toner

Abstract

This invention relates to toners. A toner comprises toner particles containing a binder resin and an external additive, wherein the toner particles further comprise a monoaliphatic alcohol having 8 to 18 carbon atoms, the monoaliphatic alcohol extracted from the toner with ethanol having a content of 30 to 300 ppm by mass in the toner, and the external additive comprises at least one selected from the group consisting of hydrotalcite particles and alumina particles.

Description

Technical Field

[0001] This disclosure relates to toners applicable to electrophotographic, electrostatic recording, and toner spraying recording methods. Background Technology

[0002] In recent years, the demand for further improvements in the performance of electrophotographic image forming equipment has been increasing, as has the requirement for further improvements in various properties of toners. From the perspective of image quality, the diversification of usage environments has increased the need to maintain image quality at a certain level over long periods in any environment (suppression of environment-dependent image quality). For example, in high-temperature and high-humidity environments, degradation of charge-carrying properties due to moisture adsorption and fusion tendencies due to wax or oil migration become problems. In low-temperature and low-humidity environments, reduced fluidity due to toner over-charge-up and uneven image density due to charge inhomogeneity tend to become problems.

[0003] Previously, charging agents such as microcarriers were used as external additives to improve the charging performance under high temperature and high humidity environments. However, simply increasing the charge of the toner can easily lead to various problems such as over-charging under low temperature and low humidity environments. Therefore, by controlling the characteristics of the toner matrix and external additives, the environmental dependence of image quality has been suppressed.

[0004] Japanese Patent Application Publication No. 2000-035692 proposes a method to suppress charge reduction under high temperature and high humidity environments by adding hydrotalcite as an external additive. In Japanese Patent Application Publication No. 2020-056914, the dielectric loss tangent is controlled by adding a magnetic material to the toner particles, and electrostatic displacement under low temperature and low humidity environments is suppressed. Summary of the Invention

[0005] Japanese Patent Application Publication No. 2000-035692 describes a toner that suppresses fogging under high temperature and high humidity conditions. However, charge increase is a problem, and under high temperature and high humidity conditions, the density at the image front tends to decrease. Furthermore, under low temperature and low humidity conditions, over-charge and ghosting are prone to occur.

[0006] Meanwhile, the toner described in Japanese Patent Application Publication No. 2020-056914 suppresses fogging by inhibiting overcharging, which tends to be a problem in low-temperature and low-humidity environments. However, in high-temperature and high-humidity environments, fogging is prone to occur due to insufficient charging, and there is room for improvement in the dependence of image quality on the environment.

[0007] This disclosure provides a toner that solves the above-mentioned problems. Specifically, the present invention provides a toner that can suppress uneven concentration, fogging, and fusion during long-term use in high temperature and high humidity environments, and can suppress ghosting in low temperature and low humidity environments.

[0008] This disclosure relates to a toner comprising:

[0009] Toner particles containing binder resin, and

[0010] External additives, among which

[0011] The colorant particles also contain monoaliphatic alcohols.

[0012] Monoaliphatic alcohols have 8 to 18 carbon atoms.

[0013] The content of monohydric aliphatic alcohols extracted from the toner using ethanol is 30 to 300 ppm by mass in the toner, and

[0014] The external additives include at least one selected from the group consisting of hydrotalcite particles and alumina particles.

[0015] According to this disclosure, a toner can be provided that can suppress uneven concentration, fogging, and fusion during long-term use in high temperature and high humidity environments, and can suppress ghosting in low temperature and low humidity environments.

[0016] Further features of the invention will become apparent from the following description of exemplary embodiments, with reference to the accompanying drawings. Attached Figure Description

[0017] Figure 1 An example of a work function measurement curve. Detailed Implementation

[0018] In this disclosure, unless otherwise stated, the description of a numerical range as "from XX to YY" or "XX to YY" refers to a numerical range that includes both the lower and upper limits as endpoints. Furthermore, when a numerical range is described in segments, the upper and lower limits of each numerical range can be arbitrarily combined.

[0019] Typically, hydrotalcite and alumina particles have a smaller work function than toner particles and provide electrons to the toner particles. Therefore, by adding hydrotalcite or alumina particles as external additives to negatively charged toners, these particles act as microcarriers and improve the charging properties of the toners. The microcarriers provide charge and charge the toner particles upon separation. Therefore, to achieve a full effect in improving charging properties, the microcarriers need to adhere to the toner particles before charging and rapidly detach from the toner particles when charging is required.

[0020] However, when the adhesion between the microcarrier and the toner particles is weakened to achieve the aforementioned effects, the charge-converting effect during dissociation decreases, resulting in a tendency for reduced charge-carrier properties in the initial stages of use. Furthermore, the microcarrier separates from the toner particles during long-term use, and the charge-carrier properties tend to change during the usage period.

[0021] Meanwhile, when the microcarriers are firmly adhered to the toner particles to improve the initial charge rise and charge changes due to durable use, the microcarriers are unlikely to dissociate from the toner particles when charge is required, and the charge-carrying performance may be reduced.

[0022] Furthermore, when the amount of microcarrier added is increased to further impart charging properties, it exhibits a greater effect in environments where charging properties tend to decrease, such as high temperature and high humidity environments. Conversely, in environments where charging properties tend to be high, such as low temperature and low humidity environments, over-charging is likely to occur, potentially leading to image defects such as ghosting. Therefore, maintaining good charging properties over a long period, regardless of the operating environment, is a significant challenge.

[0023] As a result of repeated research, the inventors have discovered that the above-mentioned problems can be solved by adding a monohydric aliphatic alcohol to the colorant, controlling the amount and number of carbon atoms of the monohydric aliphatic alcohol within a certain range, and externally adding hydrotalcite particles or alumina particles. Specifically, it has been found that the above-mentioned problems can be solved by the following colorants.

[0024] A toner comprising:

[0025] Toner particles containing binder resin, and

[0026] External additives, among which

[0027] The colorant particles also contain monoaliphatic alcohols.

[0028] Monoaliphatic alcohols have 8 to 18 carbon atoms.

[0029] The content of monohydric aliphatic alcohols extracted from the toner using ethanol is 30 to 300 ppm by mass in the toner, and

[0030] The external additives include at least one selected from the group consisting of hydrotalcite particles and alumina particles.

[0031] By adding a monohydric aliphatic alcohol to the toner, controlling the amount and carbon number of the alcohol within a certain range, and externally adding hydrotalcite or alumina particles, good charging properties can be maintained for a long time regardless of the usage environment. Specifically, the interaction between the alcohol and the hydrotalcite or alumina particles can appropriately increase the adhesion between the hydrotalcite or alumina particles and the toner particles, and enable a large charging effect upon dissociation. In addition, the alcohol facilitates charge transfer on the toner surface and can suppress excessive charging. Furthermore, by controlling the amount of alcohol added within a certain range, alcohol migration and fusion can be suppressed during durable use.

[0032] The monohydric aliphatic alcohol has 8 to 18 carbon atoms, preferably 10 to 16, and more preferably 12 to 14. When the number of carbon atoms is less than 8, the alcohol migrates to the surface of the toner particles, resulting in fogging and uneven concentration due to poor charging. Furthermore, prolonged use leads to fusion with the sleeve and developing roller. When the number of carbon atoms is greater than 18, the dispersibility of the alcohol in the toner particles decreases, and alcohol forms domains. As a result, the interaction between the hydrotalcite or alumina particles and the alcohol becomes uneven, the charging properties decrease, and the charge distribution broadens.

[0033] The content of monoaliphatic alcohols extracted from the colorant by ethanol is 30 to 300 ppm by mass, preferably 70 to 250 ppm by mass, and more preferably 110 to 200 ppm by mass.

[0034] When the content of monohydric aliphatic alcohols is less than 30 ppm by mass, the interaction between them and the hydrotalcite or alumina particles is weak, and the adhesion between the toner particles and the hydrotalcite or alumina particles decreases. As a result, the charge rise of the toner is delayed, and initial concentration inhomogeneity and fogging occur under high temperature and high humidity conditions.

[0035] When the content of monoaliphatic alcohols exceeds 300 ppm by mass, the monoaliphatic alcohols migrate to the surface of the toner particles and fuse after prolonged use. Furthermore, the interaction between the monoaliphatic alcohols and the hydrotalcite or alumina particles becomes stronger, and the adhesion between the toner particles and the hydrotalcite or alumina particles becomes excessive. As a result, uneven initial concentration and fogging occur under high temperature and humidity conditions.

[0036] The external additive is at least one selected from the group consisting of hydrotalcite particles and alumina particles. Hydrotalcite and alumina particles have low work functions and high positive charge properties. Therefore, by using such particles as external additives, the negative charge properties of the toner can be improved. Furthermore, hydrotalcite and alumina particles readily adsorb onto the hydroxyl groups of alcohols. As a result, the external additive can interact with the alcohols in the toner particles to appropriately improve adhesion, and the charge properties can be easily controlled.

[0037] The average number of major diameters of at least one of the selected materials, consisting of hydrotalcite particles and alumina particles, is preferably 60–820 nm, more preferably 300–500 nm. When the average number of major diameters is within the above range, the toner particles and hydrotalcite particles or alumina particles adhere appropriately to each other, and the charge-enhancing effect of the microcarrier is easily obtained. As a result, initial concentration inhomogeneity and fogging under high temperature and high humidity conditions can be further suppressed. The average number of major diameters of the hydrotalcite particles can be controlled by changing the proportion and type of compounds added during synthesis. Furthermore, the average number of major diameters of the alumina particles can be controlled by changing the reaction temperature and reaction time.

[0038] The total amount of hydrotalcite particles and alumina particles relative to 100 parts by weight of toner particles is preferably 0.02 parts by weight or more, more preferably 0.03 parts by weight or more, even more preferably 0.05 parts by weight or more, and even more preferably 0.15 parts by weight or more. When the amount of hydrotalcite particles and alumina particles added is within this range, the toner can exert sufficiently improved charging properties, and fogging and initial concentration unevenness under high temperature and high humidity environments can be further suppressed.

