toner

Abstract

To provide a toner having good low-temperature fixability and good charge rising property and charge stability in a high-temperature and high-humidity environment, and capable of outputting an image having high density uniformity even in an image forming apparatus employing a one component contact development system.SOLUTION: A toner comprising toner particles containing a binder resin, and an external additive, wherein the binder resin contains a polyester resin A, and when a content of the polyester resin A in the binder resin is defined as Wp (% by mass), the Wp is 50% by mass or more, and when a content ratio of a monomer unit Uiso corresponding to isophthalic acid to all monomer units corresponding to a polyvalent carboxylic acid in the polyester resin A is defined as MIPA (% by mol), the MIPA is 40% by mol or more, the external additive contains an inorganic fine powder, and the inorganic fine powder contains a silica fine particle having aluminum hydroxide on a surface thereof.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a toner used in an electrophotographic image forming apparatus. [Background technology]

[0002] Electrophotographic image forming apparatuses are being required to operate at higher speeds, be more compact, and have longer life spans, and to achieve these goals, further improvements in various performances of toners are being sought. For example, to contribute to the speedup and miniaturization of electrophotographic apparatuses, there is a demand for toners with excellent low-temperature fixability, that is, toners that can be fixed to paper with a small amount of heat. Furthermore, to contribute to miniaturization and reduce the number of parts, a one-component contact development system that does not contain carrier particles to charge the toner is preferably used. However, because this development system requires the toner to be in contact with the photoreceptor for a long period of time, a highly durable toner that is resistant to deterioration is required. Recently, due to the effects of climate change, there have been an increasing number of occasions where toner is used in higher temperature and humidity environments than expected. Because the chargeability of toner decreases due to the effect of moisture, there is a demand for toner that can maintain the charge state of the toner surface and print with good image quality for a long period of time, even in high temperature and humidity environments where chargeability tends to decrease.

[0003] For these reasons, there is an increasing demand for toners with low-temperature fixability and durability, specifically, for toners that can maintain their chargeability in high-temperature and high-humidity environments. However, toners with good low-temperature fixability tend to have low durability, and achieving both of these has sometimes been a challenge. For example, Patent Document 1 proposes that the occurrence of offset from a solid image to another image can be suppressed by using a toner in which the binder resin is a polycondensate of a polycarboxylic acid and a polyhydric alcohol, and contains a polyester resin, and the polycarboxylic acid contains a predetermined amount of isophthalic acid.

[0004] On the other hand, Patent Document 2 proposes a toner containing an inorganic external additive in which the surface of an oxide of a metal element is coated with a hydroxide of the metal element, thereby ensuring the charge build-up property of the toner, suppressing toner scattering, and providing charge stability. Furthermore, Patent Document 3 proposes a toner that can suppress the occurrence of fogging after being left in a high-temperature, high-humidity environment by having silica particles at least partly coated with aluminum hydroxide and at least partly coated with stearic acid. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2019-049629 [Patent Document 2] Japanese Patent Publication No. 2023-128532 [Patent Document 3] Japanese Patent Application Publication No. 2022-067499 Summary of the Invention [Problem to be solved by the invention]

[0006] As a result of the study by the present inventors, the toner described in Patent Document 1 has been found to have a certain improvement effect on low temperature fixability by using a binder resin that is a polycondensation product of polycarboxylic acid and polyhydric alcohol, and containing a polyester resin, and the polycarboxylic acid contains a predetermined amount of isophthalic acid. However, in an image forming apparatus that employs a one-component development system, there is a problem that the toner has a certain improvement effect on low temperature fixability under high temperature and high humidity conditions. When used for a long period of time, the chargeability of the toner may decrease due to the influence of moisture, resulting in uneven charging in the developing area. As a result, uneven density (fading) may occur in the vertical direction in images with high print coverage.

[0007] Furthermore, the toner described in Patent Document 2 contains an inorganic external additive in which the surface of a metal oxide is coated with a metal hydroxide, thereby demonstrating a certain degree of improvement in long-term charge stability. However, in image forming devices employing a one-component development system, which requires a higher level of toner durability, the charge build-up performance in high-temperature, high-humidity environments is poor, and density unevenness due to insufficient charging may occur. As a result, density uniformity may decrease in solid images with high print coverage.

[0008] Furthermore, the toner described in Patent Document 3 exhibits the effect of suppressing the occurrence of fog after storage in a high-temperature, high-humidity environment due to the presence of silica particles coated with aluminum hydroxide. However, this toner has low coating uniformity between the coated silica particles because the aluminum hydroxide is treated by vapor deposition. Therefore, when used in high-temperature, high-humidity environments, such as when printing images frequently, improvement in charging stability is insufficient, and when printing images at a high printing rate after long-term storage following prolonged use, vertical density unevenness may occur. Furthermore, there is room for improvement in low-temperature fixability.

[0009] The present disclosure provides a toner that overcomes the above drawbacks, specifically, a toner that has good low-temperature fixability, good charge buildup and charge stability in high-temperature, high-humidity environments, and that can output images with high density uniformity even in image forming apparatuses that employ a single-component development system. [Means for solving the problem]

[0010] The present disclosure provides: A toner having toner particles containing a binder resin and an external additive, The binder resin contains a polyester resin A, The content of the polyester resin A in the binder resin is W p (mass%), the W p is 50% by mass or more, the polyester resin A is a copolymer of a polycarboxylic acid and a polyol, the polycarboxylic acid includes isophthalic acid, In the polyester resin A, the ratio of the monomer unit U corresponding to the isophthalic acid to the total monomer units corresponding to the polycarboxylic acid is iso The content ratio of M IPA (mol %), the M IPA is 40 mol % or more, The external additive contains an inorganic fine powder, The toner comprises fine silica particles having aluminum hydroxide on the surface thereof. [Effects of the Invention]

[0011] According to the present disclosure, a toner having good low-temperature fixability, good charge buildup and charge stability in a high-temperature, high-humidity environment, and capable of outputting images with high density uniformity even in an image forming apparatus employing a single-component contact development system can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0012] In the present disclosure, unless otherwise specified, the description of "XX or more and YY or less" or "XX to YY" representing a numerical range means a numerical range including the lower and upper limits, which are the endpoints. In addition, when a numerical range is described in stages, the upper and lower limits of each numerical range can be arbitrarily combined. In addition, in the present disclosure, for example, "a range selected from the group consisting of XX, YY, and ZZ" means a range including the upper and lower limits. A description such as "at least one of" means any of XX, YY, ZZ, a combination of XX and YY, a combination of XX and ZZ, a combination of YY and ZZ, or a combination of XX, YY and ZZ. When XX is a group, more than one may be selected from XX, and the same applies to YY and ZZ. In the present disclosure, the term (meth)acrylate means methacrylate and / or acrylate. In this disclosure, the term "monomer unit" refers to the reacted form of a monomer substance in a polymer. For example, in a polyester, one unit is defined as an ester bond. In calculating mole percent, one unit corresponds to one molecule.

[0013] As mentioned above, in order to improve the low-temperature fixability of the toner, it is effective to add a polyester resin using a polycarboxylic acid containing a predetermined amount of isophthalic acid to the binder resin of the toner particles. However, in image forming devices that use a single-component contact development system, when used under harsh conditions such as high-temperature, high-humidity environments and frequent printing, the toner and the photoreceptor remain in contact for long periods of time, which can lead to toner deterioration due to the burial or liberation of external additives caused by the toner rubbing.

[0014] Furthermore, the inventors' investigations have revealed that, particularly in high-temperature and high-humidity environments, toner deterioration is likely to occur due to the embedding of external additives, and the chargeability of the toner is likely to decrease due to the disappearance of charge from the charging sites on the toner surface due to moisture in the environment. Therefore, when an image forming apparatus using a single-component contact development system is used again after outputting a high-coverage image in a high-temperature, high-humidity environment and then leaving it for a certain period of time, the adhesion state of the external additives to the toner particles changes. In addition, it was found that the chargeability of the toner decreases, causing uneven density in the image.

[0015] As a result of detailed investigations by the present inventors, the following has been found: When toner particles contain a polyester resin containing a monomer unit corresponding to isophthalic acid, as in the toner described in Patent Document 1, it is difficult to maintain charge build-up properties in a high-temperature, high-humidity environment and uniformity of image density over long-term use, compared to when a polyester resin containing only a monomer unit corresponding to terephthalic acid as a polycarboxylic acid is used. Although the reason for this is unclear, the monomer unit corresponding to isophthalic acid has regions with a high microscopic charge, i.e., microscopic negative regions, because the orientation of the oxygen atoms of the carbonyl groups bonded to the benzene rings tends to be aligned. When these microscopic negative regions exist on the surface of toner particles, they attract the polar groups of water molecules in the environment, thereby neutralizing the charge. It is presumed that this makes the chargeability prone to decrease when the toner is left in a high-temperature, high-humidity environment. Furthermore, it is believed that the surface of silica fine particles, which are commonly used as external additives, also experiences a similar decline in chargeability in high-temperature, high-humidity environments due to water molecules being adsorbed onto the SiOH groups, which act as charge sites. Therefore, simply adding silica fine particles externally does not improve charge buildup or the uniformity of image density over long-term use.

[0016] Therefore, the present inventors have conducted extensive research into a means for suppressing a decrease in chargeability under high-temperature, high-humidity environments in toner particles whose main binder resin component is a polyester resin containing a predetermined amount of a monomer unit corresponding to isophthalic acid. As a result, they have found that by incorporating an inorganic fine powder containing silica fine particles having aluminum hydroxide on their surfaces as an external additive, it is possible to achieve both low-temperature fixing properties of the toner and good charge rise and charge stability of the toner under high-temperature, high-humidity environments, and have completed the present disclosure.

[0017] That is, the present disclosure: A toner having toner particles containing a binder resin and an external additive, The binder resin contains a polyester resin A, The content of the polyester resin A in the binder resin is W p (mass%), the W p is 50% by mass or more, the polyester resin A is a copolymer of a polycarboxylic acid and a polyol, the polycarboxylic acid includes isophthalic acid, In the polyester resin A, the ratio of the monomer unit U corresponding to the isophthalic acid to the total monomer units corresponding to the polycarboxylic acid isiso The content ratio of M IPA (mol %), the M IPA is 40 mol % or more, The external additive contains an inorganic fine powder, The toner comprises fine silica particles having aluminum hydroxide on the surface thereof.

[0018] The above-described configuration is believed to improve the charge build-up and charge stability of the toner in a high-temperature, high-humidity environment due to the following mechanism. The inorganic fine powder contains silica particles with aluminum hydroxide on the surface. Aluminum hydroxide has a more hydrophilic structure than silica. Therefore, moisture on the surface of the inorganic fine powder is easily adsorbed by the AlOH groups of the aluminum hydroxide.

[0019] When inorganic fine powder is present on the surface of toner particles containing a binder resin with a monomer unit corresponding to isophthalic acid, it is thought that water molecules are shared between the AlOH groups on the inorganic fine powder surface and the carboxyl groups in the isophthalic acid. Because aluminum hydroxide is a substance with a relatively low volume resistivity, it forms a micro-conductive path when it shares multiple water molecules with the toner particle surface. This conductive path not only suppresses localized charge loss, but also induces a charged state in the silica fine particles that make up the core, creating an interaction that amplifies negative chargeability, resulting in the maintenance and improvement of chargeability. In addition, electrostatic adhesion occurs between the AlOH groups on the surface of the inorganic fine powder and the COO groups of isophthalic acid through the mediation of water molecules, which is thought to make it difficult for the inorganic fine powder to migrate from the toner particles even during long-term use, resulting in good long-term charging stability.

[0020] In contrast, if silica particles coated with aluminum oxide (Al2O3) or particles that form a composite of aluminum oxide and silica are added externally, the high insulating properties of aluminum oxide do not produce the effect of suppressing the decrease in charge due to moisture in the environment. Furthermore, when aluminum hydroxide fine particles are used as an external additive, the aluminum hydroxide has low powder resistivity and therefore cannot impart chargeability.

[0021] As described above, the inorganic fine powder of the present disclosure is required to contain silica fine particles having aluminum hydroxide on their surfaces. The presence of the aluminum hydroxide moiety provides a moderate conductive effect without inhibiting the charging properties of the silica fine particles, and even in a high-temperature, high-humidity environment where charge is likely to decrease, the interaction between the AlOH groups on the inorganic fine powder surface and the monomer units corresponding to isophthalic acid and the water molecules in the environment suppresses charge decrease, which is preferable because it allows for the production of a toner with little fogging in non-image areas even during long-term use.

[0022] The toner has toner particles containing a binder resin. The binder resin contains a polyester resin A. The content of polyester resin A in the binder resin is W p (mass%), W p The polyester resin A is a copolymer of a polycarboxylic acid and a polyol, the polycarboxylic acid containing isophthalic acid, and the ratio of the monomer units corresponding to isophthalic acid to the total monomer units corresponding to the polycarboxylic acid in the polyester resin A is 50% by mass or more. Nomar Unit U iso The content ratio of M IPA (mol%), M IPA is 40 mol % or more. This not only improves the fixation of halftone images, but also improves the density uniformity of solid images even when a durability test is conducted in a double-sided printing mode in a one-component contact development system.

[0023] <Binder resin> The toner particles contain a binder resin. The content of the binder resin in the toner particles is not particularly limited, but may be, for example, 80 to 99 parts by mass, or 82 to 95 parts by mass. Content of polyester resin A in binder resin W pAs mentioned above, the amount (mass %) must be 50% by mass or more. Furthermore, from the viewpoints of suppressing charging member contamination even during long-term use in a low-temperature, low-humidity environment, improving half-tone density unevenness, and improving low-temperature fixability, the amount is preferably 70% by mass or more, and more preferably 80% by mass or more. The upper limit is not particularly limited, but may be 50 to 100% by mass, 70 to 100% by mass, 80 to 100% by mass, or 80 to 95% by mass. p The measurement method will be described later.

[0024] The binder resin is not particularly limited, and examples thereof include styrene-acrylic resin, epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, mixed resins or composite resins thereof, etc. The binder resin preferably contains at least one selected from the group consisting of polyester resin and styrene-acrylic resin.

