Method for manufacturing toner for electrostatic image developing, and aqueous dispersion of resin composition particles used in the manufacture of electrostatic image developing toner.

Abstract

This invention relates to a method for producing a toner for electrostatic image development that has excellent durability, and to an aqueous dispersion of resin composition particles that can be suitably used in the method for producing the electrostatic image development toner. [Solution] A method for manufacturing toner for electrostatic image development, comprising the following steps 1 to 3. Step 1: Step to obtain an aqueous dispersion AE of resin composition particles containing amorphous polyester resin A and a hydroxyl group-containing amide compound having a specific structure. Step 2: Step to obtain an aqueous dispersion CE of resin particles containing crystalline polyester resin C. Step 3: A process to obtain toner particles by mixing the aqueous dispersion AE of resin composition particles and the aqueous dispersion CE of resin particles, and by agglomerating and fusing the resin composition particles and resin particles.

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing toner for electrostatic image developing, and to an aqueous dispersion of resin composition particles used in the manufacture of electrostatic image developing toner. [Background technology]

[0002] In the field of electrophotography, the development of electrophotographic systems has led to a demand for the development of electrophotographic toners that can handle higher image quality and higher speeds. To meet the demand for higher image quality and obtain a toner with a narrow particle size distribution, small particle size, and fast fixation that can handle high speeds, so-called chemical toners are manufactured using the emulsification agglomeration and fusion method (emulsification agglomeration method, agglomeration and fusion method, agglomeration and coalescence method), in which fine resin particles are agglomerated and fused in an aqueous medium to obtain toner.

[0003] For example, Patent Document 1 discloses an electrostatic image developing toner that can suppress paper adhesion while maintaining good low-temperature fixing and fold fixing properties even when printing images with a large amount of toner at high speed and continuous printing, and is characterized in that when the electrostatic image developing toner is measured by a differential calorimetry analyzer at a cooling rate of X°C / min, and the extrapolation crystallization termination temperature of the exothermic peak located on the lowest temperature side is denoted as Tce(X)[°C], the absolute value of the slope α of the approximate line obtained by the least squares method using at least five plots Tce(10), Tce(20), Tce(30), Tce(40), and Tce(50) is less than 0.20, and Tce(50)[°C] is 55°C or higher. Furthermore, Patent Document 2 discloses a toner that does not require filming and has excellent low-temperature fixing properties, high-temperature offset resistance, heat-resistant storage properties, and blocking resistance of the toner image after fixing, as well as a developer containing the toner, and is characterized in that it contains a crystalline polyester resin, an amorphous polyester resin, a crystal nucleating agent, a mold release agent, and a coloring agent, wherein the crystal nucleating agent is an aliphatic ester compound or aliphatic amide compound having a melting point of 60°C or more and less than 150°C, and the lowest exothermic peak temperature Tp [°C] in the range of 0 to 200°C in differential scanning calorimetry (DSC) of the crystalline polyester resin, the lowest exothermic peak temperature Tc [°C] in the range of 0 to 200°C in differential scanning calorimetry (DSC) of the crystal nucleating agent, and the lowest exothermic peak temperature Tm [°C] in the range of 0 to 200°C in differential scanning calorimetry (DSC) of the mixture of the crystalline polyester resin and the crystal nucleating agent satisfy a relationship expressed by a specific formula. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2021-76700 [Patent Document 2] Japanese Patent Publication No. 2012-168505 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] In conventional technology, using crystalline resins to improve low-temperature fixation in chemical toners tends to reduce the durability of the toner. The present invention relates to a method for producing a toner for electrostatic image development that has excellent durability, and to an aqueous dispersion of resin composition particles that can be suitably used in the method for producing the electrostatic image development toner. [Means for solving the problem]

[0006] The inventors have discovered that a durable electrostatic image developing toner can be obtained by mixing an aqueous dispersion of resin composition particles containing amorphous polyester resin and a hydroxyl group-containing amide compound having a specific structure with an aqueous dispersion of resin particles containing crystalline polyester resin, and then agglomerating and fusing the resin composition particles and the resin particles. In other words, the present invention relates to the following [1] and [2]. [1] A method for manufacturing toner for electrostatic image development, comprising the following steps 1 to 3. Step 1: Step to obtain an aqueous dispersion AE of resin composition particles containing amorphous polyester resin A and a hydroxyl group-containing amide compound. Step 2: Step to obtain an aqueous dispersion CE of resin particles containing crystalline polyester resin C. Step 3: A process to obtain toner particles by mixing the aqueous dispersion AE of resin composition particles and the aqueous dispersion CE of resin particles, and by agglomerating and fusing the resin composition particles and resin particles. The hydroxyl group-containing amide compound is a compound represented by any of the following formulas (I) to (IV). R 1 -CONH-X-NHCO-R 2 (I) (In the formula, R 1 and R 2 Each of these is independently a hydroxyalkyl group having 12 to 22 carbon atoms, and X is a divalent hydrocarbon group having 2 to 12 carbon atoms. R 3 -CONH-R 4 (II) (wherein R 3 is a hydroxyalkyl group having 12 to 22 carbon atoms, and R 4 is a hydroxyalkyl group having 2 to 22 carbon atoms) R 5 -CONH-R 6 (III) (wherein R 5 is an alkyl group having 12 to 22 carbon atoms, and R 6 is a hydroxyalkyl group having 2 to 22 carbon atoms) R 7 -CONH-R 8 (IV) (wherein R 7 is a hydroxyalkyl group having 12 to 22 carbon atoms, and R 8 is an alkyl group having 2 to 22 carbon atoms) 〔2〕 An aqueous dispersion of resin composition particles used for production of a toner for developing electrostatic latent images, wherein the resin composition particles contain an amorphous polyester resin A and a hydroxy group-containing amide compound, and the hydroxy group-containing amide compound is a compound represented by any one of the following formulas (I) to (IV): an aqueous dispersion of resin composition particles used for production of a toner for developing electrostatic latent images. R 1 -CONH-X-NHCO-R 2 (I) (wherein R 1 and R 2 are each independently a hydroxyalkyl group having 12 to 22 carbon atoms, and X is a divalent hydrocarbon group having 2 to 12 carbon atoms) R 3 -CONH-R 4 (II) (wherein R 3 is a hydroxyalkyl group having 12 to 22 carbon atoms, and R 4 is a hydroxyalkyl group having 2 to 22 carbon atoms) R 5 -CONH-R 6 (III) (In the formula, R 5 R is an alkyl group having 12 to 22 carbon atoms, 6 (It is a hydroxyalkyl group having 2 to 22 carbon atoms.) R 7 -CONH-R 8 (IV) (In the formula, R 7 R is a hydroxyalkyl group having 12 to 22 carbon atoms, 8 (This refers to an alkyl group having 2 to 22 carbon atoms.) [Effects of the Invention]

[0007] The present invention provides a method for manufacturing a toner for electrostatic image development that has excellent durability, and an aqueous dispersion of resin composition particles that can be suitably used in the method for manufacturing the electrostatic image development toner. [Modes for carrying out the invention]

[0008] [Manufacturing method for toner for electrostatic image development] The present invention's method for manufacturing toner for electrostatic image development (hereinafter also referred to as "toner manufacturing method") includes the following steps 1 to 3: Step 1: Step to obtain an aqueous dispersion AE of resin composition particles containing amorphous polyester resin A and a hydroxyl group-containing amide compound. Step 2: Step to obtain an aqueous dispersion CE of resin particles containing crystalline polyester resin C. Step 3: A process to obtain toner particles by mixing the aqueous dispersion AE of resin composition particles and the aqueous dispersion CE of resin particles, and by agglomerating and fusing the resin composition particles and resin particles. A hydroxyl group-containing amide compound is a compound represented by any of the following formulas (I) to (IV). R 1 -CONH-X-NHCO-R 2 (I) (In the formula, R 1 and R 2 Each of these is independently a hydroxyalkyl group having 12 to 22 carbon atoms, and X is a divalent hydrocarbon group having 2 to 12 carbon atoms. R3 -CONH-R 4 (II) (In the formula, R 3 R is a hydroxyalkyl group having 12 to 22 carbon atoms. 4 (This is a hydroxyalkyl group having 2 to 22 carbon atoms.) R 5 -CONH-R 6 (III) (In the formula, R 5 R is an alkyl group having 12 to 22 carbon atoms, 6 (It is a hydroxyalkyl group having 2 to 22 carbon atoms.) R 7 -CONH-R 8 (IV) (In the formula, R 7 R is a hydroxyalkyl group having 12 to 22 carbon atoms, 8 (This refers to an alkyl group having 2 to 22 carbon atoms.)

[0009] In the toner manufacturing method of the present invention, each component, such as amorphous polyester resin A or crystalline polyester resin C, may be used individually or in combination of two or more. Similarly, in the toner manufacturing method of the present invention, each raw material for components such as alcohol components and carboxylic acid components may be used individually or in combination of two or more. The toner obtained by the toner manufacturing method of the present invention contains toner particles. While the toner particles can be used as is, it is preferable to use toner that has been treated by adding a fluidizing agent or the like as an external additive to the surface of the toner particles.

