toner

Abstract

To provide a toner having both excellent low temperature fixability and high durable developability without development streaks.SOLUTION: A toner has a toner particles having a crystalline resin as a binder resin. In a relative dielectric constant εr obtained when the impedance of the toner is measured in an environment of a temperature of 25°C and a relative humidity of 50%RH, the difference Δεr between the dielectric constant εr(0.01 Hz) at a frequency of 0.01 Hz and the dielectric constant εr(383 kHz) at a frequency of 383 kHz satisfies the following formula (1). Formula (1) 0.21≤{εr(0.01 Hz)-εr(383 kHz)}≤0.48.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a toner for developing electrostatic images (electrostatic latent images) used in image formation methods such as electrophotography and electrostatic printing. [Background technology]

[0002] In recent years, the applications of electrophotography have expanded to commercial printing, such as packaging and advertising, requiring even higher speeds and image quality compared to its traditional use in offices. Furthermore, there is a growing demand for energy efficiency in copiers and printers, with attempts being made to achieve this by lowering the fuser temperature, in particular. To adapt to the demands of higher speed and energy conservation, a technology is known that lowers the fixing temperature by using crystalline resins as the binder resin for toner. Crystalline resins include main-chain crystalline resins, such as crystalline polyesters, where the main chain crystallizes, and side-chain crystalline resins, such as long-chain alkyl acrylate polymers, where the side chains crystallize. Among these, side-chain crystalline resins are known to exhibit excellent low-temperature fixing properties because it is easy to increase the degree of crystallinity, and are therefore widely studied. Patent Document 1 proposes a toner using crystalline polyester, which achieves both excellent image formation and low-temperature fixability, accommodating various user environments and image modes. Patent Document 2 discloses a toner binder that uses a vinyl resin with acrylate and / or vinyl ester as monomers, which satisfies both low-temperature fixability and storage stability, as well as hot offset resistance and electrostatic stability. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2021-140015 [Patent Document 2] Japanese Patent Publication No. 2019-214706 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] However, in Patent Document 1, the low mass proportion of crystalline polyester in the toner resulted in unsatisfactory low-temperature fixation. In Patent Document 2, the high mass proportion of alkyl acrylate and vinyl ester constituting the vinyl resin in the toner resulted in excellent low-temperature fixation, but this increased the electrostatic adhesion of the toner, leading to the problem of developing streaks. To obtain a satisfactory fixing temperature, it is effective to use a large amount of crystalline resin with excellent sharp-melt properties in the toner. However, increasing the mass ratio of crystalline resin in the toner increases the conductivity of the toner, and thus increases the polarization charge due to conductivity. This polarization charge of the toner has the effect of increasing the adhesion of the toner to the toner regulating member in the developer unit, which led to the problem that the toner was more likely to adhere to and accumulate on the toner regulating member during long-term use. Furthermore, during long-term use, the adhesion and accumulation of toner on the toner regulating member made it easier for development streaks to occur, resulting in a decrease in durable development performance. Thus, while toners with a higher crystalline resin content exhibit excellent low-temperature fixing properties, they tend to develop streaks during long-term use, making it difficult to achieve both low-temperature fixing and durable development. Therefore, the present invention aims to provide a toner that combines excellent low-temperature fixing properties with durable developability. [Means for solving the problem]

[0005] The inventors investigated how to achieve both low-temperature fixation and durable developability. As a result, they found that the electrostatic adhesion force of the toner can be controlled by controlling the polarization charge originating from conductivity (mobile charge), thereby solving the above problem. The present invention relates to a toner having toner particles having a crystalline resin as a binder resin, The binder resin contains a unit (a) represented by the following formula (2): The proportion of unit (a) represented by formula (2) is 40.0% by mass or more and 80.0% by mass or less in the binder resin. [ka] [In formula (2), R 1 represents a hydrogen atom or a methyl group, L 1 [where m represents a single bond or a divalent linking group, and m represents an integer between 15 and 35.] When measuring the impedance of the toner in an environment with a temperature of 25°C and a relative humidity of 50%RH, in the relative permittivity εr obtained, the difference Δηr between the relative permittivity εr(0.01Hz) at a frequency of 0.01Hz and the relative permittivity εr(383kHz) at a frequency of 383kHz satisfies the following formula (1) Satisfying the conditions, In measurements of the toner particle surface using time-of-flight secondary ion mass spectrometry (TOF-SIMS), when Ic1 is defined as the ion count derived from sulfonic acid groups relative to the total ion count at mass-to-charge ratios of 0.5 to 1850, if Ic1 is between 0.005 and 0.05, and is characterized by being a toner that satisfies this. 0.21 ≤ {εr(0.01Hz) - εr(383kHz)} ≤ 0.48 Formula (1)

Effect of the Invention

[0006] According to the present invention, it is possible to provide a toner having excellent low-temperature fixing properties and high durable developing properties without developing streaks.

Brief Description of the Drawings

[0007] [Figure 1] It is a graph showing an example of the dielectric relaxation characteristics of a toner to which the present invention is applicable. [Figure 2] It is a graph showing an example of the electrical conductivity characteristics of a toner to which the present invention is applicable.

Mode for Carrying Out the Invention

[0008] Hereinafter, embodiments will be described in detail, but the present invention is not limited to the following description. In the present disclosure, the description of "XX or more and YY or less" or "XX to YY" representing a numerical range means a numerical range including the lower limit and the upper limit which are the endpoints, unless otherwise specified. Also, when the numerical ranges are described stepwise, the upper limit and the lower limit of each numerical range can be arbitrarily combined.

[0009] 〔Features of the Present Invention〕 The present invention relates to a toner having toner particles containing a crystalline resin as a binder resin, wherein the relaxation intensity of dielectric relaxation obtained when impedance measurement is controlled. Crystalline resins refer to resins that exhibit a clear endothermic peak in differential scanning calorimeter (DSC) measurements, possess high crystallinity, excellent sharp melt properties, and can improve low-temperature fixing.

[0010] The relative permittivity at high frequencies consists of orientation polarization originating from the electric dipole of the toner. On the other hand, the relative permittivity at low frequencies consists of the sum of the polarization charge originating from the conductivity (mobile charge) of the toner and the constant orientation polarization. Therefore, the relaxation intensity (hereinafter referred to as polarization charge Δεr), which is the difference between the low-frequency and high-frequency values ​​of the relative permittivity, represents the polarization charge originating from conductivity (mobile charge).

[0011] The inventors have discovered that by controlling the polarization charge Δεr of the toner, they can control the electrostatic adhesion force of the toner and provide a toner that achieves both low-temperature fixing and developability. The inventors consider the reasons for this as follows.

[0012] Toners containing crystalline resins have a lower glass transition temperature (Tg) and higher orientation compared to amorphous resins. When mobile charges are present in the toner, they move through the low glass transition temperature (Tg) region due to thermal motion, contact charging (work function difference at the heterojunction interface), and an externally applied electric field. This movement can be observed as electrical conductivity. Therefore, increasing the mass proportion of crystalline resin in the toner results in higher conductivity. However, this conductivity does not exhibit ohmic properties; it falls within the category of a dielectric (insulator).

[0013] The electrostatic adhesion force of toner is primarily due to dielectric polarization resulting from orientation polarization and polarization charge Δεr, which is electrostatic induction due to conductivity (mobile charge). Toners containing crystalline resin exhibit high orientation, resulting in high orientation polarization, and also exhibit high conductivity, resulting in high polarization charge due to mobile charge. For these reasons, toners containing crystalline resin have the characteristic of high electrostatic adhesion force.

[0014] In the electrophotographic printing process, the development process includes a developing roller that rotates to transport toner to a photosensitive drum, and a toner regulating member that forms a thin layer of toner on the developing roller and controls the amount of toner transported to the photosensitive drum. In this case, toner containing crystalline resin has high electrostatic adhesion, so it tends to adhere to and accumulate on the toner regulating member during long-term use. When toner adheres to and accumulates on the toner regulating member in this way, the transport of toner to the photosensitive drum is hindered, making it easier for development defects such as development streaks (vertical white streaks) to occur.

[0015] On the other hand, by controlling the conductivity (mobile charge) of the toner, the polarization charge Δεr can be controlled, making it possible to suppress the electrostatic adhesion force of the toner, thus achieving both low-temperature fixing and durable developing properties.

[0016] In this invention, we believe that by fixing anionic structures at the ends of the crosslinked structure, on the main chain, or on the side chains, we can control the conductivity related to ion conduction through attractive and repulsive forces due to electrostatic interactions. Specifically, we fix sulfo groups at the crosslinked ends or on the main chain or side chains by hydrogen abstraction using water-soluble polymerization initiators, such as potassium persulfate, sodium persulfate, or ammonium persulfate.

[0017] In this way, by controlling the ionic conductivity of the toner, the polarization charge Δεr originating from conductivity (mobile charge) can be controlled, and the electrostatic adhesion force of the toner can be controlled.

[0018] As described above, a toner with a high mass ratio of crystalline resin and suppressed conductivity can be obtained, thus providing a toner that combines excellent low-temperature fixing properties with durable developability.

[0019] The toner according to the present invention is a toner having toner particles having a crystalline resin as a binder resin, and the relative permittivity εr obtained when the impedance of the toner is measured in an environment of temperature 25°C and relative humidity 50%RH is such that the difference between the relative permittivity εr(0.01Hz) at a frequency of 0.01Hz and the relative permittivity εr(383kHz) at a frequency of 383kHz (polarization charge Δεr) is given by the following formula (1) 0.21≦{εr(0.01Hz)-εr(383kHz)}≦0.48 Formula (1) The following conditions must be met, and preferably the polarization charge Δεr is 0.25 or more and 0.45 or less.

[0020] Here, the lower limit of the polarization charge Δεr correlates with the mass ratio of crystalline resin in the toner and indicates the upper limit of the desired fixing temperature. In other words, the larger the lower limit of the polarization charge Δεr, the better the low-temperature fixing performance. Conversely, the upper limit of the polarization charge Δεr correlates with the electrostatic adhesion force of the toner and indicates the ease with which the toner adheres to and accumulates on the developing blade, representing the limit of durable developing performance.

