JP7278751B2 - Toner manufacturing method - Google Patents

Description

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

In the field of electrophotography, with the development of electrophotographic systems, there is a demand for the development of electrophotographic toners that are compatible with higher image quality and resource saving.
For example, in Patent Document 1, a process of mixing a dispersion of colorant-containing polymer particles and a dispersion of resin particles that substantially does not contain a colorant to aggregate the colorant-containing polymer particles and the resin particles is performed. wherein the polymer has (a) structural units derived from a salt-forming group-containing monomer and (b) structural units derived from an aromatic ring-containing monomer. is described. According to this method, it is described that an electrophotographic toner having excellent dispersibility of a colorant and capable of remarkably improving image density can be obtained.
Patent Document 2 discloses a toner containing at least a binder resin, a colorant, and a pigment dispersant, wherein the colorant contains at least one pigment, and the pigment dispersant is the binder Toners are described that are characterized by having a resin-compatible base skeleton and at least one aromatic skeleton. With this toner, a uniform solid image can be obtained with reduced unevenness within the solid image and at the edges thereof, and the amount of toner adhered can be reduced, so the amount of toner consumed during image output can be reduced. It is stated that the cost per sheet can be significantly reduced.
In Patent Document 3, (i) a pigment dispersion step of dispersing a disazo pigment in a polymerizable monomer to prepare a colorant-dispersed monomer composition, or (ii) a binder resin and a disazo pigment in an organic solvent. dispersing a pigment to prepare a resin solution, wherein the disazo pigment is dispersed in the presence of a sulfonic acid group-containing linear aliphatic polyester in the pigment dispersing step. A method for producing a toner is described, comprising: According to this method, it is described that a toner excellent in dispersion speed and dispersion stability of pigment particles can be obtained.
In Patent Document 4, a carbonaceous material is blended with a monomer together with a polymerization initiator, and the monomer is polymerized by a suspension polymerization method, a bulk polymerization method, or a solution polymerization method to form a polymer of the monomer on the surface of the carbonaceous material. A polymer-coated carbonaceous material provided with a coating, wherein the polymer-coated carbonaceous material is characterized by blending 1 to 10 parts by weight of the polymerization initiator with respect to 100 parts by weight of the monomer. A toner is described which is characterized by:

Japanese Patent Application Laid-Open No. 2010-26106 Japanese Unexamined Patent Application Publication No. 2010-152208 JP 2013-142709 A JP 2007-238415 A

In recent years, in the field of electrophotography as well, there has been a strong demand for resource saving and energy saving, and there is a demand for a toner that can provide a higher image density even with a smaller amount of toner than before.
As a method for obtaining a high image density even if the amount of toner used is reduced, it is possible to improve the dispersibility of the colorant. tend to be sufficient.
In addition, since toners using chemical methods are generally produced using organic solvents, the toners cannot contain high molecular weight substances that are difficult to dissolve in organic solvents. ), when the printed matter on which the fixed image is formed is superimposed and stored, the image sticks and the like occurs, causing image roughness, and there is a problem in the storage stability of the fixed image.
TECHNICAL FIELD The present invention relates to a method for producing a toner that provides high image density and excellent storage stability of fixed images.

The present inventors have found that, in a specific production method, by using colorant particles containing a colorant and an addition polymer having an aromatic group in a specific ratio, image density is improved and fixation is improved. It was found that the image storability is improved.
The present invention includes a step of granulating by mixing a composition containing an amorphous polyester resin A, a release agent, and an organic solvent, and a dispersion of colorant particles Z in an aqueous medium,
The colorant particles Z contain a colorant and an addition polymer E having an aromatic group,
The present invention relates to a method for producing a toner, wherein the mass ratio of the colorant and the addition polymer E is 50/50 or more and 95/5 or less.

According to the production method of the present invention, a toner having a high image density and excellent storage stability of a fixed image can be obtained.

[Toner manufacturing method]
In the method for producing the toner of the present invention, a composition containing an amorphous polyester resin A (hereinafter also simply referred to as "resin A"), a release agent, and an organic solvent, and a dispersion of colorant particles Z are It includes a step of granulating by mixing in an aqueous medium.
The colorant particles Z contain a colorant and an addition polymer E 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.
According to the above production method, a toner having a high image density and excellent storage stability of a fixed image can be obtained.
The reason for this is not clear, but the addition polymer E having an aromatic group covering the colorant has a high affinity with the amorphous polyester resin A and behaves like a pseudo-crosslink, resulting in dispersibility of the colorant and It is presumed that this is because the elastic modulus of the fixed image is improved.

Definitions of various terms used in this specification are shown below.
Whether a resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is defined as the ratio of the softening point of the resin to the maximum endothermic peak temperature (softening point (°C)/maximum endothermic peak temperature (°C)) in the measurement method described in Examples below. . A crystalline resin has a crystallinity index of 0.6 or more and 1.4 or less. Amorphous resins are those having a crystallinity index of less than 0.6 or greater than 1.4. The crystallinity index can be appropriately adjusted depending on the type and ratio of raw material monomers, and production conditions such as reaction temperature, reaction time, and cooling rate.
With respect to hydrocarbon groups, references to parentheses "(iso or tertiary)" and "(iso)" mean both the presence and absence of these prefixes, and the absence of these prefixes. In some cases, the normal is shown.
"(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.
A "(meth)acryloyl group" means at least one selected from an acryloyl group and a methacryloyl group.
"Styrenic compound" means unsubstituted or substituted styrene.
By "backbone" is meant the longest relatively connecting chain in the addition polymer.

<Granulation process>
The method for producing the toner of the present invention includes a step of granulating by mixing a raw material composition and a dispersion of colorant particles Z in an aqueous medium.

[Raw material composition]
The raw material composition contains amorphous polyester resin A, a release agent, and an organic solvent.
The raw material composition may further contain a crystalline polyester resin C (hereinafter also simply referred to as “resin C”) and a modified polyester resin B. The raw material composition also contains active hydrogen compounds, charge control agents, magnetic powders, fluidity improvers, conductivity modifiers, reinforcing fillers such as fibrous substances, antioxidants, anti-aging agents, cleaning improvers, etc. may contain additives.

(Amorphous polyester resin A)
Examples of resin A include polyester resins and modified polyester resins. Examples of modified polyester-based resins include urethane-modified polyester-based resins in which polyester resins are modified with urethane bonds, epoxy-modified polyester-based resins in which polyester resins are modified with epoxy bonds, polyester resin segments, and vinyl-based resin segments. Composite resins containing
Among these, polyester resins are preferred.

（式中、ＯＲ¹及びＲ²Ｏはオキシアルキレン基であり、Ｒ¹及びＲ²はそれぞれ独立にエチレン基又はプロピレン基であり、ｘ及びｙはアルキレンオキサイドの平均付加モル数を示し、それぞれ正の数であり、ｘとｙの和の値は、１以上、好ましくは１．５以上であり、１６以下、好ましくは８以下、より好ましくは４以下である）で表されるビスフェノールＡのアルキレンオキサイド付加物である。
ビスフェノールＡのアルキレンオキサイド付加物としては、例えば、ビスフェノールＡのプロピレンオキサイド付加物（以下「ＢＰＡ－ＰＯ」ともいう）、ビスフェノールＡのエチレンオキサイド付加物（以下「ＢＰＡ－ＥＯ」ともいう）が挙げられる。これらの１種又は２種以上を用いてもよい。
これらの中でも、アルコール成分は、好ましくはＢＰＡ－ＰＯであり、より好ましくはＢＰＡ－ＰＯ及びＢＰＡ－ＥＯを含む。
アルコール成分中、ＢＰＡ－ＰＯとＢＰＡ－ＥＯとのモル比（ＢＰＡ－ＰＯ／ＢＰＡ－ＥＯ）は、好ましくは１０／９０以上、より好ましくは２０／８０以上、更に好ましくは３０／７０以上であり、そして、好ましくは１００／０以下、より好ましくは９５／５以下、更に好ましくは９０／１０以下、更に好ましくは８５／１５以下である。
ビスフェノールＡのアルキレンオキサイド付加物の含有量は、アルコール成分中、好ましくは７０モル％以上、より好ましくは９０モル％以上、更に好ましくは９５モル％以上であり、そして、１００モル％以下であり、好ましくは１００モル％である。 A polyester resin is, for example, a condensate of an alcohol component and a carboxylic acid component.
Examples of alcohol components include aromatic diols, linear or branched aliphatic diols, alicyclic diols, and polyhydric alcohols having a valence of 3 or more. Among these, aromatic diols are preferred.
The aromatic diol is preferably an alkylene oxide adduct of bisphenol A, more preferably of formula (I):

