JP2016197207A - Toner for electrostatic charge image development - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge image development that satisfies low-temperature fixability, and has an excellent heat-resistant storage property, hot offset resistance, and smear resistance of a printed matter, and a manufacturing method of the same.SOLUTION: There is provided a toner for electrostatic charge image development including core-shell particles as a binder resin, wherein the core part contains a wax and a polyester (L) obtained through condensation polymerization of a carboxylic acid component (L-ac) and an alcohol component (L-al), and the shell part contains a polyester (H) obtained through condensation polymerization of the carboxylic acid component (H-ac) and an alcohol component (H-al); the carboxylic acid component (H-ac) contains one or more selected from a specific alkenylsuccinic acid and alkylsuccinic acid; the total content of one or more selected from the alkenylsuccinic acid and the alkylsuccinic acid in the carboxylic acid component (H-ac) is 3 mol% or more; the total content of one or more selected from the alkenylsuccinic acid and the alkylsuccinic acid in the carboxylic acid component (L-ac) is less than 3 mol%.SELECTED DRAWING: None

Description

  The present invention relates to an electrostatic image developing toner and a method for producing the same.

In the field of electrophotography, with the development of an electrophotographic system, development of toner for electrophotography corresponding to higher image quality and higher speed is required.
Toners are required to have conflicting performances such as heat-resistant storage and low-temperature fixability. In order to achieve both of these contradictory performances, it has been proposed that the toner has a core-shell structure having a core part and a shell part covering the core part.

  For example, Patent Document 1 discloses that an amorphous resin (A) having a softening point of 105 ° C. or less obtained by polycondensation of a carboxylic acid component containing an alkenyl succinic acid derived from an oligomer of propylene and an alcohol component. A carboxylic acid component in which the shell part contains an aliphatic diol having 2 to 6 carbon atoms and the content of the trivalent or higher polyvalent carboxylic acid compound is 20 mol% or less in the carboxylic acid component Is an amorphous resin (B) obtained by polycondensation of a toner and an electrophotographic toner containing core-shell particles as a binder resin, whereby an electrophotographic toner excellent in heat-resistant storage, low-temperature fixability, and durability can be obtained. It is described that it is obtained.

JP 2013-235244 A

As electrophotographic printing speeds up, it is necessary to fix with less energy during printing. For this reason, toners are required to have low-temperature fixability. In order to improve the low-temperature fixability, a wax having a property that the viscosity greatly decreases near the melting point is used.
However, since the wax is poorly compatible with the resin, the wax bleeds out to the toner surface during the production and storage of the toner, so that the storage stability of the toner in a high temperature environment, so-called heat resistant storage stability is deteriorated. There was a case.
Furthermore, because the bleed-out wax adheres to the fixing roller or the like even at the time of fixing, so-called smear property of the printed matter that the image is peeled off and smeared when the image printed with the toner is rubbed. There is a problem that gets worse. Furthermore, hot offset resistance is also required from the viewpoint of reducing the adaptive load of the toner machine by expanding the high-temperature fixing region of the toner.
An object of the present invention is to provide an electrostatic charge image developing toner excellent in heat-resistant storage stability, hot offset resistance, and print smearing properties while satisfying low-temperature fixability, and a method for producing the same.

The present inventors considered and considered that the factors that affect the low-temperature fixability, heat-resistant storage stability, hot-offset resistance, and smearability of printed matter of the toner are the state of the resin and wax in the toner.
As a result, by using a polyester obtained by polymerizing a raw material monomer containing one or more selected from a specific branched alkenyl succinic acid and a branched alkyl succinic acid in the shell part, containing a wax in the core part of the core-shell particle. The inventors have found that a toner for developing an electrostatic image having excellent low-temperature fixability, heat-resistant storage stability, hot offset resistance, and smearability of printed matter can be obtained.

That is, the present invention provides the following [1] and [2].
[1] A toner for developing an electrostatic charge image containing core-shell particles as a binder resin, wherein the core is obtained by polycondensation of a carboxylic acid component (L-ac) and an alcohol component (L-al). (L) and a wax, and the shell portion contains a polyester (H) obtained by polycondensation of a carboxylic acid component (H-ac) and an alcohol component (H-al), and a carboxylic acid component (H-ac) is an alkenyl succinic acid represented by the following general formula (1) (hereinafter also referred to as “branched alkenyl succinic acid”) and an alkyl succinic acid represented by the following general formula (2) (hereinafter “ The total content of one or more selected from the alkenyl succinic acid and the alkyl succinic acid in the carboxylic acid component (H-ac) is 3 mol. Above, and the said one or more of the total content selected from alkenyl succinic acids and the alkyl succinic acid is less than 3 mol%, the toner for developing electrostatic latent images in the carboxylic acid component (L-ac).

（式中、Ｒ^１は炭素数２以上の直鎖アルケニル基、Ｒ^２は炭素数２以上の直鎖アルキル基を示し、Ｒ^３及びＲ^４はそれぞれ独立して炭素数２以上の直鎖アルキル基を示す。Ｒ^１Ｒ^２ＣＨ−で表される分岐アルケニル基及びＲ^３Ｒ^４ＣＨ−で表される分岐アルキル基の総炭素数はそれぞれ独立して９以上２４以下である。Ｘ及びＹは、それぞれ独立に水酸基若しくは炭素数１以上３以下のアルコキシ基を示すか、又は酸素原子を介して互いに結合して酸無水物を形成する基を示す。）
［２］下記工程１〜３を有する、上記［１］に記載の静電荷像現像用トナーの製造方法。
工程１：ポリエステル（Ｌ）を含有する樹脂粒子（Ｘ）と、ワックスを含有する離型剤粒子とを、水系媒体中で凝集させて、凝集粒子（１）を得る工程
工程２：工程１で得られた凝集粒子（１）に、ポリエステル（Ｈ）を含有する樹脂粒子（Ｙ）を凝集させて、凝集粒子（２）を得る工程
工程３：工程２で得られた凝集粒子（２）を融着させて、コアシェル粒子を得る工程

(In the formula, R ¹ represents a linear alkenyl group having 2 or more carbon atoms, R ² represents a linear alkyl group having 2 or more carbon atoms, and R ³ and R ⁴ are each independently a linear alkyl group having 2 or more carbon atoms. The total carbon number of the branched alkenyl group represented by R ¹ R ² CH— and the branched alkyl group represented by R ³ R ⁴ CH— is each independently 9 to 24. X and Y Are each independently a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, or a group that is bonded to each other via an oxygen atom to form an acid anhydride.
[2] The method for producing a toner for developing an electrostatic image according to the above [1], comprising the following steps 1 to 3.
Step 1: Step of aggregating resin particles (X) containing polyester (L) and release agent particles containing wax in an aqueous medium to obtain aggregated particles (1) Step 2: In Step 1 Step of aggregating resin particles (Y) containing polyester (H) to the obtained aggregate particles (1) to obtain aggregate particles (2) Step 3: Aggregate particles (2) obtained in Step 2 Process of fusing to obtain core-shell particles

  According to the present invention, it is possible to provide a toner for developing an electrostatic charge image that is excellent in heat-resistant storage stability, hot offset resistance, and smearability of a printed matter while satisfying low-temperature fixability, and a method for producing the same.

[Toner for electrostatic image development]
The electrostatic image developing toner of the present invention (hereinafter also simply referred to as “toner”) is an electrostatic image developing toner containing core-shell particles as a binder resin, and the core portion has a carboxylic acid component (L-ac ) And the alcohol component (L-al) are obtained by polycondensation of the polyester (L) and a wax, and the shell portion is composed of a carboxylic acid component (H-ac), an alcohol component (H-al), and A polyester (H) obtained by polycondensation of alkenyl succinic acid represented by the general formula (1) and an alkyl represented by the general formula (2). 1 or more types chosen from succinic acid are contained, and 1 or more types of total content chosen from the said alkenyl succinic acid and the said alkyl succinic acid in carboxylic acid component (H-ac) are 3 mol% or more, Acid component Wherein the L-ac) the total content of one or more members selected from the alkenylsuccinic acid and the alkyl succinic acid in is less than 3 mol%.

The reason why the toner of the present invention is excellent in low-temperature fixability, heat-resistant storage stability (hereinafter also simply referred to as “storage stability”), hot-offset resistance, and print smearing properties is not clear, but is considered as follows. .
The toner of the present invention contains a polyester (H) having a portion derived from one or more selected from a specific branched alkenyl succinic acid and a branched alkyl succinic acid in the shell portion, and contains a wax in the core portion. Contains core-shell particles.
The branched alkenyl group in the branched alkenyl succinic acid used in the present invention and the branched alkyl group in the branched alkyl succinic acid have one branched portion. That is, in the branched alkenyl succinic acid, a straight alkenyl group having 2 or more carbon atoms and a straight alkyl group having 2 or more carbon atoms form a bifurcated form, and the branched alkyl succinic acid has 2 or more carbon atoms. These two linear alkyl groups form a bifurcated form.
As described above, the structure having two straight-chain alkenyl groups having 2 or more carbon atoms or straight-chain alkyl groups having 2 or more carbon atoms per molecule has high affinity with the wax, so that the surface of the wax toner particles can be used. As a result, it is considered that the heat resistance storage stability of the toner particles is excellent.
In addition, by suppressing the exposure of the wax to the toner particle surface, it becomes easier for the wax to be retained on the printed material than when it is transferred to the fixing roller during printing, and the printed material is also smeared (a scratch resistance test). It is considered excellent.
Furthermore, the toner of the present invention is also excellent in hot offset resistance. This is because the core-shell particles contained in the toner of the present invention are derived from one or more selected from hydrophobic branched alkenyl succinic acid and branched alkyl succinic acid having a core part containing a wax and high affinity with the wax. This is because the wax part exists in the shell part, so that the wax exists near the core-shell interface rather than in the core part, and the wax is more easily eluted from the toner surface at the time of fixing, and the printed matter is easily released from the fixing roller. It is done.

<Shell part>
The shell part of the core-shell particle used in the present invention contains polyester (H) obtained by polycondensation of a carboxylic acid component (H-ac) and an alcohol component (H-al).

(Polyester (H))
The polyester (H) is obtained by polycondensation of a carboxylic acid component (H-ac) and an alcohol component (H-al).

[Carboxylic acid component (H-ac)]
The carboxylic acid component (H-ac) contains one or more selected from alkenyl succinic acid represented by the following general formula (1) and alkyl succinic acid represented by the following general formula (2). Among these, alkenyl succinic acid represented by the following general formula (1) is preferable from the viewpoint of improving the low-temperature fixability of the toner. These branched alkenyl succinic acids and branched alkyl succinic acids can be used alone or in combination of two or more.

In the formula, R ¹ represents a linear alkenyl group having 2 or more carbon atoms, R ² represents a linear alkyl group having 2 or more carbon atoms, and R ³ and R ⁴ are each independently a linear alkyl group having 2 or more carbon atoms. Indicates. The carbon number of the linear alkenyl group in R ^{1 and} the linear alkyl group in R ^{2 to} R ⁴ is from the viewpoint of improving the low-temperature fixability, heat-resistant storage stability, hot offset resistance of the toner, and smearing of the printed matter, respectively. Independently, it is 2 or more, preferably 3 or more, more preferably 4 or more, and preferably 21 or less, more preferably 19 or less, and still more preferably 15 or less.
The total carbon number of the branched alkenyl group represented by R ¹ R ² CH— and the branched alkyl group represented by R ³ R ⁴ CH— is independently 9 or more and 24 or less. From the viewpoint of improving the low-temperature fixability, heat-resistant storage stability, hot offset resistance of the toner, and smearability of the printed matter, the total carbon number of the branched alkyl group or branched alkenyl group is 9 or more, preferably 12 or more. Preferably, it is 16 or more, more preferably 18 or more, and from the same viewpoint, it is 24 or less, preferably 22 or less, more preferably 20 or less, still more preferably 18.
X and Y each independently represent a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, or a group that is bonded to each other via an oxygen atom to form an acid anhydride.

From the viewpoint of improving steric hindrance and improving low-temperature fixability of toner, heat-resistant storage stability, hot-offset resistance, and print smear, branched alkenyl succinic acid contains internal olefin, maleic acid, maleic anhydride and fumaric acid. It is preferably obtained by bonding one or more selected from acids by an ene reaction, and from the viewpoint of ease of production, it is obtained by bonding an internal olefin and maleic anhydride by an ene reaction. Preferably there is. As the internal olefin, those having 9 to 24 carbon atoms are preferable. In addition, in this invention, an internal olefin is an olefin which has a double bond substantially in the inside of an olefin chain, and contains the trace amount of what is called alpha-olefin in which the position of a double bond exists in the 1st position of a carbon chain. It also has a broad meaning including the case where
The branched alkyl succinic acid is preferably obtained by hydrogenating a branched alkenyl succinic acid.