[0039] The total amount of hydrotalcite particles and alumina particles relative to 100 parts by weight of toner particles is preferably 1.00 parts by weight or less, more preferably 0.80 parts by weight or less, even more preferably 0.50 parts by weight or less, and even more preferably 0.30 parts by weight or less. When the amount of hydrotalcite particles and alumina particles is within this range, excessive charging under low temperature and low humidity conditions can be suppressed, and ghosting can be further suppressed.

[0040] The binder resin preferably includes a styrene-acrylic resin. The content of the styrene-acrylic resin in the colorant is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 75% by mass or more. There is no particular upper limit, but it is preferably 90% by mass or less, more preferably 85% by mass or less. When the content of the styrene-acrylic resin is within the above range, the dispersibility of the alcohol in the binder resin can be easily controlled, and the interaction between the hydrotalcite particles or alumina particles and the alcohol can be further enhanced.

[0041] When the work function of the toner particles is represented by Wa and the work function of the hydrotalcite particles or alumina particles is represented by Wb, it is preferable that Wa-Wb satisfies the relationship of equation (1). More preferably, it satisfies the relationship of equation (1').

[0042] 0.05eV <Wa-Wb<0.50eV (1)

[0043] 0.10eV <Wa-Wb<0.30eV (1')

[0044] When Wa-Wb is greater than 0.05 eV, the charging performance is improved, and fogging in high-temperature and high-humidity environments can be further suppressed. Furthermore, when Wa-Wb is less than 0.50 eV, overcharging in low-temperature and low-humidity environments can be suppressed, and ghosting can be further suppressed. The work function of the toner particles can be controlled by changing the type of charge control agent or pigment used. For example, the work function Wa of the toner particles is preferably 5.25–5.70 eV, more preferably 5.40–5.60 eV.

[0045] Preferably, the external additive includes an external additive C that is different from the hydrotalcite particles and alumina particles. When the work function of the external additive C is represented by Wc, it is preferred that Wa, Wb and Wc satisfy the relationship of the following equation (2).

[0046] Wb <Wa<Wc(2)

[0047] When Wa, Wb, and Wc satisfy the relationship of equation (2), charge transfer on the surface of the toner becomes smoother, and ghosting under low temperature and low humidity conditions can be further suppressed. When the external additive C is, for example, silica, the work function of the external additive C can be controlled by changing the type of surface treatment agent.

[0048] At least one of the following is selected from the group consisting of hydrotalcite particles and alumina particles, preferably hydrotalcite particles. That is, the external additive preferably contains hydrotalcite particles. Hydrotalcite particles have a stronger interaction with alcohols and are more likely to improve the charge properties of the toner.

[0049] The average sphericity of the toner is preferably 0.97 or higher, more preferably 0.98 or higher. There is no particular limit to the upper limit, but it is preferably 1.00 to 0.99. When the average sphericity of the toner is within the above range, the hydrotalcite particles or alumina particles can easily and uniformly adhere to the surface of the toner particles, and the charge of the toner can easily become more uniform.

[0050] Hydrotalcite particles

[0051] The hydrotalcite particles will be described in detail. There are no particular limitations on the hydrotalcite particles, as long as the desired properties are achieved. The hydrotalcite particles preferably contain Al and Mg. Preferably, the hydrotalcite particles can be represented by the following formula (A) and have a positively charged base layer (in formula (A) [M...]). 2+ 1-x M 3+ x (OH) - 2]) and the negatively charged intermediate layer ([x / nA in formula (A)) n- Layered inorganic compounds (mH2O)

[0052] [M 2+ 1-x M 3+ x (OH) - 2][x / nA n- [·mH2O](A)

[0053] In formula (A), the divalent metal ion M 2+ Examples include Mg, Zn, Ca, Ba, Ni, Sr, Cu, and Fe, and trivalent metal ions M. 3+ Examples include Al, B, Ga, Fe, Co, and In. Divalent metal ions M 2+ and trivalent metal ions M 3+ It can form solid solutions containing a variety of different elements, and in addition to these metal ions, it can also contain trace amounts of monovalent metal ions. A n- This represents an n-valent anion, such as CO3. 2- OH - Cl - I - F - ,Br - SO4 2- HCO3 2- CH3COO - NO3 - And so on, and there can be a single such anion or multiple such anions. The integer "m" in equation (A) satisfies m≥0.

[0054] Compounds included in formula (A) can be exemplified as [Mg 2+ 0.750 Al 3+ 0.250 (OH) - 2.000 ][0.125CO3 2- ·0.500H2O].

[0055] From the perspective of charge-conferring ability, hydrotalcite particles preferably contain Mg. 2+ As a divalent metal ion M 2+ And preferably containing Al 3+ As a trivalent metal ion M 3+ Furthermore, from the viewpoint of imparting charged properties to toner particles, CO32-, as an n-valent anion, 2- and Cl - It is the preferred option.

[0056] To impart hydrophobicity and control charge properties, hydrotalcite particles can be treated with surface treatment agents. However, from the viewpoint of maintaining the strong positive effect of the high charge imparting effect on hydrotalcite particles, untreated hydrotalcite particles are preferred. When using surface treatment agents, higher fatty acids, coupling agents, esters, and oils such as silicone oils can be used.

[0057] For surface treating hydrotalcite particles with a surface treatment agent, known methods can be used. For example, the surface treatment agent can be dissolved and mixed in a solvent, or it can be melted by heating and then wet-mixed with the untreated hydrotalcite particles. Alternatively, methods for mechanically drying and mixing the micronized surface treatment agent and hydrotalcite particles can be mentioned. After surface treatment, appropriate methods such as washing, dehydration, drying, pulverizing, and grading can be selected to obtain the surface-treated hydrotalcite particles.

[0058] The work function of the hydrotalcite particles is preferably 4.95–5.40 eV, more preferably 5.10–5.30 eV. When the work function of the hydrotalcite particles is within the above range, it becomes easier to obtain the effect of a charged additive that carries a negatively charged toner. The work function of the hydrotalcite particles can be adjusted by changing the type and amount of the surface treatment agent, and the amount of M in the hydrotalcite particles. 2+ and M 3+ The types and proportions of these substances, as well as the types of n-valent anions, are controlled.

[0059] Alumina particles

[0060] Next, alumina particles will be described in detail. There are no particular limitations on the alumina particles, as long as the desired properties are achieved. Well-known methods can be used to produce alumina particles. For example, the Bayer process, underwater spark discharge process, aluminum alum pyrolysis process, aluminum ammonium carbonate pyrolysis process, methods for sintering hydrated alumina obtained by hydrolyzing aluminum alkoxides, and chemical vapor deposition (CVD) can be mentioned. Among these, alumina particles produced by CVD are preferred because such particles have a polyhedral shape and tend to have a uniform particle size distribution.

[0061] To impart hydrophobicity and control charge properties, alumina particles can be treated with surface treatment agents. However, from the viewpoint of maintaining the strong positive effect of imparting high charge to the alumina particles, it is preferable to use untreated alumina particles. When using surface treatment agents, hydrophobic oils, coupling agents, and hydrophobic resins are preferred. Among these, siloxane-based oils, coupling agents, and organic acid-based resins are preferred. Examples of suitable oils include silicone oils such as dimethylpolysiloxane and methylhydrosiloxane, paraffin wax, and mineral oil. Surface treatment of alumina particles using these hydrophobic agents can be carried out by known methods.

[0062] The work function of the alumina particles is preferably 4.95–5.40 eV, more preferably 5.10–5.30 eV. When the work function of the alumina particles is within the above range, it becomes easier to obtain the effect of a charged additive that carries a negatively charged toner. The work function of the alumina particles can be controlled by changing the type and amount of the surface treatment agent and the crystal structure of the alumina particles.

[0063] The raw materials used for toner granules will be described below. Toner granules contain a binder resin. The following polymers, etc., can be used as binder resins for toner granules.

[0064] Homopolymers of styrene and its substituted products, such as polystyrene, poly(p-chlorostyrene), and polyvinyl toluene; styrene-based copolymers such as styrene-p-chlorostyrene copolymer, styrene-vinyl toluene copolymer, styrene-vinyl naphthalene copolymer, styrene-acrylate copolymer, and styrene-methacrylate copolymer; polyvinyl chloride, phenolic resin, natural resin-modified phenolic resin, natural resin-modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyethylene resin, and polypropylene resin, etc.

[0065] From the viewpoints of developing performance, fixing performance, and compatibility with monoaliphatic alcohols, it is preferable that the main component of the binder resin is a styrene copolymer, which is a copolymer of styrene and other vinyl monomers. More preferably, the main component is a styrene-acrylic resin.

[0066] The toner particles contain monoaliphatic alcohols. Monoaliphatic alcohols include straight-chain and branched-chain aliphatic alcohols, which can be used alone or in combination of two or more. Examples of monoaliphatic alcohols with 8 to 18 carbon atoms include octanol, decanol, dodecylol, lauryl alcohol, myristyl alcohol, cetyl alcohol, and stearyl alcohol. Straight-chain aliphatic alcohols are preferred.

[0067] Toner particles may contain colorants. Examples of colorants include the following. Examples of black colorants include carbon black and those that are tinted to black using yellow, magenta, and cyan colorants. Pigments can also be used alone as colorants.

[0068] Examples of magenta tinting agents include the following pigments: 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, 5 7:1,58,60,63,64,68,81:1,83,87,88,89,90,112,114,122,123,146,147,150,163,184,202,206,207,209,238,269 and 282; CI Pigment Violet 19; and CI Vat Red 1,2,10,13,15,23,29 and 35. Examples of magenta tinting dyes include: oil-soluble 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; as well as 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.

