JP2019194686A - Method for manufacturing toner - Google Patents

Abstract

To provide a method for manufacturing a toner from which a high image density is obtained, and is excellent in low-temperature fixability and temporal stability of low-temperature fixability, and a toner.SOLUTION: (1) A method for manufacturing a toner includes a step of aggregating and fusing resin particles and colorant particles in an aqueous medium. The resin particles contain, in the same or different particles, an addition polymerization resin A that is an addition polymer of a raw material monomer containing a styrene compound, and a crystalline polyester resin; the colorant particles contain a colorant and an addition polymer E of a raw material monomer containing an addition polymerizable monomer having an aromatic group; the mass ratio of the colorant in the colorant particles to the addition polymer E is 50/50 or more and 95/5 or less. (2) A toner contains toner particles containing an addition polymerization resin A, a crystalline polyester resin, an addition polymer E, and a colorant. The addition polymerization resin A is an addition polymer of a raw material monomer containing a styrene compound; the addition polymer E is an addition polymer of a raw material monomer containing an addition polymerizable monomer having an aromatic group; the mass ratio of the colorant to the addition polymer E is 50/50 or more and 95/5 or less.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like, and the toner.

  In the field of electrophotography, with development of an electrophotographic system, development of toner for electrophotography corresponding to high image quality and high speed is demanded. Corresponding to higher image quality, a method for obtaining a toner having a narrow particle size distribution and a small particle size is obtained by agglomerating and fusing fine resin particles in an aqueous medium to obtain a toner. So-called chemical toners are produced by an agglomeration method and an aggregation coalescence method.

In Patent Document 1, a toner having a step of aggregating colorant-containing polymer particles and resin particles by mixing a dispersion of colorant-containing polymer particles and a dispersion of resin particles substantially free of colorant 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 for producing a photographic toner is described. It is described that according to the toner, the dispersibility of the colorant is excellent and the image density can be remarkably improved.
In Patent Document 2, a toner for developing an electrostatic latent image having toner base particles containing a binder resin and a release agent, the binder resin containing a crystalline resin and a vinyl resin, Toners satisfying the above conditions are described. The toner is described as having sufficient low-temperature fixability, separation property, high-temperature storage stability, and gloss uniformity of a fixed image.

JP 2010-26106 A JP 2017-167420 A

In recent years, in the field of electrophotography, there has been a strong demand for resource saving and energy saving, and higher image density can be obtained even if the amount of toner used is smaller than conventional methods such as Patent Documents 1 and 2. Therefore, low temperature fixability for fixing at a lower temperature is required. Further, when toner particles are produced by the cohesive fusion method, even if a crystalline resin is mixed with the binder resin to improve the low-temperature fixability of the toner, the low-temperature fixability may deteriorate over time.
Therefore, the present invention relates to a toner production method and a toner that can obtain high image density and are excellent in low-temperature fixability and low-temperature fixability over time.

By combining resin particles containing a specific addition polymerization resin and a crystalline polyester resin and colorant particles containing a specific addition polymer, the inventors have improved image density, low temperature fixability and low temperature. It has been found that a toner having excellent fixing stability over time can be obtained.
The present invention relates to the following [1] and [2].
[1] A method for producing a toner, comprising a step of aggregating and fusing resin particles and colorant particles in an aqueous medium,
The resin particles contain, in the same or different particles, an addition polymerization resin A that is an addition polymerization product of a raw material monomer containing a styrene compound, and a crystalline polyester resin,
The colorant particles contain a colorant and an addition polymer E of a raw material monomer containing an addition polymerizable monomer having an aromatic group,
A toner production method, wherein a mass ratio of the colorant to the addition polymer E in the colorant particles is 50/50 or more and 95/5 or less.
[2] A toner comprising toner particles containing an addition polymerization resin A, a crystalline polyester resin, an addition polymer E, and a colorant,
The addition polymerization resin A is an addition polymerization product of a raw material monomer containing a styrene compound,
The addition polymer E is an addition polymer of a raw material monomer containing an addition polymerizable monomer having an aromatic group,
A toner in which a mass ratio of the colorant to the addition polymer E is from 50/50 to 95/5.

  According to the present invention, there are provided a toner production method and a toner capable of obtaining a high image density and excellent in low-temperature fixability and low-temperature fixability over time.

[Toner Production Method]
The method for producing a 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 are the same or different in the same or different particles, the addition polymerization resin A (hereinafter also simply referred to as “resin A”) which is an addition polymerization product of a raw material monomer containing a styrene compound, and a crystalline polyester resin (hereinafter simply referred to as “ Resin C ").
The colorant particles contain a colorant and an addition polymer E of a raw material monomer containing an addition polymerizable monomer having an aromatic group (hereinafter also simply referred to as “addition polymer E”).
The mass ratio between the colorant and the addition polymer E in the colorant particles is 50/50 or more and 95/5 or less.
By the above production method, a high image density can be obtained, and a toner having excellent low-temperature fixability and low-temperature fixability over time can be obtained.

In the cohesive fusion method without a kneading step, one of the factors that lowers the image density of the resulting toner print is that the dispersibility of the colorant in the toner is not sufficient, especially when coagulating and fusing. It was mentioned that each other tends to aggregate. This was considered because the colorant was not sufficiently stabilized in the dispersion or in the binder resin constituting the toner.
In the present invention, as the resin constituting the binder resin, an addition polymerization resin A which is an addition polymer of a raw material monomer containing a styrene compound and a crystalline polyester resin are used, and further, a colorant, an aromatic group A dispersion of colorant particles obtained by mixing an addition polymer E of a raw material monomer containing an addition polymerizable monomer having a colorant is used in combination. The interaction between the addition polymerization resin A and the addition polymer E in the colorant particles makes the colorant particles easy to disperse in the resin particles, and prevents aggregation between the colorant particles when agglomerating and fusing. It is presumed that the image density of the printed matter is improved because the dispersibility of the colorant in the toner is improved.
In addition, since the colorant also acts as a nucleating agent for crystallization of the crystalline polyester resin in the toner particles, the dispersibility of the colorant in the toner is improved, so that many crystalline domains of the crystalline polyester resin are present. It is thought that it is formed and finely dispersed in the toner. Furthermore, it is considered that by maintaining the dispersibility of the colorant high, the finely dispersed crystal domains are also stabilized, thereby improving the low-temperature fixability of the toner and its stability over time.

Definitions of various terms and the like in this specification are shown below.
Whether the resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is defined by the ratio between the softening point of the resin and the maximum endothermic peak temperature (softening point (° C.) / Maximum endothermic peak temperature (° C.)) in the measurement methods described in the examples described later. The crystalline resin is one having a crystallinity index of 0.6 or more and 1.4 or less. An amorphous resin is one having a crystallinity index of less than 0.6 or greater than 1.4. The crystallinity index can be appropriately adjusted according to the production conditions such as the type and ratio of the raw material monomers, the reaction temperature, the reaction time, and the cooling rate.
With regard to hydrocarbon groups, the descriptions in parentheses “(iso or tertiary)” and “(iso)” mean both the presence and absence of these prefixes, and the absence of these prefixes. In the case of normal.
“(Meth) acrylic acid” means at least one selected from acrylic acid and methacrylic acid.
“(Meth) acrylate” means at least one selected from acrylate and methacrylate.
The “(meth) acryloyl group” means at least one selected from an acryloyl group and a methacryloyl group.
The “styrene compound” means unsubstituted or substituted styrene.
“Main chain” means the longest bond chain in the addition polymer.

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

<Step 1>
In step 1, aggregated particles are obtained by aggregating resin particles containing resin A and resin C in the same or different particles and colorant particles Z in an aqueous medium. In step 1, in addition to the resin particles and the colorant particles Z, wax and other additives may be aggregated.
In step 1, the resin particles may be any of resin particles X containing resin A, resin particles Y containing resin C, and resin particles XY containing resin A and resin C in the same particle. It is preferable to use together resin particles X containing A and resin particles Y containing resin C.

(Resin A)
The addition polymerization resin A is an addition polymerization product of a raw material monomer containing a styrene compound.
Examples of the styrenic compound include unsubstituted or substituted styrene. Examples of the substituent substituted with styrene include an alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a sulfo group, and a salt thereof.
Examples of the styrene compound include styrene, methyl styrene, α-methyl styrene, β-methyl styrene, tert-butyl styrene, chlorostyrene, chloromethyl styrene, methoxy styrene, styrene sulfonic acid or a salt thereof. Among these, styrene is preferable.
In the raw material monomer of the addition polymerization resin A, the content of the styrene compound is preferably 50% by mass or more, more preferably 65% by mass or more, still more preferably 70% by mass or more, and 100% by mass or less. The content is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less.

Examples of raw material monomers other than styrene compounds include (meth) acrylic acid esters such as alkyl (meth) acrylate, benzyl (meth) acrylate, and dimethylaminoethyl (meth) acrylate; ethylene, propylene, butadiene and the like. Olefins; Halovinyls such as vinyl chloride; Vinyl esters such as vinyl acetate and vinyl propionate; Vinyl ethers such as vinyl methyl ether; Vinylidene halides such as vinylidene chloride; N-vinyl compounds such as N-vinylpyrrolidone It is done. Among these, (meth) acrylic acid esters are preferable, and alkyl (meth) acrylates are more preferable.
The number of carbon atoms of the alkyl group in the alkyl (meth) acrylate is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, still more preferably 4 or more, from the viewpoint of obtaining a more excellent image density. And preferably it is 24 or less, More preferably, it is 20 or less, More preferably, it is 16 or less, More preferably, it is 10 or less.
Examples of the alkyl (meth) acrylate include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, (meth) acrylate (iso or tertiary) butyl, (meth ) Acrylic acid (iso) amyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid (iso) octyl, (meth) acrylic acid (iso) decyl, (meth) acrylic acid ( (Iso) dodecyl, (meth) acrylic acid (iso) palmityl, (meth) acrylic acid (iso) stearyl, (meth) acrylic acid (iso) behenyl. Among these, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, and stearyl (meth) acrylate are preferable, butyl (meth) acrylate, 2- (meth) acrylate 2- Ethylhexyl and dodecyl (meth) acrylate are more preferable, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are more preferable, and butyl acrylate and 2-ethylhexyl acrylate are still more preferable.