[0021] Furthermore, the polarization charge Δεr is correlated with conductivity, and the conductivity κ [S / m] of the toner at a frequency of 0.01 Hz, obtained when measuring the impedance of the toner under the above environment according to the present invention, is 1.2 × 10⁻⁶. -14 The above 7.1 × 10 -14 The following are preferred and exhibit electrical properties that satisfy the polarization charge Δεr. Figure 1 is a graph showing the relative permittivity with respect to frequency (example of dielectric relaxation characteristics of toner) based on the impedance measurement method of toner described later, and shows the data for Example 1, Comparative Examples 1 and 2 described later. For example, in Example 1, the polarization charge Δεr is 0.26.

[0022] Similarly, the conductivity index κ / ω [(S / m)(s / rad)] at a toner frequency of 0.01 Hz obtained when measuring the impedance of the toner under the above environment is an index indicating the conductivity of the dielectric, and is 1.9×10 -13 or more and 11.4×10 -13 or less is preferable. FIG. 2 is a graph showing the conductivity index κ / ω (example of the electrical conduction characteristics of the toner) with respect to frequency, and shows the data of Example 1 and Comparative Examples 1 and 2 described later. For example, in Example 1, κ / ω (0.01 Hz) is 4.0×10 -13 .

[0023] Furthermore, the minimum value of the conductivity index κ / ω [(S / m)(s / rad)] in the range of a sweep frequency of 0.01 Hz or more and 383 kHz or less obtained when measuring the impedance of the toner under the above environment depends on the content and electrical conductivity of the crystalline material, and is 1.3×10 -13 or more and 2.0×10 -13 or less is preferable. In Example 1 in FIG. 2, κ / ω (minimum value) is 1.6×10 -13 .

[0024] [Materials Constituting the Toner of the Present Invention] Next, the materials constituting the toner of the present invention will be specifically described.

[0025] In the present disclosure, (meth)acrylate means acrylate and / or methacrylate.

[0026] "Unit" refers to the reacted form of the monomer substance in the polymer. For example, one section of the carbon-carbon bond in the main chain where the polymerized monomer in the polymer is polymerized is defined as one unit. The polymerizable monomer can be represented by the following formula (C).

[0027] [Chemical Formula] [In formula (C), R AR represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group), B represents any substituent.

[0028] Crystalline resins are resins that exhibit a clear endothermic peak in differential scanning calorimeter (DSC) measurements.

[0029] <Binding resin> The toner of the present invention preferably contains a unit (a) represented by the following formula (2) and / or a unit (b) represented by the following formula (3) as a binder resin.

[0030] [ka] [In formula (2), R1 represents a hydrogen atom or a methyl group, L1 represents a single bond or a divalent linking group, and m represents an integer between 15 and 35.]

[0031] [ka] [In formula (3), R2 represents an elementary atom or a methyl group.]

[0032] If m in formula (2) is less than 15, crystallinity tends to be insufficient, and heat resistance for storage is impaired; therefore, a value of 17 to 29 is preferred.

[0033] Methods for introducing unit (a) into the binder resin include subjecting monomers such as α-olefins, β-olefins, (meth)acrylic acid esters, and N-alkylacrylamides having long-chain alkyl groups to vinyl polymerization.

[0034] In particular, due to the ease of controlling the physical properties of the binder resin, such as the SP value and melting point, it is preferable that the unit (a) represented by formula (2) in the binder resin is the unit represented by the following formula (4).

[0035] [ka] [In formula (4), R1 represents a hydrogen atom or a methyl group, and m represents an integer between 15 and 35.]

[0036] One method for introducing the unit represented by formula (4) is to subject a (meth)acrylic acid ester to vinyl polymerization, as illustrated below.

[0037] Specifically, these monomers include stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acrylate, octacosa (meth)acrylate, myricyl (meth)acrylate, dodoriaconta (meth)acrylate, and 2-decyltetradecyl (meth)acrylate.

[0038] A monomer having unit (a) may be used alone or in combination of two or more types.

[0039] The proportion of unit (a) in the binder resin is preferably 40.0% by mass or more and 80.0% by mass or less. By keeping it within this range, both the sharp melt properties and heat-resistant storage properties of the binder resin can be achieved. It is more preferably 40.0% by mass or more and 70.0% by mass or less, and even more preferably 40.0% by mass or more and 60.0% by mass or less.

[0040] On the other hand, a method for introducing unit (b) represented by formula (3) above into the binder resin is to subject acrylonitrile and methacrylonitrile to vinyl polymerization.

[0041] The content of monomer units (b) in the binder resin is preferably 5.0% by mass or more and 40.0% by mass or less, and more preferably 20.0% by mass or more and 35.0% by mass or less.

[0042] The binder resin may also have other units in addition to units (a) and (b). One method for introducing other units is to polymerize the monomers exemplified earlier with other vinyl monomers.

[0043] Other vinyl monomers include the following:

[0044] (Meth)acrylic acid esters such as styrene, α-methylstyrene, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0045] Monomers having a urea group: For example, monomers obtained by reacting an amine having 3 to 22 carbon atoms [primary amines (n-butylamine, t-butylamine, propylamine, and isopropylamine, etc.), secondary amines (di-normal ethylamine, di-normal propylamine, di-normal butylamine, etc.), aniline, and cycloxylamine, etc.] with an isocyanate having 2 to 30 carbon atoms and having an ethylenically unsaturated bond, by known methods.

[0046] Monomers having a carboxyl group; for example, methacrylic acid, acrylic acid, and 2-carboxyethyl (meth)acrylate. Monomers having a hydroxyl group; for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.

[0047] Monomers having an amide group; for example, acrylamide, monomers obtained by reacting an amine having 1 to 30 carbon atoms with a carboxylic acid having 2 to 30 carbon atoms having an ethylenically unsaturated bond (such as acrylic acid and methacrylic acid) by known methods.

[0048] Monomers having a urethane group: For example, alcohols with 2 to 22 carbon atoms having an ethylenically unsaturated bond (e.g., 2-hydroxyethyl methacrylate, vinyl alcohol) and isocyanates with 1 to 30 carbon atoms [monoisocyanate compounds (benzenesulfonyl isocyanate, tosyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, butyl isocyanate, hexyl isocyanate, t-butyl isocyanate, cyclohexyl isocyanate, octyl] Isocyanates, 2-ethylhexyl isocyanate, dodecyl isocyanate, adamantyl isocyanate, 2,6-dimethylphenyl isocyanate, 3,5-dimethylphenyl isocyanate, and 2,6-dipropylphenyl isocyanate, etc., aliphatic diisocyanate compounds (trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate) Diisocyanates (such as dodecamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate), alicyclic diisocyanate compounds (1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate and hydrogenated tetramethylxylylene diisocyanate), and Monomers obtained by reacting aromatic diisocyanate compounds (phenylenediisocyanate, 2,4-tolylenediisocyanate, 2,6-tolylenediisocyanate, 2,2'-diphenylmethanediisocyanate, 4,4'-diphenylmethanediisocyanate, 4,4'-toluidinediisocyanate, 4,4'-diphenyletherdiisocyanate, 4,4'-diphenyldiisocyanate, 1,5-naphthalenediisocyanate and xylylenediisocyanate, etc.) with known methods, and Alcohols with 1 to 26 carbon atoms (methanol, ethanol, propanol, isopropyl alcohol, butanol, t-butyl alcohol, pentanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, undecyl alcohol, lauryl alcohol, dodecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetanol, heptadecanol, stearyl alcohol, isostearyl alcohol, elaidyl alcohol, oleyl alcohol, linoleyl alcohol, linolenic acid Monomers obtained by reacting an isocyanate having 2 to 30 carbon atoms having an ethylenically unsaturated bond [such as 2-isocyanatoethyl (meth)acrylate, 2-(0-[1'-methylpropyleneneamino]carboxyamino)ethyl (meth)acrylic acid, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate, and 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate] by known methods.

[0049] Vinyl esters: vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl pivalate, vinyl octolate. In particular, styrene, methyl (meth)acrylate, and t-butyl (meth)acrylate are preferred.

[0050] <Other resin components> The toner of the present invention may contain resin components for various purposes other than the binder resin. Examples of usable resins include vinyl resins, polyesters, polyurethanes, epoxy resins, etc., which are not binder resins.

[0051] Polymerizable monomers that constitute vinyl resins that do not fall under the category of binder resins include those other than those that constitute unit (a) or (b) among those mentioned above. Two or more types may be used in combination as needed.

[0052] Polyesters can be obtained by the condensation polymerization reaction of a divalent or greater polycarboxylic acid and a polyhydric alcohol.

[0053] Examples of polycarboxylic acids include the following compounds.

[0054] Dibasic acids such as succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, malonic acid, and dodecenylsuccinic acid, and their anhydrides or lower alkyl esters, as well as aliphatic unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, and citraconic acid. 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, and their anhydrides or lower alkyl esters. These may be used individually or in combination of two or more.

[0055] Examples of polyhydric alcohols include the following compounds:

[0056] Alkylene glycols (ethylene glycol, 1,2-propylene glycol, and 1,3-propylene glycol); alkylene ether glycols (polyethylene glycol and polypropylene glycol); alicyclic diols (1,4-cyclohexanedimethanol); bisphenols (bisphenol A); alkylene oxide (ethylene oxide and propylene oxide) adducts of alicyclic diols. The alkyl portions of alkylene glycols and alkylene ether glycols may be linear or branched. In the present invention, branched alkylene glycols can also be preferably used. Furthermore, glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol, etc. These may be used individually or in combination of two or more.

[0057] Furthermore, monohydric acids such as acetic acid and benzoic acid, and monohydric alcohols such as cyclohexanol and benzyl alcohol may be used as needed to adjust the acid value and hydroxyl value.

[0058] The method for producing polyester is not particularly limited, but examples include the transesterification method and the direct polycondensation method.

[0059] Polyurethane is obtained by the reaction of a diol component with a diisocyanate component.