[0069] Examples of pigments for cyan colorants include: CI Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16 and 17; CI Vat Blue 6; CI Acid Blue 45; and copper phthalocyanine pigments having one or more but no more than five substituted phthalimide methyl groups on the phthalocyanine skeleton. CI Solvent Blue 70 is an example of a dye for cyan colorants. Examples of pigments for yellow toners include: 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, and 185, as well as CI Vat Yellow 1, 3, and 20. CI Solvent Yellow 162 is an example of a dye for yellow toners.

[0070] These colorants can be used individually or in mixtures, and they can also be used in a solid solution state. The colorants preferably contain at least one selected from the group consisting of CI Pigment Violet 19, CI Pigment Red 122, CI Pigment Red 202, and CI Pigment Red 209. The quinacridone skeleton contained in these colorants delocalizes the charge and makes it easier to suppress fogging. The amount of colorant relative to 100.0 parts by weight of binder resin is preferably 0.1 to 30.0 parts by weight. When the amount of colorant is within the above range, it is easy to achieve a balance in terms of hue angle, saturation, brightness, lightfastness, OHP transparency, and dispersibility in the toner.

[0071] Magnetic materials can also be included in the toner particles to obtain magnetic toner particles. Examples of magnetic materials include iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel; alloys of these metals with metals such as aluminum, copper, magnesium, tin, zinc, beryllium, calcium, manganese, selenium, titanium, tungsten, and vanadium; and mixtures thereof. Surface-modified magnetic materials are preferred.

[0072] When magnetic toners are prepared by polymerization, it is preferable that the magnetic toners are used as surface modifiers to hydrophobize substances that do not inhibit polymerization. Examples of such surface modifiers include silane coupling agents and titanium coupling agents. The number average particle size of these magnetic materials is preferably 2.0 μm or less, more preferably 0.1 to 0.5 μm. The amount of magnetic material relative to 100 parts by weight of binder resin is preferably 20 to 200 parts by weight, more preferably 40 to 150 parts by weight.

[0073] The colorant particles preferably contain a release agent. Examples of release agents include waxes containing fatty acid esters as the main component, such as carnauba wax and lignite ester wax; fatty acid esters with partially or completely removed acid components, such as deoxycarnauba wax; methyl ester compounds with hydroxyl groups obtained by hydrogenation of vegetable oils; saturated fatty acid monoesters, such as stearic acid, stearic acid, and betaine; diesterization products of saturated aliphatic dicarboxylic acids and saturated aliphatic alcohols, such as dibenzyl sebacate, distearate dodecanoate, and distearate octadecanoate; diesterization products of saturated aliphatic diols and saturated fatty acids, such as nonanediol dibenzyl ester and dodecanoic acid distearate; aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides or block copolymers of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; waxes obtained by grafting vinyl monomers such as styrene and acrylic acid onto aliphatic hydrocarbon waxes; and saturated fatty acid waxes such as palmitic acid, stearic acid, and lignite acid. And straight-chain fatty acids; such as brassinolic acid, octadecyltrienoic acid, octadecyltetraenoic acid and other unsaturated fatty acids; such as stearyl alcohol, aralkyl alcohol, betaine alcohol, carbamate alcohol, wax alcohol and beeswax alcohol and other saturated alcohols; such as sorbitol and other polyols; such as linoleic acid amides, oleic acid amides and lauryl amides and other fatty acid amides and other saturated fatty acid di ...; and other saturated fatty acid diamides and other saturated fatty acid Unsaturated fatty acid amides such as ethylene dioleamide, hexamethylene dioleamide, N,N'-dioleoyl adipamide, and N,N'-dioleoyl sebacate amide; aromatic diamides such as m-xylene distearate and N,N'-distearate isophthalamide; fatty acid metal salts (generally called metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; and long-chain alkyl alcohols or long-chain alkyl carboxylic acids with 12 or more carbon atoms; etc.

[0074] The amount of release agent in the colorant granules is preferably 1.0 to 30.0% by mass, more preferably 2.0 to 25.0% by mass.

[0075] Toner particles may contain charge control agents. Examples of charge control agents that impart a negative charge to toner particles include the compounds listed below. Examples of organometallic compounds and chelating compounds include monoazo metal compounds, acetylacetone metal compounds, aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, and hydroxycarboxylic acid and dicarboxylic acid metal compounds. Additionally, this includes aromatic hydroxycarboxylic acids, aromatic monocarboxylic acids and polycarboxylic acids and their metal salts and anhydrides, such as esters and phenolic derivatives like bisphenols. Other examples include urea derivatives, metal-containing salicylic acid compounds, metal-containing naphtholic acid compounds, boron compounds, quaternary ammonium salts, and calixarenes.

[0076] Meanwhile, examples of charge control agents that impart a positive charge to the toner particles include the compounds listed below: products modified with aniline black and fatty acid metal salts; guanidine compounds; imidazole compounds; quaternary ammonium salts and analogues such as tributylbenzylammonium-1-hydroxy-4-naphthalenesulfonate, tetrabutyltetrafluoroborate, (3-acrylamidopropyl)trimethylammonium chloride; onium salts such as phosphonium salts, and their lake pigments; triphenylmethane dyes and their lake pigments (examples of fixing agents include compounds of phosphotungstic acid, phosphomolybdic acid, phosphotungstic acid, tannic acid, lauric acid, gallic acid, ferricyanide, and ferrocyanide); metal salts of higher fatty acids; and resin-based charge control agents. One of these charge control agents may be introduced alone, or a combination of two or more may be introduced. The amount of charge control agent added is preferably 0.01 to 10.0 parts by weight relative to 100 parts by weight of the binder resin or the polymerizable monomer used to produce the binder resin.

[0077] The following describes a method for producing toner granules. Known methods can be used for producing toner granules, including wet production methods such as suspension polymerization, emulsion polymerization and aggregation, or emulsion aggregation, as well as mixing and pulverizing methods. The toner granules are preferably obtained by a wet production method, and more preferably by a suspension polymerization method.

[0078] In suspension polymerization, toner particles are produced through a granulation step, which involves dispersing a polymeric monomer composition comprising a polymeric monomer capable of producing a binder resin, a monoaliphatic alcohol, and optional additives such as colorants and waxes, in an aqueous medium to form droplet particles of the polymeric monomer composition, and a polymerization step, which produces toner particles by polymerizing the polymeric monomers in the droplet particles. Preferred examples of polymeric monomers include vinyl-based polymeric monomers. Specifically, examples are given below.

[0079] Examples of monofunctional monomers include styrene; styrene derivatives such as α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and 2,4-dimethylstyrene; acrylic polymeric monomers such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and 2-ethylhexyl acrylate; methacrylic polymeric monomers such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate; and methylene aliphatic monocarboxylic acid esters such as vinyl esters, vinyl propionate, vinyl benzoate, vinyl butyrate, and vinyl formate.

[0080] The adhesive resin is preferably a styrene-acrylic resin. That is, the adhesive resin is preferably a polymer of styrene and at least one selected from the group consisting of acryloyl polymerizable monomers and methacryl polymerizable monomers.

[0081] In the emulsion aggregation method, an aqueous dispersion of fine particles, which are sufficiently small relative to the target particle size, composed of the constituent materials of the toner particles, is prepared in advance. The fine particles are then aggregated in an aqueous medium until they reach the toner particle size, and the resin is melted by heating to produce the toner.

[0082] Preferably, the emulsification aggregation method includes a dispersion step of preparing a dispersion of fine particles of the constituent material containing toner particles, an aggregation step of agglomerating the fine particles of the constituent material containing toner particles and controlling the particle size until it reaches the particle size of the toner particles to obtain aggregated particles, and a fusion step of fusing the resin contained in the obtained aggregated particles. Furthermore, if desired, it may include a subsequent cooling step, a filtration / washing step of separating the obtained toner particles and washing them with deionized water, and a step of removing moisture from the washed toner particles and drying them.

[0083] The following describes in detail, through examples, a method for producing toner granules by pulverization. In the raw material mixing step, binder resin, monoaliphatic alcohol, and, as needed, colorants, waxes, and other additives that constitute the toner granules are weighed, compounded, and mixed in specified amounts. Examples of mixing apparatus include double-cone mixers, V-type mixers, drum mixers, super mixers, FM mixers, nitrile mixers, and the MechanoHybrid (manufactured by Nippon Coke & Engineering, Ltd.).

[0084] Next, the mixture is melt-kneaded to disperse colorants and waxes in the binder resin. In the melt-kneading step, intermittent kneaders such as pressure kneaders or Banbury mixers, or continuous kneaders, can be used. Single-screw or twin-screw extruders are primarily used due to their superior performance in continuous production. Examples include the KTK twin-screw extruder (manufactured by Kobe Steel, Ltd.), the TEM twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.), the PCM kneader (manufactured by Ikegai Corp.), the twin-screw extruder (manufactured by KCK Engineering Co.), the co-kneader (manufactured by Buss AG), and the Kneadex (manufactured by Nippon Coke & Engineering Co., Ltd.). Alternatively, the kneaded product obtained from the melt-kneading can be rolled with two rollers and cooled with water in a cooling step.

[0085] Then, the cooled material of the kneaded product can be pulverized to the desired particle size in the pulverizing step. In the pulverizing step, after coarse pulverization using a pulverizer such as a grinding mill, hammer mill, or milling mill, it is further finely pulverized using, for example, a Cryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), a Super Rotor (manufactured by Nisshin Engineering Co., Ltd.), a turbo mill (manufactured by Freund-Turbo Corporation), or a micro-pulverizer based on air jet method.

[0086] Subsequently, as needed, classifiers or sieves such as the Elbow Jet inertial classification system (manufactured by Nittetsu Mining Co., Ltd.), the Turboplex centrifugal classification system (manufactured by Hosokawa Micron Corporation), the TSP separator (manufactured by Hosokawa Micron Corporation), and the Faculty (manufactured by Hosokawa Micron Corporation) are used to obtain toner particles.