[0010] The reason why the toner manufacturing method of the present invention yields a toner for electrostatic image development with excellent durability is not entirely clear, but it is presumed to be as follows. Note that the following reason is a presumption and is not limited to this. In toners obtained by the emulsification and coagulation fusion method, amorphous polyester resin is combined with crystalline polyester resin to improve the toner's low-temperature fixability. The low-temperature fixability of toner tends to improve further when crystalline polyester resin, which has a high affinity for amorphous polyester resin, is used. However, the higher the affinity of crystalline polyester resin for amorphous polyester resin, the more compatible the amorphous and crystalline polyester resins become in the toner. This compatibility leads to insufficient recrystallization of the crystalline polyester resin in the toner, resulting in the presence of soft, uncrystallized areas, which reduces the durability of the toner. Aliphatic amide compounds are known to act as crystal nucleating agents, and it is thought that adding them to toner promotes the recrystallization of crystalline polyester resins. However, in chemical toners obtained by emulsification and coagulation fusion, which does not involve a mechanical kneading process with respect to the resin, the aliphatic amide compounds are not sufficiently dispersed in the toner and do not act sufficiently as crystal nucleating agents on the crystalline polyester resin, resulting in no improvement in toner durability. In contrast, hydroxyl group-containing amide compounds, due to their hydroxyl group presence, have higher polarity than aliphatic amide compounds and can be uniformly dispersed in amorphous polyester resin. In the present invention, the hydroxyl group-containing amide compound can be pre-dispersed in amorphous polyester resin by incorporating it together with amorphous polyester resin into the resin composition particles in an aqueous dispersion of resin composition particles. Furthermore, after mixing resin composition particles containing amorphous polyester resin and hydroxyl group-containing amide compound with resin particles containing crystalline polyester resin as a dispersion, the hydroxyl group-containing amide compound can be uniformly dispersed in toner by agglomerating and fusing the resin composition particles and resin particles. As a result, in the toner manufacturing method of the present invention, the hydroxyl group-containing amide compound effectively acts as a crystal nucleating agent in the crystalline polyester resin, and it is believed that a toner with excellent durability can be obtained regardless of the compatibility between amorphous polyester resin and crystalline polyester resin.

[0011] The definitions of various terms used in this specification are shown below. Whether a resin is crystalline or amorphous is determined by its crystallinity index. The crystallinity index is defined as the ratio of the softening point of the resin to the maximum endothermic peak temperature (softening point (°C) / maximum endothermic peak temperature (°C)) in the measurement method described in the examples below. A crystalline resin is one in which the crystallinity index is 0.6 or higher and 1.4 or lower. An amorphous resin is one in which no endothermic peak is observed, or if observed, the crystallinity index is less than 0.6 or greater than 1.4. The crystallinity index can be appropriately adjusted depending on the type and ratio of raw material monomers, as well as manufacturing conditions such as reaction temperature, reaction time, and cooling rate. The carboxylic acid component of polyester resins includes not only the compound itself, but also anhydrides that decompose during the reaction to produce acid, and alkyl esters of each carboxylic acid (alkyl groups with 1 to 3 carbon atoms).

[0012] [Process 1] Step 1 is a step to obtain an aqueous dispersion AE of resin composition particles containing amorphous polyester resin A and a hydroxyl group-containing amide compound.

[0013] <Aqueous dispersion of resin composition particles (AE)> The aqueous dispersion of resin composition particles AE (hereinafter also referred to as "resin composition particle dispersion AE") contains amorphous polyester resin A and resin composition particles containing a hydroxyl group-containing amide compound, as well as an aqueous medium. The aqueous dispersion of resin composition particles AE can be used in the manufacture of toner for electrostatic image development.

[0014] (Amorphous polyester resin A) Amorphous polyester resin A (hereinafter also referred to as "resin A") is a polycondensate of an alcohol component and a carboxylic acid component.

[0015] Examples of the alcohol component of resin A include alkylene oxide adducts of aromatic diols, aliphatic diols, alicyclic diols, and polyhydric alcohols with a valency of 3 or higher. Among these, alkylene oxide adducts of aromatic diols, aliphatic diols, and polyhydric alcohols with a valency of 3 or higher are preferred, with alkylene oxide adducts of aromatic diols and aliphatic diols being more preferred.

[0016] The alkylene oxide adduct of an aromatic diol is preferably an alkylene oxide adduct of bisphenol A, and more preferably of formula (I):

[0017] [ka] (In the formula, OR 1 and R 2 O is an oxyalkylene group, R 1 and R 2 This is an alkylene oxide adduct of 2,2-bis(4-hydroxyphenyl)propane, where each is independently an ethylene group or a propylene group, x and y represent the average number of moles of alkylene oxide added, each being a positive number, and the sum of x and y is 1 or more, preferably 1.5 or more, 16 or less, preferably 8 or less, and more preferably 4 or less.

[0018] Examples of alkylene oxide adducts of bisphenol A represented by formula (I) include propylene oxide adducts of bisphenol A and ethylene oxide adducts of bisphenol A, with propylene oxide adducts of bisphenol A being preferred. When the alcohol component contains an alkylene oxide adduct of an aromatic diol, the content of the alkylene oxide adduct of the aromatic diol in the alcohol component is preferably 60 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, and 100 mol% or less, and preferably 100 mol%.

[0019] Examples of aliphatic diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 1,6-hexanediol, and 3-methyl-1,5-pentanediol. Among these, 1,2-propanediol and neopentyl glycol are preferred, and 1,2-propanediol is more preferred. When the alcohol component contains an aliphatic diol, the aliphatic diol content in the alcohol component is preferably 60 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, and 100 mol% or less, and preferably 100 mol%.

[0020] Examples of alicyclic diols include hydrogenated bisphenol A [2,2-bis(4-hydroxycyclohexyl)propane] and alkylene oxide adducts of hydrogenated bisphenol A with 2 to 4 carbon atoms (average number of added moles: 2 to 12).

[0021] Examples of polyhydric alcohols with a valency of 3 or higher include glycerin, pentaerythritol, and trimethylolpropane.

[0022] Examples of carboxylic acid components in resin A include dicarboxylic acids and polycarboxylic acids with a valency of three or more.

[0023] Examples of dicarboxylic acids include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids. Among these, aromatic dicarboxylic acids and aliphatic dicarboxylic acids are preferred.

[0024] Examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid, and terephthalic acid. Among these, terephthalic acid is preferred. The amount of aromatic dicarboxylic acid is preferably 60 mol% or more, more preferably 70 mol% or more, even more preferably 75 mol% or more, and preferably 98 mol% or less, more preferably 95 mol% or less, and even more preferably 90 mol% or less, in the carboxylic acid component.

[0025] The number of carbon atoms in the aliphatic dicarboxylic acid is preferably 2 or more, more preferably 3 or more, and preferably 30 or less, more preferably 20 or less. Examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanediic acid, and succinic acid substituted with hydrocarbon groups. Examples of succinic acid substituted with hydrocarbon groups include dodecyl succinic acid, dodecenyl succinic acid, and octenyl succinic acid. Among these, sebacic acid and dodecenyl succinic acid are preferred. When the carboxylic acid component includes an aliphatic dicarboxylic acid, the amount of aliphatic dicarboxylic acid in the carboxylic acid component is preferably 2 mol% or more, more preferably 5 mol% or more, even more preferably 8 mol% or more, and preferably 30 mol% or less, more preferably 25 mol% or less, and even more preferably 20 mol% or less.

[0026] An example of an alicyclic dicarboxylic acid is cyclohexanedicarboxylic acid.

[0027] The preferred polycarboxylic acid with a valency of 3 or higher is a trivalent carboxylic acid, such as trimellitic acid or pyromellitic acid. Of these, trimellitic acid is preferred. When the carboxylic acid component contains a polycarboxylic acid of trivalent or higher, the amount of aliphatic dicarboxylic acid in the carboxylic acid component is preferably 1 mol% or more, more preferably 4 mol% or more, even more preferably 7 mol% or more, and preferably 35 mol% or less, more preferably 20 mol% or less, and even more preferably 15 mol% or less.

[0028] The equivalent ratio [COOH group / OH group] of the carboxyl group of the carboxylic acid component to the hydroxyl group of the alcohol component is preferably 0.7 or higher, more preferably 0.8 or higher, and preferably 1.3 or lower, more preferably 1.2 or lower.

[0029] ≪Method for producing amorphous polyester resin A≫ Resin A can be produced, for example, by polycondensation of raw material monomers containing an alcohol component and a carboxylic acid component. The polycondensation of the alcohol component and the carboxylic acid component can be carried out, for example, in an inert gas atmosphere, at a temperature of approximately 120°C to 250°C, in the presence of an esterification catalyst, esterification co-catalyst, polymerization inhibitor, etc., as needed. Examples of esterification catalysts include tin compounds such as dibutyltin oxide and tin(II) di(2-ethylhexanoate), and titanium compounds such as titanium diisopropoxybis(triethanolamine). Examples of esterification co-catalysts that can be used together with the esterification catalyst include gallic acid (3,4,5-trihydroxybenzoic acid). The amount of esterification catalyst used is preferably 0.01 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the total amount of the alcohol component and carboxylic acid component, which are raw material monomers of resin A. The amount of esterification co-catalyst used is preferably 0.001 parts by mass or more and 1 part by mass or less, per 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Furthermore, examples of polymerization inhibitors include radical polymerization inhibitors such as 4-tert-butylcatechol. When a polymerization inhibitor is used, the amount of polymerization inhibitor used is preferably 0.001 parts by mass or more and 1 part by mass or less per 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component.

[0030] ≪Physical properties of amorphous polyester resin A≫ The softening point of resin A is preferably 90°C or higher, more preferably 95°C or higher, and even more preferably 100°C or higher, from the viewpoint of the heat-resistant storage properties of the toner, and preferably 145°C or lower, more preferably 130°C or lower, even more preferably 120°C or lower, and even more preferably 115°C or lower, from the viewpoint of the low-temperature fixing properties of the toner.

[0031] The glass transition temperature of resin A is preferably 40°C or higher, more preferably 45°C or higher, and even more preferably 50°C or higher, from the viewpoint of heat-resistant storage of the toner, and preferably 80°C or lower, more preferably 75°C or lower, and even more preferably 70°C or lower, from the viewpoint of low-temperature fixing properties of the toner.

[0032] The acid value of resin A is preferably 4 mg KOH / g or more, more preferably 8 mg KOH / g or more, and more preferably 30 mg KOH / g or less, more preferably 25 mg KOH / g or less, and even more preferably 20 mg KOH / g or less.