[0060] Examples of diisocyanate components include: aromatic diisocyanates with 6 to 20 carbon atoms (excluding carbon atoms in the NCO group; the same applies hereinafter), aliphatic diisocyanates with 2 to 18 carbon atoms, alicyclic diisocyanates with 4 to 15 carbon atoms, and modified products of these diisocyanates (modified products containing urethane groups, carbodiimide groups, allophanate groups, urea groups, biuret groups, uretoidone groups, uretoimine groups, isocyanurate groups, or oxazolidone groups; hereinafter also referred to as "modified diisocyanates"), as well as mixtures of two or more of these.

[0061] Examples of aromatic diisocyanates include: m- and / or p-xylylene diisocyanate (XDI) and α,α,α',α'-tetramethylxylylene diisocyanate.

[0062] Other examples of aliphatic diisocyanates include: ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), and dodecamethylene diisocyanate.

[0063] Examples of alicyclic diisocyanates include: isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate, cyclohexylene diisocyanate, and methylcyclohexylene diisocyanate.

[0064] Among these, preferred are aromatic diisocyanates having 6 to 15 carbon atoms, aliphatic diisocyanates having 4 to 12 carbon atoms, and alicyclic diisocyanates having 4 to 15 carbon atoms, with XDI, IPDI, and HDI being particularly preferred.

[0065] In addition to diisocyanate components, isocyanate compounds of tri or higher strength can also be used.

[0066] The diol components that can be used in polyurethane are the same as the divalent alcohols that can be used in polyester as mentioned above.

[0067] <Release agent> The toner may contain a release agent. The release agent is preferably at least one selected from the group consisting of hydrocarbon waxes and ester waxes. Using hydrocarbon waxes and / or ester waxes makes it easier to ensure effective release properties. There are no particular limitations on hydrocarbon waxes, but examples include the following:

[0068] Aliphatic hydrocarbon waxes: low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymers, Fischer-Tropsch waxes, or waxes obtained by oxidation or acid addition of these.

[0069] Ester waxes only need to have at least one ester bond in each molecule, and either natural or synthetic ester waxes may be used. There are no particular limitations on the ester wax, but examples include the following:

[0070] Esters of monohydric alcohols and monocarboxylic acids, such as behenyl behenate, stearyl stearate, and palmityl palmitate; Esters of divalent carboxylic acids and monoalcohols, such as dibehenyl sebacate; Esters of dihydric alcohols such as ethylene glycol distearate and hexanediol dibehenate with monocarboxylic acids; Esters of trihydric alcohols such as glycerol tribehenate and monocarboxylic acids; Esters of tetrahydric alcohols such as pentaerythritol tetrastearate and pentaerythritol tetrapalmitate with monocarboxylic acids; Esters of hexahydritol alcohols such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate, and dipentaerythritol hexabéhenate with monocarboxylic acids; Esters of polyfunctional alcohols such as polyglycerin behenates and monocarboxylic acids; natural ester waxes such as carnauba wax and rice wax; Among these, esters of hexavalent alcohols and monocarboxylic acids, such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate, and dipentaerythritol hexabéhenate, are preferred.

[0071] The release agent may be a hydrocarbon wax or an ester wax alone, or a combination of hydrocarbon wax and an ester wax, or a mixture of two or more types of each. However, it is preferable to use a hydrocarbon wax alone or two or more types. It is more preferable that the release agent is a hydrocarbon wax.

[0072] The release agent content in the toner particles is preferably 1.0% by mass or more and 30.0% by mass or less, and more preferably 2.0% by mass or more and 25.0% by mass or less. Having the release agent content in the toner particles within this range makes it easier to ensure release properties during fixing.

[0073] The melting point of the release agent is preferably between 60°C and 120°C. A melting point within this range allows the release agent to melt during fixing and easily seep onto the toner particle surface, thus facilitating release properties. More preferably, the melting point is between 70°C and 100°C.

[0074] <Coloring agent> The toner may contain a colorant. Examples of colorants include known organic pigments, organic dyes, inorganic pigments, carbon black as a black colorant, and magnetic particles. Other colorants conventionally used in toners may also be used.

[0075] Examples of yellow colorants include: condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, CI Pigment Yellows 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, and 180 are preferably used.

[0076] Examples of magenta colorants include: condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolon compounds, thioindigo compounds, and perylene compounds. Specifically, CI Pigment Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, and 254 are preferably used.

[0077] Examples of cyan colorants include: copper phthalocyanine compounds and their derivatives, anthraquinone compounds, and basic dye lake compounds. Specifically, CI pigment blues 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and 66 are preferably used. The colorant is selected based on its hue angle, saturation, brightness, lightfastness, OHP transparency, and dispersibility in toner.

[0078] The coloring agent content is preferably 1.0 part by mass or more and 20.0 parts by mass or less per 100.0 parts by mass of the binder resin. When magnetic particles are used as the coloring agent, their content is preferably 40.0 parts by mass or more and 150.0 parts by mass or less per 100.0 parts by mass of the binder resin.

[0079] <Charge control agent> A charge control agent may be incorporated into the toner particles as needed. Alternatively, the charge control agent may be added externally to the toner particles. By incorporating a charge control agent, the charge characteristics can be stabilized, and the optimal amount of triboelectric charge can be controlled according to the developing system. Known charge control agents can be used, and those that have a fast charging speed and can stably maintain a constant amount of charge are particularly preferred.

[0080] Examples of charge control agents that control the toner's charge to match the load charge include the following: Organometallic compounds and chelate compounds are effective, and examples include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, and oxycarboxylic acid and dicarboxylic acid-based metal compounds.

[0081] Examples of substances that control the positive charge of toner include: nigrosine, quaternary ammonium salts, metal salts of higher fatty acids, diorganosucroses, guanidine compounds, and imidazole compounds. The content of the charge control agent is preferably 0.01 parts by mass to 20.0 parts by mass, more preferably 0.5 parts by mass to 10.0 parts by mass, per 100.0 parts by mass of toner particles.

[0082] <External additives> The toner particles may be used as toner as is, or they may be mixed with external additives as needed and attached to the surface of the toner particles to form toner. Examples of external additives include inorganic fine particles selected from the group consisting of silica fine particles, alumina fine particles, and titania fine particles, or composite oxides thereof. Examples of composite oxides include silica-aluminum fine particles and strontium titanate fine particles. The content of the external additive is preferably 0.01 parts by mass or more and 8.0 parts by mass or less, and more preferably 0.1 parts by mass or more and 4.0 parts by mass or less, per 100 parts by mass of toner particles.

[0083] [Toner manufacturing method] Next, we will describe the method for manufacturing the toner. The toner particles may be manufactured by any of the conventionally known methods, such as suspension polymerization, emulsification and agglutination, dissolution and suspension, or pulverization, as long as they are within the scope of the present configuration. The method for manufacturing toner by suspension polymerization will be described in detail below.

[0084] <Manufacturing method for toner using suspension polymerization> (Dispersion process) A polymerizable monomer for generating a binder resin and various materials such as colorants as needed are mixed, and a raw material dispersion is prepared by melting, dissolving, or dispersing these materials using a disperser. Furthermore, waxes, charge control agents, solvents for viscosity adjustment, and other additives listed in the materials section can be added to the raw material dispersion as appropriate. As for the solvent for viscosity adjustment, any known solvent that can dissolve and disperse the above materials well and has low solubility in water can be used without particular limitations. Examples include toluene, xylene, and ethyl acetate. Examples of dispersers include homogenizers, ball mills, colloid mills, and ultrasonic dispersers.

[0085] (granulation process) The raw material dispersion is added to a pre-prepared aqueous medium, and a suspension is prepared using a disperser such as a high-speed stirrer or ultrasonic disperser. The aqueous medium preferably contains a dispersion stabilizer for particle size adjustment and aggregation suppression. Any conventionally known dispersion stabilizer can be used without particular limitations.

[0086] Examples of inorganic dispersion stabilizers include phosphates such as hydroxyapatite, tricalcium phosphate, dicalcium phosphate, magnesium phosphate, aluminum phosphate, and zinc phosphate; carbonates such as calcium carbonate and magnesium carbonate; metal hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide; sulfates such as calcium sulfate and barium sulfate; calcium metasilicate, bentonite, silica, and alumina.

[0087] Furthermore, examples of organic dispersion stabilizers include polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salts of carboxymethylcellulose, polyacrylic acid and its salts, and starch.

[0088] Among these, inorganic dispersion stabilizers are preferred because they exhibit high charge polarization and strong adsorption to the oil phase, resulting in a strong anti-aggregation effect. Furthermore, hydroxyapatite, tricalcium phosphate, and dicalcium phosphate are even more preferred because they can be easily removed by pH adjustment.

[0089] (Polymerization process) Polymerizable monomers in a suspension are polymerized to obtain toner particles. The polymerization initiator may be mixed with other additives when preparing the raw material dispersion, or it may be mixed into the raw material dispersion immediately before suspension in an aqueous medium. It can also be added during or after the granulation process, i.e., immediately before starting the polymerization process, or during the polymerization process, in a state dissolved in polymerizable monomers or other solvents as needed. After polymerizing the polymerizable monomers to obtain polymers, desolvent treatment is performed by heating or reducing pressure as needed to obtain an aqueous dispersion of toner particles.

[0090] Any known polymerization initiator can be used without any particular restrictions. Specifically, the following are examples:

[0091] Examples of oil-soluble initiators include pigment dispersants such as 2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis(cyclohexane-1-carbonnitrile), and 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile; and peroxide-based initiators such as acetylcyclohexylsulfonyl peroxide, diisopropyl peroxycarbonate, decanonyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide, acetyl peroxide, t-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, t-butyl peroxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t-butyl peroxypivalate, and cumene hydroperoxide. Two or more oil-soluble initiators may be used.

[0092] Examples of water-soluble initiators include ammonium persulfate, potassium persulfate, 2,2'-azobis(N,N'-dimethyleneisobutyroamidine) hydrochloride, 2,2'-azobis(2-aminodinopropane) hydrochloride, azobis(isobutylamidine) hydrochloride, sodium 2,2'-azobisisobutyronitrile sulfonate, ferrous sulfate, or hydrogen peroxide. In particular, ammonium persulfate, sodium persulfate, and potassium persulfate are preferably used to adjust the amount of sulfo groups that penetrate from the toner surface using a water-soluble initiator.