[0025] <Polyester resin A> The polyester resin A is a copolymer of a polycarboxylic acid and a polyol. The polycarboxylic acid includes isophthalic acid. In the polyester resin A, the ratio of the monomer units U corresponding to isophthalic acid to the total monomer units corresponding to the polycarboxylic acid is iso The content ratio of M IPA When M IPA It is necessary that the content of M is 40 mol % or more, more preferably 60 mol % or more, and even more preferably 90 mol % or more. There is no particular upper limit, but it may be 40 to 100 mol %, 60 to 100 mol %, or 90 to 100 mol %. IPA The measurement method will be described later. The polyester resin A is preferably an amorphous polyester, which has excellent low-temperature fixing properties and, due to the large number of polar groups, improves the dispersion of pigments and charge control agents, resulting in good colorability and charging properties.

[0026] The content ratio of the monomer units corresponding to isophthalic acid to all the monomer units corresponding to polycarboxylic acids in the polyester resin A is preferably 40 to 100 mass%, more preferably 60 to 100 mass%, and even more preferably 90 to 100 mass%.

[0027] The polyester resin A may have a monomer unit corresponding to isophthalic acid, and examples thereof include the following. The polyester resin A can be obtained by selecting and combining suitable polycarboxylic acids, polyols, hydroxycarboxylic acids, etc., and synthesizing them using a known method such as transesterification or polycondensation. Preferably, the polyester resin contains a condensation polymer of a dicarboxylic acid and a diol.

[0028] The polycarboxylic acid is a compound containing two or more carboxy groups in one molecule. As described above, the polycarboxylic acid includes isophthalic acid, but may also include other polycarboxylic acids. Among polycarboxylic acids, dicarboxylic acids are compounds containing two carboxy groups in one molecule and are preferably used. 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, 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. As described above, in the polyester resin A of the present disclosure, the polycarboxylic acid includes isophthalic acid.

[0029] Examples of polycarboxylic acids other than dicarboxylic acids include trimellitic acid, trimesic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic 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. Among these, trimellitic acid is preferred.

[0030] 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-propanediol, 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, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, and 1,14-eicosanediol. Examples of suitable bisphenols include hexanediol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-butenediol, neopentyl glycol, 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.

[0031] The polyol is preferably at least one selected from the group consisting of alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferably alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. Examples of alkylene oxide adducts of bisphenol A include compounds represented by the following formula (A). [ka] (In formula (A), each R is independently at least one selected from the group consisting of an ethylene group and a propylene group, x and y are each an integer of 0 or more, and the average value of x+y is 0 or more and 10 or less.)

[0032] The alkylene oxide adduct of bisphenol A is preferably a propylene oxide adduct and / or an ethylene oxide adduct of bisphenol A, more preferably a propylene oxide adduct and an ethylene oxide adduct of bisphenol A. A propylene oxide adduct is also preferred. The average value of x+y is preferably 1 or more and 5 or less.

[0033] Examples of trivalent or higher polyols include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, hexamethylolmelamine, hexaethylolmelamine, tetramethylolbenzoguanamine, tetraethylolbenzoguanamine, sorbitol, trisphenol PA, phenol novolac, cresol novolac, alkylene oxide adducts of the above trivalent or higher polyphenols, etc. These may be used alone or in combination of two or more.

[0034] As described above, the polyester resin A is a copolymer of a polycarboxylic acid and a polyol. When the polyol contains an ethylene oxide adduct of bisphenol A and a propylene oxide adduct of bisphenol A, the ratio of the monomer unit U corresponding to the ethylene oxide adduct of bisphenol A to the total monomer units corresponding to the polyol in the polyester resin A is 1. EO and the monomer unit U corresponding to the propylene oxide adduct of bisphenol A PO The total content is preferably 90 mol % or more, more preferably 95 mol % or more. There is no particular upper limit, but it may be 90 to 100 mol %, or 95 to 100 mol %. Ethylene oxide adducts of bisphenol A and propylene oxide adducts of bisphenol A are characterized by being easily plasticized by waxes, crystalline polyesters, and the like contained in the toner particles when heated and melted during fixation. Therefore, by ensuring that the content is within the above range, the binder resin is plasticized when heated and melted during fixation, and is more likely to penetrate into paper fibers. This is preferable because it further enhances the adhesion of the toner to paper and improves the abrasion resistance of the image.

[0035] In polyester resin A, the ratio of monomer units U corresponding to ethylene oxide adduct of bisphenol A to all monomer units corresponding to polyol EO and the monomer unit U corresponding to the propylene oxide adduct of bisphenol A PO The total content of the above is preferably 96 to 100 mass %, and more preferably 98 to 100 mass %.

[0036] When the polyol contains an ethylene oxide adduct of bisphenol A and a propylene oxide adduct of bisphenol A, the ratio of the monomer units U corresponding to the ethylene oxide adduct of bisphenol A to the total monomer units corresponding to the polyol in the polyester resin A is EO and the monomer unit U corresponding to the propylene oxide adduct of bisphenol A PO When the total content of the monomer unit U is 100 parts by mole, EO The content is preferably 15 to 40 parts by mole. U PO U EO Compared to U, it has a larger carbon number and is a bisphenol A unit with a branched structure to which propylene oxide is added. PO is U EO Compared to U, it has high hydrophobicity and low intermolecular forces. EO is U PO Compared to , it has low hydrophobicity and high intermolecular forces. U EOWhen the content ratio of U is 15 parts by mole or more, the intermolecular force of the polyester resin A increases, and therefore the deformation of the polyester resin A tends to be suppressed in a high-temperature, high-humidity environment. EO By making the content of U 40 parts by mole or less, the hydrophobicity of polyester resin A is increased, so that the amount of moisture adsorbed by polyester resin A is unlikely to become excessively high in a high-temperature, high-humidity environment. EO By setting the content ratio to 15 to 40 parts by mole, the durability of the toner in a high-temperature, high-humidity environment is improved, and fogging of non-image areas is suppressed. This is preferable because it can be controlled. EO The content of U is more preferably 20 to 35 parts by mol, and further preferably 25 to 30 parts by mol. EO The method for measuring the content ratio will be described later.

[0037] In polyester resin A, the ratio of monomer units U corresponding to ethylene oxide adduct of bisphenol A to all monomer units corresponding to polyol EO and the monomer unit U corresponding to the propylene oxide adduct of bisphenol A PO When the total content of the monomer unit U is 100 parts by mass, EO The content ratio of is preferably 14 to 39 parts by mass, more preferably 19 to 34 parts by mass, and even more preferably 24 to 32 parts by mass.

[0038] The number average molecular weight of the tetrahydrofuran-soluble portion of polyester resin A measured using gel permeation chromatography (GPC) is M n and the weight average molecular weight is M w When M n is preferably 3,000 to 10,000. Number average molecular weight (M n When the number average molecular weight (M) is 3,000 or more, the durability of the toner in a high-temperature and high-humidity environment is improved, and fogging of non-image areas is easily suppressed. n) is preferably 10,000 or less, the melt fluidity of the binder resin increases during fixing, making it easier for the binder resin to penetrate into paper fibers, thereby increasing the adhesiveness to paper and improving the abrasion resistance of the image. Number average molecular weight (M n ) is more preferably 4,000 to 8,000, further preferably 4,000 to 7,000, and particularly preferably 4,000 to 5,000.

[0039] M w / M n is preferably 2.5 or more. w / M n A molecular weight distribution of 2.5 or more means that the molecular weight distribution of polyester resin A is sufficiently wide. This allows sufficient entanglement of the molecular chains of polyester resin A, which makes it easier for the toner particles to have sufficient hardness even in a high-temperature, high-humidity environment. As a result, the durability of the toner is improved, and fogging of non-image areas can be further suppressed, which is preferable. w / M n is more preferably 3.0 or more, even more preferably 4.0 or more, and particularly preferably 5.0 or more. The upper limit is not particularly limited, but may be 2.5 to 12.0, 3.0 to 11.0, 4.0 to 10.0, or 5.0 to 10.0. M n and M w / M n The measurement method will be described later.

[0040] The acid value of the polyester resin A is preferably 4.0 to 10.0 mgKOH / g, and more preferably 5.0 to 8.0 mgKOH / g.

[0041] <Release agent> A known releasing agent can be used in the toner. For example, the toner particles preferably contain a releasing agent. Specific examples include petroleum waxes and derivatives thereof, such as paraffin wax, microcrystalline wax, and petrolatum, montan wax and derivatives thereof, hydrocarbon waxes produced by the Fischer-Tropsch process and derivatives thereof, polyolefin waxes and derivatives thereof, such as polyethylene, natural waxes and derivatives thereof, such as carnauba wax and candelilla wax, ester waxes, etc. 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.

[0042] Among these, when polyolefin wax, hydrocarbon wax produced by the Fischer-Tropsch method, or petroleum wax is used, the developability and transferability tend to be improved. It is preferable. That is, the wax preferably contains at least one selected from the group consisting of polyolefin wax, hydrocarbon wax, petroleum wax, and ester wax, and more preferably contains ester wax. When ester wax is contained, low-temperature fixability tends to be improved. Furthermore, from the viewpoint of compatibility with durability, it is more preferable to use an ester wax and a hydrocarbon wax in combination. Note that these waxes may contain an antioxidant within a range that does not affect the effects of the toner.

[0043] As described above, the toner particles preferably contain an ester wax. The ester wax is not particularly limited, and examples thereof include esters of monohydric alcohols and aliphatic carboxylic acids, such as behenyl behenate, stearyl stearate, and palmityl palmitate, or esters of monohydric carboxylic acids and aliphatic alcohols; esters of dihydric alcohols and aliphatic carboxylic acids, such as ethylene glycol distearate, dibehenyl sebacate, and hexanediol dibehenate, or esters of dihydric carboxylic acids and aliphatic alcohols; esters of trihydric alcohols and aliphatic carboxylic acids, such as glycerin tribehenate, or esters of trihydric carboxylic acids and aliphatic alcohols; pentaerythritol; Esters of tetrahydric alcohols and aliphatic carboxylic acids, such as pentaerythritol tetrastearate and pentaerythritol tetrapalmitate, 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.

[0044] In addition, from the viewpoint of phase separation property relative to the binder resin or crystallization temperature, preferred examples include higher fatty acid esters such as behenyl behenate and dibehenyl sebacate. Specifically, behenyl behenate is preferred.

[0045] 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 having the above-mentioned thermal properties, the release effect is efficiently exerted and a wider fixing area is secured.

[0046] <Crystalline polyester> The binder resin preferably contains a crystalline polyester. The crystalline polyester is preferably a condensation polymer of a monomer containing an aliphatic diol and / or an aliphatic dicarboxylic acid. The crystalline polyester refers to a polyester that has a clear melting point as measured by a differential scanning calorimeter (DSC). The crystalline polyester preferably contains a monomer unit corresponding to an aliphatic diol having 2 to 12 carbon atoms (more preferably 6 to 12) and / or a monomer unit corresponding to an aliphatic dicarboxylic acid having 2 to 12 carbon atoms (more preferably 6 to 12). The crystalline polyester having such a structure improves the dispersibility of the crystalline polyester in the toner particles, and can further suppress uneven wetting and spreading between the toner particles during fixing, which tends to improve the low-temperature fixability of halftone images and line images.

[0047] Examples of the aliphatic diol having 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 1,9-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol. Among these, at least one selected from the group consisting of 1,9-nonanediol and 1,12-dodecanediol is preferred. Aliphatic diols having a double bond can also be used. Examples of the aliphatic diols having a double bond include the following compounds: 2-butene-1,4-diol, 3-hexene-1,6-diol and 4-octene-1,8-diol.

[0048] Examples of the aliphatic dicarboxylic acid having 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 can also be used. Among these, sebacic acid, adipic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, and their lower alkyl esters and acid anhydrides are preferred. Furthermore, sebacic acid, adipic acid, and 1,12-dodecanedicarboxylic acid, and their lower alkyl esters and acid anhydrides are more 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. 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, at least one selected from the group consisting of fumaric acid and maleic acid is more preferred.

[0050] 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.

[0051] The peak temperature of the maximum endothermic peak of the crystalline polyester measured using a differential scanning calorimeter (DSC) is preferably 50.0 to 100.0°C, and more preferably 60.0 to 90.0°C from the viewpoint of low-temperature fixability. The acid value of the crystalline polyester is preferably 0.5 to 8.0 mgKOH / g, more preferably 1.0 to 5.0 mgKOH / g, and even more preferably 1.5 to 4.0 mgKOH / g.

[0052] Crystalline polyester has a weight average molecular weight M w1 is preferably 4,000 to 40,000, and more preferably 10,000 to 30,000. Within this range, the degree of crystallinity of the crystalline polyester can be maintained high, and the plasticizing effect of the crystalline polyester can be rapidly obtained in the fixing step. w1 When the molecular weight is 40,000 or less, the solubility of the crystalline polyester itself is unlikely to decrease, the toner productivity improves, and the effect of improving low-temperature fixability is likely to be obtained. On the other hand, M w1 When the molecular weight is 4,000 or more, the crystalline polyester is less likely to bleed onto the toner surface, and the charging stability of the toner is improved. The number average molecular weight M of the crystalline polyester n1 Weight average molecular weight M w1 The ratio value (M w1 / M n1 ) is not particularly limited, but is preferably 1.5 to 2.5.

[0053] The content of the crystalline polyester in the binder resin is preferably 3.0 to 15.0% by mass, more preferably 5.0 to 13.0% by mass, from the viewpoint of the balance between low-temperature fixability and durability.

[0054] <Inorganic fine powder> The toner contains an external additive. The external additive contains an inorganic fine powder. The inorganic fine powder contains silica fine particles having aluminum hydroxide on their surfaces. That is, the aluminum hydroxide coats at least a portion of the surface of the silica fine particles. In this case, the silica fine particles act as a substrate. Furthermore, the silica fine particles preferably have a thin film layer having an aluminum hydroxide structure on at least a part of the surface of the silica fine particles. By coating at least a portion of the surface of the silica fine particles with aluminum hydroxide, the volume resistivity of the silica can be reduced and charge decay due to moisture can be suppressed.

