is 0.01 or more and 0.60 or less. The toner is characterized by this.

2. The toner according to claim 1, wherein a content ratio of the polyester resin in the binder resin is 50% by mass or more.

3. The toner according to claim 1 or 2, wherein the anionic surfactant having an alkyl group is represented by the following formula (A). R-X-SO ３ － Na ＋ ... (A) (In formula (A), R is an alkyl group having 8 to 18 carbon atoms. X is a single bond, -O-, a phenylene group, or -(OCH ２ CH ２ ), where n = 2 to 10.) ｎ -.)

4. The toner according to any one of claims 1 to 3, wherein the anionic surfactant having an alkyl group contains sodium linear alkylbenzene sulfonate.

5. The toner according to claim 4, wherein a difference between the number of carbon atoms of the monohydric aliphatic alcohol and the number of carbon atoms of the alkyl group of the sodium linear alkylbenzene sulfonate is 3 or less.

6. The polyester resin contains a monomer unit represented by the following formula (1), and the toner according to any one of claims 1 to 5, wherein a content ratio of the monomer unit represented by the formula (1) in the polyester resin is 5.0% by mass or less. (In formula (1), R １ and R ２ are each independently an ethylene group or a propylene group, x and y are each 0 to 8, and the sum value of x and y is 0 or more and 16 or less.)

7. The toner according to any one of claims 1 to 6, wherein the monohydric aliphatic alcohol has 10 to 16 carbon atoms.

8. The toner according to any one of claims 1 to 7, wherein the content ratio of the monohydric aliphatic alcohol extracted from the toner with ethanol is 40 ppm by mass or more and 270 ppm by mass or less in the toner.

9. The toner according to any one of claims 1 to 8, wherein a value (molar ratio) of a ratio of the monohydric aliphatic alcohol extracted from the toner with ethanol to the anionic surfactant having an alkyl group extracted from the toner with methanol is 0.02 or more and 0.45 or less. ner.

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