  In the raw material monomer of the addition polymerization resin A, the content of the (meth) acrylic acid ester 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%. It is not more than mass%, more preferably not more than 40 mass%, still more preferably not more than 30 mass%.

The addition polymerization resin A is obtained by an addition polymerization reaction of a raw material monomer containing a styrene compound.
Examples of the polymerization initiator for the addition polymerization reaction include peroxides such as dibutyl peroxide, persulfates such as sodium persulfate, and azo compounds such as 2,2′-azobis (2,4-dimethylvaleronitrile). Can be mentioned. Among these, peroxide is preferable, and dibutyl peroxide is more preferable.
The amount of the polymerization initiator used is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, with respect to 100 parts by mass of the raw material monomer of the addition polymerization resin A. Is 25 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 15 parts by mass or less.
The temperature of the addition polymerization reaction is preferably 110 ° C. or higher, more preferably 150 ° C. or higher, and preferably 250 ° C. or lower, more preferably 220 ° C. or lower.

(Physical properties of resin A)
The softening point of the resin A is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, further preferably 100 ° C. or higher, and preferably 140 ° C. or lower, more preferably 130 ° C. or lower, still more preferably 125 ° C. or lower. It is.
The glass transition temperature of the resin A is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, and preferably 80 ° C. or lower, more preferably 70 ° C. or lower, still more preferably 60 ° C. It is as follows.

The softening point and glass transition temperature of the resin A can be appropriately adjusted depending on the production conditions such as the type and amount of the raw material monomer, the type and amount of the polymerization initiator, and the reaction temperature, reaction time, and cooling rate. These values can be obtained by the method described in the examples.
In addition, when using 2 or more types of resin A in combination, it is preferable that the value of the softening point and glass transition temperature which were obtained as those mixture is in the above-mentioned range, respectively.

[Resin particles X]
The resin particles X contain the resin A from the viewpoint of improving the image density.

[Method for Producing Resin Particle X]
The dispersion liquid of the resin particle X is obtained by dispersing the resin A in an aqueous medium.
As the aqueous medium, those containing water as a main component are preferable. From the viewpoint of improving the dispersion stability of the dispersion of resin particles and from the viewpoint of environmental properties, the content of water in the aqueous medium is preferably 80 masses. % Or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and 100% by mass or less, still more preferably 100% by mass. As water, deionized water or distilled water is preferred. Examples of components other than water that may be contained in the aqueous medium include, for example, carboxylic acid esters having a total carbon number of 3 to 5 such as ethyl acetate; alkyl alcohols having a carbon number of 1 to 5; total carbon numbers of 3 such as acetone and methyl ethyl ketone The dialkyl ketone of 5 or less and the organic solvent which melt | dissolves in water, such as cyclic ethers, such as tetrahydrofuran, is mentioned.

There is no particular limitation on the production method of the dispersion liquid of resin particles X, known kneading machines, it is sufficient control so that the resin particles of a desired volume median particle diameter D ₅₀ is obtained by using a dispersing machine. Examples of the dispersion method include a method in which an aqueous medium is added to an organic solvent solution of a resin or a molten resin and emulsified.

  In order to facilitate emulsification of the resin, it is preferable to dissolve or swell the resin in advance using an organic solvent. Examples of the organic solvent used for emulsification include alcohol solvents such as ethanol, isopropanol, and isobutanol; acetone, methyl ethyl ketone, methyl isobutyl ketone, and diethyl ketone from the viewpoint of dissolving or swelling the resin and facilitating emulsification in an aqueous medium. Ketone solvents such as dibutyl ether, tetrahydrofuran and dioxane; and acetate solvents such as ethyl acetate and isopropyl acetate. Among these, from the viewpoint of easy removal from the mixed solution after addition of the aqueous medium, ketone solvents and acetate ester solvents are preferable, and methyl ethyl ketone, ethyl acetate, and isopropyl acetate are more preferable.

From the viewpoint of improving the dispersion stability of the resin particles X, the temperature during the dispersion treatment is preferably not less than the glass transition temperature of the resin constituting the resin particles X, more preferably not less than 50 ° C., more preferably not less than 60 ° C. Yes, and preferably 100 ° C. or lower, more preferably 90 ° C. or lower, and still more preferably 80 ° C. or lower.
In emulsification, a surfactant may be used from the viewpoint of improving the dispersion stability of the resin particles X. Examples of the surfactant include anionic surfactants such as alkylbenzene sulfonates and alkyl ether sulfates; and nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkenyl ethers. Among these, alkylbenzenesulfonic acid is preferable.
When a surfactant is used, the amount used is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and preferably 20 parts by mass or less, more preferably 100 parts by mass of the resin A. It is 10 mass parts or less, More preferably, it is 8 mass parts or less.
In the emulsification, the dispersion treatment may be performed using a disperser such as a homogenizer.
Examples of the disperser include an ultrasonic homogenizer (for example, “US-150T”, “US-300T”, “US-600T” (manufactured by Nippon Seiki Seisakusho Co., Ltd.), “SONIFIER (registered trademark) 4020-400”. , “SONIFIER (registered trademark) 4020-800” (manufactured by Branson), and “UP-400S” (manufactured by Hielscher).

After emulsification, the organic solvent may be removed from the obtained dispersion by distillation or the like, if necessary. In this case, the remaining amount of the organic solvent is preferably 1% by mass or less, more preferably 0.5% by mass or less, and further preferably substantially 0% in the dispersion.
The solid content concentration of the dispersion of resin particles X 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 40% by mass. It is at most 30% by mass, more preferably at most 30% by mass.

The volume median particle size D ₅₀ of the resin particles X in the dispersion is preferably 0.05 μm or more, more preferably 0.1 μm or more, and preferably from the viewpoint of obtaining a toner capable of obtaining a high-quality image. Is 1 μm or less, more preferably 0.8 μm or less, and still more preferably 0.5 μm or less.
The CV value of the resin particles X in the dispersion is preferably 10% or more, more preferably 20% or more, and preferably 40% or less, more preferably, from the viewpoint of obtaining a toner capable of obtaining a high-quality image. Is 30% or less.
Volume-median particle size D ₅₀ and CV value is obtained by the method described in Examples set forth below.

(Resin C)
Resin C is a crystalline polyester resin from the viewpoint of obtaining a toner having a high image density and excellent low-temperature fixability and low-temperature fixability over time.
Resin C is, for example, a polycondensate of an alcohol component and a carboxylic acid component.
The alcohol component preferably comprises an α, ω-aliphatic diol.
The carbon number of the α, ω-aliphatic diol is preferably 2 or more, more preferably 4 or more, still more preferably 6 or more, and is preferably 16 or less, more preferably 14 or less, still more preferably 12 or less. is there.
Examples of the α, ω-aliphatic diol 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, 1,14-tetradecanediol Can be mentioned. Among these, 1,4-butanediol and 1,6-hexanediol are preferable.

  The amount of α, ω-aliphatic diol 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 in the alcohol component, and , 100 mol% or less, and more preferably 100 mol%.

  The alcohol component may contain another alcohol component 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; alkylene oxide additions of aromatic diols such as alkylene oxide adducts of bisphenol A Product; trihydric or higher alcohols such as glycerin, pentaerythritol, and trimethylolpropane. These alcohol components may be used alone or in combination of two or more.

The carboxylic acid component preferably includes an aliphatic dicarboxylic acid.
The number of carbon atoms of the aliphatic dicarboxylic acid is preferably 4 or more, more preferably 8 or more, still more preferably 10 or more, and from the viewpoint of improving low-temperature fixability, preferably 16 or less, more preferably 14 or less, More preferably, it is 12 or less.
Examples of the aliphatic dicarboxylic acid include fumaric acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid. Among these, dodecanedioic acid or tetradecanedioic acid is preferable. These carboxylic acid components may be used alone or in combination of two or more.

  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 It is less than mol%, and more preferably 100 mol%.

  The carboxylic acid component may contain another carboxylic acid component different from the aliphatic dicarboxylic acid. Examples of other carboxylic acid components include aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid; and trivalent or higher polyvalent carboxylic acids. These carboxylic acid components may be used alone or in combination of two or more.

  The equivalent ratio of the carboxyl 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, more Preferably it is 1.2 or less.

(Physical properties of resin C)
The softening point of the resin C is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 80 ° C. or higher, and preferably 150 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 100 ° C. or lower. It is.

  The melting point of the 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 the 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 the resin C can be appropriately adjusted according to the production conditions such as the type and ratio of the raw material monomers, the reaction temperature, the reaction time, and the cooling rate. These values are determined by the method described in the examples below. In addition, when using combining 2 or more types of resin C, it is preferable that the value of the softening point, melting | fusing point, and acid value which were obtained as those mixtures is in the above-mentioned range, respectively.