[0055] The presence of aluminum hydroxide on the surface of the silica fine particles can be confirmed by energy dispersive X-ray spectroscopy mapping (TEM-EDS mapping) under a transmission electron microscope and X-ray diffraction patterns (XRD). TEM-EDS mapping can confirm the state of aluminum present on the surface of silica microparticles. XRD can also qualitatively determine whether the aluminum is an oxide or hydroxide. When aluminum exists as aluminum oxide, it shows clear peaks according to the crystal system. On the other hand, when aluminum exists as aluminum hydroxide, no clear peaks are detected in the XRD pattern. Measurement methods for TEM-EDS mapping and XRD are described below.

[0056] The amount of aluminum hydroxide to be treated is preferably determined in terms of aluminum oxide Al2O3, and specifically, it is preferably 1 to 30 mass % in terms of aluminum oxide based on the mass of silica particles. If the amount of aluminum hydroxide used is less than 1% by mass in terms of aluminum oxide, the amount of aluminum hydroxide coated on the surface of the silica fine particles is likely to be insufficient, and therefore the chargeability may not be sufficiently improved in a high-temperature, high-humidity environment. On the other hand, if the amount is more than 30% by mass, the high chargeability of the silica fine particles may be impaired.

[0057] Although details will be described later, the following method can be used to coat silica fine particles with aluminum hydroxide. First, a water-soluble salt of aluminum is prepared, and an aqueous solution is prepared using the water-soluble salt and water. The resulting aqueous solution is then added to the silica fine particles, and an alkaline substance such as an aqueous sodium hydroxide solution is added to hydrolyze the water-soluble salt of aluminum, thereby coating the silica particles with aluminum hydroxide. Examples of water-soluble aluminum salts include aluminum chloride, bromide, sulfate, nitrate, acetate, carbonate, and hydrogencarbonate, with aluminum chloride being preferred. The amount of aluminum hydroxide coated can be changed by controlling the conditions during production (such as pH and heating temperature).

[0058] The aluminum (Al) element coverage of inorganic fine powders was 40%, as determined by elemental mapping of aluminum and silicon measured by STEM-EDS mapping of inorganic fine powders. Preferably, the coverage of the inorganic fine powder with the Al element is 40% or more by area, which allows for a suitable interaction between the inorganic fine powder and water molecules in a high-temperature, high-humidity environment. This makes it easier to suppress charge deterioration, further improving charge build-up and charge stability. On the other hand, a coverage of the inorganic fine powder with the Al element of 90% or less by area is preferred because it maintains the good negative charge characteristics of the silica fine particles while exhibiting good charge characteristics. The coverage of the inorganic fine powder with the Al element is more preferably 45 to 85% by area, and even more preferably 50 to 80% by area. The coverage of the inorganic fine powder with the Al element can be changed by controlling the manufacturing conditions (such as pH and heating temperature). The method for calculating the coverage of the inorganic fine powder with the Al element will be described later.

[0059] When the value of the ratio of the number of Al atoms to Si atoms (Al / Si) measured by X-ray photoelectron spectroscopy (XPS) of the inorganic fine powder is defined as X1, and the value of the mass ratio of Al to Si atoms (Al / Si) measured by X-ray fluorescence analysis (XRF) of the inorganic fine powder is defined as X2, it is preferable that X1 and X2 satisfy formula (1). 0.80≦X1 / X2≦2.00 (1)

[0060] XPS allows for selective quantitative measurement of elements present within a few nanometers of the surface of inorganic fine powder. XRF allows for quantitative measurement of elements contained in the entire inorganic fine powder. In other words, the measurement results from XRF indicate the content of elements contained in the inorganic fine powder. Therefore, an X1 / X2 value of 0.80 or more indicates that there is a large amount of Al element corresponding to aluminum hydroxide near the surface of the inorganic fine powder. In other words, it indicates that the coating state with aluminum hydroxide is good. As a result, moisture-mediated interactions are effectively expressed between the inorganic fine powder surface and the monomer units corresponding to isophthalic acid, further improving charge buildup in high-temperature, high-humidity environments. On the other hand, an X1 / X2 value of 2.00 or less means that aluminum hydroxide exists as a thin layer on the surface of the inorganic fine powder. As a result, the aluminum hydroxide is less likely to interfere with the good chargeability of the silica fine particles, and charge buildup and charge retention in high-temperature, high-humidity environments are more likely to be improved.

[0061] The value of X1 / X2 is preferably from 0.85 to 1.95, more preferably from 0.90 to 1.85, and even more preferably from 1.00 to 1.50. The value of X1 / X2 can be adjusted by adjusting X1 and X2 by the method described below. The value of X1 / X2 can be calculated from the values ​​obtained by measuring X1 and X2 by the method described below.

[0062] The ratio of the number of Al atoms to the number of Si atoms (Al / Si)X1 measured by X-ray photoelectron spectroscopy (XPS) of the inorganic fine powder is not particularly limited, but may be, for example, 0.03 to 0.52, preferably 0.10 to 0.45, and more preferably 0.14 to 0.38. The value of X1 can be adjusted by adjusting the amount of aluminum chloride aqueous solution to be treated relative to the particle size of the silica fine particle substrate. The method for measuring the value of X1 will be described later. The mass ratio of Al to Si (Al / Si)X2 measured by X-ray fluorescence analysis (XRF) of the inorganic fine powder is not particularly limited, but may be, for example, 0.01 to 0.30, preferably 0.05 to 0.23, and more preferably 0.10 to 0.20. The value of X2 can be adjusted by adjusting the amount of aluminum chloride aqueous solution to be treated relative to the particle size of the silica fine particle substrate. The method for measuring the value of X2 will be described later.

[0063] In order to further improve the chargeability under high temperature and high humidity conditions, the inorganic fine powder is preferably subjected to a surface treatment to make the surface hydrophobic. Examples of the surface treatment include silane coupling treatment, silicone oil treatment, and carboxylic acid treatment, and the like, and the treatment can be appropriately selected. That is, the inorganic fine powder is preferably silica fine particles having aluminum hydroxide on the surface thereof treated with a silane coupling agent. Also, the inorganic fine powder is preferably silica fine particles having aluminum hydroxide on the surface thereof treated with a silicone oil. Furthermore, the inorganic fine powder is preferably silica fine particles having aluminum hydroxide on the surface thereof treated with a carboxylic acid. It is also possible to select a plurality of types of surface treatment, and the order of these treatments can be arbitrary.

[0064] The silane coupling agent used in the silane coupling treatment is not particularly limited, and known silane coupling agents can be used. For example, hexamethyldisilazane, trimethylsilane, n-propyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, octyltriethoxysilane, decyltriethoxysilane, dodecyltriethoxysilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, Examples of suitable siloxanes include chloromethyldimethylchlorosilane, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, 1-hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and dimethylpolysiloxanes having 2 to 12 siloxane units per molecule and each terminal unit containing a hydroxyl group bonded to Si. These may be used alone or in combination of two or more.

[0065] The silane coupling agent is preferably at least one selected from the group consisting of n-propyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, octyltriethoxysilane, and decyltriethoxysilane, more preferably at least one selected from the group consisting of isobutyltrimethoxysilane, octyltriethoxysilane, and decyltriethoxysilane, and even more preferably isobutyltrimethoxysilane.

[0066] The amount of the inorganic fine powder treated with the hydrophobic treatment agent is not particularly limited, but is preferably 30 to 90 mass %, more preferably 40 to 80 mass %. Within this range, the charge stabilizing effect of the OH groups on the surface of the inorganic fine powder can be improved while maintaining the hydrophobic effect of the hydrophobic treatment agent.

[0067] The powder resistivity of inorganic fine powder is 1.0 x 10 8 ~2.0×10 13 It is preferable that the powder resistivity of the inorganic fine powder is 1.0×10 8 By having a specific resistance of Ω·cm or more, the toner charge build-up is improved, and the density uniformity after being left in a high-temperature, high-humidity environment is improved. In addition, the powder resistivity of the inorganic fine powder is 2.0×10 13 A resistivity of Ω·cm or less makes it easier to prevent overcharging, and helps to reduce fogging in non-printed areas even when used for long periods in high-temperature, high-humidity environments. The powder resistivity of inorganic fine powder is 5.0 x 10 8 ~1.0×10 13 Ω·cm is more preferable, and 1.0×10 9 ~5.0×10 12 Ω·cm is more preferable, and 1.0×10 10 ~4.0×10 12 It is particularly preferable that the resistivity is Ω·cm. The powder resistivity of the inorganic fine powder can be adjusted by the number average particle size of the primary particles of the inorganic fine powder substrate, the amount of aluminum hydroxide to be treated, and the type and amount of hydrophobic treatment agent. The method for measuring the powder resistivity of the inorganic fine powder will be described later.

[0068] The number-average particle diameter of the primary particles of the inorganic fine powder is preferably 5 to 50 nm. A number-average particle diameter of 5 nm or more allows for good crushability and allows the particles to be externally added in a uniformly dispersed state on the toner surface. Furthermore, even with long-term use, embedding in the toner particle surface is suppressed, making it easier to maintain charge buildup even in high-temperature, high-humidity environments. On the other hand, a number-average particle diameter of 50 nm or less allows the toner particles to be heated and melted without impeding the heat flow from the fixing heater, making it easier to maintain low-temperature fixability. The number-average particle size of the primary particles of the inorganic fine particles can be adjusted by the number-average particle size of the primary particles of the inorganic fine powder substrate, the amount of aluminum hydroxide used for treatment, and the type and amount of hydrophobic treatment agent used for treatment. The method for measuring the number-average particle size of the primary particles of the inorganic fine particles will be described later.

[0069] The coverage ratio W of inorganic fine powder on the toner particle surface calculated from the STEM-EDS mapping image of the toner AS (area %) is preferably 3.0 to 50.0 area %. Inorganic fine powder coverage W AS When the coverage ratio W of the inorganic fine powder is 3.0% or more, the interaction between the AlOH group of the aluminum hydroxide on the surface of the inorganic fine powder and the monomer unit corresponding to isophthalic acid is effectively expressed, and charge deterioration due to moisture in a high-temperature, high-humidity environment is further suppressed. As a result, the charge rise property and charge retention rate are improved, the density uniformity after being left in a high-temperature, high-humidity environment is improved, and density unevenness is further improved. On the other hand, AS When the area of ​​the toner is 50.0% or less, the low-temperature fixability is improved, which is preferable. AS The calculation method will be described later. Inorganic fine powder coverage W AS is preferably 5.0 to 40.0 area %, more preferably 8.0 to 35.0 area %, and even more preferably 10.0 to 30.0 area %. AS can be adjusted by the number average particle size of the primary particles of the inorganic fine powder substrate, the amount of inorganic fine powder added, and the external addition treatment conditions.

[0070] The content of the inorganic fine powder relative to 100 parts by mass of the toner particles is preferably 0.1 to 5.0 parts by mass, and more preferably 0.2 to 2.0 parts by mass. AS The charge build-up property and charge retention rate under high temperature and high humidity conditions are improved, the density uniformity after being left in a high temperature and high humidity environment is improved, and density unevenness is further improved. The method for measuring the content will be described later.

[0071] The coverage of inorganic fine powder on the toner particle surface calculated from the STEM-EDS mapping image of the toner is W AS (area%), W AS , M IPA , and W p It is preferable that the following formula (2) is satisfied. IPA represents the ratio of the monomer units U corresponding to the isophthalic acid to the total monomer units corresponding to the polycarboxylic acid in the polyester resin A. iso The content (mol%) of W p indicates the content (mass %) of polyester resin A in the binder resin. 0.030 ≦ W AS / (M IPA ×W p ) ≦ 1.390 (2)

[0072] W AS / (M IPA ×W p The value of (2) indicates the number of AlOH groups derived from the inorganic fine powder present on the toner surface, which acts on the number of isophthalic acid units in the binder resin. Therefore, when the value of formula (2) is within the above range, a good balance is achieved between the distribution of AlOH groups possessed by the aluminum hydroxide on the inorganic fine powder surface and the distribution of isophthalic acid units on the toner particle surface. This results in an interaction effect on the toner surface, suppressing charge deterioration due to moisture in high-temperature, high-humidity environments. As a result, charge buildup and charge retention are further improved, and density uniformity after storage in a high-temperature, high-humidity environment is improved, resulting in further improvement in density unevenness. W AS / (M IPA ×W p The value of ) is more preferably 0.050 to 1.000, and even more preferably 0.100 to 0.400. W AS / (M IPA ×W p ) value is calculated by the above method. AS , M IPA , and W p It can be adjusted by adjusting each of W AS , MIPA , and W p Up By measuring using the above method and calculating from the obtained values, W AS / (M IPA ×W p ) value is obtained.

[0073] <Hydrotalcite particles> The external additive may contain hydrotalcite particles, which may be represented by the following composition formula (X). M 2+ y M 3+ x (OH)2A n- (x / n) mH2O (X) 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- , HCO 3- , CH3COO - , and NO3 - These may be present alone or in combination.

[0074] Hydrotalcite particles are M 3+ It is preferable that the cations contain at least Al ions. 2+ It is preferable that the catalyst contains at least Mg ions. The hydrotalcite particles may be a solid solution containing a plurality of different elements, and may also contain a trace amount of a monovalent metal.

[0075] <Coloring agent> The toner particles may contain a colorant. Known pigments and dyes can be used as the colorant. Pigments are preferred as the colorant because they have excellent weather resistance. 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.

[0076] 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.

[0077] 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.

[0078] Examples of black colorants include those toned to black using the above yellow, magenta, and cyan colorants, as well as carbon black magnetic materials. These colorants can be used alone or in a mixture, or in the form of a solid solution. The colorant is preferably used in an amount of 1.0 to 20.0 parts by mass per 100.0 parts by mass of the binder resin. In addition, the manufacturing method in an aqueous medium using a magnetic material, which will be described later, When the above method is applied, a hydrophobic treatment may be carried out in order to stably contain the magnetic material in the resin.

[0079] <Charge control agent> The toner particles may contain a charge control agent. Known charge control agents can be used. A charge control agent that exhibits high triboelectric charging speed and can stably maintain a constant triboelectric charge amount is particularly preferred. Furthermore, when the toner particles are produced by a suspension polymerization method, a charge control agent that exhibits low polymerization inhibition and is substantially free of solubilized substances in an aqueous medium is particularly preferred. 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, calixarenes, and charge control resins. That is, the charge control agent may contain a charge control resin.

