toner

Abstract

To provide a toner that achieves both low temperature fixability and durability at a high level.SOLUTION: A toner contains a toner particle and an external additive. The toner particle has a core that contains resin A and a shell that contains resin B on the surface of the core. The external additive includes hydrotalcite particles A. In line analysis in STEM-EDS mapping of the toner, fluorine and aluminum exist inside the hydrotalcite particle A. The value F / Al of the ratio of the atomic concentration of the fluorine to the atomic concentration of the aluminum in the hydrotalcite particle A, which is obtained from main component mapping of the hydrotalcite particle A according to the STEM-EDS mapping analysis of the toner, is 0.01-0.60.SELECTED DRAWING: None

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE This disclosure relates to toners used in imaging processes such as electrophotography. [Background technology]

[0002] In recent years, there has been a demand for longer life and lower power consumption in electrophotographic image forming apparatuses such as multifunction peripherals and printers. From the viewpoint of longer life, toners are required to have durability that enables stable production of high-quality images even after long-term use. Furthermore, from the viewpoint of lower power consumption, there is an increasing need for so-called low-temperature fixing toners that can be fixed with less heat.

[0003] To address the above-mentioned problems, for example, Patent Document 1 discloses a toner obtained by aggregating resin particles having a core-shell structure, in which the difference between the glass transition point of the resin constituting the core and the glass transition point of the resin constituting the shell is 20°C or more. Patent Document 2 discloses a toner in which the surface of a toner core particle is coated with a shell layer made of a resin containing a unit derived from a monomer of a thermosetting resin and a unit derived from a thermoplastic resin. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-322953 [Patent Document 2] Japanese Patent Application Laid-Open No. 2015-011077 Summary of the Invention [Problem to be solved by the invention]

[0005] However, when a shell layer is formed to enhance durability as in the toner described in the above document, while the durability of the toner is improved, the release agent in the toner tends to be less likely to bleed out during fixing, which tends to result in a decrease in low-temperature fixability, such as the occurrence of blisters and cold offset. It is generally known that a toner having a core-shell structure can suppress exposure of wax and low-melting-point components in the toner to the toner surface, resulting in good durability. Compared to a toner that does not have a core-shell structure, a toner having a core-shell structure is expected to enable low-temperature fixing while maintaining durability.

[0006] On the other hand, if the formation of a shell suppresses the exudation of wax onto the toner layer surface during fixing, the adhesive strength between the fixing member, such as a fixing film, and the toner layer increases, which may result in image defects during low-temperature fixing, such as cold offset and blistering. If the shell is made thicker to improve durability, image defects during low-temperature fixing, such as cold offset and blistering, are likely to occur. If the shell is made thin or gaps are provided in the shell in consideration of low-temperature fixability, wax and low-molecular-weight components are likely to exude onto the toner particle surface, and external additives are likely to be buried.

[0007] As a result, the chargeability and fluidity of the toner may decrease, which may result in a decrease in developability and contamination of components. Although a toner having a core-shell structure helps to achieve both durability and fixability, there is still a trade-off between fixability and developability during long-term use, and it can be said that there are still challenges to be overcome in achieving both low-temperature fixability and durability at a high level. The present disclosure provides a toner that achieves both low-temperature fixability and durability at a high level. [Means for solving the problem]

[0008] That is, the present disclosure provides a toner containing toner particles and an external additive, the toner particles have a core containing resin A and a shell containing resin B on the surface of the core, the external additive contains hydrotalcite particles A, In a line analysis of a STEM-EDS mapping analysis of the toner, fluorine and aluminum are present inside the hydrotalcite particles A, The toner has a ratio F / Al of the atomic concentration of fluorine to aluminum in the hydrotalcite particles A, which is obtained from main component mapping of the hydrotalcite particles A by STEM-EDS mapping analysis of the toner, of 0.01 to 0.60. [Effects of the Invention]

[0009] According to the present disclosure, a toner that combines low-temperature fixability and durability at a high level can be obtained. [Brief explanation of the drawings]

[0010] [Figure 1] Observation example of toner cross section [Figure 2] Schematic diagram of EDS line analysis in STEM-EDS mapping analysis DETAILED DESCRIPTION OF THE INVENTION

[0011] In the present disclosure, unless otherwise specified, the expressions "XX or more and YY or less" or "XX to YY" representing a numerical range mean a numerical range including the lower and upper limits, which are the endpoints. When a numerical range is described in stages, the upper and lower limits of each numerical range can be combined in any way. In the present disclosure, "(meth)acrylic" means "acrylic" and / or "methacrylic".

[0012] The present inventors have investigated methods for improving low-temperature fixability while maintaining durability. Specifically, in order to compensate for the lack of releasability between the fixing member and the toner layer during fixing, they have investigated ways to provide releasability by other means than by the exudation of wax from the core. As a result, they have found that the above problem can be solved by the following toner.

[0013] The present disclosure provides a toner containing toner particles and an external additive, the toner particles have a core containing resin A and a shell containing resin B on the surface of the core, the external additive contains hydrotalcite particles A, In a line analysis of a STEM-EDS mapping analysis of the toner, fluorine and aluminum are present inside the hydrotalcite particles A, The toner has a ratio F / Al of the atomic concentration of fluorine to aluminum in the hydrotalcite particles A, which is obtained from main component mapping of the hydrotalcite particles A by STEM-EDS mapping analysis of the toner, of 0.01 to 0.60.

[0014] The toner contains toner particles having a core-shell structure having a core containing resin A and a shell on the surface of the core containing resin B, and an external additive. The toner contains hydrotalcite particles A as the external additive. The toner particles having the above-mentioned core-shell structure means that the surface of the toner particles is coated with a resin component different from the wax component. The shell does not necessarily have to cover the entire surface of the core, and there may be a portion where the core is partially exposed. The presence or absence of a core-shell structure can be confirmed by observing the cross section of the toner with a transmission electron microscope (TEM).

[0015] When the toner particles have a core-shell structure, the amount of wax present near the surface of the toner is reduced in a transmission electron microscope (TEM) photograph of the cross section of the toner. Specifically, when the cross section of the toner is observed by a transmission electron microscope (TEM), the amount of wax present near the surface of the toner is reduced by 1.0 × 10 -14 m 2 The ratio of the number of toner particles in which a wax domain having the above area exists at least partially within 0.1 μm from the toner particle surface is preferably 15% or less, more preferably 10% or less, and even more preferably 8% or less.

[0016] By externally adding hydrotalcite particles A to toner particles having a core-shell structure, it is possible to significantly improve low-temperature fixability while maintaining developability during long-term use. Here, hydrotalcite particles A are hydrotalcite particles containing fluorine and aluminum inside. The mechanism by which the effects of maintaining developability and improving low-temperature fixability are obtained is thought to be as follows.

[0017] Consider the case where toner layered on paper melts to form a toner layer during fixing. The toner layer melted on the paper is in contact with a fixing member such as a fixing film, and if the releasability between the toner layer and the fixing member is insufficient, the toner layer will be pulled toward the fixing member when the fixing member separates from the paper. This reduces the adhesion between the toner layer and the paper, making fixing defects such as blisters and cold offset more likely to occur.

[0018] Because the toner particles have a shell, the hydrotalcite particles A are less likely to be embedded in the surface of the toner layer and are more likely to spread out when subjected to heat and pressure during fixing. In other words, the core-shell structure makes it possible to prevent the hydrotalcite particles A from being embedded in the surface of the toner particles during fixing.

[0019] The fluorine content of hydrotalcite particles A reduces adhesion. Therefore, the hydrotalcite particles A that spread over the surface of the toner layer provide releasability between the fixing member and the toner layer, improving releasability during low-temperature fixing. This reduces the tensile force of the toner layer toward the fixing member, maintaining adhesion between the toner layer and paper and improving low-temperature fixing.

[0020] Toner particles having a core-shell structure are less susceptible to thermal and mechanical changes on the surface, and external additives present on the particle surface are less likely to be embedded. This tendency is particularly pronounced in the range of the toner's minimum fixing temperature, and is believed to be the reason why the toner of the present disclosure has improved releasability during low-temperature fixing. In addition, the presence of a shell also tends to improve storage stability.

[0021] Furthermore, hydrotalcite is a layered compound, and when hydrotalcite particles are subjected to pressure on the surface of toner particles, slippage occurs between the layers, expanding the surface area. It is believed that not only do hydrotalcite particles A remain on the toner layer surface without being buried during fixing, but the expansion of the surface area due to interlayer slippage contributes greatly to imparting release properties. Furthermore, hydrotalcite allows fluoride ions to be easily introduced (intercalated) between the layers through anion exchange. Because fluorine treatment is easy and can be performed uniformly, it is believed that excellent release properties can be achieved.

[0022] The presence or absence of fluorine and aluminum in hydrotalcite particles can be confirmed by STEM-EDS mapping analysis of the toner. In line analysis in the STEM-EDS mapping analysis of the toner, it is necessary that fluorine and aluminum are present inside the hydrotalcite particles A.

[0023] Furthermore, the ratio of the atomic concentration of fluorine to aluminum in the hydrotalcite particles A (F / Al) obtained from the main component mapping of the hydrotalcite particles A by STEM-EDS mapping analysis of the toner must be 0.01 to 0.60. If F / Al is less than 0.01, the effect of fluorine in providing releasability is small and no effect can be obtained. If F / Al is greater than 0.60, the hydrotalcite particles A are easily detached from the toner particles and are less likely to remain in the toner transferred to paper. As a result, the effect of providing releasability cannot be obtained.

[0024] The element ratio F / Al of fluorine to aluminum in the hydrotalcite particles A is preferably 0.02 to 0.60, more preferably 0.04 to 0.60, and even more preferably 0.04 to 0.30. When the element ratio F / Al is 0.02 or more, there is a sufficient amount of fluorine to impart releasability, resulting in a better releasability effect. When the element ratio F / Al is 0.60 or less, the hydrotalcite particles tend to remain on the toner particles, resulting in better releasability and toner chargeability during fixing. F / Al can be controlled by adjusting the fluorine concentration during production of the hydrotalcite particles A. The fluorine atomic concentration in the hydrotalcite particles A is preferably 0.05 to 3.00 atomic %, more preferably 0.10 to 2.80 atomic %. The aluminum atomic concentration in the hydrotalcite particles A is preferably 1.50 to 10.00 atomic %, more preferably 2.0 to 8.0 atomic %, and even more preferably 4.00 to 7.00 atomic %.

[0025] As described above, it is believed that a good releasing effect can be obtained during low-temperature fixing due to the extremely large synergistic effect between the toner particles having a core-shell structure and the fluorine-containing hydrotalcite particles A. The reason why hydrotalcite particles A are used as an external additive for imparting releasability is also important from the viewpoint of developability. If another material with a releasability-imparting effect, such as fine wax particles, is externally added to the toner, the chargeability of the toner tends to decrease, and problems such as fogging tend to occur. Hydrotalcite is known to have the effect of improving the chargeability of toner, and by using hydrotalcite particles A, a toner with good fixing properties can be obtained without decreasing durability.

[0026] Each component constituting the toner and the method for producing the toner will be described in more detail below. The toner particles have a core-shell structure having a core containing resin A and a shell on the surface of the core containing resin B. When the toner particles have a core-shell structure, it is possible to prevent the hydrotalcite particles A from being embedded in the toner particles during fixing, thereby achieving a mold-releasing effect of the hydrotalcite particles A. As described above, the toner particles having a core-shell structure means that the surfaces of the toner particles are coated with a resin component different from the wax component.

[0027] It is also preferable that the toner particles contain wax. When a cross section of the toner is observed using a transmission electron microscope (TEM), the area of ​​the toner particles is 1.0×10 -14 m 2The ratio of the number of toner particles in which the wax domains exist, even if only partially, within 0.1 μm from the surface of the toner particle is preferably 15% or less. It is more preferably 10% or less, and even more preferably 8% or less. There is no particular lower limit, but it is 0% or more. The ratio can be controlled by the amount of resin used as the shell.

[0028] When a shell is formed on the toner particle surface and the ratio of toner particles having wax domains of a certain size or larger on the toner particle surface is within the above range, component contamination is unlikely to occur during development. As a result, in the toner after development, hydrotalcite particles are formed on the toner particle surface. Furthermore, it is easy to prevent the hydrotalcite particles A from being embedded in the toner particles during fixing, and the hydrotalcite particles A are more likely to exhibit a sufficient releasing effect. The wax domain size is 1.0 × 10 -14 m 2 The reason for selecting the above is that the size of the hydrotalcite particles is taken into consideration: if the wax domains are sufficiently small compared to the size of the hydrotalcite particles, they are less susceptible to the above-mentioned effects.

[0029] Here, the range of 0.1 μm from the toner particle surface does not necessarily specify the thickness of the shell, but refers to the thickness necessary to support the shell. The shell thickness may be thinner or thicker than 0.1 μm. The shell thickness is preferably 0.1 μm or less, more preferably 50 nm or less, and preferably 1 nm or more. An example of a method for analyzing the shell thickness is shown below.