The internal olefin is preferably obtained by a dehydration reaction of a primary aliphatic alcohol having 9 to 24 carbon atoms in the presence of a solid catalyst.
The primary aliphatic alcohol may be an alcohol derived from petroleum or an alcohol derived from natural raw materials.
Examples of the primary aliphatic alcohol derived from petroleum include 1-nonanol, 1-decanol, 1-dodecanol, 1-tetradecanol, 1-hexadecanol, 1-octadecanol, 1-eicosanol, 1- Examples include docosanol and 1-tetracosanol.
Examples of the primary aliphatic alcohols derived from natural raw materials include those made from raw materials such as coconut oil, palm oil, palm kernel oil, soybean oil, rapeseed oil, beef tallow, lard, tall oil, fish oil and the like.
As the solid catalyst, a solid acid catalyst is preferable from the viewpoint of increasing the reaction rate of the dehydration reaction.
From the same viewpoint, the solid acid catalyst preferably contains one or more elements selected from aluminum, iron, and gallium, and more preferably contains aluminum. As a specific solid acid catalyst, γ-alumina and aluminum phosphate are preferable.
There is no restriction | limiting in particular as a method of dehydration reaction, A well-known method can be used.
The internal olefin is obtained as a mixture having a distribution at the double bond sites by the dehydration reaction described above.
The content of the olefin having a double bond at the 2-position in the internal olefin is preferably 40% by mass from the viewpoint of improving low-temperature fixability, heat-resistant storage stability, hot offset resistance, and smearability of the printed matter. Hereinafter, it is more preferably 35% by mass or less, further preferably 30% by mass or less, and still more preferably 20% by mass or less. The lower limit of the content is preferably as small as possible, but is preferably 0% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more from the viewpoint of ease of production.

A well-known method can be used for manufacture of the branched alkenyl succinic acid by ene reaction. For example, selection of the type of raw material or catalyst used for the synthesis of olefin, a method of adjusting reaction rate, reaction time, reaction pressure, solvent, etc., a method of adjusting distillation conditions during alkenyl succinic acid production, etc. are all used. (See JP-A-48-23405, JP-A-48-23404, US Pat. No. 3,374,285, etc.).
Ratio between the number of moles of internal olefin charged and one or more moles selected from maleic acid, maleic anhydride and fumaric acid (internal olefin / one or more selected from maleic acid, maleic anhydride and fumaric acid) Is preferably 0.8 or more, more preferably 0.9 or more, still more preferably 0.95 or more, and is preferably 3 or less, more preferably 2 or less, still more preferably 1.5 or less.

As described above, an alkenyl succinic acid mixture containing an alkenyl succinic acid represented by the general formula (1) is obtained by utilizing an ene reaction using an internal olefin having a distribution at double bond sites. The content of the alkenyl succinic acid represented by the general formula (1) is preferably 98% by mass or more, more preferably 98.5% by mass or more, and further preferably 99% by mass or more in the alkenyl succinic acid mixture. And preferably it is 100 mass% or less, More preferably, it is substantially 100 mass%, More preferably, it is 100 mass%.
The alkyl succinic acid represented by the general formula (2) can be obtained by hydrogenating the alkenyl succinic acid represented by the general formula (1), more preferably hydrogenating the alkenyl succinic acid mixture. Contained in the resulting alkyl succinic acid mixture. There is no restriction | limiting in particular as a method of hydrogenation, A well-known method can be used.
In the alkyl succinic acid mixture, the content of the alkyl succinic acid represented by the general formula (2) is preferably 98% by mass or more, more preferably 98.5% by mass or more, and further preferably 99% by mass or more. And preferably it is 100 mass% or less, More preferably, it is substantially 100 mass%, More preferably, it is 100 mass%.

The alkenyl succinic acid in which the carbon number of the linear alkenyl group of R ^{1 and} the linear alkyl group of R ^{2 in} the general formula (1) is 4 or more and the linear chain of R ³ and R ⁴ in the general formula (2) The total content of alkyl succinic acid having an alkyl group with 4 or more carbon atoms in the carboxylic acid component (H-ac) depends on the low-temperature fixability, heat-resistant storage stability, hot offset resistance of the toner, and smear of the printed matter. From the viewpoint of improving the properties, the total amount of the alkenyl succinic acid represented by the general formula (1) and the alkyl succinic acid represented by the general formula (2) is preferably 10% by mass or more, more preferably 35%. % By mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 80% by mass. It is below mass%.
The total carbon number of the branched alkenyl group represented by R ¹ R ² CH— in the general formula (1) is 14 or more and 24 or less, and the carbon number of the linear alkenyl group of R ¹ or the linear alkyl group of R ² The total carbon number of the alkenyl succinic acid having 6 or more carbon atoms and the branched alkyl group represented by R ³ R ⁴ CH— in the general formula (2) is 14 or more and 24 or less, and R ³ or R ⁴ The total content of alkyl succinic acid having 6 or more carbon atoms in the chain alkyl group is represented by the general formula (1) from the viewpoint of improving low-temperature fixability, heat-resistant storage stability, hot-offset resistance, and smearability of printed matter. ) Is preferably 1% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more, based on the total amount of alkenyl succinic acid represented by formula (2) and alkyl succinic acid represented by formula (2). And more Preferably 30 wt% or more, and preferably 70 mass% or less, more preferably 60 wt% or less, even more preferably not more than 50 wt%.
The alkenyl succinic acid in which the carbon number of the linear alkenyl group of R ¹ in the general formula (1) or the alkyl group of R ² is 2 or less, and the linear alkyl group of R ³ or R ⁴ in the general formula (2) The total content of alkyl succinic acid having 2 or less carbon atoms is preferably as small as possible from the viewpoint of improving low-temperature fixability, heat-resistant storage stability, hot offset resistance, and smearability of printed matter of toner. Preferably it is 60 mass% or less with respect to the total amount of the alkenyl succinic acid represented by Formula (1) and the alkyl succinic acid represented by General formula (2), More preferably, it is 50 mass% or less, More preferably, it is 45. % By mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, still more preferably substantially 0% by mass, and still more preferably 0% by mass. .

  The total content of one or more selected from branched alkenyl succinic acid and branched alkyl succinic acid in the carboxylic acid component (H-ac) is low temperature fixability, heat resistant storage stability, hot offset resistance of the toner, From the viewpoint of improving smearing properties, it is 3 mol% or more, and from the viewpoint of low-temperature fixability of toner, heat-resistant storage stability, and smearability of printed matter, it is preferably 5 mol% or more, more preferably 7 mol% or more. From the viewpoint of improving the low-temperature fixability, heat-resistant storage stability, hot offset resistance, and smearing properties of the printed matter of the toner, it is preferably 20 mol% or less, more preferably 18 mol from the viewpoint of heat-resistant storage stability of the toner. % Or less, more preferably 15 mol% or less, still more preferably 13 mol% or less.

  Examples of the carboxylic acid component (H-ac) used in addition to the branched alkenyl succinic acid and the branched alkyl succinic acid include dicarboxylic acids other than the branched alkenyl succinic acid and the branched alkyl succinic acid, and trivalent or higher polyvalent carboxylic acids. Among these, dicarboxylic acids are preferable, and it is more preferable to use dicarboxylic acids and trivalent or higher polyvalent carboxylic acids in combination. These carboxylic acid components (H-ac) can be used alone or in combination of two or more.

As the dicarboxylic acid, aliphatic dicarboxylic acids and aromatic dicarboxylic acids are preferable, and aromatic dicarboxylic acids are more preferable.
The carboxylic acid component (H-ac) includes not only dicarboxylic acids and trivalent or higher polyvalent carboxylic acids, but also anhydrides thereof and alkyl esters having 1 to 3 carbon atoms.
As the aliphatic dicarboxylic acid, an aliphatic dicarboxylic acid having 2 to 18 carbon atoms is preferable from the viewpoint of improving low-temperature fixability and heat-resistant storage stability of the toner. From the same viewpoint, the aliphatic dicarboxylic acid preferably has 2 or more carbon atoms, more preferably 3 or more carbon atoms, and preferably 18 or less, more preferably 6 or less.
Aliphatic dicarboxylic acids having 2 to 18 carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, azelaic acid Etc. Among these, fumaric acid and succinic acid are preferable, and succinic acid is more preferable from the viewpoint of improving low-temperature fixability and heat-resistant storage stability of the toner.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, and the like. From the viewpoint of improving the heat resistant storage stability of the toner, isophthalic acid and terephthalic acid are preferable, and terephthalic acid is more preferable.
In the carboxylic acid component (H-ac), the content of the aromatic dicarboxylic acid is preferably 50 mol% or more, more preferably from the viewpoint of improving the low-temperature fixability of the toner, heat-resistant storage stability, and smearability of the printed matter. It is 60 mol% or more, more preferably 70 mol% or more, still more preferably 75 mol% or more, and from the same viewpoint, it is preferably 90 mol% or less, more preferably 85 mol% or less.
Examples of the trivalent or higher aromatic carboxylic acid include trimellitic acid, 2,5,7-naphthalene tricarboxylic acid, pyromellitic acid and the like. Among these, from the viewpoint of improving the heat resistant storage stability of the toner, trimellitic acid and its acid anhydride are preferable, and trimellitic anhydride is more preferable.

[Alcohol component (H-al)]
Examples of the alcohol component (H-al) include aliphatic diols, aromatic diols, and trivalent or higher polyhydric alcohols. These alcohol components (H-al) can be used alone or in combination of two or more.

The aliphatic diol is preferably an aliphatic diol having 2 to 12 carbon atoms, specifically, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1, 3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,6 -Hexanediol, neopentyl glycol, 2,3-pentanediol, 2,4-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol and the like can be mentioned.
Among these, aliphatic diols having 2 to 6 carbon atoms are preferable from the viewpoint of improving the low-temperature fixability of the toner, and ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-pentane are preferable. One or more selected from diol, 1,5-pentanediol, and 1,6-hexanediol are more preferable, and 1,2-propanediol is more preferable.
In the alcohol component (H-al), the content of the aliphatic diol, preferably the aliphatic diol having 2 to 6 carbon atoms is from the viewpoint of improving the low-temperature fixability of the toner, the heat-resistant storage stability, and the smearing property of the printed matter. , Preferably 60 mol% or more, more preferably 70 mol% or more, further preferably 80 mol% or more, still more preferably 90 mol% or more, and preferably 100 mol% or less, more preferably substantially 100 mol%, more preferably 100 mol%.

  Specific examples of the aromatic diol include an alkylene oxide adduct of bisphenol A represented by the following formula (I).

(In the formula, R represents an alkylene group having 2 or 3 carbon atoms. X and y represent the average number of added moles, and the sum of x and y is 1 or more and 16 or less, preferably 1.5 or more and 5 or less. is there.)

  Examples of the alkylene oxide adduct of bisphenol A represented by the formula (I) include 2,2-bis (4-hydroxyphenyl) propane polyoxypropylene adduct and 2,2-bis (4-hydroxyphenyl) propane. And polyoxyethylene adducts.

Examples of the trivalent or higher alcohol include glycerin, pentaerythritol, trimethylolpropane, and the like, and glycerin is preferable from the viewpoint of reactivity and molecular weight adjustment.
From the viewpoints of molecular weight adjustment and physical property adjustment, the alcohol component (H-al) may optionally contain a monovalent alcohol, and the carboxylic acid component (H-ac) contains a monovalent carboxylic acid compound. May be appropriately contained.

<Molar ratio of alcohol component (H-al) and carboxylic acid component (H-ac)>
The molar ratio of the alcohol component (H-al) to the carboxylic acid component (H-ac) in the polycondensation reaction (carboxylic acid component (H-ac) / alcohol component (H-al)) is the reactivity, molecular weight adjustment and From the viewpoint of adjusting physical properties, it is preferably 0.5 or more, more preferably 0.7 or more, still more preferably 0.85 or more, and preferably 1.5 or less, more preferably 1.3 or less, still more preferably. Is 1.15 or less.