(Wherein, OR ¹ and R ² O are oxyalkylene groups, R ¹ and R ² are each independently an ethylene group or a propylene group, x and y represent the average number of added moles of alkylene oxide, each positive and the sum of x and y is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, more preferably 4 or less). It is an oxide adduct.
Examples of the alkylene oxide adduct of bisphenol A include a propylene oxide adduct of bisphenol A (hereinafter also referred to as "BPA-PO") and an ethylene oxide adduct of bisphenol A (hereinafter also referred to as "BPA-EO"). . You may use these 1 type(s) or 2 or more types.
Among these, the alcohol component is preferably BPA-PO, and more preferably includes BPA-PO and BPA-EO.
In the alcohol component, the molar ratio of BPA-PO to BPA-EO (BPA-PO/BPA-EO) is preferably 10/90 or more, more preferably 20/80 or more, still more preferably 30/70 or more. , and preferably 100/0 or less, more preferably 95/5 or less, even more preferably 90/10 or less, and even more preferably 85/15 or less.
The content of the alkylene oxide adduct of bisphenol A is preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol% or less, in the alcohol component, Preferably it is 100 mol %.

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

Examples of the carboxylic acid component include dicarboxylic acids and polycarboxylic acids having a valence of 3 or more.
Dicarboxylic acids include, for example, aromatic dicarboxylic acids, linear or branched aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids. Among these, at least one selected from aromatic dicarboxylic acids and linear or branched aliphatic dicarboxylic acids is preferred.
Examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid, and terephthalic acid. Among these, isophthalic acid and terephthalic acid are preferred, and terephthalic acid is more preferred.
The amount of the aromatic dicarboxylic acid in the carboxylic acid component is preferably 60 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, and 100 mol% or less, preferably 99 mol%. 95 mol % or less, more preferably 95 mol % or less.

The number of carbon atoms in the linear or branched aliphatic dicarboxylic acid is preferably 2 or more, more preferably 3 or more, and is preferably 30 or less, more preferably 20 or less, still more preferably 10 or less.
Linear or branched aliphatic dicarboxylic acids include, for example, oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, and azelaic acid. , and succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms. Examples of the succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms include dodecylsuccinic acid, dodecenylsuccinic acid, and octenylsuccinic acid. Among these, adipic acid, sebacic acid and dodecanedioic acid are preferred, and adipic acid is more preferred.
The amount of linear or branched aliphatic dicarboxylic acid in the carboxylic acid component is preferably 1 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, and preferably 30 mol%. Below, more preferably 20 mol % or less, still more preferably 10 mol % or less.

The trivalent or higher polyvalent carboxylic acid is preferably a trivalent carboxylic acid, such as trimellitic acid or its anhydride.
When a trivalent or higher polycarboxylic acid is contained, the amount of the trivalent or higher polycarboxylic acid is preferably 1 mol% or more, more preferably 2 mol% or more, in the carboxylic acid component, and preferably It is 40 mol % or less, more preferably 20 mol % or less, still more preferably 10 mol % or less.
One or more of these carboxylic acid components may be used.

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

(Method for producing resin A)
Resin A is obtained, for example, by polycondensation of an alcohol component and a carboxylic acid component.
If necessary, an esterification catalyst such as di(2-ethylhexanoic acid) tin (II), dibutyl tin oxide, titanium tetraisopropoxide, titanium diisopropylate bistriethanolamine, etc. is added to the alcohol component and the carboxylic acid component. 0.01 part by mass or more and 5 parts by mass or less per 100 parts by mass of the total amount; an esterification co-catalyst such as gallic acid (same as 3,4,5-trihydroxybenzoic acid), the total amount of the alcohol component and the carboxylic acid component Polycondensation may be carried out using 0.001 parts by mass or more and 0.5 parts by mass or less per 100 parts by mass.
The temperature of the polycondensation reaction is preferably 120° C. or higher, more preferably 160° C. or higher, still more preferably 170° C. or higher, and preferably 250° C. or lower, more preferably 240° C. or lower. In addition, you may perform polycondensation in an inert gas atmosphere.

(Physical properties of resin A)
The softening point of Resin A is preferably 70° C. or higher, more preferably 90° C. or higher, still more preferably 100° C. or higher, and preferably 150° C. or lower, more preferably 140° C. or lower, still more preferably 130° C. or lower. is.
The glass transition temperature of Resin A is preferably 30°C or higher, more preferably 35°C or higher, still more preferably 40°C or higher, and is preferably 80°C or lower, more preferably 75°C or lower, and still more preferably 70°C. It is below.

The acid value of Resin A is preferably 3 mgKOH/g or more, more preferably 5 mgKOH/g or more, still more preferably 8 mgKOH/g or more, and preferably 40 mgKOH/g or less, more preferably 30 mgKOH/g or less, and further preferably Preferably, it is 20 mgKOH/g or less.

The softening point, glass transition temperature, and acid value of Resin A can be appropriately adjusted depending on the type and amount of raw material monomers used, and production conditions such as reaction temperature, reaction time, and cooling rate. is determined by the method described in Examples.
When two or more resins A are used in combination, the softening point, glass transition temperature, and acid value obtained as a mixture thereof are preferably within the ranges described above.

The content of resin A is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and 100% by mass or less, preferably 98% by mass, in the resin component of the raw material composition. % or less, more preferably 90 mass % or less.

(Crystalline polyester resin C)
Examples of the crystalline polyester resin C (hereinafter also simply referred to as "resin C") include crystalline polyester resins and modified crystalline polyester resins. Examples of modified crystalline polyester resins include urethane-modified crystalline polyester resins in which polyester resins are modified with urethane bonds, epoxy-modified crystalline polyester resins in which polyester resins are modified with epoxy bonds, and polyester resin segments. and crystalline composite resins containing addition polymerized resin segments.
Among these, crystalline polyester resins are preferred.

A crystalline polyester resin 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 number of carbon atoms in the α,ω-aliphatic diol is preferably 2 or more, more preferably 4 or more, still more preferably 6 or more, and preferably 16 or less, more preferably 14 or less, still more preferably 12 or less. be.
Examples of α,ω-aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, and 1,14-tetradecanediol mentioned. Among these, ethylene glycol, 1,6-hexanediol and 1,10-decanediol are preferred.

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

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

The carboxylic acid component preferably comprises an aliphatic dicarboxylic acid.
The number of carbon atoms in the aliphatic dicarboxylic acid is preferably 4 or more, more preferably 6 or more, still more preferably 8 or more, and preferably 16 or less, more preferably 14 or less, still more preferably 12 or less.
Aliphatic dicarboxylic acids include, for example, fumaric acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid. These may be used alone or in combination of two or more. Among these, sebacic acid is preferred.

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

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

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

The polyester resin can be produced by a method similar to that exemplified for resin A above.

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

The melting point of Resin C is preferably 50° C. or higher, more preferably 60° C. or higher, and preferably 100° C. or lower, more preferably 90° C. or lower, and still more preferably 80° C. or lower.

The softening point and melting point of Resin C can be appropriately adjusted depending on the type and amount of raw material monomers used, and production conditions such as reaction temperature, reaction time, and cooling rate. Obtained by the method described.
When two or more resins C are used in combination, it is preferable that the softening point and the melting point of the mixture are within the ranges described above.

The content of Resin C is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, and preferably 50% by mass or less in the resin component of the raw material composition. , more preferably 30% by mass or less, and still more preferably 25% by mass or less.