[0030] Measurement by time-of-flight secondary ion mass spectrometry: When a depth profile measurement is performed, the shell thickness is the depth at which the ratio of the signal derived from the shell to the signal derived from the core is 1:1. The shell thickness can be controlled by the amount of raw materials added to the shell during the production of toner particles.

[0031] <Binder resin> The core contains resin A as a binder resin. Examples of resin A include polyester resins and vinyl resins, and other binder resins such as the following resins or polymers: styrene-acrylic resin, polyester resin, epoxy resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, and mixed or composite resins thereof. Resin A is preferably a polyester resin, a styrene-acrylic resin, or a hybrid resin thereof, and more preferably a polyester resin or a styrene-acrylic resin, because they are inexpensive, easily available, and have excellent low-temperature fixing properties.

[0032] The polyester resin can be obtained by selecting and combining suitable compounds from polycarboxylic acids, polyols, hydroxycarboxylic acids, etc., and synthesizing them using a conventionally known method such as transesterification or polycondensation.

[0033] Polycarboxylic acids are compounds containing two or more carboxy groups in one molecule, and among these, dicarboxylic acids are compounds containing two carboxy groups in one molecule and are preferably used.

[0034] Examples of dicarboxylic acids include oxalic acid, succinic acid, glutaric acid, maleic acid, adipic acid, β-methyladipic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-carboxylic acid, hexahydroterephthalic acid, malonic acid, pimelic acid, suberic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediacetic acid, o-phenylenediacetic acid, diphenylacetic acid, diphenyl-p,p'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracenedicarboxylic acid, and cyclohexanedicarboxylic acid.

[0035] Examples of polycarboxylic acids other than dicarboxylic acids include trimellitic acid, trimesic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrene Examples of the carboxylic acid include tricarboxylic acid, pyrenetetracarboxylic acid, itaconic acid, glutaconic acid, n-dodecylsuccinic acid, n-dodecenylsuccinic acid, isododecylsuccinic acid, isododecenylsuccinic acid, n-octylsuccinic acid, and n-octenylsuccinic acid. These may be used alone or in combination of two or more.

[0036] Polyols are compounds containing two or more hydroxyl groups in one molecule, and among these, diols are compounds containing two hydroxyl groups in one molecule and are preferably used. Specifically, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosanedecanediol, diethylene glycol, Examples of the alkylene oxide include triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-butenediol, neopentyl glycol, 1,4-cyclohexanediol, polytetramethylene glycol, hydrogenated bisphenol A, bisphenol A, bisphenol F, bisphenol S, and alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above bisphenols.

[0037] Among these, alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols are preferred, and alkylene oxide adducts of bisphenols and their combined use with alkylene glycols having 2 to 12 carbon atoms are particularly preferred.

[0038] Examples of trivalent or higher polyols include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, hexamethylolmelamine, hexaethylolmelamine, tetramethylolbenzoguanamine, tetraethylolbenzoguanamine, sorbitol, trisphenol PA, phenol novolac, cresol novolac, and alkylene oxide adducts of the above trivalent or higher polyphenols. These may be used alone or in combination of two or more. The polyester resin may also be a polyester resin containing a urea group. It is preferable that the carboxyl groups of the polyester resin, such as terminal groups, are not capped.

[0039] Examples of the styrene-acrylic resin include homopolymers made of the following polymerizable monomers, copolymers obtained by combining two or more of these, and mixtures thereof. Styrenic monomers such as styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene and p-phenylstyrene; Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, dimethyl phosphate ethyl (meth)acrylate, diethyl phosphate ethyl (meth)acrylate (Meth)acrylic monomers such as acrylate, dibutyl phosphate ethyl (meth)acrylate and 2-benzoyloxyethyl (meth)acrylate, (meth)acrylonitrile, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid, and maleic acid; Vinyl ether monomers such as vinyl methyl ether and vinyl isobutyl ether; vinyl ketone monomers such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; Polyolefins such as ethylene, propylene, and butadiene.

[0040] The styrene-acrylic resin may contain a polyfunctional polymerizable monomer, if necessary. Examples of the polyfunctional polymerizable monomer include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 2,2'-bis(4-((meth)acryloxydiethoxy)phenyl)propane, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, divinylbenzene, divinylnaphthalene, and divinyl ether. In order to control the degree of polymerization, it is also possible to further add a known chain transfer agent and polymerization inhibitor.

[0041] Examples of the polymerization initiator for obtaining the styrene-acrylic resin include organic peroxide-based initiators and azo-based polymerization initiators. Examples of organic peroxide initiators include benzoyl peroxide, lauroyl peroxide, di-α-cumyl peroxide, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, bis(4-t-butylcyclohexyl)peroxydicarbonate, 1,1-bis(t-butylperoxy)cyclododecane, t-butylperoxymaleic acid, bis(t-butylperoxy)isophthalate, methyl ethyl ketone peroxide, tert-butylperoxy-2-ethylhexanoate, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, and tert-butylperoxypivalate.

[0042] Examples of the azo polymerization initiator include 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobismethylbutyronitrile, and 2,2'-azobis-(methyl isobutyrate).

[0043] Furthermore, a redox initiator, which is a combination of an oxidizing substance and a reducing substance, can also be used as the polymerization initiator. The oxidizing substances include inorganic peroxides such as hydrogen peroxide, persulfates (sodium, potassium and ammonium salts) and oxidizing metal salts such as tetravalent cerium salts. Examples of reducing substances include reducing metal salts (divalent iron salts, monovalent copper salts, and trivalent chromium salts), ammonia, lower amines (amines having approximately 1 to 6 carbon atoms, such as methylamine and ethylamine), amino compounds such as hydroxylamine, reducing sulfur compounds such as sodium thiosulfate, sodium hydrosulfite, sodium hydrogensulfite, sodium sulfite, and sodium formaldehyde sulfoxylate, lower alcohols (having 1 to 6 carbon atoms), ascorbic acid or a salt thereof, and lower aldehydes (having 1 to 6 carbon atoms).

[0044] The polymerization initiator is selected based on its 10-hour half-life temperature and is used alone or in combination. The amount of polymerization initiator added varies depending on the desired degree of polymerization, but is generally 0.5 to 20.0 parts by mass per 100.0 parts by mass of polymerizable monomer.

[0045] Resin A may also contain a crystalline polyester. Examples of the crystalline polyester include a condensation polymer of an aliphatic diol and an aliphatic dicarboxylic acid. It is preferably a condensation polymer of an aliphatic diol having from 2 to 12 carbon atoms and an aliphatic dicarboxylic acid having from 2 to 12 carbon atoms. Examples of the aliphatic diol having from 2 to 12 carbon atoms include the following compounds: 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol.

[0046] Aliphatic diols having a double bond can also be used, such as 2-butene-1,4-diol, 3-hexene-1,6-diol, and 4-octene-1,8-diol.

[0047] Examples of aliphatic dicarboxylic acids having from 2 to 12 carbon atoms include the following compounds: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, lower alkyl esters and acid anhydrides of these aliphatic dicarboxylic acids.

[0048] Among these, sebacic acid, adipic acid, 1,10-decanedicarboxylic acid, and lower alkyl esters and acid anhydrides thereof are preferred. These may be used alone or in combination of two or more.

[0049] Aromatic dicarboxylic acids can also be used. Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and 4,4'-biphenyldicarboxylic acid. Among these, terephthalic acid is preferred because it is easily available and can easily form a polymer with a low melting point.

[0050] Furthermore, dicarboxylic acids having a double bond can also be used, which can be suitably used to suppress hot offset during fixing, since the double bond can be utilized to crosslink the entire resin. Examples of such dicarboxylic acids include fumaric acid, maleic acid, 3-hexenedioic acid, and 3-octenedioic acid. Also included are lower alkyl esters and acid anhydrides of these. Among these, fumaric acid and maleic acid are more preferred.

[0051] The method for producing the crystalline polyester is not particularly limited, and the crystalline polyester can be produced by a general polyester polymerization method in which a dicarboxylic acid component and a diol component are reacted. For example, the crystalline polyester can be produced by a direct polycondensation method or an ester exchange method, which are selected depending on the type of monomer.

[0052] The content of the crystalline polyester is preferably 1.0 parts by mass or more and 30.0 parts by mass or less, and more preferably 3.0 parts by mass or more and 25.0 parts by mass or less, relative to 100 parts by mass of the binder resin.

[0053] The maximum endothermic peak of crystalline polyester measured using a differential scanning calorimeter (DSC) The peak temperature is preferably 50.0° C. or higher and 100.0° C. or lower, and from the viewpoint of low-temperature fixability, more preferably 60.0° C. or higher and 90.0° C. or lower.

[0054] The molecular weight of resin A is preferably a peak molecular weight Mp of 5,000 or more and 100,000 or less, more preferably 10,000 or more and 40,000 or less. The glass transition temperature Tg of resin A is preferably 40°C or more and 70°C or less, more preferably 40°C or more and 60°C or less. The content of resin A is preferably 50% by mass or more with respect to the total amount of resin components in the toner particles. Furthermore, the content of resin A in the binder resin is preferably 50% by mass or more and 100% by mass or less.

[0055] The shell contains resin B. Examples of resin B include polyester resins, vinyl resins, and other binder resins, which are similar to the materials described above for resin A. Resin B is preferably a polyester resin, a styrene-acrylic resin, or a hybrid resin thereof, and more preferably a polyester resin or a styrene-acrylic resin, because they are inexpensive, easily available, and have excellent low-temperature fixing properties.

[0056] Resin B can be the same or different from Resin A. For example, styrene-acrylic resins can be used as Resin A and Resin B, polyester resins can be used as Resin A and Resin B, or a styrene-acrylic resin can be used as Resin A and a polyester resin can be used as Resin B. Preferably, resin A contains a styrene-acrylic resin, and resin B contains a styrene-acrylic resin. Also, preferably, resin A contains a polyester resin, and resin B contains a polyester resin. Also, preferably, resin A contains a styrene-acrylic resin, and resin B contains a polyester resin. The molecular weight of Resin B, Mp, is preferably 5,000 or more and 100,000 or less, and more preferably 15,000 or more and 80,000 or less.

[0057] The glass transition temperature Tg of resin B is preferably 50 to 100° C., more preferably 55 to 80° C., and even more preferably 60 to 80° C. From the viewpoint of suppressing embedding of hydrotalcite particles A in toner particles during fixing, it is preferable to select a material for resin B having a higher Tg than resin A. The content of Resin B is preferably 1% by mass or more and 30% by mass or less with respect to the total amount of resin components in the toner particles.

[0058] <Crosslinking agent> In order to control the molecular weight of the binder resin constituting the toner particles, a crosslinking agent may be added during polymerization of the polymerizable monomer. For example, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, divinylbenzene, bis(4-acryloxypolyethoxyphenyl)propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol #200, #400, and #600 diacrylates, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester diacrylate (MANDA Nippon Kayaku), and the above acrylates can be methacrylated. Something that has been changed to Related. The amount of the crosslinking agent added is preferably 0.001 parts by mass or more and 15,000 parts by mass or less per 100 parts by mass of the polymerizable monomer.

[0059] <Release agent> The toner may contain a known wax as a release agent. Specific examples include petroleum waxes such as paraffin wax, microcrystalline wax, and petrolatum and their derivatives, montan wax and its derivatives, hydrocarbon waxes produced by the Fischer-Tropsch process and their derivatives, polyolefin waxes such as polyethylene and polypropylene and their derivatives, and natural waxes such as carnauba wax and candelilla wax and their derivatives. Derivatives also include oxides, block copolymers with vinyl monomers, and graft-modified products. Other examples include alcohols such as higher aliphatic alcohols, fatty acids such as stearic acid and palmitic acid or their acid amides, esters, and ketones, hydrogenated castor oil and its derivatives, vegetable waxes, and animal waxes.These may be used alone or in combination.

[0060] Among these, the use of hydrocarbon wax or ester wax tends to improve the developing property and fixing property, and is therefore preferred. That is, the wax preferably includes hydrocarbon wax and ester wax. Note that these waxes may contain an antioxidant to the extent that it does not affect the properties of the toner. In addition, from the viewpoint of phase separation property with respect to the binder resin or crystallization temperature, preferred examples include higher fatty acid esters such as behenyl behenate and dibehenyl sebacate. Furthermore, ester waxes as plasticizers, which will be described later, can also be preferably used.

[0061] The content of the release agent is preferably 1.0 part by mass or more and 30.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin. The melting point of the release agent is preferably 30° C. or higher and 120° C. or lower, and more preferably 60° C. or higher and 100° C. or lower. By using a release agent with a melting point of 30° C. or higher and 120° C. or lower, the release effect is efficiently exerted and a wider fixing area is ensured.