Resin C is obtained, for example, by polycondensation of an alcohol component and a carboxylic acid component.
If necessary, the alcohol component and the carboxylic acid component may be prepared by converting an esterification catalyst such as di (2-ethylhexanoic acid) tin (II), dibutyltin oxide, titanium diisopropylate bistriethanolaminate into the alcohol component and the carboxylic acid component. 0.01 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight in total; an esterification cocatalyst such as gallic acid (same as 3,4,5-trihydroxybenzoic acid) as an alcohol component and a carboxylic acid component You may carry out polycondensation by using 0.001 mass part or more and 0.5 mass part or less with respect to 100 mass parts of total amounts.
In addition, when using a monomer having an unsaturated bond such as fumaric acid in the polycondensation reaction, preferably 0.001 part by mass with respect to 100 parts by mass of the alcohol component and the carboxylic acid component as necessary. More than 0.5 parts by mass of radical polymerization inhibitor may be used. Examples of the radical polymerization inhibitor 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 230 ° C. or lower. The polycondensation may be performed in an inert gas atmosphere.

[Resin particles Y]
The resin particles Y contain the resin C from the viewpoint of improving the image density.

[Method for Producing Resin Particle Y]
A dispersion of resin particles Y is obtained by dispersing resin C in an aqueous medium.
Examples of the aqueous medium include the same solvents as described above.

  Dispersion can be carried out using a known method, but it is preferably dispersed by a phase inversion emulsification method. Examples of the phase inversion emulsification method include a method of phase inversion emulsification by adding an aqueous medium to an organic solvent solution of a resin or a molten resin.

The organic solvent used for phase inversion emulsification is not particularly limited as long as the resin is dissolved. For example, alcohol solvents such as ethanol, isopropanol and isobutanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diethyl ketone; Examples include ether solvents such as dibutyl ether, tetrahydrofuran, and dioxane; acetate solvents such as ethyl acetate and isopropyl acetate. Among these, from the viewpoint of easy removal from the mixed solution after addition of the aqueous medium, ketone solvents and acetate solvents are preferable, and methyl ethyl ketone, ethyl acetate, and isopropyl acetate are more preferable.
It is preferable to add a neutralizing agent to the organic solvent solution. Examples of the neutralizing agent include basic substances. Examples of the basic substance include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; nitrogen-containing basic substances such as ammonia, trimethylamine and diethanolamine.
The degree of neutralization of the resin contained in the resin particles Y 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 Is 100 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less.
In addition, the neutralization degree of resin contained in the resin particles can be obtained by the following formula.
Degree of neutralization (mol%) = [{addition mass of neutralizer (g) / equivalent of neutralizer} / [{weighted average acid value of resin constituting resin particle Y (mgKOH / g) × resin particle Y (G)} / (56 × 1000)]] × 100

While stirring the organic solvent solution or the molten resin, the aqueous medium is gradually added to cause phase inversion.
From the viewpoint of improving the dispersion stability of the resin particles Y, the organic solvent solution temperature when adding the aqueous medium is preferably not less than the glass transition temperature of the resin constituting the resin particles Y, more preferably not less than 50 ° C., and still more preferably Is 60 ° C. or higher, more preferably 70 ° C. or higher, and preferably 100 ° C. or lower, more preferably 90 ° C. or lower, still more preferably 80 ° C. or lower.

  After the phase inversion emulsification, the organic solvent may be removed from the obtained dispersion by distillation or the like, if necessary. In this case, the residual amount of the organic solvent is preferably 1% by mass or less, more preferably 0.5% by mass or less, and further preferably substantially 0% in the dispersion.

The volume median particle size D ₅₀ of the resin particles Y 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 a high-quality image. Is 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.3 μm or less.
The CV value of the resin particles Y in the dispersion is preferably 10% or more, more preferably 20% or more, and preferably 40% or less, more preferably, from the viewpoint of obtaining a toner capable of obtaining a high-quality image. Is 30% or less.
Volume-median particle size D ₅₀ and CV value is obtained by the method described in Examples set forth below.

[Colorant particles Z]
The colorant particles Z contain a colorant and an addition polymer E from the viewpoint of obtaining a toner having a high image density and excellent low-temperature fixability and low-temperature fixability over time. The colorant particle Z has, for example, an addition polymer E on the surface of the colorant, and preferably the surface of the colorant is coated with the addition polymer E.

(Coloring agent)
As the colorant, all of dyes and pigments used as toner colorants can be used. For example, carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine-B Base, solvent red 49, solvent red 146, solvent blue 35, quinacridone, carmine 6B, monoazo yellow, disazo yellow, isoindoline yellow. The toner may be either black toner or color toner other than black.
Among these, as a yellow pigment, from the viewpoint of image density, monoazo yellow and isoindoline yellow are preferable, and monoazo yellow is more preferable.
Among these, as the colorant, carbon black is preferable.
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 coloring power and charge control.
From the viewpoint of further improving the image density, 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 9 or less, more preferably 8 or less, More preferably, it is 7.5 or less.
Specifically, the pH value of carbon black can be measured by the following procedure.
(1) Collect 5 g of carbon black and 50 mL of distilled water of pH 7 in a container and mix.
(2) This is boiled for 15 minutes and then cooled to room temperature in 30 minutes.
(3) The pH meter electrode is immersed in the supernatant and the pH is measured.
Examples of the pH meter include “HM30R” (manufactured by Toa DKK Corporation).

The carbon black dibutyl phthalate (DBP) oil absorption is preferably 20 mL / 100 g or more, more preferably 30 mL / 100 g or more, still more preferably 35 mL / 100 g or more, and still more preferably, from the viewpoint of toner charge distribution and image density. Is 40 mL / 100 g or more, and preferably 90 mL / 100 g or less, more preferably 75 mL / 100 g or less, still more preferably 50 mL / 100 g or less.
The DBP oil absorption of carbon black is measured in accordance with “How to Obtain Oil Oil Absorption” of ISO 4656 (JIS K6217-4: 2008).

The BET specific surface area of carbon black is preferably 50 m ² / g or more, more preferably 60 m ² / g or more, still more preferably 90 m ² / g or more, and even more preferably 100 m ² / g or more, from the viewpoint of coloring power. is there. Further, from the viewpoint of charge amount distribution, it is preferably 150 m ² / g or less, more preferably 130 m ² / g or less, and still more preferably 115 m ² / g or less.
The BET specific surface area of carbon black is measured according to JIS K 6217-2: 2017.

(Addition polymer E)
The addition polymer E is an addition polymerizable monomer a having an aromatic group (hereinafter, simply referred to as “monomer a”), from the viewpoint of obtaining a toner having a high image density and excellent low-temperature fixability and low-temperature fixability over time. (Also referred to as a polymer). And the addition polymer E contains the structural unit derived from the addition-polymerizable monomer a which has an aromatic group in a principal chain from a viewpoint of improving image density, low-temperature fixability, and low-temperature fixability temporal stability more.
The raw material monomer of the addition polymer E contains, in addition to the addition polymerizable monomer a having an aromatic group, preferably an addition polymerizable monomer b having an ionic group (hereinafter also simply referred to as “monomer b”).
In addition to the monomer b, the raw material monomer of the addition polymer E is more preferably an addition polymerizable monomer c having a polyalkylene oxide group (hereinafter also simply referred to as “monomer c”) or a macromonomer d (hereinafter referred to as “monomer c”). It further contains at least one selected from “monomer d”).

The addition polymer E is preferably a water-insoluble addition polymer from the viewpoint of improving the image density.
Here, “water-insoluble” means that when a sample dried at 105 ° C. for 2 hours is dissolved in 100 g of ion-exchanged water at 25 ° C. until it is saturated, the amount of dissolution is less than 10 g. . The dissolution amount is measured in a state where the ionic group of the addition polymer E is neutralized 100%. For example, in the case of an addition polymer having a carboxy group, the dissolution amount is the dissolution amount when the carboxy group of the addition polymer is neutralized 100% with sodium hydroxide.
The amount of addition polymer E dissolved in water is preferably 5 g or less, more preferably 1 g or less.

The molecular weight of the addition polymerizable monomer a having an aromatic group is preferably less than 1,000, more preferably 800 or less, still more preferably 500 or less, even more preferably 300 or less, and preferably 80 or more, more Preferably it is 90 or more, More preferably, it is 100 or more.
The addition polymerizable monomer a having an aromatic group is preferably nonionic.
Examples of the addition polymerizable monomer a having an aromatic group include a styrene compound a-1 and an aromatic group-containing (meth) acrylate a-2.
Examples of the styrene compound a-1 include substituted or unsubstituted styrene. Examples of the substituent substituted with styrene include an alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a sulfo group, and a salt thereof.
The molecular weight of the styrenic compound a-1 is preferably less than 1,000, more preferably 800 or less, still more preferably 500 or less, still more preferably 300 or less, and preferably 80 or more, more preferably 90 or more. More preferably, it is 100 or more.
Examples of the styrene compound a-1 include styrene, methyl styrene, α-methyl styrene, β-methyl styrene, tert-butyl styrene, chlorostyrene, chloromethyl styrene, methoxy styrene, styrene sulfonic acid or a salt thereof. . Among these, styrene is preferable.
The amount of the styrene compound a-1 is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more in the raw material monomer of the addition polymer E from the viewpoint of further improving the image density. , More preferably 20% by mass or more, still more preferably 30% by mass or more, still more preferably 35% by mass or more, and preferably 98% by mass or less, more preferably 80% by mass or less, still more preferably. It is 65 mass% or less, More preferably, it is 50 mass% or less.

Examples of the aromatic group-containing (meth) acrylate a-2 include benzyl (meth) acrylate and phenoxyethyl (meth) acrylate, and benzyl (meth) acrylate is preferred.
From the viewpoint of further improving the image density, the amount of the aromatic group-containing (meth) acrylate a-2 is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably, in the raw material monomer of the addition polymer E. Is 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, still more preferably 35% by mass or more, and preferably 98% by mass or less, more preferably 80% by mass. Hereinafter, it is more preferably 65% by mass or less, and still more preferably 50% by mass or less.