[0080] Examples of the charge control resin include resins having sulfone-based functional groups such as sulfonic acid groups, sulfonate salt groups, sulfonate ester groups, etc. As such a resin, a polymer containing at least one monomer selected from the group consisting of a sulfonic acid group-containing acrylamide monomer and a sulfonic acid group-containing methacrylamide monomer in a copolymerization ratio of 2% by mass or more, and more preferably 5% by mass or more.

[0081] 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 used, it is easy to impart desirable triboelectric charging characteristics without affecting the thermal characteristics required of 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 coloring power, transparency, and triboelectric charging characteristics. These charge control agents or charge control resins may be added alone or in combination of two or more. The amount of charge control agent or charge control resin added is preferably 0.01 parts by mass or more and 20.0 parts by mass or less, and more preferably 0.5 parts by mass or more and 10.0 parts by mass or less, relative to 100.0 parts by mass of binder resin.

[0082] The average circularity of the toner is preferably 0.950 to 0.980. Within this range, the transferability is improved in a wide range of environments, and better images can be obtained even after long-term use. Specifically, when the average circularity is 0.950 or more, the non-electrostatic adhesion between toner particles does not become excessively high even after long-term use in a high-temperature, high-humidity environment, making it easier to maintain good transferability. This is preferable because it improves the density uniformity of solid images. On the other hand, an average circularity of 0.980 or less makes it easier for toner particles to have a moderate non-electrostatic adhesion force between them even in a low-temperature, low-humidity environment where the non-electrostatic adhesion force between toner particles tends to be low. This is also preferable because it can suppress toner scattering during the transfer process and improve dot reproducibility. It is more preferable that the average circularity of the toner is 0.955 to 0.975.

[0083] In order to adjust the average circularity of the toner, it is preferable to employ a chemical toner manufacturing method such as an emulsion aggregation method, a suspension polymerization method, or a suspension granulation method as a method for manufacturing toner particles. When the emulsion aggregation method is used, the toner particles are spherically formed to obtain the desired surface shape. It is preferable to provide a step to adjust the circularity. When the pulverization method is used, the circularity of the toner can be adjusted by subjecting the toner to a surface treatment using hot air in a thermal sphering process.

[0084] <Toner manufacturing method> The method for producing the toner is not particularly limited, and known methods such as a pulverization method, a suspension polymerization method, a solution suspension method, an emulsion aggregation method, and a dispersion polymerization method can be used. Here, the toner is preferably produced by the following method. That is, the toner is preferably produced by an emulsion aggregation method.

[0085] The toner manufacturing method includes the following steps (1) to (3): (1) a dispersion step of preparing a binder resin particle dispersion containing a binder resin; (2) an aggregation step of aggregating the binder resin fine particles contained in the binder resin fine particle dispersion to form aggregates; and (3) Fusion process in which the aggregates are heated to fuse them together It is preferable to have these in this order.

[0086] The toner manufacturing method further comprises the steps (4) to (6) below during or after the fusion step: (4) a spheronization step in which the agglomerates are further heated at an elevated temperature; (5) a cooling step of cooling the aggregate at a cooling rate of 0.1°C / second or more; and (6) An annealing step in which the aggregate is heated and maintained at a temperature equal to or higher than the crystallization temperature or glass transition temperature of the binder resin. It is preferable to have these in this order. When the toner is produced by the emulsion aggregation method, the polyester resin A is easily dispersed uniformly near the surface, and the toner shape can be controlled, which is preferable. Details of the emulsion aggregation method are described below.

[0087] <Emulsification aggregation method> The emulsion aggregation method is a method of producing toner particles by preparing in advance an aqueous dispersion of fine particles made of the constituent materials of toner particles that are sufficiently small relative to the target particle size, aggregating the fine particles in an aqueous medium until they reach the particle size of toner particles, and fusing the resin by heating or the like. In the emulsion aggregation method, toner particles are produced through, for example, a dispersion process in which a fine particle dispersion liquid made of the constituent materials of toner particles is prepared, an aggregation process in which fine particles made of the constituent materials of toner particles are aggregated and the particle size is controlled until the particle size reaches that of toner particles, a fusion process in which the resin contained in the resulting aggregated particles is fused, a spheronization process in which the particles are melted by heating or the like and the surface shape of the toner is controlled, a subsequent cooling process, a metal removal process in which the resulting toner is filtered and excess polyvalent metal ions are removed, a filtration and washing process in which the toner is washed with ion-exchanged water or the like, and a process in which the washed toner particles are dehydrated and dried.

[0088] <Step of preparing a resin particle dispersion (dispersion step)> The resin particle dispersion can be prepared by a known method, but is not limited to these methods. Examples of known methods include emulsion polymerization, self-emulsification, phase inversion emulsification in which a resin is emulsified by adding an aqueous medium to a resin solution dissolved in an organic solvent, and forced emulsification in which a resin is forcibly emulsified by high-temperature treatment in an aqueous medium without using an organic solvent. Specifically, the binder resin is dissolved in an organic solvent capable of dissolving the binder resin, and a surfactant and a basic compound are added. In this case, if the binder resin is a crystalline resin having a melting point, it can be dissolved by heating it to a temperature above the melting point. Next, while stirring with a homogenizer or the like, an aqueous medium is slowly added to precipitate resin particles. After that, the solvent is removed by heating or reducing the pressure, and the resin particles are precipitated. An aqueous dispersion of the above is prepared. The organic solvent used to dissolve the binder resin is not particularly limited as long as it can dissolve the binder resin. However, it is preferable to use an organic solvent that forms a homogeneous phase with water, such as toluene, from the viewpoint of suppressing the generation of coarse powder.

[0089] The surfactant used during the emulsification is not particularly limited, but examples thereof include anionic surfactants such as sulfate ester salts, sulfonate salts, carboxylate salts, phosphate esters, and soap-based surfactants; cationic surfactants such as amine salts and quaternary ammonium salts; and nonionic surfactants such as polyethylene glycols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. The surfactants may be used alone or in combination of two or more.

[0090] Examples of the basic compound used in the dispersion step include inorganic bases such as sodium hydroxide and potassium hydroxide, and organic bases such as ammonia, triethylamine, trimethylamine, dimethylaminoethanol, and diethylaminoethanol. The basic compound may be used alone or in combination of two or more. The 50% particle diameter (D50) of the binder resin particles in the binder resin particle dispersion is preferably 0.05 μm to 1.0 μm, more preferably 0.05 μm to 0.4 μm. By adjusting the 50% particle diameter (D50) of the volume distribution to fall within the above range, it becomes easy to obtain toner particles with a volume average particle diameter of 3 μm to 10 μm, which is an appropriate size for toner particles. The 50% particle size (D50) based on volume distribution is measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso).

[0091] <Colorant particle dispersion> In the emulsion aggregation method, a colorant particle dispersion may be used as needed. The colorant particle dispersion can be prepared by the following known methods, but is not limited to these. It can be prepared by mixing a colorant, an aqueous medium, and a dispersant using a known mixer such as a stirrer, an emulsifier, or a disperser. The dispersant used here can be a known one such as a surfactant or a polymer dispersant.

[0092] Both surfactants and polymer dispersants can be removed in the washing step described below, but surfactants are preferred from the viewpoint of washing efficiency. Examples of surfactants include anionic surfactants such as sulfate ester salts, sulfonate salts, phosphate esters, and soap-based surfactants; cationic surfactants such as amine salts and quaternary ammonium salts; and nonionic surfactants such as polyethylene glycols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, nonionic surfactants or anionic surfactants are preferred. A nonionic surfactant and an anionic surfactant may also be used in combination. The surfactants may be used alone or in combination of two or more. The concentration of the surfactant in the aqueous medium is preferably 0.5% by mass to 5% by mass. The content of the colorant particles in the colorant particle dispersion is not particularly limited, but is preferably 1% by mass to 30% by mass relative to the total mass of the colorant particle dispersion.

[0093] From the viewpoint of dispersibility of the colorant in the final toner, the dispersed particle size of the colorant particles in the aqueous dispersion of the colorant is preferably 0.5 μm or less in terms of the 50% particle size (D50) based on volume distribution, and for the same reason, preferably 2 μm or less in terms of the 90% particle size (D90) based on volume distribution. The particle size of the dispersed colorant particles in the colorant particle dispersion is measured using a dynamic light scattering particle size distribution analyzer (Nanotrac UPA-EX150, manufactured by Nikkiso Co., Ltd.).

[0094] Known mixers such as stirrers, emulsifiers, and dispersers used when dispersing a colorant in an aqueous medium include ultrasonic homogenizers, jet mills, pressure homogenizers, colloid mills, ball mills, sand mills, and paint shakers. These may be used alone or in combination.

[0095] <Release agent particle dispersion> In the emulsion aggregation method, a dispersion of releasing agent particles may be used as needed. The dispersion of releasing agent particles can be prepared by the following known methods, but is not limited to these methods. A release agent microparticle dispersion can be prepared by adding the release agent to an aqueous medium containing a surfactant, heating the mixture to above the melting point of the release agent, dispersing the mixture into particles using a homogenizer with strong shearing capabilities (such as the Clearmix W Motion manufactured by M Technique) or a pressure discharge type disperser (such as the Gaulin Homogenizer manufactured by Gaulin), and then cooling the mixture to below the melting point of the release agent.

[0096] The particle size of the release agent particles dispersed in the release agent particle dispersion liquid is preferably 0.03 μm to 1.0 μm, more preferably 0.1 μm to 0.5 μm, in terms of the 50% particle size (D50) based on volume distribution. It is also preferable that no coarse particles of 1 μm or more exist. When the dispersed particle size of the release agent fine particle dispersion is within the above range, the release agent can be finely dispersed and present in the toner, and the exudation effect during fixing can be maximized, making it possible to obtain good separability. The particle size of the release agent particles dispersed in the release agent particle dispersion is measured using a dynamic light scattering particle size distribution analyzer (Nanotrac UPA-EX150, manufactured by Nikkiso Co., Ltd.).

[0097] <Mixing process> The toner manufacturing method may include a mixing step. In the mixing step, a mixed liquid is prepared by mixing a resin particle dispersion and, if necessary, at least one of a release agent particle dispersion and a colorant particle dispersion. This can be performed using a known mixing device such as a homogenizer or a mixer.

[0098] <Step of forming aggregate particles (aggregation step)> In the aggregating step, the binder resin microparticles contained in the binder resin microparticle dispersion liquid prepared in the mixing step are aggregated to form aggregates having a target particle size. At this time, an aggregating agent is added and mixed, and at least one of heat and mechanical power is appropriately applied as needed to form aggregates in which the resin microparticles and, as needed, at least one of the release agent microparticles and the colorant microparticles are aggregated.

[0099] Examples of the flocculant include organic flocculants such as quaternary salt cationic surfactants and polyethyleneimine; inorganic metal salts such as sodium sulfate, sodium nitrate, sodium chloride, calcium chloride, and calcium nitrate; inorganic ammonium salts such as ammonium sulfate, ammonium chloride, and ammonium nitrate; and inorganic flocculants such as divalent or higher metal complexes. It is also possible to add an acid to lower the pH and cause soft flocculation, and examples of such acids include sulfuric acid and nitric acid.

[0100] The flocculant may be added in the form of either a dry powder or an aqueous solution dissolved in an aqueous medium, but it is preferable to add it in the form of an aqueous solution in order to cause uniform flocculation. The addition and mixing of the flocculant is preferably carried out at a temperature below the glass transition temperature or melting point of the resin contained in the mixed solution. By carrying out the mixing under these temperature conditions, the flocculation proceeds relatively uniformly. The flocculant can be mixed into the mixed solution using a known mixing device such as a homogenizer or a mixer. The aggregation step is a step of forming aggregates of the toner particle size in an aqueous medium. The volume average particle size of the aggregates produced in the aggregation step is preferably 3 μm to 10 μm. The volume average particle size can be measured using a particle size distribution analyzer (Coulter Multisizer III, manufactured by Coulter) by the Coulter method.

[0101] <Step of Obtaining a Dispersion Containing Toner Particles (Fusion Step)> In the fusion step, the aggregates obtained in the aggregation step are fused by heating. Specifically, for example, aggregation is first stopped in a dispersion containing the aggregates under stirring in the same manner as in the aggregation step. The aggregation is stopped by adding an aggregation stopper, such as a base capable of adjusting the pH, a chelating compound, or an inorganic salt compound such as sodium chloride. After the dispersion state of the aggregated particles in the dispersion liquid becomes stable due to the action of the aggregation terminator, the dispersion is heated to a temperature equal to or higher than the glass transition temperature or melting point of the binder resin to fuse the aggregated particles and adjust the particle size to the desired size. The 50% particle size (D50) on a volume basis of the toner particles is preferably 3 μm to 10 μm. The heating temperature is not particularly limited, but is preferably 40 to 60°C, for example. The heating time is not particularly limited, but is preferably 1 to 5 hours, for example.

[0102] <Step for obtaining the desired toner surface shape (spheronization step)> The toner manufacturing method preferably includes a spheronization step in which the aggregates are heated at a higher temperature during or after the fusion step. The spheronization step is a step in which the toner particles are maintained at a desired temperature until they achieve a desired circularity or surface shape. Specific temperatures in the spheronization step are, for example, 90°C or higher, preferably 92°C or higher, and preferably 95°C or lower. The heating time in the spheronization step can be, for example, 3 hours or more, 5 hours or more, or 8 hours or more.

[0103] <Cooling process> The toner manufacturing method preferably includes a cooling step, after the spheronization step, in which the aggregates are cooled at a cooling rate of 0.1°C / sec or more. The cooling step is a step in which the temperature of the dispersion containing the toner particles obtained in the spheronization step is cooled by controlling the cooling rate to a temperature lower than the crystallization temperature or glass transition temperature of the binder resin. By undergoing the cooling step, the formation of irregularities on the toner particle surface due to volume changes such as expansion or contraction of the materials in the toner particles is suppressed. A specific cooling rate is 0.1°C / sec or more, preferably 0.5°C / sec or more, more preferably 2°C / sec or more, and even more preferably 4°C / sec or more.