[0062] <Plasticizer> In order to improve the sharp melting property of the toner, it is preferable to use a crystalline plasticizer. The plasticizer is not particularly limited, and known plasticizers used in toners such as those described below can be used. Esters of monohydric alcohols and fatty carboxylic acids, such as behenyl behenate, stearyl stearate, and palmityl palmitate, or esters of monohydric carboxylic acids and fatty alcohols; esters of dihydric alcohols and fatty carboxylic acids, such as ethylene glycol distearate, dibehenyl sebacate, and hexanediol dibehenate, or esters of dihydric carboxylic acids and fatty alcohols; esters of trihydric alcohols and fatty carboxylic acids, such as glycerin tribehenate, or esters of trihydric carboxylic acids and fatty alcohols; pentaerythritol tetrastearate esters of tetrahydric alcohols and aliphatic carboxylic acids, such as dipentaerythritol hexastearate and dipentaerythritol hexapalmitate, or esters of tetrahydric carboxylic acids and aliphatic alcohols; esters of hexahydric alcohols and aliphatic carboxylic acids, such as dipentaerythritol hexastearate and dipentaerythritol hexapalmitate, or esters of hexahydric carboxylic acids and aliphatic alcohols; esters of polyhydric alcohols and aliphatic carboxylic acids, such as polyglycerol behenate, or esters of polyhydric carboxylic acids and aliphatic alcohols; and natural ester waxes, such as carnauba wax and rice wax. These may be used alone or in combination.

[0063] <Coloring agent> The toner particles may contain a colorant. Known pigments and dyes may be used as the colorant. In view of excellent weather resistance, pigments are preferred as colorants. Examples of cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specific examples include: CI Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62 and 66. Examples of magenta colorants include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specific examples include CI Pigment Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221 and 254, and CI Pigment Violet 19.

[0064] Examples of yellow colorants include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specific examples include the following: CI Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185, 191 and 194. Examples of black colorants include those toned to black using the above yellow, magenta, and cyan colorants, as well as carbon black. These colorants can be used alone or in mixture, or further in the state of a solid solution. The colorant is preferably used in an amount of 1.0 part by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin.

[0065] <Charge control agents and charge control resins> The toner particles may contain a charge control agent or a charge control resin. Known charge control agents can be used, and charge control agents that have a high triboelectric charging speed and can stably maintain a constant triboelectric charge amount are particularly preferred. Furthermore, when the toner particles are produced by a suspension polymerization method, charge control agents that have low polymerization inhibition properties and are substantially free of solubilized substances in aqueous media are particularly preferred.

[0066] Examples of substances that control the toner to be negatively charged include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic and dicarboxylic acid-based metal compounds, aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, phenol derivatives such as bisphenol, urea derivatives, metal-containing salicylic acid-based compounds, metal-containing naphthoic acid-based compounds, boron compounds, quaternary ammonium salts, calixarene, and charge control resins.

[0067] Examples of the charge control resin include polymers or copolymers having sulfonic acid groups, sulfonate salt groups, or sulfonate ester groups. As the polymer having sulfonic acid groups, sulfonate salt groups, or sulfonate ester groups, a polymer containing 2% by mass or more, more preferably 5% by mass or more, of a sulfonate group-containing acrylamide monomer or a sulfonate group-containing methacrylamide monomer in copolymerization ratio is preferred.

[0068] The charge control resin preferably has a glass transition temperature (Tg) of 35°C or higher and 90°C or lower, a peak molecular weight (Mp) of 10,000 or higher and 30,000 or lower, and a weight average molecular weight (Mw) of 25,000 or higher and 50,000 or lower. When this resin is used, it is possible to impart desirable triboelectric charging properties to the toner particles without affecting the thermal properties required for the toner particles. Furthermore, when the charge control resin contains a sulfonic acid group, the dispersibility of the charge control resin itself in the polymerizable monomer composition and the dispersibility of colorants and the like are improved, thereby further improving the coloring power, transparency, and triboelectric charging properties. These charge control agents or charge control resins may be added singly or in combination of two or more kinds. The amount of the charge control agent or charge control resin added is preferably 0.01 to 20.0 parts by mass, more preferably 0.5 to 10.0 parts by mass, relative to 100.0 parts by mass of the binder resin.

[0069] <External additives> The toner contains hydrotalcite particles A as an external additive. The hydrotalcite particles that can be used are those represented by the following structural formula (1): M 2+ y M 3+ x (OH)2A n- (x / n) ·mH2O formula (1) where 0 <x≦0.5、y=1-x、m≧0である。 M 2+ , and M 3+ represent divalent and trivalent metals, respectively. M 2+ is preferably at least one divalent metal ion selected from the group consisting of Mg, Zn, Ca, Ba, Ni, Sr, Cu, and Fe. M 3+ is preferably at least one trivalent metal ion selected from the group consisting of Al, B, Ga, Fe, Co, and In. A n- is an n-valent anion, CO3 2- , O.H. - , Cl - , I - , F - , Br - , SO4 2- , HCO3 - , CH3COO - , and NO3 - These may be present alone or in combination.

[0070] Hydrotalcite particles A are M 3+ Contains at least Al as the n- It contains at least F as the 2+ Preferably, the particulate hydrotalcite A further contains magnesium. That is, the hydrotalcite particles A contain fluorine and aluminum. Preferably, the hydrotalcite particles A contain fluorine, aluminum, and magnesium. Specifically, Mg8.6 Al4(OH) 25.2 F2CO3·mH2O, Mg 12 Al4(OH) 32 Examples include Al4(OH)F2CO3·mH2O and the like. The hydrotalcite particles may be a solid solution containing a plurality of different elements. They may also contain a trace amount of a monovalent metal.

[0071] The value of the atomic number concentration ratio of magnesium to aluminum (element ratio) Mg / Al in the hydrotalcite particles A obtained from the main component mapping of the hydrotalcite particles A by STEM-EDS mapping analysis of the toner is preferably 1.5 to 4.0, and more preferably 1.6 to 3.8. Mg / Al can be controlled by adjusting the amount of raw materials during the production of hydrotalcite. The atomic number concentration of the above magnesium is preferably 3.00 to 20.00 atomic%, more preferably 4.00 to 16.00 atomic%, and still more preferably 9.00 to 14.00 atomic%.

[0072] Also, the hydrotalcite particles A preferably have water in their molecules, and in formula (1), it is preferably 0.1 < m < 0.6.

[0073] The number average particle diameter of the primary particles of the hydrotalcite particles A is preferably 6,000 to 1,000 nm, more preferably 60 to 800 nm, and still more preferably 200 to 600 nm. When the number average particle diameter is 1,000 nm or less, the fluidity of the toner is likely to be improved, and the chargeability during durability becomes better. The chargeability becomes better.

[0074] The hydrotalcite particles may be hydrophobically treated with a surface treatment agent. As the surface treatment agent, higher fatty acids, coupling agents, esters, oils such as silicone oil can be used. Among them, higher fatty acids are preferably used, and specifically, stearic acid, oleic acid, and lauric acid are exemplified.

[0075] The content of the hydrotalcite particles A is not particularly limited, but is preferably 0.01 to 3.00 parts by mass, and more preferably 0.05 to 0.50 parts by mass, relative to 100 parts by mass of the toner particles. The content of the hydrotalcite particles A can be quantified using a calibration curve prepared from a standard sample using fluorescent X-ray analysis.

[0076] Furthermore, the area ratio of the hydrotalcite particles A to the toner particles in the EDS measurement field of view, as measured by STEM-EDS mapping analysis of the toner, is preferably 0.07 to 0.54%, more preferably 0.25 to 0.50%, and even more preferably 0.35 to 0.45%. The above area ratio represents the proportion of the hydrotalcite particles present in the toner particles. When the area ratio is within the above range, the effect of the hydrotalcite particles can be easily obtained. The area ratio can be controlled by changing the amount of the hydrotalcite particles added to the toner particles.

[0077] The toner particles preferably contain at least one polyvalent metal element selected from the group consisting of aluminum, magnesium, calcium, and iron, and more preferably contain aluminum. It is believed that the fluorine in the hydrotalcite particles is captured by the polyvalent metal element in the toner particles, thereby achieving a higher release effect during fixing. The content (atomic number concentration) of the polyvalent metal element in the toner particles is preferably 0.01 to 0.09, more preferably 0.01 to 0.06, when the carbon element in the toner particles is taken as 100. The content of the polyvalent metal element in the toner particles can be measured from the main component mapping of the toner particles by STEM-EDS mapping analysis, which will be described later.

[0078] More preferably, the toner particles contain aluminum as a polyvalent metal element. Furthermore, in a main component mapping of the toner particles by STEM-EDS mapping analysis of the toner, the aluminum content in the toner particles is preferably 0.01 to 0.07, where the carbon atom number concentration in the toner particles is 100. It is more preferably 0.02 to 0.05. By being in the above range, better fixability and durability can be obtained.

[0079] Furthermore, in the main component mapping of the toner particles and the main component mapping of the hydrotalcite particles A by STEM-EDS mapping analysis of the toner, the ratio of the fluorine content in the hydrotalcite particles A to the polyvalent metal element content in the toner particles (fluorine / polyvalent metal element) is preferably 2.0 to 100.0, more preferably 3.0 to 95.0, and even more preferably 4.0 to 60.0. When this ratio is within the above range, better release properties are obtained during fixing. It is believed that this is because the fluorine in the hydrotalcite particles A is efficiently captured by the polyvalent metal elements in the toner particles, resulting in a high release effect during fixing.

[0080] The polyvalent metal element is preferably present on the surface of the toner particles and dispersed inside the toner particles. The presence of the polyvalent metal element inside the toner particles also allows the charge imparted to the surface of the toner particles to accumulate inside the particles. This makes it difficult for the charging characteristics of the toner to fluctuate, suppresses detachment of the hydrotalcite particles A from the toner particles, and ensures a stable release effect.

[0081] There is no particular restriction on the means for making the polyvalent metal element present inside the toner particles. For example, when toner particles are produced by a pulverization method, the polyvalent metal element may be incorporated into the raw material resin in advance, or the polyvalent metal element may be added to the toner particles when the raw materials are melted and kneaded. When toner particles are produced by a wet production method such as a suspension polymerization method or an emulsion aggregation method, the polyvalent metal element may be incorporated into the raw materials, or the polyvalent metal element may be added via an aqueous medium during the production process.

[0082] In emulsion aggregation, metal ions may be added as a flocculant. In this case, the metal elements can be ionized in an aqueous medium and then incorporated into the toner particles, which is preferable from the viewpoint of uniformity. Furthermore, in emulsion aggregation toner, carboxy groups may be present in the molecular chains constituting the binder resin. The metal ions added as a flocculant coordinate with the carboxy groups, thereby forming excellent conductive paths in the resin particles. Furthermore, trivalent aluminum can coordinate with carboxy groups in smaller amounts than divalent magnesium and calcium, or iron, which can assume mixed valences, and therefore tends to achieve better charging characteristics. Preferably, the resin A has a carboxy group. There are no particular limitations on the means for incorporating a carboxy group into the resin A. When the resin A is a styrene-acrylic resin, a monomer having a carboxy group, such as (meth)acrylic acid, may be used.

[0083] <Toner manufacturing method> The method for producing toner particles is not particularly limited, and known means can be used, such as a kneading and pulverization method or a wet production method. From the viewpoints of uniform particle size, shape controllability, and ease of obtaining toner particles with a core-shell structure, a wet production method is preferred. Examples of wet production methods include a suspension polymerization method, a solution suspension method, an emulsion polymerization aggregation method, and an emulsion aggregation method, and from the viewpoint of dispersing the polyvalent metal element on the surface of the toner particles and inside the toner particles, an emulsion aggregation method is more preferred.

[0084] In the emulsion aggregation method, first, a dispersion of each material, such as binder resin particles and colorant, is prepared. The resulting dispersion of each material is dispersed and mixed, with the addition of a dispersion stabilizer as needed. Then, an aggregating agent is added to aggregate the particles to the desired toner particle size, and then, or simultaneously with the aggregation, the resin particles are fused together. If necessary, the shape is controlled by heat to form toner particles.

[0085] Here, the binder resin microparticles can also be composite particles formed of two or more layers composed of resins with different compositions. For example, they can be produced by emulsion polymerization, miniemulsion polymerization, phase inversion emulsification, or a combination of several production methods. When an internal additive is contained in the toner particles, the internal additive may be contained in the resin microparticles. Alternatively, a dispersion of internal additive microparticles consisting only of the internal additive may be separately prepared, and the internal additive microparticles may be aggregated together with the resin microparticles when aggregating them. Furthermore, toner particles with layered compositions can be produced by adding resin microparticles with different compositions at different times during aggregation. After aggregating resin microparticles containing resin A to form a core portion, resin microparticles containing shell resin B can be added at different times and aggregated to form a shell portion.

[0086] Specifically, the method includes a shell formation step in which aggregated particles (core particles) containing resin A are formed in an aggregation step, and then resin fine particles containing shell resin B are further added and aggregated to form a shell. Shell resin B may have the same composition as core resin A, or a resin with a different composition may be used. The amount of shell resin added is preferably 1.0 to 10.0 parts by mass, and more preferably 2.0 to 7.0 parts by mass, per 100 parts by mass of the binder resin contained in the core particles.