[Physical properties of polyester (H)]
The glass transition temperature of the polyester (H) is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, from the viewpoint of improving the low-temperature fixability of the toner, heat-resistant storage stability, hot offset resistance, and smearability of the printed matter. Preferably it is 55 degreeC or more, Preferably it is 90 degrees C or less, More preferably, it is 80 degrees C or less, More preferably, it is 70 degrees C or less.
The softening point of the polyester (H) is preferably more than 105 ° C., more preferably 110 ° C. or more, still more preferably 115 ° C. or more from the viewpoint of low-temperature fixability of the toner. Is 170 ° C. or lower, more preferably 160 ° C. or lower, still more preferably 150 ° C. or lower, and still more preferably 140 ° C. or lower.
In addition, when using 2 or more types of polyester (H) mixed, the glass transition temperature and the softening point were obtained by the method as described in an Example as a mixture of 2 or more types of polyester (H), respectively. Value.
The acid value of the polyester (H) is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, from the viewpoint of improving low-temperature fixability, heat storage stability, hot offset resistance of the toner, and smearing properties of the printed matter More preferably, it is 15 mgKOH / g or more, and from the same viewpoint, it is preferably 35 mgKOH / g or less, more preferably 30 mgKOH / g or less, still more preferably 25 mgKOH / g or less.

The number average molecular weight of the polyester (H) is preferably 1,000 or more, more preferably 1,500 or more, still more preferably 2,000 or more, and preferably 6,000 or more from the viewpoint of heat-resistant storage stability of the toner. 000 or less, more preferably 5,000 or less, and still more preferably 4,000 or less.
Further, the weight average molecular weight of the polyester (H) is preferably 6,000 or more, more preferably 8,000 or more, still more preferably 10,000 or more, and preferably from the viewpoint of heat-resistant storage stability of the toner. 1,000,000 or less, more preferably 700,000 or less, still more preferably 500,000 or less, and still more preferably 100,000 or less.
The number average molecular weight and the weight average molecular weight are both values obtained by measuring the tetrahydrofuran-soluble content.

  The glass transition temperature, softening point, acid value, number average molecular weight, and weight average molecular weight of polyester (H) can be easily adjusted by adjusting the composition of raw material monomers, molecular weight, catalyst amount, etc., or by selecting reaction conditions. Can do. The glass transition temperature, softening point, acid value, number average molecular weight, and weight average molecular weight are determined by the methods described in the examples.

(Method for producing polyester (H))
The polyester (H) is obtained by a polycondensation reaction between an alcohol component (H-al) and a carboxylic acid component (H-ac). The polycondensation reaction is preferably performed in the presence of an esterification catalyst, and more preferably performed in the presence of an esterification catalyst and a pyrogallol compound from the viewpoints of reactivity, molecular weight adjustment, and physical property adjustment of the polyester (H). .

<Esterification catalyst>
Examples of the esterification catalyst suitably used for the polycondensation include a titanium compound and a tin (II) compound having no Sn—C bond. These esterification catalysts can be used alone or in combination of two or more.
As the titanium compound, a titanium compound having a Ti—O bond is preferable, and a compound having an alkoxy group, an alkenyloxy group or an acyloxy group having 1 to 28 carbon atoms in total is more preferable.
Examples of the tin (II) compound having no Sn—C bond include a tin (II) compound having a Sn—O bond, a tin (II) compound having a Sn—X (X represents a halogen atom) bond, and the like. Preferred is a tin (II) compound having a Sn-O bond, and among them, di (2-ethylhexanoic acid) tin (II) or dioctylic acid from the viewpoints of reactivity, molecular weight adjustment and polyester physical property adjustment. Tin (II) salts are still more preferred, and tin (II) dioctylate salts are even more preferred.
The amount of the esterification catalyst used is 100 parts by mass with respect to the total amount of the alcohol component (H-al) and the carboxylic acid component (H-ac) from the viewpoints of reactivity, molecular weight adjustment and physical property adjustment of the polyester (H). The amount is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.6 parts by mass or less.

<Pyrogallol compound>
The pyrogallol compound has a benzene ring in which three adjacent hydrogen atoms are substituted with a hydroxyl group. Examples of pyrogallol compounds include pyrogallol, gallic acid, gallic acid esters, 2,3,4-trihydroxybenzophenone, benzophenone derivatives such as 2,2 ′, 3,4-tetrahydroxybenzophenone, epigallocatechin, epigallocatechin gallate, etc. From the viewpoint of reactivity, gallic acid is preferable.
From the viewpoint of reactivity, the amount of the pyrogallol compound used in the polycondensation reaction is 100 parts by mass with respect to a total amount of alcohol component (H-al) and carboxylic acid component (H-ac) subjected to the polycondensation reaction. Preferably it is 0.001 part by mass or more, more preferably 0.005 part by mass or more, further preferably 0.01 part by mass or more, and preferably 1 part by mass or less, more preferably 0.4 part by mass or less, More preferably, it is 0.2 parts by mass or less.
From the viewpoint of reactivity, the mass ratio of the pyrogallol compound to the esterification catalyst (pyrogallol compound / esterification catalyst) is preferably 0.01 or more, more preferably 0.03 or more, and still more preferably 0.05 or more. And preferably 0.5 or less, more preferably 0.3 or less, still more preferably 0.15 or less.

The polycondensation reaction between the alcohol component (H-al) and the carboxylic acid component (H-ac) can be carried out, for example, by heating in an inert gas atmosphere in the presence of the esterification catalyst and pyrogallol compound. it can.
The temperature of the polycondensation reaction is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and preferably 250 ° C. or lower, more preferably 240 ° C. or lower, still more preferably 235 ° C. or lower. It is.
For example, in order to increase the strength of the resin, it is preferable to add all the monomers to the reaction system at once, and in order to reduce the low molecular weight component, after reacting the divalent monomer first, the trivalent or higher monomer. It is preferable to add and react. Moreover, it is preferable to accelerate the reaction by reducing the pressure of the reaction system in the latter half of the polymerization.

  The polyester (H) may be modified with a vinyl resin like a hybrid resin.

(Optional component)
The shell portion constituting the toner of the present invention may contain a known resin used for the toner, for example, a styrene-acrylic copolymer, an epoxy, a polycarbonate, a polyurethane, or the like, as long as the effects of the present invention are not impaired. Good.
In the binder resin contained in the shell portion, the content of the polyester (H) is preferably 90% by mass or more, more preferably 93% by mass or more, still more preferably 95% by mass or more, and preferably 100% by mass. % Or less, more preferably substantially 100% by mass, still more preferably 100% by mass.

  The shell portion constituting the toner of the present invention further includes a colorant, a charge control agent, magnetic powder, a fluidity improver, a conductivity modifier, an extender, a reinforcing filler such as a fibrous substance, an antioxidant, and an aging agent. Additives such as an inhibitor and a cleaning property improver may be appropriately contained.

<Core part>
The core part of the core-shell particles used in the present invention contains polyester (L) obtained by polycondensation of a carboxylic acid component (L-ac) and an alcohol component (L-al), and a wax.

(Polyester (L))
The polyester (L) is obtained by polycondensation of a carboxylic acid component (L-ac) and an alcohol component (L-al).

[Carboxylic acid component (L-ac)]
The total content of at least one selected from the alkenyl succinic acid represented by the general formula (1) and the alkyl succinic acid represented by the general formula (2) in the carboxylic acid component (L-ac) From the viewpoint of improving the low-temperature fixing property, heat-resistant storage stability, hot offset resistance, and smearing properties of the printed matter, it is less than 3 mol%, preferably 2 mol% or less, more preferably 1 mol% or less. More preferably, the acid component (L-ac) does not contain the alkenyl succinic acid represented by the general formula (1) and the alkyl succinic acid represented by the general formula (2).
In the carboxylic acid component (H-ac), which is a raw material monomer of the polyester (H) contained in the shell portion, the alkenyl succinic acid represented by the general formula (1) and the alkyl succinic acid represented by the general formula (2) Alkenyl succinic acid represented by the general formula (1) in the carboxylic acid component (L-ac), which is a raw material monomer of the polyester (L) contained in the core part, and a total content of at least one selected from acids And the difference from the total content of one or more selected from the alkyl succinic acid represented by the general formula (2) (the number of moles containing the shell portion-the number of moles containing the core portion) is low temperature fixability of the toner and heat resistant storage 3 mol% or more from the viewpoint of improving the properties, hot offset resistance, and smear properties of the printed material, and preferably 5 mol% from the viewpoint of low-temperature fixability of toner, heat-resistant storage stability, and smear properties of the printed material. Further, it is more preferably 7 mol% or more, and from the viewpoint of improving low-temperature fixability, heat-resistant storage stability, hot offset resistance, and smearing properties of the printed matter, it is preferably 20 mol% or less. From the viewpoint of storage stability, it is more preferably at most 18 mol%, further preferably at most 15 mol%, still more preferably at most 13 mol%.

  Examples of the carboxylic acid component (L-ac) include dicarboxylic acids and trivalent or higher polyvalent carboxylic acids. Among these, dicarboxylic acids are preferable, and it is more preferable to use dicarboxylic acids and trivalent or higher polyvalent carboxylic acids in combination. These carboxylic acid components (L-ac) can be used alone or in combination of two or more.

As the dicarboxylic acid, aliphatic dicarboxylic acids and aromatic dicarboxylic acids are preferable, and aromatic dicarboxylic acids are more preferable.
The carboxylic acid component (L-ac) includes not only dicarboxylic acids and trivalent or higher polyvalent carboxylic acids, but also anhydrides thereof and alkyl esters having 1 to 3 carbon atoms.
Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, azelaic acid, the above general formula (1) And alkenyl succinic acid represented by the general formula (2).
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, and the like. From the viewpoint of improving the heat resistant storage stability of the toner, isophthalic acid and terephthalic acid are preferable, and terephthalic acid is more preferable.
In the carboxylic acid component (L-ac), the content of the aromatic dicarboxylic acid is preferably 60 mol% from the viewpoint of improving the low-temperature fixability, heat-resistant storage stability, hot-offset resistance, and smearability of the printed matter. More preferably, it is 70 mol% or more, more preferably 75 mol% or more, and preferably 95 mol% or less, more preferably 90 mol% or less, still more preferably 85 mol% or less.
Examples of the trivalent or higher aromatic carboxylic acid include trimellitic acid, 2,5,7-naphthalene tricarboxylic acid, pyromellitic acid and the like. Among these, trimellitic acid and its acid anhydride are preferable, and trimellitic anhydride is more preferable from the viewpoint of improving low-temperature fixability, heat-resistant storage stability, hot offset resistance of the toner, and smearability of the printed matter.

[Alcohol component (L-al)]
Examples of the alcohol component (L-al) include aliphatic diols, aromatic diols, and trihydric or higher polyhydric alcohols. These alcohol components (L-al) can be used alone or in combination of two or more.

The aliphatic diol is preferably an aliphatic diol having 2 to 12 carbon atoms, specifically, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1, 3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,6 -Hexanediol, neopentyl glycol, 2,3-pentanediol, 2,4-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol and the like can be mentioned. Among these, aliphatic diols having 2 to 6 carbon atoms are preferable from the viewpoints of low-temperature fixability, heat-resistant storage stability, and smear properties of printed matter, and ethylene glycol, 1,2-propanediol, 1,3-propanediol. , 1,4-pentanediol, 1,5-pentanediol, and 1,6-hexanediol are more preferable, and 1,2-propanediol is more preferable.
In the alcohol component (L-al), the content of the aliphatic diol, preferably the aliphatic diol having 2 to 6 carbon atoms is from the viewpoint of improving the low-temperature fixability of the toner, the heat-resistant storage stability, and the smearability of the printed matter. , Preferably 60 mol% or more, more preferably 70 mol% or more, further preferably 80 mol% or more, still more preferably 90 mol% or more, and preferably 100 mol% or less, more preferably substantially 100 mol%, more preferably 100 mol%.

Examples of the aromatic diol include alkylene oxide adducts of bisphenol A represented by the above formula (I).
Examples of the alkylene oxide adduct of bisphenol A represented by the formula (I) include 2,2-bis (4-hydroxyphenyl) propane polyoxypropylene adduct and 2,2-bis (4-hydroxyphenyl) propane. And polyoxyethylene adducts.
Examples of the trivalent or higher alcohol include glycerin, pentaerythritol, trimethylolpropane, and the like, and glycerin is preferable from the viewpoint of reactivity and molecular weight adjustment.
In addition, from the viewpoints of molecular weight adjustment and physical property adjustment, the alcohol component (L-al) may appropriately contain a monovalent alcohol, and the carboxylic acid component (L-ac) has a monovalent carboxylic acid compound. May be appropriately contained.

