JP7161336B2 - Toner manufacturing method - Google Patents

Description

The present invention relates to a method for producing a toner used for developing a latent image formed by an electrophotography method, an electrostatic recording method, an electrostatic printing method, or the like.

In the field of electrophotography, with the development of electrophotographic systems, there is a demand for the development of electrophotographic toners capable of achieving higher image quality and higher speed. As a method of obtaining a toner with a narrow particle size distribution and a small particle size corresponding to high image quality, the aggregation fusion method (emulsification So-called chemical toner is produced by agglomeration method, aggregation coalescence method).

Patent Document 1 discloses a toner for developing an electrostatic charge image having a core-shell structure, in which a binder resin containing a composite resin (A) and a crystalline polyester (B) and a wax are contained in the core portion, and a polyester resin (C ) in the shell portion, and the composite resin (A) is obtained by polycondensation of an alcohol component containing 80 mol % or more of a propylene oxide adduct of bisphenol A and a polyvalent carboxylic acid component. A composite resin containing a segment (a1) made of a polyester resin and a vinyl resin segment (a2) containing a structural unit derived from a styrene compound, wherein the crystalline polyester (B) has from 8 to 16 carbon atoms. Obtained by polycondensation of an alcohol component containing 80 mol% or more of an α,ω-aliphatic diol and a polycarboxylic acid component containing 80 mol% or more of an aliphatic saturated dicarboxylic acid having 8 to 16 carbon atoms It is a crystalline polyester, and the polyester resin (C) is a polyester resin obtained by polycondensation of an alcohol component containing 80 mol% or more of an ethylene oxide adduct of bisphenol A and a polyvalent carboxylic acid component. Image developing toners are described. It is described that the toner achieves both excellent low-temperature fixability and heat-resistant storage stability, and is also excellent in chargeability.

Patent Document 2 includes mixing an emulsion latex containing an amine, a sulfonated polyester resin, and a colorant dispersion, including heating the resulting mixture, and optionally cooling. Processes for toner preparation are described, including: The process is said to economically prepare toners useful in forming high gloss images in high yield without the use of surfactants.

In Patent Document 3, a toner having a step of mixing a dispersion of colorant-containing polymer particles and a dispersion of resin particles that do not substantially contain a colorant to aggregate the colorant-containing polymer particles and the resin particles. wherein the polymer constituting the colorant-containing polymer particles has (a) a structural unit derived from a salt-forming group-containing monomer and (b) a structural unit derived from an aromatic ring-containing monomer. A method of making a photographic toner is described. It is described that the production method is excellent in the dispersibility of the colorant and can significantly improve the image density.

Patent Document 4 discloses a toner containing at least a binder resin, a colorant, and a pigment dispersant, wherein the colorant contains at least one pigment, and the pigment dispersant is the binder Toners are described that are characterized by having a resin-compatible base skeleton and at least one aromatic skeleton. With this toner, a uniform solid image can be obtained with reduced unevenness within the solid image and at the edges thereof, and the amount of toner adhered can be reduced, so the amount of toner consumed during image output can be reduced. It is stated that the cost per sheet can be significantly reduced.

JP 2016-114934 A JP-A-11-258851 Japanese Patent Application Laid-Open No. 2010-26106 Japanese Unexamined Patent Application Publication No. 2010-152208

In recent years, in the field of electrophotography as well, there has been a strong demand for resource saving and energy saving, and there is a demand for a toner that can provide a higher image density even with a smaller amount of toner than before.
Furthermore, due to the demand for energy saving, excellent low-temperature fixability is required. On the other hand, by adding a crystalline polyester resin, the low-temperature fixability can be improved. The charging property of the toner varies, and the charging stability may be impaired.
Although conventional techniques such as those disclosed in Patent Documents 1 to 3 are known to address these problems, they are still not at a sufficient level.
The present invention relates to a method for producing a toner that provides high image density and exhibits excellent low-temperature fixability and charge stability.

The present inventors have found that in a method for producing a toner comprising a step of aggregating and fusing resin particles and colorant particles, an amorphous polyester resin A and a crystalline polyester resin C are used, and furthermore, as colorant particles, A toner is obtained by using coloring agent particles obtained by dispersing a coloring agent in a mixed liquid containing an amorphous polyester resin E, an organic solvent, and water, and fusing them at a predetermined temperature. The inventors have found that the image density obtained by the method is increased, and the low-temperature fixability and charging stability are improved.
The present invention provides a method for producing a toner, comprising a step of aggregating and fusing resin particles and colorant particles,
The resin particles contain an amorphous polyester resin A and a crystalline polyester resin C in the same or different particles,
The colorant particles are obtained by dispersing a colorant in a mixed liquid containing an amorphous polyester resin E, an organic solvent, and water,
The present invention relates to a method for producing a toner, wherein the fusion-bonding temperature is at least 10° C. lower than the melting point of the crystalline polyester resin C and at most 60° C. higher than the melting point.

According to the present invention, there is provided a production method that provides a toner that provides high image density and exhibits excellent low-temperature fixability and charge stability.

[Toner manufacturing method]
The method for producing the toner of the present invention includes a step of aggregating and fusing resin particles and colorant particles (hereinafter also referred to as “colorant particles Z”).
The resin particles contain an amorphous polyester resin A (hereinafter also referred to as "resin A") and a crystalline polyester resin C (hereinafter also referred to as "resin C") in the same or different particles. .
In addition, the colorant particles are obtained by dispersing a colorant in a mixed liquid containing an amorphous polyester resin E (hereinafter also referred to as "resin E"), an organic solvent, and water. is.
Furthermore, the fusion bonding temperature is not less than 10°C lower than the melting point of the crystalline polyester resin C and not more than 60°C higher than the melting point.
By the production method described above, a toner can be obtained which can provide a high image density and which exhibits excellent low-temperature fixability and charge stability.

In order to obtain high image density and low-temperature fixability, it is preferable to finely disperse the crystalline polyester resin in the toner particles. When toner particles containing a crystalline polyester resin are produced by an aggregation fusion method that does not require a kneading step, from the viewpoint of improving low-temperature fixability, the temperature is at least 10° C. lower than the melting point of the crystalline polyester resin and at least 60° C. higher than the melting point of the crystalline polyester resin. Fusing is performed as follows, but under these temperature conditions, the crystalline polyester resin softens or melts, so the viscosity of the binder resin is greatly reduced, and the colorant particles tend to aggregate within the fused particles. Become. For this reason, it was thought that the image density of the resulting toner printed matter would be lowered and that the charging characteristics would be uneven.
On the other hand, by dispersing a mixture of a coloring agent, an amorphous polyester resin, an organic solvent, and water, the amorphous polyester resin can be adsorbed on the surface of the coloring agent.
Perhaps because the amorphous polyester resin on the surface of the colorant and the amorphous polyester resin used as the binder resin have a high affinity, aggregation of the colorants in the fusion bonding step can be suppressed. It is believed that the toner thus obtained exhibits a very high image density. Furthermore, when the resin particles containing the obtained colorant particles and the amorphous polyester resin are aggregated, the aggregation stability is high and the homogeneity of the toner is improved, and the charge amount distribution of the toner becomes sharp.

Definitions of various terms used in this specification are shown below.
Whether a resin is crystalline or amorphous is determined by the 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 has a crystallinity index of 0.6 or more and 1.4 or less. Amorphous resins are those having a crystallinity index of 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, and production conditions such as reaction temperature, reaction time, and cooling rate.

A method for producing a toner according to an embodiment of the present invention includes, for example, a step of aggregating resin particles containing resin A and resin B in the same or different particles and colorant particles Z to obtain aggregated particles (hereinafter referred to as " Also referred to as "step 1"), and a step of fusing aggregated particles in an aqueous medium (hereinafter also referred to as "step 2")
including.
The present invention will be described below by taking the embodiment as an example.

<Step 1>
In step 1, resin particles containing resin A and resin C and colorant particles Z are aggregated in the same or different particles to obtain aggregated particles. In step 1, in addition to resin particles and colorant particles Z, wax and other additives may be aggregated.
In step 1, the resin particles XY containing the resin A and the resin C may be used, or the resin particles X containing the resin A and the resin particles Y containing the resin C may be used together.

(Resin A)
Resin A is, for example, an amorphous polyester resin that is a polycondensate of an alcohol component and a carboxylic acid component.