[0087] In this case, the method for producing the toner preferably includes the following steps. (1) a dispersion step for preparing a dispersion of binder resin particles containing a binder resin such as resin A; (2) an aggregation step of aggregating the binder resin fine particles contained in the binder resin fine particle dispersion to form aggregates; (3) a shell formation step in which resin fine particles containing a shell resin B are further added to the dispersion containing the aggregates to aggregate them, thereby forming aggregates having a shell; and (4) a fusion step of heating and fusing the aggregates

[0088] In addition, during the step (4) or after the steps (1) to (4), the following step (5) (5) a spheronization step of heating the aggregates at a further elevated temperature may be performed. It is preferred that the compound has the following structure: Then, after the step (5), the following steps (6) and (7) are carried out: (6) a cooling step of cooling the aggregate at a cooling rate of 0.1°C / sec or more; (7) an annealing step of heating and maintaining the temperature at or above the crystallization temperature or glass transition temperature of the binder resin after the cooling step; It is more preferable that the .alpha.-hydroxybenzoate has the following structure:

[0089] The following can be used as the dispersion stabilizer. As the surfactant, known cationic surfactants, anionic surfactants, and nonionic surfactants can be used. Examples of inorganic dispersion stabilizers include tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, and alumina. Examples of organic dispersion stabilizers include polyvinyl alcohol, gelatin, methyl cellulose, methylhydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, and starch.

[0090] As the aggregating agent, in addition to surfactants having a polarity opposite to that of the surfactants used in the dispersion stabilizer, inorganic salts and inorganic metal salts having a valence of two or more can be suitably used. In particular, inorganic metal salts are preferred because they ionize polyvalent metal elements in an aqueous medium, making it easy to control aggregating properties and toner chargeability. Specific examples of preferred inorganic metal salts include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, iron chloride, aluminum chloride, and aluminum sulfate, as well as inorganic metal salt polymers such as polyiron chloride, polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. Among these, aluminum salts and their polymers are particularly preferred. In general, to obtain a sharper particle size distribution, the valence of the inorganic metal salt is preferably divalent rather than monovalent, and more preferably trivalent or higher rather than divalent. Furthermore, even if the valence is the same, inorganic metal salt polymers are more suitable. From the viewpoint of high definition and high resolution of images, the volume-based median diameter of the toner particles is preferably 3.0 μm or more and 10.0 μm or less.

[0091] <Toner manufacturing method> The toner contains hydrotalcite particles A as an external additive. If necessary, other external additives may be added. In this case, the total content of the external additives, such as inorganic and organic fine particles including the hydrotalcite particles, is preferably 0.50 parts by mass to 5.00 parts by mass per 100 parts by mass of the toner particles.

[0092] The mixer for externally adding the external additive to the toner particles is not particularly limited, and any known mixer may be used, regardless of whether it is a dry or wet type. Such mixers can be used. Examples include FM Mixer (manufactured by Nippon Coke & Engineering Co., Ltd.), Super Mixer (manufactured by Kawata Corporation), Nobilta (manufactured by Hosokawa Micron Corporation), and Hybridizer (manufactured by Nara Kikai Co., Ltd.). To control the coating state of the external additive, the rotation speed, processing time, and water temperature and amount in the jacket of the external additive device can be adjusted to prepare the toner.

[0093] In addition, examples of sieving devices used to sift out coarse particles after external addition include Ultrasonic (manufactured by Koei Sangyo Co., Ltd.); Resonaseave, Gyrosifter (Tokuju Kogyo Co., Ltd.); Vibrasonic System (manufactured by Dalton Co., Ltd.); Soniclean (manufactured by Shinto Kogyo Co., Ltd.); Turbo Screener (manufactured by Turbo Kogyo Co., Ltd.); and Microsifter (manufactured by Makino Sangyo Co., Ltd.).

[0094] The methods for measuring the physical properties of the toner and each material will be described below. <Method for identifying hydrotalcite particles> The hydrotalcite particles, which are external additives, can be identified by a combination of shape observation using a scanning electron microscope (SEM) and elemental analysis using energy dispersive X-ray analysis (EDS). Using a scanning electron microscope "S-4800" (product name; manufactured by Hitachi, Ltd.), the toner is observed at a maximum magnification of 50,000 times. The focus is set on the surface of the toner particles, and the external additive to be identified is observed. EDS analysis of the external additive to be identified is performed, and the hydrotalcite particles can be identified from the type of element peak. When element peaks observed include an element peak of at least one metal selected from the group consisting of Mg, Zn, Ca, Ba, Ni, Sr, Cu, and Fe, which are metals that can constitute hydrotalcite particles, and an element peak of at least one metal selected from the group consisting of Al, B, Ga, Fe, Co, and In, the presence of hydrotalcite particles containing the two types of metals can be inferred. A sample of the hydrotalcite particles identified by EDS analysis is prepared separately, and its shape is observed by SEM and analyzed by EDS. The results of the analysis of the sample are compared to determine whether they match the results of the analysis of the particles to be identified, and it is determined whether they are hydrotalcite particles.

[0095] <Method for measuring the element ratio of polyvalent metal elements in hydrotalcite particles and toner particles> The element ratios of polyvalent metal elements in hydrotalcite particles and toner particles are measured by EDS mapping of the toner using a scanning transmission electron microscope (STEM). EDS mapping measurements obtain spectral data for each pixel in the analysis area. Using a silicon drift detector with a large detection element area allows for highly sensitive EDS mapping measurements. By performing statistical analysis on the spectral data for each pixel obtained by EDS mapping measurement, it is possible to obtain a principal component mapping that extracts pixels with similar spectra, making it possible to map specific components.

[0096] The sample for observation is prepared according to the following procedure. 0.5 g of toner is weighed out and placed in a cylindrical mold with a diameter of 8 mm using a Newton press, which is left to stand for 2 minutes under a load of 40 kN to prepare a cylindrical toner pellet with a diameter of 8 mm and a thickness of approximately 1 mm. A 200 nm thick slice is prepared from the toner pellet using an ultramicrotome (Leica, FC7).

[0097] The STEM-EDS analysis is carried out using the following equipment and conditions. Scanning transmission electron microscope: JEOL JEM-2800 EDS detector: JEOL JED-2300T dry SD100GV detector (detector area: 100 mm 2 ) EDS analyzer: NORAN Sy manufactured by Thermo Fisher Scientific stem 7 [Conditions for STEM-EDS] STEM accelerating voltage: 200kV ·Magnification: 20,000x Probe size 1nm

[0098] STEM image size: 1024 x 1024 pixels (EDS elemental mapping images are acquired at the same position.) EDS mapping size: 256 x 256 pixels, Dwell time: 30 μs, Integration count: 100 frames The ratio of polyvalent metal elements in the toner particles and the ratio of each element in the hydrotalcite particles are calculated based on multivariate analysis as follows.

[0099] The EDS mapping was obtained using the STEM-EDS analyzer. The collected spectral mapping data was then subjected to multivariate analysis using the COMPASS (PCA) mode in the measurement command of the NORAN System 7, and principal component map images were extracted. In this case, the setting values ​​are as follows: Kernel size: 3×3 Quantitative map setting: High (slow) Filter Fit Type: High Precision (Slow) At the same time, this operation calculates the area ratio of each extracted principal component to the EDS measurement field of view.Quantitative analysis is then performed on the EDS spectrum of each principal component mapping obtained using the Cliff-Lorimer method.

[0100] Distinguishing between toner particles and hydrotalcite particles is done based on the quantitative analysis results of the obtained STEM-EDS principal component mapping. Particles can be identified as hydrotalcite particles based on particle size, shape, content of polyvalent metals such as aluminum and magnesium, and their quantitative ratios. Furthermore, when fluorine and aluminum are present inside hydrotalcite particles, the particles can be determined to be hydrotalcite particles A by the following method.

[0101] (Method for analyzing fluorine and aluminum in hydrotalcite particles) Based on the mapping data obtained by the STEM-EDS mapping analysis using the method described above, the fluorine and aluminum in the hydrotalcite particles are analyzed. Specifically, EDS line analysis is performed in the normal direction to the outer periphery of the hydrotalcite particles, and the fluorine and aluminum present inside the particles are analyzed. A schematic diagram of the line analysis is shown in Figure 2(a). For toner particle 1 and hydrotalcite particle 3 adjacent to toner particle 2, line analysis is performed in the normal direction to the outer periphery of hydrotalcite particle 3, i.e., in the direction of 5. Note that 4 indicates the boundary of the toner particle. The area in the acquired STEM image where hydrotalcite particles exist is selected using the rectangular selection tool, and line analysis is performed under the following conditions. Line analysis conditions STEM magnification: 800,000x Line length: 200nm Line width: 30nm Number of line divisions: 100 points (intensity measurement every 2 nm)

[0102] In the EDS spectrum of the hydrotalcite particles, the element peak intensity of fluorine or aluminum is 1.5 times or more the background intensity, and in the line analysis When the peak intensity of fluorine or aluminum at both ends of the hydrotalcite particle (points a and b in FIG. 2(a)) does not exceed 3.0 times the peak intensity at point c, the element is determined to be contained inside the hydrotalcite particle. Point c is the midpoint of line segment ab (i.e., the midpoint of the above-mentioned both ends). Examples of X-ray intensities of fluorine and aluminum obtained by line analysis are shown in Figures 2(b) and 2(c). When hydrotalcite particles contain fluorine and aluminum inside, the graph of X-ray intensity normalized by peak intensity shows a shape like that shown in Figure 2(b). When hydrotalcite particles contain fluorine derived from a surface treatment agent, the graph of X-ray intensity normalized by peak intensity has peaks near points a and b, both ends of the fluorine graph, as shown in Figure 2(c). By checking the X-ray intensities derived from fluorine and aluminum in line analysis, it can be confirmed that the hydrotalcite particles contain fluorine and aluminum inside.

[0103] (Method for calculating the ratio of the atomic concentration of fluorine to aluminum in hydrotalcite particles A (element ratio) F / Al) The atomic concentration ratio (element ratio) F / Al of fluorine to aluminum in hydrotalcite particles A obtained from the main component mapping derived from hydrotalcite particles A by the above-mentioned STEM-EDS mapping analysis is obtained from multiple fields of view, and the arithmetic average of the values ​​for 100 or more relevant particles is taken to determine the atomic concentration ratio (element ratio) F / Al of fluorine to aluminum in hydrotalcite particles A.

[0104] (Method for calculating the ratio of the atomic concentration of magnesium to aluminum (element ratio) Mg / Al in hydrotalcite particles A) The same method as that for calculating the atomic concentration ratio (element ratio) F / Al of fluorine to aluminum in the hydrotalcite particles A described above is performed for magnesium and aluminum to calculate the atomic concentration ratio (element ratio) Mg / Al of magnesium to aluminum in the hydrotalcite particles A.

[0105] (Method for calculating the content of polyvalent metal elements in toner particles) The elemental amounts (atomic number concentrations) of polyvalent metal elements and carbon in the toner particles can be obtained from the principal component mapping derived from the toner particles by the above-mentioned STEM-EDS mapping analysis. The elemental amount (atomic number concentration) of polyvalent metal elements such as aluminum when the elemental amount (atomic number concentration) of carbon is set to 100 is defined as the "content of polyvalent metal elements in the toner particles." The mapping data is obtained from multiple fields of view, and the arithmetic average is taken for 100 or more toner particles to calculate the "content of polyvalent metal elements in the toner particles."

[0106] (Method for calculating the ratio of the fluorine content in hydrotalcite particles A to the polyvalent metal element content in toner particles) From the main component mapping derived from hydrotalcite particle A by the above-mentioned STEM-EDS mapping analysis, quantitative analysis of the element amounts is performed for Mg, Zn, Ca, Ba, Ni, Sr, Cu, Fe, Al, B, Ga, Co, In, C, O, and fluorine, which are detectable by EDS among the elements that can constitute hydrotalcite particle A. The element amounts (atomic number concentrations) of fluorine and other elements are obtained. The obtained amount of fluorine (atomic number concentration) is defined as the "fluorine content in the hydrotalcite particles A." The mapping data is obtained from multiple fields of view, and the arithmetic average is taken for 100 or more hydrotalcite particles to calculate the fluorine content in the hydrotalcite particles A. The value obtained by taking the "fluorine content in hydrotalcite particles A" as the numerator and the "polyvalent metal content in toner particles" as the denominator is calculated as the "ratio of the fluorine content in hydrotalcite particles A to the polyvalent metal element content in toner particles."

[0107] (Method of calculating the area ratio of hydrotalcite particles A to toner particles) Based on the mapping data obtained by the STEM-EDS mapping analysis of the toner using the method described above, the area ratio of each extracted main component in the EDS measurement field of view can be calculated. The value obtained by taking the "area of ​​the hydrotalcite particles" as the numerator and the "total area of ​​the hydrotalcite particles and the toner particle" as the denominator is used to calculate the area ratio of hydrotalcite particles A to the toner particles. The mapping data is obtained from a plurality of visual fields, and the area ratio of the hydrotalcite particles A to the toner particles in the EDS measurement visual fields is calculated. The arithmetic average of the 30 visual fields is taken as the area ratio of the hydrotalcite particles A to the toner particles.