[0087] Furthermore, the toner particles can be spherical. For example, after pulverization, sphericalization can be achieved using a hybrid system (manufactured by NaraMachinery Co., Ltd.), a Mechanofusion system (manufactured by Hosokawa Micron Corporation), a Faculty system (manufactured by Hosokawa Micron Corporation), or a Meteorainbow MR type system (manufactured by Nippon Pneumatic Mfg. Co., Ltd.). From the viewpoint of low-temperature fixing, the glass transition temperature (Tg) of the toner particles is preferably 40–60°C.

[0088] A toner can be obtained by externally adding at least one selected from the group consisting of hydrotalcite particles and alumina particles, along with an external additive C as needed, to the obtained toner particles and mixing them. External addition and mixing can be carried out using known methods such as a Henschel mixer.

[0089] The toner particles preferably comprise a core-shell structure, which includes a core particle and a shell on the surface of the core particle. When the toner particles comprise a core-shell structure, the durability and charge-carrying properties of the toner can be improved. The shell does not necessarily have to cover the entire core particle, and there may be portions of the core particle exposed.

[0090] The resin forming the shell of the toner particles preferably includes resins such as polyester resin and styrene-acrylic resin, with polyester resin being more preferred. Since polyester resin is readily compatible with alcohols, when the shell contains polyester resin, the monoaliphatic alcohol effectively concentrates near the surface of the toner particles, and the effect can be easily obtained by adding a small amount of alcohol.

[0091] In the cross-section of the toner observed using a transmission electron microscope, the shell preferably exists inside the cross-sectional profile of the toner particles, and the shell comprises polyester resin. The thickness of the shell is preferably 0.8–100 nm, more preferably 1–30 nm.

[0092] Durability is easily improved when the shell thickness is 0.8 nm or more. Furthermore, the polyester resin facilitates the concentration of monoaliphatic alcohols near the surface of the toner particles. Fixing performance is improved when the shell thickness is below 100 nm. Additionally, the alcohol is appropriately concentrated near the surface of the toner particles, and fusion is more easily suppressed during long-term use. The method for measuring shell thickness will be described later.

[0093] As monomers used in polyester resins, polyols (di- or ternary alcohols), polycarboxylic acids (di- or ternary carboxylic acids), their anhydrides, or their lower alkyl esters can be used.

[0094] The following polyol monomers can be used as polyol monomers for polyester resins.

[0095] Examples of diol components include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentanediol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A and bisphenols and their derivatives represented by formula (A); and diols represented by formula (B).

[0096]

[0097] (In formula (A), R represents ethylidene or propyleneide, x and y are each integers greater than or equal to 0, and the average value of x+y is 0 to 10)

[0098]

[0099] (In formula (B), R' represents -CH2CH2-, -CH2CH(CH3)-, or -CH2C(CH3).) 2- (where x and y are integers greater than or equal to 0, and the average of x + y is greater than or equal to 0 and less than 10.)

[0100] Examples of alcohol components with three or more ions include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitol, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trimethylolbenzene.

[0101] Glycerol, trimethylolpropane, and pentaerythritol are preferred ingredients. These diols and triols or higher can be used alone or in combination of two or more.

[0102] The following polycarboxylic acid monomers can be used as polycarboxylic acid monomers for use in polyester resins.

[0103] Examples of dicarboxylic acid components include maleic acid, fumaric acid, citracic acid, itaconic acid, glutaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, dodecenylsuccinic acid, isododecenylsuccinic acid, dodecylsuccinic acid, isododecylsuccinic acid, octenylsuccinic acid, octylsuccinic acid, isoctenylsuccinic acid, isooctenylsuccinic acid, isooctylsuccinic acid, the anhydrides of these acids, and their lower alkyl esters.

[0104] Among them, maleic acid, fumaric acid, terephthalic acid, and dodecenylsuccinic acid are preferred.

[0105] Examples of trivalent or higher carboxylic acids, their anhydrides, or their lower alkyl esters include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra(methylenecarboxy)methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, Empol trimeric acid, their anhydrides, or their lower alkyl esters.

[0106] 1,2,4-Benzotricarboxylic acid, namely trimellitic acid or its derivatives, is preferred because such acids are inexpensive and their reaction is easy to control.

[0107] These dicarboxylic acids and tricarboxylic acids or more can be used alone or in combination of two or more.

[0108] There are no particular limitations on the production method of polyester resin, and known methods can be used. For example, polyester resin can be produced by simultaneously adding the above-mentioned alcohol monomer and carboxylic acid monomer through esterification or transesterification and condensation reactions and then polymerizing.

[0109] As the styrene-acrylic resin for the shell, the aforementioned vinyl polymerizable monomers can be used. Furthermore, monomers with polar groups, such as acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate, are preferred. The styrene-acrylic resin for the shell is preferably a polymer selected from at least one of the group consisting of acrylic polymerizable monomers and methacrylic polymerizable monomers, or from at least one of the group consisting of monomers with polar groups and styrene.

[0110] To improve the performance of the toner, it is preferable that the external additive contains an external additive C that is different from the hydrotalcite particles and alumina particles.

[0111] External additive C can be, for example, fluorinated resin particles such as fine particles of vinylidene fluoride and fine powder of polytetrafluoroethylene; fine particles of silica such as wet silica or dry silica, fine particles of titanium dioxide and fine particles of alumina; hydrophobic fine particles obtained by surface treatment of the above fine particles with hydrophobic agents such as silane compounds, titanium coupling agents and silicone oils; oxides such as zinc oxide and tin oxide; composite oxides such as strontium titanate, barium titanate, calcium titanate, strontium zirconate and calcium zirconate; and carbonate compounds such as calcium carbonate and magnesium carbonate; etc.

[0112] The external additive C is preferably fine silica particles, and fine silica particles that are so-called dry silica or fumed silica obtained by the gas-phase oxidation of silica halide compounds are preferred.

[0113] Dry production methods, for example, utilize the pyrolysis and oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame. The basic reaction formula is as follows.

[0114] SiCl4 + 2H2 + O2 → SiO2 + 4HCl

[0115] In this production method, silicon halide compounds can also be used with other metal halide compounds such as aluminum chloride or titanium chloride to obtain composite fine particles of silicon dioxide and other metal oxides, and the silicon dioxide fine particles are also included in the composite fine particles.

[0116] Preferably, the number-average particle size of the external additive C is 3–200 nm, as this ensures high charge-carrying properties and flowability. The number-average particle size of the primary particles of the external additive C is more preferably 5–20 nm. The amount of external additive C relative to 100 parts by weight of toner particles is preferably 0.01–3.0 parts by weight, more preferably 0.5–2.0 parts by weight. When the amount of external additive C is within the above range, fixing performance can be improved while maintaining good flowability. Furthermore, the external additive C is preferably surface-treated with a hydrophobic agent. By surface-treating the external additive C, good images can be easily obtained regardless of the operating environment.

[0117] The following will explain the methods for measuring various physical properties.

[0118] Identification and Quantification of Mono-Aliphatic Alcohols in Toners

[0119] Preparation of extracted samples

[0120] Add a total of 2g of toner and 18g of ethanol, homogenize manually, and then irradiate with ultrasound for 5 minutes. The mixture is then incubated at 60°C for 24 hours, followed by incubation at room temperature for 3 days. The supernatant of the sample is then collected and filtered through a PTFE injection filter (250nm pore size); the filtrate is used for sample extraction.

[0121] GC / MS Analysis

[0122] The GC / MS instrument was a GC TRACE-1310 (manufactured by Thermo Fisher Scientific Corp.), the detector was a single quadrupole analyzer MS ISQ LT (manufactured by Thermo Fisher Scientific Corp.), and the autosampler was a TRIPLUS RSH (manufactured by Thermo Fisher Scientific Corp.). Measurements were performed under the conditions shown below.

[0123] Sample volume: 1 μL (liquid spray)

[0124] Column: HP5-MS (manufactured by Agilent Technologies, Inc.)

[0125] Length: 30m, inner diameter: 0.25mm, membrane thickness: 0.25μm

[0126] Flow split ratio: 10

[0127] Split flow rate: 15 mL / min

[0128] Inlet temperature: 250℃

[0129] Helium flow rate inside the column: 1.5 mL / min

[0130] MS ionization: EI

[0131] Column temperature conditions: Hold at 40°C for 3 minutes, then increase to 300°C at 10°C / min and hold for 10 minutes.

[0132] Ion source temperature: 250℃

[0133] Quality range: m / z 45-1000

[0134] Delivery pipeline temperature: 250℃

[0135] Creating calibration curves

[0136] Calibration curves were prepared using samples with mass-based concentrations (10 ppm, 50 ppm, 100 ppm, and 250 ppm) of monoaliphatic alcohols in ethanol solutions. These samples were measured under these conditions, and calibration curves were created from the peak area values ​​of the monoaliphatic alcohols. The extracted samples were analyzed using the obtained calibration curves, and the proportion of monoaliphatic alcohols in the toner extracted with ethanol was calculated.

[0137] The structure of monoaliphatic alcohols was determined using an FT NMR apparatus, JNM-EX400 (manufactured by JEOL Ltd.). 1 H-NMR 400MHz, CDCl3, room temperature (25℃)] (Also used 13 The extracted samples were analyzed by C-NMR and their structures were determined.

[0138] Measurement of the work function of toner particles and external additives

[0139] The work function of the toner particles and external additives was measured using the following method. The work function was quantified as the energy (eV) required to extract electrons from the substance. The work function was measured using a surface analyzer (AC-2, manufactured by Richen Keiki Co., Ltd.). In this apparatus, a deuterium lamp was used, and the determination was performed under the following conditions.

[0140] Irradiation amount: 800nW

[0141] Spectrometer: Monochromatic light

[0142] Spot size: 4 mm × 4 mm

[0143] Energy scan range: 3.6–6.2 [eV]

[0144] Anode voltage: 2910V

[0145] Measurement time: 30 seconds per point

[0146] Then, photoelectrons emitted from the sample surface are detected and arithmetically processed using work function calculation software built into the surface analyzer. The work function is measured with a repeatability (standard deviation) of 0.02 eV. When measuring powder, a unit specifically designed for powder measurement is used.