（式中、ＯＲ¹及びＲ²Ｏはオキシアルキレン基であり、Ｒ¹及びＲ²はそれぞれ独立にエチレン基又はプロピレン基であり、ｘ及びｙはアルキレンオキサイドの平均付加モル数を示し、それぞれ正の数であり、ｘとｙの和の値は、１以上、好ましくは１．５以上であり、１６以下、好ましくは８以下、より好ましくは４以下である）で表されるビスフェノールＡのアルキレンオキサイド付加物である。
ビスフェノールＡのアルキレンオキサイド付加物としては、ビスフェノールＡ〔２，２－ビス（４－ヒドロキシフェニル）プロパン〕のプロピレンオキサイド付加物、ビスフェノールＡのエチレンオキサイド付加物が好ましい。これらは、１種又は２種以上を用いてもよい。これらの中でも、ビスフェノールＡのプロピレンオキサイド付加物がより好ましく、ビスフェノールＡのプロピレンオキサイド付加物及びビスフェノールＡのエチレンオキサイド付加物を用いるのが更に好ましい。
ビスフェノールＡのプロピレンオキサイド付加物及びビスフェノールＡのエチレンオキサイド付加物を用いる際の、ビスフェノールＡのプロピレンオキサイド付加物とビスフェノールＡのエチレンオキサイド付加物のモル比は、好ましくは５０／５０以上、より好ましくは６０／４０以上、更に好ましくは６５／３５以上であり、そして、好ましくは９５／５以下、より好ましくは９０／１０以下、更に好ましくは８０／２０以下である。
ビスフェノールＡのアルキレンオキサイド付加物の量は、アルコール成分中、好ましくは７０モル％以上、より好ましくは９０モル％以上、更に好ましくは９５モル％以上であり、そして、１００モル％以下であり、更に好ましくは１００モル％である。 Examples of alcohol components include aromatic diols, linear or branched aliphatic diols, alicyclic diols, and polyhydric alcohols having a valence of 3 or more. Among these, aromatic diols are preferred.
The amount of the aromatic diol in the alcohol component is preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol% or less, more preferably 100 mol%. %.
The aromatic diol is preferably an alkylene oxide adduct of bisphenol A, more preferably of formula (I):

(Wherein, OR ¹ and R ² O are oxyalkylene groups, R ¹ and R ² are each independently an ethylene group or a propylene group, x and y represent the average number of added moles of alkylene oxide, each positive and the sum of x and y is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, more preferably 4 or less). It is an oxide adduct.
As the alkylene oxide adduct of bisphenol A, a propylene oxide adduct of bisphenol A [2,2-bis(4-hydroxyphenyl)propane] and an ethylene oxide adduct of bisphenol A are preferable. These may be used alone or in combination of two or more. Among these, the propylene oxide adduct of bisphenol A is more preferred, and the propylene oxide adduct of bisphenol A and the ethylene oxide adduct of bisphenol A are more preferred.
When the propylene oxide adduct of bisphenol A and the ethylene oxide adduct of bisphenol A are used, the molar ratio of the propylene oxide adduct of bisphenol A and the ethylene oxide adduct of bisphenol A is preferably 50/50 or more, more preferably 60/40 or more, more preferably 65/35 or more, and preferably 95/5 or less, more preferably 90/10 or less, and even more preferably 80/20 or less.
The amount of the alkylene oxide adduct of bisphenol A in the alcohol component is preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol% or less, and further Preferably it is 100 mol %.

Examples of linear or branched aliphatic diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol and 1,4-butanediol. , 2,3-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1 , 12-dodecanediol.
Examples of alicyclic diols include hydrogenated bisphenol A [2,2-bis(4-hydroxycyclohexyl)propane], alkylene oxide of hydrogenated bisphenol A having 2 to 4 carbon atoms (average addition mole number 2 to 12 below) adducts.
Examples of trihydric or higher polyhydric alcohols include glycerin, pentaerythritol, trimethylolpropane, and sorbitol.
One or more of these alcohol components may be used.

Examples of the carboxylic acid component include dicarboxylic acids and polycarboxylic acids having a valence of 3 or more.
Dicarboxylic acids include, for example, aromatic dicarboxylic acids, linear or branched aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids. Among these, aromatic dicarboxylic acids and linear or branched aliphatic dicarboxylic acids are preferred.
Examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid, and terephthalic acid. Among these, isophthalic acid and terephthalic acid are preferred, and terephthalic acid is more preferred.
The amount of the aromatic dicarboxylic acid in the carboxylic acid component is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, and preferably 90 mol% or less, more preferably 80 mol % or less, more preferably 75 mol % or less.

The number of carbon atoms in the linear or branched aliphatic dicarboxylic acid is preferably 2 or more, more preferably 3 or more, and preferably 30 or less, more preferably 20 or less.
Linear or branched aliphatic dicarboxylic acids include, for example, oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, and azelaic acid. , succinic acid or an anhydride thereof substituted with a hydrocarbon group having 8 to 20 carbon atoms. Examples of the succinic acid or anhydride thereof substituted with a hydrocarbon group having 8 to 20 carbon atoms include octenylsuccinic acid, decenylsuccinic acid, undecenylsuccinic acid, dodecylsuccinic acid, dodecenylsuccinic acid, and anhydrides thereof. be done. Among these, fumaric acid, adipic acid and sebacic acid are preferred, and adipic acid is more preferred.
The amount of linear or branched aliphatic dicarboxylic acid in the carboxylic acid component is preferably 1 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, and preferably 50 mol%. Below, more preferably 40 mol % or less, still more preferably 35 mol % or less.

The trivalent or higher polyvalent carboxylic acid is preferably a trivalent carboxylic acid, such as trimellitic acid or its anhydride.
When a trivalent or higher polycarboxylic acid is contained, the amount of the trivalent or higher polycarboxylic acid is preferably 3 mol% or more, more preferably 5 mol% or more, and still more preferably 8 mol% in the carboxylic acid component. and preferably 30 mol % or less, more preferably 20 mol % or less, still more preferably 15 mol % or less.
One or more of these carboxylic acid components may be used.

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

Resin A may be produced, for example, by a method including step A of performing a polycondensation reaction with an alcohol component and a carboxylic acid component.
In step A, an esterification catalyst such as di(2-ethylhexanoic acid)tin (II), dibutyltin oxide, titanium diisopropylate bistriethanolamine, etc., is added to the alcohol component and the carboxylic acid component in a total amount of 100, if necessary. 0.01 parts by mass or more and 5 parts by mass or less per part by mass; Esterification promoter such as gallic acid (same as 3,4,5-trihydroxybenzoic acid), total amount of alcohol component and carboxylic acid component is 100 mass 0.001 parts by mass or more and 0.5 parts by mass or less may be used for polycondensation.
Further, when a monomer having an unsaturated bond such as fumaric acid is used in the polycondensation reaction, it is preferably 0.001 part by mass with respect to 100 parts by mass as the total amount of the alcohol component and the carboxylic acid component, if necessary. More than 0.5 parts by mass or less of the radical polymerization inhibitor may be used. Examples of radical polymerization inhibitors include 4-tert-butylcatechol.
The temperature of the polycondensation reaction is preferably 120° C. or higher, more preferably 160° C. or higher, still more preferably 180° C. or higher, and preferably 250° C. or lower, more preferably 240° C. or lower. In addition, you may perform polycondensation in an inert gas atmosphere.

(Physical properties of resin A)
The softening point of resin A is preferably 70° C. or higher, more preferably 90° C. or higher, and still more preferably 100° C. or higher from the viewpoint of improving image density. It is 140° C. or lower, more preferably 130° C. or lower, and still more preferably 125° C. or lower.
The glass transition temperature of Resin A is preferably 30°C or higher, more preferably 40°C or higher, still more preferably 50°C or higher, and is preferably 80°C or lower, more preferably 70°C or lower, and still more preferably 60°C. It is below.

The acid value of Resin A is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, still more preferably 13 mgKOH/g or more, and preferably 40 mgKOH/g or less, more preferably 35 mgKOH/g or less, and further preferably Preferably, it is 30 mgKOH/g or less.
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 monomers used, and production conditions such as reaction temperature, reaction time, and cooling rate. is determined by the method described in Examples.
When two or more resins A are used in combination, the softening point, glass transition temperature and acid value of the mixture are preferably within the ranges described above.

(Resin C)
Resin C is, for example, a crystalline polyester resin that is a polycondensate of an alcohol component and a carboxylic acid component.
The alcohol component preferably comprises an α,ω-aliphatic diol.
The number of carbon atoms in the α,ω-aliphatic diol is preferably 2 or more, more preferably 4 or more, still more preferably 6 or more, and preferably 16 or less, more preferably 14 or less, still more preferably 12 or less. be.
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 mentioned. Among these, 1,6-hexanediol and 1,10-decanediol are preferred, and 1,10-decanediol is more preferred.

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

The alcohol component may contain other alcohol components different from the α,ω-aliphatic diol. Examples of other alcohol components include aliphatic diols other than α,ω-aliphatic diols such as 1,2-propylene glycol and neopentyl glycol; aromatic diols such as alkylene oxide adducts of bisphenol A; trihydric or higher alcohols such as erythritol and trimethylolpropane; One or more of these alcohol components may be used.

The carboxylic acid component preferably comprises an aliphatic dicarboxylic acid.
The number of carbon atoms in the aliphatic dicarboxylic acid is preferably 4 or more, more preferably 8 or more, still more preferably 10 or more, and preferably 14 or less, more preferably 12 or less.
Aliphatic dicarboxylic acids include, for example, fumaric acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid. Among these, sebacic acid, dodecanedioic acid and tetradecanedioic acid are preferred, and sebacic acid and dodecanedioic acid are more preferred. One or more of these carboxylic acid components may be used.

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

The carboxylic acid component may contain other carboxylic acid components different from the aliphatic dicarboxylic acid. Other carboxylic acid components include, for example, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid; and trivalent or higher polyvalent carboxylic acids. One or more of these carboxylic acid components may be used.

The equivalent ratio of the carboxy group of the carboxylic acid component to the hydroxyl group of the alcohol component (COOH group/OH group) is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, or more. It is preferably 1.2 or less.

(Physical properties of resin C)
The softening point of Resin C is preferably 60° C. or higher, more preferably 70° C. or higher, still more preferably 75° C. or higher, and is preferably 150° C. or lower, more preferably 120° C. or lower, and still more preferably 100° C. or lower. is.

The melting point of Resin C is preferably 50° C. or higher, more preferably 60° C. or higher, still more preferably 70° C. or higher, and preferably 100° C. or lower, more preferably 95° C. or lower.

The acid value of Resin C is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, and preferably 35 mgKOH/g or less, more preferably 30 mgKOH/g or less, still more preferably 25 mgKOH/g or less. .

The softening point, melting point, and acid value of Resin C can be appropriately adjusted depending on the type and ratio of raw material monomers, and production conditions such as reaction temperature, reaction time, and cooling rate. Those values are determined by the method described in Examples below. When two or more resins C are used in combination, the softening point, melting point, and acid value of the mixture are preferably within the ranges described above.