[0104] <Annealing process> The toner manufacturing method preferably includes an annealing step in which the aggregate is heated and maintained at a temperature equal to or higher than the crystallization temperature or glass transition temperature of the binder resin. The annealing step is a step in which, after the cooling step, the aggregate is heated and maintained at a temperature equal to or higher than the crystallization temperature or glass transition temperature of the binder resin, and, if a release agent is contained, equal to or lower than the crystallization temperature of the release agent. The annealing step further suppresses the volume change, thereby preventing the occurrence of depressions on the toner particle surface and enabling the control of the circularity or surface shape. The specific annealing temperature is 45°C to 75°C, preferably 50°C to 70°C, and more preferably 55°C to 65°C. The heat treatment time in the annealing step is, for example, within 5 hours, preferably 2 to 3 hours.

[0105] <Post-processing process> In the toner production method, post-treatment steps such as a washing step, a solid-liquid separation step, and a drying step may be further carried out, and by carrying out the post-treatment steps, toner particles in a dried state can be obtained.

[0106] <External addition process> The toner manufacturing method may include an external addition step, in which inorganic fine powder is externally added to the toner particles obtained in the drying step, as needed. If necessary, other known fine particles may be used in combination. The amount of inorganic fine powder added is not particularly limited, but may be, for example, 0.1 to 5.0 parts by mass relative to 100 parts by mass of toner particles. From the viewpoint of achieving both durability, including the charge retention characteristics of the toner, and low-temperature fixability, the amount is preferably 0.2 to 3.0 parts by mass, and more preferably 0.2 to 2.0 parts by mass.

[0107] Next, the measurement methods for each physical property will be described. <Method for isolating inorganic fine powder and method for measuring the content of inorganic fine powder in toner particles> A dispersion medium is prepared by adding 0.50 g of Triton-X100 (Kishida Chemical Co., Ltd.) to 100 g of ion-exchanged water. (1) 1.00 g of toner is accurately weighed into a vial, and the dispersion medium is added to make the total weight 10.00 g, and the solution is left to stand for 24 hours to prepare a sample liquid. (2) The sample liquid is subjected to an ultrasonic homogenizer treatment to liberate the external additives from the toner and disperse them in the dispersion medium. The apparatus and conditions used are as follows: Ultrasonic treatment device: Ultrasonic homogenizer VP-050 (manufactured by Taitec Co., Ltd.) Microchip: Stepped microchip, tip diameter φ2mm Microchip tip position: Center of glass vial, 5 mm above the bottom of the vial Ultrasonic conditions: intensity 30%, 180 minutes. During this time, ultrasonic waves are applied while cooling the vial with ice water to prevent the dispersion from heating up.

[0108] (3) Using suction filtration (10 μm membrane filter), the toner particles in the sample liquid are separated from the dispersion medium (filtrate) in which the external additives are dispersed. (4) The toner particles after filtration are collected, and the dispersion medium is added again to make the total weight 10.00 g. Then, the above steps (2) and (3) are repeated 10 times, and all the filtrate is collected. (5) If other external additives are added, the recovered filtrate is centrifuged to separate it from the other external additives and recover the inorganic fine powder. (6) The collected inorganic fine powder is thoroughly dried in a vacuum dryer at 60°C for 24 hours to isolate the dried inorganic fine powder. The mass of the inorganic fine powder after drying is measured, the toner particles are isolated by the method described below, and the mass of the isolated toner particles is measured to determine the parts by mass of the inorganic fine powder contained in 100 parts by mass of the toner particles.

[0109] <Method for measuring the number average particle size (D1) of inorganic fine powder> The number average particle diameter (D1) of the primary particles of the inorganic fine powder is measured using a scanning electron microscope "S-4800" (trade name; manufactured by Hitachi, Ltd.). Toner with externally added inorganic fine powder is observed, and the major axis of 100 primary particles of the inorganic fine powder is measured at a maximum magnification of 200,000 times to determine the number average particle diameter (D1). If multiple types of inorganic fine powder are present, an elemental mapping image is simultaneously obtained using energy dispersive X-ray spectroscopy when obtaining an electron microscope image, and the major axis of particles present in positions where silicon and aluminum are detected is measured to determine the number average particle diameter (D1). The observation magnification is adjusted appropriately depending on the size of the inorganic fine powder.

[0110] <X-ray fluorescence analysis of inorganic fine powders> Measurement of inorganic fine powder by X-ray fluorescence analysis (XRF) is carried out according to the following procedure. The measurement equipment used was a wavelength dispersive X-ray fluorescence analyzer "Axios" (manufactured by PANalytical) and the accompanying dedicated software "Sup An erQ ver.4.0F (PANalytical) is used. Elements from Na to U in inorganic fine powder are directly measured under a helium atmosphere. Using the liquid sample cup provided with the instrument, a 6 μm thick Mylar film is attached to the bottom, a sufficient amount of isolated inorganic fine powder is placed in, and a layer of uniform thickness is formed on the bottom, and the lid is then placed. The net strength of the aluminum and silicon elements obtained by measurement at an output of 2.4 kW is taken as the aluminum and silicon content in the inorganic fine powder. The ratio of these strengths, Al (kcps) / Si (kcps), is taken as X2.

[0111] <X-ray photoelectron spectroscopy analysis of inorganic fine powders> Measurement of inorganic fine powder by X-ray photoelectron spectroscopy (XPS) is carried out according to the following procedure. The isolated inorganic fine powder is measured under the following conditions: The XPS device and measurement conditions are as follows. Equipment used: ULVAC-PHI Quantum 2000 Analysis method: Narrow analysis Measurement conditions: X-ray source: Al-Kα X-ray conditions: beam diameter 100 μm, 25 W, 15 kV Photoelectron capture angle: 45° Pass Energy: 58.70 eV Measurement range: φ100μm

[0112] The analysis method is as follows. First, the peak corresponding to the C-C bond of the carbon 1s orbital is corrected to 285 eV. Then, using the relative sensitivity factor provided by ULVAC-PHI, the silicon atom percentage A (atomic %) and aluminum atom percentage B (atomic %) are calculated from the peak area corresponding to the silicon 2p orbital, whose peak top is detected between 100 eV and 105 eV, and the peak area corresponding to the aluminum 2p orbital, whose peak top is detected between 72.5 eV and 74.6 eV. The ratio B / A is defined as X1.

[0113] <Method for measuring X-ray diffraction patterns of inorganic fine powders> The crystal system of the inorganic fine powder can be identified by X-ray diffraction analysis of the inorganic fine powder collected from the toner. The X-ray diffraction measurement was performed using the measurement device "RINT-TTRII" (manufactured by Rigaku Corporation) and the control software and analysis software that came with the device. The measurement conditions were as follows: X-ray:Cu / 50kV / 300mA Goniometer: Rotor horizontal goniometer (TTR-2) Attachment: Standard sample holder Divergence slit: open Divergence vertical limit slit: 10.00 mm Scattering slit: open Receiving slit: open Counter: Scintillation counter Scanning mode: Continuous Scan speed: 4.0000° / min Sampling width: 0.0200° Scan axis: 2θ / deg Scanning range: 3.0000°~60.0000°

[0114] The obtained spectrum is analyzed using the software attached to the instrument, and the crystal structure is identified. When the inorganic fine powder is composed of amorphous silica and aluminum hydroxide, clear peaks are observed. On the other hand, if the aluminum component contains aluminum oxide (Al2O3), a clear peak reflecting the alumina crystal structure is detected.

[0115] <Method for isolating toner particles> In the method for isolating inorganic fine powder and the method for measuring the content of inorganic fine powder in toner particles (4), the filtration is repeated 10 times to recover the obtained toner particles, and the obtained toner particles are then sufficiently dried at 45°C for 24 hours to isolate the toner particles.

[0116] <Method for isolating binder resin from toner particles> Method for isolating binder resin from toner particles 100 mg of the toner particles isolated using the method described above was dissolved in 3 ml of chloroform. Next, the chloroform-insoluble material 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 chloroform-soluble material 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 the chloroform eluent was pumped. Once a peak was confirmed in the resulting chromatographic display, the retention time corresponding to a molecular weight of 2,000 or greater using a monodisperse polystyrene standard sample was collected. The resulting fraction solution was dried and solidified to separate it from the release agent and collect the binder resin.

[0117] <Composition analysis of polyester resin A and crystalline polyester> The chloroform-soluble portion of the separated binder resin is used as the sample. The sample is adjusted with chloroform so that the toner particle concentration is 0.1% by mass, and the solution is filtered through a 0.45 μm PTFE filter before being used for measurement. The gradient polymer LC measurement conditions are as follows: Equipment: UlTIMATE3000 (Thermo Fisher Scientific) Mobile phase: A chloroform (HPLC), B acetonitrile (HPLC) Gradient: 2 min (A / B = 0 / 100) → 25 min (A / B = 100 / 0) (Note: The gradient of the mobile phase change should be linear.) Flow rate: 1.0mL / min Injection: 0.1% by mass x 20μL Column: Tosoh TSKgel ODS (4.6mmφ x 150mm x 5μm) Column temperature: 40℃ Detector: Corona Charged Aerosol Detector (Corona-CAD) (Thermo Fisher Scientific)

[0118] The polyester resin A is separated at a separation time corresponding to the polyester resin A. The crystalline polyester is also separated at a separation time corresponding to the crystalline polyester. In the separation, the required amount of each chloroform / acetonitrile solution is collected, dried, and concentrated to obtain samples of polyester resin A and crystalline polyester. From the amount of the obtained polyester resin A and the amount of the separated binder resin, the content W of polyester resin A in the binder resin is calculated. p Calculate.

[0119] Using a sample of the polyester resin component A, the composition ratio and mass ratio are measured by nuclear magnetic resonance spectroscopy (NMR) as follows. 1 mL of deuterated chloroform is added to 20 mg of a sample of polyester resin component A, and the proton NMR spectrum of the dissolved resin is measured. From the obtained NMR spectrum, the molar ratio and mass ratio of each monomer can be calculated, and the content ratio of each monomer unit can be determined. The following equipment and measurement conditions can be used for nuclear magnetic resonance spectroscopy (NMR). NMR device: JEOL RESONANCE ECX500 Observation nucleus: Proton Measurement mode: Single pulse

[0120] <Quantification method of U, U, U in polyester resin A by NMR measurement iso , U EO , U PO > · Identification of components of polyester resin A and measurement of molar ratio and mass ratio by nuclear magnetic resonance spectroscopy (NMR) Add 1 mL of deuterated chloroform to 20 mg of the obtained polyester resin A and dissolve it, and measure the proton NMR spectrum of the dissolved polyester resin A. From the obtained NMR spectrum, calculate the molar ratio and mass ratio of each monomer with the smallest unit sandwiched by ester bonds as the structure derived from the monomer. For example, the composition ratio and mass ratio can be calculated based on the following peaks (chemical shift value, number of protons). Unit derived from isophthalic acid: 7.5 ppm (1), 8.2 ppm (2), 8.7 ppm (1) Unit derived from terephthalic acid: 8.1 ppm (4) Unit derived from ethylene oxide adduct of bisphenol A: 1.6 ppm (6), 4.3 ppm (4), 4.7 ppm (4), 6.8 ppm (4), 7.1 ppm (4) Unit derived from propylene oxide adduct of bisphenol A: 1.5 ppm (6), 1.6 ppm (6), 4.1 ppm (4), 5.5 ppm (2), 6.8 ppm (4), 7.1 ppm (4) Unit derived from ethylene glycol: 4.3 ppm (4) NMR apparatus: JEOL RESONANCE ECX500 Observation nucleus: Proton Measurement mode: Single pulse Reference peak: TMS

[0121] By this NMR analysis, determine the content ratio (mol%) of the monomer unit U corresponding to isophthalic acid with respect to all monomer units corresponding to polycarboxylic acids. Also, determine the content ratio of U with respect to all monomer units corresponding to polyol and U iso EO and the content ratio of U PO ​The total content (mol%) of U EO The content ratio and U PO When the total of the content ratio of U and EO Calculate the content (molar parts). When the content ratio is expressed in mass % or mass parts, it is calculated in the same manner as above.

[0122] <Method for measuring weight average molecular weight and number average molecular weight> The molecular weight of samples such as polyester resin A, crystalline polyester, and styrene-acrylic resin is measured by gel permeation chromatography (GPC) as follows. First, dissolve the sample in tetrahydrofuran (THF). In the case of polyester resin A or styrene acrylic, dissolve the sample in THF at room temperature for 24 hours. In the case of crystalline polyester, heat the THF to 40°C to dissolve the sample, then leave it for 24 hours. The solution containing each sample was filtered through a solvent-resistant membrane filter "Myshoridisc" (Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. The sample solution was adjusted so that the concentration of components soluble in THF was 0.8% by mass. Measurements were performed using this sample solution under the following conditions.

[0123] 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. From the weight average molecular weight and number average molecular weight thus obtained, the ratio of the weight average molecular weight to the number average molecular weight is calculated.

[0124] <Method for measuring melting point> The melting points of samples such as crystalline polyester, release agent, and plasticizer are 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. The peak temperature of the maximum endothermic peak at this time is taken as the melting point.

[0125] <Measurement of glass transition temperature Tg> The glass transition temperature (Tg) is measured in accordance with ASTM D3418-82 using a differential scanning calorimeter (Q2000, manufactured by TA Instruments). The melting points of indium and zinc are used for temperature correction of the detector, and the heat of fusion of indium is used for heat correction. Specifically, approximately 2 mg of sample is weighed out and placed in an aluminum pan. An empty aluminum pan is used as a reference. Measurements are performed at a temperature range of -10 to 200°C at a heating rate of 10°C / min. The sample is heated to 200°C, then cooled to -10°C, and then heated again. During this second heating process, the specific heat change is measured in the temperature range of 30°C to 100°C. The glass transition temperature (Tg) is determined as the intersection of the line midway between the baselines before and after the specific heat change and the differential heat curve.

[0126] <Acid value measurement> The acid value is the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1 g of sample. The acid value in this disclosure is measured in accordance with JIS K 0070-1992, and specifically, is measured according to the following procedure. Titration is performed using a 0.1 mol / L potassium hydroxide ethyl alcohol solution (Kishida Chemical Co., Ltd.). The factor of the potassium hydroxide ethyl alcohol solution can be determined using a potentiometric titrator (Kyoto Electronics Manufacturing Co., Ltd., Potentiometric Titrator AT-510). 100 ml of 0.100 mol / L hydrochloric acid is placed in a 250 ml tall beaker and titrated with the potassium hydroxide ethyl alcohol solution, and the factor is determined from the amount of potassium hydroxide ethyl alcohol solution required for neutralization. The 0.100 mol / L hydrochloric acid used is prepared in accordance with JIS K 8001-1998.