<Molar ratio of alcohol component (L-al) and carboxylic acid component (L-ac)>
The molar ratio of the alcohol component (L-al) and the carboxylic acid component (L-ac) in the polycondensation reaction (carboxylic acid component (L-ac) / alcohol component (L-al)) is the reactivity, molecular weight adjustment and From the viewpoint of adjusting physical properties, it is preferably 0.5 or more, more preferably 0.7 or more, still more preferably 0.8 or more, and preferably 1.5 or less, more preferably 1.3 or less, still more preferably. Is 1.1 or less.

[Physical properties of polyester (L)]
The glass transition temperature of the polyester (L) is preferably 25 ° C. or higher, more preferably 30 ° C. or higher, from the viewpoint of improving low-temperature fixability, heat-resistant storage stability, hot offset resistance, and smearing properties of printed matter. Preferably it is 35 degreeC or more, Preferably it is 60 degrees C or less, More preferably, it is 50 degrees C or less, More preferably, it is 45 degrees C or less.
The softening point of the polyester (L) is preferably 75 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 85 ° C. or higher, and preferably 120 ° C. or lower, from the viewpoint of heat resistant storage stability of the toner. Is 110 ° C. or lower, more preferably 105 ° C. or lower.
The difference in softening point between the polyester (H) and the polyester (L) (polyester (H) -polyester (L)) is preferably 10 ° C. or more from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner. More preferably, it is 20 ° C. or higher, more preferably 25 ° C. or higher, and preferably 40 ° C. or lower.
In addition, when using 2 or more types of polyester (L) in mixture, the glass transition temperature and softening point were obtained by the method as described in an Example as a mixture of 2 or more types of polyester (L), respectively. Value.
The acid value of the polyester (L) is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, from the viewpoint of improving the low-temperature fixability, heat storage stability, hot offset resistance of the toner and smearing property of the printed matter. More preferably, it is 15 mgKOH / g or more, and from the same viewpoint, it is preferably 35 mgKOH / g or less, more preferably 30 mgKOH / g or less, still more preferably 25 mgKOH / g or less.

The number average molecular weight of the polyester (L) is preferably 1,000 or more, more preferably 1,500 or more, still more preferably 2,000 or more, and preferably 6,000 or more from the viewpoint of heat-resistant storage stability of the toner. 000 or less, more preferably 5,000 or less, and still more preferably 4,000 or less.
From the same viewpoint, the weight average molecular weight of the polyester (L) is preferably 4,000 or more, more preferably 6,000 or more, still more preferably 8,000 or more, and preferably 100,000 or less. More preferably, it is 50,000 or less, More preferably, it is 30,000 or less, More preferably, it is 15,000 or less.

  The glass transition temperature, softening point, acid value, number average molecular weight, and weight average molecular weight of polyester (L) can be easily adjusted by adjusting the composition of raw material monomers, molecular weight, catalyst amount, etc., or by selecting reaction conditions. Can do. The glass transition temperature, softening point, acid value, number average molecular weight, and weight average molecular weight are determined by the methods described in the examples.

(Production method of polyester (L))
The polyester (L) is obtained by a polycondensation reaction between an alcohol component (L-al) and a carboxylic acid component (L-ac). The polycondensation reaction is preferably performed in the presence of an esterification catalyst, and more preferably performed in the presence of an esterification catalyst and a pyrogallol compound from the viewpoint of reactivity, molecular weight adjustment, and physical property adjustment of the polyester (L). .
The esterification catalyst and pyrogallol compound preferably used for the polycondensation are the same as the esterification catalyst and pyrogallol compound used for the polycondensation reaction of polyester (H), and the preferred embodiments are also the same.

<Esterification catalyst>
The amount of the esterification catalyst used is 100 parts by mass with respect to the total amount of the alcohol component (L-al) and the carboxylic acid component (L-ac) from the viewpoints of reactivity, molecular weight adjustment, and physical property adjustment of the polyester (L). The amount is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.6 parts by mass or less.

<Pyrogallol compound>
From the viewpoint of reactivity, the amount of the pyrogallol compound used in the polycondensation reaction is 100 parts by mass with respect to a total amount of the alcohol component (L-al) and carboxylic acid component (L-ac) subjected to the polycondensation reaction. Preferably it is 0.001 part by mass or more, more preferably 0.005 part by mass or more, further preferably 0.01 part by mass or more, and preferably 1 part by mass or less, more preferably 0.4 part by mass or less, More preferably, it is 0.2 parts by mass or less.
From the viewpoint of reactivity, the mass ratio of the pyrogallol compound to the esterification catalyst (pyrogallol compound / esterification catalyst) is preferably 0.01 or more, more preferably 0.03 or more, and still more preferably 0.05 or more. And preferably 0.5 or less, more preferably 0.3 or less, still more preferably 0.15 or less.

The polycondensation reaction between the alcohol component (L-al) and the carboxylic acid component (L-ac) can be performed, for example, by heating in an inert gas atmosphere in the presence of the esterification catalyst and the pyrogallol compound. it can.
The temperature of the polycondensation reaction is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and preferably 250 ° C. or lower, more preferably 240 ° C. or lower, still more preferably 235 ° C. or lower. It is.
For example, in order to increase the strength of the resin, it is preferable to add all the monomers to the reaction system at once, and in order to reduce the low molecular weight component, after reacting the divalent monomer first, the trivalent or higher monomer. It is preferable to add and react. Moreover, it is preferable to accelerate the reaction by reducing the pressure of the reaction system in the latter half of the polymerization.

  The polyester (L) may be modified with a vinyl resin like a hybrid resin.

(wax)
The core part of the core-shell particle used in the present invention contains a wax.
Examples of the wax used in the present invention include plant waxes such as rice wax, candelilla wax, tree wax, and jojoba oil; animal waxes such as beeswax; montan wax, ozokerite, ceresin, microcrystalline wax, and Fischer-Tropsch wax. Mineral waxes such as petroleum wax, polyolefin waxes such as polyethylene, polypropylene, polybutene, paraffin wax, silicone waxes; ester waxes such as carnauba wax, synthetic ester wax, polyester wax; oleic acid amide, ethylene bis Examples thereof include amide waxes such as stearic acid amide. Among these, paraffin wax, ester wax, and amide wax are preferable, and paraffin wax is more preferable. These waxes can be used alone or in combination of two or more.
The melting point of the wax is preferably 70 ° C. or higher, more preferably 75 ° C. or higher, and still more preferably 80 ° C. or higher, from the viewpoint of improving low-temperature fixability, heat-resistant storage stability, hot offset resistance, and smearing properties of printed matter. And preferably 110 ° C. or lower, more preferably 105 ° C. or lower, and still more preferably 100 ° C. or lower.
The content of the wax in the core is to improve the low-temperature fixability, heat-resistant storage stability, hot-offset resistance of the toner, and the smearing property of the printed matter, and to improve the dispersibility of the wax in the polyester (L). From 100 parts by mass of polyester (L), preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, still more preferably 3 parts by mass or more, and preferably 10 parts by mass or less. Preferably it is 8 mass parts or less, More preferably, it is 6 mass parts or less.
The content of the wax in the toner obtained by the production method of the present invention is 100% of the total amount of polyester in the toner from the viewpoint of improving the low-temperature fixability, heat-resistant storage stability, hot offset resistance, and smearing properties of the printed matter. Preferably, it is 0.5 parts by mass or more, more preferably 1 part by mass or more, further preferably 3 parts by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass or less. More preferably, it is 6 parts by mass or less.

(Optional component)
The core part constituting the toner of the present invention may contain a known resin used for the toner, for example, a styrene-acrylic copolymer, an epoxy, a polycarbonate, a polyurethane, etc., as long as the effects of the present invention are not impaired. Good.
In the binder resin contained in the core part, the content of the polyester (L) is preferably 90% by mass or more, more preferably 93% by mass or more, still more preferably 95% by mass or more, and preferably 100% by mass. % Or less, more preferably substantially 100% by mass, still more preferably 100% by mass.
The core part constituting the toner of the present invention further comprises a colorant, a release agent, a charge control agent, a magnetic powder, a fluidity improver, a conductivity modifier, an extender pigment, a reinforcing filler such as a fibrous substance, an oxidation Additives such as an inhibitor, an anti-aging agent, and a cleaning property improver may be appropriately contained.

  The mass ratio (core / shell) between the core portion and the shell portion in the toner of the present invention is preferably from the viewpoint of improving the low-temperature fixing property, heat-resistant storage property, hot-offset resistance, and smearing property of the printed matter. 100/5 or less, more preferably 100/10 or less, still more preferably 100/13 or less, preferably from the viewpoint of improving the low-temperature fixability, heat-resistant storage stability, hot offset resistance of the toner, and smearing properties of the printed matter. Is preferably 100/60 or more, more preferably 100/50 or more, and more preferably 100/30 or more, and still more preferably 100/20 or more, from the viewpoint of low-temperature fixability of toner, heat-resistant storage stability, and smear properties of printed matter. is there.

(Physical properties of toner)
The volume-median particle size (D ₅₀ ) of the toner of the present invention is preferably 3.0 μm or more from the viewpoint of improving low-temperature fixability, heat-resistant storage stability, hot-offset resistance, and smearability of printed matter. Preferably it is 3.5 μm or more, more preferably 4.0 μm or more, even more preferably 4.5 μm or more, and preferably 8.5 μm or less, more preferably 8.0 μm or less, and even more preferably 7.5 μm or less. More preferably, it is 7.0 micrometers or less, More preferably, it is 5.5 micrometers or less.
Here, the volume-median particle size is a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size, and is determined by the method described in the examples described later. .
Further, from the same viewpoint, the coefficient of variation (CV value) (%) of the toner particle size distribution is preferably 40% or less, more preferably 35% or less, still more preferably 30% or less, and still more preferably 21%. From the viewpoint of improving the productivity of the toner, it is preferably 5% or more, more preferably 10% or more, and still more preferably 15% or more. In addition, CV value is a value represented by the following formula, and is calculated | required by the method as described in an Example.
CV value (%) = [standard deviation of particle size distribution (μm) / volume median particle size (μm)] × 100

[Method for producing toner for developing electrostatic image]
The method for producing an electrostatic charge image developing toner of the present invention includes the following steps 1 to 3.
Step 1: Step of aggregating resin particles (X) containing polyester (L) and release agent particles containing wax in an aqueous medium to obtain aggregated particles (1) Step 2: In Step 1 Step of aggregating resin particles (Y) containing polyester (H) to the obtained aggregate particles (1) to obtain aggregate particles (2) Step 3: Aggregate particles (2) obtained in Step 2 Process of fusing to obtain core-shell particles

<Step 1>
Step 1 is a step of obtaining aggregated particles (1) by aggregating resin particles (X) containing polyester (L) and release agent particles containing wax in an aqueous medium.

The particles constituting the agglomerated particles (1) may include particles other than the resin particles (X) containing polyester (L) and the release agent particles containing wax.
In step 1, as a supply source of the resin particles (X) containing the polyester (L), an aqueous dispersion obtained by dispersing the resin particles (X) containing the polyester (L) in an aqueous medium (hereinafter referred to as “ It is preferable to use a resin particle (X) aqueous dispersion ”.
Further, it is preferable to add a flocculant in order to efficiently agglomerate, and colorants, charge control agents, mold release agents, conductivity modifiers, reinforcing fillers such as fibrous substances, antioxidants, anti-aging Aggregation may be performed after an additive such as an agent is added. The additive can also be used as an aqueous dispersion.
Next, an aqueous dispersion and an additive are demonstrated.

The aqueous dispersion of the resin particles (X) is prepared by adding an aqueous medium and, if necessary, optional components such as a surfactant to the polyester (L) and emulsifying, preferably by a phase inversion emulsification step. It can be suitably obtained.
The aqueous dispersion is prepared by mixing the polyester (L) and an organic solvent to obtain a mixture (step 1-1), adding an aqueous medium to the mixture, phase-inverting and emulsifying the resin particles (X). A step of obtaining a dispersion of the precursor (Step 1-2), a step of obtaining an aqueous dispersion of the resin particles (X) by distilling off the organic solvent from the precursor dispersion of the resin particles (X) (Step 1). -3), and a step of mixing a surfactant with the obtained aqueous dispersion (step 1-4), can be suitably produced. However, step 1-4 may be omitted, and step 1-3 may be omitted without using the organic solvent in step 1-1.