[0093] In this invention, by fixing the sulfo groups of the water-soluble initiator to the ends, main chain, and side chains of the crosslinked structure, electrostatic interaction with mobile ions present inside the toner can be controlled, thereby controlling the ionic conductivity. This allows control of the polarization charge Δεr derived from conductivity, and thus control the electrostatic adhesion force of the toner. At this time, the amount of sulfo groups present on the surface of the toner can be measured by time-of-flight secondary ion mass spectrometry (TOF-SIMS), described later, and it is preferable that the ion count Ic1 is 0.005 or more and 0.05 or less. The lower limit of the ion count Ic1 indicates a boundary value that suppresses the interfacial polarization Δεr derived from conductivity. Furthermore, the upper limit of the ion count Ic1 indicates a value that satisfies low-temperature fixation, as the crosslinked structure varies depending on the binder resin formulation.

[0094] The concentration of the polymerization initiator is preferably in the range of 0.1 parts by mass to 20 parts by mass per 100 parts by mass of polymerizable monomer, and more preferably in the range of 0.1 parts by mass to 10 parts by mass. The type of polymerization initiator varies slightly depending on the polymerization method, but it is used alone or in mixtures, with the 10-hour half-temperature as a reference.

[0095] In this invention, by using a water-soluble polymerization initiator and an oil-soluble polymerization initiator in combination, and by fixing the anionic structure of the polymerization initiator to the ends, main chain, and side chains of the crosslinked structure, the ionic conductivity of the toner can be controlled.

[0096] In the polymerization process, the first polymerizable monomer represented by formula (A) below forms the monomer unit (a) represented by formula (2), and the second polymerizable monomer represented by formula (B) below forms the monomer unit (b) represented by formula (3).

[0097] [ka] [In formula (A), R1 represents a hydrogen atom or a methyl group, L1 represents a single bond or a divalent linking group, and m represents an integer between 15 and 35.]

[0098] [ka] [In formula (B), R2 represents a hydrogen atom or a methyl group.]

[0099] Furthermore, in the polymerization process, it is preferable to add a water-soluble polymerization initiator separately from the oil-soluble polymerization initiator when the polymerization conversion rate of the first polymerizable monomer (A) is 30.0% or more and the polymerization conversion rate of the second polymerizable monomer (B) is 90.0% or less. By adding the water-soluble polymerization initiator within this timing range, the anionic structure of the water-soluble polymerization initiator can be fixed to the ends of the crosslinked structure, on the main chain, and on the side chains of the toner surface layer. As a result, the electrostatic adhesion force of the toner can be controlled by the interfacial polarization Δεr derived from the conductivity of the toner, thereby suppressing the adhesion and accumulation of toner on the toner regulating member.

[0100] (filtration process, washing process, drying process, classification process, external addition process) The toner particles are obtained by a filtration process to separate the solid components from an aqueous dispersion of toner particles, followed by washing, drying, and classification processes as needed. The toner particles may be used as toner as is. Alternatively, the toner particles can be mixed and attached with external additives such as inorganic fine powders using a mixer to obtain toner.

[0101] [Method for measuring the physical properties of the toner of the present invention] The following describes various measurement methods.

[0102] <Method for measuring toner impedance> The electrical AC characteristics of toner (powder) can be obtained by impedance measurement using the parallel plate capacitor method.

[0103] The apparatus uses a powder measurement jig consisting of a 4-terminal sample holder SH2-Z (manufactured by Toyo Technica Co., Ltd.) and a torque wrench adapter SH-TRQ-AD (optional), as well as a ModuLab XM MTS material testing system (manufactured by Solartron Corporation). In addition, a noise-cutting transformer NCT-I3 1.4kVA (manufactured by Denken Seiki Kenkyusho Co., Ltd.) to suppress commercial power supply noise and a shielded box to suppress electromagnetic noise are used.

[0104] The jig for powder measurement uses a 4-terminal sample holder and the optional torque wrench adapter SH-TRQ-AD. Parallel plate electrodes are used: an upper electrode (Φ25mm solid electrode) SH-H25AU and a lower electrode for liquids / powder (center electrode Φ10mm; guard electrode Φ26mm) SH-2610AU. This configuration allows for the measurement of resistances from 0.1Ω to 1TΩ for electrical signals up to 500Vp-p and DC~1MHz. Furthermore, to adjust the pressure of the powder sample, a torque wrench adapter SH-TRQ-AD (manufactured by Toyo Technica Co., Ltd.) is attached to a micrometer used for measuring film thickness between the upper and lower electrodes, which is mounted on the 4-terminal sample holder. For pressure control, a torque driver RTD15CN (manufactured by Tohnichi Manufacturing Co., Ltd.) and a 6.35mm square bit are used, allowing for the tightening torque for toner measurement to be controlled to 6.5cN·m.

[0105] Electrical AC characteristics are measured using the ModuLab XM MTS material testing system (manufactured by Solartron), with impedance measurements being performed. The ModuLab XM MTS consists of a control module XM MAT 1MHz, a high-voltage module XM MHV100, a femtocurrent module XM MFA, and a frequency response analysis module XM MRA 1MHz. The control software used is Solartron's XM-studio MTS Ver.3.4.

[0106] For measuring dielectric (insulating) powders such as toner, the measurement conditions are set to Normal Mode, which is used only for measurement, with a DC bias of 0V and a sweep frequency of 1MHz to 0.01Hz (12 points / decade).

[0107] Furthermore, considering noise suppression and reduction of measurement time, the following settings will be added for each sweep frequency. Sweep frequency 1MHz~100Hz, AC level 1Vrms, measurement integration time 1 second; 768 cycles Sweep frequency 100Hz~10Hz, AC level 7Vrms, measurement integration time 1 second; 96 cycles Sweep frequency 10Hz~1Hz, AC level 7Vrms, measurement integration time 1 second; 32 cycles Sweep frequency 1Hz~0.1Hz, AC level 7Vrms, measurement integration time 10 seconds; 4 cycles Sweep frequency 0.1Hz~0.01Hz, AC level 7Vrms, measurement integration time 10 seconds; 1 cycle

[0108] Under the above measurement conditions, the impedance characteristics, which are electrical AC characteristics, will be measured.

[0109] By performing measurements under the above conditions, the impedance characteristics of air and sample at a film thickness d corresponding to the pressurized torque can be obtained using a powder measurement jig based on the parallel plate condenser method, with a Φ10 mm measuring electrode S.

[0110] From the obtained impedance characteristics of the air and sample, data correction processing of the measurement system is performed to obtain highly reliable capacitance C and conductance G. From the obtained capacitance C, conductance G, and the geometric shape of the powder measurement jig (parallel plate electrode size S and sample film thickness), the electrical properties relative permittivity and conductivity are determined.

[0111] When using the SH2-Z 4-terminal sample holder for the first time, there are individual differences between the SH2-Z 4-terminal sample holders used in powder measurement jigs. Therefore, the following two verifications must be performed to find the optimal measurement conditions. The first verification is the film thickness dependence characteristic of the 4-terminal sample holder. Measure the dependence on air thickness (distance between upper and lower electrodes), check the error between the theoretical value and the measured value of capacitance, and determine the optimal range or film thickness at which the measurement error is minimized. The second verification is the measurement of mechanical errors. When measuring powder samples, a torque-controlled load is applied to maintain a constant volume density. In contrast, air is measured under no-load conditions. In this case, film thickness errors occur due to the influence of dimensional factors such as mechanical processing accuracy. Therefore, check the offset value between the loaded and unloaded states of the tightening torque control value (6.5 cN·m in this jig), and use this as the offset correction value.

[0112] The specific sample preparation and measurement procedures are as follows: (1) Place the powder sample on the central electrode portion of the lower electrode and shape it into a trapezoidal shape with a height of 5 mm. (2) Attach the lower electrode, on which the powder sample is placed, to the 4-terminal sample holder SH2-Z, and lower the upper electrode. (3) At this time, the upper electrode is lowered to the upper end of the powder sample while keeping it constant so as not to rotate unintentionally. (4) While rotating the upper electrode from side to side, perform a smoothing process to make the powder sample smooth. (5) Using a micrometer, adjust the film thickness to the desired level while maintaining a consistent CW direction of rotation for the upper electrode. (6) In the case of toner, apply pressure using a torque driver with a tightening torque controlled to 6.5 cN·m. (7) Use a micrometer to measure the film thickness of the powder sample. (8) Perform impedance measurements under the above conditions. (9) After the measurement is complete, raise the upper electrode and remove the lower electrode. At this time, remove the lower electrode carefully, making sure that no powder sample enters the contact terminals for the lower electrode of the 4-terminal sample holder, and protect them with masking tape. (10) Clean the upper and lower electrodes. (11) Remove the masking tape and attach the lower electrode. (12) Adjust the air thickness t to the sample film thickness d obtained in step (7), taking into account the offset correction under no-load conditions, and maintain the rotation direction of the upper electrode in a uniform, constant direction. (13) Measure the impedance of the air. (14) If the measured air data (dielectric loss tangent; tanδ) measured in step (13) is greater than 0.001 in the frequency range of 100Hz to 0.021Hz, the cleaning is insufficient, and the process is repeated starting from the cleaning step in step (10).

[0113] The measurement will be conducted at 25°C.

[0114] The specific data processing procedure is as follows: (15) From the measured impedance characteristics of the air, the error in the phase characteristics relative to the theoretical value is calculated, and phase correction data is obtained for the ModuLab XM MTS material testing system (manufactured by Solartron). (16) The phase correction data calculated in step (15) is applied to the impedance characteristics of the air measured in step (13) to obtain the impedance characteristics of the air after phase correction processing. (17) The capacitance Ca is calculated from the admittance Ya = Ga + jωCa of the phase-corrected air impedance characteristics, and the error with the theoretical value is calculated to obtain correction data α for the film thickness error. (18) The phase correction process obtained in step (15) is applied to the impedance characteristics of the powder sample measured in step (8). (19) The relative permittivity and conductivity of the powder sample can be obtained with high reliability by calculating the complex admittance Ym = Gm + jωCm of the characteristic after the phase correction processing in step (18) using the capacitance of air Ca obtained in step (17) and its correction data α.