(Organic solvent)
Examples of organic solvents include alcohol solvents such as ethanol, isopropanol and isobutanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diethyl ketone; ether solvents such as dibutyl ether, tetrahydrofuran and dioxane; Acetate solvents such as isopropyl acetate can be used. Among these, ketone-based solvents and acetic acid ester-based solvents are preferred, and methyl ethyl ketone, ethyl acetate, and isopropyl acetate are more preferred, from the viewpoint of ease of removal from the mixed solution after addition of the aqueous medium.

(Release agent)
Examples of release agents include waxes.
Waxes include, for example, hydrocarbon waxes, ester waxes, silicone waxes, and fatty acid amide waxes.
Hydrocarbon waxes include, for example, mineral or petroleum hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax; synthetic hydrocarbon waxes such as polyolefin waxes such as polyethylene wax, polypropylene wax and polybutene wax.
Examples of ester waxes include mineral or petroleum ester waxes such as montan wax; vegetable ester waxes such as carnauba wax, rice wax and candelilla wax; and animal ester waxes such as beeswax.
Fatty acid amide waxes include, for example, oleic acid amide and stearic acid amide. These can use 1 type(s) or 2 or more types.
Among these, hydrocarbon waxes and ester waxes are preferred, and hydrocarbon waxes are more preferred.

The melting point of the release agent is preferably 60° C. or higher, more preferably 65° C. or higher, still more preferably 70° C. or higher, and is preferably 160° C. or lower, more preferably 150° C. or lower, further preferably 140° C. or lower. is.

The content of the release agent is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, still more preferably 2 parts by mass or more, and preferably 20 parts by mass with respect to 100 parts by mass of the resin component. parts or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less.

(Modified polyester resin B)
The raw material composition may contain a modified polyester-based resin B (hereinafter also simply referred to as "resin B") having a reactive group reactive with an active hydrogen group.
Active hydrogen groups include active hydrogen groups described later. As the reactive group, an isocyanato group is preferred.
As the modified polyester resin B, for example, a polyester resin B having at least one selected from urethane bonds and urea bonds is preferable.

The glass transition temperature of Resin B is preferably −60° C. or higher, more preferably −50° C. or higher, still more preferably −45° C. or higher, and preferably 0° C. or lower, more preferably −10° C. or lower. It is preferably -20°C or lower.
The weight average molecular weight of Resin B is preferably 2,000 or more, more preferably 10,000 or more, still more preferably 100,000 or more, and preferably 1,000,000 or less, more preferably 800,000. 300,000 or less, more preferably 300,000 or less.

The content of the resin B in the resin component of the raw material composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 13% by mass or more, and preferably 25% by mass or less. It is preferably 20% by mass or less.

When the resin B described above is used, the raw material composition preferably contains an active hydrogen group-containing compound.
Examples of active hydrogen groups in active hydrogen group-containing compounds include hydroxyl groups, amino groups, carboxyl groups, and mercapto groups. Among them, it is preferable to contain an amino group.
Examples of compounds containing an amino group include phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminocyclohexane, isophoronediamine, ethylenediamine, diamines such as tetramethylenediamine and hexamethylenediamine; trivalent or higher amines such as diethylenetriamine and triethylenetetramine; aminoalcohols such as ethanolamine and hydroxyethylaniline; aminomercaptans such as aminoethylmercaptan and aminopropylmercaptan; and those in which the amino group of is blocked.
Among these, those obtained by blocking the amino group of diamine are more preferable, those obtained by blocking the amino group of isophoronediamine are more preferable, and those obtained by blocking the amino group of isophoronediamine with methyl ethyl ketone are even more preferable.

The content of the active hydrogen group compound is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, relative to 100 parts by mass of the resin B, and preferably is 10 parts by mass or less, more preferably 5 parts by mass or less.

The solid content concentration in the raw material composition is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, and preferably 80% by mass or less, more preferably 75% by mass. 70% by mass or less, more preferably 70% by mass or less.

[Colorant particles Z]
The colorant particles Z preferably contain a colorant and an addition polymer E having an aromatic group from the viewpoint of obtaining a toner that provides a high image density and excellent storage stability of fixed images.
From the viewpoint of further improving the image density and the storage stability of the fixed image, the colorant particles Z are preferably particles obtained by dispersing them in a mixed liquid containing a colorant, the addition polymer E, and water. is.
Colorant particles Z are preferably obtained by mixing a colorant, addition polymer E and water with a bead mill or a homogenizer, from the viewpoint of further improving the image density and storage stability of fixed images.
The colorant particles Z have, for example, the addition polymer E on the surface of the colorant, and the surface of the colorant is preferably coated with the addition polymer E.

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

(Addition polymer E)
From the viewpoint of further improving the image density and storage stability of the fixed image, the addition polymer E is preferably a raw material monomer containing an addition polymerizable monomer Ea having an aromatic group (hereinafter also simply referred to as "monomer Ea"). It is an addition polymer. That is, the addition polymer E preferably contains, in its main chain, structural units derived from the addition-polymerizable monomer Ea having an aromatic group.
Raw material monomers for the addition polymer E include an addition-polymerizable monomer Ea having an aromatic group, and preferably an addition-polymerizable monomer Eb having an ionic group (hereinafter also simply referred to as "monomer Eb").
In addition to the monomer Eb, the raw material monomers for the addition polymer E are more preferably an addition polymerizable monomer Ec having a polyalkylene oxide group (hereinafter also simply referred to as "monomer Ec") or a macromonomer Ed (hereinafter referred to as simply referred to as "monomer Ed").

The addition polymer E is preferably a water-insoluble addition polymer from the viewpoint of improving the image density.
Here, the term "water-insoluble" means the property that the dissolved amount is less than 10 g when a sample dried at 105°C for 2 hours is dissolved in 100 g of deionized water at 25°C until saturated. . The dissolution amount is measured in a state where the ionic groups of the addition polymer E are 100% neutralized. For example, in the case of an addition polymer having a carboxy group, the dissolved amount is the amount dissolved when the carboxy group of the addition polymer is 100% neutralized with sodium hydroxide.
The amount of the 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 Ea having an aromatic group 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 is 90 or more, more preferably 100 or more.
The addition polymerizable monomers Ea with aromatic groups are preferably nonionic.
The addition polymerizable monomer Ea having an aromatic group includes, for example, a styrene compound Ea-1 and an aromatic group-containing (meth)acrylate Ea-2.
Examples of the styrenic compound Ea-1 include unsubstituted or substituted styrene. Examples of substituents for styrene include alkyl groups having 1 to 5 carbon atoms, halogen atoms, alkoxy groups having 1 to 5 carbon atoms, sulfo groups, and salts thereof.
The molecular weight of the styrene compound Ea-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, It is more preferably 100 or more.
Styrenic compounds Ea-1 include, for example, styrene, methylstyrene, α-methylstyrene, β-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrenesulfonic acid and salts thereof. . Among these, styrene is preferable from the viewpoint of increasing the image density.
From the viewpoint of further improving the image density, the amount of the styrene compound Ea-1 is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more in the raw material monomers of the addition polymer E. , 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 65% by mass 60% by mass or less, more preferably 60% by mass or less.

Examples of the aromatic group-containing (meth)acrylate Ea-2 include benzyl (meth)acrylate.
From the viewpoint of further improving the image density, the amount of the aromatic group-containing (meth)acrylate Ea-2 is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 5% by mass or more in the raw material monomers of the addition polymer E. is 10% by mass or more, more preferably 20% by mass or more, 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, and further It is preferably 65% by mass or less, more preferably 60% by mass or less.

From the viewpoint of further improving the image density, the amount of the addition polymerizable monomer Ea having an aromatic group is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more, more preferably 20% by mass or more, 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, and still more preferably is 90 mass % or less, more preferably 80 mass % or less, still more preferably 65 mass % or less, still more preferably 60 mass % or less.