[0147] In surface analysis, when the excitation energy of monochromatic light is scanned from low to high at intervals of 0.05 eV, photon emission starts from a certain energy value [eV], and the work function [eV] is taken as the energy threshold.

[0148] Figure 1 An example of a measurement curve of the work function obtained through measurement under the above conditions is shown. Figure 1 In the diagram, the horizontal axis represents the excitation energy [eV], and the vertical axis represents the 0.5 power of the emitted photon count, Y (normalized photon yield). Generally, when the excitation energy exceeds a certain threshold, the photon emission, i.e., the normalized photon yield, increases rapidly, and the work function measurement curve rises rapidly. The rising point is defined as the photoelectric work function value [Wf]. This photoelectric work function value [Wf] is taken as the work function of the sample.

[0149] In the measurement of work function, the sample uses toner particles, hydrotalcite particles, alumina particles, or external additive C.

[0150] Regarding toner particles, toner particles obtained by removing external additives from the toner using the following methods can be used as samples.

[0151] A total of 160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) was added to 100 mL of ion-exchanged water and dissolved in a water bath to prepare a sucrose concentrate. A total of 31 g of the sucrose concentrate and 6 mL of Contaminone N (a 10% by mass aqueous solution of a neutral detergent for washing precision measuring instruments, consisting of nonionic surfactants, anionic surfactants, and organic detergent builders, with a pH of 7, manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a centrifuge tube to prepare a dispersion. 1 g of toner was added to the dispersion, and the toner clumps were loosened using a spatula or similar tool.

[0152] The centrifuge tubes were placed in a KM Shaker (model: V.SX, manufactured by Iwaki Sangyo Co., Ltd.) and shaken for 20 minutes at 350 reciprocating motions per minute. After shaking, the solution was transferred to a 50 mL glass tube with a vibrating rotor and centrifuged at 3500 rpm for 30 min. In the centrifuged glass tube, the toner particles were present on the top layer, and the external additives were present on the lower aqueous side. The toner particles on the top layer were separated. Shaking and centrifugation could be repeated as needed for complete separation.

[0153] When hydrotalcite particles or alumina particles and external additive C are available individually, they can be measured separately. When these cannot be used individually, the toner is dispersed in a solvent such as chloroform, and then the hydrotalcite particles, alumina particles, and external additive are separated according to their specific gravity by centrifugation or the like. The method is as follows.

[0154] First, 1g of toner was added to 31g of chloroform in a vial and dispersed to separate the hydrotalcite particles, alumina particles, and external additive C from the toner. For dispersion, an ultrasonic homogenizer was used for 30 minutes to prepare the dispersion. The processing conditions are as follows.

[0155] Ultrasonic processing device: VP-050 ultrasonic homogenizer (manufactured by TIETECH Co., Ltd.)

[0156] Microchip: Stepped microchip, tip diameter φ2mm

[0157] Microchip tip position: The center of the glass vial, 5mm from the bottom of the vial.

[0158] Ultrasonic conditions: intensity 30%, 30 minutes. During this time, apply ultrasound while cooling the vial with ice water to prevent the temperature of the dispersion from rising.

[0159] The dispersion was transferred to a 50 mL glass tube for use with a oscillating rotor and centrifuged (H-9R; manufactured by Kokusan Co., Ltd.) at 58.33 s. -1 Centrifuge for 30 minutes under the specified conditions. In the centrifuged glass tube, the fraction mainly composed of hydrotalcite or alumina particles and external additive C can be separated by gravity. If separation is unsuccessful, adjust the centrifugation speed and time. Dry the obtained fraction under vacuum conditions (40℃ / 24 hours) to obtain the sample.

[0160] Method for measuring the weight-average particle size (D4) of toners

[0161] The weight-average particle size (D4) of the toner was calculated as follows. Measurements were performed using a precision particle size distribution measuring device with a 100 μm inlet tube (Coulter CounterMultisizer 3 (registered trademark), manufactured by Beckman Coulter, Inc.), a fine-pore resistance method-based device, and dedicated software for setting measurement conditions and analyzing measurement data (Beckman CoulterMultisizer 3 Version 3.51, manufactured by Beckman Coulter, Inc.). Measurements were performed using 25,000 effective measurement channels, and the measurement data were then analyzed and calculated. The aqueous electrolyte solution used in the determination could be a solution such as "ISOTON II" (manufactured by Beckman Coulter) obtained by dissolving premium sodium chloride in ion-exchanged water at a concentration of approximately 1% by mass.

[0162] Before performing measurements and analysis, configure the dedicated software as follows. On the "Change Standard Measurement Method (SOM) Screen" of the dedicated software, set the total count in the control mode to 50,000 particles, the number of measurements to 1, and the Kd value to the value obtained using "Standard Particle 10.0 μm" (Beckman Coulter). Automatically set the threshold and noise level by pressing the "Threshold / Noise Level Measurement Button". Additionally, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check "Flush the port after measurement". On the "Pulse to Particle Size Conversion Setting Screen" of the dedicated software, set the element spacing to logarithmic particle size, the number of particle size elements to 256, and the particle size range to 2 μm to 60 μm. The specific measurement method is as follows.

[0163] 1. Place approximately 200 mL of electrolyte solution into a 250 mL round-bottom glass beaker specifically designed for Multisizer 3, and place the beaker on the sample stage. Rotate the stir bar counterclockwise at 24 rpm. Remove contaminants and air bubbles from the beaker by using the "Vessel Rinse" function in the dedicated software.

[0164] 2. Place approximately 30 mL of the electrolyte solution in a 100 mL flat-bottomed glass beaker. Add approximately 0.3 mL of the following diluent as a dispersant to the beaker: a diluent obtained by diluting "Contaminon N" (a 10% by mass aqueous solution of a neutral detergent for washing precision measuring instruments, consisting of a nonionic surfactant, anionic surfactant, and organic detergent builder, with a pH of 7, manufactured by Wako Pure Chemical Industries, Ltd.) three times by mass with deionized water.

[0165] 3. Prepare an ultrasonic disperser (Ultrasonic Dispersion System Tetra 150, manufactured by Nikkaki BiosCo.,Ltd.) with two built-in oscillators at a frequency of 50kHz, a phase shift of 180 degrees, and a power output of 120W. Place a predetermined amount of ion-exchanged water into the water tank of the ultrasonic dispersion system, and add approximately 2 mL of Contaminon N to the water tank.

[0166] 4. Place the beaker from step (2) into the beaker fixing hole of the ultrasonic disperser and start the ultrasonic disperser. Adjust the height of the beaker to maximize the resonance state of the electrolyte aqueous solution surface in the beaker.

[0167] 5. While irradiating the electrolyte solution in the beaker mentioned in section (4) with ultrasound, add approximately 10 mg of toner little by little to the electrolyte solution and disperse it therein. Then, continue the ultrasonic dispersion treatment for another 60 seconds. When performing ultrasonic dispersion, adjust the temperature in the water bath appropriately to a temperature between 10°C and 40°C.

[0168] 6. Using a pipette, dropwise add the electrolyte aqueous solution containing the toner mentioned in section (5) above into the round-bottom beaker mentioned in section (1) above, which is set on the sample stage, and adjust the measurement concentration to about 5%. Perform the measurement until the number of particles measured reaches 50,000.

[0169] 7. Calculate the weight-average particle size (D4) by analyzing the measurement data using the accompanying dedicated software. When the dedicated software is set to Graph / Volume %, the "Average Diameter" on the "Analysis / Volume Statistics (Arithmetic Mean)" screen is the weight-average particle size (D4).

[0170] Method for measuring the average roundness of toners

[0171] Under the measurement and analysis conditions of the calibration operation, the average roundness of the toner was measured using an FPIA-3000 flow cytometer (Sysmex Corporation). The specific measurement method is as follows.

[0172] First, 20 mL of deionized water, after removing solid impurities, was placed in a glass container. Then, 0.2 mL of a 10% by mass aqueous solution of "Contaminon N" (a neutral detergent for washing precision measuring instruments, pH 7, composed of nonionic surfactants, anionic surfactants, and organic additives, manufactured by Wako PureChemical Industries, Ltd.) diluted three times by mass with deionized water was added as a dispersant. Next, 0.02 g of the measurement sample was added, and the mixture was dispersed using an ultrasonic disperser for 2 minutes to obtain a dispersion for measurement. During this process, the mixture was appropriately cooled to maintain a dispersion temperature of 10–40°C.

[0173] A benchtop ultrasonic cleaner and disperser (e.g., "VS-150", manufactured by Velvo-Clear) with an oscillation frequency of 50 kHz and an electrical output of 150 W was used as the ultrasonic disperser. A predetermined amount of ion-exchanged water was placed in a water tank, and 2 mL of Contaminon N was added to the tank. For measurements, a flow cytometer equipped with an "UPlanApro" (10x magnification, 0.40 numerical aperture) as the objective lens was used, and a particle sheath "PSE-900A" (manufactured by Sysmex Corporation) was used as the sheath fluid.

[0174] The dispersion obtained through the above steps was introduced into a flow particle imager, and 3,000 toner particles were measured in HPF measurement mode and total count mode. Then, the average roundness of the toner was determined during particle analysis with an 85% binarization threshold, wherein the analyzed particle size was limited to a round equivalent diameter of 1.985 μm to less than 39.69 μm.

[0175] Before the measurement begins, autofocus is adjusted using standard latex particles (e.g., Duke Scientific Corporation "RESEARCH AND TEST PARTTICLES Latex Microsphere Suspensions 5100A" diluted with deionized water). Autofocus is then adjusted again every two hours after the measurement begins.