[0108] <Method for measuring the number average particle size of primary particles of hydrotalcite particles> The number-average particle size of hydrotalcite particles is measured using a scanning electron microscope "S-4800" (trade name; manufactured by Hitachi, Ltd.) in combination with elemental analysis by energy dispersive X-ray analysis (EDS). The toner to which external additives have been added is observed, and the hydrotalcite particles are photographed at a magnification of up to 200,000 times. Hydrotalcite particles are selected from the photographed image, and the major axis of the primary particles of 100 randomly selected hydrotalcite particles is measured to determine the number-average particle size. The observation magnification is adjusted appropriately depending on the size of the external additive. Here, particles that appear as a single particle upon observation are considered to be primary particles.

[0109] <Method for measuring the glass transition temperature (Tg) of a resin> The glass transition temperature of the resin is measured in accordance with ASTM D3418-97. Specifically, 10 mg of the dried resin was weighed out and placed in an aluminum pan. An empty aluminum pan was used as a reference. The glass transition temperature of the weighed resin was measured using a differential scanning calorimeter (manufactured by SII NanoTechnology, Inc., product name: DSC6220) in accordance with ASTM D 3418-97 at a heating rate of 10°C / min over a temperature range of 0°C to 150°C.

[0110] <Method for observing cross sections of toner using a transmission electron microscope (TEM) and evaluating wax domains> Cross-sectional observation of the toner using a transmission electron microscope (TEM) and evaluation of the wax domains are carried out as follows. Ruthenium dyeing of the toner cross section provides a clear contrast between crystalline materials. Wax, which is a crystalline material, is dyed less strongly than amorphous materials. This is thought to be because the dye penetrates less deeply into crystalline materials than amorphous materials due to differences in density. The amount of ruthenium atoms varies depending on the intensity of the dyeing, so areas that are strongly dyed have many ruthenium atoms, making it difficult for the electron beam to penetrate, and appear black in the observation image.On the other hand, areas that are weakly dyed have few ruthenium atoms, making it easy for the electron beam to penetrate, and appear white in the observation image.In addition, among the crystalline materials contained in toner, it is possible to distinguish between polymer crystals such as crystalline polyester and low-molecular-weight crystals such as wax by their crystal structures.Specifically, in the case of polymer crystals, a lamellar structure is confirmed in the observation image, while in the case of low-molecular-weight crystals, a lamellar structure is not confirmed in the observation image.

[0111] Using an osmium plasma coater (Filgen, OPC80T), a protective film of osmium (5 nm) and a naphthalene film (20 nm) were applied to the toner, which was then embedded in photocurable resin D800 (JEOL). A toner cross section with a thickness of 60 nm was then prepared using an ultrasonic ultramicrotome (Leica, UC7) at a cutting speed of 1 mm / s. The obtained cross section was stained for 15 minutes in a 500 Pa atmosphere of RuO4 gas using a vacuum electron staining device (Filgen, VSC4R1H) and then observed under a TEM (JEOL, JEM2800). STEM observation is performed using the STEM mode. The STEM probe size is 1 nm, and the image size is 1024 pixels x 1024 pixels. The obtained images are binarized (threshold 120 / 255 levels) using the image processing software "Image-Pro Plus (Media Cybernetics)". Binarization allows the extraction of crystalline domains.

[0112] The toner particles are extracted so that the major axis of the cross section is within ±10% of the volume-based median diameter of the toner obtained by the measurement described below. -14 m 2 Next, a line is drawn to separate the area from the surface (outline of the cross section) of the toner particle to within 0.1 μm, and the number of toner particles in which even a portion of the wax domain exists within a range of 0.1 μm from the surface is counted, and the ratio of the number of wax domains to the observed toner particles is calculated. Figures 1(a) and 1(b) show schematic diagrams of the cross section of a toner particle. The solid line indicates the outline of the cross section, and the dotted line indicates the area extending 0.1 μm inward from the outline of the cross section. Figure 1(a) shows an example in which no wax domains exist within 0.1 μm from the surface, while Figure 1(b) shows an example in which wax domains exist within 0.1 μm from the surface. Measurement is carried out on at least 100 toner particles randomly selected except for particle size, and the number ratio of the toner particles is calculated.

[0113] <Identification of wax in toner> (1) Method for separating wax from toner First, the melting point of the wax in the toner was measured using a thermal analyzer (DSC Q2000, manufactured by TA Instruments Japan Co., Ltd.). 3.0 mg of the toner sample was placed in a sample container in an aluminum pan (KIT No. 0219-0041), which was then placed on a holder unit and placed in an electric furnace. Under a nitrogen atmosphere, the sample was heated from 30°C to 200°C at a rate of 10°C / min. The DSC curve was measured using a differential scanning calorimeter (DSC), and the melting point of the wax in the toner sample was calculated. Next, the toner is dispersed in ethanol, a poor solvent for the toner, and the temperature is raised to a temperature above the melting point of the wax. If necessary, pressure may be applied during this process. By this operation, the wax has exceeded its melting point and is melted and extracted into the ethanol. The wax can be separated from the toner by heating, and if pressure is applied, by performing solid-liquid separation while still under pressure. The extracted liquid is then dried and solidified to obtain the wax.

[0114] (2) Identification of wax by pyrolysis GCMS The specific conditions for identifying wax by pyrolysis GCMS are shown below. Mass spectrometer: ThermoFisherScinetific ISQ GC equipment: ThermoFisher Scientific FocusGC Ion source temperature: 250℃ Ionization method: EI Mass range: 50-1000 m / z Column: HP-5MS [30 m] Pyrolysis equipment: Japan Analytical Industry Co., Ltd. JPS-700

[0115] A small amount of the wax separated by extraction and 1 μL of tetramethylammonium hydroxide (TMAH) are added to a pyrofoil at 590°C. The resulting sample is subjected to pyrolysis GCMS measurement under the above conditions, and peaks derived from the wax are obtained. If the wax is an ester compound, peaks are obtained for the alcohol and carboxylic acid components. Due to the action of TMAH, a methylating agent, the alcohol and carboxylic acid components are detected as methylated products. By analyzing the peaks obtained and identifying the structure of the ester compound, the molecular weight can also be obtained.

[0116] <Binder resin composition analysis> -Method for separating binder resin from toner 100 mg of toner was dissolved in 3 ml of chloroform. Next, the insoluble matter was removed by suction filtration using a syringe equipped with a sample processing filter (pore size 0.2 μm to 0.5 μm, such as a Myshoridisk H-25-2 (Tosoh Corporation)). The soluble matter was introduced into a preparative HPLC (apparatus: Japan Analytical Industry Co., Ltd. LC-9130 NEXT preparative column [60 cm], exclusion limits: 20,000 and 70,000, two columns connected), and chloroform eluent was pumped. Once a peak was confirmed in the resulting chromatographic display, fractions with retention times greater than 2,000 molecular weight were collected using a monodisperse polystyrene standard sample. The resulting fraction solution was dried and solidified to obtain the binder resin.

[0117] - Identification of binder resin components and measurement of mass ratios using nuclear magnetic resonance spectroscopy (NMR) 1 mL of deuterated chloroform is added to 20 mg of toner, and the NMR spectrum of the protons in the dissolved binder resin is measured. The molar and mass ratios of each monomer are calculated from the obtained NMR spectrum, and the content of the constituent monomer units of the binder resin, such as styrene-acrylic resin, can be determined. For example, in the case of a styrene-acrylic copolymer, the composition ratio and mass ratio can be calculated based on the peak at around 6.5 ppm derived from the styrene monomer and the peak at around 3.5-4.0 ppm derived from the acrylic monomer. Furthermore, in the case of a polyester resin and a styrene-acrylic resin copolymer, the molar and mass ratios are calculated based on the peaks derived from each monomer constituting the polyester resin and the peak derived from the styrene-acrylic copolymer. NMR device: JEOL RESONANCE ECX500 Observation nucleus: Proton Measurement mode: Single pulse Base peak: TMS

[0118] Identification of the components of shell resin B using time-of-flight secondary ion mass spectrometry (TOF-SIMS) Time-of-flight secondary ion mass spectrometry (TOF-SIMS) can obtain information from the surface of toner particles down to a few nanometers, making it possible to identify the constituent materials near the outermost surface of the toner particles. To identify the shell resin present on the surface of toner particles using TOF-SIMS, a TRIFT-IV manufactured by ULVAC-PHI, Inc. is used. The analysis conditions are as follows: Sample preparation: Adhesion of toner to an indium sheet Sample preparation: None Primary ions: Au ions Accelerating voltage: 30 kV Charge neutralization mode: On Measurement mode: Negative Raster: 100 μm

[0119] From each peak, the composition of the resin present on the surface of the toner particle is identified and its abundance ratio is calculated. For example, S211 is a peak derived from bisphenol A. Also, for example, S85 is a peak derived from butyl acrylate. Calculation of the peak intensity (S85) derived from vinyl resin: Total counts of mass numbers 84.5 to 85.5 according to ULVAC-PHI's standard software (Win Cadense) is the peak intensity (S85). Calculation of the peak intensity (S211) derived from amorphous polyester: According to the standard software (Win Cadense) of ULVAC-PHI, the peak intensity of mass numbers 210.5 to 211.5 was calculated. The total count number is taken as the peak intensity (S211).

[0120] <Method for measuring the average circularity of toner particles> The average circularity of the toner or toner particles is measured using a flow particle image analyzer, "FPIA-3000" (manufactured by Sysmex Corporation), under the measurement and analysis conditions used during calibration work. To 20 mL of ion-exchanged water, an appropriate amount of surfactant and alkylbenzene sulfonate was added as a dispersant, and then 0.02 g of the measurement sample was added and dispersed for 2 minutes using a tabletop ultrasonic cleaner disperser (product name: VS-150, manufactured by Vervoclear Co., Ltd.) with an oscillation frequency of 50 kHz and an electrical output of 150 watts to obtain a dispersion for measurement. At this time, the dispersion was appropriately cooled so that the temperature was between 10°C and 40°C. For the measurement, the flow particle image analyzer equipped with a standard objective lens (10x) is used, and the particle sheath "PSE-900A" (manufactured by Sysmex Corporation) is used as the sheath liquid. The dispersion liquid prepared according to the above procedure is introduced into the flow particle image analyzer, and 3,000 toner particles (particles) are measured in HPF measurement mode and total count mode. The binarization threshold for particle analysis is set to 85%, and the analyzed particle diameter is limited to a circle-equivalent diameter of 1.98 μm or more and 19.92 μm or less, and the average circularity of the toner particles (particles) is determined. Before starting the measurement, automatic focus adjustment is performed using standard latex particles (for example, 5100A (trade name) manufactured by Duke Scientific diluted with ion-exchanged water). After that, it is preferable to perform focus adjustment every two hours from the start of the measurement.

[0121] <Measurement of weight average molecular weight Mw, number average molecular weight Mn, and peak molecular weight> The molecular weight distribution (weight average molecular weight Mw, number average molecular weight Mn, peak molecular weight) of a resin or the like is measured by gel permeation chromatography (GPC) as follows. First, the sample is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. The resulting solution is then filtered through a solvent-resistant membrane filter "Myshoridisc" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of components soluble in THF is 0.8 mass%. This sample solution is used for measurements under the following conditions. Apparatus: HLC8120GPC (detector: RI) (Tosoh Corporation) Column: Shodex KF-801, 802, 803, 804, 805, 806, 807 (7 columns, manufactured by Showa Denko Co., Ltd.) Eluent: tetrahydrofuran (THF) ·Flow rate: 1.0ml / min Oven temperature: 40.0℃ Sample injection volume: 0.10 ml To calculate the molecular weight of a sample, a molecular weight calibration curve prepared using standard polystyrene resins (for example, trade names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation) is used.

[0122] <Method for measuring melting point> The melting point of the crystalline material (crystalline resin or wax) is measured using a differential scanning calorimeter (DSC) Q2000 (manufactured by TA Instruments) under the following conditions. Heating rate: 10℃ / min Measurement start temperature: 20℃ Measurement end temperature: 180℃ The melting points of indium and zinc are used to correct the temperature of the detector, and the heat of fusion of indium is used to correct the amount of heat. Specifically, approximately 5 mg of sample is weighed out and placed in an aluminum pan, and a single measurement is performed. An empty aluminum pan is used as a reference, and the peak temperature of the maximum endothermic peak at that time is taken as the melting point.