The ionic group in the monomer Eb means a group that dissociates ions in water.
The ionic group includes, for example, a carboxy group, a sulfo group (--SO ₃ H), a sulfate ester group (--OSO ₃ H), a phosphate group, an amino group, or salts thereof.
From the viewpoint of improving the dispersion stability of the colorant particles, the ionic group is preferably an anionic group. As an anionic group, 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 still more preferable.
Addition-polymerizable monomers having a carboxy group include, for example, (meth)acrylic acid, itaconic acid, maleic acid, fumaric acid, and 2-methacryloyloxymethylsuccinic acid.
Among these, addition polymerizable monomers having an anionic group are preferable, (meth)acrylic acid is more preferable, and methacrylic acid is still more preferable, from the viewpoint of improving the dispersion stability of the colorant particles in the ink.
When the monomer Eb is contained, the amount of the monomer Eb is preferably 2% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, in the raw material monomers of the addition polymer E. 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 groups of the monomer Ec 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, and still more preferably 10. It is below.
Monomer Ec is preferably nonionic.
Examples of the monomer Ec include polyalkylene glycol (meth)acrylates such as polyethylene glycol (meth)acrylate and polypropylene glycol (meth)acrylate; alkoxypolyalkylene glycol (meth)acrylates such as methoxypolyethyleneglycol (meth)acrylate; phenoxy ( and aryloxypolyalkylene glycol (meth)acrylates such as ethylene glycol-propylene glycol copolymer) (meth)acrylates. Among these, methoxypolyethylene glycol (meth)acrylate is preferred.
When the monomer Ec is contained, the amount of the monomer Ec is preferably 3% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, in the raw material monomers of the addition polymer E. is 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less.

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

Further, the raw material monomers of the addition polymer E may contain addition polymerizable monomers (other monomers) other than the monomers Ea to Ed.
Other monomers include, for example, alkyl (meth)acrylates having an alkyl group having 1 to 22 carbon atoms (preferably 6 to 18 carbon atoms).
When other monomers are contained, the amount of the other monomers is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, still more preferably 20% by mass or less, in the raw material monomers of the addition polymer E. It 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 10,000 or more, still more preferably 20,000 or more, still more preferably 30,000 or more, from the viewpoint of further improving the image density. It is more preferably 40,000 or more, and preferably 200,000 or less, more preferably 90,000 or less, even more preferably 60,000 or less, still more preferably 53,000 or less. The weight average molecular weight can be measured by the method described in Examples.

The addition polymer E is obtained, for example, by an addition polymerization reaction of raw material monomers containing styrene compounds.
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). mentioned. Among these, azo compounds are preferred, and 2,2′-azobis(2,4-dimethylvaleronitrile) is more preferred.
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, relative to 100 parts by mass of the raw material monomer of the addition polymer E. 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 50° C. or higher, more preferably 60° C. or higher, and preferably 250° C. or lower, more preferably 150° C. or lower, still more preferably 100° C. or lower.

In the colorant particles, the mass ratio of the colorant and the addition polymer E is 50/50 or more, preferably 55/45, from the viewpoint of obtaining a toner having high image density and excellent fixed image storage stability. more preferably 60/40 or more, more preferably 65/35 or more, still more preferably 70/30 or more, and 95/5 or less, preferably 90/10 or less, more preferably 85/15 or less be.

(Method for producing colorant particles Z)
Colorant particles Z are obtained by mixing a colorant and an addition polymer E, for example. The mixing method is not particularly limited, but for example, the colorant and the addition polymer E may be mixed at a temperature equal to or higher than the melting point of the addition polymer E under dry conditions.
Further, as the colorant particles Z, it is preferable to use a dispersion liquid of the colorant particles Z in which the colorant is dispersed with the addition polymer E from the viewpoint of further improving the image density and the storage stability of the fixed image.
There is no particular limitation on the method for producing the dispersion liquid of the colorant particles Z, as long as it can be controlled to obtain colorant particles having a desired volume-median particle size (D ₅₀ ) using a known kneader, disperser, or the like. It is preferable to obtain by mixing the colorant and the addition polymer E with a bead mill or a homogenizer.

The method for producing the colorant particles Z preferably comprises
Step a: A step of mixing the addition polymer E with an organic solvent, then optionally mixing a neutralizing agent, and further mixing an aqueous medium to obtain a dispersion of the addition polymer E, and Step b: This method has a step of obtaining a dispersion of colorant particles Z by dispersing the dispersion obtained in step a and a colorant.
By containing 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 enhanced.

In step a, it is preferable to first mix 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, dialkyl ketones having a total carbon number of 3 or more and 5 or less are 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.

Neutralizing agents include, for example, basic substances. Basic substances include, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; and nitrogen-containing basic substances such as ammonia, trimethylamine and diethanolamine.
The degree of neutralization of 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, still more preferably 95 mol % or less.
The degree of neutralization of the addition polymer E can be determined by the following formula.
Degree of neutralization (mol%) = [(mass of neutralizing agent added (g)/equivalent weight of neutralizing agent)/{mass ratio of addition polymerizable monomer having acidic group constituting addition polymer E × addition polymer mass of E (g)/molecular weight of addition polymerizable monomer having acidic group}]×100
In step a, the device used for mixing includes, for example, a mixing and stirring device equipped with anchor blades, disper blades, and the like.
The temperature during mixing is preferably 0° C. or higher, more preferably 10° C. or higher, and preferably 40° C. or lower, more preferably 30° C. or lower, and still more preferably 25° C. or lower.
The mixing time is preferably 5 minutes or longer, more preferably 10 minutes or longer, and preferably 10 hours or shorter, more preferably 5 hours or shorter, and even more preferably 1 hour or shorter.

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

Examples of the apparatus used in step b include kneaders such as roll mills and kneaders, homogenizers such as Microfluidizer (manufactured by Microfluidic), media type dispersers such as paint shakers and bead mills. One or more of these devices may be used. Among these, a bead mill and a homogenizer are preferable from the viewpoint of reducing the particle size of the pigment, 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 higher, more preferably 100 MPa or higher, still more preferably 130 MPa or higher, and preferably 270 MPa or lower, more preferably 200 MPa or lower, and still more preferably 180 MPa or lower.
The number of passes is preferably 5 or more, more preferably 10 or more, still more preferably 12 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 to filter the dispersion liquid of the colorant particles Z 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 Z may be crosslinked.
Various additives such as organic solvents, preservatives, and antifungal agents may be added to the dispersion liquid of the colorant particles Z.

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

The volume-median particle size (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, from the viewpoint of improving image density, and , preferably 0.3 μm or less, more preferably 0.2 μm or less.
From the viewpoint of improving the image density, the CV value of the colorant particles Z is preferably 10% or more, more preferably 20% or more, and preferably 40% or less, more preferably 35% or less.
The volume-median particle size (D ₅₀ ) and CV value of the colorant particles Z are measured by the methods in Examples.

The colorant particles Z are preferably used after removing a liquid component such as a dispersion medium from a dispersion liquid of the colorant particles Z.

From the viewpoint of further improving the image density, the amount of the colorant particles Z is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass with respect to 100 parts by mass of the resin component in the raw material composition. It is at least 40 parts by mass, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less.

[Aqueous medium]
The aqueous medium preferably contains water as a main component, and from the viewpoint of improving the dispersion stability of the resin particle dispersion and from the viewpoint of environmental friendliness, the content of water in the aqueous medium is preferably 80 mass. % or more, more preferably 90 mass % or more, still more preferably 95 mass % or more, still more preferably 98 mass % or more, and 100 mass % or less, more preferably 100 mass %. As water, deionized water or distilled water is preferred. Components other than water that can be contained in the aqueous medium include, for example, alkyl alcohols having 1 to 5 carbon atoms; dialkyl ketones having 3 to 5 carbon atoms such as acetone and methyl ethyl ketone; and cyclic ethers such as tetrahydrofuran dissolved in water. and organic solvents.

In the granulation step, granulation is performed by mixing the raw material composition described above and the dispersion liquid of the colorant particles Z described above in an aqueous medium.
The granulating step is preferably
Step 1-1: Step of obtaining a raw material composition in which resin A is dissolved or dispersed in an organic solvent Step 1-2: The raw material composition and a dispersion of colorant particles Z are introduced into an aqueous medium and mixed. to obtain an aqueous dispersion of toner particles.