[0115] <Monomer analysis of resin components such as binder resins> The types of monomers in the binder resin and other resin components are determined by analyzing samples of each resin component separated from the toner using a pyrolysis GC / MS instrument under the following conditions. Measurement device: "Voyager" (product name, manufactured by ThermoElectron) Pyrolysis temperature: 600℃ Column: HP-1 (15m x 0.25mm x 0.25μm) Inlet: 300℃, Split: 20.0 Injection volume: 1.2mL / min Heating: 50℃ (4 min) - 300℃ (20℃ / min)

[0116] <Measurement of secondary ions on the surface of toner particles using time-of-flight secondary ion mass spectrometry (TOF-SIMS)> The depth profile of ions originating from the resin constituting the toner particle surface was measured using ULVAC-PHIE TOF-SIMS (TRIFTIV). The conditions were as follows:

[0117] [Sample adjustment] Place an indium plate on the sample holder and attach toner particles to it. If the toner particles move around on the sample holder, you can place an indium plate on the sample holder, apply carbon paste, and then fix the toner particles on top of that. When using fixing aids such as carbon paste or silicon wafers, measure the background under the same conditions without toner particles and convert it to the new background.

[0118] [Spatter Conditions] Sputter ion species: Argon cluster ion ((Arn) + , n=2000) Acceleration voltage: 10kV Current value: 8.5nA Sputtering area: 600 x 600 μm 2 Sputtering time: 2 sec / cycle Sputtering rate: 1 nm / sec

[0119] The above sputtering rate was calculated by sputtering a polymethyl methacrylate resin with a film thickness of 300 nm under the above sputtering conditions, determining the time required to complete sputtering to a film thickness of 300 nm, and then normalizing the result.

[0120] [Analysis conditions] Primary ion species: Gold ion (Au) + ) Acceleration voltage: 30 keV Current value: 2pA Analysis area: 300×300μm 2 Pixel count: 64 x 64 pixels Analysis time: 4sec / cycle Repetition frequency: 8.2kHz Neutralizing charge: ON Secondary ion polarity: Positive Secondary ion mass-to-charge ratio (m / z) range: 0.5~1850

[0121] [Calculation of Ic1] After identifying the monomer species of the binder resin by the monomer analysis described above, Ic1 is defined as the intensity ratio of the ion count with a secondary ion mass-charge ratio of 80 derived from the sulfonic acid group to the total ion count derived from all resins, including the binder resin, in the range of secondary ion mass-charge ratio of 0.5 to 1850 on the outermost surface of the toner particles.

[0122] (Isolation of toner particles from toner) The above measurement can also be performed using toner particles isolated from the toner in the following manner.

[0123] Add 160g of sucrose (manufactured by Kishida Chemical Co., Ltd.) to 100mL of deionized water and dissolve it while heating in a water bath to prepare a concentrated sucrose solution. Add 31g of the above concentrated sucrose solution and 6mL of Contaminon N (a 10% by mass aqueous solution of pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) to a centrifuge tube (capacity 50mL). Add 1.0g of toner and break up any clumps of toner with a spatula or similar tool. Shake the centrifuge tube in a shaker (AS-1N, sold by AS ONE Corporation) at 300 spm (strokes per min) for 20 minutes. After shaking, transfer the solution to a glass tube for a swing rotor (50mL) and separate it using a centrifuge (H-9R, manufactured by Kokusan Co., Ltd.) at 3500 rpm for 30 minutes.

[0124] This operation separates the toner particles from the external additive. Visually confirm that the toner particles and aqueous solution are sufficiently separated, and collect the toner particles separated to the top layer using a spatula or similar tool. Filter the collected toner particles using a vacuum filter, then dry them in a dryer for at least one hour to obtain a sample for measurement. Repeat this operation multiple times to obtain the required amount.

[0125] <Method for measuring the content ratio of various monomer units in the binder resin> The measurement of the content ratio of various monomer units in the binder resin is performed as follows: 1 The procedure is performed using H-NMR under the following conditions. ·Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) • Measurement frequency: 400MHz • Pulse condition: 5.0 μs • Frequency range: 10500Hz • Total number of times: 64 ·Measurement temperature: 30℃ • Sample: Place 50 mg of the sample to be measured into a sample tube with an inner diameter of 5 mm, add deuterated chloroform (CDCl3) as a solvent, and dissolve it in a constant temperature bath at 40°C to prepare the sample.

[0126] obtained 1From the H-NMR chart, select a peak from among the peaks attributed to the components of monomer unit (a) that is independent of the peaks attributed to the components of other monomer units, and calculate the integral value S1 of this peak. Similarly, select a peak from among the peaks attributed to the components of monomer unit (b) that is independent of the peaks attributed to the components of other monomer units, and calculate the integral value S2 of this peak.

[0127] Furthermore, if a third and fourth monomer unit is present, a peak independent of the peaks attributed to the components of the other monomer units is selected from the peaks attributed to the components of the third and fourth monomer units, and the integral values ​​S3 and S4 of this peak are calculated.

[0128] The content of monomer unit (a) is determined using the integral values ​​S1, S2, S3, and S4 as follows. Note that n1, n2, n3, and n4 are the number of hydrogen atoms in the constituent element to which the peak of interest belongs for each part.

[0129] Percentage of monomer unit (a) (mol%) = {(S1 / n1) / ((S1 / n1)+(S2 / n2)+(S3 / n3)+(S4 / n4))}×100

[0130] Similarly, the proportions of monomer unit (b), the third and fourth monomer units are determined as follows. Percentage of monomer unit (b) content (mol%) = {(S2 / n2) / ((S1 / n1)+(S2 / n2)+(S3 / n3)+(S4 / n4))}×100 The content percentage (mol%) of the third monomer unit = {(S3 / n3) / ((S1 / n1)+(S2 / n2)+(S3 / n3)+(S4 / n4))}×100 Percentage of the fourth monomer unit (mol%) = {(S4 / n4) / ((S1 / n1)+(S2 / n2)+(S3 / n3)+(S4 / n4))}×100

[0131] Furthermore, in the case of a binder resin in which a polymerizable monomer is used in which no hydrogen atoms are contained in components other than the vinyl group, 13 The atomic nuclei were measured using C-NMR. 13 Let C be used, and the measurement will be performed in single-pulse mode. 1 The same calculation is performed using 1H-NMR. Furthermore, when toner is manufactured by suspension polymerization, the peaks of the release agent and shell resin may overlap, preventing the observation of independent peaks. This can result in the inability to calculate the content ratio of various units in the binder resin. In such cases, a binder resin ' can be produced by performing the same suspension polymerization without using the release agent or other resins, and this binder resin ' can be analyzed as the binder resin.

[0132] <Method for measuring the polymerization conversion rate of polymerizable monomers> The polymerization conversion rate of polymerizable monomers is measured using gas chromatography (GC) as follows: 500 mg of toner particle dispersion is accurately weighed and placed in a sample bottle. 10 g of accurately weighed acetone is added, the bottle is capped, and thoroughly mixed. Ultrasound is then applied for 30 minutes using a benchtop ultrasonic cleaner (product name "B2510J-MTH", manufactured by Branson Corporation) with an oscillation frequency of 42 kHz and an electrical output of 125 W. The mixture is then filtered using a solvent-resistant membrane filter "Myshoridisk" (manufactured by Tosoh Corporation) with a pore diameter of 0.2 μm, and 2 μL of the filtrate is analyzed by gas chromatography. GC: HP 6890GC Column: HP INNOWax (200μm × 0.40μm × 25m) Carrier gas: He (Constant pressure mode: 20 psi) Oven: (1) Hold at 50°C for 10 minutes, (2) Increase temperature to 200°C at a rate of 10°C / minute, (3) Hold at 200°C for 5 minutes. Inlet: 200℃, pulsed splitless mode (20→40 psi, until 0.5 minutes) Split ratio: 5.0:1.0 Detector: 250℃ (FID)

[0133] Then, the "remaining amount" of polymerizable monomers is calculated using a calibration curve created with the polymerizable monomers used beforehand. Subsequently, the polymerization conversion rate (mass%) of the polymerizable monomers is determined according to the following formula. Polymerization conversion rate (mass%) = 100 × (1 - (Amount of polymerizable monomer remaining) / (Total amount of polymerizable monomer used))

[0134] Furthermore, in the case of polymerizable monomers that cannot be detected by gas chromatography (e.g., behenyl acrylate), the polymerization conversion rate is measured using gel permeation chromatography (GPC) as follows. First, approximately 500 mg of the toner particle dispersion during polymerization is accurately weighed and placed in a sample bottle. This is then dissolved in approximately 10 g of accurately weighed tetrahydrofuran (THF). The resulting solution is then filtered through a solvent-resistant membrane filter with a pore diameter of 0.2 μm, "Myshoridisk" (manufactured by Tosoh Corporation), to obtain a sample solution. This sample solution is then measured under the following conditions.

[0135] • Equipment: HLC8120 GPC (Detector: RI) (Manufactured by Tosoh Corporation) • Columns: Shodex KF-801, 802, 803, 804, 805, 806, 807 (7 columns, manufactured by Showa Denko) • Eluent: Tetrahydrofuran (THF) ·Flow rate: 1.0ml / min Oven temperature: 40.0℃ • Sample injection volume: 0.10 ml

[0136] Then, the "remaining amount" of polymerizable monomers is calculated using a calibration curve created with the polymerizable monomers used beforehand. Subsequently, the polymerization conversion rate (mass%) of the polymerizable monomers is determined according to the following formula. The measuring device and measurement conditions are the same as those for the measurement method of the molecular weight of the resin described above. Polymerization conversion rate (mass%) = 100 × (1 - (Amount of polymerizable monomer remaining) / (Total amount of polymerizable monomer used)) [Examples]

[0137] The present invention will be described in detail below with reference to examples, but these examples are not intended to limit the present invention in any way. In the following formulations, parts refer to parts by mass unless otherwise specified.