  The amount of the addition polymerizable monomer a having an aromatic group is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably, in the raw material monomer of the addition polymer E from the viewpoint of further improving the image density. 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, still more preferably 35% by mass or more, and preferably 98% by mass or less, more preferably 95% by mass or less. More preferably, it is 90 mass% or less, More preferably, it is 80 mass% or less, More preferably, it is 65 mass% or less, More preferably, it is 50 mass% or less.

The ionic group in the monomer b means a group that ionically dissociates in water.
Examples of the ionic group include a carboxy group, a sulfo group, a phosphate group, an amino group, and salts thereof.
The ionic group is preferably an anionic group from the viewpoint of improving the dispersion stability of the colorant particles. As an anionic property, an acidic group or a salt thereof is preferable, a carboxy group, a sulfo group, or a salt thereof is more preferable, and a carboxy group or a salt thereof is further preferable.
Examples of the addition polymerizable monomer having a carboxy group include (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, and 2-methacryloyloxymethyl succinic acid.
Among these, an addition polymerizable monomer having an anionic group is preferable, (meth) acrylic acid is more preferable, and methacrylic acid is further preferable.
When the monomer b is contained, the amount of the monomer b in the raw material monomer of the addition polymer E is preferably 2% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, and preferably Is 40% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less.

The average added mole number of the polyalkylene oxide group of the monomer c is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and is preferably 30 or less, more preferably 20 or less, still more preferably 10 It is as follows.
Monomer c is preferably nonionic.
Examples of the monomer c include polyalkylene glycol (meth) acrylates such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate; alkoxy polyalkylene glycol (meth) acrylates such as methoxypolyethylene glycol (meth) acrylate; phenoxy ( And aryloxypolyalkylene glycol (meth) acrylates such as (ethylene glycol-propylene glycol copolymer) (meth) acrylate. Among these, methoxypolyethylene glycol (meth) acrylate is preferable.
When the monomer c is contained, the amount of the monomer c in the raw material monomer of the addition polymer E is preferably 3% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and preferably Is 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less.

Examples of the monomer d include a styrene compound polymer having an addition polymerizable functional group at one end (hereinafter also referred to as “styrene macromonomer”). Examples of the addition polymerizable functional group include a vinyl group, an allyl group, and a (meth) acryloyl group. Among these, a (meth) acryloyl group is preferable.
In the monomer d, the styrene compound is preferably styrene.
The number average molecular weight of the monomer d is preferably 1,000 or more and 10,000 or less. The number average molecular weight is measured using polystyrene as a standard substance by gel permeation chromatography using chloroform containing 1 mmol / L dodecyldimethylamine as a solvent.
Examples of commercially available styrenic macromonomers include “AS-6”, “AS-6S”, “AN-6”, “AN-6S”, “HS-6”, “HS-6S” (above, Toagosei Co., Ltd.).
When the monomer d is contained, the amount of the monomer d in the raw material monomer of the addition polymer E is preferably 3% by mass or more, more preferably 6% by mass or more, further preferably 10% by mass or more, and preferably Is 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less.

Furthermore, as a raw material monomer of the addition polymer E, an addition polymerizable monomer (other monomers) other than the monomers a to d may be contained.
Examples of the other monomer include alkyl (meth) acrylates having an alkyl group having 1 to 22 carbon atoms (preferably 6 to 18 carbon atoms).
When the other monomer is contained, the amount of the other monomer is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and still more preferably in the raw material monomer of the addition polymer E. Is 10% by mass or less, more preferably 5% by mass or less.

  The weight average molecular weight of the addition polymer E is preferably 3,000 or more, more preferably 5,000 or more, still more preferably 20,000 or more, and still more preferably 40,000 or more, from the viewpoint of further improving the image density. More preferably, it is 48,000 or more, and preferably 200,000 or less, more preferably 90,000 or less, still more preferably 60,000 or less, and still more preferably 53,000 or less. In addition, the measurement of a weight average molecular weight can be performed by the method as described in an Example.

  The addition polymer E can be produced, for example, by the same method as the above addition polymerization resin A.

  In the colorant particles, the mass ratio between the colorant and the addition polymer E is 50/50 or more from the viewpoint of obtaining a toner having high image density and excellent low-temperature fixability and low-temperature fixability over time. , Preferably 55/45 or more, more preferably 60/40 or more, still more preferably 65/35 or more, and 95/5 or less, preferably 90/10 or less, more preferably 85/15 or less. is there.

[Production Method of Colorant Particle Z]
The colorant particle Z is obtained, for example, by mixing the colorant and the addition polymer E.
There is no particular limitation on the production method of a dispersion of colorant particles Z, known kneading machines, it is sufficient can control so that the colorant particles of the desired volume median particle size D ₅₀ by using a disperser or the like is obtained, preferably Is obtained by mixing a dispersion of the colorant and the addition polymer E with a bead mill or a homogenizer.

The method for producing the colorant particle Z is preferably
Step a: After adding the addition polymer E and the organic solvent, if necessary, a neutralizing agent is mixed, an aqueous medium is further mixed to obtain a dispersion of the addition polymer E, and step b: In this method, the dispersion obtained in step a and the colorant are dispersed to obtain a dispersion of colorant particles Z.
By including the organic solvent, the colorant and the addition polymer are dissolved in the organic solvent, and the addition polymer is easily adsorbed to the colorant, so that the dispersibility of the colorant can be further improved.
Moreover, it is preferable that the process b is a process which disperse | distributes the dispersion liquid and colorant obtained at the process a by a bead mill or a homogenizer.

In step a, it is preferable to first add the addition polymer 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, a dialkyl ketone having 3 to 5 carbon atoms in total is preferable, and methyl ethyl ketone is more preferable. When the addition polymer E is synthesized by a solution polymerization method, the solvent used in the polymerization may be used as it is.

Examples of the neutralizing agent include basic substances. Examples of the basic substance include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; nitrogen-containing basic substances such as ammonia, trimethylamine and diethanolamine.
The degree of neutralization of the addition polymer 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, still more preferably 80 mol% or more. And preferably 100 mol% or less, more preferably 98 mol% or less, and still more preferably 95 mol% or less.
In addition, the neutralization degree of the addition polymer E can be calculated | required by a following formula.
Degree of neutralization (mol%) = [{addition mass of neutralizing agent (g) / equivalent of neutralizing agent} / {mass ratio of addition polymerizable monomer having acidic group constituting addition polymer E × addition polymer] E mass (g) / molecular weight of addition polymerizable monomer having acidic group}] × 100
In the step a, as an apparatus used for mixing, for example, a mixing and stirring apparatus including an anchor blade, a disper blade, and the like can be given.
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 even more preferably 25 ° C. or lower.
The mixing time is preferably 1 minute or more, more preferably 3 minutes or more, still more preferably 5 minutes or more, and preferably 10 hours or less, more preferably 1 hour or less, still more preferably 0.5 hours or less. is there.

  In step b, the mass ratio of the colorant to the addition polymer E [colorant / addition polymer E] is as described above.

In step b, it is preferable to add a colorant to the dispersion liquid obtained in step a and mix, and then perform a dispersion treatment. The apparatus used for mixing in step b and the temperature during mixing are the same as the apparatus used for mixing in step a and the temperature during mixing, and the preferred range is also the same. In step b, the mixing time after adding the colorant to the dispersion obtained in step a is preferably 0.5 hours or more, more preferably 0.8 hours or more, and preferably 30 hours or less, More preferably, it is 10 hours or less, More preferably, it is 5 hours or less.
Examples of the apparatus used in the dispersion treatment in step b include a kneader such as a roll mill and a kneader, a homogenizer such as a microfluidizer (manufactured by Microfluidic), a starburst (manufactured by Sugino Machine), a media type such as a paint shaker and a bead mill. Examples include a disperser. These apparatuses may use 1 type (s) or 2 or more types. Among these, a bead mill and a homogenizer are preferable from the viewpoint of reducing the particle size of the pigment, and a homogenizer is more preferable from the viewpoint of further improving the image density.
When using a homogenizer, the treatment pressure is preferably 60 MPa or more, more preferably 100 MPa or more, still more preferably 130 MPa or more, and preferably 270 MPa or less, more preferably 200 MPa or less, and even more preferably 180 MPa or less.
The number of passes is preferably 5 or more, more preferably 10 or more, still more preferably 15 or more, and preferably 30 or less, more preferably 25 or less.

It is preferable to remove the organic solvent from the obtained dispersion liquid of the colorant particles Z.
Further, it is preferable that the dispersion liquid of the colorant particles Z is filtered through a wire mesh or the like to remove coarse particles and the like. Further, from the viewpoint of improving the productivity and storage stability of the dispersion, the addition polymer E of the colorant particles may be subjected to a crosslinking treatment.
Various additives such as organic solvents, preservatives, and antifungal agents may be added to the dispersion of the colorant particles Z.

In the dispersion 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, and still more preferably. It is 30 mass% or less, More preferably, it is 25 mass% or less.
The solid content concentration of the dispersion 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 mass% or less, More preferably, it is 30 mass% or less.

From the viewpoint of improving the image density, the volume median particle size D ₅₀ 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, and preferably 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 particle 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 size D ₅₀ and CV value of the colorant particle Z are measured by the method of the example.

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

〔wax〕
The aggregation of the resin particles X, the resin particles Y, and the colorant particles Z may be performed in the presence of wax.
Examples of the wax include hydrocarbon waxes such as polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, sazol wax, or oxides thereof; carnauba wax, montan wax Or ester waxes such as deoxidized wax and fatty acid ester wax; fatty acid amides, fatty acids, higher alcohols, and fatty acid metal salts. These may use 1 type (s) or 2 or more types.
Among these, hydrocarbon wax and ester wax are preferable, and hydrocarbon wax is more preferable.

  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, and still more preferably 140 ° C. or lower.