Resin C is obtained, for example, by polycondensation of an alcohol component and a carboxylic acid component. As the conditions for polycondensation, for example, the conditions shown for the polycondensation of resin A described above can be applied.

The mass ratio [C/A] of resin C and resin A is preferably 1/99 or more, more preferably 5/95 or more, still more preferably 8/92 or more, and preferably 50/50 or less, More preferably 40/60 or less, still more preferably 30/70 or less.

In the resin component of the toner, the content of resin A and resin C is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and 100% by mass or less. , and preferably 100% by mass.

[Resin particles]
In step 1, preferably resin particles XY containing resin A and resin C are used.

[Method for producing resin particles XY]
A dispersion liquid of resin particles XY is obtained by dispersing resin A and resin C in an aqueous medium.
The aqueous medium preferably contains water as a main component, and the content of water in the aqueous medium is preferably 80 mass from the viewpoint of improving the dispersion stability of the dispersion liquid of the resin particles and from the viewpoint of environmental friendliness. % or more, more preferably 90 mass % or more, still more preferably 95 mass % or more, and 100 mass % or less, more preferably 100 mass %. As water, deionized water or distilled water is preferred. Components other than water that can be contained in the aqueous medium include, for example, alkyl alcohols having 1 to 5 carbon atoms; dialkyl ketones having 3 to 5 total carbon atoms such as acetone and methyl ethyl ketone; and cyclic ethers such as tetrahydrofuran. Dissolving organic solvents are included.

Dispersion can be carried out using a known method, but it is preferable to disperse by a phase inversion emulsification method. The phase inversion emulsification method includes, for example, a method in which an aqueous medium is added to an organic solvent solution of a resin or a molten resin to effect phase inversion emulsification.

The organic solvent used for phase inversion emulsification is not particularly limited as long as it dissolves the resin, but from the viewpoint of facilitating phase inversion, for example, alcoholic solvents such as ethanol, isopropanol, and isobutanol; acetone, methyl ethyl ketone, and methyl isobutyl ketone. , diethyl ketone and the like; ether solvents such as dibutyl ether, tetrahydrofuran and dioxane; and acetate solvents such as ethyl acetate and isopropyl acetate. Among these, ketone-based solvents and acetic acid ester-based solvents are preferable, and methyl ethyl ketone, ethyl acetate, and isopropyl acetate are more preferable, from the viewpoint of easy removal from the mixed solution after addition of the aqueous medium.
A neutralizing agent is preferably added to the organic solvent solution. Neutralizing agents include, for example, basic substances. Basic substances include, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; and nitrogen-containing basic substances such as ammonia, trimethylamine and diethanolamine.
The neutralization degree of the resin contained in the resin particles XY is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 40 mol% or more, and preferably It is 100 mol % or less, more preferably 80 mol % or less, still more preferably 70 mol % or less.
The degree of neutralization of the resin contained in the resin particles can be determined by the following formula.
Degree of neutralization (mol %)=[{neutralizing agent added mass (g)/neutralizing agent equivalent}/[{weighted average acid value of resin constituting resin particles XY (mgKOH/g)×resin particles XY Mass (g) of the resin constituting the } / (56 × 1000)]] × 100

While stirring the organic solvent solution or molten resin, the aqueous medium is gradually added to cause phase inversion.
From the viewpoint of improving the dispersion stability of the resin particles XY, the temperature of the organic solvent solution when adding the aqueous medium is preferably the glass transition temperature or higher of the resin A constituting the resin particles XY, more preferably 60° C. or higher. It is preferably 70° C. or higher, and preferably 100° C. or lower, more preferably 90° C. or lower, and even more preferably 80° C. or lower.

After the phase inversion emulsification, if necessary, the organic solvent may be removed from the resulting dispersion by distillation or the like. In this case, the residual amount of the 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.

The volume-median particle size _D50 of the resin particles XY in the dispersion is preferably 0.05 μm or more, more preferably 0.08 μm or more, from the viewpoint of obtaining a toner capable of obtaining high-quality images. is 1 μm or less, more preferably 0.5 μm or less, still more preferably 0.3 μm or less.
The CV value of the resin particles XY in the dispersion is preferably 10% or more, more preferably 20% or more, and more preferably 40% or less, more preferably 40% or less, from the viewpoint of obtaining a toner capable of obtaining high-quality images. is 30% or less.
The volume-median particle size _D50 and CV value are determined by the methods described in Examples below.
Both the resin particles X containing the resin A and the resin particles Y containing the resin C can be produced according to the method described above. Preferred ranges for the volume-median particle size _D50 and CV value of resin particles X and resin particles Y are the same as those described above.

[Colorant particles Z]
The colorant particles Z are a mixture containing an amorphous polyester resin E, an organic solvent, and water from the viewpoint of obtaining a toner that provides a high image density and exhibits excellent low-temperature fixability and charge stability. It is obtained by dispersing a coloring agent in a liquid, and more preferably by removing the organic solvent after the dispersion. The colorant particles Z have, for example, an amorphous polyester resin E on the surface of the colorant, and the surface of the colorant is preferably coated with the amorphous polyester resin E.

(coloring agent)
As the colorant, all dyes, pigments, etc. used as colorants for toners can be used. Examples thereof include carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, and rhodamine-B. Base, Solvent Red 49, Solvent Red 146, Solvent Blue 35, Quinacridone, Carmine 6B, Disazo Yellow. The toner may be black toner or color toner other than black.
Among these, carbon black is preferred.
Examples of carbon black include furnace black, thermal lamp black, acetylene black, and channel black. Among these, furnace black is preferable from the viewpoint of improving image density and charging stability.
The pH value of carbon black is preferably 5 or more, more preferably 6 or more, still more preferably 6.5 or more, and preferably 8 or less, more preferably 7.5, from the viewpoint of further improving the image density. It is below.
Specifically, the pH value of carbon black can be measured by the following procedure.
(1) 5 g of carbon black and 50 mL of distilled water having a pH of 7 are collected in a container and mixed.
(2) It is boiled for 15 minutes and then cooled to room temperature in 30 minutes.
(3) Immerse the electrode of a pH meter in this supernatant to measure the pH.
Examples of pH meters include "HM30R" (manufactured by Toa DKK Corporation).

(Resin E)
Resin E is, for example, an amorphous polyester resin that is a polycondensate of an alcohol component and a carboxylic acid component. The alcohol component and the carboxylic acid component are the same as in the resin A described above.

The mass ratio of the colorant to the resin E in the colorant particles is preferably 50/50 or more, more preferably 60/40 or more, more preferably 70/30 or more, still more preferably 75/25 or more, and preferably 95/5 or less, more preferably 90/10 or less, still more preferably 85/15 or less be.

[Method for producing colorant particles Z]
Colorant particles Z can be obtained, for example, by dispersing a colorant in a mixed liquid containing resin E, an organic solvent, and water. When the colorant is dispersed, the mixed liquid contains the organic solvent, so that the resin E is dissolved in the organic solvent, and the resin E is easily adsorbed to the colorant, so that the dispersibility of the colorant can be further improved. The colorant particles Z are more preferably freed from the organic solvent after the dispersion. This step promotes adsorption of the resin E to the colorant.
There is no particular limitation on the method for producing the dispersion liquid of the colorant particles Z, and it is sufficient if a known kneader, disperser, or the like can be used and controlled so as to obtain colorant particles having a desired volume-median particle size _D50 . , is obtained by mixing the colorant and resin E with a bead mill or a homogenizer.

The method for producing the colorant particles Z preferably comprises
Step a: After mixing Resin E and an organic solvent, if necessary, a neutralizing agent is mixed, and further mixed with an aqueous medium to obtain a dispersion of Resin E; and Step b: Obtained in Step a. a step of obtaining a dispersion of colorant particles Z by dispersing the obtained dispersion and the colorant; Step c: a step of removing the organic solvent from the dispersion of colorant particles Z obtained in step b. be.

In step a, it is preferable to first mix the resin E and the organic solvent.
Examples of the organic solvent used here include alkyl alcohols having 1 to 3 carbon atoms, dialkyl ketones having 3 to 5 carbon atoms in total, and cyclic ethers. Among these, dialkyl ketones having a total carbon number of 3 or more and 5 or less are preferable, and methyl ethyl ketone is more preferable.

Neutralizing agents include, for example, basic substances. Basic substances include, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; and nitrogen-containing basic substances such as ammonia, trimethylamine and diethanolamine.
The degree of neutralization of Resin E is preferably 15 mol% or more, more preferably 20 mol% or more, still more preferably 40 mol% or more, still more preferably 60 mol% or more, and preferably 100 mol% or less, It is more preferably 98 mol % or less, still more preferably 95 mol % or less.
The degree of neutralization of resin E can be determined by the following formula.
Degree of neutralization (mol%) = [{neutralizing agent added mass (g)/neutralizing agent equivalent}/{weighted average acid value of resin E (mgKOH/g) x mass of resin E (g)/( 56×1000)}]×100
In step a, the device used for mixing includes, for example, a mixing and stirring device equipped with anchor blades, disper blades, and the like.
The temperature during mixing is preferably 0° C. or higher, more preferably 10° C. or higher, and preferably 40° C. or lower, more preferably 30° C. or lower, and still more preferably 25° C. or lower.
The mixing time is preferably 5 minutes or longer, more preferably 8 minutes or longer, and preferably 3 hours or shorter, more preferably 1 hour or shorter, and even more preferably 30 minutes or shorter.

In step b, the mass ratio of the colorant and resin E [colorant/resin E] is as described above.