[Step 1-1]
In step 1-1, a raw material composition in which resin A is dissolved or dispersed in an organic solvent is obtained.
Here, each component of the raw material composition described above may be mixed.

The release agent is preferably added as a dispersion of release agent particles.
An organic solvent is preferable as the dispersion medium. Examples of the organic solvent include the organic solvents described above.
The dispersion can be obtained by a known method. For example, the temperature is raised to near the melting point of the release agent in an organic solvent to dissolve the release agent. A dispersion of release agent particles can be prepared.
The volume-median particle diameter ( _D50 ) of the dispersion liquid of the release agent particles is preferably 0.05 μm or more, more preferably 0.1 μm or more, still more preferably 0.2 μm or more, and preferably 0.2 μm or more. It is 6 μm or less, more preferably 0.55 μm or less, still more preferably 0.5 μm or less. The volume-median particle size ( _D50 ) of the release agent particles is determined by the method described in Examples below.
The amount of the release agent particle dispersion to be added is the amount corresponding to the content of the release agent in the raw material composition described above.
Part of the resin may be added as a resin dispersion.

[Step 1-2]
The raw material composition described above and the dispersion liquid of the colorant particles Z described above are put into an aqueous medium and mixed to obtain an aqueous dispersion liquid of toner particles.

Here, the aqueous medium may contain a polymer dispersant, a dispersion stabilizer and an anionic surfactant.
Polymeric dispersants include, for example, addition polymers of polymerizable monomers containing addition polymerizable monomers having ionic groups.
The addition-polymerizable monomer having an ionic group includes, for example, an addition-polymerizable monomer having a (meth)acrylic acid, a polyalkylene oxide group having a sulfo group or a sulfate ester group.
The polymerizable monomer of the addition polymer may contain a styrenic compound. Examples of styrene compounds include styrenes such as styrene, methylstyrene, α-methylstyrene, β-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrenesulfonic acid and salts thereof. be done. Among these, styrene is preferred.
Among these polymeric dispersants, addition polymers of raw material monomers containing addition polymerizable monomers having (meth)acrylic acid and a polyalkylene oxide group having a sulfo group or a sulfate ester group are preferred. ) Addition polymers of raw material monomers containing acrylic acid and an addition polymerizable monomer having a polyalkylene oxide group having a sulfo group or a sulfate ester group are more preferred.
The polymeric dispersant may be subjected to suspension polymerization by stirring in an aqueous medium containing raw material monomers and a polymerization initiator.
The content of the polymeric dispersant in the aqueous dispersion medium is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and preferably 20% by mass. Below, more preferably 10% by mass or less, still more preferably 5% by mass or less.

Dispersion stabilizers include, for example, carbonates, metal phosphates, sulfates, and metal hydroxides.
Carbonates include, for example, barium carbonate, calcium carbonate, and magnesium carbonate. Examples of metal phosphates include aluminum phosphate, magnesium phosphate, calcium phosphate, barium phosphate, and zinc phosphate. Sulfates include, for example, barium sulfate and calcium sulfate. Examples of metal hydroxides include calcium hydroxide, aluminum hydroxide, magnesium hydroxide, and ferric hydroxide. Among these, calcium phosphate is preferred.
The content of the dispersion stabilizer in the aqueous dispersion medium is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and preferably 20% by mass or less. , more preferably 10% by mass or less, and still more preferably 5% by mass or less.

As the anionic surfactant, an alkylbenzenesulfonate is preferred, dodecylbenzenesulfonate is more preferred, and sodium dodecylbenzenesulfonate is even more preferred.
The content of the anionic surfactant in the aqueous dispersion medium is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and preferably 15% by mass. % by mass or less, more preferably 8% by mass or less, and even more preferably 3% by mass or less.

As an apparatus used in step 1-2, for example, a vertical stirring vessel equipped with a stirrer having a high shearing force can be used. Examples of commercially available stirrers with high shear force include "High Shear Mixer" (manufactured by IKA), "TK Homomixer", and "TK Filmix" (manufactured by Primix Co., Ltd.). , Clearmix (manufactured by M Technic Co., Ltd.).

The organic solvent may be removed after the raw material composition is added to the aqueous dispersion medium. The organic solvent can be removed by, for example, a method of gradually raising the temperature while stirring the entire system and distilling off the organic solvent in the droplets, or a method of reducing the pressure while stirring the entire system and distilling off the organic solvent. be done.

From the viewpoint of easiness of separation, it is preferable to add a mineral acid aqueous solution to dissolve the dispersion stabilizer after the mixture is put into the aqueous dispersion medium.

From the viewpoint of obtaining high quality images, the volume median particle size (D ₅₀ ) of the toner particles is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 10 μm or less. It is preferably 8 μm or less, more preferably 6 μm or less.

The toner manufacturing method may further include a step of mixing the obtained toner particles and an external additive.
Examples of external additives include inorganic material particles such as hydrophobic silica, titanium oxide, alumina, cerium oxide, and carbon black, and polymer particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, hydrophobic silica is preferred.
The average particle size of the external additive is preferably 1 nm or more, more preferably 5 nm or more, still more preferably 10 nm or more, and is preferably 500 nm or less, more preferably 300 nm or less, still more preferably 100 nm or less.
When the toner particles are surface-treated using an external additive, the amount of the external additive added is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, relative to 100 parts by mass of the toner particles. and is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and still more preferably 3 parts by mass or less.

Toners are used for developing latent images formed in electrophotography, electrostatic recording, electrostatic printing, and the like. Further, the toner can be used as a one-component developer, or mixed with a carrier and used as a two-component developer.

Each physical property value of resin etc. was measured and evaluated by the following methods. Regarding the notation of alkylene oxide (X), X means the average number of added moles of alkylene oxide. In the following examples, room temperature means a temperature of 20.degree. C. to 25.degree.

[Measuring method]
[Softening point]
Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), while heating a 1 g sample at a temperature increase rate of 6 ° C./min, a load of 1.96 MPa is applied with a plunger, and the diameter is 1 mm and the length is 1 mm. extruded from the nozzle of Plot the amount of plunger descent of the flow tester against the temperature, and let the softening point be the temperature at which half of the sample flows out.

[Maximum Endothermic Peak Temperature and Melting Point]
Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of the sample is weighed in an aluminum pan, and the temperature is lowered from room temperature at a rate of 10 ° C./min. to 0° C. and held at 0° C. for 1 minute. After that, the temperature is measured at a heating rate of 10° C./min. Among the observed endothermic peaks, the temperature of the peak on the highest temperature side is defined as the maximum endothermic peak temperature (1), and (softening point (°C)) / (maximum endothermic peak temperature (1) (°C)) Determine the crystallinity index. If the maximum peak temperature is within 20°C of the softening point, it is taken as the melting point.

〔Glass-transition temperature〕
Using a differential scanning calorimeter "Q-20" (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of the sample is weighed in an aluminum pan, heated to 200 ° C., and Cool from the temperature to 0°C at a cooling rate of 10°C/min. Next, the sample is heated at a heating rate of 10° C./min, and the endothermic peak is measured. Among the observed endothermic peaks, the temperature of the peak on the highest temperature side is defined as the maximum endothermic peak temperature (2), and the extension line of the baseline below the maximum endothermic peak temperature and the distance from the rising portion of the peak to the top of the peak The temperature at the point of intersection with the tangent line showing the maximum slope is defined as the glass transition temperature.

[Acid value]
It is measured based on the method of JIS K 0070:1992. However, only the measurement solvent is a mixed solvent of ethanol and ether specified in JIS K 0070:1992, and the amorphous resin is a mixed solvent of acetone and toluene (acetone:toluene = 1:1 (volume ratio)), and the crystalline resin is changed to a mixed solvent of chloroform:dimethylformamide (chloroform:dimethylformamide=7:3 (volume ratio)).

[Amine value]
It is measured based on the method of JIS K 7237:1995. However, only the measurement solvent is changed from the mixed solvent of o-nitrotoluene and acetic acid specified in JIS K 7237:1995 to the mixed solvent of chloroform and ethanol.