[0123] <Method for measuring particle size such as volume-based median diameter of toner> The particle size, such as the volumetric median diameter of the toner, is calculated as follows. The measurement device used is the Coulter Counter Multisizer 3 (registered trademark, manufactured by Beckman Coulter, Inc.), a precision particle size distribution measurement device using the narrow-pore electrical resistance method and equipped with a 100 μm aperture tube. The measurement conditions are set and the measurement data is analyzed using the accompanying dedicated software, Beckman Coulter Multisizer 3 Version 3.51 (manufactured by Beckman Coulter, Inc.). The measurement is performed using an effective number of 25,000 measurement channels. The aqueous electrolyte solution used for the measurement is prepared by dissolving special grade sodium chloride in ion-exchanged water to a concentration of approximately 1% by mass, such as "ISOTON II" (manufactured by Beckman Coulter). Before carrying out the measurement and analysis, the dedicated software is set up as follows. On the "Change Standard Measurement Method (SOMME)" screen of the dedicated software, set the total count in control mode to 50,000 particles, the number of measurements to 1, and the Kd value to the value obtained using "Standard Particles 10.0 μm" (Beckman Coulter). Press the "Threshold / Noise Level Measurement Button" to automatically set the threshold and noise level. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check "Flush aperture tube after measurement." On the "Pulse to particle size conversion setting" screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bins, and the particle size range is set to 2 μm to 60 μm. The specific measurement method is as follows.

[0124] (1) Pour approximately 200 mL of the electrolyte solution into a 250 mL round-bottom glass beaker made specifically for the Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 revolutions per second. Then, use the "aperture tube flush" function of the dedicated software to remove any dirt and air bubbles from inside the aperture tube. (2) Approximately 30 mL of the above-mentioned aqueous electrolyte solution is placed in a 100 mL flat-bottom glass beaker, and approximately 0.3 mL of a solution prepared by diluting Contaminon N (a 10% aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) as a dispersant with ion-exchanged water by approximately three times its mass is added. (3) Prepare an ultrasonic disperser "Ultrasonic Dispersion System Tetra150" (manufactured by Nikkaki Bios Co., Ltd.) with an electrical output of 120 W and two built-in oscillators with an oscillation frequency of 50 kHz and a phase shift of 180 degrees. Place approximately 3.3 L of ion-exchanged water in the ultrasonic disperser's water tank and add approximately 2 mL of Contaminon N to this water tank. (4) Set the beaker (2) in the beaker fixing hole of the ultrasonic disperser, operate the ultrasonic disperser, and adjust the height of the beaker so that the resonance state of the liquid surface of the electrolytic solution in the beaker is maximized. (5) While the electrolyte solution in the beaker in (4) is irradiated with ultrasonic waves, approximately 10 mg of toner is added little by little to the electrolyte solution and dispersed. The ultrasonic dispersion process is then continued for another 60 seconds. During the ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be between 10°C and 40°C. (6) Using a pipette, the electrolytic solution (5) containing the dispersed toner is dropped into the round-bottom beaker (1) placed in the sample stand, and the measurement concentration is adjusted to approximately 5%. Then, measurements are continued until the number of particles measured reaches 50,000. (7) The measurement data is analyzed using the dedicated software provided with the device, and the volume-based median diameter is calculated. [Example]

[0125] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited thereto. "Parts" used in the examples are by mass unless otherwise specified.

[0126] An example of toner production will be described below. <Toner 1 manufacturing example> <Preparation example of resin particle dispersion 1> 70.0 parts styrene 28.7 parts butyl acrylate 1.3 parts acrylic acid 3.2 parts n-lauryl mercaptan The above materials were placed in a container and mixed by stirring. An aqueous solution of 1.5 parts of Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 150.0 parts of ion-exchanged water was added to this solution and dispersed. An aqueous solution of 0.3 parts potassium persulfate and 10.0 parts ion-exchanged water was added with slow stirring for an additional 10 minutes. After nitrogen substitution, emulsion polymerization was carried out at 70°C for 6 hours. After polymerization was completed, the reaction solution was cooled to room temperature, and ion-exchanged water was added to obtain resin particle dispersion 1 with a solids concentration of 12.5% ​​by mass and a glass transition temperature of 48°C. The particle size distribution of the resin particles contained in this resin particle dispersion 1 was measured using a particle size analyzer (HORIBA, Ltd., LA-920), and the number-average particle size of the resin particles contained was 0.2 μm. Furthermore, no coarse particles exceeding 1 μm were observed.

[0127] <Preparation example of resin particle dispersion 2> 78.0 parts styrene 20.7 parts butyl acrylate 1.3 parts acrylic acid 3.2 parts n-lauryl mercaptan The above materials were placed in a container and mixed by stirring. An aqueous solution of 1.5 parts of Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 150.0 parts of ion-exchanged water was added to this solution and dispersed. While slowly stirring for another 10 minutes, an aqueous solution of 0.3 parts potassium persulfate and 10.0 parts ion-exchanged water was added. After nitrogen substitution, emulsion polymerization was carried out at 70°C for 6 hours. After polymerization was completed, the reaction solution was cooled to room temperature, and ion-exchanged water was added to obtain resin particle dispersion 2 with a solids concentration of 12.5% ​​by mass and a glass transition temperature of 60°C. The particle size distribution of the resin particles contained in this resin particle dispersion 2 was measured using a particle size analyzer (HORIBA, Ltd., LA-920), and the number-average particle size of the resin particles contained was 0.2 μm. Furthermore, no coarse particles exceeding 1 μm were observed.

[0128] <Preparation example of release agent dispersion 1> 100.0 parts of behenyl behenate (melting point: 72.1°C) and 15.0 parts of NEOGEN RK were mixed with 385.0 parts of ion-exchanged water, and the mixture was dispersed for about 1 hour using a wet jet mill JN100 (manufactured by Joko Co., Ltd.) to obtain a release agent dispersion 1. The wax concentration in the release agent dispersion 1 was 20.0% by mass. The particle size distribution of the release agent particles contained in this release agent dispersion 1 was measured using a particle size measuring device (LA-920, manufactured by Horiba, Ltd.), and the number average particle size of the release agent particles contained was 0.35 μm. Furthermore, no coarse particles exceeding 1 μm were observed.

[0129] <Preparation example of release agent dispersion 2> 100.0 parts of hydrocarbon wax HNP-9 (manufactured by Nippon Seiro Co., Ltd., melting point: 75.5°C) and 15 parts of Neogen RK were mixed with 385.0 parts of ion-exchanged water, and the mixture was milled in a wet jet mill JN1 00 (manufactured by Joko Co., Ltd.) for about 1 hour to obtain release agent dispersion 2. The wax concentration in release agent dispersion 2 was 20.0% by mass. The particle size distribution of the release agent particles contained in this release agent dispersion 2 was measured using a particle size measuring device (LA-920, manufactured by Horiba, Ltd.), and the number average particle size of the release agent particles contained was 0.35 μm. Furthermore, no coarse particles exceeding 1 μm were observed.

[0130] <Preparation example of colorant dispersion 1> As a colorant, 50.0 parts of copper phthalocyanine (Pigment Blue 15:3) and 5.0 parts of Neogen RK were mixed with 200.0 parts of ion-exchanged water, and the mixture was dispersed for about 1 hour using a wet jet mill JN100 to obtain colorant dispersion 1. The solids concentration of colorant dispersion 1 was 20.0% by mass. The particle size distribution of the colorant particles contained in this colorant dispersion 1 was measured using a particle size analyzer (LA-920 manufactured by Horiba, Ltd.), and the number average particle size of the colorant particles contained was 0.20 μm. Furthermore, no coarse particles exceeding 1 μm were observed.

[0131] <Preparation of Toner Particles 1> ·Resin particle dispersion 1:265.0 parts Release agent dispersion 1:10.0 parts Release agent dispersion 2: 8.0 parts 8.0 parts colorant dispersion In the core formation process, the above materials were placed in a round stainless steel flask and mixed. Then, a homogenizer (IKA Ultra Turrax T50) was used to mix the materials at 5000 rpm. The temperature inside the container was adjusted to 30°C while stirring, and a 1 mol / L aqueous solution of sodium hydroxide was added to adjust the pH to 8.0.

[0132] As a flocculant, an aqueous solution of 0.25 parts aluminum chloride dissolved in 10.0 parts ion-exchanged water was added to the mixture at 30°C over 10 minutes with stirring. After leaving the mixture for 3 minutes, the temperature was raised to 60°C to form aggregated particles (core formation). The volume-based median diameter of the formed aggregated particles was conveniently measured using a Coulter Counter Multisizer 3 (registered trademark, manufactured by Beckman Coulter). When the volume-based median diameter reached 7.0 μm, 2:15.0 parts of resin particle dispersion was added and the mixture was stirred for another hour to form a shell.

[0133] Thereafter, a 1 mol / L aqueous solution of sodium hydroxide was added to adjust the pH to 9.0, and the temperature was raised to 95° C. to spheronize the aggregated particles. When the average circularity reached 0.980, the temperature was lowered and the mixture was cooled to room temperature, thereby obtaining toner particle dispersion 1.

[0134] Hydrochloric acid was added to the obtained toner particle dispersion 1 to adjust the pH to 1.5 or less, and the mixture was stirred and left for 1 hour before undergoing solid-liquid separation using a pressure filter to obtain a toner cake. This was reslurried with ion-exchanged water to make a dispersion again, and then subjected to solid-liquid separation using the aforementioned filter. The reslurrying and solid-liquid separation were repeated until the electrical conductivity of the filtrate reached 5.0 μS / cm or less, after which solid-liquid separation was finally performed to obtain a toner cake. The obtained toner cake was dried and further classified using a classifier so that the volume-based median diameter was 7.0 μm, obtaining toner particles 1.

[0135] The formulation and physical properties of the obtained toner particles are shown in Tables 1 and 2. [Table 1] In the table, "Parts of shell" is the number of parts by mass of the resin for the shell relative to 100 parts by mass of the resin for the core particles. "Toner number ratio" is the ratio of the area of ​​1.0 x 10 -14 m 2 The wax domains are the ratio of the number of toner particles that exist, even if only partially, within a range of 0.1 μm from the surface of the toner particle.

[0136] [Table 2]

[0137] <Preparation of Hydrotalcite Particles 1> A mixed aqueous solution of 1.03 mol / L magnesium chloride and 0.239 mol / L aluminum sulfate (liquid A), a 0.753 mol / L sodium carbonate aqueous solution (liquid B), and a 3.39 mol / L sodium hydroxide aqueous solution (liquid C) were prepared. Next, liquids A, B, and C were poured into the reaction vessel using a metering pump at a flow rate such that the volume ratio of liquid A to liquid B was 4.5:1. The pH value of the reaction solution was maintained in the range of 9.3 to 9.6 using liquid C, and the reaction temperature was 40°C to produce a precipitate. After filtration and washing, the precipitate was re-emulsified in ion-exchanged water to obtain a raw material hydrotalcite slurry. The hydrotalcite concentration in the obtained hydrotalcite slurry was 5.6% by mass. The obtained hydrotalcite slurry was dried under vacuum at 40°C overnight. NaF was dissolved in ion-exchanged water to a concentration of 100 mg / L, and a solution was prepared by adjusting the pH to 7.0 using 1 mol / L HCl or 1 mol / L NaOH. The dried hydrotalcite was added to the solution to a concentration of 0.1% (w / v%). The solution was stirred at a constant speed using a magnetic stirrer for 48 hours to prevent settling. The solution was then filtered through a membrane filter with a pore size of 0.5 μm and washed with ion-exchanged water. The obtained hydrotalcite was dried under vacuum at 40°C overnight and then crushed. The composition and physical properties of the obtained hydrotalcite particles 1 are shown in Table 3.

[0138] <Preparation of Hydrotalcite Particles 2 to 13> Except for appropriately adjusting the concentrations of Solution A, Solution B, and the NaF aqueous solution, hydrotalcite particles 2 to 13 were obtained in the same manner as in the production example of hydrotalcite particles 1. The compositions and physical properties of the obtained hydrotalcite particles 2 to 13 are shown in Table 3.

[0139] <Preparation of Hydrotalcite Particles 14> Hydrotalcite particles 14 were obtained in the same manner as in Production Example of Hydrotalcite Particles 1, except that ion-exchanged water was used instead of the NaF aqueous solution in Production Example of Hydrotalcite Particles 1. The composition and physical properties of the obtained hydrotalcite particles 14 are shown in Table 3.

[0140] <Preparation of Hydrotalcite Particles 15> Hydrotalcite particles 15 were obtained in the same manner as in the production example of hydrotalcite particles 14, except that the obtained slurry containing the hydrotalcite compound was surface-treated by adding 5 parts by mass of fluorosilicone oil to 95 parts by mass of solids before being vacuum-dried overnight at 40° C. The composition and physical properties of the obtained hydrotalcite particles 15 are shown in Table 3. [Table 3] The average particle size indicates the number-average particle size of primary particles.