[0176] In the embodiments of this application, the flow cytometer used has been calibrated by Sysmex Corporation, and a calibration certificate from Sysmex Corporation has been issued. Measurements were performed under the same measurement and analysis conditions as when the calibration certificate was obtained, except that the analyzed particle size was limited to a circular equivalent diameter of 1.985 μm to 39.69 μm.

[0177] Measurement of the proportion of styrene-acrylic resin in toners

[0178] For the analysis of resin content ratio, pyrolysis gas chromatography-mass spectrometry (hereinafter, pyrolysis GC / MS) and NMR were used. In this disclosure, components with a molecular weight of 1500 or higher were selected for measurement. This is because the region with a molecular weight of less than 1500 is considered to be a region with a high proportion of wax and essentially free of resin components.

[0179] In pyrolysis GC / MS, the constituent monomers of all resins in the toner can be identified and the peak areas of each monomer can be obtained. However, for quantification, it is necessary to use a sample of known concentration as a reference to normalize the peak intensities. Meanwhile, in NMR, the constituent monomers can be identified and quantified without using a sample of known concentration. Therefore, based on this, the constituent monomers can be identified by comparing the spectra of NMR and pyrolysis GC / MS.

[0180] Specifically, when the amount of resin component in which deuterated chloroform is insoluble in the extraction solvent used for NMR measurement is less than 5.0% by mass, quantification is performed by NMR measurement. Simultaneously, when the amount of resin component in which deuterated chloroform is insoluble in the extraction solvent used for NMR measurement is 5.0% by mass or more, the soluble components of deuterated chloroform are measured by both NMR and pyrolysis GC / MS. The insoluble components of deuterated chloroform are measured by pyrolysis GC / MS.

[0181] In this case, firstly, NMR measurements of the deuterated chloroform-soluble components were performed, and the constituent monomers were determined and quantified (quantification result 1). Next, pyrolysis GC / MS measurements of the deuterated chloroform-soluble components were performed, and the peak areas attributable to each constituent monomer were determined. Using the quantification result 1 obtained by NMR measurements, the relationship between the amount of each constituent monomer and the peak areas of the pyrolysis GC / MS was determined.

[0182] Next, pyrolysis GC / MS measurements of the deuterated chloroform-insoluble components were performed, and the peak areas attributable to each constituent monomer were determined. Based on the relationship between the amounts of each constituent monomer obtained by measuring the deuterated chloroform-soluble components and the peak areas of the pyrolysis GC / MS, the constituent monomers in the deuterated chloroform-insoluble components were quantified (quantification result 2). Then, quantification result 1 and quantification result 2 were combined to obtain the final quantitative results for each constituent monomer.

[0183] Specifically, perform the following operations.

[0184] (1) Weigh a total of 500 mg of toner into a 30 mL glass sample bottle, add 10 mL of deuterated chloroform, cap the bottle, and disperse and dissolve it using an ultrasonic disperser for 1 h. Then, filter the solution through a 0.4 μm diameter membrane filter and collect the filtrate. At this point, the insoluble components of deuterated chloroform remain on the membrane filter.

[0185] (2) Using high performance liquid chromatography (HPLC), components with a molecular weight less than 1500 were removed from the 3 mL filtrate using a fractionating collector, and the resin solution was collected. Chloroform was removed from the collected solution using a rotary evaporator to obtain the resin. Components with a molecular weight less than 1500 were determined by pre-measuring polystyrene resin with a known molecular weight and obtaining the elution time.

[0186] (3) Dissolve a total of 20 mg of the obtained resin in 1 mL of deuterated chloroform and perform 1H-NMR measurement. The spectrum is assigned to each constituent unit used in the polyester resin and quantitative values ​​are obtained.

[0187] (4) If it is necessary to analyze the insoluble components of deuterated chloroform, the analysis shall be performed by pyrolysis GC / MS. Derivatization treatments such as methylation may be performed as needed.

[0188] NMR measurement conditions

[0189] Apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)

[0190] Measurement frequency: 400MHz

[0191] Pulse condition: 5.0 μs

[0192] Frequency range: 10,500Hz

[0193] Total number of times: 1024

[0194] Temperature measured: 25℃

[0195] Sample: Prepared by placing 50 mg of the measurement sample into a sample tube with an inner diameter of 5 mm, adding deuterated chloroform (CDCl3) as a solvent, and dissolving it in a thermostat at 40 °C.

[0196] The molar ratio of each monomer component is obtained from the integral value of the obtained spectrum, and the composition ratio (mass%) is calculated based on this.

[0197] Measurement conditions of pyrolysis GC / MS

[0198] Pyrolysis unit: JPS-700 (Japan Analytical Industry Co., Ltd.)

[0199] Decomposition temperature: 590℃

[0200] GC / MS device: Focus GC / ISQ (Thermo Fisher Scientific Corp.)

[0201] Column: HP-5MS, length 60m, inner diameter 0.25mm, film thickness 0.25μm

[0202] Inlet temperature: 200℃

[0203] Flow pressure: 100 kPa

[0204] Split: 50 mL / min

[0205] MS ionization: EI

[0206] Ion source temperature: 200℃

[0207] Quality range: 45-650

[0208] Identification of the type of shell resin in toner particles

[0209] The resin type of the toner particle shell was analyzed using time-of-flight secondary ion mass spectrometry (TOF-SIMS). For the measurement of the amount of polyester on the surface of the toner particles, for example, when the polyester resin has a structure derived from phthalic acid, isophthalic acid, or terephthalic acid, TRIFT-IV manufactured by ULVAC-PHI, Inc. was used. The analytical conditions are as follows.

[0210] Sample preparation: The toner is attached to an indium sheet. Toner particles obtained by separating external additives from the toner can be used as samples.

[0211] Sample pretreatment: None

[0212] Primary ion: Au +

[0213] Accelerating voltage: 30kV

[0214] Charge neutralization mode: On

[0215] Measurement mode: positive

[0216] Grating: 100μm

[0217] Calculation of peak intensity (EI) for ester-containing phthalic acid, isophthalic acid or terephthalic acid: According to the ULVAC-PHI standard software (WinCadence), the total number of count peaks with mass numbers of 148 to 150 is taken as the peak intensity (EI).

[0218] Calculation of peak intensities derived from other resins: According to the ULVAC-PHI standard software (WinCadence), the total number of peaks with a mass number of 90 to 105 is taken as the peak intensities derived from other resins.

[0219] The sum of this peak intensity and the peak intensities (EI) derived from phthalic acid, isophthalic acid, or terephthalic acid containing ester groups is taken as the peak intensity (ZI) of the resin originating from the surface of the toner particles. EI / ZI is calculated from the peak intensity. For example, when EI / ZI ≥ 0.5, it is determined that polyester resin is present on the surface of the toner particles. The mass number in the peak intensity (EI) measurement can vary depending on the constituent monomers of the polyester resin used.

[0220] Shell thickness measurement

[0221] The thickness of the shell was measured using a transmission electron microscope. The following is a cross-section of the toner observed using a transmission electron microscope.

[0222] First, the toner is sprayed onto a coverslip (Matsunami Glass Co., Ltd., angular coverslip, Square No. 1) to form a single layer, and an Os film (5nm) and a naphthalene film (20nm) are applied as protective films using an osmium plasma coating machine (Filgen Co., Ltd., OPC80T). Next, a PTFE tube (Φ1.5mm×Φ3mm×3mm) is filled with photocurable resin D800 (JEOL Ltd.), and the coverslip is gently placed on the tube with the toner in contact with the photocurable resin D800. After the resin is cured by light in this state, the coverslip and the tube are removed to form a cylindrical resin with the toner embedded in the outermost surface.

[0223] Using an ultrasonic microtome (Leica Biosystems Nussloch GmbH, UC7), a layer equal to half the toner particle size (4.0 μm when the weight-average particle size (D4) is 8.0 μm) was cut from the outermost surface of the cylindrical resin at a cutting speed of 0.6 mm / s to expose the cross-section of the toner particles. Next, the magnetic toner was cut into 100 nm thick films to prepare sheet-like samples of the toner particle cross-section. This cutting method allows for the acquisition of the cross-section of the central portion of the toner particles.

[0224] TEM images of the toner were prepared using a transmission electron microscope (TEM) (JEM2800, manufactured by JEOL Ltd.) at an accelerating voltage of 200 kV. Images with a TEM probe size of 1 nm and an image size of 1024 × 1024 pixels were acquired. In the obtained TEM images, the binder resin contained in the core particles and shell was observed at different contrasts.

[0225] The difference in brightness varies depending on the material, but in this disclosure, the portion observed that differs in contrast from the binder resin contained in the core particle is referred to as the shell. Ten particles with diameters in the weight-average particle size (D4) ± 1.0 μm were selected from the observed toners and their images were captured. The magnification was 20,000x.

[0226] For thickness measurements, the commercially available image analysis software WinROOF (manufactured by Mitani Corporation) was used. In TEM images of 10 toner particles randomly selected according to the above criteria, the shell thickness was measured at four points on each particle. Specifically, two perpendicular lines were drawn substantially through the center of the toner cross-section, and the shell thickness was measured at the four points where the two lines intersect the shell. The shell thickness is the distance from the cross-sectional profile of the toner particle to the interface between the binder resin and the shell. The arithmetic mean of all measurements was taken as the toner particle shell thickness.

[0227] The average number of major diameters of hydrotalcite or alumina particles and the average number of primary particles of external additive C. Methods for measuring particle size

[0228] The positions of hydrotalcite and alumina particles, as well as external additives such as silica particles, present on the surface of the toner can be determined by observation and elemental analysis using an ultra-high resolution field emission scanning electron microscope (SEM-EDX) S-4800 (Hitachi High Technologies Co., Ltd.). For example, observation and elemental mapping at 20,000x magnification in a continuous field of view, confirming the presence of both Mg and Al in the observed particles, indicates that they are hydrotalcite particles. Similarly, the presence of Al in the observed particles indicates that they are alumina particles, and the presence of Si indicates that they are silica particles.