Examples of the apparatus used in step b include kneaders such as roll mills and kneaders, homogenizers such as Microfluidizer (manufactured by Microfluidic), media type dispersers such as paint shakers and bead mills. One or more of these devices may be used. Among these, a bead mill and a homogenizer are preferable from the viewpoint of reducing the particle size of the pigment.
When using a homogenizer, the treatment pressure is preferably 60 MPa or higher, more preferably 100 MPa or higher, still more preferably 130 MPa or higher, and preferably 270 MPa or lower, more preferably 200 MPa or lower, and still more preferably 180 MPa or lower.
The number of passes is preferably 5 or more, more preferably 10 or more, and preferably 30 or less, more preferably 25 or less.

In the step c, it is preferable to remove the organic solvent from the dispersion of the colorant particles Z obtained. In other words, the colorant particles are preferably obtained by removing the organic solvent after dispersion.
The organic solvent can be removed, for example, by distilling off under reduced pressure. At this time, part of the water may be distilled off.
Further, it is preferable to filter the dispersion liquid of the colorant particles Z through a wire mesh or the like to remove coarse particles and the like. Moreover, from the viewpoint of improving the productivity and storage stability of the dispersion, the resin E of the colorant particles may be subjected to a cross-linking treatment.
Various additives such as organic solvents, preservatives, and antifungal agents may be added to the dispersion liquid of the colorant particles Z.

In the dispersion liquid of the colorant particles Z, the colorant is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less.
The solid content concentration of the dispersion liquid of the colorant particles Z is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably It is 40% by mass or less, more preferably 30% by mass or less.

The volume-median particle size _D50 of the colorant particles Z is preferably 0.05 μm or more, more preferably 0.08 μm or more, still more preferably 0.1 μm or more, from the viewpoint of improving image density. is 0.3 μm or less, more preferably 0.2 μm or less.
From the viewpoint of improving the image density, the CV value of the colorant particles Z is preferably 10% or more, more preferably 20% or more, and preferably 40% or less, more preferably 35% or less.
The volume-median particle diameter _D50 and CV value of the colorant particles Z are measured by the method in the Examples.

The amount of the colorant particles Z is preferably 3 parts by mass or more, more preferably 6 parts by mass or more, and still more preferably 10 parts by mass with respect to 100 parts by mass of the resin particles, from the viewpoint of further improving the image density and durability. and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less.

〔wax〕
Aggregation of resin particles and colorant particles Z may be performed in the presence of wax.
Waxes include, for example, hydrocarbon waxes such as polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, Sasol wax, or oxides thereof; carnauba wax, montan wax. or ester waxes such as deacidified waxes and fatty acid ester waxes thereof; fatty acid amides, fatty acids, higher alcohols and fatty acid metal salts. These may be used alone or in combination of two or more.
Among these, hydrocarbon waxes and ester waxes are preferred, and combined use of hydrocarbon waxes and ester waxes is more preferred.

The melting point of the wax is preferably 60° C. or higher, more preferably 70° C. or higher, and preferably 160° C. or lower, more preferably 150° C. or lower, still more preferably 140° C. or lower.

The amount of wax in the toner is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 5% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass. 20% by mass or less, more preferably 20% by mass or less.

(Wax particle dispersion)
The wax is preferably mixed with the resin particles X and the colorant particles Z in the form of a dispersion of wax particles and aggregated.
A dispersion of wax particles can be obtained using a surfactant, but is preferably obtained by mixing wax and resin particles P described later. By preparing the wax particles using the wax and the resin particles P, the wax particles are stabilized by the resin particles P, and the wax can be dispersed in the aqueous medium without using a surfactant. It is considered that the dispersion of wax particles has a structure in which a large number of resin particles P adhere to the surfaces of the wax particles.
The type and amount of wax to be added are the same as those of the wax described above.

The resin constituting the resin particles P that disperse the wax is preferably a polyester resin, and from the viewpoint of improving the dispersibility of the wax in an aqueous medium, a polyester resin that is a polycondensate of an alcohol component and a carboxylic acid component. It is more preferable to use a composite resin D having an addition polymerized resin segment, which is an addition polymer of a raw material monomer containing a segment and styrene.
The softening point of composite resin D is preferably 70° C. or higher, more preferably 80° C. or higher, and preferably 140° C. or lower, more preferably 120° C. or lower, and still more preferably 100° C. or lower.
The other preferred ranges of resin properties of Composite Resin D, preferred examples of the alcohol component and the carboxylic acid component, and the like are the same as those shown for Resin A. The raw material monomer for the addition polymerized resin segment may contain an alkyl (meth)acrylate having an alkyl group having 4 to 22 carbon atoms.
A dispersion of the resin particles P can be obtained, for example, by the above-described phase inversion emulsification method.
From the viewpoint of the dispersion stability of the wax particles, the volume-median particle diameter _D50 of the resin particles P is preferably 0.01 μm or more, more preferably 0.03 μm or more, and preferably 0.3 μm or less, and more preferably 0.3 μm or less. It is preferably 0.2 μm or less.
From the viewpoint of the dispersion stability of the wax particles, the CV value of the resin particles P is preferably 10% or more, more preferably 20% or more, and preferably 40% or less, more preferably 35% or less, and even more preferably. is 30% or less.

The wax particle dispersion is prepared, for example, by subjecting a dispersion of wax and resin particles P, and optionally an aqueous medium, to a temperature equal to or higher than the melting point of the wax, and applying a strong shearing force such as a homogenizer, a high-pressure disperser, or an ultrasonic disperser. obtained by dispersing using a dispersing machine having
The heating temperature during dispersion is preferably the melting point of the wax or higher and 80° C. or higher, more preferably 85° C. or higher, and still more preferably 90° C. or higher. The temperature is less than 10°C higher and 100°C or less, more preferably 98°C or less, still more preferably 95°C or less.

The amount of the resin particles P is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, still more preferably 10 parts by mass or more, and preferably 100 parts by mass or less, or more, relative to 100 parts by mass of the wax. It is preferably 80 parts by mass or less, more preferably 60 parts by mass or less.

The volume-median particle diameter _D50 of the wax particles is preferably 0.05 μm or more, more preferably 0.2 μm or more, still more preferably 0.3 μm or more, from the viewpoint of obtaining uniform aggregated particles. It is 1 μm or less, more preferably 0.8 μm or less, still more preferably 0.6 μm or less.
The CV value of the wax particles is preferably 10% or more, more preferably 20% or more, and is preferably 40% or less, more preferably 35% or less, still more preferably 30% or less.
The volume-median particle size _D50 and CV value of the wax particles are measured according to the methods described in Examples.

Aggregation of resin particles and colorant particles Z may be performed in the presence of other additives besides wax.
Other additives include, for example, charge control agents, magnetic powders, fluidity improvers, conductivity modifiers, reinforcing fillers such as fibrous substances, antioxidants, anti-aging agents, and cleanability improvers. .

[Surfactant]
In step 1, the dispersion of each particle is mixed to prepare a mixed dispersion, and the dispersion stability of optional components such as resin particles, colorant particles Z, and optionally added wax particles is improved. From a point of view, it may be carried out in the presence of a surfactant. Examples of surfactants include anionic surfactants such as alkylbenzenesulfonates and alkylether sulfates; nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkenyl ethers.
When a surfactant is used, the amount used is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and preferably 10 parts by mass with respect to 100 parts by mass of the resin particles. It is not more than 5 parts by mass, more preferably not more than 3 parts by mass.

The dispersion of the resin particles, the dispersion of the colorant particles Z, and the optional ingredients are mixed by a conventional method. From the viewpoint of efficient aggregation, it is preferable to add a flocculant to the mixed dispersion obtained by the mixing.

[Flocculant]
Examples of flocculants include cationic surfactants such as quaternary salts, organic flocculants such as polyethyleneimine, and inorganic flocculants. Examples of inorganic flocculants include inorganic metal salts such as sodium sulfate, sodium nitrate, sodium chloride, calcium chloride and calcium nitrate; inorganic ammonium salts such as ammonium sulfate, ammonium chloride and ammonium nitrate; and divalent or higher metal complexes. .
From the viewpoint of improving cohesiveness and obtaining uniform aggregated particles, an inorganic flocculant having a valence of 1 to 5 is preferable, an inorganic metal salt having a valence of 1 to 2 and an inorganic ammonium salt are more preferable, and an inorganic ammonium salt is preferable. More preferred is ammonium sulfate.

Using an aggregating agent, for example, 5 parts by mass or more and 50 parts by mass or less of an aggregating agent is added to a mixed dispersion containing resin particles and colorant particles Z at a temperature of 0° C. or higher and 40° C. or lower with respect to the total amount of 100 parts by mass of the resin. Then, the resin particles and the colorant particles Z are aggregated in an aqueous medium to obtain aggregated particles. Furthermore, from the viewpoint of promoting aggregation, it is preferable to raise the temperature of the dispersion after adding the aggregating agent.

Resin particles containing resin A and resin C are further added to aggregated particles obtained by aggregating resin particles containing resin A and resin C and colorant particles Z, and resin particles containing resin A' are further added to contain resin A and resin C. Aggregated particles may be obtained by attaching resin particles containing resin A′ to aggregated particles containing resin particles and colorant particles Z. As a result, toner particles having a core-shell structure containing resin particles containing resin A and resin C and colorant particles Z in the core portion and resin A' in the shell portion can be obtained.
As the resin A', a polyester resin which is a polycondensate of an alcohol component and a carboxylic acid component is preferable. Resin A' is preferably an amorphous polyester resin.
Preferred examples of the alcohol component and the carboxylic acid component of Resin A′ and preferred ranges of their physical properties are the same as those shown for Resin A. The method for obtaining a dispersion of resin particles containing resin A' is the same as the method for producing resin particles XY.
The mass ratio [A'/A+C] of resin particles containing resin A' to resin particles containing resin A and resin C is preferably 0.05 or more, more preferably 0.1 or more, and still more preferably It is 0.13 or more, more preferably 0.15 or more, and preferably 0.5 or less, more preferably 0.3 or less, and still more preferably 0.25 or less.