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

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

[Volume Median Particle Diameter (D ₅₀ ) and CV Value of Resin Particles, Colorant Particles, and Release Agent Particles]
(1) Measuring device: Laser diffraction particle size measuring machine “LA-920” (manufactured by HORIBA, Ltd.)
(2) Measurement conditions: A sample dispersion is placed in a measurement cell, distilled water is added, and the volume median particle diameter (D ₅₀ ) and volume average particle diameter (D _v ) are measured at a concentration at which the absorbance is within the appropriate range. . Also, the CV value is calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution/volume average particle size ( _Dv )) x 100

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

[Volume Median Particle Diameter ( _D50 ) and CV Value of Toner Particles]
The volume median particle size ( _D50 ) and CV value of the toner particles are measured as follows.
・Measuring machine: “Coulter Multisizer (registered trademark) III” (manufactured by Beckman Coulter, Inc.)
・Aperture diameter: 50 μm
・ Analysis software: “Multisizer (registered trademark) III version 3.51” (manufactured by Beckman Coulter, Inc.)
・ Electrolyte: “Isoton (registered trademark) II” (manufactured by Beckman Coulter, Inc.)
- Dispersion: Polyoxyethylene lauryl ether "Emulgen (registered trademark) 109P" (manufactured by Kao Corporation, HLB (Hydrophile-Lipophile Balance) = 13.6) is dissolved in the electrolytic solution to obtain a dispersion with a concentration of 5% by mass. get
Dispersion conditions: 10 mg of a measurement sample of dried toner particles was added to 5 mL of the dispersion liquid, dispersed for 1 minute with an ultrasonic disperser, and then 25 mL of the electrolytic solution was added. and disperse for 1 minute to prepare a sample dispersion.
Measurement conditions: By adding the sample dispersion to 100 mL of the electrolytic solution, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured. The volume median particle size (D ₅₀ ) and volume average particle size (D _V ) are determined from the distribution.
Also, the CV value (%) was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution/volume average particle size (D _V )) x 100

[Evaluation method]
[Image density of printed matter]
First, the following fixing test was conducted and the lowest fixing temperature was set.
Using a printer "Microline (registered trademark) 5400" (manufactured by Oki Data Co., Ltd.) on high-quality A4 paper "J paper A4 size" (manufactured by Fuji Xerox Co., Ltd.), the amount of toner adhering to the paper was 1.48 to 1.5. A solid image of 52 mg/cm ² was printed on high-quality A4 paper with a margin of 5 mm from the top edge and a length of 50 mm without being fixed.
Next, we prepared the same printer with a variable temperature fusing device, set the temperature of the fusing device to 110°C, and fixed the toner vertically on high-quality A4 paper at a speed of 1.2 seconds per sheet, and produced printed matter. Obtained.
By the same method, the temperature of the fixing device was increased by 5° C. to fix the toner, and a printed matter was obtained.
A piece of mending tape "Scotch (registered trademark) Mending Tape 810" (manufactured by Sumitomo 3M Co., Ltd., width 18 mm) cut into a length of 50 mm is lightly pasted from the top margin of the printed image to the solid image. After that, a cylindrical weight of 500 g (contact area: 157 mm ² ) was put on and pressed once at a speed of 10 mm/s. After that, the attached tape was peeled off from the lower end side at a peeling angle of 180° and a speed of 10 mm/s to obtain a print after tape peeling. Thirty sheets of high-quality A4 paper "Excellent white paper A4 size" (manufactured by Oki Data Co., Ltd.) were placed under the printed matter before and after the tape was applied, and the reflected image density of the fixed image portion of each printed matter before the tape was applied and after the tape was removed. was measured using a calorimeter "SpectroEye" (manufactured by GretagMacbeth Co., light irradiation conditions; standard light source D50, observation field of view 2°, density standard DINNB, absolute white standard), and fixed according to the following formula from each reflected image density: rate was calculated.
Fixing rate (%) = (reflected image density after tape removal/reflected image density before tape application) x 100
The lowest temperature at which the fixing rate was 90% or higher was defined as the lowest fixing temperature.
Next, using a printer "Microline (registered trademark) 5400" (manufactured by Oki Data Co., Ltd.) on high-quality A4 paper "J paper A4 size" (manufactured by Fuji Xerox Co., Ltd.), the toner adhesion amount on the paper was 0.25 mg. A solid image of 1/cm ² was output.
The temperature of the fixing device was set to the lowest fixing temperature obtained in the above fixing test + 10°C, and the toner was fixed on high-quality A4 paper at a speed of 1.2 seconds per sheet in the longitudinal direction to obtain a printed matter. .
Thirty sheets of high-quality A4 paper "Excellent white paper A4 size" (manufactured by Oki Data Co., Ltd.) were placed under the printed matter, and the reflected image density of the solid image portion of the output printed matter was measured using a colorimeter "SpectroEye" (manufactured by GretagMacbeth, Inc.). Measurement was performed using light irradiation conditions: standard light source D50, observation field of view 2°, density standard DINNB, absolute white standard), and the image density was obtained by averaging the values obtained by measuring arbitrary 10 points on the image. The higher the numerical value, the better the image density.

[Fixed Image Preservability]
A temperature 20°C higher than the minimum fixing temperature was set as the appropriate fixing temperature, and a copier "AR-505" (manufactured by Sharp Co., Ltd.) was used on high-quality A4 paper "J paper A4 size" (manufactured by Fuji Xerox Co., Ltd.). Then, two solid images (4 cm×4 cm) having a toner adhesion amount on paper of 0.90 mg/cm ² were printed, and the glossiness of the printed surface was measured. Immediately after printing, high-quality A4 papers were placed face to face so that the solid images were in contact with each other, and a vertical load of 100 g/cm ² was applied, and the stacks were allowed to stand in an environment of 55° C./41% relative humidity for one day. After that, the two images were separated, and the glossiness of the printed surface was measured. Glossiness was measured using a handy gloss meter "Gloss Meter PG-3D" (manufactured by Nippon Denshoku Industries Co., Ltd.) under the condition of a light incident angle of 75°. In addition, the ratio of the area in the evaluation is the number of squares containing the mark by marking the point where the glossiness is less than 80%, applying a transparent film on which a 1 cm × 1 cm square is printed, and , and the number of squares not containing marks, and the area where the glossiness is less than 80% immediately after printing was calculated.
(Evaluation criteria: fixed image storability)
A: No image defects (0% of the area where the glossiness is less than 80% immediately after printing)
B: A portion where the glossiness of the image is partially changed is observed (the area ratio where the glossiness is less than 80% immediately after printing is less than 5%)
C: Decreased image gloss (area ratio of 5% or more and less than 10% where the glossiness is less than 80% immediately after printing)
D: Many image defects (area ratio of 10% or more where the glossiness is less than 80% immediately after printing)

[Method for producing amorphous polyester resin]
Production Examples A1 to A2 (production of amorphous polyester resins A-1 and A-2)
A 20 L stainless steel kettle equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple was charged with raw material monomers (P) of the type and amount shown in Table 1, excluding trimellitic anhydride. Next, after reacting at 230° C. for 8 hours, reacting under reduced pressure of 1.3 kPa to 2.0 kPa for 4 hours. Furthermore, after adding trimellitic anhydride in an amount shown in Table 1, the mixture was reacted at 180° C. for 3 hours to obtain amorphous polyester resins A-1 and A-2. Various physical properties were measured and shown in Table 1.

[Production of polyester resin B]
Production Example B1 (polyester resin B-1)
A separable flask equipped with a stirrer and a thermometer was charged with 170 parts by mass of isophoronediamine and 75 parts by mass of methyl ethyl ketone, and reacted at 50° C. for 5 hours to obtain ketimine compound K-1. The amine value of ketimine compound K-1 was 418 mgKOH/g.