(Step 1-1)
In Step 1-1, polyester (L) and an organic solvent are mixed to obtain a mixture.
From the viewpoint of improving the dispersibility of the polyester (L), the organic solvent is preferably 15.0 MPa ^1/2 when expressed by a solubility parameter (SP value: POLYMER HANDBOOK THIRD EDITION 1989 by John Wiley & Sons, Inc). or more, more preferably 16.0MPa ^1/2, and even more preferably at 17.0MPa ^1/2 or more, and, preferably 26.0MPa ^1/2 or less, more preferably 24.0MPa ^1/2 or less, further Preferably, it is 22.0 MPa ^1/2 or less.
Specific examples include the following organic solvents. In addition, the numerical value shown in the parenthesis on the right side of the name of the next organic solvent is an SP value, and the unit is MPa ^1/2 . That is, specific examples include alcohol solvents such as ethanol (26.0), isopropanol (23.5), isobutanol (21.5); acetone (20.3), methyl ethyl ketone (19.0), methyl isobutyl. Ketone solvents such as ketone (17.2) and diethyl ketone (18.0); ether solvents such as dibutyl ether (16.5), tetrahydrofuran (18.6) and dioxane (20.5); ethyl acetate ( 18.6), and acetate solvents such as isopropyl acetate (17.4). Among these, from the viewpoint of improving the dispersibility of the polyester (L), preferably one or more selected from ketone solvents and acetate solvents, more preferably one or more selected from methyl ethyl ketone, ethyl acetate, and isopropyl acetate. More preferably, it is methyl ethyl ketone.
From the viewpoint of improving the dispersibility of the polyester (L), the mass ratio of the organic solvent to the polyester (L) (organic solvent / polyester (L)) is preferably 0.5 or more, more preferably 1 or more, still more preferably. Is 2 or more, and preferably 7 or less, more preferably 6 or less, and still more preferably 5 or less.

Examples of the neutralizing agent used in the present invention include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; ammonia; organics such as trimethylamine, ethylamine, diethylamine, triethylamine, triethanolamine, and tributylamine. A base. Among these, ammonia is preferable from the viewpoint of improving the low-temperature fixability, heat-resistant storage stability, hot-offset resistance of the toner, and smearability of the printed matter.
From the same viewpoint, the degree of neutralization of the polyester (L) with the neutralizing agent is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and preferably 150 mol%. % Or less, more preferably 120 mol% or less, still more preferably 110 mol% or less.
In addition, the neutralization degree (mol%) of resin can be calculated | required by a following formula.
Degree of neutralization = {[mass of neutralizer (g) / equivalent of neutralizer] / [[acid value of resin (mgKOH / g) × mass of resin (g)] / (56 × 1000)]} × 100

In addition, you may add arbitrary components to a mixture in the range which does not affect the effect of this invention. Examples thereof include inorganic salts, organic solvents other than those described above, and surfactants described later.
A mixture can be obtained by mixing polyester (L) mentioned above, an organic solvent, and the neutralizing agent as needed.
In the method for producing the mixture, the order of adding the raw materials is not limited, but it is preferable to mix the neutralizing agent after mixing the polyester (L) and the organic solvent.
At the time of mixing, it is preferable to stir with a commonly used mixing and stirring device such as an anchor blade or an external circulation stirring device.
The temperature at the time of mixing is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, further preferably 20 ° C. or higher, from the viewpoints of stabilizing the process temperature, shortening the process time, reducing the viscosity of the solution, and the like. The temperature is preferably 85 ° C. or lower, more preferably 80 ° C. or lower, and still more preferably 75 ° C. or lower.
Further, the stirring is preferably performed until there is no significant phase separation or insoluble matter, and the stirring time depends on the stirring speed and temperature conditions, but preferably 0.5 hours or more, more preferably 1 hour or more, and preferably 5 hours or less, more preferably 3 hours or less.

(Step 1-2)
Step 1-2 is a step of adding a water-based medium and, if necessary, a surfactant to the mixture obtained in Step 1-1, and phase inversion emulsifying to obtain a dispersion of precursors of resin particles (X). is there.

As the aqueous medium, those mainly containing water are preferable.
Components other than water include aliphatic alcohols having 1 to 5 carbon atoms such as methanol, ethanol, isopropanol and butanol; dialkyl ketones having 3 to 7 carbon atoms such as acetone and methyl ethyl ketone; water such as cyclic ethers such as tetrahydrofuran Organic solvents that dissolve in Among these, from the viewpoint of preventing mixing into the toner, an organic solvent that does not dissolve the resin is preferable, and alcohol-based organic solvents such as methanol, ethanol, isopropanol, and butanol can be suitably used.
The content of water in the aqueous medium is preferably 80% by mass or more, more preferably 90% by mass or more, and preferably 100% by mass or less, more preferably, from the viewpoint of improving the emulsion stability of the resin. 100% by mass. The water is preferably deionized water or distilled water.

The temperature at which the aqueous medium is added is preferably 20 ° C. or higher, more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, and preferably 90 ° C. or lower, from the viewpoint of improving the emulsion stability of the resin. More preferably, it is 80 degrees C or less, More preferably, it is 70 degrees C or less.
From the viewpoint of obtaining resin particles having a small particle size, the addition rate of the aqueous medium is preferably 1 part by mass / min or more, more preferably 3 parts per 100 parts by mass of the polyester (L) until phase inversion is completed. It is at least 5 parts by weight, more preferably at least 5 parts by weight, more preferably at most 30 parts by weight, more preferably at most 20 parts by weight, even more preferably at most 10 parts by weight / minute. . There is no restriction | limiting in the addition rate of the aqueous medium after phase inversion.
The amount of the aqueous medium used is preferably 100 parts by mass or more, more preferably 300 parts by mass or more, still more preferably from 100 parts by mass of the polyester (L) from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation process. 400 parts by mass or more, and preferably 3000 parts by mass or less, more preferably 2000 parts by mass or less, and still more preferably 1000 parts by mass or less.
In addition, the amount of the aqueous medium used is such that the mass ratio of the aqueous medium to the organic solvent (aqueous medium / organic solvent) is preferably 10/90 or more from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation step. The amount is preferably 20/80 or more, more preferably 30/70 or more, and preferably 90/10 or less, more preferably 80/20 or less, and still more preferably 70/30 or less.

Examples of the surfactant include nonionic surfactants, anionic surfactants, and cationic surfactants. Among these, from the viewpoint of dispersibility of the polyester (L), nonionic surfactants and / or anionic surfactants are preferable, and anionic surfactants are more preferable.
Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl aryl ethers such as polyoxyethylene lauryl ether or polyoxyethylene alkyl ethers, polyethylene glycol monolaurate, Examples include polyoxyethylene fatty acid esters such as polyethylene glycol monostearate and polyethylene glycol monooleate, and oxyethylene / oxypropylene block copolymers. Among these, from the viewpoint of emulsion stability of the resin, polyoxyethylene alkyl ether Are preferred.
Examples of the anionic surfactant include alkylbenzene sulfonates such as sodium alkylbenzene sulfonate, alkyl sulfates such as sodium alkyl sulfate, polyoxyalkylene alkyl ether sulfates such as sodium polyoxyalkylene alkyl ether sulfate, and the like. Among these, from the viewpoint of emulsion stability of the resin, sodium alkylbenzene sulfonate and polyoxyalkylene alkyl ether sulfate are preferable, and polyoxyalkylene alkyl ether sulfate is more preferable.
Examples of the cationic surfactant include alkyltrimethylammonium chloride and dialkyldimethylammonium chloride.
Among these, from the viewpoint of the dispersibility of the polyester (L) and the emulsion stability of the resin, polyoxyethylene alkyl ethers and polyoxyalkylene alkyl ether sulfates are preferable, and polyoxyalkylene alkyl ether sulfates are more preferable.

(Step 1-3)
Step 1-3 is a step of obtaining an aqueous dispersion of resin particles (X) by distilling off the organic solvent from the dispersion obtained in Step 1-2.
The method for removing the organic solvent is not particularly limited, and any method can be used. However, since it is dissolved in water, distillation is preferable. Further, the organic solvent may not be completely removed and may remain in the aqueous dispersion. 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 still more preferably substantially 0% by mass in the aqueous dispersion.
When removing the organic solvent by distillation, it is preferable to raise the temperature to a temperature equal to or higher than the boiling point of the organic solvent to be distilled while stirring. Further, from the viewpoint of maintaining the dispersion stability of the polyester (L), it is more preferable to raise the temperature to a temperature equal to or higher than the boiling point of the organic solvent to be used under reduced pressure. Note that the temperature may be increased after the pressure is reduced, or the pressure may be decreased after the temperature is increased. From the viewpoint of maintaining the dispersion stability of the polyester (L), it is preferable to distill off at a constant temperature and pressure.

(Step 1-4)
Step 1-4 is a step of mixing a surfactant with the obtained aqueous dispersion.
Specific examples and preferred examples of the surfactant added in Step 1-4 include the same as those mentioned in Step 1-2.

  The solid content concentration of the aqueous dispersion obtained through the production process of the aqueous dispersion including Step 1-1 to Step 1-4 is preferably 3% by mass or more from the viewpoint of the stability of the aqueous dispersion and ease of handling. More preferably, it is 5% by mass or more, more preferably 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less. The solid content concentration can be adjusted by appropriately adding water to the aqueous dispersion.

The volume median particle size (D ₅₀ ) of the resin particles (X) is preferably 50 nm or more, more preferably 100 nm or more, and preferably 1000 nm or less, from the viewpoint of uniform aggregation in the subsequent aggregation step. More preferably, it is 500 nm or less, More preferably, it is 400 nm or less, More preferably, it is 350 nm or less.

(Release agent particles)
The release agent particles are preferably obtained as a dispersion of release agent particles by dispersing the release agent in an aqueous medium.
The dispersion of the release agent particles is preferably obtained by dispersing the release agent and the aqueous medium using a disperser in the presence of a surfactant at a temperature equal to or higher than the melting point of the release agent. As the disperser to be used, a homogenizer, an ultrasonic disperser and the like are preferable from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner.
Further, before using the disperser, it is preferable to preliminarily disperse the release agent, the optionally used surfactant, and the aqueous medium in advance using a mixer such as a homomixer or a ball mill.
What is used when obtaining the said resin particle (X) as an aqueous medium is used preferably.

The dispersion of the release agent particles in the aqueous medium may be performed in the presence of a surfactant from the viewpoint of improving the dispersion stability of the release agent particles and obtaining uniform aggregated particles in the subsequent aggregation step. Good.
Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants and the like, and the same ones used for the production of the resin particles (X) can be used. From the viewpoint of improving the cohesiveness between the release agent particles and the resin particles (X), a cationic surfactant is preferable.
The content of the surfactant in the dispersion of the release agent particles is to improve the dispersion stability of the release agent particles, and to improve the cohesiveness of the release agent particles at the time of toner preparation and prevent the release. From the viewpoint, it is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.4% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less. More preferably, it is 2% by mass or less.

The solid content concentration of the dispersion of the release agent particles is preferably 7% by mass or more, more preferably 10% by mass or more from the viewpoint of improving the productivity of the toner and improving the dispersion stability of the release agent particles. And preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less. In addition, solid content is the total amount of non-volatile components, such as a mold release agent and surfactant.
The volume-median particle size of the release agent particles is a viewpoint of obtaining uniform aggregated particles in the subsequent aggregation process, and a viewpoint of improving low-temperature fixability, heat-resistant storage stability, hot offset resistance of the toner, and smearing properties of the printed matter. Therefore, it is preferably 100 nm or more, more preferably 200 nm or more, still more preferably 300 nm or more, and preferably 1000 nm or less, more preferably 800 nm or less, and further preferably 600 nm or less.

(Flocculant)
As the flocculant, a quaternary salt cationic surfactant, an organic flocculant such as polyethyleneimine; and an inorganic flocculant such as inorganic metal salt and inorganic ammonium salt are used. From the viewpoint of improving the low-temperature fixability of toner, heat-resistant storage stability, hot offset resistance, and smearability of printed matter, an inorganic flocculant is preferable, and calcium chloride is more preferable.
When the flocculant is added, the addition amount thereof is based on 100 parts by mass of the resin particles (X) from the viewpoint of improving the low-temperature fixability, heat-resistant storage stability, hot offset resistance, and smearing properties of the printed matter of the toner. Preferably it is 0.001 mass part or more, More preferably, it is 0.1 mass part or more, More preferably, it is 0.2 mass part or more, Preferably it is 10 mass parts or less, More preferably, it is 5 mass parts or less, More preferably Is 1 part by mass or less.
The flocculant is preferably added after being dissolved in an aqueous medium, and it is preferable that the flocculant is sufficiently stirred at the time of addition of the flocculant and after completion of the addition.