[0033] The softening point, glass transition temperature, and acid value of resin A can be appropriately adjusted depending on the type and amount of raw material monomer used, as well as manufacturing conditions such as reaction temperature, reaction time, and cooling rate. These values ​​can be determined by the method described in the examples. Furthermore, when using two or more types of resin A in combination, it is preferable that the softening point, glass transition temperature, and acid value obtained from the mixture thereof are all within the above ranges.

[0034] (Hydroxy group-containing amide compounds) A hydroxyl group-containing amide compound (hereinafter also referred to as "amide compound") is a compound represented by any of the following formulas (I) to (IV). From the viewpoint of toner durability, a compound represented by any of the formulas (I) to (III) is preferred, a compound represented by formula (I) or (II) is more preferred, and a compound represented by formula (II) is even more preferred.

[0035] R 1 -CONH-X-NHCO-R 2 (I) In formula (I), R 1 and R 2 Each of these is independently a hydroxyalkyl group having 12 to 22 carbon atoms, and X is a divalent hydrocarbon group having 2 to 12 carbon atoms. R 1 and R 2 The number of carbon atoms in the hydroxyalkyl group having 12 to 22 carbon atoms, represented by , is preferably 13 or more, more preferably 15 or more, and preferably 21 or less, more preferably 19 or less. Examples of divalent hydrocarbon groups represented by X, having 2 to 12 carbon atoms, include divalent aliphatic hydrocarbon groups and divalent aromatic hydrocarbon groups. The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less. Examples of aliphatic hydrocarbon groups include alkylene groups. Alkylene groups may be linear or branched, with linear being preferred. Specific examples of alkylene groups include ethylene groups, propylene groups, and hexamethylene groups. The number of carbon atoms in the divalent aromatic hydrocarbon group is preferably 6 or more, and preferably 10 or less. Specific examples of divalent aromatic hydrocarbon groups include phenylene groups and naphthylene groups, with phenylene groups being preferred. The divalent aromatic hydrocarbon group may have substituents such as alkyl groups, and the number of carbon atoms in the alkyl group is, for example, 1 to 3. An example of a substituted divalent aromatic hydrocarbon group is the xylylene group. Specific examples of compounds represented by formula (I) include N,N'-ethylenebis(12-hydroxystearamide), N,N'-hexamethylenebis(12-hydroxystearamide), and N,N'-xylylenebis(12-hydroxystearamide).

[0036] R 3 -CONH-R 4 (II) In formula (II), R 3 R is a hydroxyalkyl group having 12 to 22 carbon atoms. 4 This is a hydroxyalkyl group having 2 to 22 carbon atoms. R3 The number of carbon atoms in the hydroxyalkyl group having 12 to 22 carbon atoms, represented by , is preferably 13 or more, more preferably 15 or more, and preferably 21 or less, more preferably 19 or less. R 4 The number of carbon atoms in the hydroxyalkyl group having 2 to 22 carbon atoms, represented by , is preferably 19 or less, more preferably 14 or less, even more preferably 9 or less, and even more preferably 4 or less. Specific examples of hydroxyl group-containing amide compounds represented by formula (II) include N-(2-hydroxyethyl)12-hydroxystearamide and N-(3-hydroxypropyl)12-hydroxystearamide.

[0037] R 5 -CONH-R 6 (III) In formula (III), R 5 R is an alkyl group having 12 to 22 carbon atoms, 6 It is a hydroxyalkyl group having 2 to 22 carbon atoms. R 5 The number of carbon atoms in the alkyl group having 12 to 22 carbon atoms, represented by , is preferably 13 or more, more preferably 15 or more, and preferably 21 or less, more preferably 19 or less. R 6 The number of carbon atoms in the hydroxyalkyl group having 2 to 22 carbon atoms, represented by , is preferably 14 or less, more preferably 9 or less, and even more preferably 4 or less. Specific examples of compounds represented by formula (III) include N-(2-hydroxyethyl)stearamide, N-(2-hydroxyethyl)oleamide, and N-(2-hydroxyethyl)palmitamide.

[0038] R 7 -CONH-R 8 (IV) In formula (IV), R 7 R is a hydroxyalkyl group having 12 to 22 carbon atoms, 8 This is an alkyl group having 2 to 22 carbon atoms. R 7 The number of carbon atoms in the hydroxyalkyl group having 12 to 22 carbon atoms, represented by , is preferably 13 or more, more preferably 15 or more, and preferably 21 or less, more preferably 19 or less. R 8 The number of carbon atoms in the alkyl group having 2 to 22 carbon atoms, represented by , is preferably 7 or more, more preferably 13 or more, even more preferably 15 or more, and preferably 19 or less. Specific examples of compounds represented by formula (IV) include N-stearyl (12-hydroxystearate amide).

[0039] The alkyl group in the amide compound may be linear or branched, but linear is preferred.

[0040] From the viewpoint of toner durability, the melting point of the amide compound is preferably 150°C or lower, more preferably 145°C or lower, even more preferably 130°C or lower, even more preferably 120°C or lower, and preferably 90°C or higher, more preferably 95°C or higher, and even more preferably 100°C or higher.

[0041] In the resin composition particle dispersion AE, the total content of resin A and amide compound in the resin composition particles is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 98% by mass or more, and 100% by mass or less, preferably 100% by mass, from the viewpoint of toner durability.

[0042] In resin composition particles containing resin A and an amide compound, the content of the amide compound is preferably 0.2 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 0.9 parts by mass or more, even more preferably 1.3 parts by mass or more, even more preferably 1.7 parts by mass or more, and preferably 5.0 parts by mass or less, more preferably 4.0 parts by mass or less, even more preferably 3.5 parts by mass or less, and even more preferably 3.0 parts by mass or less, from the viewpoint of toner durability.

[0043] From the viewpoint of toner durability, the content of amide compounds in toner particles is preferably 0.1 parts by mass or more, more preferably 0.4 parts by mass or more, even more preferably 0.7 parts by mass or more, and preferably 3.0 parts by mass or less, more preferably 2.5 parts by mass or less, and even more preferably 2.0 parts by mass or less, per 100 parts by mass of the resin component (for example, the total of resin A, amorphous polyester resin A', and crystalline polyester resin C).

[0044] (aqueous medium) The aqueous medium is a medium whose main component is water, and the water content in the aqueous medium is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and 100% by mass or less. Deionized water or distilled water is preferred as the water. Other components that can form an aqueous medium together with water include alkyl alcohols having 1 to 5 carbon atoms; dialkyl ketones having 3 to 5 carbon atoms such as acetone and methyl ethyl ketone; and organic solvents that dissolve in water, such as cyclic ethers such as tetrahydrofuran.

[0045] The dispersion of resin composition particles containing resin A and amide compounds in an aqueous medium can be carried out by known methods, but dispersion by phase inversion emulsification is preferred. As a phase inversion emulsification method, a method of adding an aqueous medium to an organic solvent solution of resin A and amide compounds and then performing phase inversion emulsification is preferred. Step 1 is preferably a step (Step 1b) in which resin A and amide compound are dissolved in the same organic solvent, and an aqueous medium is added to perform phase inversion emulsification to obtain an aqueous dispersion AE of resin composition particles. The organic solvent used for phase inversion emulsification is not particularly limited as long as it dissolves resin A and amide compound and is water-soluble, but an organic solvent that dissolves both resin A and amide compound is an example, methyl ethyl ketone.

[0046] In step 1, the organic solvent solution may be prepared by mixing resin A, the amide compound, and the organic solvent, or the organic solvent solution may be prepared by mixing the resin composition obtained by mixing resin A and the amide compound with the organic solvent. The former is preferred from the viewpoint of suppressing a decrease in the effect of the amide compound as a crystal nucleating agent, while the latter is preferred from the viewpoint of ease of raw material storage. When obtaining the resin composition, the temperature at which resin A and the amide compound are mixed is, for example, 130°C to 180°C. Furthermore, the preferred ranges for the softening point, glass transition temperature, and acid value of the resin composition obtained by mixing resin A and the amide compound are the same as the preferred ranges for the softening point, glass transition temperature, and acid value of resin A, respectively, and these values ​​can be determined by the method described in the examples.

[0047] A neutralizing agent may be added to the organic solvent solution. Examples of neutralizing agents include basic substances. Examples of basic substances include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; and nitrogen-containing basic substances such as ammonia, trimethylamine, and diethanolamine. Among these, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are preferred. The degree of neutralization of the resin constituting the resin composition particles is preferably 50 mol% or more, more preferably 55 mol% or more, even more preferably 60 mol% or more, and preferably 80 mol% or less, more preferably 75 mol% or less, and even more preferably 70 mol% or less. The degree of neutralization of the resin constituting the resin composition particles can be determined by the following formula. Degree of neutralization (mol%) = [{Mass of neutralizing agent added (g) / Equivalent amount of neutralizing agent} / [{Weighted average acid value of the resin constituting the resin composition particles (mgKOH / g) × Mass of the resin constituting the resin composition particles (g)} / (56 × 1000)] × 100

[0048] While stirring the organic solvent solution, gradually add the aqueous medium to induce phase inversion. The temperature at which resin A and the amide compound are dissolved in the organic solvent, and the temperature of the organic solvent solution when the aqueous medium is added, is preferably above the glass transition temperature of the resin and below the melting point of the amide compound, more preferably 80°C or lower, even more preferably 75°C or lower, and even more preferably 70°C or lower.

[0049] After phase inversion emulsification, the organic solvent may be removed from the resulting dispersion by distillation or other means, if necessary. Alternatively, the resin composition particles may be isolated by filtration or other means. It is preferable to use an aqueous dispersion of the resin composition particles obtained by removing the organic solvent from the dispersion after phase inversion emulsification. In this case, the amount of residual organic solvent in the dispersion is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably substantially 0% by mass.

[0050] Volume-intermediate particle size D of resin composition particles containing resin A and amide compound 50 The particle size is preferably 0.01 μm or more, more preferably 0.03 μm or more, even more preferably 0.05 μm or more, and preferably 0.8 μm or less, more preferably 0.5 μm or less, and even more preferably 0.2 μm or less. Volume-intermediate particle size D of resin composition particles containing resin A and amide compound 50 It is measured by the method described in the examples.