[0141] <Toner 1 manufacturing example> To the toner particles 1 (100.0 parts) obtained above, hydrotalcite particles 1 (0.3 parts) and silica particles 1 (RX200: primary average particle size 12 nm, HMDS treatment, manufactured by Nippon Aerosil Co., Ltd.) (1.5 parts) were externally added and mixed using an FM10C (manufactured by Nippon Coke and Engineering Co., Ltd.). The external addition conditions were as follows: the lower blade was set to A0 blade, the gap to the deflector wall was set to 20 mm, the amount of toner particles charged was 2.0 kg, and the rotation speed was set to 66.6 s -1 The external addition time was 10 minutes, and the cooling water temperature was 20°C and the flow rate was 10 L / min. Thereafter, the mixture was sieved through a mesh having an opening of 200 μm to obtain Toner 1. The physical properties of Toner 1 obtained are shown in Tables 4 and 5.

[0142] <Production examples of toners 2 to 12> Toners 2 to 12 were obtained in the same manner as in the production example of Toner 1, except that the type and amount of hydrotalcite particles added were changed as shown in Table 4. The physical properties of Toners 2 to 12 obtained are shown in Tables 4 and 5.

[0143] <Production example of toners 13 to 20> <Production Examples of Toner Particles 2 to 9> In the production example of toner particle 1, except that the type and amount of aggregating agent were changed as shown in Table 2 Toner particles 2 to 9 were obtained in the same manner. The physical properties of the obtained toner particles 2 to 9 are shown in Tables 1 and 2. Toners 13 to 20 were obtained in the same manner as in the production example of toner 1, except that toner particle 1 was changed to toner particles 2 to 9. The physical properties of the obtained toners 13 to 20 are shown in Tables 4 and 5.

[0144] <Production Example of Toners 21-22> Toners 21 to 22 were obtained in the same manner as in the production example of Toner 1, except that the toner particles and hydrotalcite particles were changed as shown in Table 4. The physical properties of Toners 21 to 22 obtained are shown in Tables 4 and 5.

[0145] <Production Example of Toners 23 to 26> Toner particles 10 to 13 were obtained in the same manner as in the production example of toner particles 1, except that the amount of resin particle dispersion 2 added was changed as shown in Table 1. The formulations and physical properties of the obtained toner particles 10 to 13 are shown in Tables 1 and 2. Furthermore, toners 23 to 26 were obtained in the same manner as in the production example of toner 1, except that toner particles 10 to 13 were used instead of toner particles 1. The physical properties of toners 23 to 26 thus obtained are shown in Tables 4 and 5.

[0146] <Production example of toner 27-30> <Preparation example of resin particle dispersion 3> 66.0 parts styrene 32.7 parts butyl acrylate 1.3 parts acrylic acid 3.2 parts n-lauryl mercaptan The above materials were placed in a container and mixed by stirring. An aqueous solution of 1.5 parts of Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 150.0 parts of ion-exchanged water was added to this solution and dispersed. While slowly stirring for another 10 minutes, an aqueous solution of 0.3 parts potassium persulfate and 10.0 parts ion-exchanged water was added. After nitrogen substitution, emulsion polymerization was carried out at 70°C for 6 hours. After polymerization was completed, the reaction solution was cooled to room temperature, and ion-exchanged water was added to obtain resin particle dispersion 3 with a solids concentration of 12.5% ​​by mass and a glass transition temperature of 40°C. The particle size distribution of the resin particles contained in this resin particle dispersion 3 was measured using a particle size analyzer (HORIBA, Ltd., LA-920), and the number-average particle size of the resin particles contained was 0.2 μm. Furthermore, no coarse particles exceeding 1 μm were observed.

[0147] <Preparation example of resin particle dispersion 4> 90.0 parts styrene 8.7 parts butyl acrylate 1.3 parts acrylic acid 3.2 parts n-lauryl mercaptan The above materials were placed in a container and mixed by stirring. An aqueous solution of 1.5 parts of Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 150.0 parts of ion-exchanged water was added to this solution and dispersed. While slowly stirring for another 10 minutes, an aqueous solution of 0.3 parts potassium persulfate and 10.0 parts ion-exchanged water was added. After nitrogen substitution, emulsion polymerization was carried out at 70°C for 6 hours. After polymerization was completed, the reaction solution was cooled to room temperature, and ion-exchanged water was added to obtain resin particle dispersion 4 with a solids concentration of 12.5% ​​by mass and a glass transition temperature of 80°C. The particle size distribution of the resin particles contained in this resin particle dispersion 4 was measured using a particle size analyzer (HORIBA, Ltd., LA-920), and the number-average particle size of the resin particles contained was 0.2 μm. Furthermore, no coarse particles exceeding 1 μm were observed.

[0148] <Preparation example of resin particle dispersion 5> 85.0 parts styrene 13.7 parts butyl acrylate 1.3 parts acrylic acid 3.2 parts n-lauryl mercaptan The above materials were placed in a container and mixed by stirring. An aqueous solution of 1.5 parts of Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 150.0 parts of ion-exchanged water was added to this solution and dispersed. While slowly stirring for another 10 minutes, an aqueous solution of 0.3 parts potassium persulfate and 10.0 parts ion-exchanged water was added. After nitrogen substitution, emulsion polymerization was carried out at 70°C for 6 hours. After polymerization was completed, the reaction solution was cooled to room temperature, and ion-exchanged water was added to obtain Resin Particle Dispersion 5 with a solids concentration of 12.5% ​​by mass and a glass transition temperature of 73°C. The particle size distribution of the resin particles contained in Resin Particle Dispersion 5 was measured using a particle size analyzer (HORIBA, Ltd., LA-920), and the number-average particle size of the resin particles contained was 0.2 μm. Furthermore, no coarse particles exceeding 1 μm were observed.

[0149] <Preparation example of resin particle dispersion 6> 76.0 parts styrene 22.7 parts butyl acrylate 1.3 parts acrylic acid 3.2 parts n-lauryl mercaptan The above materials were placed in a container and mixed by stirring. An aqueous solution of 1.5 parts of Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 150.0 parts of ion-exchanged water was added to this solution and dispersed. While slowly stirring for another 10 minutes, an aqueous solution of 0.3 parts potassium persulfate and 10.0 parts ion-exchanged water was added. After nitrogen substitution, emulsion polymerization was carried out at 70°C for 6 hours. After polymerization was completed, the reaction solution was cooled to room temperature, and ion-exchanged water was added to obtain Resin Particle Dispersion 6 with a solids concentration of 12.5% ​​by mass and a glass transition temperature of 58°C. The particle size distribution of the resin particles contained in Resin Particle Dispersion 6 was measured using a particle size analyzer (HORIBA, Ltd., LA-920). The number-average particle size of the resin particles contained was 0.2 μm. Furthermore, no coarse particles exceeding 1 μm were observed.

[0150] <Preparation example of resin particle dispersion 7> 72.0 parts styrene 26.7 parts butyl acrylate 1.3 parts acrylic acid 3.2 parts n-lauryl mercaptan The above materials were placed in a container and mixed by stirring. An aqueous solution of 1.5 parts of Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 150.0 parts of ion-exchanged water was added to this solution and dispersed. While slowly stirring for another 10 minutes, an aqueous solution of 0.3 parts potassium persulfate and 10.0 parts ion-exchanged water was added. After nitrogen substitution, emulsion polymerization was carried out at 70°C for 6 hours. After polymerization was completed, the reaction solution was cooled to room temperature, and ion-exchanged water was added to obtain Resin Particle Dispersion 7 with a solids concentration of 12.5% ​​by mass and a glass transition temperature of 51°C. The particle size distribution of the resin particles contained in Resin Particle Dispersion 7 was measured using a particle size analyzer (HORIBA, Ltd., LA-920), and the number-average particle size of the resin particles contained was 0.2 μm. Furthermore, no coarse particles exceeding 1 μm were observed.

[0151] Toner particles 14 to 17 were obtained in the same manner as in the production example of toner particles 1, except that the types and amounts of resin particle dispersions 1 and 2 were changed as shown in Table 4. The formulations and physical properties of the obtained toner particles 14 to 17 are shown in Tables 1 and 2. Furthermore, toners 27 to 30 were obtained in the same manner as in the production example of toner 1, except that toner particles 14 to 17 were used instead of toner particles 1. The physical properties of toners 27 to 30 thus obtained are shown in Tables 4 and 5.

[0152] <Toner 31 manufacturing example> <Preparation example of release agent dispersion 3> 100.0 parts of pentaerythritol tetrabehenate (melting point: 84.2°C) and 15 parts of Neogen RK were mixed with 385.0 parts of ion-exchanged water, and the mixture was dispersed for about 1 hour using a wet jet mill JN100 (manufactured by Jokou Co., Ltd.) to obtain release agent dispersion 3. The wax concentration of release agent dispersion 3 was 20.0% by mass. The particle size distribution of the release agent particles contained in this release agent dispersion 3 was measured using a particle size measuring device (LA-920, manufactured by Horiba, Ltd.), and the number average particle size of the release agent particles contained was 0.35 μm. Furthermore, no coarse particles exceeding 1 μm were observed.

[0153] <Preparation example of colorant dispersion 2> As a colorant, 100.0 parts of carbon black "Nipex 35 (manufactured by Orion Engineered Carbons)" and 15 parts of Neogen RK were mixed with 885.0 parts of ion-exchanged water, and dispersed for about 1 hour using a wet jet mill JN100 to obtain a colorant dispersion. The particle size distribution of the colorant particles contained in this colorant particle dispersion 2 was measured using a particle size analyzer (LA-920 manufactured by Horiba, Ltd.), and the number average particle size of the colorant particles contained was 0.2 μm. Furthermore, no coarse particles exceeding 1 μm were observed.

[0154] In the production example of toner 1, release agent dispersion 1 was changed to release agent dispersion 3. In addition, colorant dispersion 1 was changed to colorant particle dispersion 2, and the number of parts added was changed from 8 parts to 16 parts. Except for this, toner particles 18 were obtained in the same manner. Furthermore, toner 31 was obtained in the same manner as in the production example of toner 1, except that toner particles 1 were changed to toner particles 18. The physical properties of the obtained toner 31 are shown in Tables 4 and 5.

[0155] <Toner 32 Manufacturing Example> <Preparation example of release agent dispersion 4> 100.0 parts of ethylene glycol distearate (melting point: 75.9°C) and 15 parts of Neogen RK were mixed with 385.0 parts of ion-exchanged water, and the mixture was dispersed for about 1 hour using a wet jet mill JN100 (manufactured by Jokou Co., Ltd.) to obtain release agent dispersion 4. The wax concentration in release agent dispersion 4 was 20.0% by mass. The particle size distribution of the release agent particles contained in this release agent dispersion 4 was measured using a particle size measuring device (LA-920, manufactured by Horiba, Ltd.), and the number average particle size of the release agent particles contained was 0.35 μm. Furthermore, no coarse particles exceeding 1 μm were observed. In the production example of toner 31, release agent dispersion 1 was changed to release agent dispersion 4. Otherwise, toner particles 19 were obtained in the same manner as above, and toner 32 was also obtained. The physical properties of the obtained toner 32 are shown in Tables 4 and 5.

[0156] <Toner 33 manufacturing example> <Preparation example of resin particle dispersion liquid 8> <Synthesis of polyester resin 1> Bisphenol A ethylene oxide 2 mole adduct 9 mol parts Bisphenol A propylene oxide 2 mole adduct 95 mol parts Terephthalic acid 50 mol parts Fumaric acid 30 mol parts Dodecenyl succinic acid 25 mol parts The above monomers were charged into a flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and distillation column, and the temperature was raised to 195°C over 1 hour. It was confirmed that the reaction system was uniformly stirred. 1.0 part of tin distearate was added to 100 parts of these monomers. The temperature was then raised from 195°C to 250°C over 5 hours while distilling off the water produced. The dehydration condensation reaction was continued for another 2 hours. As a result, polyester resin 1 having a glass transition temperature of 60° C., an acid value of 16.8 mgKOH / g, a hydroxyl value of 28.2 mgKOH / g, a weight average molecular weight of 11,200, and a number average molecular weight of 4,100 was obtained.

[0157] 100 parts polyester resin 50 parts methyl ethyl ketone 20 parts isopropyl alcohol The above-mentioned methyl ethyl ketone and isopropyl alcohol were added to a container. Then, the above-mentioned polyester resin 1 was gradually added and stirred until completely dissolved, yielding a polyester resin 1 solution. The container containing this polyester resin 1 solution was set to 65°C, and while stirring, a 10% aqueous ammonia solution was gradually added dropwise to a total of 5 parts, and then 230 parts of ion-exchanged water was gradually added dropwise at a rate of 10 ml / min to cause phase inversion emulsification. The pressure was then reduced in an evaporator to remove the solvent, yielding a resin particle dispersion 8 of polyester resin 1. The solid content of the resin particle dispersion 8 was adjusted to 20% with ion-exchange water. The particle size distribution of the resin particles contained in the resin particle dispersion 8 was measured using a particle size measuring device (LA-920, manufactured by Horiba, Ltd.), and the number average particle size of the resin particles contained was 0.15 μm. No coarse particles exceeding 1 μm were observed.