In the agglomeration step, the solid content concentration in the system is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and preferably, in order to cause uniform aggregation. It is 50 mass% or less, More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less.
The holding temperature after adding the flocculant is preferably 35 ° C or higher, more preferably 40 ° C or higher, still more preferably 45 ° C or higher, and preferably 65 ° C or lower, more preferably 60 ° C or lower, still more preferably. Is 55 ° C. or lower.

(Coloring agent)
There is no restriction | limiting in particular as a coloring agent, A well-known coloring agent is mentioned, According to the objective, it can select suitably. Specifically, carbon black, inorganic composite oxide, chrome yellow, hansa yellow, benzidine yellow, selenium yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brilliantamine 3B, Brilliantamine 6B, Dupont Oil Red, Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C, Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Phthalocyanine Green, Malachite Green Oxalate, etc. Various pigments: acridine, xanthene, azo, benzoquinone, azine, anthraquinone, indico, thioy Zico type, phthalocyanine type, aniline black, polymethine, triphenylmethane dyes, diphenylmethane dyes, thiazine, include various dyes of thiazole, and the like. These colorants can be used alone or in combination of two or more.
The addition amount of the colorant is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and further preferably 2 parts by mass with respect to 100 parts by mass of the resin particles (X) from the viewpoint of improving the image quality. More preferably, it is 2.5 parts by mass or more, and preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 8 parts by mass or less, and still more preferably 4 parts by mass or less. .
The colorant may be added as a colorant dispersion containing colorant fine particles. The volume median particle size (D ₅₀ ) of the colorant fine particles is preferably 50 nm or more, more preferably 100 nm or more, and preferably 200 nm or less, more preferably 150 nm or less.

(Charge control agent)
Examples of the charge control agent include chromium azo dyes, iron azo dyes, aluminum azo dyes, and salicylic acid metal complexes. These various charge control agents can be used alone or in combination of two or more.
When the charge control agent is added, the addition amount is preferably 0.1 parts by mass or more, more preferably 0.4 parts by mass with respect to 100 parts by mass of the resin particles (X) from the viewpoint of improving image quality. More preferably, it is 0.6 parts by mass or more, and preferably 8 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 2 parts by mass or less.
The charge control agent may be added as a charge control agent dispersion containing charge control agent fine particles. The volume median particle size (D ₅₀ ) of the charge control agent fine particles is preferably 100 nm or more, more preferably 200 nm or more, still more preferably 300 nm or more, and preferably 800 nm or less, more preferably 700 nm or less, Preferably it is 600 nm or less.

(Volume-median particle size of aggregated particles (1))
The volume-median particle size (D ₅₀ ) of the obtained aggregated particles (1) is preferably 2 μm or more from the viewpoint of improving low-temperature fixability, heat-resistant storage stability, hot offset resistance, and smearing properties of the printed matter of the toner. More preferably, it is 3 μm or more, further preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, and further preferably 6 μm or less.

<Step 2>
Step 2 is a step in which the aggregated particles (1) obtained in Step 1 are aggregated with the resin particles (Y) containing the polyester (H) to obtain aggregated particles (2).

In step 2, as a supply source of the resin particles (Y) containing the polyester (H), an aqueous dispersion obtained by dispersing the resin particles (Y) containing the polyester (H) in an aqueous medium (hereinafter, “ It is preferable to use a resin particle (Y) aqueous dispersion ”. That is, by adding an aqueous dispersion of resin particles (Y) to the dispersion liquid of the aggregated particles (1) obtained in step 1, the resin particles (Y) are further adhered to the aggregated particles (1), thereby aggregating. It is preferable to obtain a dispersion of particles (2). When the aqueous dispersion of resin particles (Y) is added to the dispersion of aggregated particles (1), the aggregating agent is added in this step in order to efficiently attach the resin particles (Y) to the aggregated particles (1). It may be used.
The manufacturing method of the aqueous dispersion of resin particles (Y) is the same as the manufacturing method of the aqueous dispersion of resin particles (X), and the preferred embodiment is also the same.

(Drip temperature)
The temperature at which the aqueous dispersion of resin particles (Y) is added is preferably 35 ° C. or higher, more preferably 40 ° C. or higher, still more preferably 45 ° C. or higher, and preferably 65 ° C. or lower, more preferably 60 ° C or lower, more preferably 55 ° C or lower.

The aqueous dispersion of resin particles (Y) may be added continuously over a certain period of time, may be added at a time, or may be added in multiple portions.
The total amount of the resin particles (Y) may be added, and aggregation may be stopped when the toner particles have grown to an appropriate particle size.
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.

As the aggregation terminator, a surfactant is preferably used, and an anionic surfactant is more preferably used. As the anionic surfactant, one or more selected from alkyl ether sulfates, alkyl sulfates, and linear alkylbenzene sulfonates are preferable, and alkyl ether sulfates are more preferable. These aggregation terminators can be used alone or in combination of two or more.
The addition amount of the aggregation terminator is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the total amount of the resin particles (X) and the resin particles (Y) from the viewpoint of surely preventing unnecessary aggregation. The amount is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 2 from the viewpoint of reducing residual toner. It is below mass parts. The aggregation terminator is preferably added as an aqueous solution from the viewpoint of improving toner productivity.

The volume median particle size (D ₅₀ ) of the resin particles (Y) is preferably 50 nm or more, more preferably 100 nm or more, and preferably 1000 nm or less, from the viewpoint of uniform aggregation in the subsequent aggregation step. More preferably, it is 500 nm or less, More preferably, it is 400 nm or less, More preferably, it is 350 nm or less.

(Mass ratio of resin particles (Y) and resin particles (X))
The addition amount of the resin particles (Y) is preferably a mass ratio of the resin particles (Y) to the resin particles (X) (resin particles (Y) / resin particles (X)) from the viewpoint of heat resistant storage stability of the toner. Is not less than 0.01, more preferably not less than 0.05, still more preferably not less than 0.07, still more preferably not less than 0.1, and from the viewpoint of improving the low-temperature fixability of the toner and the smearability of the printed matter. The amount is preferably 0.6 or less, more preferably 0.4 or less, still more preferably 0.3 or less, and still more preferably 0.2 or less.

(Volume median particle size of aggregated particles (2))
The volume-median particle size (D ₅₀ ) of the obtained aggregated particles (2) is preferably 2 μm or more from the viewpoint of improving low-temperature fixability, heat-resistant storage stability, hot offset resistance, and smearing properties of the printed matter of the toner. More preferably, it is 3 μm or more, further preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, and further preferably 6 μm or less.

<Step 3>
Step 3 is a step in which the agglomerated particles (2) obtained in Step 2 are fused to obtain core-shell particles.
The agglomerated particles (2), which are mainly physically attached to each other, are fused and united to form core-shell particles.
The temperature in the system in step 3 is the target toner particle size, particle size distribution, shape control, and particle fusing viewpoint, as well as low-temperature fixability, heat-resistant storage stability, hot offset resistance of the toner, and printed matter. From the viewpoint of improving the smearing property, it 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 90 ° C. or lower, still more preferably 85 It is below ℃.
The holding time at the above temperature is preferably 1 minute or more, more preferably 10 minutes or more, and still more preferably from the viewpoint of improving low-temperature fixability of toner, heat-resistant storage stability, hot offset resistance, and smearability of printed matter. It is 30 minutes or more, and preferably 240 minutes or less, more preferably 180 minutes or less, and further preferably 120 minutes or less.

The volume-median particle size (D ₅₀ ) of the core-shell particles obtained in Step 3 is preferably 2 μm or more from the viewpoint of improving the low-temperature fixability, heat-resistant storage stability, hot offset resistance, and smearability of the printed matter of the toner. More preferably, it is 3 μm or more, further preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, and further preferably 6 μm or less.
In addition, it is preferable that the volume median particle size of the core-shell particles obtained in Step 3 is not more than the volume median particle size of the aggregated particles (2). That is, in the step 3, it is preferable that the aggregated particles (2) are not aggregated or fused.

Toner particles can be suitably obtained by subjecting the core-shell particles obtained in step 3 to a solid-liquid separation step such as filtration, a washing step, and a drying step as appropriate.
In the washing step, it is preferable to completely remove the added nonionic surfactant by washing, and washing with an aqueous solution below the cloud point of the nonionic surfactant is preferred. The washing is preferably performed a plurality of times.
In the drying step, any method such as a vibration type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method, or the like can be employed. The water content after drying of the toner is preferably 1.5% by mass or less, more preferably 1.0% by mass or less, from the viewpoint of chargeability.

  The toner particles obtained by drying or the like can be used as the electrostatic charge image developing toner as they are, but it is preferable to use the toner particles whose surface has been treated as the electrostatic charge image developing toner.

An external additive may be added to the toner particles for the purpose of further improving fluidity. Examples of the external additive include silica fine particles whose surface is hydrophobized, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, and inorganic fine particles such as carbon black; polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin, and the like. Fine particles can be used.
The number average particle size of the external additive is preferably 4 nm or more, more preferably 6 nm or more, still more preferably 8 nm or more, and preferably 200 nm or less, more preferably 50 nm or less, from the viewpoint of toner fluidity. More preferably, it is 30 nm or less.
When the external additive is added, the addition amount is preferably from 100 parts by weight of the toner before the processing with the external additive, from the viewpoint of the fluidity of the toner, the environmental stability of the charging degree, and the storage stability. 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, further preferably 0.2 parts by mass or more, and preferably 5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 1 It is below mass parts.

  Each property such as resin, resin particles, and toner was measured and evaluated by the following method.

[Acid value of resin]
The acid value of the resin was measured based on the method of JIS K 0070. However, only the measurement solvent was changed from a mixed solvent of ethanol and ether specified in JIS K 0070 to a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

[Resin softening point, glass transition temperature, etc.]
(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 amount of plunger drop 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) Maximum temperature of endothermic peak Using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), it is 0 ° C. at a temperature decreasing rate of 10 ° C./min from room temperature (20 ° C.). The sample cooled to 0 ° C. was allowed to stand for 1 minute, and then measured while heating up to 180 ° C. at a heating rate of 10 ° C./min. Of the endothermic peaks observed, the peak temperature on the highest temperature side was defined as the highest endothermic peak temperature.
(3) Glass transition temperature Using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of a sample is weighed into an aluminum pan, and 200 ° C. The temperature was raised to 0 ° C. from the temperature at a temperature drop rate of 10 ° C./min. Next, the measurement was performed while increasing the temperature to 150 ° C. at a temperature increase rate of 10 ° C./min. The glass transition temperature was defined as the temperature at the intersection of the base line extension below the maximum temperature of the endothermic peak and the tangent line indicating the maximum slope from the peak rising portion to the peak apex.

[Number average molecular weight and weight average molecular weight of polyester]
The molecular weight distribution was measured by the gel permeation chromatography (GPC) method according to the following method, and the number average molecular weight and the weight average molecular weight of the resin were determined.
(1) Preparation of sample solution The resin was dissolved in chloroform so that the concentration was 0.5 g / 100 mL. Subsequently, this solution was filtered using a fluororesin filter having a pore size of 2 μm (trade name: FP-200, manufactured by Sumitomo Electric Industries, Ltd.) to remove insoluble components to obtain a sample solution.
(2) Molecular weight measurement Using the following apparatus, chloroform was flowed as an eluent at a flow rate of 1 ml per minute, and the column was stabilized in a constant temperature bath at 40 ° C. Measurement was performed by injecting 100 μl of the sample solution. The molecular weight of the sample was calculated based on a calibration curve prepared in advance. In the calibration curve at this time, several types of monodisperse polystyrenes with known molecular weights (manufactured by Tosoh Corporation; 2.63 × 10 ³ , 2.06 × 10 ⁴ , 1.02 × 10 ⁵ , GL Sciences Inc.); 2.10 × 10 ³ , 7.00 × 10 ³ , 5.04 × 10 ⁴ (numbers are molecular weights) prepared as standard samples were used.
Measuring device: CO-8010 (trade name, manufactured by Tosoh Corporation)
Analytical column: GMH _XL + G3000H _XL (both trade names, manufactured by Tosoh Corporation)

[Aggregated Particles (1), Toner Particles, and Volume Median Particle Size (D ₅₀ ) and CV Value of Toner]
Aggregated particles (1), toner particles, and the volume median particle size of the toner were measured as follows.
-Measuring machine: Coulter Multisizer III (trade name, manufactured by Beckman Coulter)
・ Aperture diameter: 50μm
・ Analysis software: Multisizer III version 3.51 (trade name, manufactured by Beckman Coulter)
・ Electrolyte: Isoton II (trade name, manufactured by Beckman Coulter)
-Dispersion: Polyoxyethylene lauryl ether (trade name: Emulgen 109P, HLB: 13.6) manufactured by Kao Corporation was dissolved in the electrolytic solution to obtain a dispersion having a concentration of 5% by mass.
-Dispersion conditions: 10 mg of a measurement sample was added to 5 mL of the dispersion, and dispersed for 1 minute with an ultrasonic disperser. Then, 25 mL of electrolyte was added, and further dispersed for 1 minute with an ultrasonic disperser. A sample dispersion was prepared.
Measurement conditions: The sample dispersion is added to 100 mL of the electrolytic solution to adjust the particle size of 30,000 particles to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured and the particle size distribution thereof. From this, the volume median particle size (D ₅₀ ) was determined.
Further, the volume average particle size was determined in the same manner as the volume median particle size, and the CV value (%) was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size) × 100

[Volume Median Particle Size (D ₅₀ ) of Colorant Particle, Charge Control Agent Particle, and Release Agent Particle]
(1) Measuring apparatus: Laser diffraction type particle size measuring instrument “LA-920” (manufactured by Horiba, Ltd.)
(2) Measurement conditions: Distilled water was added to the measurement cell, and the volume-median particle size (D ₅₀ ) was measured at a concentration at which the absorbance was in an appropriate range.