The aggregation may be stopped when the aggregated particles have grown to a particle size suitable for toner particles.
Methods for stopping aggregation include a method of cooling the dispersion, a method of adding an aggregation inhibitor, and a method of diluting the dispersion. From the viewpoint of reliably preventing unnecessary aggregation, a method of stopping aggregation by adding an aggregation terminator is preferred.

[Aggregation terminating agent]
As the aggregation terminator, a surfactant is preferred, and an anionic surfactant is more preferred. Examples of anionic surfactants include alkylbenzene sulfonates, alkyl sulfates, alkyl ether sulfates, polyoxyalkylene alkyl ether sulfates, and the like. These may be used alone or in combination of two or more. The aggregation terminator may be added in the form of an aqueous solution.
The addition amount of the aggregation terminator is preferably 1 part by mass or more, more preferably 5 parts by mass or more with respect to 100 parts by mass of the resin in the resin particles, from the viewpoint of reliably preventing unnecessary aggregation, and , preferably 60 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less, from the viewpoint of reducing the residual amount in the toner.

The volume-median particle diameter _D50 of the aggregated particles is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, further preferably 6 μm or less. be. The volume-median particle diameter _D50 of the aggregated particles is determined by the method described in Examples below.

<Step 2>
In step 2, for example, the aggregated particles are fused together in an aqueous medium.
By fusion, each particle contained in the aggregated particles is fused to obtain fused particles.
The temperature for fusing (hereinafter also referred to as “fusing temperature”) is 10° C. higher than the melting point of Resin C from the viewpoint of obtaining a toner that provides high image density and exhibits excellent low-temperature fixability and charge stability. It is not less than a low temperature and not more than a temperature 60° C. higher than the melting point.
From the viewpoint of improving the image density, the fusing temperature is preferably at least 5°C lower than the melting point of Resin C, more preferably at least 3°C lower, and more preferably at least 40°C higher than the melting point of Resin C. is no higher than 20°C, more preferably no higher than 10°C, more preferably no higher than 5°C.
The time for holding at the fusion temperature is not particularly limited, and the fusion may be terminated when the degree of circularity of the fusion particles is monitored and within an appropriate range.

In step 2, an acidic substance may be added for fusing.
[Acidic substance]
Examples of acidic substances include inorganic acids and organic acids.
Inorganic acids include, for example, nitric acid, sulfuric acid, hydrochloric acid, and phosphoric acid.
Examples of organic acids include carboxylic acid compounds such as monocarboxylic acid, dicarboxylic acid and tricarboxylic acid, sulfonic acid compounds such as methanesulfonic acid, benzenesulfonic acid and toluenesulfonic acid, ascorbic acid, phenol, and cresol. Among these, carboxylic acid compounds are preferred.
Carboxylic acid compounds include, for example, acetic acid, lactic acid, tartaric acid, propionic acid, benzoic acid, oxalic acid, terephthalic acid, fumaric acid, succinic acid, acrylic acid, and adipic acid.
Among these, inorganic acids are preferred, and sulfuric acid is more preferred.

The acidic substance is preferably added to the system as an aqueous solution of the acidic substance.
When added as an aqueous solution of the acidic substance, the concentration of the acidic substance in the aqueous solution of the acidic substance is preferably 0.01 mol/L or more, more preferably 0.05 mol/L or more, and preferably 1 mol/L or less. , more preferably 0.5 mol/L or less.

The method of adding the acidic substance may be any of a method of adding all at once, a method of adding the total amount in two or more portions, and a method of continuously adding over a certain period of time. From the viewpoint of suppressing further agglomeration of particles, it is preferable to use either a method of dividing addition or a method of continuously adding over a certain period of time. The temperature at which the acidic substance is added is preferably within the aforementioned fusion temperature range.

The volume-median particle diameter _D50 of the fused particles obtained by fusion is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less. , and more preferably 6 μm or less.

The degree of circularity of the fused particles obtained by fusion bonding is preferably 0.955 or more, more preferably 0.960 or more, and is preferably 0.990 or less, more preferably 0.985 or less, and still more preferably 0.980 or less.

<Post-treatment process>
A post-treatment step may be performed after step 2 to obtain toner particles by isolating the fusing particles. Since the fused particles obtained in step 2 are present in the aqueous medium, it is preferable to perform solid-liquid separation first. A suction filtration method or the like is preferably used for the solid-liquid separation.
Washing is preferably performed after solid-liquid separation. At this time, since it is preferable to also remove the added surfactant, it is preferable to wash with an aqueous medium at a temperature not higher than the cloud point of the surfactant. Washing is preferably performed multiple times.
Drying is then preferably carried out. Drying methods include, for example, vacuum low-temperature drying, vibratory fluidized drying, spray drying, freeze drying, and flash drying.

[Toner particles]
The volume-median particle diameter _D50 of the toner particles is preferably 2 μm or more, more preferably 3 μm or more, and still more preferably 4 μm or more, from the viewpoint of obtaining high-quality images and further improving the cleanability of the toner. And it is preferably 10 μm or less, more preferably 8 μm or less, still more preferably 6 μm or less.

The CV value of the toner particles is preferably 12% or more, more preferably 14% or more, and still more preferably 16% or more from the viewpoint of improving toner productivity. It is preferably 30% or less, more preferably 26% or less.
The volume-median particle diameter _D50 and CV value of the toner particles can be measured by the methods described in Examples.
The toner particles contain the aforementioned resin A, resin C, resin E and colorant.

[toner]
Although the above-mentioned toner particles can be used as the toner as it is, the toner preferably contains an external additive. A toner includes, for example, toner particles and an external additive.
The content of the toner particles in the toner is preferably 90% by mass or more, more preferably 95% by mass or more, and is 100% by mass or less, preferably 99% by mass or less, more preferably 98% by mass or less. , more preferably 97% by mass or less.

[External additive]
Examples of external additives include fine particles of inorganic materials such as hydrophobic silica, titanium oxide, alumina, cerium oxide, and carbon black, and fine particles of polymers such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, hydrophobic silica is preferred.
When the toner particles are surface-treated using an external additive, the amount of the external additive added is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and still more preferably 100 parts by mass of the toner particles. It is 3 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 4 parts by mass or less.

Toners are used for electrostatic image development in electrophotographic printing. The toner can be used, for example, as a one-component developer or mixed with a carrier as a two-component developer.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples. Each property value was measured and evaluated by the following methods.
In addition, in descriptions such as "alkylene oxide (X)", the numerical value X in parentheses means the average number of added moles of alkylene oxide.

[Measuring method]
[Acid value of resin]
The acid value of the resin was measured according to the neutralization titration method described in JIS K 0070:1992. However, chloroform was used as the measurement solvent.

[Resin softening point, crystallinity index, melting point and glass transition temperature]
(1) Softening point Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), while heating a 1 g sample at a temperature increase rate of 6 ° C./min, a load of 1.96 MPa is applied with a plunger, and the diameter It was extruded through a 1 mm, 1 mm long nozzle. The amount of plunger depression of the flow tester was plotted against the temperature, and the softening point was defined as the temperature at which half of the sample flowed out.
(2) Crystallinity index Using a differential scanning calorimeter "Q100" (manufactured by TA Instrument Japan Co., Ltd.), 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. did. Next, the sample was allowed to stand still for 1 minute, then heated to 180°C at a heating rate of 10°C/min, and the calorific value was measured. Among the observed endothermic peaks, the temperature of the peak with the maximum peak area is defined as the maximum endothermic peak temperature (1), and (softening point (°C)) / (maximum endothermic peak temperature (1) (°C)) A crystallinity index was determined.
(3) Melting point and glass transition temperature Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of the sample was weighed into an aluminum pan, heated to 200 ° C., and the temperature It was cooled to 0°C at a cooling rate of 10°C/min. Then, the temperature of the sample was increased at a temperature increase rate of 10°C/min, and the calorie was measured. Among the observed endothermic peaks, the temperature of the peak with the maximum peak area was defined as the maximum endothermic peak temperature (2). In the case of a crystalline resin, the peak temperature was taken as the melting point.
In the case of an amorphous resin, when a peak is observed, the temperature of the peak is measured. The temperature at the point of intersection with the extended line of the baseline on the low temperature side was defined as the glass transition temperature.

[Weight Average Molecular Weight of Addition Polymer]
Gel permeation chromatography [GPC apparatus "HLC-8320GPC" ( manufactured by Tosoh Corporation), column "TSKgel Super AWM-H, TSKgel SuperAW3000, TSKgel guardcolumn Super AW-H" (manufactured by Tosoh Corporation), flow rate: 0.5 mL/min], monodisperse polystyrene with a known molecular weight as a standard substance Kit [PStQuick B (F-550, F-80, F-10, F-1, A-1000), PStQuick C (F-288, F-40, F-4, A-5000, A-500), manufactured by Tosoh Corporation].

[Melting point of wax]
Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of the sample was weighed in an aluminum pan, heated to 200 ° C., and then cooled from 200 ° C. at a cooling rate of 10 ° C./min. was cooled to 0°C. Next, the temperature of the sample was increased at a temperature increase rate of 10° C./min, the calorie was measured, and the maximum endothermic peak temperature was defined as the melting point.