[0138] <Example 1> [Toner manufacturing by suspension polymerization method] (Manufacturing of toner particles 1) • Methacrylonitrile (polymerizable monomer B; equivalent to unit (b)) 30.0 parts • Styrene 13.0 parts • Ethyl methacrylate 7.0 parts • Aluminum di-t-butylsalicylate 1.0 part • Coloring agent: Carbon black 8.0 parts A mixture consisting of the above was prepared. The above mixture was placed in an attritor (manufactured by Nippon Coke Co., Ltd.) and dispersed using 5 mm diameter zirconia beads at 200 rpm for 2 hours to obtain a raw material dispersion.

[0139] Meanwhile, 735.0 parts of deionized water and 16.0 parts of trisodium phosphate (dodecahydrate) were added to a container equipped with a high-speed stirring device homomixer (Primix Corporation) and a thermometer, and the temperature was raised to 60°C while stirring at 12,000 rpm. Then, an aqueous calcium chloride solution, prepared by dissolving 9.0 parts of calcium chloride (dihydrate) in 65.0 parts of deionized water, was added, and the mixture was stirred at 12,000 rpm for 30 minutes while maintaining the temperature at 60°C. Then, 10% hydrochloric acid was added to adjust the pH to 6.0, obtaining an aqueous medium in which an inorganic dispersion stabilizer containing hydroxyapatite was dispersed in water.

[0140] Next, the above raw material dispersion was transferred to a container equipped with a stirring device and a thermometer, and heated to 60°C while being stirred at 100 rpm. Behenyl acrylate (polymerizable monomer A; equivalent to unit (a)) 50.0 parts • Release agent 1 10.0 parts (Release agent 1: DP18 (Dipentaerythritol stearate wax, melting point 79°C, manufactured by Nippon Seiro Co., Ltd.) After adding the mixture and stirring at 100 rpm for 30 minutes while maintaining a temperature of 60°C, 7.0 parts of t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) as oil-soluble polymerization initiator 1 and 1.0 part of t-butyl peroxyisobutyrate (manufactured by Arkema Yoshitomi Co., Ltd.: L80) as oil-soluble polymerization initiator 2 were added and stirred for a further minute. Then, the mixture was added to an aqueous medium being stirred at 12000 rpm using the high-speed stirring device described above. Stirring was continued at 12000 rpm for 20 minutes while maintaining a temperature of 60°C using the high-speed stirring device described above to obtain a granulated liquid.

[0141] The above granulated liquid was transferred to a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube. The temperature was raised to 70°C while stirring at 150 rpm under a nitrogen atmosphere, and the first stage of polymerization was carried out at 150 rpm. When the polymerization conversion rate of polymerizable monomer A reached 50% by mass and the polymerization conversion rate of polymerizable monomer B reached 80%, 1.0 part of potassium persulfate (KPS) was added as a water-soluble polymerization initiator. The holding time for the first stage of polymerization was set to 5 hours. Thereafter, the temperature was raised to 90°C, and the second polymerization reaction was carried out for 4 hours while maintaining 90°C. The temperature was then raised further to 99°C, and the third polymerization reaction was carried out for 3 hours while maintaining 99°C to obtain a toner particle dispersion.

[0142] The obtained toner particle dispersion was cooled to 45°C while being stirred at 150 rpm, and then heat-treated for 5 hours while maintaining the temperature at 45°C. After that, while maintaining stirring, dilute hydrochloric acid was added until the pH reached 1.5 to dissolve the dispersion stabilizer. The solid components were filtered off, and after thorough washing with deionized water, the mixture was vacuum-dried at 30°C for 24 hours to obtain toner particles 1 with a weight-average particle size (D4) of 6.4 μm.

[0143] (Preparation of Toner 1) For the above toner particles in a 1:100.0 ratio, silica microparticles (hydrophobized with hexamethyldisilazane, primary particle number average particle size: 10 nm, BET specific surface area: 170 m²) are used as an external additive. 22.0 parts of ( / g) were added and mixed for 15 minutes at 3000 rpm using a Henschel mixer (manufactured by Nippon Coke Co., Ltd.) to obtain Toner 1. The physical properties of the obtained Toner 1 are shown in Tables 3, 4, and 5.

[0144] Examples 2-8, 10-17 (Examples 3, 6, 7, and 11 are for reference only.) > In the production of toner 1 of Example 1, toner particles 2-8 and 10-17 were obtained in the same manner as in Example 1, except that the type and amount of polymerizable monomer used, the type and amount of oil-soluble initiator and water-soluble initiator, and the polymerization conditions were changed as shown in Tables 1 and 2.

[0145] Furthermore, the same external addition process as for toner particle 1 was performed to obtain toners 2-8 and 10-17. The physical properties of the obtained toners are shown in Tables 3, 4, and 5.

[0146] <Example 9> (Reference example) > (Manufacturing of toner particles 9) • Methacrylonitrile (polymerizable monomer B; equivalent to unit (b)) 30.0 parts • Styrene 13.0 parts • Ethyl methacrylate 7.0 parts • Aluminum di-t-butylsalicylate 1.0 part • Coloring agent: Carbon black 8.0 parts A mixture consisting of the above was prepared. The above mixture was placed in an attritor (manufactured by Nippon Coke Co., Ltd.) and dispersed using 5 mm diameter zirconia beads at 200 rpm for 2 hours to obtain a raw material dispersion.

[0147] Meanwhile, 735.0 parts of deionized water and 16.0 parts of trisodium phosphate (dodecahydrate) were added to a container equipped with a high-speed stirring device homomixer (Primix Corporation) and a thermometer, and the temperature was raised to 60°C while stirring at 12,000 rpm. Then, an aqueous calcium chloride solution, prepared by dissolving 9.0 parts of calcium chloride (dihydrate) in 65.0 parts of deionized water, was added, and the mixture was stirred at 12,000 rpm for 30 minutes while maintaining the temperature at 60°C. Then, 10% hydrochloric acid was added to adjust the pH to 6.0, obtaining an aqueous medium in which an inorganic dispersion stabilizer containing hydroxyapatite was dispersed in water.

[0148] Next, the above raw material dispersion was transferred to a container equipped with a stirring device and a thermometer, and heated to 60°C while being stirred at 100 rpm. Behenyl acrylate (polymerizable monomer A; equivalent to unit (a)) 49.0 parts • Release agent 1 10.0 parts (Release agent 1: DP18 (Dipentaerythritol stearate wax, melting point 79°C, manufactured by Nippon Seiro Co., Ltd.) After adding the mixture and stirring at 100 rpm for 30 minutes while maintaining a temperature of 60°C, 7.0 parts of t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) as oil-soluble polymerization initiator 1 and 1.0 part of t-butyl peroxyisobutyrate (manufactured by Arkema Yoshitomi Co., Ltd.: L80) as oil-soluble polymerization initiator 2 were added and stirred for a further minute. Then, the mixture was added to an aqueous medium being stirred at 12000 rpm using the high-speed stirring device described above. Stirring was continued at 12000 rpm for 20 minutes while maintaining a temperature of 60°C using the high-speed stirring device described above to obtain a granulated liquid.

[0149] The above granulated liquid was transferred to a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube. The temperature was raised to 70°C while stirring at 150 rpm under a nitrogen atmosphere, and the first stage of polymerization was carried out at 150 rpm. After stirring for 2 hours, 2.0 parts of methacrylonitrile were added and stirred for 5 minutes. When the polymerization conversion rate of polymerizable monomer A reached 50% by mass and the polymerization conversion rate of polymerizable monomer B reached 75%, as measured during the above reaction, 1.0 part of potassium persulfate (KPS) was added as a water-soluble polymerization initiator. The holding time for the first stage of polymerization was a total of 5 hours. Subsequently, the temperature was raised to 90°C, and the second polymerization reaction was carried out for 4 hours while maintaining 90°C. Then, the temperature was further raised to 99°C, and the third polymerization reaction was carried out for 3 hours while maintaining 99°C to obtain a toner particle dispersion.

[0150] The obtained toner particle dispersion was cooled to 45°C while being stirred at 150 rpm, and then heat-treated for 5 hours while maintaining the temperature at 45°C. After that, while maintaining stirring, dilute hydrochloric acid was added until the pH reached 1.5 to dissolve the dispersion stabilizer. The solid components were filtered off, thoroughly washed with deionized water, and then vacuum-dried at 30°C for 24 hours to obtain toner particles 9.

[0151] (Preparation of Toner 9) For the above toner particles in a 1:100.0 ratio, silica microparticles (hydrophobized with hexamethyldisilazane, primary particle number average particle size: 10 nm, BET specific surface area: 170 m²) are used as an external additive. 2 2.0 parts of ( / g) were added and mixed using a Henschel mixer (manufactured by Nippon Coke Co., Ltd.) at 3000 rpm for 15 minutes to obtain toner 9. The physical properties of the obtained toner are shown in Tables 3 and 4.

[0152] <Comparative Example 1> (Example of manufacturing crystalline polyester A) In a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet tube, and vacuum device, 100 parts of xylene were heated under nitrogen purging and refluxed at a liquid temperature of 140°C. To this solution, a mixture of 100 parts of styrene and 8.00 parts of Dimethyl 2,2'-azobis (2-methylpropionate) as a polymerization initiator was added dropwise over 3 hours. After the addition was complete, the solution was stirred for 3 hours. Subsequently, the xylene and residual styrene were removed by distillation at 160°C and 1 hPa to obtain a vinyl polymer.

[0153] Next, the following materials were added to a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet tube, dewatering tube, and vacuum device, and the mixture was reacted under a nitrogen atmosphere at 150°C for 4 hours. • 95.1 parts of the vinyl polymer obtained above • Xylene as an organic solvent: 120.0 parts 1,12-Dodecanediol 78.6 parts • 0.500 parts of titanium(IV) isopropoxide as an esterification catalyst. Subsequently, 65.5 parts of sebacic acid were added and the mixture was reacted at 150°C for 3 hours. Furthermore, 9.5 parts of stearic acid were added and the mixture was reacted at 180°C for 4 hours. Subsequently, the mixture was further reacted at 180°C and 1 hPa until the desired acid value and hydroxyl value were achieved to obtain crystalline polyester A.