[Solid content concentration of aqueous dispersion]
Using an infrared moisture meter “FD-230” (manufactured by Kett Science Laboratory Co., Ltd.), 5 g of the sample was subjected to a drying temperature of 150 ° C. and a measurement mode of 96 (monitoring time 2.5 minutes / variation width 0.05%). The sample was dried and the moisture content (% by mass) of the sample was measured. The solid content was calculated according to the following formula.
Solid content concentration (mass%) = 100-sample moisture (mass%)

[Low-temperature fixability of toner]
The toner was mounted on an apparatus in which the fixing machine of the copying machine “AR-505” (manufactured by Sharp Corporation) was improved so that fixing outside the apparatus was possible, and a printed matter was obtained in an unfixed state (printing area: 2 cm). × 12 cm, adhesion amount: 0.5 mg / cm ² ). After that, using a fixing machine (fixing speed 300 mm / sec) adjusted so that the total fixing pressure becomes 40 kgf, the fixing roll temperature is increased from 100 ° C. to 240 ° C. by 5 ° C., and unfixed at each temperature. A fixing test of the printed matter in the state was performed. A cellophane adhesive tape “UNICEF cellophane” (Mitsubishi Pencil Co., Ltd., width: 18 mm, JIS Z1522) is attached to the image portion of the obtained printed matter, and a fixing roller set at 30 ° C., separate from the fixing roll of the fixing machine. Then, the tape was peeled off. The optical reflection density before and after the tape was peeled was measured using a reflection densitometer “RD-915” (manufactured by Gretag Macbeth Co.), and the ratio between the two (after peeling / before sticking × 100) was initially 90%. The temperature of the fixing roll exceeding the temperature was set as the minimum fixing temperature. The lower the minimum fixing temperature, the better the low temperature fixing property. As the fixing paper, “CopyBond SF-70NA” (manufactured by Sharp Corporation, 75 g / m ² ) was used.

[Toner hot offset resistance]
During the evaluation of the low-temperature fixability, the occurrence of hot offset on the fixing roller was visually observed, and the temperature at which hot offset occurred first was confirmed as the hot offset occurrence temperature. The higher the hot offset generation temperature, the better the hot offset resistance.

[Heat resistant storage stability of toner]
10 g of toner was put in a 50 ml polycup and kept in an environment of 55 ° C. and 60% RH for 24 hours. Then, on a powder tester (manufactured by Hosokawa Micron Corporation), in order from the top, three sieves of sieve A (aperture 250 μm), sieve B (aperture 150 μm), and sieve C (aperture 75 μm) are stacked and installed, 10 g of toner was placed on the sieve A, and vibration was applied for 60 seconds. Next, α obtained from the following formula was calculated to evaluate the fluidity. The greater the value of α, the better the heat resistant storage.

  α = 100 − [(toner mass remaining on sieve A (g)) + (toner mass remaining on sieve B (g)) × 0.6 + (toner mass remaining on sieve C (g)) × 0.2] / 10 (g) × 100

[Smearing property of printed matter]
The toner was mounted on a copier “AR-505” (trade name, manufactured by Sharp Corporation), and a solid image was taken out before passing through the fixing machine to obtain a printed matter in an unfixed state (printing area: 2 cm × 12 cm). , Adhesion amount: 0.5 mg / cm ² ). Further, an unfixed image was printed twice on the same paper, and the layer thickness was 1.5 mg / cm ² . The unfixed image thus obtained was fixed at 180 ° C. and 300 mm / sec to obtain a printed matter.
A stainless steel weight having a length x width x height = 3 cm x 3 cm x 6.5 cm and a weight of 500 g was placed on the obtained printed matter and reciprocated on the print at a speed of 0.5 m / s. One reciprocation was taken as one time and the upper limit was 50 times. The number of times that a black belt-like toner deposit appeared on the non-printing portion was visually confirmed to evaluate smearing properties. The larger the number of times, the better the smearing property.

[Double bond positions of internal olefins (1) to (5)]
The double bond position of the internal olefin was measured by gas chromatography (hereinafter also referred to as “GC”). Specifically, dimethyl disulfide was reacted with an internal olefin to obtain a dithiolated derivative, and then each component was separated by GC. The double bond position of the internal olefin was determined from each peak area.
In addition, the apparatus and analysis conditions used for the measurement are as follows.
-GC device: manufactured by HEWLETT PACKARD, product name: HP6890
Column: manufactured by Frontier Laboratories, Inc., trade name: Ultra-Alloy-1HT capillary column 30 m × 250 μm × 0.15 μm
・ Detector: Hydrogen flame ion detector (FID)
・ Injection temperature: 300 ℃
・ Detector temperature: 350 ℃
-Helium flow rate: 4.6 mL / min

[Distribution of alkylene compound (6)]
The distribution of the alkylene compound (6) was determined by the method described in paragraph [0092] to [0103] [Analysis of alkylene compound A by mass spectrometry gas chromatography] in JP-A-2013-222001.

[Production of alkenyl succinic anhydride]
Production Example 1
(Production of alkenyl succinic anhydride (a))
7000 g (25.9 mol) of 1-octadecanol (manufactured by Kao Corporation, product name: Calcoal 8098) and 1050 g of γ-alumina (STREM Chemicals, Inc.) as a solid acid catalyst in a flask equipped with a stirrer (based on the raw alcohol) The reaction was carried out for 13 hours while flowing nitrogen (7000 mL / min.) Through the system at 285 ° C. with stirring. After the reaction, the alcohol conversion was 100%, and the C18 internal olefin purity was 98.5%. The obtained crude internal olefin was transferred to a distillation flask and distilled at 148 to 158 ° C./0.5 mmHg to obtain an 18-carbon internal olefin (1) having an olefin purity of 100%. The double bond distribution of the obtained internal olefin (1) is as follows: C1-position 0.7% by mass, C2-position 16.9% by mass, C3-position 15.9% by mass, C4-position 16.0% by mass, C5-position 14 The total of C5 position, 11.2 mass%, C7 position, 10.2 mass%, C8, 9th position was 14.6 mass%.
Next, 1 L of autoclave manufactured by Nitto High Pressure Co., Ltd., internal olefin (1) 542.4 g, maleic anhydride 157.2 g, antioxidant Chelex-O (SC Organic Chemical Co., Ltd., Triisooctyl phosphite) 0.4 g, As a polymerization inhibitor, 0.1 g of butylhydroquinone was charged, and pressurized nitrogen substitution (0.2 MPaG) was repeated three times. After stirring was started at 60 ° C., the temperature was raised to 230 ° C. over 1 hour and the reaction was performed for 6 hours. The pressure when the reaction temperature was reached was 0.3 MPaG. After completion of the reaction, the mixture was cooled to 80 ° C., returned to normal pressure (101.3 kPa), and transferred to a 1 L four-necked flask. The temperature was raised with stirring to 180 ° C., and the remaining internal olefin at 1.3 kPa was distilled off in 1 hour. Subsequently, after cooling to room temperature (25 ° C.), the pressure was returned to normal pressure (101.3 kPa) to obtain 406.1 g of the desired alkenyl succinic anhydride (a). The average molecular weight of the alkenyl succinic anhydride (a) determined from the acid value was 364.

Production Example 2
(Production of alkenyl succinic anhydride (b))
An internal olefin (2) having 12 carbon atoms was obtained in the same manner as in Production Example 1 except that 1-octadecanol used in Production Example 1 was changed to 1-dodecanol. The double bond distribution of the obtained internal olefin (2) is as follows: C1-position 0.4% by mass, C2-position 30.4% by mass, C3-position 29.6% by mass, C4-position 16.2% by mass, C5, C6 The total position was 23.4% by mass.
Next, an alkenyl succinic anhydride (b) was obtained in the same manner as in Production Example 1 except that the internal olefin (1) used in Production Example 1 was changed to the internal olefin (2). The average molecular weight of the alkenyl succinic anhydride (b) determined from the acid value was 280.

Production Example 3
(Production of alkenyl succinic anhydride (c))
An internal olefin (3) having 9 carbon atoms was obtained in the same manner as in Production Example 1 except that 1-octadecanol used in Production Example 1 was changed to 1-nonanol. The double bond distribution of the obtained internal olefin (3) was 0.3 mass% at C1, 37.1 mass% at C2, 35.2 mass% at C3, 27.4 mass at C4, and 5-position. %Met.
Next, an alkenyl succinic anhydride (c) was obtained in the same manner as in Production Example 1 except that the internal olefin (1) used in Production Example 1 was changed to the internal olefin (3). The average molecular weight of the alkenyl succinic anhydride (c) determined from the acid value was 238.

Production Example 4
(Production of alkenyl succinic anhydride (d))
The amount of γ-alumina used in Production Example 1 is 10% by mass with respect to 1-octadecanol (product of Kao Corporation, product name: Calcoal 8098) as a raw material alcohol, the reaction temperature is 280 ° C., and the reaction time is Was produced in the same manner as in Production Example 1 except that the distillation conditions were 148 to 158 ° C./0.5 mmHg, and an internal olefin (4) having 18 carbon atoms was obtained. The double bond distribution of the obtained internal olefin (4) is as follows: C1-position 0.8 mass%, C2-position 31.3 mass%, C3-position 22.9 mass%, C4-position 15.5 mass%, C5-position 10 The total of C8-position 7.2 mass%, C7-position 5.3 mass%, C8-position 9 was 6.2 mass%.
Next, an alkenyl succinic anhydride (d) was obtained in the same manner as in Production Example 1 except that the internal olefin (1) used in Production Example 1 was changed to the internal olefin (4). The average molecular weight of alkenyl succinic anhydride (d) determined from the acid value was 359.

Production Example 5
(Production of alkenyl succinic anhydride (e))
An internal olefin (5) having 8 carbon atoms was obtained in the same manner as in Production Example 1 except that 1-octanol was used as 1-octanol in Production Example 1. The double bond distribution of the obtained internal olefin (5) was 0.3 mass% at C1 position, 40.8 mass% at C2 position, and 58.9 mass% in total at C3 and C4 positions.
Next, an alkenyl succinic anhydride (e) was obtained in the same manner as in Production Example 1 except that the internal olefin (1) used in Production Example 1 was changed to the internal olefin (5). The average molecular weight of the alkenyl succinic anhydride (e) determined from the acid value was 224.

Production Example 6
(Production of alkenyl succinic anhydride (f))
Using propylene tetramer (manufactured by Shin Nippon Oil Co., Ltd., trade name: Light Tetramer), an alkylene compound (6) was obtained by fractional distillation under heating conditions of 183 to 208 ° C. Distribution of the obtained alkylene compound (6) is C ₉ H ₁₈ : 0.5% by mass, C ₁₀ H ₂₀ : 4% by mass, C ₁₁ H ₂₂ : 20% by mass, C ₁₂ H ₂₄ : 66% by mass, C ₁₃ H _26: 9 _{mass%, C 14} H 28: was 0.5% by mass.
Next, an alkenyl succinic anhydride (f) was obtained in the same manner as in Production Example 1 except that the internal olefin (1) used in Production Example 1 was changed to the alkylene compound (6). The average molecular weight of alkenyl succinic anhydride (f) determined from the acid value was 268.