2,954 g of 3-methyl-1,5-pentanediol, 1,697 g of isophthalic acid, and 1,825 g of adipic acid were added to a 10 L stainless steel kettle equipped with a condenser, a stirrer, and a nitrogen inlet tube. 97 g of methylolpropane and 6.6 g of titanium tetraisopropoxide as an esterification catalyst were added together. Next, after raising the temperature to 200° C. in about 4 hours, the temperature was raised to 230° C. in 2 hours, and the reaction was carried out until no water flowed out. Further, reaction was carried out under a reduced pressure of 1.3 kPa to 2.0 kPa for 5 hours to obtain a polyester resin having hydroxyl groups.
Next, 410 parts by mass of a polyester resin having a hydroxyl group, 89 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate were added to a separable flask equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, followed by heating at 100°C for 5 hours. A polyester resin B-1i having an isocyanate group was obtained by reaction.

After stirring a 50% by mass ethyl acetate solution of the obtained polyester resin B-1i having an isocyanate group in a separable flask equipped with a nitrogen inlet tube, a stirrer, and a thermocouple, the equivalent of the amino group to the isocyanate group was determined. A ketimine compound was added dropwise so that the ratio [NCO]/[NH ₂ ] was 1.0. Next, after stirring at 45° C. for 10 hours, the mixture was dried under reduced pressure at 50° C. until the content of ethyl acetate became 100 ppm or less to obtain polyester resin B-1. The polyester resin B-1 had a glass transition temperature of -40°C.

[Production of crystalline polyester resin]
Production Example C1 (Production of crystalline polyester resin C-1)
A 20 L four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple was charged with the alcohol component and the carboxylic acid component shown in the table, heated to 140° C. and reacted for 6 hours. The reaction was carried out while raising the temperature to 200°C at a rate of 10°C/h. After reacting at 200° C. until the reaction rate reached 80%, tin (II) di(2-ethylhexanoate) was added as an esterification catalyst, and the reaction was further carried out at 200° C. for 2 hours. Furthermore, the reaction was carried out at 8 kPa for 2 hours to obtain a crystalline polyester resin C-1.

Production Examples C2 and C3 (production of crystalline polyester resins C-2 and C-3)
Crystalline polyester resins C-2 and C-3 were obtained in the same manner as in Production Example C1, except that the raw material monomers of the types and amounts shown in Table 2 were added.

[Production of resin particle dispersion]
Production Example D1 (Production of Dispersion D-1)
100 g of crystalline polyester resin C-1 and 400 g of ethyl acetate were placed in a 2-liter metal container, dissolved by heating at 75° C., and then rapidly cooled in an ice water bath at a rate of 27° C./min. 500 mL of glass beads (diameter 3 mm) were added to this and pulverized for 10 hours with a batch-type sand mill (manufactured by Campe Hapio Co., Ltd.) to obtain a dispersion D-1 of crystalline polyester resin particles having a solid content concentration of 20% by mass. .

Production Examples D2, D3 (Production of Dispersions D-2 to D-3)
Dispersions D-2 to D-3 were obtained in the same manner as in Production Example D1, except that the resins shown in Table 3 were used.

[Production of Release Agent Particle Dispersion]
Production Example W1 (Production of Release Agent Particle Dispersion W-1)
In a container equipped with a stirrer and a thermometer, 50 parts by mass of paraffin wax "HNP-9" (manufactured by Nippon Seiro Co., Ltd., melting point 75 ° C.) and 450 parts by mass of ethyl acetate were added, and then heated to 80 ° C. while stirring. and held for 5 hours. Next, after cooling to 30 ° C. in 1 hour, using a bead mill "Ultra Viscomill UVM-2 type" (manufactured by Imex Co., Ltd.), the liquid feeding speed is 1 kg / h, and the peripheral speed of the disk is 6 m / s. 80% by volume of zirconia beads with a diameter of 0.5 mm were filled and dispersed under the condition of three passes to obtain a release agent particle dispersion W-1 having a solid content concentration of 10% by mass.

[Production of addition polymer E having an aromatic group]
Production Examples E1 to E3 (Production of addition polymers E-1 to E-3)
Raw material monomers of the types and amounts shown in Table 4 were mixed to prepare a monomer mixed solution of 100 g of the total amount of monomers.
The inside of a four-necked flask equipped with a nitrogen inlet tube, a dropping funnel, a stirrer, and a thermocouple is replaced with nitrogen, and 18 g of methyl ethyl ketone, 0.03 g of 2-mercaptoethanol, and 10% by mass of the monomer mixture are added, The temperature was raised to 75° C. while stirring. While maintaining the temperature 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 a polymerization initiator “V-65” (2,2′-azobis(2,4- Dimethylvaleronitrile) and 3 g of FUJIFILM Wako Pure Chemical Industries, Ltd.) were added dropwise from the dropping funnel over 3 hours. After the temperature was maintained at 75° C. for 2 hours after completion of dropping, a solution of 3 g of polymerization initiator “V-65” dissolved in 5 g of methyl ethyl ketone was added, and the temperature was further maintained at 75° C. for 2 hours and at 80° C. for 2 hours. Thereafter, methyl ethyl ketone was distilled off under reduced pressure to obtain addition polymers E-1 to E-3. Table 4 shows the weight average molecular weight of the obtained addition polymer.

Production Example E4 (production of addition polymer E-4)
An addition polymer E-4 was obtained in the same manner as in Production Example E1, except that no 2-mercaptoethanol was added. The weight average molecular weight was measured by the method described above and shown in Table 4.

[Production of colorant particle dispersion]
Production Examples Z1 to Z5 (Production of Colorant Particle Dispersions Z-1 to Z-5)
75 g of the addition polymer shown in Table 5 and 630 g of methyl ethyl ketone were placed in a container having an internal volume of 5 L equipped with a stirrer equipped with a disper blade, a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet tube, and the resin was allowed to cool at 20°C. Dissolved. To the resulting solution, 101 g of a 5% by mass sodium hydroxide aqueous solution (the degree of neutralization of the addition polymer E-1 becomes 91 mol%) was added, 955 g of deionized water was further added, and the mixture was heated to 20° C. with a disper blade. and stirred for 10 minutes. Then, 300 g of the coloring agent shown in Table 5 was added and stirred at 20° C. for 2 hours with a disper blade at 6400 r/min. Then, it was passed through a 200-mesh filter and treated with a homogenizer "Microfluidizer M-110EH" (manufactured by Microfluidics) at a pressure of 150 MPa for 15 passes. Methyl ethyl ketone and a portion of water were removed from the resulting dispersion at 70° C. under reduced pressure while stirring. 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 colorant particle dispersions Z-1 to Z-5. Table 5 shows the volume-median particle size (D ₅₀ ) and CV value of the obtained colorant particle dispersion.

Production Example Z6 (Production of Colorant Particle Dispersion Z-6)
A colorant particle dispersion Z-6 was obtained in the same manner as in Production Example Z1, except that 30 g of the addition polymer E-1 and 675 g of methyl ethyl ketone were used. Table 5 shows the volume-median particle size (D ₅₀ ) and CV value of the obtained colorant particle dispersion.

Production Example Z7 (Production of Colorant Particle Dispersion Z-7)
A colorant particle dispersion liquid Z-7 was obtained in the same manner as in Production Example Z7, except that 141 g of the addition polymer E-1 and 564 g of methyl ethyl ketone were used. Table 5 shows the volume-median particle size (D ₅₀ ) and CV value of the obtained colorant particle dispersion.

Production Example Z8 (Production of Colorant Particle Dispersion Z-8)
75 g of addition polymer E-1 and 630 g of methyl ethyl ketone were placed in a container with an internal volume of 5 L equipped with a stirrer equipped with a disper blade, a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet tube, and the resin was dissolved at 20°C. let me To the resulting solution were added 101 g of a 5% by mass sodium hydroxide aqueous solution as a neutralizing agent (the degree of neutralization of the addition polymer E-1 was 91 mol%) and 955 g of deionized water. C. for 10 minutes. Then, 300 g of carbon black “Regal-330R” (manufactured by Cabot Corporation) was added, and the mixture was stirred at 20° C. for 2 hours at 6400 r/min with a disper blade.
Then, it is passed through a 200-mesh filter, using a bead mill "NVM-2" (manufactured by Imex Co., Ltd.), using glass beads with a diameter of 0.6 mm, a filling rate of 80% by volume, and a peripheral speed of 10 m / s. Five passes were applied at a liquid speed of 0.6 kg/min. Methyl ethyl ketone and a portion of water were removed from the resulting dispersion at 70° C. under reduced pressure while stirring. After cooling, the mixture was passed through a 200-mesh filter and deionized water was added so that the solid content concentration was 20% by mass, thereby obtaining a colorant particle dispersion liquid Z-8. Table 5 shows the volume-median particle size (D ₅₀ ) and CV value of the obtained colorant particle dispersion.