[0158] Toner particles 20 were obtained in the same manner as in the production example of toner 31, except that resin particle dispersion 2 was changed to resin particle dispersion 8, and then toner 33 was obtained. The physical properties of the obtained toner 33 are shown in Tables 4 and 5.

[0159] <Toner 34 Manufacturing Example> <Preparation of Resin Particle Dispersion 9> <Synthesis of polyester resin 2> Bisphenol A-ethylene oxide 2 mole adduct 48 mol parts Bisphenol A-propylene oxide 2 mole adduct 38 mole parts Bisphenol A-propylene oxide 3 mole adduct 10 mole parts Terephthalic acid 65 mol parts Dodecenyl succinic acid 30 mol parts The above monomers were added to a flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and distillation column, and the temperature was raised to 195°C over one hour, confirming that the reaction system was uniformly stirred. 0.7 parts of tin distearate were added to 100 parts of these monomers. The temperature was then raised from 195°C to 240°C over five hours while distilling off the water produced, and a dehydration condensation reaction was carried out at 240°C for another two hours. The temperature was then lowered to 190°C, and 5 mol parts of trimellitic anhydride were gradually added, and the reaction was continued at 190°C for one hour. As a result, polyester resin 2 having a glass transition temperature of 52° C., an acid value of 13.8 mgKOH / g, a hydroxyl value of 21.2 mgKOH / g, a weight average molecular weight of 43,000, and a number average molecular weight of 6,400 was obtained.

[0160] 100 parts polyester resin 2 50 parts methyl ethyl ketone 20 parts isopropyl alcohol The above-mentioned methyl ethyl ketone and isopropyl alcohol were added to a container. Then, the above-mentioned polyester resin 2 was gradually added and stirred until completely dissolved, yielding a polyester resin 2 solution. The container containing this polyester resin 2 solution was set to 40°C, and while stirring, a 10% aqueous ammonia solution was gradually added dropwise to a total of 3.5 parts, and then 230 parts of ion-exchanged water was gradually added dropwise at a rate of 10 ml / min to cause phase inversion emulsification. The pressure was then reduced to remove the solvent, yielding a resin particle dispersion 9 of polyester resin 2. The solid content of the resin particle dispersion 9 was adjusted to 20% with ion-exchange water. The particle size distribution of the resin particles contained in the resin particle dispersion 9 was measured using a particle size measuring device (LA-920, manufactured by Horiba, Ltd.), and the number average particle size of the resin particles contained was 0.15 μm. No coarse particles exceeding 1 μm were observed.

[0161] Toner particles 21 were obtained in the same manner as in the production example of toner 33, except that resin particle dispersion 1 was changed to resin particle dispersion 9, and toner 34 was also obtained. The physical properties of the obtained toner 34 are shown in Tables 4 and 5.

[0162] <Toner 35 manufacturing example> Toner 35 was obtained in the same manner as in the production example of Toner 1, except that hydrotalcite particles 1 were changed to hydrotalcite particles 13. The physical properties of the obtained Toner 35 are shown in Tables 4 and 5.

[0163] <Toner 36 manufacturing example> Toner 36 was obtained in the same manner as in the production example of Toner 1, except that hydrotalcite particles 1 were changed to hydrotalcite particles 14. Note that hydrotalcite particles 14 are hydrotalcite particles that do not contain fluorine. The physical properties of the obtained Toner 36 are shown in Tables 4 and 5.

[0164] <Toner 37 manufacturing example> Toner 37 was obtained in the same manner as in the production example of Toner 1, except that hydrotalcite particles 1 were replaced with polytetrafluoroethylene (PTFE) fine particles "Fluoro A" (manufactured by Shamrock, average primary particle diameter 0.3 μm). The physical properties of the obtained Toner 37 are shown in Tables 4 and 5.

[0165] <Toner 38 manufacturing example> Toner 38 was obtained in the same manner as in the production example of Toner 1, except that the hydrotalcite particles 1 were changed to fluorine-containing alumina particles. The physical properties of Toner 38 obtained are shown in Tables 4 and 5. Fluorine-containing alumina particles have a BET specific surface area of ​​120m 2 / g of alumina was placed in a reaction vessel, and a mixed solution of 8 parts heptadecafluorodecyltrimethoxysilane and 1.8 parts hexamethyldisilazane was sprayed onto 100 parts of alumina particles while stirring under a nitrogen atmosphere. The mixture was heated and stirred at 220°C for 150 minutes, and then cooled to prepare the powder.

[0166] <Toner 39 manufacturing example> Toner particles 22 were produced in the same manner as in the production of toner particles 1, except that the shell formation step was not carried out. Furthermore, toner 39 was obtained in the same manner as in the production example of toner 1, except that toner particles 1 were changed to toner particles 22. Note that toner particles 22 do not form a shell and are toner particles without a core-shell structure. The physical properties of the obtained toner 39 are shown in Tables 4 and 5.

[0167] <Toner 40 manufacturing example> Toner 40 was obtained in the same manner as in the production example of toner 1, except that hydrotalcite particles 15 were used instead of hydrotalcite particles 1. Note that hydrotalcite particles 15 are hydrotalcite particles that have been surface-treated with a treatment agent containing fluorine. The physical properties of toner 40 obtained are shown in Tables 4 and 5. [Table 4] The average particle size indicates the number-average particle size of primary particles. "Parts of hydrotalcite particles in toner" indicates the number of parts by mass relative to 100 parts by mass of toner particles.

[0168] [Table 5] In the table, atomic % is the atomic concentration of each atom in hydrotalcite particles A obtained from the main component mapping of hydrotalcite particles A by STEM-EDS mapping analysis of the toner. * indicates whether fluorine atoms are contained inside the hydrotalcite particles, and "present" and "absent" indicate that fluorine atoms are contained inside the hydrotalcite particles and that fluorine atoms are not contained inside the hydrotalcite particles, respectively. In the table, "area ratio" indicates the area ratio of hydrotalcite particles A to toner particles in the EDS measurement field of view, and "fluorine / polyvalent metal" indicates the ratio of the fluorine content in hydrotalcite particles A to the content of the polyvalent metal element in the toner particles.

[0169] <Image evaluation> Image evaluation was performed using a commercially available color laser printer (HP LaserJet Enterprise Color M555dn, manufactured by HP) that had been partially modified so that it could operate with only one color process cartridge installed. The printer was also modified so that the fixing unit temperature could be adjusted as desired. The toner was removed from the container, and 180 g of the toner to be evaluated was filled in its place, and the evaluation was carried out.

[0170] [Fixing performance (cold offset resistance)] Solid image on transfer material (toner amount: 0.9 mg / cm 2) were printed three times in succession at different fixing temperatures, and the image on the third sheet was evaluated according to the following criteria. In a room temperature, low humidity environment (23°C, 5% RH), the temperature was increased in 10°C increments in the range from 170°C to 190°C, and fixed images were obtained at each temperature. The fixed images obtained were evaluated for cold offset resistance. The fixing temperature was measured using a non-contact thermometer on the surface of the fixing roller before paper was passed through. The transfer material was letter-size plain paper (XEROX 4200, manufactured by XEROX Corporation, 75 g / m 2 ) was used. The fixed image was visually evaluated for cold offset and judged according to the following criteria: C or better was judged as good. Evaluation criteria A: No offset at 170℃ B: Offset occurs at 170℃ C: Offset occurs at 180℃ D: Offset occurs at 190℃

[0171] [Durability] For the purpose of testing the durability (charge stability) of the toner, fogging in a high temperature and high humidity environment (30° C. / 80% RH) (HH fogging) was evaluated by the following method. In a high temperature and humidity environment, Canon color laser copier paper (A4: 81.4 g / m 2 (Hereinafter, unless otherwise specified, this paper is assumed to be used) images with a print rate of 1.0% were printed with a 2-second break every two sheets, for a total of 2,000 sheets per day. Fog on the drum of the cartridge was taped and collected for evaluation at the initial stage and after printing 8,000 sheets.

[0172] Fog was measured using a reflection densitometer (Reflectometer Model TC-6DS, manufactured by Tokyo Denshoku Co., Ltd.). The fog density (%) was calculated by (Ds - Dr), where Ds is the worst reflection density value of the white background of the tape area and Dr is the average reflection density value of the paper in the taped area. Three types of filters, green, amber, and blue, were used for measurement, and the worst value was taken as the fog density. In this evaluation method, if the toner deteriorates over time and its charging properties decrease, the fog density on the drum will increase. The fog density was evaluated according to the following criteria: C or higher was considered to be good. Evaluation criteria A: Fog density less than 0.5% B: Fog density 0.5% or more and less than 1.5% C: Fog density 1.5% or more and less than 3.0% D: Fog density 3.0% or more

[0173] [Storability] 5g of each toner was placed in a 50mL resin cup, left at a temperature of 50°C and a humidity of 10%RH for 3 days, then removed and visually inspected for the presence of agglomerates. The evaluation was based on the following criteria. A grade of C or higher was considered good. Evaluation criteria A: No agglomerates formed B: Slight clumps formed, crumbles when lightly pressed with fingers C: Agglomerates formed, but they do not crumble even when lightly pressed with a finger. D: Completely agglomerated

[0174] Examples 1 to 34 In Examples 1 to 34, the above evaluations were carried out using toners 1 to 34, respectively. The evaluation results are shown in Table 6.

[0175] [Table 6]

[0176] Comparative Examples 1 to 6 In Comparative Examples 1 to 6, the above evaluations were carried out using toners 35 to 40, respectively. The evaluation results are shown in Table 7. [Table 7]

[0177] In Examples 1 to 34, good results were obtained in all evaluation items. In Examples 1 to 6, the results were inferior to those of the Examples in any of the above evaluation items. As can be seen from the above results, according to the present disclosure, a toner having excellent low-temperature fixability and good durability can be obtained. [Explanation of symbols]

[0178] 1: Toner particle 1, 2: Toner particle 2, 3: Hydrotalcite particle A, 4: Boundary of toner particle, 5: Analysis direction of line analysis

Claims

1. A toner containing toner particles and an external additive, the toner particles have a core containing resin A and a shell containing resin B on the surface of the core, the external additive contains hydrotalcite particles A, In a line analysis of the STEM-EDS mapping analysis of the toner, fluorine and aluminum are present inside the hydrotalcite particles A, a value F / Al of the ratio of the atomic concentration of fluorine to that of aluminum in the hydrotalcite particles A, obtained from a main component mapping of the hydrotalcite particles A by STEM-EDS mapping analysis of the toner, is 0.01 to 0.60; A toner characterized by:

2. the toner particles contain at least one polyvalent metal element selected from the group consisting of aluminum, magnesium, calcium, and iron, In a main component mapping of the toner particles and a main component mapping of the hydrotalcite particles A by STEM-EDS mapping analysis of the toner, a ratio of the content of fluorine in the hydrotalcite particles A to the content of the polyvalent metal element in the toner particles is 2.0 to 100.

0. The toner according to claim 1 .

3. the toner particles contain a wax, In the cross-section observation of the toner using a transmission electron microscope, an area of ​​1.0 × 10 －１４ m ２ the ratio of the number of toner particles in which the wax domains having a size equal to or larger than this exist at least partially within a range of 0.1 μm from the surface of the toner particle is 15% or less; The toner according to claim 1 or 2.

4. 4. The toner according to claim 1, wherein the hydrotalcite particles A further contain magnesium.

5. 5. The toner according to claim 4, wherein a value Mg / Al of the ratio of the atomic concentration of magnesium to aluminum in the hydrotalcite particles A obtained from main component mapping of the hydrotalcite particles A by STEM-EDS mapping analysis of the toner is 1.5 to 4.

0.

6. 6. The toner according to claim 1, wherein the number average particle size of the primary particles of the hydrotalcite particles A is 60 to 1000 nm.

7. the toner particles contain aluminum as a polyvalent metal element, 7. The toner according to claim 1, wherein, in a main component mapping of the toner particles by STEM-EDS mapping analysis of the toner, the content of the aluminum in the toner particles is 0.01 to 0.07, where the atomic concentration of carbon in the toner particles is taken as 100.

8. 8. The toner according to claim 1, wherein an area ratio of the hydrotalcite particles A to the toner particles shown in an EDS measurement field of view, as measured by STEM-EDS mapping analysis of the toner, is 0.07 to 0.54%.

9. the toner particles contain a wax, 9. The method according to claim 1, wherein the wax comprises a hydrocarbon wax and an ester wax. Toner in item 1.

10. The resin A contains a styrene-acrylic resin, The resin B contains a styrene-acrylic resin. The toner according to any one of claims 1 to 9.

11. The resin A includes a polyester resin, The resin B includes a polyester resin. The toner according to any one of claims 1 to 9.

12. The resin A contains a styrene-acrylic resin, The resin B includes a polyester resin. The toner according to any one of claims 1 to 9.

13. The toner according to any one of claims 1 to 12, wherein the resin B has a glass transition temperature Tg of 55 to 80°C.

14. 14. The toner according to claim 1, wherein the ratio F / Al is 0.02 to 0.60.

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