[0229] The following describes the method for measuring the average number of major diameters of hydrotalcite particles. The major diameters of at least 300 hydrotalcite particles on the toner surface are measured and the average is calculated. Some hydrotalcite particles exist as aggregates, but these aggregates are not measured for particle size. Furthermore, the maximum diameter of the particle is taken as the major diameter. Additionally, the average major diameter of the alumina particles is measured and calculated in the same manner as the average major diameter of the hydrotalcite particles. When the external additive C is silica particles, the number-average particle size of the primary particles is calculated by taking the absolute maximum length of the particle as the particle size when the particle is spherical, and by taking the major diameter as the particle size when the particle has both a major and minor diameter.

[0230] Methods for measuring the amounts of hydrotalcite particles, alumina particles, and external additive C

[0231] The amounts of hydrotalcite particles, alumina particles, and external additive C were calculated using elemental intensities of these particles in the toner, measured by X-ray fluorescence (XRF). For example, the amount of hydrotalcite particles could be analyzed and calculated from the intensities of Al and Mg using a calibration curve method. Similarly, the amount of alumina particles could be analyzed and calculated from the intensities of Al. In the case where the external additive C is silica particles, its amount could be analyzed and calculated from the intensities of Si.

[0232] As the measuring apparatus, an Axios wavelength dispersive fluorescence X-ray analyzer (manufactured by PANalytical) equipped with dedicated software "SuperQ ver. 4.0F" (manufactured by PANalytical) for setting measurement conditions and analyzing measurement data was used. Rh was used as the anode of the X-ray tube, the measurement atmosphere was vacuum, the measurement diameter (collimator mask diameter) was 10 mm, and the measurement time was 10 seconds. Furthermore, a proportional counter (PC) was used for detection when measuring light elements, and a scintillation counter (SC) was used for detection when measuring heavy elements. Measurements were performed under the above conditions, elements were identified based on the peak positions of the obtained X-rays, and their concentrations were calculated using the count rate (unit: cps), which is the number of X-ray photons per unit time.

[0233] Granules prepared by placing approximately 1g of toner into a special aluminum ring for pressing, flattening it, applying pressure at 20MPa for 60 seconds, and shaping it to a thickness of approximately 2mm using a sheet forming compressor "BRE-32" (manufactured by Maekawa Testing Machine Mfg.Co.,Ltd.) were used as measurement samples. The amount was calculated from the obtained peak intensity based on a pre-plotted calibration curve from a sample of known quantity.

[0234] Example

[0235] The present invention will now be described in more detail with reference to embodiments and comparative examples, but the invention is not limited thereto. Unless otherwise stated, the quantities used in the embodiments are based on mass.

[0236] Production example of external additive B1

[0237] A total of 203.3 g of magnesium chloride hexahydrate and 96.6 g of aluminum chloride hexahydrate were dissolved in 1 L of deionized water. While maintaining the solution at 25 °C, the pH was adjusted to 10.5 using a solution obtained by dissolving 60 g of sodium hydroxide in 1 L of deionized water. The solution was then aged at 98 °C for 24 hours. After cooling, the precipitate was washed with deionized water until the conductivity of the filtrate was below 100 μS / cm to obtain a slurry with a concentration of 5% by mass. While stirring the slurry, external additive B1 was obtained by spraying using a spray dryer (DL-41, manufactured by Yamato Scientific Co., Ltd.) at a drying temperature of 180 °C, a spray pressure of 0.16 MPa, and a spray rate of approximately 150 mL / min. The physical properties are shown in Table 1.

[0238] [Table 1]

[0239]

[0240] The particle size is the average number of particles in the major axis (for silica, it is the number-average particle size of primary particles). The abbreviations in the table are as follows.

[0241] PDMS: Polydimethylsiloxane

[0242] Production examples of external additives B2 to B10

[0243] Except for adjusting the amounts of magnesium chloride hexahydrate and aluminum chloride hexahydrate added, as well as the spray pressure and spray speed of the spray dryer, external additives B2 to B10 were obtained in the same manner as in the production of external additive B1. Their physical properties are shown in Table 1.

[0244] Production example of external additive B11

[0245] The experiment was conducted using aluminum hydroxide as the alumina raw material, with 0.02 parts of α-alumina added as seed crystals (this amount is relative to 100 parts of alumina obtained from the alumina raw material, the same below), and hydrogen chloride gas was introduced as the atmosphere gas into a tube furnace. The atmosphere gas introduction temperature was 900°C, the holding temperature (firing temperature) was 1200°C, and the holding time (firing time) was 30 minutes. The physical properties of the external additive B11 are shown in Table 1.

[0246] Production example of external additive B12

[0247] A total of 10.0 parts of polydimethylsiloxane were sprayed onto 100 parts of fumed silica (trade name: AEROSIL 380S, BET method, specific surface area: 380 m²). 2 / g, average particle size of primary particles: 7nm, manufactured by Nippon Aerosil Co., Ltd.), then stirred for 30 minutes. Then, the temperature was raised to 300°C with stirring, and further stirred for 2 hours to prepare external additive B12. Physical properties are shown in Table 1.

[0248] Production example of external additive B13

[0249] Except that amino-modified silicone oil was used instead of polydimethylsiloxane, external additive B13 was prepared by the same method as external additive B12. Its physical properties are shown in Table 1.

[0250] Production example of external additive B14

[0251] Anatase titanium oxide was treated with 12% by mass of isobutyltrimethoxysilane to obtain external additive B14. Physical properties are shown in Table 1.

[0252] Production example of shell resin 1

[0253] In a reaction vessel equipped with a nitrogen inlet pipe, a dehydration pipe, a stirrer, and a thermocouple, a total of 40 mol% terephthalic acid, 10 mol% trimellitic acid, and 50 mol% bisphenol A-propylene oxide (PO)2 molar adduct were added, with 1.5 parts dibutyltin oxide added as a catalyst relative to 100 parts of the total monomer content. The temperature was then rapidly raised to 180°C under atmospheric pressure and a nitrogen atmosphere, and then heated from 180°C to 210°C at a rate of 10°C / h while distilling off water to carry out polycondensation. After reaching 210°C, the pressure inside the reaction vessel was reduced to below 5 kPa, and polycondensation was carried out at 210°C and below 5 kPa to obtain shell resin 1. At this point, the polymerization time was adjusted so that the softening point of the resulting shell resin 1 was 120°C.

[0254] Production example of shell resin 2

[0255] A total of 300 parts xylene (boiling point 144℃) were placed into a pressurized and depressurized flask. The inside of the container was thoroughly purged with nitrogen while stirring, then heated and refluxed. A mixed solution of the following raw materials was added.

[0256] -Styrene: 91.7 parts

[0257] -Methyl methacrylate: 2.50 parts

[0258] - Methacrylic acid: 3.30 parts

[0259] 2-Hydroxyethyl methacrylate: 2.50 parts

[0260] - Di-tert-butyl peroxide: 2.00 parts

[0261] Polymerization was carried out at a polymerization temperature of 175°C and a reaction pressure of 0.125 MPa for 5 h. Then, a solvent removal step was performed under reduced pressure for 3 h to remove xylene, and the product was pulverized to obtain shell resin 2 (acid value = 10.9, molecular weight (Mp) = 14,500).

[0262] Production example of colorant granules A1

[0263] A total of 390.0 parts of ion-exchanged water and 14.0 parts of sodium phosphate (12-hydrate) [manufactured by Rasa Industries., Ltd.] were placed in a reaction vessel, and the components were kept at 65°C for 1.0 h while purging with nitrogen. Next, while stirring at 12,000 rpm using a TK homogenizer, an aqueous solution of calcium chloride prepared by dissolving 9.2 parts of calcium chloride (dihydrate) in 10.0 parts of ion-exchanged water was added in batches to prepare an aqueous medium containing a dispersant stabilizer. Further, hydrochloric acid was added to the aqueous medium to adjust the pH to 6.0, resulting in aqueous medium 1.

[0264] Meanwhile, the following materials were placed in a grinder (manufactured by Nippon Coke Industries, Ltd.), and zirconia particles with a diameter of 1.7 mm were further placed in the grinder and dispersed at 220 rpm for 5.0 hours. Then, the zirconia particles were removed to prepare a dispersion 1 in which the colorant was dispersed.

[0265] -Styrene: 60.0 parts

[0266] - Colorant (Pigment Red 122): 6.5 parts

[0267] Next, the following materials are added to the prepared dispersion 1.

[0268] -Styrene: 15.0 parts

[0269] - n-Butyl acrylate: 25.0 parts

[0270] -Shell resin 1:4.0 parts

[0271] - Charge control agent (di-tert-aluminum salicylate): 0.7 parts

[0272] - Hydrocarbon wax (HNP-51, produced by Nippon Seiro Co., Ltd.): 9.0 parts

[0273] - Dodecaneol: 0.5 parts

[0274] The mixture was then heated to 60°C and stirred at 9000 rpm using a TK homogenizer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to induce dissolution and dispersion. A total of 10.0 parts of polymerization initiator 2,2'-azobis(2,4-dimethylpentanonitrile) were dissolved in the mixture to prepare the monomer composition. The monomer composition was placed in an aqueous medium and granulated for 15 minutes while rotating a CLEARMIX at 15,000 rpm at 60°C. The mixture was then transferred to a propeller stirrer and stirred at 100 rpm while reacting at 70°C for 5 hours, followed by heating to 80°C and reacting for an additional 5 hours to produce toner granules.

[0275] After the polymerization reaction is complete, the slurry containing particles is cooled, hydrochloric acid is added to adjust the pH to below 1.4, the mixture is stirred for 1 hour, and then solid-liquid separation is performed using a filter press to obtain a toner cake. It is then re-slurryed with deionized water to form a dispersion again, and then solid-liquid separation is performed using the same filter. Re-slurrying and solid-liquid separation are repeated until the conductivity of the filtrate is below 5.0 μS / cm, and then final solid-liquid separation is performed to obtain the toner cake.