[0127] The conditions for measuring the acid value are shown below. Titrator: Potentiometric titrator AT-510 (Kyoto Electronics Manufacturing Co., Ltd.) Electrode: Composite glass electrode double junction type (Kyoto Electronics Manufacturing Co., Ltd.) Titrator control software: AT-WIN Titration analysis software: Tview The titration parameters and control parameters during titration are as follows: Titration parameters Titration mode: Blank titration Titration method: Total volume titration Maximum titration volume: 20ml Waiting time before titration: 30 seconds Titration direction: automatic Control parameters End point determination potential: 30dE End point potential: 50 dE / dmL End point detection judgment: Not set Control speed mode: Standard Gain: 1 Data collection potential: 4mV Data collection titration volume: 0.1 ml

[0128] Main test: Accurately weigh 0.100 g of the sample to be measured into a 250 ml tall beaker, add 150 ml of a toluene / ethanol (3:1) mixture, and dissolve over 1 hour. Using the potentiometric titrator, titrate with the potassium hydroxide ethyl alcohol solution. Blank test: Perform titration in the same manner as above, except that no sample is used (i.e., only a toluene / ethanol (3:1) mixed solution is used). Substitute the obtained results into the following formula to calculate the acid value. A=[(CB)×f×5.611] / S (In the formula, A: acid value (mgKOH / g), B: amount of potassium hydroxide ethyl alcohol solution added for the blank test (ml), C: amount of potassium hydroxide ethyl alcohol solution added for the main test (ml), f: factor of the potassium hydroxide solution, and S: sample (g).)

[0129] <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-type 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-type 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.

[0130] <Method for measuring weight average particle size (D4) of toner particles> The weight-average particle size (D4) of the toner particles is calculated as follows. The measurement device used is a precision particle size distribution analyzer, "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.), equipped with a 100 μm aperture tube and employing the narrow-pore electrical resistance method. The measurement conditions and measurement data are analyzed using the accompanying dedicated software, "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.). Measurements are performed using an effective number of 25,000 measurement channels. The electrolyte solution used for the measurements is prepared by dissolving special-grade sodium chloride in ion-exchange water to a concentration of approximately 1% by mass; for example, "ISOTON II" (manufactured by Beckman Coulter, Inc.).

[0131] Before performing measurements and analysis, the dedicated software was configured as follows. In the "Change Standard Measurement Method (SOM) screen" of the dedicated software, the total count in control mode was set to 50,000 particles, the number of measurements was set to 1, and the Kd value was set to the value obtained using a "Standard Particle 10.0 μm" (Beckman Coulter). The threshold and noise level were automatically set by pressing the "Threshold / Noise Level Measurement Button." The current was set to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and the "Flush aperture tube after measurement" checkbox was checked. In the "Pulse to Particle Size Conversion Setting Screen" of the dedicated software, the bin spacing was set to logarithmic particle size, the particle size bins to 256 particle size bins, and the particle size range from 2 μm to 60 μm.

[0132] The specific measurement method is as follows. 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 flush" function of the analysis software to remove any dirt and air bubbles from inside the aperture tube. 2. Place approximately 30 ml of the electrolyte solution into a 100 ml flat-bottom glass beaker. Add 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, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) three times with ion-exchanged water as a dispersant. 3. 3.3 L of ion-exchanged water was placed in the water tank of an ultrasonic disperser, "Ultrasonic Dispersion System Tetora150" (manufactured by Nikkaki Bios Co., Ltd.), which had two built-in oscillators with an oscillation frequency of 50 kHz and a phase difference of 180 degrees and an electrical output of 120 W, and approximately 2 ml of the above-mentioned Contaminon N was added to this water tank. 4. Place the beaker from step 2 into 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 ultrasonic waves are being applied to the electrolyte solution in the beaker from step 4, 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 process, the water temperature in the water tank is appropriately adjusted to be between 10°C and 40°C. 6. Using a pipette, add the electrolyte solution prepared in step 5, in which the toner has been dispersed, to the round-bottom beaker prepared in step 1, placed inside the sample stand, and adjust the measurement concentration to approximately 5%. Then, measurements are continued until the number of particles measured reaches 50,000. 7. Analyze the measurement data using the dedicated software provided with the device and calculate the weight-average particle size (D4). Note that when the dedicated software is set to Graph / Volume %, the "Average diameter" on the "Analysis / Volume Statistics (Arithmetic Mean)" screen is the weight-average particle size (D4).

[0133] <Toner particle surface coverage of inorganic fine powder W AS Measurement method> Coverage of inorganic fine powder on the toner particle surface W AS was performed using a scanning transmission electron microscope. It can be calculated from elemental mapping images of aluminum and silicon obtained by energy dispersive spectroscopy (STEM-EDS). EDS elemental mapping measurements use a silicon drift detector with a large detection element area, making it possible to measure elemental mapping images with high sensitivity, even for trace elements. Statistical analysis of the spectral data for each pixel obtained by EDS elemental mapping measurements makes it possible to obtain a principal component map that extracts pixels with similar spectra, enabling mapping of specific components.

[0134] The sample for observation is prepared according to the following procedure. An appropriate amount of liquid curing epoxy resin is placed in an Eppendorf tube, a small amount of toner is added, and the mixture is stirred to disperse the toner. This is left overnight to harden the epoxy resin, creating a sample pellet. The pellet is then processed using an ultramicrotome (Leica, FC7) to create a 200 nm thick slice, which is then held on a Cu grid mesh with a support film. The slice is then observed using a STEM to obtain a transmission image of the area near the top of the cut toner. The STEM-EDS mapping 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: Thermo Fisher Scientific NORAN System 7

[0135] [Conditions for STEM-EDS] STEM accelerating voltage: 200kV ·Magnification: 100,000x Probe size 1nm 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

[0136] After the measurement is completed, quantitative mapping is obtained by the following analysis process. Kernel size: 3×3 Quantitative map setting: High (slow) Filter Fit Type: High Precision (Slow) The above STEM-EDS analysis yields an Al-K line mapping image and an Si-K line EDS mapping image. Since inorganic fine powder has aluminum hydroxide on the surface of silica particles, particles at positions detected in both the Al-K line mapping image and the Si-K line EDS mapping image in the observation field are inorganic fine powder. The mapping image obtained by STEM-EDS mapping is analyzed using the image analysis software ImageJ. From the mapping image, the number of pixels occupied by the inorganic fine powder, S1, and the number of pixels occupied by the top of the mapped toner, S2, are measured, and the coverage rate W of the inorganic fine powder on the toner particle surface is determined by calculating (S1 / S2) x 100. AS (%) is calculated.

[0137] <Method for measuring the coverage of aluminum element on inorganic fine powder> The coverage rate of the aluminum element with respect to the inorganic fine powder can be calculated from elemental mapping images of aluminum and silicon obtained by energy dispersive spectroscopy using a scanning transmission electron microscope (STEM-EDS), in the same manner as in the above <Method for measuring coverage rate of inorganic fine powder on toner surface>. The sample for observation was prepared by ultrasonically dispersing 10 mg of the inorganic fine powder isolated by the above method in 2 ml of a solvent such as isopropyl alcohol, and then dropping the resulting liquid onto a Cu grid mesh with a support film. It can be produced by evaporating the solvent.

[0138] The STEM-EDS mapping 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: Thermo Fisher Scientific NORAN System 7

[0139] [Conditions for STEM-EDS] STEM accelerating voltage: 200kV ·Magnification: 1,000,000x Probe size 0.5nm 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

[0140] After the measurement is completed, quantitative mapping is obtained by the following analysis process. Kernel size: 3×3 Quantitative map setting: High (slow) Filter Fit Type: High Precision (Slow) The above STEM-EDS analysis yields Al-K line mapping images and Si-K line EDS mapping images. The mapping images obtained by STEM-EDS mapping are analyzed using the image analysis software ImageJ. From the mapping images, the number of pixels occupied by silicon in the inorganic fine powder, S3, and the number of pixels occupied by aluminum, S4, are measured, and the coverage rate (area %) of aluminum element relative to the inorganic fine powder is calculated by calculating (S4 / S3) x 100.

[0141] <Method for measuring the volume resistivity of inorganic fine powder> The volume resistivity of the inorganic fine powder is measured as follows. The device used is a Keithley Instruments 6517 Electrometer / High Resistance System. Electrodes with a diameter of 25 mm are connected, and inorganic fine powder is placed between the electrodes to a thickness of approximately 0.5 mm. Then, the distance between the electrodes is measured with a load of approximately 2.0 N applied. A voltage of 1,000 V is applied to the inorganic fine powder for 1 minute, the resistance is measured, and the volume resistivity is calculated using the following formula. Volume resistivity (Ω cm)=R×L R: Resistance value (Ω) L: Distance between electrodes (cm) [Example]

[0142] The present disclosure will be described in more detail below with reference to examples and comparative examples, but the present disclosure is not limited thereto. Parts used in the examples are by weight unless otherwise specified.

[0143] <Production Example of Polyester Resin A-1> Bisphenol A ethylene oxide 2 mole adduct 27 mol parts Bisphenol A propylene oxide 2 mole adduct 73 moles Isophthalic acid 100 mol parts The above monomers were charged into a flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectification column, and the temperature was raised to 190°C in 1 hour. After confirming that the reaction system was uniformly stirred, To 100 parts of these monomers, 1.0 part of tin distearate was added. The temperature was then raised from 190°C to 245°C over 5 hours while distilling off the water produced, and a dehydration condensation reaction was carried out at 245°C for a further 2 hours. As a result, the glass transition temperature was 60.1°C, the acid value was 9mgKOH / g, the hydroxyl value was 25mgKOH / g, and the M n 4800, M w / M n Polyester resin A-1 having a viscosity of 6.7 was obtained. [Table 1] In the table, "Total Acids" indicates the total polycarboxylic acids used as raw materials for polyester resin A, and Uiso / Total Acids is the content ratio M of the monomer units corresponding to isophthalic acid to the total monomer units corresponding to polycarboxylic acids in polyester resin A. IPA (mol %), total alcohols represent all polyols used as raw materials for polyester resin A, and (U EO +U PO ) / total alcohol is the ratio of the monomer units U corresponding to the ethylene oxide adduct of bisphenol A to the total monomer units corresponding to polyol in polyester resin A. EO and the monomer unit U corresponding to the propylene oxide adduct of bisphenol APO The total content ratio of [Table 2] In the table, "Total Acids" indicates the total polycarboxylic acids used as raw materials for polyester resin A, and "Uiso / Total Acids" indicates the total monomer units corresponding to the polycarboxylic acids in polyester resin A. The content ratio M of the monomer unit corresponding to isophthalic acid IPA The total alcohols represent all polyols used as raw materials for polyester resin A, and (U EO +U PO ) / total alcohol is the ratio of the monomer units U corresponding to the ethylene oxide adduct of bisphenol A to the total monomer units corresponding to polyol in polyester resin A. EO and the monomer unit U corresponding to the propylene oxide adduct of bisphenol A PO The total content ratio of In the table, the abbreviations represent the following compounds. IPA: isophthalic acid, TPA: terephthalic acid, AA: adipic acid, TMA: trimellitic acid, DSA: dodecenylsuccinic acid, FA: fumaric acid, EG: ethylene glycol

[0144] <Production Examples of Polyester Resins A-2 to A-15> In the production example of polyester resin A-1, the monomers used were changed as shown in Tables 1 and 2, and the M of the resulting polyester resin A was n and M w / M n Polyester resins A-2 to A-15 were obtained in the same manner as in Production Example 1 for Polyester Resin A-1, except that the reaction temperature and dehydration condensation time were changed so that the values ​​shown in Table 1 or Table 2 were obtained. The results are shown in Tables 1 and 2.

[0145] <Production example of styrene acrylic resin> Styrene 77 parts by mass Butyl acrylate 23 parts by weight Di-t-butyl peroxide 1.0 parts by mass After 200 parts by mass of xylene was heated to 200° C., the above components were added dropwise to the xylene over 4 hours, and the mixture was further maintained under reflux with xylene for 1 hour to complete the polymerization. The physical properties of the resulting styrene acrylic resin are shown in Table 3. [Table 3]

[0146] <Production example of crystalline polyester 1> 1,10-Decanedicarboxylic acid 100 mol parts 1,9-nonanediol 100 mol parts 0.8 parts by mass of tin dioctylate as a catalyst based on the total weight of the acid and alcohol The above materials were placed in a heated, dried two-neck flask equipped with a nitrogen inlet tube, dehydration tube, stirrer, and thermocouple. Nitrogen gas was introduced into the vessel to maintain an inert atmosphere, and the temperature was raised with stirring. Stirring was then continued at 170°C for 6 hours. The temperature was then gradually raised to 230°C under reduced pressure while continuing to stir, and maintained at that temperature for an additional 3 hours. When the mixture reached a viscous state, it was air-cooled to terminate the reaction, producing Crystalline Polyester 1. The physical properties of the resulting Crystalline Polyester 1 are shown in Table 4. [Table 4]

[0147] <Production Examples of Crystalline Polyesters 2 and 3> Crystalline polyesters 2 and 3 were obtained in the same manner as in the production example of crystalline polyester 1, except that the alcohol monomer and acid monomer used were changed as shown in Table 4. The physical properties of crystalline polyesters 2 and 3 are shown in Table 4.

[0148] <Silica Microparticle Production Examples 1 to 5> A mixture of methanol, water, and aqueous ammonia was heated and stirred, while tetramethoxysilane was added dropwise to obtain a suspension of silica microparticles. The heating temperature, stirring speed, and addition time were adjusted so that the particle size of the resulting silica microparticles would be the values ​​shown in Table 5. The resulting silica microparticles were passed through a wet sieve to remove coarse particles. The solvent was then removed, and the resulting mixture was dried to obtain silica microparticles 1 to 5 (sol-gel silica).