Production Example Z81 (Production of Colorant Particle Dispersion Z-81)
In a beaker with an internal volume of 1 L, 100 g of carbon black "Regal-330R" (manufactured by Cabot Corporation) and 15% by mass of sodium dodecylbenzenesulfonate aqueous solution "Neopelex G-15" (manufactured by Kao Corporation, anionic surfactant) 167 g. , and 102 g of deionized water are mixed, and using a homomixer "TK AGI HOMOMIXER 2M-03" (manufactured by Tokushu Kika Kogyo Co., Ltd.), at 20 ° C., 1 at a stirring blade rotation speed of 8000 r / min. After being dispersed over time, it was subjected to 15 passes at a pressure of 150 MPa using a homogenizer "Microfluidizer M-110EH" (manufactured by Microfluidics). Thereafter, the mixture was passed through a 200-mesh filter and deionized water was added so that the solid content concentration was 20% by mass, thereby obtaining a colorant particle dispersion liquid Z-81. Table 5 shows the volume-median particle size (D ₅₀ ) and CV value of the obtained colorant particle dispersion.

Production Example Z82 (Production of Colorant Particle Dispersion Z-82)
Dissolve 75 g of amorphous polyester resin A-2 in 630 g of methyl ethyl ketone in a container with an internal volume of 5 L equipped with a stirrer equipped with a disper blade, a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet tube, and then disperse. Stir with a wing at 20° C. for 10 minutes. Thereafter, a colorant particle dispersion liquid Z-82 was obtained in the same manner as in Production Example Z8. Table 5 shows the volume-median particle size (D ₅₀ ) and CV value of the obtained colorant particle dispersion.

[Toner manufacturing]
Example 1: Production of Toner 1 [Preparation of Oil Phase I]
Release agent particle dispersion W-1 300 parts by mass, polyester resin B-1 150 parts by mass, crystalline polyester resin dispersion 500 parts by mass shown in Table 6, amorphous polyester resin A-1 750 parts by mass, and 2 parts by mass of ketimine compound K-1 were placed in a container, and then mixed at 5,000 rpm for 60 minutes using "TK Homomixer" (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain an oil phase I.

[Preparation of aqueous phase II]
A flask equipped with a stirrer and a thermometer was charged with 683 parts by mass of water, 11 parts by mass of sodium salt of ethylene oxide adduct sulfate of methacrylate "Eleminol RS-30" (manufactured by Sanyo Chemical Industries, Ltd.), 138 parts by mass of styrene, 138 parts by mass of methacrylic acid and 1 part by mass of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes to obtain a white emulsion. The system temperature was raised to 75° C. by heating, and the reaction was carried out for 5 hours. Further, 30 parts by mass of a 1% by mass ammonium persulfate aqueous solution is added and aged at 75° C. for 5 hours to form an aqueous dispersion of a polymeric dispersant (styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sodium salt copolymer of sulfate ester). A liquid (polymeric dispersant dispersion liquid (1)) was obtained. The volume-median particle size (D ₅₀ ) of the polymer dispersant dispersion (1) measured with “LA-920” (Horiba, Ltd.) was 0.14 μm.

990 parts by mass of water, 83 parts by mass of the above polymer dispersant dispersion (1), 48.5% by mass aqueous solution of sodium dodecyl diphenyl ether disulfonate "Eleminol MON-7" (manufactured by Sanyo Chemical Industries, Ltd.) 37 parts by mass, 90 parts by mass of ethyl acetate was mixed and stirred to obtain a milky white liquid. This was designated as aqueous phase II.

[Adjustment of dispersion slurry III]
After adding 333 parts by mass of the colorant particle dispersion Z-1 and 200 parts by mass of the aqueous phase II to a container containing 1702 parts by mass of the oil phase I, using "TK Homomixer" (manufactured by Primix Co., Ltd.), Mixed at 13,000 rpm for 20 minutes to obtain an emulsified slurry. The emulsified slurry was placed in a container equipped with a stirrer and a thermometer, and after the solvent was removed at 30°C for 8 hours, it was aged at 45°C for 4 hours to obtain a dispersed slurry.

100 parts by mass of the dispersed slurry was filtered under reduced pressure. The following operations (1) to (4) were repeated twice on the obtained filter cake.
(1) 100 parts by mass of ion-exchanged water was added to the filter cake, and the mixture was mixed at 12,000 rpm for 10 minutes using "TK Homomixer" (manufactured by Primix Co., Ltd.), and then filtered.
(2) Add 100 parts by mass of a 10% by mass sodium hydroxide aqueous solution to the filter cake of (1), mix for 30 minutes at 12,000 rpm using "TK Homomixer" (manufactured by Primix Co., Ltd.), and then filter under reduced pressure. bottom.
(3) 100 parts by mass of 10% by mass hydrochloric acid was added to the filter cake of (2), mixed at 12,000 rpm for 10 minutes using "TK Homomixer" (manufactured by Primix Co., Ltd.), and then filtered.
(4) 300 parts by mass of ion-exchanged water was added to the filter cake of (3), mixed at 12,000 rpm for 10 minutes using "TK Homomixer" (manufactured by Primix Co., Ltd.), and then filtered.
The resulting filter cake was dried at 45° C. for 48 hours using a circulating air dryer, and then sieved through a mesh having an opening of 75 μm to obtain toner particles. Various physical properties of the obtained toner particles were measured, and the results are shown in Table 6.

100 parts by mass of toner particles and 1.0 part by mass of hydrophobic silica "HDK-2000" (manufactured by Wacker-Chemie) are mixed with a Henschel mixer (manufactured by Nippon Coke Kogyo Co., Ltd.) at a peripheral speed of 30 m / s. After mixing for 5 seconds and resting for 1 minute, the mixture was sieved with a mesh having an opening of 35 μm, and Toner 1 was obtained. Various evaluations were performed on the obtained toner, and the results are shown in Table 6.

Examples 2-11, Comparative Examples 1-2 (manufacture of toners 2-11, 81-82)
Toners 2 to 11 and 81 to 82 were obtained in the same manner as in Example 1 except that the colorant particle dispersion and oil phase I shown in Table 6 were used. Various physical properties of the obtained toner particles were measured, and various evaluations were performed on the obtained toner. Table 6 shows the results.

As shown in Examples and Comparative Examples, the toners of Examples provide high image densities and are excellent in preservability of fixed images.

Claims (6)

A raw material composition containing an amorphous polyester resin A, a release agent, and an organic solvent, and a dispersion of colorant particles Z are mixed in an aqueous medium to form granules,
The colorant particles Z contain a colorant and an addition polymer E having an aromatic group,
mass ratio of the colorant to the addition polymer E is 50/50 or more and 95/5 or less;
A method for producing a toner, wherein the raw material monomer of the addition polymer E contains methoxypolyethylene glycol (meth)acrylate . 2. The method for producing a toner according to claim 1, wherein the amorphous polyester resin A is a polycondensate of an alcohol component containing an alkylene oxide adduct of bisphenol A and a carboxylic acid component. 3. The method for producing a toner according to claim 1, wherein the releasing agent is hydrocarbon wax. 4. The method for producing a toner according to claim 1, wherein the colorant particles are obtained by mixing the colorant and the addition polymer E by a bead mill or a homogenizer. 5. The method for producing a toner according to claim 1, wherein the addition polymer E contains an addition polymer of raw material monomers containing a styrene compound. The method for producing a toner according to any one of claims 1 to 5, wherein the colorant is carbon black.