[0276] The toner cake was dried using a Flash Jet Dryer (manufactured by Seishin Enterprise Co., Ltd.). For drying conditions, the air temperature was 90°C and the dryer outlet temperature was 40°C. The feed rate of the toner cake was adjusted according to its moisture content to ensure the outlet temperature did not deviate from 40°C. Furthermore, a multi-stage classifier utilizing the wall adhesion effect was used to separate the fine and coarse powders to obtain toner particles A1 with a weight-average particle size (D4) of 6.8 μm.

[0277] The physical properties are shown in Table 2.

[0278] [Table 2]

[0279]

[0280] Production example of toner 1

[0281] External additives of the types and proportions shown in Table 3-1 were added using FM10C (manufactured by Nippon Coke Industries Co., Ltd.) and mixed with 100 parts of the resulting toner granules 1. The external addition conditions were as follows: toner granule addition amount: 1.8 kg, rotation speed: 60 s. -1 External addition time: 15 minutes. Then, toner 1 was obtained by sieving through a mesh screen with an opening of 200 μm.

[0282] The physical properties are shown in Tables 3-1 and 3-2.

[0283] [Table 3-1]

[0284]

[0285] [Table 3-2]

[0286]

[0287] In the table, the amount of StAc resin is the percentage (by mass) of styrene-acrylic resin in the colorant.

[0288] Production examples of colorant granules A2 to A20

[0289] Except for changes in the type and amount of alcohol, the amount and type of shell resin, and the type of pigment as shown in Table 2, toner particles A2 to A20 were obtained in the same manner as toner particles 1. Physical properties are shown in Table 2.

[0290] Production examples of colorants 2 to 27

[0291] Except for changing the types and amounts of external additives as shown in Table 3-1, toners 2 to 27 were obtained in the same manner as toner 1. Their physical properties are shown in Table 3-2. Furthermore, when measuring the amount of external additives in the obtained toners, it was confirmed that each external additive was included in the proportions shown in Table 3-1.

[0292] Example 1

[0293] The following evaluation was performed on toner 1. A cartridge filled with the toner 1 obtained above was installed in a Canon LBP652C laser beam printer, and the following evaluation was conducted. As a transfer material, A4-sized CS-680 (basic weight 68 g / cm³) was used. 2 The aforementioned machines were evaluated after being left to stand for 3 days in each evaluation environment.

[0294] <1> Evaluation of front-end concentration

[0295] Evaluation was conducted under high temperature and high humidity (H / H) conditions (32.5°C, 80% RH). Solid images were output, and the image density of the first revolution of the developing roller starting from the top of the solid image, the second revolution, and subsequent revolutions were measured using a color reflectance density meter (X-Rite 404A). The evaluation was based on the differences in these image densities as follows. The evaluation results are shown in Table 4.

[0296] A: The difference in image density is less than 0.05.

[0297] B: The difference in image density is greater than 0.05 and less than 0.10.

[0298] C: The difference in image density is greater than 0.10 and less than 0.15.

[0299] D: The difference in image density is greater than 0.15.

[0300] <2> Evaluation of fogging

[0301] Evaluation was conducted under high temperature and high humidity (H / H) conditions (32.5°C, 80% RH). Under H / H conditions, after continuously printing 1000 images at 1% print percentage, a solid white image at 0% print percentage was printed, and its reflectance (%) was measured using a "REFLECTOMETER MODEL TC-6DS" (manufactured by Tokyo Denshoku Co., Ltd.). The evaluation was performed using the value (hazing value) obtained by subtracting the obtained reflectance from the reflectance (%) of unused printed output paper (standard paper) measured in the same manner. A lower value indicates better suppression of image hazing. The evaluation results are shown in Table 4.

[0302] Evaluation criteria

[0303] A: Fogging value is less than 1.0%.

[0304] B: Fogging value is above 1.0% and below 3.0%.

[0305] C: Fogging value is 3.0% or higher but less than 5.0%

[0306] D: Fogging value above 5.0%

[0307] <3> Double image evaluation

[0308] Evaluation was conducted under low temperature and low humidity (L / L) conditions (15.0℃, 10% RH). After continuously outputting 1000 solid white monochrome images with a 0% printing percentage, a monochrome ghosting determination image was output. This was achieved by horizontally arranging seven 15mm × 15mm solid images at 15mm intervals, positioned 5mm from the top edge of the transfer paper, with a toner loading of 0.20 mg / cm² below these images. 2 Halftone images were used to obtain images for ghosting determination. Visual determination was made based on the density difference caused by the 15mm × 15mm solid image in the halftone portion of the image. The evaluation results are shown in Table 4.

[0309] Evaluation criteria

[0310] A: No concentration difference was observed.

[0311] B: The concentration is slightly different.

[0312] C: Some concentration differences were observed.

[0313] D: Clearly identify the concentration difference

[0314] <4> Evaluation of fusion

[0315] The evaluation was conducted under high temperature and high humidity (H / H) conditions (32.5°C, 80% RH). After continuously printing 7000 images at a 1% print percentage, the developing container was disassembled, and the surface and edges of the toner carrier were visually evaluated. The evaluation results are shown in Table 4.

[0316] Evaluation criteria

[0317] A: There are no circumferential streaks on the surface or edges of the toner carrier component caused by foreign matter trapped between the toner adjusting component and the toner carrier component due to toner breakage or fusion.

[0318] B: Some foreign matter is trapped between the toner carrier and the toner end seal.

[0319] C: One to four circumferential stripes can be seen at the end.

[0320] D: More than five circumferential stripes can be seen throughout the area.

[0321] Examples 2 to 21

[0322] Toners 2 to 21 were evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0323] Comparative Examples 1 to 6

[0324] Toners 22 to 27 were evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0325] [Table 4]

[0326]

[0327] Although the invention has been described with reference to exemplary embodiments, it should be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the appended claims should be interpreted in the broadest sense to cover all such modifications and equivalent structures and functions.

Claims

1. A toner comprising: Toner particles containing binder resin, and External additives, characterized in that, The colorant particles also contain monoaliphatic alcohols. The monohydric aliphatic alcohol has 8 to 18 carbon atoms. The content ratio of the monoaliphatic alcohol extracted from the toner with ethanol in the toner, as measured by the following steps, is 30 to 300 ppm by mass: Add a total of 2g of the toner and 18g of ethanol, and homogenize manually; then, irradiate with ultrasound for 5 minutes; then, let the mixture stand in a 60°C incubator for 24 hours, and further stand at room temperature for 3 days; then, collect the supernatant of the sample and filter it through a PTFE injection filter with a pore size of 250nm, and use the filtrate as the extracted sample; analyze the extracted sample by gas chromatography-mass spectrometry to obtain the content ratio of the monoaliphatic alcohol extracted from the toner with ethanol in the toner, and The external additive comprises at least one selected from the group consisting of hydrotalcite particles and alumina particles.

2. The toner according to claim 1, wherein... The external additive comprises the hydrotalcite particles, and The average number of major diameters of the hydrotalcite particles is 60 to 820 nm.

3. The toner according to claim 1, wherein... The external additive comprises the alumina particles, and The average number of major diameters of the alumina particles is 60 to 820 nm.

4. The toner according to any one of claims 1 to 3, wherein the total content of the hydrotalcite particles and alumina particles is 0.02 to 1.00 parts by weight relative to 100 parts by weight of the toner particles.

5. The toner according to any one of claims 1 to 3, wherein the total content of the hydrotalcite particles and alumina particles is 0.05 to 0.50 parts by weight relative to 100 parts by weight of the toner particles.

6. The toner according to any one of claims 1 to 3, wherein The adhesive resin comprises a styrene-acrylic resin, and The content of the styrene-acrylic resin in the colorant is 50% by mass or more.

7. The toner according to any one of claims 1 to 3, wherein When the work function of the toner particles is represented by Wa and the work function of the hydrotalcite particles is represented by Wb, Wa and Wb satisfy the following equation (1): 0.05eV <Wa-Wb<0.50eV(1)。 8. The toner according to any one of claims 1 to 3, wherein When the work function of the toner particles is represented by Wa and the work function of the alumina particles is represented by Wb, Wa and Wb satisfy the following equation (1): 0.05eV <Wa-Wb<0.50eV(1)。 9. The toner according to any one of claims 1 to 3, wherein The toner particles contain colorants, and The colorant comprises at least one selected from the group consisting of CI Pigment Violet 19, CI Pigment Red 122, CI Pigment Red 202 and CI Pigment Red 209.

10. The toner according to any one of claims 1 to 3, wherein The external additive comprises an external additive C that is different from the hydrotalcite particles and the alumina particles. When the work function of the toner particles is represented by Wa, the work function of the hydrotalcite particles is represented by Wb, and the work function of the external additive C is represented by Wc, Wa, Wb, and Wc satisfy the following equation (2): Wb <Wa<Wc(2)。 11. The toner according to any one of claims 1 to 3, wherein The external additive comprises an external additive C that is different from the hydrotalcite particles and the alumina particles. When the work function of the toner particles is represented by Wa, the work function of the alumina particles by Wb, and the work function of the external additive C by Wc, Wa, Wb, and Wc satisfy the following equation (2): Wb <Wa<Wc(2)。 12. The colorant according to any one of claims 1 to 3, wherein the external additive comprises the hydrotalcite particles.

13. The toner according to any one of claims 1 to 3, wherein The toner particles comprise a core-shell structure containing a core particle and a shell on the surface of the core particle. In cross-sectional observation of the toner using a transmission electron microscope, The shell exists inside the cross-sectional profile of the toner particles. The shell comprises polyester resin, and The thickness of the shell is 0.8 to 100 nm.

14. The toner according to any one of claims 1 to 3, wherein the average roundness of the toner is 0.97 or higher.

15. The toner according to any one of claims 1 to 3, wherein The adhesive resin comprises at least one resin selected from the group consisting of styrene-acrylic resins and polyester resins, and does not contain any other resins.

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