[Volume-median particle diameter _D50 and CV value of resin particles, colorant particles, and wax particles]
(1) Measuring device: Laser diffraction particle size measuring machine “LA-920” (manufactured by HORIBA, Ltd.)
(2) Measurement conditions: A sample dispersion was placed in a measurement cell, distilled water was added, and the volume median particle diameter _D50 and the volume average particle diameter _Dv were measured at a concentration at which the absorbance was within the appropriate range. Also, the CV value was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution/volume average particle size _Dv ) x 100

[Solid Content Concentration of Resin Particle Dispersion, Colorant Particle Dispersion, and Wax Particle Dispersion]
Using an infrared moisture meter "FD-230" (manufactured by Ketsuto Kagaku Kenkyusho Co., Ltd.), 5 g of the measurement sample is dried at 150 ° C., measurement mode 96 (monitoring time 2.5 minutes, fluctuation range of water content 0.05% ), the moisture content (% by mass) was measured. The solid content concentration was calculated according to the following formula.
Solid content concentration (mass%) = 100 - moisture (mass%)

[Water Content of Toner Particles]
Using an infrared moisture meter "FD-230" (manufactured by Ketsuto Kagaku Kenkyusho Co., Ltd.), 5 g of toner particles are dried at a temperature of 150 ° C., measurement mode 96 (monitoring time 2.5 minutes, fluctuation range of moisture content 0.05%). ), the moisture content (% by mass) was measured.

[Volume Median Particle Size D ₅₀ of Aggregated Particles]
The volume median particle size _D50 of the aggregated particles was measured as follows.
・Measuring machine: “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 solution: “Isoton (registered trademark) II” (manufactured by Beckman Coulter, Inc.)
Measurement conditions: By adding the sample dispersion to 100 mL of the electrolytic solution, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured again, and the particle size The volume median particle size _D50 was determined from the distribution.

[Circularity of fused particles]
The circularity of the fused particles was measured under the following conditions.
・ Measuring device: Flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation)
- Preparation of dispersion liquid: A dispersion liquid of fused particles was diluted with deionized water so that the solid content concentration was 0.001 to 0.05% by mass.
・Measurement mode: HPF measurement mode

[Volume Median Particle Diameter _D50 and CV Value of Toner Particles]
The volume median particle size _D50 of the toner particles was measured as follows.
The measuring device, aperture diameter, analysis software, and electrolytic solution used were the same as those used in the measurement of the volume-median particle diameter _D50 of the aggregated particles described above.
- Dispersion: Polyoxyethylene lauryl ether "Emulgen (registered trademark) 109P" (manufactured by Kao Corporation, HLB (Hydrophile-Lipophile Balance) = 13.6) is dissolved in the electrolytic solution to obtain a dispersion with a concentration of 5% by mass. got
Dispersion conditions: 10 mg of a measurement sample of dried toner particles was added to 5 mL of the dispersion liquid, dispersed for 1 minute with an ultrasonic disperser, and then 25 mL of the electrolytic solution was added. and dispersed for 1 minute to prepare a sample dispersion.
Measurement conditions: By adding the sample dispersion to 100 mL of the electrolytic solution, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured. The volume median particle size _D50 and volume average particle size _DV were determined from the distribution.
Also, the CV value (%) was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution/volume average particle size D _V ) x 100

[Evaluation method]
[Low Temperature Fixability of Toner]
Using a commercially available printer "Microline (registered trademark) 5400" (manufactured by Oki Data Co., Ltd.) on high-quality A4 paper "J paper A4 size" (manufactured by Fuji Xerox Co., Ltd.), the toner adhesion amount on the paper is 0.40 ~ A solid image of 0.46 mg/cm ² was printed on high-quality A4 paper with a margin of 5 mm from the top edge and a length of 50 mm without being fixed.
Next, the same printer with a variable temperature fixing device was prepared, the temperature of the fixing device was set to 100° C., and the toner was fixed at a speed of 2.5 seconds per sheet of A4 paper in the longitudinal direction to obtain printed matter.
By the same method, the temperature of the fixing device was increased by 5° C. to fix the toner, and a printed matter was obtained.
A piece of mending tape "Scotch (registered trademark) Mending Tape 810" (manufactured by Sumitomo 3M Co., Ltd., width 18 mm) cut into a length of 50 mm is lightly pasted from the top margin of the printed image to the solid image. After that, a cylindrical weight of 500 g (contact area: 1963 mm ² ) was placed and pressed once at a speed of 10 mm/s. After that, the attached tape was peeled off from the lower end side at a peeling angle of 180° and a speed of 10 mm/s to obtain a print after tape peeling. Thirty sheets of high-quality paper "Excellent White Paper A4 size" (manufactured by Oki Data Co., Ltd.) were placed under the printed matter before and after the tape was applied, and the reflected image density of the fixed image portion of each printed matter was measured before and after the tape was applied. , SpectroEye colorimeter (manufactured by GretagMacbeth, light irradiation conditions; standard light source D50, observation field of view 2°, density standard DINNB, absolute white standard). was calculated.
Fixing rate (%) = (reflected image density after tape removal/reflected image density before tape application) x 100
The lowest temperature at which the fixation rate was 90% or more was defined as the lowest fixation temperature, and the low-temperature fixability was evaluated at this temperature. The lower the minimum fixing temperature, the better the low-temperature fixability.

[Image density of printed matter]
Using a commercially available printer "Microline (registered trademark) 5400" (manufactured by Oki Data Co., Ltd.) on high-quality paper "J paper A4 size" (manufactured by Fuji Xerox Co., Ltd.), the toner adhesion amount on the paper is 0.25 mg / cm A solid image of ² was output without being fixed.
Next, the temperature of the fixing device is set to the minimum fixing temperature +10°C obtained in the above low-temperature fixability test, and the toner is fixed at a speed of 2.5 seconds per A4 sheet in the vertical direction, and the printed matter is produced. Obtained.
Thirty sheets of high-quality paper "Excellent White Paper A4" (manufactured by Oki Data Co., Ltd.) are placed under the printed matter, and the reflected image density of the solid image portion of the output printed matter is measured with a colorimeter "SpectroEye" (manufactured by GretagMacbeth). Measurement was performed using the irradiation conditions: standard light source D50, observation field of view 2°, density standard DINNB, absolute white standard), and the values obtained by measuring arbitrary 10 points on the image were averaged to obtain the image density. The higher the numerical value, the better the image density.

[Toner charge stability (charge amount distribution)]
0.6 g of toner and 19.4 g of ferrite carrier (ferrite core, silicone coat, saturation magnetization: 71 Am ² /kg) were placed in a 50 mL polypropylene bottle “PP Sample Bottle Wide Mouth” (manufactured by Sun Platec Co., Ltd.) and subjected to ball milling. After stirring for 20 minutes, 5 g of the mixture was sampled and measured under the following measurement conditions using a charge amount measuring device "q-test" (manufactured by Epping).
・Toner Flow (mL/min): 160
・Electrode Voltage (V): 4000
・Deposition Time (s): 2
The median q/d was defined as the toner charge amount Q/d (fC/10 μm). At that time, the Specific Density (specific gravity) was set to 1.2 g/cm ³ , and the value of the volume median particle size D ₅₀ of the toner was adopted as the Median Diameter. The resulting Q/d ranged from -0.4 to 0.4 (fC/10 μm) with a straight line to prepare a graph of charge amount distribution.
The charge amount distribution was evaluated based on the half width of the maximum peak of the charge amount distribution (cut width when the distribution is cut at half the maximum peak height in the distribution). The smaller the value, the narrower the charge amount distribution and the better the charge stability.

[Production of resin]
[Production of amorphous polyester resin A/amorphous polyester resin E]
Production Example A1 (Production of Resin A-1)
The inside of a four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, and 3880 g of 2,2-bis(4-hydroxyphenyl)propane-propylene oxide (2.2) adduct was added. , 1544 g of ethylene oxide (2.2) adduct of 2,2-bis(4-hydroxyphenyl)propane, 1578 g of terephthalic acid, 694 g of adipic anhydride, and 40 g of tin di(2-ethylhexanoate) were charged and nitrogen was added. In an atmosphere, the temperature was raised to 235° C. with stirring, and after holding at 235° C. for 6 hours, the pressure in the flask was further lowered and held at 8.3 kPa for 1 hour. Then, after cooling to 215 ° C. and returning to atmospheric pressure, 304 g of trimellitic anhydride was added and maintained at 215 ° C. for 1 hour. to obtain Resin A-1. Table 1 shows the physical properties of the obtained resin.

Production Examples A2 and A3 (Production of resins A-2 and A-3)
Resins A-2 and A-3 were obtained in the same manner as in Production Example A1, except that the composition of the raw material monomer (P) was changed as shown in Table 1. Table 1 shows the physical properties of the obtained resin.

Production Examples A4 and A5 (production of resins A-4 and A-5)
Amorphous polyesters A-4 and A- Got 5. Physical properties are shown in Table 1.

Production Example A6 (Production of Resin A-6)
A four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, and 3885 g of 2,2-bis(4-hydroxyphenyl)propane-propylene oxide (2.2) adduct was added. , 1546 g of ethylene oxide (2.2) adduct of 2,2-bis(4-hydroxyphenyl)propane, 2106 g of terephthalic acid, and 40 g of tin di(2-ethylhexanoate) were added and stirred under a nitrogen atmosphere. , and held at 235° C. for 8 hours, the pressure in the flask was further lowered and held at 8.3 kPa for 1 hour. Then, after cooling to 180° C. and returning to atmospheric pressure, 463 g of adipic anhydride was added, the temperature was raised to 215° C. at a rate of 10° C./h, and the temperature was maintained at 215° C. for 1 hour. The internal pressure was lowered and the reaction was carried out to the desired softening point at 8.3 kPa to obtain Resin A-6. Table 1 shows the physical properties of the obtained resin.

[Production of crystalline polyester resin C]
Production Example C1 (Production of Resin C-1)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, 3416 g of 1,10-decanediol and 4084 g of sebacic acid were added, and while stirring, 135 C. and held at 135.degree. C. for 3 hours, then heated from 135.degree. C. to 200.degree. C. over 10 hours. After that, 23 g of tin (II) di(2-ethylhexanoate) was added, and the temperature was maintained at 200° C. for 1 hour. C-1 was obtained. Table 2 shows the physical properties of the obtained resin.