  The amount of the 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. Hereinafter, it is more preferably 20% by mass or less.

(Wax particle dispersion)
The wax is preferably mixed and aggregated with the resin particles X and the colorant particles Z as a dispersion of wax particles.
The dispersion of wax particles can be obtained using a surfactant, but is preferably obtained by mixing a wax and resin particles P described later. By preparing 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 wax particle dispersion has a structure in which a large number of resin particles P adhere to the surface of the wax particles.
The kind and addition amount of the wax are the same as those of the aforementioned wax.

As the resin constituting the resin particles P in which the wax is dispersed, a normal resin used as a binder resin for the toner can be used, but is preferably a polyester-based resin, and the viewpoint of improving the dispersibility of the wax in an aqueous medium. Therefore, it is more preferable to use a composite resin D having a polyester resin segment made of a polycondensate of an alcohol component and a carboxylic acid component and an addition polymerization resin segment. Examples of the alcohol component include aromatic diols, linear or branched aliphatic diols, alicyclic diols, and trihydric or higher polyhydric alcohols. Examples of the carboxylic acid component include dicarboxylic acids and trivalent or higher polyvalent carboxylic acids.
The softening point of the 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 further preferably 100 ° C. or lower.
The glass transition temperature of the composite resin D is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and preferably 80 ° C. or lower, more preferably 60 ° C. or lower.
The preferred range of other resin characteristics of the composite resin D, the preferred examples of the raw material monomers constituting the addition polymerization resin segment, and the like are the same as the examples shown for the resin A. The dispersion of resin particles P can be obtained, for example, by the above-described phase inversion emulsification method.
The volume median particle size D ₅₀ 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, more preferably from the viewpoint of dispersion stability of the wax particles. Preferably it is 0.2 micrometer or less.
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 still more preferably, from the viewpoint of dispersion stability of the wax particles. Is 30% or less.

The wax particle dispersion is, for example, a dispersion of wax and resin particles P and, if necessary, an aqueous medium at a temperature equal to or higher than the melting point of the wax. It can be obtained by dispersing using a dispersing machine.
The heating temperature during dispersion is preferably not less than the melting point of the wax and not less than 80 ° C., more preferably not less than 85 ° C., more preferably not less than 90 ° C., and preferably from the softening point of the resin contained in the resin particles P It is less than 10 ° C higher and 100 ° C or less, more preferably 98 ° C or less, and still more preferably 95 ° C or less.

  The amount of the resin particles P is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, with respect to 100 parts by mass of the wax. The amount is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, and still more preferably 50 parts by mass or less.

From the viewpoint of obtaining uniform aggregated particles, the volume median particle size D ₅₀ 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, and preferably It is 1 μm or less, more preferably 0.8 μm or less, and 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 preferably 40% or less, more preferably 35% or less, and even more preferably 30% or less.
Method of measuring the volume-median particle size D ₅₀ and CV value of the wax particles according to the method described in Example.

The aggregation of the resin particles X, the resin particles Y, and the colorant particles Z may be performed in the presence of other additives in addition to the wax.
Examples of other additives include 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, when preparing a mixed dispersion by mixing the dispersion of each particle, dispersion of optional components such as resin particles X, resin particles Y and colorant particles Z, and wax particles added as necessary You may carry out in presence of surfactant from a viewpoint of improving stability. Examples of the surfactant include anionic surfactants such as alkylbenzene sulfonates and alkyl ether sulfates; and 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 with respect to 100 parts by mass of the total amount of the resin particles X and resin particles Y. And, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 3 parts by mass or less.

  The above-mentioned dispersion of resin particles X, dispersion of resin particles Y, dispersion of colorant particles Z, and optional components are mixed by a conventional method. It is preferable to add an aggregating agent to the mixed dispersion obtained by the mixing from the viewpoint of efficiently aggregating.

[Flocculant]
Examples of the flocculant include a cationic surfactant such as a quaternary salt, an organic flocculant such as polyethyleneimine, and an inorganic flocculant. Examples of the inorganic flocculant 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; divalent or higher metal complexes. .
From the viewpoint of improving the cohesiveness and obtaining uniform aggregated particles, monovalent to pentavalent inorganic flocculants are preferred, monovalent to divalent inorganic metal salts and inorganic ammonium salts are more preferred, and inorganic ammonium salts are preferred. More preferably, ammonium sulfate is even more preferable.

  Using a flocculant, for example, 5 to 50 parts by mass with respect to 100 parts by mass of the total amount of resin in the mixed dispersion containing resin particles X, resin particles Y and colorant particles Z of 0 to 40 ° C. The aggregating agent is added, and the resin particles X, the resin particles Y, 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 increase the temperature of the dispersion after adding the aggregating agent.

Aggregation may be stopped when the aggregated particles grow to an appropriate particle size as toner particles.
Examples of the method for stopping the aggregation include a method of cooling the dispersion, a method of adding an aggregation stopper, and a method of diluting the dispersion. From the viewpoint of reliably preventing unnecessary aggregation, a method of stopping aggregation by adding an aggregation stopper is preferable.

(Aggregation stop agent)
As the aggregation terminator, a surfactant is preferable, and an anionic surfactant is more preferable. Examples of the anionic surfactant include alkyl benzene sulfonate, alkyl sulfate, alkyl ether sulfate, polyoxyalkylene alkyl ether sulfate and the like. These may use 1 type (s) or 2 or more types. The aggregation terminator may be added as 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. From the viewpoint of reducing residual toner, it is preferably 60 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 20 parts by mass or less.

Volume-median particle size _{D 50} of the aggregate particles is preferably 2μm or more, more preferably 3μm or more, more preferably 4μm or more, and, preferably 10μm or less, more preferably 8μm or less, more preferably at 6μm or less is there. Volume-median particle size D ₅₀ of the aggregate particles is obtained by the method described in Examples set forth below.

<Step 2>
In step 2, for example, the aggregated particles are fused in an aqueous medium.
By fusing, each particle contained in the aggregated particles is fused to obtain fused particles.
The volume median particle size D ₅₀ 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. More preferably, it is 6 μm or less.

The circularity of the fused particles obtained by the fusion is preferably 0.955 or more, more preferably 0.960 or more, and preferably 0.990 or less, more preferably 0.985 or less, and still more preferably. 0.980 or less.
The fusion is preferably terminated after reaching the preferred circularity.

<Post-processing process>
A post-treatment step may be performed after step 2, and the toner particles are obtained by isolating the fused particles. Since the fused particles obtained in step 2 are present in the aqueous medium, it is preferable to first perform solid-liquid separation. For solid-liquid separation, a suction filtration method or the like is preferably used.
Washing is preferably performed after solid-liquid separation. At this time, since it is also preferable to remove the added surfactant, it is preferable to wash with an aqueous medium below the cloud point of the surfactant. The washing is preferably performed a plurality of times.
Next, it is preferable to perform drying. Examples of the drying method include a vacuum low temperature drying method, a vibration type fluid drying method, a spray drying method, a freeze drying method, and a flash jet method.

[Toner particles]
The volume median particle size D ₅₀ of the toner particles is preferably 2 μm or more, more preferably 3 μm or more, and further preferably 4 μm or more, from the viewpoint of obtaining a high-quality image and further improving the cleaning properties of the toner. And preferably it is 10 micrometers or less, More preferably, it is 8 micrometers or less, More preferably, it is 6 micrometers or less.

The CV value of the toner particles is preferably 12% or more, more preferably 14% or more, and further preferably 16% or more from the viewpoint of improving the productivity of the toner, and from the viewpoint of obtaining a high-quality image. Preferably it is 40% or less, More preferably, it is 36% or less, More preferably, it is 30% or less.
The volume median particle size D ₅₀ and CV value of the toner particles can be measured by the method described in the examples.

[toner]
The toner includes toner particles. The toner particles contain the aforementioned resin A, the aforementioned resin C, the addition polymer E, and a colorant. And the mass ratio of a coloring agent and the addition polymer E is 50/50 or more and 95/5 or less. A preferable range of the mass ratio of the colorant to the addition polymer E is as described above.

(External additive)
The toner particles can be used as the toner as they are, but it is preferable to use a toner obtained by adding a fluidizing agent or the like to the toner particle surface as an external additive.
Examples of the external additive include fine particles of inorganic materials such as hydrophobic silica, titanium oxide, alumina, cerium oxide, and carbon black, and fine polymer particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, hydrophobic silica is preferable.
When the surface treatment of toner particles is performed 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 with respect to 100 parts by mass of the toner particles. It is 3 parts by mass or more, and preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less, and still more preferably 4 parts by mass or less.

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

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 method.
In addition, in the notation such as “alkylene oxide (X)”, the numerical value X in parentheses means the average added mole number of alkylene oxide.

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

[Softening point, crystallinity index, melting point and glass transition temperature of resin]
(1) Softening point Using a flow tester “CFT-500D” (manufactured by Shimadzu Corporation), a 1 g sample was heated at a heating rate of 6 ° C./min, and a load of 1.96 MPa was applied by a plunger. The nozzle was extruded from a nozzle having a length of 1 mm and a length of 1 mm. The plunger drop amount of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was taken as the softening point.
(2) Crystallinity Index Using a differential scanning calorimeter “Q100” (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of a sample is weighed into an aluminum pan and cooled to 0 ° C. at a temperature lowering rate of 10 ° C./min. did. Next, the sample was allowed to stand still for 1 minute, and then the temperature was raised to 180 ° C. at a temperature rising rate of 10 ° C./min, and the amount of heat was measured. Of the observed endothermic peaks, the temperature of the peak with the largest peak area is defined as the endothermic maximum peak temperature (1), and (softening point (° C.)) / (Maximum endothermic peak temperature (1) (° C.)) The 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 a sample was weighed into an aluminum pan, heated to 200 ° C., and the temperature Then, it was cooled to 0 ° C. at a temperature lowering rate of 10 ° C./min. Next, the sample was heated at a temperature rising rate of 10 ° C./min, and the amount of heat was measured. Of the endothermic peaks observed, the temperature of the peak with the largest 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 the peak is observed, the temperature of the peak is measured. When the step is observed without the peak being observed, the tangent indicating the maximum slope of the curve of the step and the step The temperature at the intersection with the extension of the base line 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” (with GPC apparatus “HLC-8320GPC”) was prepared by using a solution obtained by dissolving phosphoric acid and lithium bromide in N, N-dimethylformamide so as to have concentrations of 60 mmol / L and 50 mmol / L, respectively. Manufactured by Tosoh Corporation), columns “TSKgel SuperAWM-H, TSKgel SuperAW3000, TSKgel guardcolumn Super AW-H” (manufactured by Tosoh Corporation), flow rate: 0.5 mL / min], monodisperse polystyrene having 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), Measured using Tosoh Corporation] It was.