[0051] The solid content concentration of the resin composition particle dispersion AE is preferably 15% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, and preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less. Note that the solid content represents the total amount of non-volatile components.

[0052] [Process 1A'] The toner manufacturing method of the present invention may include a step of obtaining an aqueous dispersion AE' of resin particles containing amorphous polyester resin A'.

[0053] <Aqueous dispersion of resin particles AE'> The aqueous dispersion of resin particles AE' (hereinafter also referred to as "resin particle dispersion AE'") contains resin particles containing amorphous polyester resin A' and an aqueous medium. The resin particle dispersion AE' does not contain amide compounds.

[0054] (Amorphous polyester resin A') Amorphous polyester resin A' (hereinafter also referred to as "resin A'") is a polycondensate of an alcohol component and a carboxylic acid component, and can be produced in the same manner as resin A, for example, using the alcohol component and carboxylic acid component of resin A.

[0055] ≪Physical properties of amorphous polyester resin A'≫ From the viewpoint of low-temperature fixability and fixation width, resin A' is preferably an amorphous polyester resin with a different softening point from resin A. Furthermore, while it is not a problem if either resin A or resin A' has a higher softening point, it is preferable that resin A' has a higher softening point. The difference (absolute value) between the softening points of resin A' and resin A is preferably 10°C or more, preferably 40°C or less, more preferably 30°C or less, and even more preferably 25°C or less. The softening point of resin A' is preferably 90°C or higher, more preferably 100°C or higher, and even more preferably 120°C or higher, from the viewpoint of toner durability, and preferably 145°C or lower, more preferably 135°C or lower, and even more preferably 130°C or lower, from the viewpoint of toner low-temperature fixation.

[0056] The glass transition temperature of resin A' is preferably 35°C or higher, more preferably 40°C or higher, and even more preferably 45°C or higher, and from the viewpoint of low-temperature fixing properties of the toner, it is preferably 70°C or lower, more preferably 65°C or lower, and even more preferably 60°C or lower.

[0057] The acid value of resin A' is preferably 5 mg KOH / g or more, more preferably 10 mg KOH / g or more, and preferably 35 mg KOH / g or less, more preferably 30 mg KOH / g or less, and even more preferably 25 mg KOH / g or less.

[0058] The softening point, glass transition temperature, and acid value of resin A' can be appropriately adjusted depending on the type and amount of raw material monomer used, as well as manufacturing conditions such as reaction temperature, reaction time, and cooling rate. These values ​​can be determined by the method described in the examples. Furthermore, when using two or more types of resin A' in combination, it is preferable that at least one of them falls within the range of the above physical properties. It is even more preferable that the softening point, glass transition temperature, and acid value obtained as a mixture thereof are each within the above range.

[0059] In step 1A', the volume median particle size D of the resin particles 50 The preferred range is the volume median particle size D of the resin composition particles contained in the resin composition particle dispersion AE. 50 This is the same as the preferred range.

[0060] From the viewpoint of toner durability, the content of resin A' in the resin particles contained in the resin particle dispersion AE' is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 98% by mass or more, and 100% by mass or less, preferably 100% by mass.

[0061] When the toner manufacturing method of the present invention includes step 1A', the mass ratio [resin A' / resin A] of resin A' in the resin particle dispersion AE' to resin A in the resin composition particle dispersion AE is preferably 35 / 65 or more, more preferably 40 / 60 or more, even more preferably 45 / 55 or more, and preferably 65 / 35 or less, more preferably 60 / 40 or less, and even more preferably 55 / 45 or less.

[0062] The total content of resin A and resin A' in the toner particles is preferably 65% ​​by mass or more, more preferably 70% by mass or more, even more preferably 75% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less, from the viewpoint of toner durability.

[0063] The resin particle dispersion AE' can be obtained in the same manner as in step 1, except that resin A' is used instead of resin A and the amide compound.

[0064] [Process 2] Step 2 is a step to obtain an aqueous dispersion CE of resin particles containing crystalline polyester resin C.

[0065] <Aqueous dispersion of resin particles CE> The aqueous dispersion of resin particles CE (hereinafter also referred to as "resin particle dispersion CE") contains resin particles containing crystalline polyester resin C and an aqueous medium.

[0066] (Crystalline polyester resin C) Crystalline polyester resin C (hereinafter also referred to as "resin C") is a polycondensate of an alcohol component and a carboxylic acid component.

[0067] As the alcohol component, α,ω-aliphatic diols are preferred. The number of carbon atoms in the α,ω-aliphatic diol is preferably 2 or more, preferably 16 or less, more preferably 14 or less, even more preferably 12 or less, and still more preferably 10 or less. Examples of α,ω-aliphatic diols include ethylene glycol, 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, and 1,14-tetradecanediol. Among these, ethylene glycol and 1,9-nonanediol are preferred.

[0068] The amount of α,ω-aliphatic diol is preferably 80 mol% or more, more preferably 85 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, and 100 mol% or less, and preferably 100 mol%, in the alcohol component.

[0069] The alcohol component may contain other alcohol components different from α,ω-aliphatic diols. Other alcohol components include, for example, aliphatic monoalcohols such as stearyl alcohol and behenyl alcohol; alkylene oxide adducts of aromatic diols such as alkylene oxide adducts of bisphenol A; and trivalent or higher alcohols such as glycerin, pentaerythritol, and trimethylolpropane.

[0070] As the carboxylic acid component, α,ω-aliphatic dicarboxylic acids are preferred. The number of carbon atoms in the α,ω-aliphatic dicarboxylic acid is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, even more preferably 10 or more, and preferably 16 or less, more preferably 14 or less, and even more preferably 12 or less. Specific examples of aliphatic dicarboxylic acids include succinic acid, fumaric acid, maleic acid, adipic acid, sebacic acid, 1,11-undecanediic acid, 1,12-dodecanediic acid, and 1,14-tetradecanediic acid. Among these, sebacic acid and 1,12-dodecanediic acid are preferred.

[0071] The amount of aliphatic dicarboxylic acid is preferably 80 mol% or more, more preferably 85 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, and 100 mol% or less, and preferably 100 mol%, in the carboxylic acid component.

[0072] The carboxylic acid component may contain other carboxylic acid components other than aliphatic dicarboxylic acids. Examples of other carboxylic acid components include monocarboxylic acids such as stearic acid; aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid; and polycarboxylic acids with a valency of three or more, such as trimellitic acid.

[0073] The equivalent ratio [COOH group / OH group] of the carboxyl group of the carboxylic acid component to the hydroxyl group of the alcohol component is preferably 0.7 or higher, more preferably 0.8 or higher, and preferably 1.3 or lower, more preferably 1.2 or lower.

[0074] Resin C can be manufactured, for example, in the same manner as resin A.

[0075] ≪Physical properties of crystalline polyester resin C≫ The softening point of resin C is preferably 55°C or higher, more preferably 60°C or higher, and even more preferably 65°C or higher. Furthermore, from the viewpoint of further improving low-temperature fixability, it is preferably 125°C or lower, more preferably 115°C or lower, and even more preferably 105°C or lower.

[0076] The melting point of resin C is preferably 55°C or higher, more preferably 60°C or higher, and even more preferably 65°C or higher. Furthermore, from the viewpoint of further improving low-temperature fixability, it is preferably 120°C or lower, more preferably 110°C or lower, and even more preferably 100°C or lower.

[0077] The acid value of resin C is preferably 5 mg KOH / g or more, more preferably 8 mg KOH / g or more, even more preferably 10 mg KOH / g or more, and preferably 40 mg KOH / g or less, more preferably 35 mg KOH / g or less, and even more preferably 30 mg KOH / g or less.

[0078] The softening point, melting point, and acid value of resin C can be appropriately adjusted depending on the type and amount of raw material monomer used, as well as manufacturing conditions such as reaction temperature, reaction time, and cooling rate. The softening point, melting point, and acid value can be determined by the method described in the examples. When two or more types of resin C are used in combination, it is preferable that the softening point, melting point, and acid value obtained from the mixture thereof are within the aforementioned ranges.

[0079] The content of resin C in the resin particles contained in the resin particle dispersion CE is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 98% by mass or more, and 100% by mass or less, and preferably 100% by mass, from the viewpoint of the low-temperature fixing properties of the toner.

[0080] In step 3, the ratio of the mass of resin C to the total mass of resin A and resin A' [resin C / (resin A + resin A')] mixed as a dispersion is preferably 1 / 99 or more, more preferably 3 / 97 or more, even more preferably 5 / 95 or more, and preferably 25 / 75 or less, more preferably 20 / 80 or less, and even more preferably 15 / 85 or less, from the viewpoint of the toner's low-temperature fixability.

[0081] From the viewpoint of the low-temperature fixability of the toner, the content of resin C in the toner particles is preferably 2% by mass or more, more preferably 4% by mass or more, even more preferably 6% by mass or more, and preferably 18% by mass or less, more preferably 15% by mass or less, and even more preferably 12% by mass or less.

[0082] In toner particles, the ratio of the mass of resin C to the total mass of resin A and resin A' [resin C / (resin A + resin A')] is preferably 1 / 99 or more, more preferably 3 / 97 or more, even more preferably 5 / 95 or more, and preferably 25 / 75 or less, more preferably 20 / 80 or less, and even more preferably 15 / 85 or less.

[0083] The resin particle dispersion CE can be obtained in the same manner as in step 1A'.

[0084] Furthermore, steps 1, 1A', and 2 may be performed before step 3, and there are no restrictions on the order in which steps 1, 1A', and 2 are performed.

[0085] [Step 3] Step 3 is a step of mixing the resin composition particle dispersion AE and the resin particle dispersion CE, and agglomerating and fusing the resin composition particles and resin particles to obtain toner particles. In other words, Step 3 includes a mixing and agglomeration step and a fusing step.