Production Example C2 (Production of Resin C-2)
Resin C-2 was obtained in the same manner as in Production Example C1, except that the raw material composition was changed as shown in Table 2. Table 2 shows the physical properties of the obtained resin.

Production Example D1 (Production of Resin D-1)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 4313 g of a polyoxypropylene (2.2) adduct of bisphenol A, 818 g of terephthalic acid, 727 g of succinic acid, 30 g of di(2-ethylhexanoic acid) tin (II), and 3.0 g of 3,4,5-trihydroxybenzoic acid were added, and the temperature was raised to 235°C under a nitrogen atmosphere while stirring. After maintaining the temperature at 235° C. for 5 hours, the pressure in the flask was lowered and the pressure was maintained at 8 kPa for 1 hour. After returning to atmospheric pressure, the system was cooled to 160°C, and a mixture of 2756 g of styrene, 689 g of stearyl methacrylate, 142 g of acrylic acid, and 413 g of dibutyl peroxide was added dropwise over 1 hour while maintaining the temperature at 160°C. Then, after holding at 160° C. for 30 minutes, the temperature was raised to 200° C., the pressure in the flask was further lowered, and the reaction was carried out to the desired softening point at 8 kPa to obtain Resin D-1. As a result of measuring the physical properties, the softening point was 91° C., the glass transition temperature was 42° C., the acid value was 24 mgKOH/g, and the crystallinity index was 1.8.

[Production of resin particle dispersion]
Production Example XY1 (Production of Resin Particle Dispersion Liquid XY-1)
270 g of resin A-1, 30 g of resin C-1, 360 g of methyl ethyl ketone, and 59 g of deionized water were placed in a container having an internal volume of 3 L equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet tube. , 73° C. for 2 hours to dissolve the resin. A 5% by mass sodium hydroxide aqueous solution was added to the resulting solution so that the degree of neutralization would be 60 mol % with respect to the acid value of the resin, and the mixture was stirred for 30 minutes.
Next, 600 g of deionized water was added over 60 minutes while stirring at 280 r/min (peripheral speed of 88 m/min) while maintaining the temperature at 73° C., and phase inversion emulsification was performed. While the temperature was maintained at 73° C., methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. After that, the aqueous dispersion is cooled to 30° C. while stirring at 280 r/min (peripheral speed 63 m/min), and then deionized water is added so that the solid content concentration becomes 20% by mass, thereby dispersing the resin particles. Liquid XY-1 was obtained. Table 3 shows the volume-median particle diameter _D50 and CV value of the obtained resin particles.

Production Example XY2 (Production of Resin Particle Dispersion XY-2)
A resin particle dispersion XY-2 was obtained in the same manner as in Production Example XY1, except that the type of resin used was changed as shown in Table 3. Table 3 shows the volume-median particle diameter _D50 and CV value of the obtained resin particles.

Production Example X1 (Production of Resin Particle Dispersion X-1)
A resin particle dispersion liquid X-1 was obtained in the same manner as in Production Example XY1, except that the type of resin used was changed to 300 g of resin A-1. Table 3 shows the volume-median particle diameter _D50 and CV value of the obtained resin particles.

Production Example P1 (Production of Resin Particle Dispersion P-1)
200 g of resin D-1 and 200 g of methyl ethyl ketone are placed in a container having an internal volume of 3 L equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet tube, and the resin is dissolved at 73° C. for 2 hours. rice field. A 5 mass % sodium hydroxide aqueous solution was added to the obtained solution so that the degree of neutralization was 60 mol % with respect to the acid value of Resin D-1, and the mixture was stirred for 30 minutes.
Next, 700 g of deionized water was added over 50 minutes while stirring at 280 r/min (peripheral speed of 88 m/min) while maintaining the temperature at 73° C. to effect phase inversion emulsification. Methyl ethyl ketone was distilled off under reduced pressure while the temperature was maintained at 73° C. to obtain an aqueous dispersion. Thereafter, the aqueous dispersion is cooled to 30°C while stirring at 280 r/min (peripheral speed of 88 m/min), and then deionized water is added so that the solid content concentration becomes 20% by mass, thereby dispersing the resin particles. A liquid P-1 was obtained. The obtained resin particles had a volume-median particle size _D50 of 0.09 μm and a CV value of 23%.

[Production of Wax Particle Dispersion]
Production Example W1 (Production of Wax Particle Dispersion W-1)
120 g of deionized water, 86 g of resin particle dispersion liquid P-1, and 40 g of paraffin wax "HNP-9" (manufactured by Nippon Seiro Co., Ltd., melting point 75 ° C.) were added to a beaker with an internal volume of 1 L, and the temperature was adjusted to 90 to 95 ° C. The mixture was melted while maintaining the temperature at , and stirred to obtain a molten mixture.
While maintaining the temperature of the obtained molten mixture at 90 to 95 ° C., using an ultrasonic homogenizer "US-600T" (manufactured by Nippon Seiki Seisakusho Co., Ltd.), dispersion treatment was performed for 20 minutes, and then cooled to room temperature (20 ° C.). cooled. Deionized water was added to adjust the solid content concentration to 20% by mass to obtain a wax particle dispersion W-1. The volume median particle diameter _D50 of the wax particles in the dispersion was 0.47 μm, and the CV value was 27%.

[Production of addition polymer]
Production Example F81 (Synthesis of addition polymer F-81)
Methacrylic acid 16 g, benzyl methacrylate 44 g, styrene macromonomer "AS-6S" (manufactured by Toagosei Co., Ltd., number average molecular weight 6,000, solid content concentration 50% by mass) 30 g, methoxy polyethylene glycol methacrylate "Blenmer PME-200" (manufactured by NOF Corporation) were mixed to prepare a monomer mixed solution with a total monomer amount of 100 g.
The inside of a four-necked flask equipped with a nitrogen inlet tube, a dropping funnel, a stirrer, and a thermocouple is replaced with nitrogen, and 18 g of methyl ethyl ketone, 0.03 g of 2-mercaptoethanol, and 10% by mass of the monomer mixture are added, The temperature was raised to 75° C. while stirring. The remaining 90% by mass of the monomer mixture, 0.27 g of 2-mercaptoethanol, 42 g of methyl ethyl ketone, and 2,2′-azobis(2,4-dimethylvaleronitrile) “V-65” while being maintained at 75° C. (manufactured by Wako Pure Chemical Industries, Ltd.) 3 g of the mixture was dropped from the dropping funnel over 3 hours. After the temperature was maintained at 75° C. for 2 hours after completion of dropping, a solution of 3 g of V-65 dissolved in 5 g of methyl ethyl ketone was added, and the temperature was further maintained at 75° C. for 2 hours and at 80° C. for 2 hours. Thereafter, methyl ethyl ketone was distilled off under reduced pressure to obtain addition polymer F-81. The weight average molecular weight of the obtained addition polymer was 49,000.

[Production of colorant particle dispersion]
Production Example Z1 (Production of Colorant Particle Dispersion Z-1)
75 g of resin A-1 and 596 g of methyl ethyl ketone as resin E were placed in a container with an internal volume of 5 L equipped with a stirrer equipped with a disper blade, a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet tube, and the resin was heated at 20 ° C. was dissolved. To the resulting solution, 16 g of a 5% by mass sodium hydroxide aqueous solution (the degree of neutralization of Resin A-1 becomes 80 mol %) was added, and 834 g of deionized water was further added, followed by dispersing at 20° C. with a disper blade. Stirred for 10 minutes. Then, 300 g of carbon black “Regal-330R” (manufactured by Cabot Corporation) was added, and the mixture was stirred at 20° C. for 2 hours at 6400 r/min with a disper blade. Then, it was passed through a 200-mesh filter and treated with a homogenizer "Microfluidizer M-110EH" (manufactured by Microfluidics) at a pressure of 150 MPa for 15 passes. Methyl ethyl ketone and part of water were distilled off at 70° C. under reduced pressure while stirring the resulting dispersion. After cooling, the mixture was passed through a 200-mesh filter and deionized water was added so that the solid content concentration was 20% by mass, thereby obtaining a colorant particle dispersion liquid Z-1. Table 4 shows the volume median particle diameter _D50 and CV value of the obtained colorant particles.

Production Examples Z2 to Z9 (Production of Colorant Particle Dispersions Z-2 to Z-9)
Colorant particle dispersions Z-2 to Z-9 were obtained in the same manner as in Production Example Z1, except that the types and amounts of the raw materials used were changed as shown in Table 1. Table 4 shows the volume median particle diameter _D50 and CV value of the obtained colorant particles.

Production Example Z81 (Production of Colorant Particle Dispersion Z-81)
Except for changing resin A-1 to addition polymer F-81 and changing the amount of 5 mass% sodium hydroxide aqueous solution added to 101 g (the addition polymer F-81 has a degree of neutralization of 91 mol%). A colorant particle dispersion Z-81 was obtained in the same manner as in Production Example Z1. Table 4 shows the volume median particle diameter _D50 and CV value of the obtained colorant particles.

Production Example Z82 (Production of Colorant Particle Dispersion Z-82)
75 g of Resin A-1 and 16 g of a 5% by mass sodium hydroxide aqueous solution (Resin A- The degree of neutralization of 1 becomes 80 mol %) was added, and the mixture was stirred at 95° C. for 1 hour with a disper blade. Then, 834 g of deionized water was added dropwise at 95° C. at a rate of 10 g/min.
After that, the temperature in the system was lowered to 20° C., 300 g of carbon black “Regal-330R” (manufactured by Cabot Corporation) was added, and the mixture was stirred at 20° C. with a disper blade at 6400 r/min for 2 hours. After that, it was passed through a 200-mesh filter and subjected to 15 passes at a pressure of 150 MPa using a homogenizer "Microfluidizer M-110EH" (manufactured by Microfluidics). Thereafter, the mixture was passed through a 200-mesh filter and deionized water was added so that the solid content concentration was 20% by mass, thereby obtaining a colorant particle dispersion liquid Z-82. Table 4 shows the volume median particle diameter _D50 and CV value of the obtained colorant particles.