[0149] <Production example of hydrophobic treated silica fine particles> A mixture of methanol, water, and aqueous ammonia was heated and stirred, while tetramethoxysilane was added dropwise to obtain a suspension of silica microparticles. The heating temperature, stirring speed, and addition time were adjusted so that the particle size of the resulting silica microparticles would be 20 nm. Hexamethyldisilazane, a hydrophobic treatment agent, was added to the dispersion obtained by solvent substitution at room temperature in an amount of 10 parts per 100 parts of the resulting silica microparticles. The mixture was then heated to 120°C to react, thereby hydrophobizing the surface of the silica microparticles. The obtained silica fine particles were passed through a wet sieve to remove coarse particles, and then the solvent was removed and the particles were dried to obtain hydrophobic treated silica fine particles (sol-gel silica).

[0150] <Production example of inorganic fine powder 1> 100 g of silica microparticles 1 was dispersed in 2 L of water and heated to 80°C. An aluminum chloride aqueous solution was added in an amount equivalent to 10% by mass of the silica microparticles in terms of Al2O3 to obtain a mixed solution. The mixed solution was then adjusted to pH 5.5 with a sodium hydroxide aqueous solution and held under stirring for 1 hour to coat the surfaces of the silica microparticles with aluminum hydroxide. Next, isobutyltrimethoxysilane was added to the mixture in an amount equivalent to 60% by mass of the silica fine particles. The mixture was then adjusted to pH 7.0 with aqueous sodium hydroxide and stirred for 1 hour to obtain a slurry of inorganic fine powder coated with a silane coupling agent. The resulting slurry was filtered, and the residue on the filter was washed with water to obtain a washed cake. This washed cake was dried at 120°C and then pulverized in a media-type pulverizer to produce Inorganic Fine Powder 1. The resulting physical properties are shown in Table 5. [Table 5] In the table, the Al coverage indicates the coverage (area %) of aluminum element on inorganic fine powder. Regarding the volume resistivity of inorganic fine powder, for example, 1.0E+12 means 1.0×10 12 Shows.

[0151] <Inorganic fine powder manufacturing examples 2 to 12> Inorganic fine powders 2 to 12 were obtained in the same manner as in Inorganic Fine Powder Production Example 1, except that the amount of aluminum chloride aqueous solution added and the type of hydrophobic treatment agent were changed as shown in Table 5, and the amount of treatment with the hydrophobic treatment agent was changed so that the coverage rate of the hydrophobic treatment agent would be the value shown in Table 5. The physical properties of Inorganic Fine Powders 2 to 12 are shown in Table 5.

[0152] <Production example of inorganic fine powder 13> Silica fine particles 1, 100 mass parts to 945 mass parts of methanol, 28% ammonia 45 parts by mass of water and 135 parts by mass of water were added and mixed. The temperature of this solution was adjusted to 35°C, and 405 parts by mass of tetramethoxysilane was added dropwise over 6 hours while stirring. Stirring was then continued for 1 hour to carry out hydrolysis, thereby preparing a dispersion of silica fine particles. While the resulting dispersion was heated and maintained at 70°C, a 5 mol / L aqueous sodium hydroxide solution was added dropwise to adjust the pH of the dispersion to 8.0. Sodium aluminate was then added to the silica particles so that the alumina content was 30% by mass, thereby preparing a slurry containing alumina-coated silica particles. The pH of the slurry was then neutralized to 5.0, and the slurry was aged by maintaining it at 80°C for 30 minutes while stirring. The slurry was then distilled under reduced pressure and dried, after which the particles were crushed to prepare inorganic fine powder 13. The number average particle diameter (D50) of the primary particles of the inorganic fine powder 13 obtained by the above method was measured and found to be 20 nm.

[0153] <Preparation Example of Resin Particle Dispersion of Polyester Resin A-1> Polyester resin A-1 100 parts 50 parts methyl ethyl ketone 20 parts isopropyl alcohol The above methyl ethyl ketone and isopropyl alcohol were added to a container. Then, polyester resin A-1 was gradually added and stirred until completely dissolved, yielding a polyester resin A-1 solution. The container containing the polyester resin A-1 solution was set to 65°C, and while stirring, 10% aqueous ammonia solution was gradually added dropwise to a total of 5 parts. 230 parts of ion-exchanged water was then gradually added dropwise at a rate of 10 ml / min to induce phase inversion emulsification. The pressure was then reduced in an evaporator to remove the solvent, yielding a resin particle dispersion of polyester resin A-1. The volume average particle size of the resin particles contained in the resulting resin particle dispersion was 130 nm. The resin particle solid content was adjusted to 20% with ion-exchanged water.

[0154] <Preparation Examples of Resin Particle Dispersions of Polyester Resins A-2 to A-15> Resin particle dispersions of polyester resins A-2 to A-15 were obtained in the same manner as in the preparation example of resin particle dispersion of polyester resin A-1, except that polyester resins A-2 to A-15 were used instead of polyester resin A-1.

[0155] <Preparation example of resin particle dispersion of crystalline polyester 1> 100 parts crystalline polyester 50 parts methyl ethyl ketone 20 parts isopropyl alcohol The methyl ethyl ketone and isopropyl alcohol were added to a container. Then, the crystalline polyester 1 was gradually added and stirred until completely dissolved, yielding a crystalline polyester 1 solution. The container containing the crystalline polyester 1 solution was set to 40°C, and a 10% aqueous ammonia solution was gradually added dropwise with stirring to a total of 3.5 parts. 230 parts of ion-exchanged water was then gradually added dropwise at a rate of 10 ml / min to induce phase inversion emulsification. The pressure was then reduced in an evaporator to remove the solvent, yielding a resin particle dispersion of crystalline polyester 1. The volume average particle size of the resin particles contained in the resulting resin particle dispersion was 150 nm. The resin particle solid content was adjusted to 20% with ion-exchanged water.

[0156] <Preparation example of resin particle dispersion of crystalline polyester 2-3> Resin particle dispersions of crystalline polyesters 2 and 3 were obtained in the same manner as in the preparation example of the resin particle dispersion of crystalline polyester 1, except that crystalline polyesters 2 and 3 were used instead of crystalline polyester 1, respectively.

[0157] <Preparation of Colorant Particle Dispersion> Copper phthalocyanine (pigment blue 15:3) 45 parts 5 parts of ionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 190 parts ion-exchanged water The above components were mixed and dispersed for 10 minutes using a homogenizer (Ultra Turrax, manufactured by IKA). Then, using an Ultimizer (a counter-impact wet grinder, manufactured by Sugino Machine Co., Ltd.), dispersion was carried out at a pressure of 250 MPa for 20 minutes to obtain a colorant particle dispersion. The resulting colorant particle dispersion had a volume average particle size of 120 nm and a solid content of 20%.

[0158] <Preparation of Release Agent Particle Dispersion> Release agent (hydrocarbon wax, melting point: 79°C) 15 parts 2 parts of ionic surfactant Neogen RK (Dai-ichi Kogyo Seiyaku Co., Ltd.) 240 parts ion-exchanged water The above components were mixed, heated to 100°C, and thoroughly dispersed using an Ultra Turrax T50 manufactured by IKA. Thereafter, the mixture was heated to 115°C using a pressure discharge Gaulin homogenizer and subjected to a dispersion treatment for 1 hour, thereby obtaining a release agent particle dispersion liquid having a volume average particle size of 160 nm and a solid content of 20%.

[0159] <Production of Toner Particles 1> 900 parts of polyester resin A-1 dispersion 100 parts of crystalline polyester resin particle dispersion Colorant particle dispersion 50 parts Release agent particle dispersion 80 parts First, the above materials were placed in a round stainless steel flask and mixed. Then, the mixture was dispersed using an Ultra-Turrax T50 homogenizer (manufactured by IKA) at 5,000 rpm for 10 minutes. A 1.0% aqueous nitric acid solution was added to adjust the pH of the mixture to 3.0. The mixture was then heated to 58°C in a heated water bath using a stirring blade, while appropriately adjusting the rotation speed to ensure proper stirring.

[0160] The volume average particle size of the formed aggregated particles was appropriately confirmed using a Coulter Multisizer III, and the aggregation step was terminated when aggregated particles having a size of 6.0 μm were formed. Thereafter, in the spheronization step, the pH of the mixture was adjusted to 9.0 using a 5% aqueous sodium hydroxide solution, and the mixture was heated to 92°C while continuing to stir. When the desired surface shape of the toner particles was obtained, heating was stopped, and as a cooling step, ice was quickly added so that the cooling rate was 10°C / sec or more to cool to 40°C. Furthermore, as an annealing step, annealing treatment was carried out at 55°C for 3 hours. The mixture was then cooled to 25°C, filtered, and subjected to solid-liquid separation, followed by washing with ion-exchanged water. After washing, the mixture was dried using a vacuum dryer to obtain toner particles 1 having a weight average particle size (D4) of 7.1 μm. The physical properties of toner particles 1 are shown in Table 6. [Table 6]

[0161] <Production Examples of Toner Particles 2 to 10 and 12 to 25> Toner particles 2 to 10 and 12 to 25 were obtained in the same manner as in the production example of toner particle 1, except that the blending of materials used and production conditions were changed so as to obtain the formulation and physical properties shown in Table 6. The physical properties of the obtained toner particles 2 to 10 and 12 to 25 are shown in Table 6.

[0162] <Production Example of Toner Particle 11> (Production of toner particles by pulverization method) The following materials were thoroughly mixed in an FM mixer (manufactured by Nippon Coke and Engineering Co., Ltd.), and then melt-kneaded in a twin-screw kneader (manufactured by Ikegai Iron Works Co., Ltd.) set at a temperature of 100°C. Polyester resin A-1 90.0 parts Crystalline polyester 1 10.0 parts Hydrocarbon wax, melting point: 79°C 8.0 parts ·CIPigment Blue 15:3 5.0 copies The obtained kneaded product was cooled and coarsely crushed to 1 mm or less using a hammer mill to obtain a coarsely crushed product. Next, the obtained coarsely crushed material was pulverized using a turbo mill manufactured by Turbo Kogyo Co., Ltd. to obtain finely crushed material of about 6.5 μm, and then a multi-division classifier utilizing the Coanda effect was used to remove fine and coarse particles to obtain toner particles 11. The weight average particle size (D4) of the toner particles 11 was 7.1 μm, Tg was 58.4° C., and the average circularity was 0.940. Table 6 shows the physical properties.

[0163] <Production Example of Toner Particles 26> Toner particles 26 were obtained in the same manner as in the production example of toner particles 11, except that the blending of materials used and production conditions were changed so as to obtain the formulation and physical properties shown in Table 6. The physical properties of the obtained toner particles 26 are shown in Table 6.

[0164] <Production example 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 a 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 mixture 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 vacuum-dried overnight at 40° C. and then crushed to a desired particle size to obtain hydrotalcite particles 1. The number-average particle size of the primary particles of the hydrotalcite particles 1 was 400 nm.

[0165] <Toner 1 manufacturing example> External addition was carried out on toner particles 1. Using an FM mixer (FM10 manufactured by Nippon Coke & Engineering Co., Ltd.), 0.50 parts by mass of inorganic fine powder 1, 1.00 parts by mass of hydrophobic treated silica fine particles, and 0.25 parts by mass of hydrotalcite particles 1 were added to 100 parts by mass of toner particles 1, and then the mixture was mixed at 3000 rpm for 5 minutes to carry out external addition. Thereafter, the toner was sieved through a mesh with 75 μm openings to obtain Toner 1. The physical properties of Toner 1 are shown in Table 7.

[0166] <Toner 2-40 manufacturing example> Toners 2 to 40 were obtained in the same manner as in Production Example of Toner 1, except that the types of toner particles and inorganic fine powder and the content of inorganic fine powder were changed in Production Example of Toner 1. The physical properties of the obtained Toners 2 to 40 are shown in Table 7. Here, the inorganic fine powders 14 and 15 used in the toners 38 and 39 were as follows: Inorganic fine powder 14: Alumina fine particles (VPAlu65RK, manufactured by Nippon Aerosil Co., Ltd., number average primary particle diameter 20 nm, isobutylsilane treatment) Inorganic fine powder 15: Aluminum hydroxide fine particles (C-301N, manufactured by Sumitomo Chemical Co., Ltd., number average primary particle diameter 400 nm, isobutylsilane treatment) [Table 7] In the table, the content of inorganic fine powder indicates the content of inorganic fine powder relative to 100 parts by mass of toner particles.

[0167] <Examples 1 to 32 and Comparative Examples 1 to 8> The following actual machine evaluation was carried out using toners 1 to 40. The evaluation results are shown in Table 8. The color laser printer used was an HP LaserJet Enterprise Color M555dn equipped with a one-component toner contact development blade cleaning system, and a modified HP212X cyan toner cartridge CRG, which is a consumable cartridge for the printer. The main body was modified so that the process speed was 150% and printing tests could be performed only on the cyan station. The cartridge also had a larger toner container capacity, as shown below. The test was carried out after modifying the machine so that the toner filling amount could be measured. This enabled a longer lifespan durability test to be carried out on a machine that was faster than before.

[0168] <Evaluation 1. Low-temperature fixability of halftone images in a low-temperature, low-humidity environment (decrease in density due to rubbing)> The test was carried out in a low temperature, low humidity environment (temperature 15°C, relative humidity 10%), which is a severe environment for evaluating low temperature fixability. The printer body and a toner cartridge filled with 550g of evaluation toner were left in an environment of 15°C and 10% RH for 24 hours in order to control the temperature and humidity in the evaluation environment. The evaluation paper used was COTTON BOND LIGHT COCKLE (basis weight 90g), a rough paper that is prone to being disadvantageous in low temperature fixability due to its uneven surface. The evaluation procedure was as follows: starting from room temperature, the fixing unit was heated to a set temperature of 170°C, and the density of the halftone image was adjusted so that the image density was 0.75 to 0.80, and 10 sheets were printed. The image density at this time was measured using a portable spectrophotometer, Exact Advance (manufactured by X-Rite).