[Melting point of wax]
Using a differential scanning calorimeter “Q100” (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of a sample was weighed into an aluminum pan, heated to 200 ° C., and then cooled down from 200 ° C. to 10 ° C./min. At 0 ° C. Next, the sample was heated at a temperature rising rate of 10 ° C./min, the amount of heat was measured, and the maximum peak temperature of endotherm was taken as the melting point.

[Volume Median Particle Size D ₅₀ and CV Value of Resin Particles, Colorant Particles, and Wax Particles]
(1) Measuring apparatus: Laser diffraction type particle size measuring instrument “LA-920” (manufactured by Horiba, Ltd.)
(2) Measurement conditions: Samples were taken dispersion measuring cell, distilled water was added, the absorbance was measured volume-median particle size D ₅₀ and the volume-average particle diameter D _v at a concentration comprised within a proper range. The CV value was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size D _v ) × 100

[Solid content concentration of resin particle dispersion, colorant particle dispersion, and wax particle dispersion]
Using an infrared moisture meter “FD-230” (manufactured by Kett Scientific Laboratory), 5 g of a measurement sample was dried at 150 ° C., measurement mode 96 (monitoring time 2.5 minutes, fluctuation range of moisture content 0.05% ), Moisture (mass%) was measured. The solid content concentration was calculated according to the following formula.
Solid content concentration (% by mass) = 100-water content (% by mass)

[Moisture content of toner particles]
Using an infrared moisture meter “FD-230” (manufactured by Kett Science Laboratory Co., Ltd.), toner particles 5 g were dried at a temperature of 150 ° C., measurement mode 96 (monitoring time 2.5 minutes, moisture content fluctuation range 0.05%) ), Moisture (mass%) was measured.

[Volume Median Particle Size D _{50 of} Aggregated Particles]
The volume median particle diameter D ₅₀ of aggregated particles was measured as follows.
Measuring instrument: “Coulter Multisizer (registered trademark) III” (manufactured by Beckman Coulter, Inc.)
・ Aperture diameter: 50μm
Analysis software: “Multisizer (registered trademark) III version 3.51” (manufactured by Beckman Coulter, Inc.)
Electrolyte: “Isoton (registered trademark) II” (manufactured by Beckman Coulter, Inc.)
Measurement conditions: After adjusting the particle size of 30,000 particles to a concentration that can be measured in 20 seconds by adding the sample dispersion to 100 mL of the electrolyte, 30,000 particles are measured again, and the particle size The volume median particle size D ₅₀ was determined from the distribution.

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

[Volume Median Particle Size D ₅₀ and CV Value of Toner Particles]
Volume-median particle size D ₅₀ of the toner particles was measured as follows.
Measuring device, aperture diameter, analysis software, the electrolytic solution used was the same as that used in the measurement of the volume-median particle size D ₅₀ of the aggregated particles described above.
Dispersion: Polyoxyethylene lauryl ether “Emalgen (registered trademark) 109P” (manufactured by Kao Corporation, HLB (Hydrophile-Lipophile Balance) = 13.6) is dissolved in the electrolyte solution, and the dispersion solution has a concentration of 5% by mass. Got.
-Dispersion condition: 10 mg of a measurement sample of toner particles after drying is added to 5 mL of the dispersion, and dispersed for 1 minute with an ultrasonic disperser. Then, 25 mL of the electrolytic solution is added, and further to the ultrasonic disperser. For 1 minute to prepare a sample dispersion.
Measurement conditions: 30,000 particles were measured after adjusting the particle size of 30,000 particles to a concentration that can be measured in 20 seconds by adding the sample dispersion to 100 mL of the electrolyte solution. From the distribution, the volume median particle size D ₅₀ and the volume average particle size _DV were determined.
The CV value (%) was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size D _V ) × 100

[Evaluation methods]
[Low-temperature fixability of toner]
<Low temperature fixability>
Using a commercially available printer “Microline (registered trademark) 5400” (manufactured by Oki Data Corporation) on high-quality paper “J paper A4 size” (manufactured by Fuji Xerox Co., Ltd.), the toner adhesion amount on the paper is 1.45 to 1. A solid image of 50 mg / cm ² was output without fixing it at a length of 50 mm, leaving a margin of 5 mm from the top edge of the A4 paper.
Next, the same printer with a variable temperature fixing device was prepared, the fixing device temperature was set to 120 ° C., and the toner was fixed at a speed of 1.5 seconds per sheet in the A4 longitudinal direction to obtain a printed matter.
In the same manner, the temperature of the fixing device was increased by 5 ° C. to fix the toner, and a printed matter was obtained.
From the margin at the top edge of the printed image to the solid image, lightly paste the mending tape “Scotch (registered trademark) mending tape 810” (manufactured by Sumitomo 3M Limited, width 18 mm) to a length of 50 mm. After that, 500 g of a cylindrical weight (contact area: 157 mm ² ) was placed and pressed once back and forth at a speed of 10 mm / s. Thereafter, the affixed 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 printed matter after the tape was peeled off. 30 high-quality paper “Excellent White Paper A4 Size” (made by Oki Data Co., Ltd.) is laid under the printed material before and after the tape is applied, and the reflected image density of the fixed image portion before and after the tape is applied to each printed material. , Using a colorimeter “SpectroEye” (manufactured by GretagMacbeth, light conditions; standard light source D50, observation field of view 2 °, density standard DINNB, absolute white standard), and fixing rate according to the following formula from each reflected image density Was calculated.
Fixing rate (%) = (Reflected image density after peeling tape / Reflected image density before applying tape) × 100
The lowest temperature at which the fixing rate was 90% or more was defined as the lowest fixing temperature (T ₁ ). The lower the minimum fixing temperature, the better the low temperature fixing property.
<Stability of low temperature fixability over time>
After the toner was stored in a constant temperature bath at 40 ° C. for 100 hours, the minimum fixing temperature (T ₂ ) was evaluated by the same method as the evaluation of the low temperature fixing property.

[Image density of printed matter]
Using a commercially available printer “Microline (registered trademark) 5400” (manufactured by Oki Data Corporation) on high-quality paper “J paper A4 size” (manufactured by Fuji Xerox Co., Ltd.), the toner adhesion amount on the paper is 0.30 mg / cm. ^A solid image of ² was output.
Next, the temperature of the fixing device is set to the minimum fixing temperature + 10 ° C. obtained in the low temperature fixing property test, and the toner is fixed at a speed of 1.5 seconds per sheet in the A4 longitudinal direction. Obtained.
30 sheets of high quality paper “Excellent White Paper A4 Size” (Oki Data Co., Ltd.) was laid under the printed material, and the reflected image density of the solid image portion of the printed material was measured using the colorimeter “SpectroEye” (manufactured by GretagMacbeth, Hikari Shooting conditions: standard light source D50, observation field of view 2 °, density standard DINNB, absolute white standard), and measured values of 10 arbitrary points on the image were averaged to obtain an image density. The larger the value, the better the image density.

[Production of resin]
[Production of styrene acrylic resin]
Production Example A1 (Production of Resin A-1)
2 L of xylene was placed in a four-necked flask having an internal volume of 10 L equipped with a thermometer, a stainless stir bar, a falling condenser, a dropping funnel and a nitrogen introducing tube, and 880 g of styrene, 220 g of n-butyl acrylate, and 100 g of a radical polymerization initiator dibutyl peroxide was added. Under a nitrogen atmosphere, xylene was heated to 135 ° C. with stirring, and the mixture in the dropping funnel was added dropwise over 1 hour. Then, after heating up to 200 degreeC and hold | maintaining at 200 degreeC for 2 hours, the pressure in a flask was further reduced, it hold | maintained at 8 kPa for 1 hour, xylene was removed, and resin A-1 was obtained. Table 1 shows the physical properties of the obtained resin A-1.

Production Example A2 (Production of Resin A-2)
Styrene acrylic resin A-2 was obtained in the same manner as in Production Example A1, except that the monomer used and the amount charged were changed to Table 1. Table 1 shows the physical properties of the obtained resin A-2.

[Manufacture of polyester resin]
Production Example A51 (Production of Resin A-51)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 3880 g of propylene oxide (2.2) adduct of bisphenol A, ethylene oxide of bisphenol A (2.2) Add 1544 g of adduct, 694 g of terephthalic acid, 1578 g of adipic acid and 40 g of di (2-ethylhexanoic acid) tin, raise the temperature to 230 ° C. with stirring in a nitrogen atmosphere, and hold at 230 ° C. for 6 hours. The pressure in the flask was 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 held at 215 ° C. for 1 hour, then the pressure in the flask was further lowered and maintained at 8.3 kPa for 3 hours. Resin A-51 was obtained.
As a result of measuring the physical properties, the softening point was 119 ° C., the glass transition temperature was 57 ° C., the acid value was 15 mgKOH / g, and the crystallinity index was 1.8.