[0086] <Mixing / agglomeration process> In the mixing and agglomeration step, the resin composition particle dispersion AE, the resin particle dispersion CE, and optionally the resin particle dispersion AE' are mixed, and then the resin composition particles and resin particles are agglomerated to obtain agglomerated particles 1. In addition to the resin composition particles and resin particles, it is preferable to further agglomerate at least one of a colorant and a release agent, and it is preferable to mix the resin particle dispersions AE and CE, the colorant particle dispersion, and the release agent particle dispersion, and agglomerate these particles to obtain agglomerated particles 1.

[0087] <Coloring agent> As a coloring agent, all dyes, pigments, etc. used as coloring agents for toners can be used. Examples of colorants include carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine-B base, solvent red 49, solvent red 146, solvent blue 35, quinacridone, carmine 6B, and disazo yellow. The toner may be either black toner or a color toner other than black. The colorant content in the toner particles is preferably 0.05% by mass or more, more preferably 1% by mass or more, from the viewpoint of toner image density, and preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, from the viewpoint of toner charge stability.

[0088] (Method for producing a dispersion of coloring agent particles) The colorant particle dispersion is preferably obtained by dispersing the colorant and an aqueous medium using a disperser such as a homomixer, homogenizer, or ultrasonic disperser. From the viewpoint of improving the dispersion stability of the colorant, this dispersion is preferably carried out in the presence of a surfactant. Examples of surfactants include nonionic surfactants, anionic surfactants, and cationic surfactants. Furthermore, the dispersion of colorant particles may be carried out in the presence of addition polymer E, from the viewpoint of improving the dispersion stability of the colorant particles. For a colorant particle dispersion using addition polymer E, refer to the addition polymer E described in Japanese Patent Application Publication No. 2024-25642.

[0089] From the viewpoint of improving the dispersion stability of the colorant particles, the surfactant content in the colorant particle dispersion is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, and preferably 35 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 250 parts by mass or less, per 100 parts by mass of colorant.

[0090] From the viewpoint of improving toner productivity, the colorant content in the colorant particle dispersion is preferably 5% by mass or more, more preferably 10% by mass or more, and from the viewpoint of improving the dispersion stability of the colorant particles, it is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less. From the viewpoint of improving toner productivity, the solid content concentration of the colorant particle dispersion is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. From the viewpoint of improving the dispersion stability of the colorant particles, it is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.

[0091] Volume-intermediate particle size D of colorant particles 50 From the viewpoint of the dispersibility of the colorant in the toner particles, the wavelength is preferably 50 nm or more, more preferably 80 nm or more, and preferably 400 nm or less, more preferably 300 nm or less, and even more preferably 200 nm or less. Volume-intermediate particle size D of colorant particles 50 This is measured by the method of the example.

[0092] The amount of colorant particles added in the mixing and aggregation process is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more, per 100 parts by mass of the total of the resin composition particles and resin particles, from the viewpoint of improving the image quality of the toner, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, from the viewpoint of the low-temperature fixability of the toner.

[0093] <Release agent> Examples of release agents include hydrocarbon waxes or oxides thereof such as polypropylene wax, polyethylene wax, ethylene propylene copolymer wax, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; ester waxes such as carnauba wax, montane wax or their deoxidizing waxes, and fatty acid ester waxes; and fatty acids, higher alcohols, and fatty acid metal salts.

[0094] The melting point of the release agent is preferably 60°C or higher, more preferably 70°C or higher, from the viewpoint of the storage stability of the toner, and preferably 160°C or lower, more preferably 140°C or lower, even more preferably 120°C or lower, and even more preferably 100°C or lower, from the viewpoint of the low-temperature fixability of the toner.

[0095] The content of the release agent in the toner particles is preferably 0.05% by mass or more, more preferably 1% by mass or more, from the viewpoint of the release properties of the toner, and preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, from the viewpoint of the electrostatic stability of the toner.

[0096] (Method for manufacturing a release agent particle dispersion) Release agent particle dispersions can also be obtained by mixing a release agent and resin particles. By preparing release agent particles using a release agent and resin particles, the resin constituting the resin particles stabilizes the release agent particles, making it possible to disperse the release agent in an aqueous medium without using a surfactant. In a release agent particle dispersion, it is thought that the release agent particles have a structure in which many resin particles adhere to the surface. Furthermore, release agent particle dispersions can also be obtained using a surfactant. The resin constituting the resin particles that disperse the mold release agent may be a polyester resin, or a composite resin D having a polyester resin segment and an addition polymerization resin segment may be used. For details on the mold release agent particle dispersion and composite resin D, please refer to Japanese Patent Application Publication No. 2024-25642. Alternatively, the aforementioned resin A may be used.

[0097] Release agent particle volume median particle size D 50 From the viewpoint of obtaining uniform toner particles through aggregation, the wavelength is preferably 300 nm or more, more preferably 350 nm or more, even more preferably 400 nm or more, and preferably 600 nm or less, more preferably 550 nm or less, and even more preferably 500 nm or less. Release agent particle volume median particle size D 50 It is measured by the method described in the examples.

[0098] The amount of release agent particles added in the mixing and agglomeration process is preferably 1 part by mass or more, more preferably 2 parts by mass or more, per 100 parts by mass of the total of the resin composition particles and resin particles, from the viewpoint of toner release properties, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, from the viewpoint of toner electrostatic stability.

[0099] The aggregated particles 1 may also contain other additives such as charge control agents, magnetic powders, flowability enhancers, conductivity modifiers, reinforcing fillers such as fibrous materials, antioxidants, anti-aging agents, and cleaning properties enhancers.

[0100] - Surfactants - In the mixing and coagulation process, when mixing the dispersions of each particle to prepare a mixed dispersion, the process may be carried out in the presence of a surfactant to improve the dispersion stability of each particle. Examples of surfactants include anionic surfactants such as alkylbenzene sulfonates, alkyl ether sulfates, and polyoxyalkylene alkyl ether sulfates; and nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkenyl ethers. When a surfactant is used, the total amount used is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, even more preferably 0.5 parts by mass or more, and preferably 10 parts by mass or less, and more preferably 5 parts by mass or less, based on 100 parts by mass of the total amount of resin composition particles and resin particles.

[0101] Methods for stopping aggregation include cooling the dispersion, adding an aggregation inhibitor, and diluting the dispersion. From the viewpoint of reliably preventing unnecessary aggregation, adding an aggregation inhibitor to stop aggregation is preferred. Furthermore, if the process involves agglomerating shell resin particles for the purpose of manufacturing toner having a core-shell structure, the aggregation process may be carried out without stopping the aggregation, once the aggregated particles 1 have grown to an appropriate particle size. Volume-intermediate particle size D of aggregated particle 1 50 The particle size is preferably 2 μm or more, more preferably 3 μm or more, even more preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, and even more preferably 7 μm or less. Volume-intermediate particle size D of aggregated particles 50 It is measured by the method described in the examples. In the present invention, the process may include a step of using the obtained aggregated particle 1 as a core, attaching and agglomerating shell resin particles to it, and obtaining aggregated particle 2. By including a step of agglomerating the shell resin particles, toner particles having a core-shell structure can be obtained. The resin particles for the shell are preferably amorphous resins, and more preferably amorphous polyester resin A as described above. The resin particle dispersion for the shell is obtained in the same manner as the resin composition particle dispersion AE described above. The mass ratio of shell resin particles to the mass of aggregated particles 1 [shell resin particles / aggregated particles 1] is preferably 1 / 99 or more, more preferably 3 / 97 or more, even more preferably 5 / 95 or more, and preferably 20 / 80 or less, more preferably 15 / 85 or less, and even more preferably 10 / 90 or less, from the viewpoint of toner's low-temperature fixation. If the toner manufacturing method includes a step of agglomerating resin particles for the shell, it is preferable to stop the agglomeration in this step when the agglomerated particles 2 have grown to a size appropriate for toner particles, and it is preferable to stop the agglomeration by adding an agglomeration inhibitor.

[0102] -Agglutination inhibitor- As the flocculation inhibitor, surfactants are preferred, and anionic surfactants are more preferred. Examples of anionic surfactants include alkylbenzene sulfonates, alkyl sulfates, alkyl ether sulfates, and polyoxyalkylene alkyl ether sulfates. One or more of these may be used. The flocculation inhibitor may be added in aqueous solution. The amount of flocculation inhibitor added is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and preferably 15 parts by mass or less, and more preferably 10 parts by mass or less, per 100 parts by mass of flocculated particles immediately before adding the flocculation inhibitor.

[0103] [Fusing process] In the fusion process, the aggregated particles obtained in the aggregation process are fused together in an aqueous medium. Fusion bonding is used to fuse the individual particles contained within the aggregated particles, thereby obtaining fused particles. In the fusion process, from the viewpoint of improving the fusion properties of the aggregated particles and improving the productivity of the toner, it is preferable to maintain the aggregated particles at a temperature above the glass transition temperature of the amorphous resin with the highest glass transition temperature among those contained in the aggregated particles. The holding temperature when fusing the aggregated particles is preferably 5°C or higher, more preferably 10°C or higher, than the glass transition temperature of the resin having the highest glass transition temperature among the amorphous resins contained in the aggregated particles, and more preferably 30°C or lower, more preferably 25°C or lower, and even more preferably 20°C or lower, than the glass transition temperature of the resin having the highest glass transition temperature among the amorphous resins. In this case, the time for holding the amorphous resin at a temperature above its glass transition temperature is preferably 1 minute or more, more preferably 10 minutes or more, even more preferably 30 minutes or more, and preferably 240 minutes or less, more preferably 180 minutes or less, even more preferably 120 minutes or less, and even more preferably 90 minutes or less, from the viewpoint of improving toner productivity. Furthermore, it is preferable to maintain the temperature mentioned above until the desired degree of circularity is achieved.