[0154] (Example of manufacturing polar resin A) 300 parts xylene were added to an autoclave equipped with a stirrer, thermometer, nitrogen inlet tube, vacuum device, and dewatering tube, and heated while purging with nitrogen until refluxed at a liquid temperature of 140°C. A mixture of the following materials was then added, and polymerization was carried out for 5 hours at a polymerization temperature of 160°C and a reaction pressure of 0.150 MPa. • Styrene 91.50 parts, • Butyl acrylate 1.00 part, Methyl methacrylate 2.50 parts, • Methacrylic acid 2.50 parts 2.50 parts of 2-hydroxyethyl methacrylate, • Polymerization initiator (di-tert-butyl peroxide) 2.00 parts Subsequently, a solvent removal process was carried out under reduced pressure for 3 hours to remove xylene, and then the material was pulverized to obtain polar resin A.

[0155] (Manufacturing of Toner 18) The following materials were added to a four-necked container equipped with a reflux tubing, stirrer, thermometer, and nitrogen inlet tube, and the mixture was stirred at 12,000 rpm using a high-speed stirring device TK Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) while maintaining the temperature at 60°C. • 700 bottles of deionized water 1000 parts of 0.1 mol / liter Na3PO4 aqueous solution 24.0 parts of 1.0 mol / liter aqueous solution of HCl Here, 85 parts of a 1.0 mol / liter CaCl2 aqueous solution were gradually added to prepare an aqueous dispersion medium containing fine, poorly water-soluble dispersion stabilizer Ca3(PO4)2.

[0156] • Styrene monomer 75.5 parts n-butyl acrylate 24.5 parts Crystalline polyester A 27.0 parts • Polar resin A 10.0 parts • Release agent (behenyl behenate) 10.0 parts • Carbon Black 8.0 parts • Charge control agent (Bontron E-88, manufactured by Orient Chemical Industries, Ltd., an aluminum 3:1 compound of 3,5-di-tert-butylsalicylic acid) 0.7 parts The polymerizable monomer composition 1, obtained by dispersing the above materials in an attritor (manufactured by Mitsui Miike Chemical Machinery Co., Ltd.) for 3 hours, was held at a temperature of 60°C for 20 minutes. Subsequently, 10.0 parts of t-butyl peroxypivalate (70% toluene solution), which is a polymerization initiator, was added to polymerizable monomer composition 1. This polymerizable monomer composition 1 was then placed in an aqueous medium and granulated for 10 minutes while maintaining the rotation speed of the high-speed stirrer at 12,000 rpm. After that, the high-speed stirrer was replaced with a propeller-type stirrer, the internal temperature was raised to 70°C, and the reaction was carried out for 5 hours with slow stirring. At this time, the pH of the aqueous medium was 5.1. Next, the temperature inside the container was raised to 85°C and maintained for 5 hours. After that, the reflux tubing was removed, a distillation apparatus was attached, and distillation was carried out at a temperature of 100°C inside the container for 5 hours. After cooling to 30°C, 10% hydrochloric acid was added to remove the dispersion stabilizer. Furthermore, the toner particles 18 with a weight-average particle size (D4) of 6.4 μm were obtained by filtering, washing, and drying.

[0157] 100 toner particles 18, BET value 300m 2 Toner 18 was obtained by mixing 1.6 parts of hydrophobic silica fine powder, which was 1 / g and had a primary particle number average size of 8 nm, with a Mitsui Henschel mixer (manufactured by Mitsui Miike Chemical Machinery Co., Ltd.). The physical properties of the obtained toner 18 are shown in Tables 3 and 4.

[0158] <Comparative Example 2> (Manufacturing of toner particles 19) • Methacrylonitrile (polymerizable monomer B; equivalent to unit (b)) 30.0 parts • Styrene 13.0 parts • Ethyl methacrylate 7.0 parts • Aluminum di-t-butylsalicylate 1.0 part • Coloring agent: Carbon black 8.0 parts A mixture consisting of the above was prepared. The above mixture was placed in an attritor (manufactured by Nippon Coke Co., Ltd.) and dispersed using 5 mm diameter zirconia beads at 200 rpm for 2 hours to obtain a raw material dispersion.

[0159] Meanwhile, 735.0 parts of deionized water and 16.0 parts of trisodium phosphate (dodecahydrate) were added to a container equipped with a high-speed stirring device homomixer (Primix Corporation) and a thermometer, and the temperature was raised to 60°C while stirring at 12,000 rpm. Then, an aqueous calcium chloride solution, prepared by dissolving 9.0 parts of calcium chloride (dihydrate) in 65.0 parts of deionized water, was added, and the mixture was stirred at 12,000 rpm for 30 minutes while maintaining the temperature at 60°C. Then, 10% hydrochloric acid was added to adjust the pH to 6.0, obtaining an aqueous medium in which an inorganic dispersion stabilizer containing hydroxyapatite was dispersed in water.

[0160] Next, the above raw material dispersion was transferred to a container equipped with a stirring device and a thermometer, and heated to 60°C while being stirred at 100 rpm. Behenyl acrylate (polymerizable monomer A; equivalent to unit (a)) 50.0 parts • Release agent 1 10.0 parts (Release agent 1: DP18 (Dipentaerythritol stearate wax, melting point 79°C, manufactured by Nippon Seiro Co., Ltd.) After adding the mixture and stirring at 100 rpm for 30 minutes while maintaining a temperature of 60°C, 7.0 parts of t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) as oil-soluble polymerization initiator 1 and 1.0 part of t-butyl peroxyisobutyrate (manufactured by Arkema Yoshitomi Co., Ltd.: L80) as oil-soluble polymerization initiator 2 were added and stirred for a further minute. Then, the mixture was added to an aqueous medium being stirred at 12000 rpm using the high-speed stirring device described above. Stirring was continued at 12000 rpm for 20 minutes while maintaining a temperature of 60°C using the high-speed stirring device described above to obtain a granulated liquid.

[0161] The above granulated liquid was transferred to a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube. The temperature was raised to 70°C while stirring at 150 rpm under a nitrogen atmosphere, and the first polymerization reaction was carried out at 150 rpm for 5 hours. Subsequently, the temperature was raised to 90°C, and the second polymerization reaction was carried out for 4 hours while maintaining the temperature at 90°C. The temperature was then raised further to 99°C, and the third polymerization reaction was carried out for 3 hours while maintaining the temperature at 99°C to obtain a toner particle dispersion.

[0162] The obtained toner particle dispersion was cooled to 45°C while being stirred at 150 rpm, and then heat-treated for 5 hours while maintaining the temperature at 45°C. After that, while maintaining stirring, dilute hydrochloric acid was added until the pH reached 1.5 to dissolve the dispersion stabilizer. The solid components were filtered off, thoroughly washed with deionized water, and then vacuum-dried at 30°C for 24 hours to obtain toner particles 19.

[0163] (Preparation of Toner 19) For the above toner particles in a ratio of 19:100.0 parts, silica microparticles (hydrophobized with hexamethyldisilazane, primary particle number average particle size: 10 nm, BET specific surface area: 170 m²) are used as an external additive. 2 2.0 parts of ( / g) were added and mixed for 15 minutes at 3000 rpm using a Henschel mixer (manufactured by Nippon Coke Co., Ltd.) to obtain toner 19. The physical properties of the obtained toner 19 are shown in Tables 3 and 4.

[0164] <Comparative Example 3> (Manufacturing of Toner 20) In the production of toner 1, toner particles 20 were obtained in the same manner as in Tables 1 and 2, except that the type and amount of polymerizable monomer used, the type and amount of oil-soluble initiator and water-soluble initiator, and the polymerization conditions were changed.

[0165] Furthermore, toner 20 was obtained by adding toner particles 1 in the same manner as before. The physical properties of the toner are shown in Tables 3 and 4.

[0166] <Comparative Example 4> [Manufacturing of toner 21 by emulsification and agglutination method] (Preparation of resin particle dispersion 1) • Styrene 280.0 parts • Methacrylonitrile 220.0 parts • Stearyl acrylate 500.0 parts Dodecyl mercaptan 6.0 parts Decanediol acrylic acid ester 4.0 parts The above ingredients were mixed and dissolved. This mixture was then dispersed and emulsified in a flask with 20.0 parts of the anionic surfactant Newlex Paste H (manufactured by NOF Corporation) dissolved in 1300.0 parts of deionized water. While stirring for 10 minutes, 200.0 parts of deionized water containing 20.0 parts of ammonium persulfate was added, followed by nitrogen purging. The mixture was then heated to 70°C, and emulsion polymerization was carried out for 6 hours. After that, the reaction solution was cooled to room temperature to prepare resin particle dispersion 1.

[0167] (Preparation of resin particle dispersion 2) • Styrene 280.0 parts • Methacrylonitrile 220.0 parts • Stearyl acrylate 500.0 parts 20.0 parts of acrylic acid Dodecyl mercaptan 12.0 parts Decanediol acrylic acid ester 4.0 parts The above ingredients were mixed and dissolved, and then dispersed and emulsified in a flask in a solution of 20.0 parts of the anionic surfactant Newlex Paste H (manufactured by NOF Corporation) dissolved in 1300.0 parts of deionized water. While stirring for 10 minutes, 200.0 parts of deionized water containing 20.0 parts of ammonium persulfate was added, followed by nitrogen purging. The mixture was then heated until it reached 70°C, and emulsion polymerization was carried out for 6 hours. After that, the reaction solution was cooled to room temperature to prepare resin particle dispersion 2.

[0168] (Preparation of colorant dispersion) Phthalocyanine pigment ··········250 copies (Manufactured by Dainichi Seika Co., Ltd.: PV FAST BLUE) Anionic surfactants ··········20 copies (Manufactured by Daiichi Kogyo Seiyaku Co., Ltd.: Neogen RK) Ion-exchanged water ··········730 copies The above ingredients were mixed and dissolved, then dispersed using a homogenizer (IKA Ultra-Turrax) to obtain a colorant dispersion.