[0169] The image was then output at a set temperature of 150°C, and the fixed image was rubbed 10 times with Silbon paper under a load of 5.4 kPa. The density reduction rate at 150°C was calculated using the following formula from the image density before and after rubbing. Density reduction rate (%) = ((image density before rubbing - image density after rubbing) / image density before rubbing) × 100 Similarly, the fixing temperature was increased by 5°C increments up to 200°C, and the density reduction rate was calculated. From the evaluation results of the fixing temperature and density drop rate obtained through a series of operations, a quadratic polynomial approximation was performed to obtain a relationship between the fixing temperature and density drop rate. Using this relationship, the temperature at which the density drop rate was 15% was calculated, and this temperature was set as the fixing temperature that indicates the threshold for good low-temperature fixability. The lower the fixing temperature, the better the low-temperature fixability. (Evaluation criteria) A. The fixing temperature is less than 180°C. B. The fixing temperature is 180°C or higher and lower than 190°C. C. The fixing temperature is 190°C or higher and lower than 200°C. D. The fixing temperature is 200°C or higher.

[0170] <Evaluation 2. Fog after double-sided durability test under high temperature and humidity environment> The printer body and the toner cartridge filled with 550g of evaluation toner were left in a high temperature and humidity environment (32.5°C, 85% RH) for 24 hours in order to control the temperature and humidity in the evaluation environment. After leaving it, a letter-size Xerox Vitality (LTR 75g / m) toner cartridge was also placed in the same high temperature and humidity environment. 2 ) was used, and a durability evaluation was conducted in which the printer was set to double-sided printing, with two double-sided sheets per job, and 30,000 sheets (60,000 images) of horizontal line images with a print rate of 1.0% and a margin of 5 mm were output. After that, the printer was switched to single-sided printing mode, and a piece of paper with a 5cm x 5cm sticky note attached to the center of the printing surface was placed in the cassette. The printer was then switched back to single-sided printing mode, and an all-white image was output as the 30,001st sheet (60,001st image) (All-white image 1). After removing the sticky note from the all-white image 1, a white light meter TC-6DX (manufactured by Tokyo Denshoku Co., Ltd.) was used to measure the reflectance (%) of the area where the sticky note was attached and the reflectance (%) of the area where the sticky note was not attached, and the difference between the two was calculated as the fog (%). Evaluation was then performed according to the following criteria.

[0171] (Evaluation criteria) A. The fog after durability evaluation is less than 0.5 B. The fog after the durability test is 0.5 or more and less than 1.0 C. After durability evaluation, the fog is 1.0 or more and less than 1.5. D. The fog after durability evaluation is 1.5 or more.

[0172] <Evaluation 3. Density uniformity and fading of solid images after exposure to high temperature and humidity> The printer body and the toner cartridge filled with 550g of evaluation toner were left in a high temperature and humidity environment (32.5°C, 85% RH) for 24 hours in order to control the temperature and humidity in the evaluation environment. After leaving it, a letter-size Xerox Vitality (LTR 75g / m) toner cartridge was also placed in the same high temperature and humidity environment. 2) was used, and a durability evaluation was conducted in which 5,000 sheets (10,000 images) were printed using the double-sided printing setting, with an all-white image on the first side and a solid image with a 5mm margin on the second side, with two double-sided sheets counted as one job.

[0173] Initially during the durability evaluation and after printing 5,000 sheets (10,000 images), the printer was left powered off for 72 hours. The printer was then powered on, switched to simplex printing mode, and one solid image was printed. The resulting solid image was measured at a total of 15 points using a portable spectrophotometer, the Exact Advance (X-Rite). The measurement points were the center row, the row 20 mm from the left edge, and the row 20 mm from the right edge. Image density was measured at five points, 50 mm apart, in the vertical direction from the leading edge to the trailing edge of the paper, for a total of 15 points. The density uniformity of the solid image was then determined by the difference between the maximum and minimum image density values. Further, the solid image was visually inspected for band-like areas of low density and evaluated according to the following criteria to determine the vertical density unevenness (fading).

[0174] (Evaluation criteria for density uniformity) A. The density difference of the solid image is less than 0.05 B. The density difference of the solid image is 0.05 or more and less than 0.10 C. The density difference of the solid image is 0.10 or more and less than 0.15 D. The density difference of the solid image is 0.15 or more.

[0175] (Fading evaluation criteria) A: No areas of low density are observed B: Slight areas of low density are observed C: Low density areas are visible D: Significant density difference is observed

[0176] <Evaluation 4. Charge amount and charge stability after exposure to high temperature and humidity> The printer body and the toner cartridge filled with 550g of evaluation toner were left in a high temperature and humidity environment (32.5°C, 85% RH) for 24 hours in order to control the temperature and humidity in the evaluation environment. After leaving it, a letter-size Xerox Vitality (LTR 75g / m) toner cartridge was also placed in the same high temperature and humidity environment. 2 A durability evaluation was carried out using a printer with double-sided printing settings, outputting 5,000 sheets (10,000 images) of double-sided images, with one job consisting of two sheets on each side, with an all-white image on the first side and a solid image with a 5mm margin on the second side. Charging stability was then evaluated.

[0177] Initially during the durability evaluation and after printing 5,000 sheets (10,000 images), the printer was left for 72 hours with the power turned off. The printer was then turned on, a solid image was printed, and the charge amount (μC / g) of the toner on the developer carrier in the toner cartridge was measured using a TB-200 blow-off powder charge amount measuring device (manufactured by Toshiba Chemical Corporation). This was used to evaluate the chargeability in a high-temperature, high-humidity environment. The larger the absolute value of the chargeability value, the higher the chargeability, and the smaller the difference in charge amount between the initial and endurance evaluations, the better the charge stability of the toner. The evaluation ranks for charge amount and charge stability were determined and evaluated as follows:

[0178] (Evaluation criteria for charge amount) A: Charge amount less than -30.0 μC / g B: Charge amount is -30.0 μC / g or more and less than -27.5 μC / g C: Charge amount is -27.5μC / g or more and less than -22.5μC / g D: Charge amount is -22.5μC / g or more

[0179] (Charging stability) The difference in charge amount between the initial state and the state after the durability evaluation was evaluated according to the following criteria. A: Less than -2.0 μC / g B: -2.0μC / g or more and less than -4.0μC / g C: -4.0μC / g or more and less than -6.0μC / g D: -6.0μC / g or more and less than -8.0μC / g [Table 8]

[0180] The present disclosure includes the following configurations. (Configuration 1) A toner having toner particles containing a binder resin and an external additive, The binder resin contains a polyester resin A, The content of the polyester resin A in the binder resin is W p (mass%), the W p is 50% by mass or more, the polyester resin A is a copolymer of a polycarboxylic acid and a polyol, the polycarboxylic acid includes isophthalic acid, In the polyester resin A, the ratio of the monomer unit U corresponding to the isophthalic acid to the total monomer units corresponding to the polycarboxylic acid is iso The content ratio of M IPA (mol%), the M IPA is 40 mol % or more, The external additive contains an inorganic fine powder, The toner is characterized in that the inorganic fine powder contains silica fine particles having aluminum hydroxide on the surface thereof. (Configuration 2) Said M IPA 2. The toner according to claim 1, wherein the amount of the hydroxyl group is 90 mol % or more. (Configuration 3) the polyol comprises an ethylene oxide adduct of bisphenol A and a propylene oxide adduct of bisphenol A; In the polyester resin A, the ratio of the monomer unit U corresponding to the ethylene oxide adduct of bisphenol A to the total monomer units corresponding to the polyol is EO and the monomer unit U corresponding to the propylene oxide adduct of bisphenol A PO 3. The toner according to claim 1, wherein the total content of the above is 90 mol % or more. (Configuration 4) the polyol comprises an ethylene oxide adduct of bisphenol A and a propylene oxide adduct of bisphenol A; In the polyester resin A, the ratio of the monomer unit U corresponding to the ethylene oxide adduct of bisphenol A to the total monomer units corresponding to the polyol is EO and the monomer unit U corresponding to the propylene oxide adduct of bisphenol A PO When the total content of the monomer units U is 100 parts by mole, EO 4. The toner according to any one of configurations 1 to 3, wherein the content ratio of is 15 to 40 parts by mole. (Configuration 5) The number average molecular weight of the tetrahydrofuran-soluble portion of the polyester resin A measured by gel permeation chromatography is M n and the weight average molecular weight is M w When this is the case, the M n is 3000 to 10000, and M w / M n 5. The toner according to any one of configurations 1 to 4, wherein the value of is 2.5 or more. (Configuration 6) 6. The toner according to any one of Configurations 1 to 5, wherein the binder resin further contains a crystalline polyester. (Configuration 7) 7. The toner according to any one of configurations 1 to 6, wherein the toner has an average circularity of 0.950 to 0.980. (Configuration 8) The number average particle size of the primary particles of the inorganic fine powder is 5 to 50 nm, 8. The toner according to any one of configurations 1 to 7, wherein the content of the inorganic fine powder is 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the toner particles. (Configuration 9) The ratio of the number of Al atoms to Si atoms (Al / Si) measured by X-ray photoelectron spectroscopy of the inorganic fine powder is defined as X1, and the ratio of Si atoms to Al atoms measured by X-ray fluorescence analysis of the inorganic fine powder is defined as X2. 9. The toner according to any one of configurations 1 to 8, wherein when the mass ratio of Al (Al / Si) is X2, X1 and X2 satisfy formula (1). 0.80≦X1 / X2≦2.00 (1) (Configuration 10) 10. The toner according to any one of configurations 1 to 9, wherein a coverage of aluminum element with respect to the inorganic fine powder obtained from an elemental mapping image of aluminum and silicon measured by STEM-EDS mapping of the inorganic fine powder is 40 to 90 area %. (Configuration 11) The coverage ratio W of the inorganic fine powder on the toner particle surface calculated from the STEM-EDS mapping image of the toner AS 11. The toner according to any one of configurations 1 to 10, wherein (area %) is 3.0 to 50.0 area %. (Configuration 12) The powder resistivity of the inorganic fine powder is 1.0 × 10 8 ~2.0×10 13 12. The toner according to any one of configurations 1 to 11, wherein the toner has a viscosity of Ω·cm. (Configuration 13) The coverage of the inorganic fine powder on the toner particle surface calculated from the STEM-EDS mapping image of the toner is W AS (area%), the W AS , said M IPA , and the W p 13. The toner according to any one of configurations 1 to 12, wherein the following formula (2) is satisfied: 0.030 ≦ W AS / (M IPA ×W p ) ≦ 1.390 (2)

Claims

1. A toner having toner particles containing a binder resin and an external additive, The binder resin contains a polyester resin A, The content of the polyester resin A in the binder resin is W ｐ (mass%), the W ｐ is 50% by mass or more, the polyester resin A is a copolymer of a polycarboxylic acid and a polyol, the polycarboxylic acid includes isophthalic acid, In the polyester resin A, the ratio of the monomer unit U corresponding to the isophthalic acid to the total monomer units corresponding to the polycarboxylic acid is ｉｓｏ The content ratio of M ＩＰＡ (mol %), the M ＩＰＡ is 40 mol % or more, The external additive contains an inorganic fine powder, The toner is characterized in that the inorganic fine powder contains silica fine particles having aluminum hydroxide on the surface thereof.

2. Said M ＩＰＡ 2. The toner according to claim 1, wherein the amount of the hydroxyl group is 90 mol % or more.

3. the polyol comprises an ethylene oxide adduct of bisphenol A and a propylene oxide adduct of bisphenol A; In the polyester resin A, the ratio of the monomer unit U corresponding to the ethylene oxide adduct of bisphenol A to the total monomer units corresponding to the polyol is ＥＯ and the content ratio of the monomer unit U corresponding to the propylene oxide adduct of bisphenol A. ＰＯ 2. The toner according to claim 1, wherein the total content of the above is 90 mol % or more.

4. the polyol comprises an ethylene oxide adduct of bisphenol A and a propylene oxide adduct of bisphenol A; In the polyester resin A, the ratio of the monomer unit U corresponding to the ethylene oxide adduct of bisphenol A to the total monomer units corresponding to the polyol is ＥＯ and the content ratio of the monomer unit U corresponding to the propylene oxide adduct of bisphenol A. ＰＯ When the total content of the monomer units U is 100 parts by mole, ＥＯ 2. The toner according to claim 1, wherein the content ratio of

5. The number average molecular weight of the tetrahydrofuran-soluble portion of the polyester resin A measured by gel permeation chromatography is M ｎ and the weight average molecular weight is M ｗ When this is the case, the M ｎ is 3000 to 10000, and M ｗ / M ｎ 2. The toner according to claim 1, wherein the value of

6. The toner according to claim 1 , wherein the binder resin further contains a crystalline polyester.

7. 2. The toner according to claim 1, wherein the toner has an average circularity of 0.950 to 0.

980.

8. the number average particle diameter of the primary particles of the inorganic fine powder is 5 to 50 nm; 2. The toner according to claim 1, wherein the content of said inorganic fine powder relative to 100 parts by mass of said toner particles is 0.1 to 5.0 parts by mass.

9. The ratio of the number of Al atoms to Si atoms (Al / Si) measured by X-ray photoelectron spectroscopy of the inorganic fine powder is expressed as X １ The mass ratio of Al to Si (Al / Si) measured by fluorescent X-ray analysis of the inorganic fine powder is defined as X ２ 2. The toner according to claim 1, wherein X1 and X2 satisfy formula (1). 0.80≦X １ / X ２ ≦2.00 (1)

10. 2. The toner according to claim 1, wherein a coverage of aluminum element with respect to the inorganic fine powder, obtained from an elemental mapping image of aluminum and silicon measured by STEM-EDS mapping of the inorganic fine powder, is 40 to 90 area %.

11. The coverage ratio W of the inorganic fine powder on the surface of the toner particles calculated from the STEM-EDS mapping image of the toner. ＡＳ 2. The toner according to claim 1, wherein (area %) is 3.0 to 50.0 area %.

12. The powder resistivity of the inorganic fine powder is 1.0×10 ８ ~2.0 x 10 １３ 2. The toner according to claim 1, wherein the toner has a viscosity of Ω·cm.

13. The coverage of the inorganic fine powder on the toner particle surface calculated from the STEM-EDS mapping image of the toner is W ＡＳ (area%), the W ＡＳ , said M ＩＰＡ , and the W ｐ The toner according to any one of claims 1 to 12, wherein the following formula (2) is satisfied: 0.030 ≦ W ＡＳ / (M ＩＰＡ ×W ｐ ) ≦ 1.390 (2)

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