[0104] Volume median particle size D of fused particles obtained by fusion 50 The particle size is preferably 2 μm or more, more preferably 3 μm or more, even more preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, and even more preferably 7 μm or less.

[0105] The circularity of the fused particles obtained by fusion is preferably 0.955 or higher, more preferably 0.960 or higher, and more preferably 0.990 or lower, more preferably 0.985 or lower, and even more preferably 0.980 or lower. It is preferable to terminate the fusion process after achieving the desired degree of circularity described above. The roundness is measured by the method described in the examples.

[0106] [Post-processing steps] In the toner manufacturing method of the present invention, a post-processing step may be performed after the fusion step, and it is preferable to obtain toner particles by isolation. Since the fused particles obtained in the fusion process are present in an aqueous medium, it is preferable to first perform solid-liquid separation. Suction filtration or the like is preferably used for solid-liquid separation. It is preferable to perform washing after solid-liquid separation. At this time, it is also preferable to remove any added surfactants, etc., so if the surfactant has a cloud point, it is preferable to wash with an aqueous medium at or below the cloud point of the surfactant. It is preferable to perform washing multiple times.

[0107] Next, drying is preferable. The drying temperature should preferably be such that the temperature of the fused particles themselves is lower than the glass transition temperature of resin A, and more preferably 10°C or more lower. Preferred drying methods include vacuum low-temperature drying, vibratory fluid drying, spray drying, freeze-drying, and flash jet drying.

[0108] [Toner particles] Volume-intermediate particle size D of toner particles 50 From the viewpoint of further improving the cleaning performance of the toner, the particle size is preferably 2 μm or more, more preferably 3 μm or more, even more preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, and even more preferably 7 μm or less.

[0109] The circularity of the toner particles is preferably 0.955 or higher, more preferably 0.960 or higher, even more preferably 0.965 or higher, and preferably 0.990 or lower, more preferably 0.985 or lower, and even more preferably 0.980 or lower. Volume-intermediate particle size D of toner particles 50 This can be measured by the method described in the examples. The circularity of the toner particles can be measured in the same manner as the circularity of the fused particles.

[0110] [Toner for developing electrostatic images] As described above, the electrostatic image developing toner obtained by the toner manufacturing method of the present invention contains toner particles. Although the toner particles can be used as toner as is, it is preferable to use toner that has been treated by adding a fluidizing agent or the like as an external additive to the surface of the toner particles.

[0111] [External additives] Examples of external additives include fine particles of inorganic materials such as hydrophobic silica, titanium dioxide, alumina, cerium oxide, and carbon black, as well as polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, hydrophobic silica is preferred. External additives may be used individually or in combination of two or more. In addition, two or more types of hydrophobic silica with different particle sizes may be used. When surface treatment of toner particles is performed using an external additive, the amount of external additive added is preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, and preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less, and even more preferably 4 parts by mass or less, per 100 parts by mass of toner particles.

[0112] Toner is used in electrophotographic printing for electrostatic image development. Toner can be used, for example, as a one-component developer, or mixed with a carrier to form a two-component developer. [Examples]

[0113] The present invention will be specifically described below with reference to examples, but the present invention is not limited in any way by these examples. Each property value was measured and evaluated by the following method. In notations such as "alkylene oxide (X)," the number X in parentheses represents the average number of moles of alkylene oxide added.

[0114] [Measurement method] [Softening point, crystallinity index, melting point, and glass transition temperature of resins or resin compositions] (1) Softening point Using a flow tester "CFT-500EX" (manufactured by Shimadzu Corporation), 1 g of sample was heated at a heating rate of 6°C / min while a load of 1.96 MPa was applied by a plunger, and the sample was extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. The amount of plunger descent of the flow tester was plotted against temperature, and the temperature at which half of the sample flowed out was defined as the softening point. (2) Crystallinity index Using a differential scanning calorimeter "Q-20" (manufactured by T.A. Instruments Japan Co., Ltd.), 0.01 to 0.02 g of the sample was weighed into an aluminum pan and cooled to 0°C at a cooling rate of 10°C / min. The sample was then held for 1 minute, and subsequently heated to 180°C at a heating rate of 10°C / min, and the amount of heat was measured. Among the observed endothermic peaks, the temperature of the peak with the largest peak area was defined as the maximum endothermic peak temperature (1), and the crystallinity index was determined by (softening point (°C)) / (maximum endothermic peak temperature (1) (°C)). (3) Melting point and glass transition temperature Using a differential scanning calorimeter "Q-20" (manufactured by T.A. Instruments Japan), 0.01 to 0.02 g of the sample was weighed into an aluminum pan, heated to 200°C, and then cooled to 0°C at a rate of 10°C / min to prepare the sample for measurement. Subsequently, the temperature was increased at a rate of 10°C / min and the amount of heat was measured. Among the observed endothermic peaks, the peak temperature with the largest peak area was defined as the maximum endothermic peak temperature (2). In the case of crystalline resins, this peak temperature was defined as the melting point. Furthermore, in the case of amorphous resins, if a peak is observed, the temperature of that peak was used as the glass transition temperature. If no peak is observed but a step is observed, the temperature at the intersection of the extension of the baseline below the maximum endothermic peak temperature (2) and the tangent line indicating the maximum slope from the rising portion of the peak to the peak's apex was used as the glass transition temperature.

[0115] [Acid value of resin or resin composition] The measurement was performed according to the neutralization titration method described in JIS K 0070:1992. However, the measurement solvent was a mixed solvent of acetone and toluene [acetone:toluene = 1:1 (volume ratio)].

[0116] [Melting Point of Release Agent] Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Inc.), 0.02 g of a sample was weighed into an aluminum pan, heated to 200°C, and then cooled from 200°C to 0°C at a cooling rate of 10°C / min. Subsequently, the sample was heated at a temperature increase rate of 10°C / min, the amount of heat was measured, and the maximum endothermic peak temperature was taken as the melting point.

[0117] [Volume-median particle diameter D of resin composition particles, resin particles, release agent particles, and colorant particles 50 (1) Measuring device: Laser diffraction particle size analyzer "LA-920" (manufactured by HORIBA, Ltd.) (2) Measurement conditions: A sample dispersion is placed in a measurement cell, distilled water is added, and the volume-median particle diameter D is measured at a concentration where the absorbance falls within an appropriate range 50 was measured.

[0118] [Solid content concentration of resin composition particle dispersion, resin particle dispersion, release agent particle dispersion, and colorant particle dispersion] Using an infrared moisture meter "FD-230" (manufactured by Kett Scientific Research Institute Co., Ltd.), the moisture content (% by mass) of 5 g of a measurement sample was measured at a drying temperature of 150°C in measurement mode 96 (monitoring time: 2.5 min / fluctuation range: 0.05%). The solid content concentration was calculated according to the following formula. Solid content concentration (% by mass) = 100 - Moisture content (% by mass)

[0119] [Volume-median particle diameter D of aggregated particles 50 · Measuring instrument: "Coulter Multisizer (Registered Trademark) III" (manufactured by Beckman Coulter, Inc.) · Aperture diameter: 50 μm · Analysis software: "Multisizer (Registered Trademark) III version 3.51" (manufactured by Beckman Coulter, Inc.) · Electrolyte: "Isoton (Registered Trademark) II" (manufactured by Beckman Coulter, Inc.) ​​• Measurement conditions: The sample dispersion was added to 100 mL of the electrolyte solution to adjust the concentration so that the particle size of 30,000 particles could be measured in 20 seconds. Then, 30,000 particles were measured again, and the volume median particle size D was determined from the particle size distribution. 50 They sought it.

[0120] [Circularity of fused particles] • Measurement device: Flow-type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) • Preparation of dispersion: The dispersion of fused particles was prepared by diluting it with deionized water to a solid content concentration of 0.001 to 0.05% by mass. • Measurement mode: The circularity of the fused particles was determined using the HPF measurement mode.

[0121] [Toner particle volume median particle size D] 50 ] The measuring device, aperture diameter, analysis software, and electrolyte are the volume median particle size D of the aggregated particles as described above. 50 The same equipment used in the measurement was employed. • Dispersion: Polyoxyethylene lauryl ether "Emulgen® 109P" (manufactured by Kao Corporation, HLB (Hydrophile-Lipophile Balance): 13.6) was dissolved in the electrolyte to obtain a dispersion with a concentration of 5% by mass. • Dispersion conditions: 10 mg of the measurement sample of dried toner particles was added to 5 mL of the dispersion and dispersed for 1 minute using an ultrasonic disperser. Then, 25 mL of the electrolyte was added and dispersed for another minute using an ultrasonic disperser to prepare the sample dispersion. • Measurement conditions: The sample dispersion is added to 100 mL of the electrolyte to adjust the concentration to a level that allows for the measurement of 30,000 particle sizes in 20 seconds. Then, 30,000 particles are measured, and the volume median particle size D is determined from the particle size distribution. 50 They sought it.

[0122] [Manufacturing of resins and resin compositions] [Production of amorphous polyester resin and amorphous polyester resin composition] Manufacturing Example A1 (Manufacturing of Resin A-1) A four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer, and thermocouple was purged with nitrogen. 5270g of bisphenol A propylene oxide (2.2) adduct, 2075g of terephthalic acid, 40g of tin di(2-ethylhexanoate), and 0.8g of gallic acid were added. Under a nitrogen atmosphere, the mixture was heated to 235°C with stirring and held for 7 hours. Then, the pressure inside the flask was reduced and held at 8.3kPa for 1 hour. After returning to atmospheric pressure, the mixture was cooled to 220°C, and 655g of dodecenyl succinic anhydride was added. The reaction system was held at 220°C for 2 hours, then the pressure inside the flask was reduced to 8.3kPa and the reaction was carried out until the softening point shown in Table 1 was reached, yielding resin A-1. The physical properties are shown in Table 1.