[0169] (Preparation of mold release agent particle dispersion) -Preparation of a mold release agent particle dispersion- Polyethylene wax ··········400 copies (Manufactured by Toyo Petrolite Co., Ltd.: Polywax725) Anionic surfactants ··········20 copies (Manufactured by Nippon Oil & Fats Co., Ltd.: Newlex®) Ion-exchanged water ··········580 copies After mixing and dissolving the above, the mixture was dispersed using a homogenizer (IKA Ultra-Turrax), and then dispersed again using a pressure-discharge homogenizer to prepare a release agent particle dispersion containing release agent particles (polyethylene wax).

[0170] (Preparation of resin particle dispersion for shells) In a reaction vessel equipped with a reflux condenser, stirrer, and nitrogen inlet tube, the following materials are placed under a nitrogen atmosphere. Ta. • Toluene 100.0 parts Styrene (St) 84.5 parts n-butyl acrylate (BA) 11.3 parts • Methyl methacrylate (MMA) 2.5 parts • Methacrylic acid (MAA) 1.7 parts t-butyl peroxypivalate 3.0 parts The contents of the container were stirred at 200 revolutions per minute and heated to 70°C, where stirring continued for 10 hours. Further, the mixture was heated to 100°C and polymerized for 6 hours. The solvent was then removed by distillation to obtain shell resin 1. Shell resin 1 had a Tg of 71°C, an SP value of 9.9, and a peak molecular weight (Mp) of 15000.

[0171] The following raw materials were placed in a reaction vessel equipped with a stirrer, condenser, thermometer, and nitrogen inlet tube, and heated to 80°C to dissolve. • Shell resin 1 100.0 parts Methyl ethyl ketone 45.0 parts Tetrahydrofuran 45.0 parts • Diethylaminoethanol 1.0 part Next, under stirring, 300.0 parts of ion-exchanged water at a temperature of 80°C were slowly added to induce phase inversion emulsification. The resulting aqueous dispersion was then transferred to a distillation apparatus and distilled until the fractionation temperature reached 100°C.

[0172] After cooling, deionized water was added to the resulting aqueous dispersion to adjust the shell resin concentration in the dispersion to 20%. This was designated as shell resin dispersion A. A portion of shell resin dispersion A was extracted, and the volume-based median diameter (D50) was measured to be 480 nm.

[0173] (Manufacturing of toner particles 21) Resin particle dispersion 1 900.0 parts Resin particle dispersion 2 225.0 parts Colorant particle dispersion 100.0 parts Release agent particle dispersion 63.0 parts Aluminum sulfate 5.0 parts (Manufactured by Wako Pure Chemical Industries, Ltd.) 1000.0 parts of deionized water The above mixture was placed in a round stainless steel flask, adjusted to pH 2.0, dispersed using a homogenizer (IKA Ultra-Turrax T50), and then heated in a heating oil bath to 64°C while stirring. After holding at 61°C for 3 hours, observation with an optical microscope confirmed the formation of aggregated particles with an average particle size of approximately 5.0 μm. After further heating and stirring at 61°C for 4 hours, observation with an optical microscope confirmed the formation of aggregated particles with an average particle size of approximately 5.4 μm.

[0174] Deionized water was added to the resulting dispersion to adjust the resin concentration in the dispersion to 20%, which was then used as the core particle dispersion.

[0175] 6 parts of a 10% aqueous solution of polyaluminum chloride were added dropwise to 500.0 parts (100.0 parts of solid content) of the core particle dispersion, and then 50 parts (10.0 parts of solid content) of the shell resin dispersion 1 was added, the pH was adjusted to 4, and stirring was continued for 30 minutes. This suspension was heated to 71 °C and stirring was continued for another 3 hours. Then, it was filtered, thoroughly washed with ion-exchanged water, and dried in a vacuum dryer to obtain toner particles 21.

[0176] (Preparation of Toner 21) To 100.0 parts of the above toner particles 21, 2.0 parts of silica fine particles (hydrophobically treated with hexamethyldisilazane, number average particle diameter of primary particles: 10 nm, BET specific surface area: 170 m 2 / g) were added and mixed at 3000 rpm for 15 minutes using a Henschel mixer (manufactured by Nippon Coke Co., Ltd.) to obtain toner 21. The physical properties of the obtained toner 21 are shown in Tables 3 and 4.

[0177]

Table 1

[0178]

Table 2

[0179]

Table 3

[0180]

Table 4

[0181] 〔Evaluation Method of Toner〕 Regarding toners 1 to 17 according to Examples 1 to 17 and toners 18 to 21 according to Comparative Examples 1 to 4, performance evaluations were conducted in the following manner. The evaluation results of each toner are shown in Table 5. In addition, the values of the weight average particle diameter (D4) of each toner particle are also shown in Table 5.

[0182] (Evaluation of Low-Temperature Fixing Property) In the evaluation of low-temperature fixing property, a Hewlett-Packard laser beam printer: HP LaserJet Enterprise 600 M603 with the fixing unit removed was prepared. Also, the removed fixing unit was modified so that the temperature could be set arbitrarily and the process speed was set to 400 mm / sec.

[0183] Under normal temperature and humidity environment (temperature 23.5°C, humidity 60%RH), using the above printer, an unfixed image with a toner loading amount per unit area of 0.5 mg / cm 2 was produced. Then, the unfixed image was passed through the above fixing unit adjusted to 130°C. Note that the recording medium used was "Prover Bond Paper" (105 g / m 2 , manufactured by Fox River). The obtained fixed image was rubbed back and forth 5 times with a silicone paper under a load of 4.9 kPa (50 g / cm 2 ), and evaluated by the reduction rate (%) of the image density before and after rubbing. The measurement of the image density was performed using a spectrophotometer 500 series (manufactured by X-Rite). A: The reduction rate of the image density is less than 5.0%. B: The reduction rate of the image density is 5.0% or more and less than 10.0%. C: The reduction rate of the image density is 10.0% or more and less than 15.0%. D: The reduction rate of the image density is 15.0% or more.

[0184] (Durable Development Property; Evaluation of Development Streaks) A modified machine of a commercially available Canon laser beam printer LBP7600C was used. The modification points were to change the evaluation machine body and software so that the process speed was 400 mm / sec and the fixing temperature was 130°C.

[0185] The toner was removed from the process cartridge for the black toner that was installed in this color laser printer, the inside was cleaned with compressed air, and then 40g of each toner was introduced into the process cartridge. The refilled process cartridge was then installed in the color laser printer, and the following image evaluation was performed. The specific image evaluation items are as follows.

[0186] Under high temperature and high humidity conditions (temperature 33°C / humidity 85%RH), the above printer was used with letter-sized Xerox 4200 paper (Xerox Corporation, 75g / m²). 2 Print out 10,000 images with horizontal lines and a print density of 0.5%. Then, apply halftone (toner amount 0.2 mg / cm²). 2 The images and development streaks on the developing roller were evaluated. The evaluation criteria were set as follows, and a score of C or higher was considered good.

[0187] (Evaluation Criteria) A: Two or fewer circumferential development streaks are visible on the developing roller. Or, no vertical streaks in the paper output direction are visible on the image. B: Three to five circumferential development streaks are visible on the developing roller. Alternatively, very slight vertical streaks in the paper output direction are visible on the image. C: Six to twenty thin streaks running circumferentially are visible on the developing roller. Alternatively, five or fewer fine vertical streaks running in the paper output direction are visible on the image. D: More than 21 circumferential streaks are visible on the developing roller. Alternatively, streaks of 0.5 mm or larger, or more than 6 fine streaks, are visible on the image.

[0188] [Table 5]

Claims

1. A toner having toner particles containing a crystalline resin as a binder resin, The binder resin contains a unit (a) represented by the following formula (2), The proportion of unit (a) represented by formula (2) is 40.0% by mass or more and 80.0% by mass or less in the binder resin. 【Chemistry 1】 [In formula (2), R1 represents a hydrogen atom or a methyl group, L1 represents a single bond or a divalent linking group, and m represents an integer between 15 and 35.] In an environment with a temperature of 25°C and a relative humidity of 50% RH, the relative permittivity εr obtained when measuring the impedance of toner satisfies the following equation (1): A toner characterized in that, when the surface of toner particles is measured by time-of-flight secondary ion mass spectrometry (TOF-SIMS), Ic1 is defined as the ion count derived from sulfonic acid groups relative to the total ion count at a mass-to-charge ratio of 0.5 to 1850, and Ic1 is between 0.005 and 0.

05. 0.21≦{εr(0.01Hz)−εr(383kHz)}≦0.48 Formula (1)

2. The toner according to claim 1, wherein, when the impedance of the toner is measured in an environment of 25°C and 50% RH relative humidity, the difference Δεr between the relative permittivity εr (0.01 Hz) at a frequency of 0.01 Hz and the relative permittivity εr (383 kHz) at a frequency of 383 kHz is 0.25 or more and 0.45 or less.

3. In an environment with a temperature of 25°C and a relative humidity of 50% RH, the conductivity κ obtained when measuring the impedance of the toner is 1.2 × 10⁻¹⁰. -14 The above 7.1 x 10 -14 The toner according to claim 1 or 2, wherein the following [S / m].

4. When the impedance of the toner is measured under conditions of 25°C and 50% RH, the conductivity index κ / ω obtained is 1.9 × 10⁻¹⁰ [(S / m)(s / rad)] at a frequency of 0.01 Hz. -13 The above 11.4 x 10 -13 The toner according to claim 1 or 2, wherein the toner is as follows:

5. When the impedance of the toner is measured under conditions of 25°C and 50% RH, the minimum value of the conductivity index κ / ω [(S / m)(s / rad)] obtained for the toner's sweep frequency between 0.01 Hz and 383 kHz is 1.3 × 10⁻¹⁰. -13 The above 2.0 x 10 -13 The toner according to claim 1 or 2, wherein the toner is as follows:

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