Production Example D1 (Production of Resin D-1)
The inside of a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, and 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. with stirring in a nitrogen atmosphere. After holding at 235 ° C. for 5 hours, the pressure in the flask was lowered and held at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture of styrene 2756g, stearyl methacrylate 689g, acrylic acid 142g, and dibutyl peroxide 413g was dripped over 1 hour in the state which cooled to 160 degreeC and was hold | maintained at 160 degreeC. Then, after maintaining 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 at 8 kPa to the desired softening point to obtain Resin D-1. As a result of measuring 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 crystalline resin]
Production Example C1 (Production of Resin C-1)
The inside of a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen. The temperature was raised to 135 ° C., held at 135 ° C. for 3 hours, and then heated from 135 ° C. to 200 ° C. over 10 hours. Thereafter, 20 g of di (2-ethylhexanoic acid) tin (II) was added, and the mixture was further maintained at 200 ° C. for 1 hour, and then the pressure in the flask was lowered and maintained at 8.3 kPa under reduced pressure for 1 hour. C-1 was obtained. The physical properties are shown in Table 2.

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. The physical properties are shown in Table 2.

[Production of resin particle dispersion]
Production Example X1 (Production of resin particle dispersion X-1)
200 g of resin A-1, 110 g of ethyl acetate, and 15% by mass of sodium dodecylbenzenesulfonate aqueous solution “Neo” in a 3 L internal vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen introduction tube 40 g of PELEX G-15 ”(manufactured by Kao Corporation, an anionic surfactant) was added and dissolved at 70 ° C. over 2 hours. 760 g of deionized water at 70 ° C. was added to the obtained solution, and dispersion treatment was performed at an output of 350 W for 30 minutes using an ultrasonic homogenizer “UP-400S” (manufactured by Hielscher). Thereafter, while maintaining the temperature at 70 ° C., ethyl acetate was distilled off under reduced pressure, deionized water was added to adjust the solid content concentration to 20% by mass, and a resin particle dispersion X-1 was obtained. Volume-median particle size D ₅₀ and CV value of the obtained resin particles shown in Table 3.

Production Example X2 (Production of resin particle dispersion X-2)
A resin particle dispersion X-2 was obtained in the same manner as in Production Example X1, except that the resin A-1 used was changed to the resin A-2. Volume-median particle size D ₅₀ and CV value of the obtained resin particles shown in Table 3.

Production Example X51 (Production of resin particle dispersion X-51)
300 g of resin A-51, 360 g of methyl ethyl ketone and 59 g of deionized water were placed in a 3 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet tube, and the mixture was heated at 73 ° C. for 2 hours. To dissolve the resin. A 5% by mass aqueous sodium hydroxide solution was added to the resulting solution so that the degree of neutralization was 60 mol% with respect to the acid value of the resin, and the mixture was stirred for 30 minutes.
Next, while maintaining the temperature at 73 ° C., 600 g of deionized water was added over 60 minutes while stirring at 280 r / min (peripheral speed 88 m / min), and phase inversion emulsification was performed. While maintaining the temperature at 73 ° C., methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. Thereafter, the aqueous dispersion is cooled to 30 ° C. while stirring at 280 r / min (circumferential 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. A liquid X-51 was obtained. Volume-median particle size D ₅₀ and CV value of the obtained resin particles shown in Table 3.

Production Example Y1 (Production of resin particle dispersion Y-1)
73 g of crystalline resin C-1 and a mixed solvent of 300 g of methyl ethyl ketone and 41 g of deionized water were placed in a 3 L internal vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen introduction tube. The resin was dissolved at 2 ° C. for 2 hours. A 5% by mass aqueous sodium hydroxide solution was added to the resulting solution so that the neutralization degree was 55 mol% with respect to the acid value of the crystalline resin C-1, and the mixture was stirred for 30 minutes.
Next, while maintaining the temperature at 73 ° C., 600 g of deionized water was added over 60 minutes while stirring at 280 r / min (peripheral speed 88 m / min), and phase inversion emulsification was performed. While maintaining the temperature at 73 ° C., methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. Thereafter, the aqueous dispersion is cooled to 30 ° C. while stirring at 280 r / min (peripheral speed 88 m / min), and then deionized water is added so that the solid content concentration becomes 20% by mass, thereby dispersing the resin particles. Liquid Y-1 was obtained. Volume-median particle size D ₅₀ and CV value of the obtained resin particles shown in Table 3.

Production Example Y2 (Production of resin particle dispersion Y-2)
Resin particle dispersion Y-2 was obtained in the same manner as in Production Example Y1, except that the type of resin used was changed as shown in Table 3. Volume-median particle size D ₅₀ and CV value of the obtained resin particles shown in Table 3.

Production Example P1 (Production of resin particle dispersion P-1 for wax emulsification)
200 g of resin D-1 and 200 g of methyl ethyl ketone are placed in a 3 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen introduction tube, and the resin is dissolved at 73 ° C. over 2 hours. It was. 5 mass% sodium hydroxide aqueous solution was added to the obtained solution so that the neutralization degree might be 60 mol% with respect to the acid value of resin D-1, and it stirred for 30 minutes.
Next, while maintaining at 73 ° C., 700 g of deionized water was added over 50 minutes while stirring at 280 r / min (peripheral speed 88 m / min), and phase inversion emulsification was performed. While maintaining the temperature at 73 ° C., methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. Thereafter, the aqueous dispersion is cooled to 30 ° C. while stirring at 280 r / min (circumferential speed 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 D ₅₀ 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 P-1 and 40 g of paraffin wax “HNP-9” (manufactured by Nippon Seiwa Co., Ltd., melting point 75 ° C.) are added to a beaker having an internal volume of 1 L, and 90 to 95 ° C. The mixture was melted while maintaining the temperature and stirred to obtain a molten mixture.
The obtained molten mixture was further dispersed for 20 minutes using an ultrasonic homogenizer “US-600T” (manufactured by Nippon Seiki Seisakusyo Co., Ltd.) while maintaining the temperature at 90 to 95 ° C. until room temperature (20 ° C.). Cooled down. 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 size D ₅₀ of the wax particles in the dispersion was 0.47 μm, and the CV value was 27%.

[Production of addition polymer E]
Production Examples E1 and E2 (synthesis of addition polymers E-1 and E-2)
The types and amounts of raw material monomers shown in Table 4 were mixed to prepare a monomer mixed solution having a total monomer amount of 100 g.
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dropping funnel, a stirrer, and a thermocouple was replaced with nitrogen, and 18 g of methyl ethyl ketone, 0.03 g of 2-mercaptoethanol, and 10% by mass of the monomer mixture were added. The temperature was raised to 75 ° C. with stirring. While maintaining at 75 ° C., 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” 3 g of a mixture (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped from the dropping funnel over 3 hours. After maintaining at 75 ° C. for 2 hours after the completion of dropping, a solution prepared by dissolving 3 g of V-65 in 5 g of methyl ethyl ketone was added, and the mixture 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 polymers E-1 and E-2. Table 4 shows the weight average molecular weight of the obtained addition polymer.

[Production of Colorant Particle Dispersion]
Production Example Z1 (Production of Colorant Particle Dispersion Z-1)
75 g of addition polymer E-1 and 630 g of methyl ethyl ketone are placed in a 5 L internal vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen introducing tube equipped with a disper blade, and the resin is dissolved at 20 ° C. I let you. To the obtained solution, 101 g of 5% by mass aqueous sodium hydroxide solution (addition polymer E-1 has a neutralization degree of 91 mol%) was added, and 955 g of deionized water was further added. For 10 minutes. Next, 300 g of carbon black “Regal-330R” (manufactured by Cabot) was added, and stirring was performed at 6400 r / min with a disper blade at 20 ° C. for 2 hours. Thereafter, the mixture was passed through a 200-mesh filter and treated for 15 passes at a pressure of 150 MPa using a homogenizer “Microfluidizer M-110EH” (manufactured by Microfluidics). While stirring the obtained dispersion, methyl ethyl ketone and a part of water were distilled off at 70 ° C. under reduced pressure. 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 to obtain a colorant particle dispersion Z-1. Table 5 shows the volume median particle size D ₅₀ and CV value of the obtained colorant particles.

Production Example Z2 (Production of Colorant Particle Dispersion Z-2)
A colorant particle dispersion Z-2 was obtained in the same manner as in Production Example Z1, except that the colorant used was changed to the yellow pigment “HANSA YELLOW 5GX01” (CI Pigment Yellow 74, manufactured by Clariant Chemicals Co., Ltd.). . Table 5 shows the volume median particle size D ₅₀ and CV value of the obtained colorant particles.

Production Example Z3 (Production of Colorant Particle Dispersion Z-3)
A colorant particle dispersion Z-3 was obtained in the same manner as in Production Example Z1, except that the colorant used was changed to carbon black “Regal-T30R” (manufactured by Cabot Corporation). Table 5 shows the volume median particle size D ₅₀ and CV value of the obtained colorant particles.

Production Example Z4 (Production of Colorant Particle Dispersion Z-4)
A colorant particle dispersion Z-4 was obtained in the same manner as in Production Example Z1, except that the colorant used was changed to carbon black “Regal-T40R” (manufactured by Cabot Corporation). Table 5 shows the volume median particle size D ₅₀ and CV value of the obtained colorant particles.

Production Example Z5 (Production of Colorant Particle Dispersion Z-5)
A colorant particle dispersion liquid Z-5 was obtained in the same manner as in Production Example Z1, except that the colorant used was changed to the yellow pigment “Pariotol Yellow D1155” (BASF Corporation, CI Pigment Yellow 185). . Table 5 shows the volume median particle size D ₅₀ and CV value of the obtained colorant particles.