[0123] Manufacturing example A2 (Manufacturing of resin A-2) A four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer, and thermocouple was purged with nitrogen. 5297g of bisphenol A propylene oxide (2.2) adduct, 2161g of terephthalic acid, 40g of tin di(2-ethylhexanoate), and 0.8g of gallic acid were added. Under a nitrogen atmosphere, the mixture was heated to 235°C with stirring and held for 7 hours. The pressure inside the flask was then reduced to 8.3kPa and held for 1 hour. After returning to atmospheric pressure, the mixture was cooled to 220°C, 542g of sebacin was added, and the reaction system was held at 220°C for 2 hours. The pressure inside the flask was then reduced to 8.3kPa and the reaction was carried out until the softening point shown in Table 1 was reached, yielding resin A-2. The physical properties are shown in Table 1.

[0124] Manufacturing Example A'3 (Manufacturing of Resin A'-3) A four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer, and thermocouple was purged with nitrogen. 3481g of bisphenol A propylene oxide (2.2) adduct, 1741g of bisphenol A ethylene oxide (2.2) adduct, 1702g of terephthalic acid, 705g of sebacic acid, 40g of tin di(2-ethylhexanoate), and 0.8g of gallic acid were added. Under a nitrogen atmosphere, the mixture was heated to 235°C with stirring and held for 8 hours. The pressure inside the flask was then reduced to 8.3kPa and held for 1 hour. After returning to atmospheric pressure, the mixture was cooled to 210°C. 371g of trimellitic anhydride was added, and the reaction system was held at 210°C for 1 hour. The pressure inside the flask was then reduced to 8.3kPa, and the reaction was carried out until the softening point shown in Table 1 was reached, yielding resin A'-3. The physical properties are shown in Table 1.

[0125] Manufacturing example A4 (Manufacturing of resin A-4) A four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer, and thermocouple was purged with nitrogen. 2388g of 1,2-propanediol, 4486g of terephthalic acid, and 40g of tin(II) di(2-ethylhexanoate) were added. Under a nitrogen atmosphere, the mixture was heated to 180°C with stirring and held for 2 hours, then heated to 220°C over 6 hours. After holding at 220°C for 2 hours, the pressure inside the flask was further reduced to 8.3kPa and held for 1 hour. After returning to atmospheric pressure, 1126g of dodecenyl succinic anhydride was added and the mixture was held at 220°C for 1 hour. The pressure inside the flask was then further reduced to 8.3kPa and the reaction was carried out until the softening point shown in Table 1 was reached, yielding resin A-4. The physical properties are shown in Table 1.

[0126] Manufacturing example A5 (Manufacturing of resin A-5) A four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer, and thermocouple was purged with nitrogen. 3033g of neopentyl glycol, 4261g of terephthalic acid, and 40g of tin(II) di(2-ethylhexanoate) were added. Under a nitrogen atmosphere, the mixture was heated to 180°C with stirring and held for 1 hour, then heated to 220°C over 6 hours. After holding at 220°C for 2 hours, the pressure inside the flask was further reduced to 8.3kPa and held for 1 hour. After returning to atmospheric pressure, 707g of sebacic acid was added and the mixture was held at 220°C for 2 hours. The pressure inside the flask was further reduced to 8.3kPa and the reaction was carried out until the softening point shown in Table 1 was reached, yielding resin A-5. The physical properties are shown in Table 1.

[0127] Manufacturing Example A'6 (Manufacturing of Resin A'-6) A four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer, and thermocouple was purged with nitrogen. 2463 g of 1,2-propanediol, 3874 g of terephthalic acid, and 40 g of tin(II) di(2-ethylhexanoate) were added. Under a nitrogen atmosphere, the mixture was heated to 180°C with stirring and held for 2 hours, then heated to 220°C over 6 hours. After holding at 220°C for 1 hour, the pressure inside the flask was further reduced to 8.3 kPa and held for 1 hour. After returning to atmospheric pressure, the mixture was cooled to 210°C, and 747 g of sebacic acid and 917 g of trimellitic anhydride were added. The mixture was held at 210°C for 2 hours, then the pressure inside the flask was further reduced to 8.3 kPa and the reaction was carried out until the softening point shown in Table 1 was reached, yielding resin A'-6. The physical properties are shown in Table 1.

[0128] Note that resin A'-3 produced in production example A'3 and resin A'-6 produced in production example A'6 are resin A, but they are denoted with an apostrophe because they are not used in the production of aqueous dispersions of resin composition particles containing amide compounds.

[0129] Manufacturing Example A7 (Manufacturing of Resin Composition A-7) The resin was manufactured in the same manner as in manufacturing example A1, and after obtaining a resin equivalent to resin A-1, the mixture was returned to atmospheric pressure, and the temperature inside the flask was cooled to 160°C while stirring. Then, 150g of N-hydroxyethyl (12-hydroxystearic acid amide) (ITOHWAX J-420, manufactured by Ito Oil Co., Ltd.) was added and stirred for 20 minutes to obtain resin composition A-7. The physical properties of resin composition A-7 are shown in Table 1.

[0130] Manufacturing Example A8 (Manufacturing of Resin Composition A-8) The resin was manufactured in the same manner as in manufacturing example A4, and after obtaining a resin equivalent to resin A-4, it was returned to atmospheric pressure, and the temperature in the flask was cooled to 160°C while stirring. Then, 138g of N-hydroxyethyl (12-hydroxystearic acid amide) (ITOHWAX J-420, manufactured by Ito Oil Co., Ltd.) was added and stirred for 20 minutes to obtain resin composition A-8. The physical properties of resin composition A-8 are shown in Table 1.

[0131] Manufacturing Example A9 (Manufacturing of Resin Composition A-9) Resin composition A-9 was obtained in the same manner as in production example A8, except that N,N'-ethylenebis(12-hydroxystearamide) (ITOHWAX J-530, manufactured by Ito Oil Co., Ltd.) was used instead of N-(2-hydroxyethyl)12-hydroxystearamide. The physical properties of resin composition A-9 are shown in Table 1.

[0132] [Table 1]

[0133] [Manufacturing of crystalline polyester resin] Manufacturing examples C1 and C2 (manufacturing of resins C-1 and C-2) The inside of a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, and the alcohol component and carboxylic acid component shown in Table 2 were charged. While stirring, the temperature was raised to 135°C, held at 135°C for 3 hours, and then increased from 135°C to 200°C over 10 hours. Thereafter, the esterification catalyst shown in Table 2 was added, the mixture was further held at 200°C for 1 hour, then the pressure inside the flask was reduced, and the reaction was held at 8.3 kPa until the acid value reached the value shown in Table 2, to obtain Resins C-1 and C-2. Physical property values are shown in Table 2.

[0134]

Table 2

[0135] [Production of Resin Composition Particle Dispersion and Resin Particle Dispersion] Production Examples AE1 to AE3, AE6 to AE8, AE10 to AE12, AE14 to AE16 (Production of Resin Composition Particle Dispersions AE-1 to AE-3, AE-6 to AE-8, AE-10 to AE-12, AE-14 to AE-16) Into a 2 L four-necked flask equipped with a reflux condenser, a stirrer, and a thermocouple, the amorphous polyester resin, amorphous polyester resin composition, and amide compound shown in Table 3 were charged in the amounts described in Table 3, mixed with 400 g of methyl ethyl ketone at room temperature, then the temperature was raised to 65°C under stirring to dissolve the resin. After cooling to room temperature, a 5 mass% aqueous sodium hydroxide solution was added such that the equivalent of sodium hydroxide used was 65 mol% relative to the acid value of Resin A, and the mixture was stirred at room temperature for 60 minutes. Then, 540 g of deionized water was added dropwise at a rate of 9 mL / min under stirring at room temperature to perform phase inversion emulsification. Thereafter, the temperature was raised to 65°C, and while maintaining 65°C, methyl ethyl ketone was distilled off while gradually reducing the pressure from 80 kPa to 30 kPa, and a portion of water was further distilled off. After cooling to room temperature, the mixture was filtered through a 150-mesh wire mesh, and the solid content concentration was adjusted to 30 mass% with deionized water, to obtain Resin Composition Particle Dispersions AE-1 to AE-3, AE-6 to AE-8, AE-10 to AE-12, AE-14 to AE-16. Volume median particle diameter D 50 are shown in Table 3.

[0136] Manufacturing Example AE'4 (Manufacturing of Resin Composition Particle Dispersion AE'-4) Resin composition particle dispersion AE'-4 was obtained in the same manner as in Production Example AE1, except that the polyester resin and amide compound listed in Table 3 were used in the amounts listed in Table 3. Medium volume particle size D 50 This is shown in Table 3.

[0137] Manufacturing examples AE'5, AE'9, AE'13 (Manufacturing of resin particle dispersions AE'-5, AE'-9, AE'-13) Resin particle dispersions AE'-5, AE'-9, and AE'-13 were obtained in the same manner as in Production Example AE1, except that the amorphous polyester resins listed in Table 3 were used in the amounts listed in Table 3. Medium volume particle size D 50 This is shown in Table 3.

[0138] Manufacturing examples CE17, CE18 (Manufacturing of resin particle dispersions CE-1 and CE-2) In a 2L four-necked flask equipped with a reflux condenser, stirrer, and thermocouple, 200g of crystalline polyester resin shown in Table 3 was placed and mixed with 400g of methyl ethyl ketone. The mixture was heated to 65°C while stirring to dissolve the resin. Next, while maintaining 65°C, a 5% by mass aqueous sodium hydroxide solution was added so that the amount of sodium hydroxide used was 65 mol% relative to the acid value of resin C, and the mixture was stirred for 60 minutes. Next, while maintaining 65°C and stirring, 540g of deionized water was added dropwise at a rate of 9 mL / min to emulsify the mixture through phase inversion. Subsequently, while maintaining 65°C, the methyl ethyl ketone was removed by gradually reducing the pressure from 80kPa to 30kPa, and then some of the water was removed by distillation. After cooling to room temperature, the mixture was filtered through a 150-mesh wire mesh, and the solid content concentration was adjusted to 30% by mass with deionized water to obtain resin particle dispersions CE-1 and CE-2. Volume-intermediate particle size D 50 This is shown in Table 3.