Production Example Z83 (Production of Colorant Particle Dispersion Z-83)
In a beaker with an internal volume of 1 L, 100 g of carbon black "Regal-330R" (manufactured by Cabot Corporation) and 15% by mass of sodium dodecylbenzenesulfonate aqueous solution "Neopelex G-15" (manufactured by Kao Corporation, anionic surfactant) 167 g. , and 102 g of deionized water are mixed, and using a homomixer "TK AGI HOMOMIXER 2M-03" (manufactured by Tokushu Kika Kogyo Co., Ltd.), at 20 ° C., 1 at a stirring blade rotation speed of 8000 r / min. After being dispersed over time, it was subjected to 15 passes at a pressure of 150 MPa using a homogenizer "Microfluidizer M-110EH" (manufactured by Microfluidics). Thereafter, the mixture was passed through a 200-mesh filter and deionized water was added so that the solid content concentration was 20% by mass, thereby obtaining a colorant particle dispersion liquid Z-83. Table 4 shows the volume median particle diameter _D50 and CV value of the obtained colorant particles.

[Toner manufacturing]
Example 1 (Production of Toner 1)
500 g of resin particle dispersion XY-1, 82 g of wax particle dispersion W-1, and colorant particle dispersion Z-1 were placed in a four-necked flask with an internal volume of 3 L equipped with a dehydration tube, a stirrer and a thermocouple. 81 g, 15 g of a 10% by weight aqueous solution of polyoxyethylene (50) lauryl ether "Emulgen 150" (manufactured by Kao Corporation, nonionic surfactant), and 15% by weight aqueous solution of sodium dodecylbenzenesulfonate "Neopelex G-15 (manufactured by Kao Corporation, anionic surfactant) 17 g were mixed at a temperature of 25°C. Next, while stirring the mixture, an aqueous solution of 40 g of ammonium sulfate dissolved in 568 g of deionized water was added with a 4.8% by mass aqueous potassium hydroxide solution to adjust the pH to 8.6. After that, the temperature was raised to 62° C. over 2 hours and maintained at 62° C. until the volume median particle diameter D ₅₀ of the aggregated particles reached 5.2 μm, to obtain a dispersion liquid of aggregated particles.
To the dispersion of the obtained aggregated particles, 48 g of sodium polyoxyethylene lauryl ether sulfate "Emal E-27C" (manufactured by Kao Corporation, an anionic surfactant, effective concentration of 27% by mass), 600 g of deionized water, and 0 An aqueous solution mixed with 60 g of a 1 mol/L sulfuric acid aqueous solution was added. After that, the temperature was raised to 76° C. over 1 hour and maintained at 76° C. for 30 minutes, then 10 g of 0.1 mol/L sulfuric acid aqueous solution was added and further maintained at 76° C. for 15 minutes. Thereafter, 10 g of a 0.1 mol/L sulfuric acid aqueous solution was added again, and the temperature was maintained at 76° C. until the circularity reached 0.970, thereby obtaining a dispersion of fused particles in which aggregated particles were fused.
The fused particle dispersion thus obtained was cooled to 30° C., the dispersion was suction filtered to separate the solid content, washed with deionized water at 25° C., and suction filtered at 25° C. for 2 hours. Thereafter, vacuum drying was performed at 33° C. for 24 hours using a constant temperature vacuum dryer “DRV622DA” (manufactured by ADVANTEC) to obtain toner particles having a moisture content of 0.5% by mass or less. Table 6 shows the physical properties of the obtained toner particles.
100 parts by mass of toner particles, 2.5 parts by mass of hydrophobic silica “RY50” (manufactured by Nippon Aerosil Co., Ltd., number average particle diameter: 0.04 μm), and hydrophobic silica “Cabosil (registered trademark) TS720” (Cabot Japan Co., Ltd. Toner 1 was obtained by adding 1.0 parts by mass of the toner (manufactured by the company, number average particle diameter: 0.012 μm) into a Henschel mixer, stirring, and passing it through a 150-mesh sieve. Table 5 shows the evaluation results of the obtained toner.

Examples 2, 5 to 9, 12 and Comparative Examples 1 to 3, 5 (production of toners 2, 5 to 9, 12, 81 to 83, 85)
Toners 2, 5 to 9, 12, 81 to 83, and 85 were prepared in the same manner as in Example 1, except that the type of resin particle dispersion and the type of colorant particle dispersion used were changed as shown in Table 5. made. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Example 3 (Production of Toner 3)
Toner 3 was prepared in the same manner as in Example 1, except that the type of colorant particle dispersion used was changed to dispersion Z-3 and the amount added was changed to 96 g. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.
Here, the addition amount of the colorant particle dispersion liquid was adjusted in order to compare the evaluation results by comparison with Example 1 by matching the addition amount of the colorant to that of Example 1.

Example 4 (Production of Toner 4)
Toner 4 was prepared in the same manner as in Example 1, except that the type of colorant particle dispersion used was changed to dispersion Z-4 and the amount added was changed to 72 g. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.
Here, the addition amount of the colorant particle dispersion liquid was adjusted in order to compare the evaluation results by comparison with Example 1 by matching the addition amount of the colorant to that of Example 1.

Example 10 (Production of Toner 10)
After obtaining aggregated particles in the same manner as in Example 1, polyoxyethylene lauryl ether sodium sulfate "Emal E-27C" (manufactured by Kao Corporation, anionic surfactant, effective An aqueous solution obtained by mixing 48 g (concentration 27% by mass), 600 g of deionized water, and 60 g of a 0.1 mol/L sulfuric acid aqueous solution was added. After that, the temperature was raised to 72° C. over 1 hour and maintained at 72° C. for 30 minutes, then 15 g of 0.1 mol/L sulfuric acid aqueous solution was added and further maintained at 72° C. for 15 minutes. Thereafter, 15 g of a 0.1 mol/L sulfuric acid aqueous solution was added again, and the temperature was maintained at 72° C. until the circularity reached 0.970, thereby obtaining a dispersion of fused particles in which aggregated particles were fused. Thereafter, toner 10 was produced in the same manner as after obtaining the dispersion liquid of the fusible particles in Example 1. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Example 11 (Production of Toner 11)
After obtaining aggregated particles in the same manner as in Example 1, polyoxyethylene lauryl ether sodium sulfate "Emal E-27C" (manufactured by Kao Corporation, anionic surfactant, effective An aqueous solution obtained by mixing 48 g (concentration 27% by mass), 600 g of deionized water, and 60 g of a 0.1 mol/L sulfuric acid aqueous solution was added. After that, the temperature was raised to 85° C. over 1 hour and maintained at 85° C. for 30 minutes, then 7 g of 0.1 mol/L sulfuric acid aqueous solution was added and further maintained at 85° C. for 15 minutes. Then, 7 g of a 0.1 mol/L sulfuric acid aqueous solution was added again, and the temperature was maintained at 85° C. until the circularity reached 0.970, thereby obtaining a dispersion of fused particles in which aggregated particles were fused. Thereafter, Toner 11 was produced in the same manner as after obtaining the dispersion of fusible particles in Example 1. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Comparative Example 4 (Production of Toner 84)
After obtaining aggregated particles in the same manner as in Example 1, polyoxyethylene lauryl ether sodium sulfate "Emal E-27C" (manufactured by Kao Corporation, anionic surfactant, effective An aqueous solution obtained by mixing 48 g (concentration 27% by mass), 600 g of deionized water, and 60 g of a 0.1 mol/L sulfuric acid aqueous solution was added. After that, the temperature was raised to 66° C. over 1 hour and maintained at 66° C. for 30 minutes, then 22 g of 0.1 mol/L sulfuric acid aqueous solution was added and further maintained at 66° C. for 15 minutes. Thereafter, 22 g of a 0.1 mol/L sulfuric acid aqueous solution was added again, and the temperature was maintained at 66° C. until the circularity reached 0.970, thereby obtaining a dispersion of fused particles in which aggregated particles were fused. Thereafter, a toner 84 was produced in the same manner as after obtaining the dispersion liquid of the fusible particles in Example 1. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

From the results of the examples and the comparative examples, it can be seen that according to the present invention, it is possible to obtain a toner having high image density in printed matter and excellent low-temperature fixability and charge stability.

Claims (5)

A method for producing a toner, comprising a step of aggregating and fusing resin particles and colorant particles,
The resin particles contain an amorphous polyester resin A and a crystalline polyester resin C in the same or different particles,
The colorant particles are obtained by dispersing a colorant in a mixed liquid containing an amorphous polyester resin E, an organic solvent, and water,
The method for producing a toner, wherein the fusion-bonding temperature is at least 10°C lower than the melting point of the crystalline polyester resin C and at most 10 °C higher than the melting point. 2. The method for producing a toner according to claim 1, wherein the colorant particles are obtained by dispersing a colorant with a bead mill or a homogenizer. 3. The method for producing a toner according to claim 1, wherein a mass ratio of said colorant to said amorphous polyester resin E in said colorant particles is 50/50 or more and 95/5 or less. The amorphous polyester resin A and the amorphous polyester resin E are each independently a polycondensate of an alcohol component containing an alkylene oxide adduct of bisphenol A and a carboxylic acid component containing an aromatic dicarboxylic acid. 4. The method for producing a toner according to claim 1. The method for producing a toner according to any one of claims 1 to 4, wherein the colorant is carbon black.