Production Example Z6 (Production of Colorant Particle Dispersion Z-6)
In the same manner as in Production Example Z1, after 75 g of addition polymer E-1 was dissolved in 630 g of methyl ethyl ketone, 101 g of 5% by weight aqueous sodium hydroxide solution (the degree of neutralization of addition polymer E-1 was 91 Then, 955 g of deionized water was added, and the mixture was stirred with a disper blade at 20 ° C. for 10 minutes. Next, 300 g of carbon black “Regal-330R” (manufactured by Cabot) was added, and stirring was performed at 6400 r / min with a disper blade at 20 ° C. for 2 hours.
Thereafter, the filter was passed through a 200 mesh filter, and a bead mill “NVM-2” (manufactured by Imex Co., Ltd.) was used. Five passes were processed at a liquid feed rate of 0.6 kg / min. While stirring the obtained dispersion, methyl ethyl ketone and a part of water were distilled off at 70 ° C. under reduced pressure. 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 to obtain a colorant particle dispersion Z-6. Table 5 shows the volume median particle size D ₅₀ and CV value of the obtained colorant particles.

Production Example Z7 (Production of Colorant Particle Dispersion Z-7)
138 g of addition polymer E-1, 825 g of methyl ethyl ketone, 185 g of 5 mass% sodium hydroxide aqueous solution (neutralization degree of addition polymer E-1 is 91 mol%), and deionized water were changed to 1198 g, respectively. Except that, Colorant particle dispersion liquid Z-7 was obtained in the same manner as in Production Example Z1. Table 5 shows the volume median particle size D ₅₀ and CV value of the obtained colorant particles.

Production Example Z8 (Production of Colorant Particle Dispersion Z-8)
30 g of addition polymer E-1, 490 g of methyl ethyl ketone, 40 g of 5 mass% aqueous sodium hydroxide solution (neutralization degree of addition polymer E-1 is 91 mol%), and deionized water were changed to 780 g, respectively. Except for this, in the same manner as in Production Example Z1, a colorant particle dispersion Z-8 was obtained. Table 5 shows the volume median particle size D ₅₀ and CV value of the obtained colorant particles.

Production Example Z9 (Production of Colorant Particle Dispersion Z-9)
A colorant particle dispersion Z-9 was obtained in the same manner as in Production Example Z1, except that the addition polymer E-1 was changed to the addition polymer E-2. Table 5 shows the volume median particle size D ₅₀ and CV value of the obtained colorant particles.

Production Example Z51 (Production of Colorant Particle Dispersion Z-51)
Carbon black “Regal-330R” (Cabot Corporation) 100 g, 15 mass% sodium dodecylbenzenesulfonate aqueous solution “Neopelex G-15” (Kao Corporation, anionic surfactant) 167 g in a 1 L beaker. , And 102 g of deionized water, and using a homomixer “TKAGI HOMOMIXER 2M-03” (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 20 ° C. with a rotating speed of the stirring blade of 8000 r / min. After time dispersion, 15 passes were performed at a pressure of 150 MPa using a homogenizer “Microfluidizer M-110EH” (manufactured by Microfluidics). Then, the colorant particle dispersion liquid Z-51 was obtained by passing through a 200 mesh filter and adding deionized water so that solid content concentration might be 20 mass%. Table 5 shows the volume median particle size D ₅₀ and CV value of the obtained colorant particles.

[Production of toner]
Example 1 (Production of Toner 1)
In a 3 L four-necked flask equipped with a dehydration tube, a stirrer and a thermocouple, 450 g of resin particle dispersion X-1, 50 g of resin particle dispersion Y-1, and 84 g of wax particle dispersion W-1 72 g of the colorant particle dispersion Z-1, 25 g of a 10% by mass aqueous solution of polyoxyethylene (50) lauryl ether “Emulgen 150” (manufactured by Kao Corporation, nonionic surfactant), and 15% by mass dodecylbenzene 20 g of an aqueous sodium sulfonate solution “Neopelex G-15” (manufactured by Kao Corporation, an anionic surfactant) was mixed at a temperature of 25 ° C. Next, while stirring the mixture, a solution adjusted to pH 8.4 by adding 4.8 mass% potassium hydroxide aqueous solution to an aqueous solution in which 40 g of ammonium sulfate was dissolved in 625 g of deionized water was added at 25 ° C. for 10 minutes. After dropping, the temperature was raised to 63 ° C. over 2 hours, and kept at 63 ° C. until the volume median particle size D _{50 of} the aggregated particles became 5.7 μm to obtain a dispersion of aggregated particles.
In a dispersion of the obtained aggregated particles, 48 g of sodium polyoxyethylene lauryl ether sulfate “Emar E-27C” (manufactured by Kao Corporation, an anionic surfactant, effective concentration 27 mass%), 600 g of deionized water, and 0 An aqueous solution mixed with 50 g of a 1 mol / L sulfuric acid aqueous solution was added. Then, after heating up to 85 degreeC over 1 hour and hold | maintaining at 85 degreeC for 30 minutes, 10 g of 0.1 mol / L sulfuric acid aqueous solution was added, and also it hold | maintained at 85 degreeC for 15 minutes. Thereafter, 10 g of a 0.1 mol / L sulfuric acid aqueous solution was added again and held at 85 ° C. until the circularity reached 0.970, thereby obtaining a dispersion of fused particles in which aggregated particles were fused.
The obtained fused particle dispersion was cooled to 30 ° C., and the dispersion was subjected to suction filtration to separate the solid content, then washed with deionized water at 25 ° C., and suction filtered at 25 ° C. for 2 hours. Thereafter, using a vacuum constant temperature dryer “DRV622DA” (manufactured by ADVANTEC), vacuum drying was performed at 33 ° C. for 24 hours to obtain toner particles having a water content of 0.5 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 size: 0.04 μm), and hydrophobic silica “Cabosil® TS720” (Cabot Japan Co., Ltd.) 1.0 part by mass (manufactured by company, number average particle size; 0.012 μm) was put in a Henschel mixer and stirred, and then passed through a 150-mesh sieve to obtain toner 1. Table 6 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Examples 2-6, 9-11, Comparative Examples 1 and 2 (Production of Toners 2-6, 9-11, 51, 52)
Toners 2 to 6, 9 to 11, 51 and 52 were produced in the same manner as in Example 1 except that the type of resin particle dispersion used and the type of colorant particle dispersion were changed as shown in Table 6. . Table 6 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Example 7 (Production of Toner 7)
Toner 7 was produced in the same manner as in Example 1 except that the type of colorant particle dispersion used was changed to Z-7 and the addition amount was changed to 85 g. Table 6 shows the physical properties of the obtained toner particles and the evaluation results of the toner.
Here, in order to compare the evaluation results by comparing with the example 1 by aligning the amount of the colorant with that of the example 1, the addition amount of the colorant particle dispersion was adjusted.

Example 8 (Production of Toner 8)
Toner 8 was prepared in the same manner as in Example 1 except that the type of colorant particle dispersion used was changed to Z-8 and the addition amount was changed to 63 g. Table 6 shows the physical properties of the obtained toner particles and the evaluation results of the toner.
Here, in order to compare the evaluation results by comparing with the example 1 by aligning the amount of the colorant with that of the example 1, the addition amount of the colorant particle dispersion was adjusted.

  As described above, it can be seen from the results of Examples and Comparative Examples that according to the present invention, a high image density can be obtained, and a toner having excellent low-temperature fixability and low-temperature fixability over time can be obtained.

Claims (10)

A method for producing a toner, comprising a step of aggregating and fusing resin particles and colorant particles in an aqueous medium,
The resin particles contain, in the same or different particles, an addition polymerization resin A that is an addition polymerization product of a raw material monomer containing a styrene compound, and a crystalline polyester resin,
The colorant particles contain a colorant and an addition polymer E of a raw material monomer containing an addition polymerizable monomer having an aromatic group,
A toner production method, wherein a mass ratio of the colorant to the addition polymer E in the colorant particles is 50/50 or more and 95/5 or less.   The method for producing a toner according to claim 1, wherein the crystalline polyester resin is a polycondensate of an alcohol component containing an α, ω-aliphatic diol and a carboxylic acid component.   The method for producing a toner according to claim 1, wherein the raw material monomer of the addition polymerization resin A further contains an alkyl (meth) acrylate.   The method for producing a toner according to claim 1, wherein the addition polymerizable monomer having an aromatic group in the addition polymer E has a molecular weight of 80 or more and less than 1,000.   The method for producing a toner according to claim 1, wherein the raw material monomer of the addition polymer E further contains an addition polymerizable monomer having an anionic group.   The toner production method according to claim 1, wherein the raw material monomer of the addition polymer E further contains an addition polymerizable monomer having a polyalkylene oxide group.   The method for producing a toner according to claim 1, wherein the colorant is carbon black. The colorant particles are
Step a: A step of mixing the addition polymer E and an organic solvent, and further mixing an aqueous medium to obtain a dispersion of the addition polymer E; and Step b: a dispersion and coloring obtained in the step a. The method for producing a toner according to claim 1, wherein the toner is obtained by a method including a step of dispersing a colorant to obtain a dispersion of colorant particles.   The toner production method according to claim 8, wherein the step b is a step of dispersing the dispersion and colorant obtained in the step a with a bead mill or a homogenizer. A toner comprising toner particles containing an addition polymerization resin A, a crystalline polyester resin, an addition polymer E and a colorant,
The addition polymerization resin A is an addition polymerization product of a raw material monomer containing a styrene compound,
The addition polymer E is an addition polymer of a raw material monomer containing an addition polymerizable monomer having an aromatic group,
A toner in which a mass ratio of the colorant to the addition polymer E is from 50/50 to 95/5.