[0139] [Table 3]

[0140] [Manufacturing of colorant particle dispersion] In a 1L beaker, 50g of copper phthalocyanine pigment "ECB-301" (manufactured by Dainichi Seika Kogyo Co., Ltd.), 66.7g of anionic surfactant "Neoperex G-15" (manufactured by Kao Corporation, 15% by mass sodium dodecylbenzenesulfonate aqueous solution), and 184g of deionized water were mixed and dispersed at room temperature for 3 hours using an ultrasonic homogenizer "US-600AT" (manufactured by Nippon Seiki Seisakusho Co., Ltd.). After filtration through a 150-mesh wire mesh, deionized water was added to obtain a colorant particle dispersion with a solid content concentration of 20% by mass. Volume median particle size D of the colorant particles 50 It was 120 nm.

[0141] [Manufacturing of mold release agent particle dispersion] In a 1L beaker, 3.8g of the anionic surfactant "Poise 521" (manufactured by Kao Corporation, effective concentration 40% by mass, aqueous solution of sodium acrylate-sodium maleate copolymer) was dissolved in 200g of deionized water. Then, 5g of carnauba wax "Carnauba Wax No. 1" (manufactured by Kato Yoko Co., Ltd., melting point 83℃) and 45g of paraffin wax "HNP-9" (manufactured by Nippon Seiro Co., Ltd., melting point 75℃) were added, and the mixture was melted while maintaining a temperature of 90-95℃. Next, while maintaining a temperature of 90-95℃, the mixture was dispersed for 30 minutes using an ultrasonic homogenizer "US-600AT" (manufactured by Nippon Seiki Seisakusho Co., Ltd.), and then cooled to room temperature (25℃). The mixture was filtered through a 150-mesh wire mesh, deionized water was added, and the solid content concentration was adjusted to 20% by mass to obtain a release agent particle dispersion. Volume median particle size D of the release agent particles 50 It was 440nm.

[0142] [Toner manufacturing] Examples 1-5, 7-14 and Comparative Examples 1, 2 (Manufacturing of toners 1-5, 7-14, c1, c2) In a 2L four-necked flask equipped with a reflux condenser, a stirrer, and a thermocouple, 112.5g each of the resin composition particle dispersion AE and resin particle dispersion AE' shown in Table 4, 25g of resin particle dispersion CE, 19.3g of mold release agent particle dispersion, 22.5g of coloring agent particle dispersion, 5.0g of the anionic surfactant "Neoperex G-15" (manufactured by Kao Corporation, a 15% by mass aqueous solution of sodium dodecylbenzenesulfonate), and 7.5g of a 10% by mass aqueous solution prepared by dissolving the nonionic surfactant "Emulgen 150" (manufactured by Kao Corporation, polyoxyethylene (average number of added moles of oxyethylene 50) lauryl ether) in deionized water were mixed at room temperature. Next, while stirring the resulting mixture, an aqueous solution of 17.2 g of ammonium sulfate dissolved in 242 g of deionized water was added dropwise over 15 minutes. Then, the temperature was raised to 65°C over 2 hours and maintained at 65°C to obtain a dispersion of aggregated particles 1. Volume-median particle size D of aggregated particles 1 50 The particle size was 6.0 μm. To the dispersion of the obtained aggregated particles 1, an aqueous solution was added, which consisted of 12.1 g of the anionic surfactant "Emal E-27C" (manufactured by Kao Corporation, sodium polyoxyethylene lauryl ether sulfate, effective concentration 27% by mass) and 952 g of deionized water. The mixture was then heated to 80°C over 1 hour and maintained at 80°C until the circularity reached 0.970, thereby obtaining a dispersion of toner particles (fused particles) in which the aggregated particles had fused together. The resulting toner particle dispersion was cooled to room temperature, filtered through a 150-mesh wire mesh, then the dispersion was suction filtered to separate the solid components, washed with deionized water, and suction filtered again at room temperature for 6 hours. Subsequently, it was vacuum dried at 40°C for 48 hours using a vacuum dryer to obtain the medium volume particle size D 50 This yielded toner particles with a size of 6 μm. To 100 parts by mass of the obtained toner particles, 2.5 parts by mass of hydrophobic silica "RY50" (manufactured by Nippon Aerosil Co., Ltd., hydrophobic treatment agent: silicone oil, average particle size: 40 nm) and 1 part by mass of hydrophobic silica "Cabosil® TS720" (manufactured by Cabot Japan Co., Ltd., hydrophobic treatment agent: silicone oil, average particle size: 12 nm) were added to a Henschel mixer and stirred. The mixture was then passed through a 150-mesh sieve to obtain toner.

[0143] Example 6 (Manufacturing of Toner 6) In Example 1, toner was obtained in the same manner as in Example 1, except that 225 g of resin composition particle dispersion AE-1 was used and resin particle dispersion AE'-9 was not used.

[0144] [Evaluation of toner durability] Toner was placed in the developing cartridge of the non-magnetic single-component developing machine "Microline5400" (manufactured by OKI Electric Industry Co., Ltd.), and the machine was run empty at 60 rpm (equivalent to a 30-sheet A4 machine) under conditions of 25°C and 65% relative humidity. The occurrence of streaks on the surface of the developing roll was observed visually every 0.5 hours, and the time until streaks appeared (the time when streaks were first observed) was measured and used as an indicator of durability. In a single-component developer, toner becomes charged as it passes through the blade. However, if there are mechanically or physically weak areas inside or outside the toner, toner can adhere to the blade or developing roll, resulting in unevenness. Therefore, toners with a longer time to develop unevenness are more durable. The results are shown in Table 4.

[0145] [Table 4]

[0146] Table 4 shows that the toner obtained by the toner manufacturing method of the present invention has excellent durability (Examples 1-14). In contrast, toners manufactured using an amide compound that does not contain a hydroxyl group (ethylenebisstearamide) (Comparative Example 1) and toners manufactured without using an amide compound containing a hydroxyl group (Comparative Example 2) exhibit inferior durability.

Claims

1. A method for manufacturing toner for electrostatic image development, comprising the following steps 1 to 3. Step 1: Step to obtain an aqueous dispersion AE of resin composition particles containing amorphous polyester resin A and a hydroxyl group-containing amide compound. Step 2: Step to obtain an aqueous dispersion CE of resin particles containing crystalline polyester resin C. Step 3: A process to obtain toner particles by mixing the aqueous dispersion AE of resin composition particles and the aqueous dispersion CE of resin particles, and by agglomerating and fusing the resin composition particles and resin particles together. The hydroxyl group-containing amide compound is a compound represented by one of the following formulas (I) to (IV). R １ -CONH-X-NHCO-R ２ (I) (In the formula, R １ and R ２ Each of these is independently a hydroxyalkyl group having 12 to 22 carbon atoms, and X is a divalent hydrocarbon group having 2 to 12 carbon atoms. R ３ -.ONH-R ４ (-I) (In the formula, R ３ R is a hydroxyalkyl group having 12 to 22 carbon atoms. ４ (This is a hydroxyalkyl group having 2 to 22 carbon atoms.) ( ５ ________________ ６ (_=) (In the formula, R ５ R is an alkyl group having 12 or more carbon atoms and 22 or less carbon atoms. ６ (It is a hydroxyalkyl group having 2 to 22 carbon atoms.) R ７ -CONH-R ８ (IV) (In the formula, R ７ R is a hydroxyalkyl group having 12 to 22 carbon atoms, ８ (This refers to an alkyl group having 2 to 22 carbon atoms.)

2. A method for manufacturing electrostatic image developing toner according to claim 1, wherein step 1 is step 1b below. Step 1b: A process to dissolve amorphous polyester resin A and a hydroxyl group-containing amide compound in the same organic solvent, add an aqueous medium, and obtain an aqueous dispersion AE of resin composition particles.

3. The method for producing a toner for electrostatic image developing according to claim 2, wherein in step 1b, the temperature at which the toner is dissolved in an organic solvent is below the melting point of the hydroxyl group-containing amide compound.

4. A method for producing electrostatic image developing toner according to claim 1 or 2, wherein the content of the hydroxyl group-containing amide compound in the resin composition particles containing amorphous polyester resin A and hydroxyl group-containing amide compound is 0.2 parts by mass or more and 5 parts by mass or less per 100 parts by mass of amorphous polyester resin A.

5. An aqueous dispersion of resin composition particles used in the manufacture of toner for electrostatic image developing, The resin composition particles contain amorphous polyester resin A and a hydroxyl group-containing amide compound. An aqueous dispersion of resin composition particles used in the manufacture of toner for electrostatic image development, wherein the hydroxyl group-containing amide compound is a compound represented by any of the following formulas (I) to (IV). R １ -CONH-X-NHCO-R ２ (I) (In the formula, R １ and R ２ Each of these is independently a hydroxyalkyl group having 12 to 22 carbon atoms, and X is a divalent hydrocarbon group having 2 to 12 carbon atoms. R ３ -.ONH-R ４ (-I) (In the formula, R ３ R is a hydroxyalkyl group having 12 to 22 carbon atoms. ４ (This is a hydroxyalkyl group having 2 to 22 carbon atoms.) ( ５ ________________ ６ (_=) (In the formula, R ５ R is an alkyl group having 12 to 22 carbon atoms, ６ (It is a hydroxyalkyl group having 2 to 22 carbon atoms.) R ７ -CONH-R ８ (IV) (In the formula, R ７ R is a hydroxyalkyl group having 12 to 22 carbon atoms, ８ (This refers to an alkyl group having 2 to 22 carbon atoms.)

6. Volume-intermediate particle size D of resin composition particles ５０ An aqueous dispersion of resin composition particles used in the manufacture of electrostatic image developing toner according to claim 5, wherein the particle size is 0.01 μm or more and 0.8 μm or less.

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