[Production of polyester]
Production Examples 7, 9-15, 17-21
(Production of polyester L-1, H-1 to H-7, and polyester H-9 to H-13)
As shown in Tables 1-3, a raw material monomer of polyester other than trimellitic anhydride, an esterification catalyst and gallic acid, a dehydration tube equipped with a nitrogen introduction tube, a fractionation tube through which hot water of 98 ° C. is passed, a stirrer, and Place in a 5 liter four-necked flask equipped with a thermocouple, incubate at 180 ° C for 1 hour in a nitrogen atmosphere, then increase the temperature from 180 ° C to 210 ° C at a rate of 10 ° C / hour, then at 210 ° C for 10 hours. Condensed. Thereafter, trimellitic anhydride was added and reacted at 210 ° C. for 1 hour, and further reacted at 210 ° C. under reduced pressure of 10 kPa to the softening point shown in Tables 1 to 3 to obtain a polyester. The physical properties are shown in Tables 1-3.

Production Example 8
(Production of polyester L-2)
The raw material monomers of the polyester other than adipic acid and trimellitic anhydride shown in Table 1, the esterification catalyst and gallic acid were placed in a 5-liter four-necked flask equipped with a nitrogen inlet tube, a stirrer and a thermocouple, In a nitrogen atmosphere, the temperature was raised to 235 ° C., and then polycondensed at 235 ° C. for 6 hours. Thereafter, the temperature was lowered to 180 ° C., adipic acid and trimellitic anhydride were added, the temperature was raised to 210 ° C. at 10 ° C./hour, and then reacted at 210 ° C. for 1 hour. Thereafter, the reaction was carried out at 210 ° C. under a reduced pressure of 10 kPa until the softening point shown in Table 1 to obtain a polyester. The physical properties are shown in Table 1.

Production Example 16
(Production of polyester H-8)
The raw material monomer of polyester other than trimellitic anhydride, esterification catalyst and gallic acid shown in Table 2 were put into a 5-liter four-necked flask equipped with a nitrogen inlet tube, a stirrer and a thermocouple, and under a nitrogen atmosphere. The temperature was raised to 235 ° C., and then polycondensed at 235 ° C. for 6 hours. Thereafter, the temperature was lowered to 210 ° C., trimellitic anhydride was added, and the mixture was reacted at 210 ° C. for 1 hour, and further reacted at 210 ° C. under a reduced pressure of 10 kPa until the softening point shown in Table 2 to obtain a polyester. Obtained. The physical properties are shown in Table 2.

[Production of aqueous dispersion of core resin particles]
Production Example 22
Into a 5 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen introduction tube, 600 g of methyl ethyl ketone was added, and 150 g of polyester L-1 produced in Production Example 7 was added at 60 ° C. Dissolved. A 20% by mass aqueous ammonia solution (pKa: 9.3) was added to the obtained solution so that the degree of neutralization was 100 mol% with respect to the acid value of the resin, and the mixture was stirred for 30 minutes to obtain a mixture. . Subsequently, 675 g of ion-exchanged water was added over 77 minutes. Next, while stirring at 250 r / min, methyl ethyl ketone was distilled off under reduced pressure at a temperature of 50 ° C. or lower, and then an anionic surfactant “Emar E27C” (polyoxyethylene lauryl ether sodium sulfate, manufactured by Kao Corporation, 16.7 g of a solid content (28% by mass) was mixed and completely dissolved. Thereafter, the solid concentration of the aqueous dispersion was measured, and ion exchange water was added to adjust the solid concentration of the aqueous dispersion to 20% by mass.

Production Example 23
An aqueous dispersion of resin particles was obtained in the same manner as in Production Example 22 except that the polyester used in Production Example 22 was changed to the polyester L-2 obtained in Production Example 8.

[Production of aqueous dispersion of resin particles for shell]
Production Examples 24-36
In Production Example 22, an aqueous dispersion of shell resin particles is obtained in the same manner as in Production Example 22 except that the polyester used is changed to polyesters H-1 to H-13 obtained in Production Examples 9 to 21. It was.

[Production of release agent dispersion]
Production Example 37
Heat 50 g of paraffin wax (Nippon Seiwa Co., Ltd., trade name: HNP0190, melting point: 85 ° C.), 5 g of cationic surfactant (trade name: Sanisol B50, manufactured by Kao Corporation) and 200 g of ion-exchanged water to 95 ° C. Then, the paraffin wax was dispersed using a homogenizer, and then dispersed with a pressure discharge type homogenizer to obtain a release agent dispersion liquid containing release agent particles having a solid content concentration of 20% by mass. The volume median particle size of the release agent particles was 550 nm.

[Production of colorant dispersion]
Production Example 38
50 g of copper phthalocyanine “ECB-301” (manufactured by Dainichi Seika Kogyo Co., Ltd.), 5 g of nonionic surfactant “Emulgen 150” (manufactured by Kao Corporation, polyoxyethylene lauryl ether) and 200 g of ion-exchanged water are mixed. A colorant dispersion containing colorant particles was obtained by dispersing for 10 minutes at 25 ° C. using a homogenizer. The volume median particle size (D ₅₀ ) of the colorant particles having a solid content concentration of 20% by mass was 120 nm.

[Production of charge control agent dispersion]
Production Example 39
50 g of a salicylic acid compound “Bontron E-84” (made by Orient Chemical Co., Ltd.) as a charge control agent, 5 g of “Emulgen 150” (made by Kao Corporation) and 200 g of ion-exchanged water are mixed as a nonionic surfactant, Glass beads were used and dispersed at 25 ° C. for 10 minutes using a sand grinder to obtain a charge control agent dispersion liquid containing charge control agent particles. The volume median particle size (D ₅₀ ) of the charge control agent particles having a solid content concentration of 20% by mass was 500 nm.

[Manufacture of toner for developing electrostatic image]
Example 1
300 g of the aqueous dispersion of core resin particles prepared in Production Example 22, 15 g of the release agent dispersion, 8 g of the colorant dispersion, and 2 g of the charge control agent dispersion are placed in a 3 L container, and an anchor type stirrer is used. Under stirring at 100 r / min (circumferential speed 31 m / min), 150 g of a 0.1% by mass calcium chloride aqueous solution was added dropwise at 20 ° C. over 30 minutes. Then, it heated up to 50 degreeC, stirring. When 3 hours had elapsed, aggregated particles (1) having a volume-median particle size of 5 μm were obtained. Thereafter, 45 g of the aqueous dispersion of shell resin particles prepared in Production Example 24 was added and dispersed by stirring to obtain aggregated particles (2) in which the shell resin particles were aggregated into aggregated particles (1). . Thereafter, a dilute solution obtained by diluting 4.2 g of an anionic surfactant “Emar E27C” (manufactured by Kao Corporation, solid content: 28% by mass) as a coagulation terminator with a dispersion of aggregated particles (2) with 37 g of deionized water. Was added to obtain an aggregate. Next, the temperature was raised to 80 ° C., and after maintaining at 80 ° C. for 1 hour from the time when the temperature reached 80 ° C., the heating was terminated. After forming fused particles by this, it is gradually cooled to 20 ° C., filtered through a 150 mesh (mesh opening 150 μm) wire mesh, suction filtered, sufficiently washed with ion-exchanged water, and then dried. To obtain toner particles. The obtained toner particles had a volume-median particle size (D ₅₀ ) of 5.1 μm.
To 100 parts by mass of toner particles, 0.5 part by mass of an external additive (hydrophobic silica, manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil R-972, number average particle size: 16 nm) is added. Coke Kogyo Co., Ltd., 3600 r / min (peripheral speed 31.7 m / sec) and mixing for 5 minutes to perform external additive treatment to obtain a toner (volume median particle size D ₅₀ = 5.1 μm). .

Examples 2-12 and Comparative Examples 1-5
A toner was obtained in the same manner as in Example 1 except that the type and amount of the aqueous dispersion of resin particles used in Example 1 were changed to the type and amount of the aqueous dispersion of resin particles shown in Table 4. . Table 4 shows the evaluation results of the obtained toner.

Comparative Example 6
In Example 1, a toner was obtained in the same manner as in Example 1 except that the release agent dispersion was not used. Table 4 shows the evaluation results of the obtained toner.

When Example 1 is compared with Comparative Examples 1 and 3 to 5, the toner of Example 1 containing polyester (H) obtained by polycondensation of alkenyl succinic acid represented by the general formula (1) in the shell portion. Compared to the toners of Comparative Examples 1 and 3 to 5 containing polyester obtained by polycondensation of other alkenyl succinic acid in the shell portion, low temperature fixability, heat resistant storage stability, hot offset resistance, and smear of printed matter It turns out that it is excellent in property.
A comparison of Examples 1 to 3 shows that when the mass ratio of the core part to the shell part (core / shell) is 100/15, the low-temperature fixability, the heat-resistant storage property, and the smearing property of the printed matter are excellent. .
When Examples 1, 4, and 12 are compared, a polyester obtained by polycondensation of a carboxylic acid component containing 10 mol% of alkenyl succinic acid represented by the general formula (1) and an alcohol component is used as a shell portion. It can be seen that the toner of Example 1 containing the toner has an excellent balance of low-temperature fixability, heat-resistant storage stability, hot-offset resistance, and smearability of the printed matter.
Comparing Example 1 and Example 11, the toner of Example 1 using a polyester obtained by polycondensation of an aliphatic diol (alcohol having a secondary hydroxyl group) having 2 to 6 carbon atoms in the core part. Is superior to the toner of Example 11 using a polyester obtained by polycondensation of an alkylene oxide adduct of bisphenol A, with excellent low-temperature fixability, heat-resistant storage stability, and smearability of printed matter.
Comparing Examples 10 and 12, the toner of Example 12 using a polyester obtained by polycondensation of an aliphatic diol (alcohol having a secondary hydroxyl group) having 2 to 6 carbon atoms in the shell portion, It can be seen that the toner of Example 10 using a polyester obtained by polycondensation of an alkylene oxide adduct of bisphenol A is superior in low-temperature fixability, heat-resistant storage stability, and smearability of printed matter.
When Examples 1, 5, 6 and Comparative Example 5 are compared, Example 1 in which the branched alkenyl group (R ¹ R ² CH—) of alkenyl succinic acid has 18 carbon atoms has a low temperature fixing property and heat resistant storage stability. It can be seen that it is excellent in hot offset resistance and smearing properties of the printed matter.
When Example 1 is compared with Example 7, the content of alkenyl succinic acid in which the carbon number of the linear alkenyl group of R ^{1 and} the linear alkyl group of R ^{2 in} the general formula (1) is 4 or more is included. It can be seen that the toner of Example 1 having a larger amount of toner has excellent low-temperature fixability, heat-resistant storage stability, hot offset resistance, and smearability of printed matter.
When Example 1 and Example 8 are compared, the toner of Example 1 using a polyester having 80 mol% of aromatic dicarboxylic acid as the carboxylic acid component in the shell portion is excellent in heat resistance storage and smearing properties of the printed matter. You can see that
When Example 1 and Example 9 are compared, the toner of Example 1 in which the acid value of the polyester in the shell part is 20.6 mgKOH / g is low temperature fixability, heat resistant storage stability, hot offset resistance, and It turns out that it is excellent in smear property. This is presumably because the polyester used in the shell part of Example 9 has a low acid value, and the emulsifiability when producing the aqueous dispersion of the resin particles for the shell is lowered, so that the inclusion property of the wax is lowered. .

Claims (8)

An electrostatic charge image developing toner containing core-shell particles as a binder resin,
The core part contains polyester (L) obtained by polycondensation of carboxylic acid component (L-ac) and alcohol component (L-al), and wax,
The shell part contains polyester (H) obtained by polycondensation of carboxylic acid component (H-ac) and alcohol component (H-al),
The carboxylic acid component (H-ac) contains at least one selected from alkenyl succinic acid represented by the following general formula (1) and alkyl succinic acid represented by the following general formula (2). The total content of one or more selected from the alkenyl succinic acid and the alkyl succinic acid in (H-ac) is 3 mol% or more,
A toner for developing an electrostatic charge image, wherein the total content of at least one selected from the alkenyl succinic acid and the alkyl succinic acid in the carboxylic acid component (L-ac) is less than 3 mol%.

(In the formula, R ¹ represents a linear alkenyl group having 2 or more carbon atoms, R ² represents a linear alkyl group having 2 or more carbon atoms, and R ³ and R ⁴ are each independently a linear alkyl group having 2 or more carbon atoms. The total carbon number of the branched alkenyl group represented by R ¹ R ² CH— and the branched alkyl group represented by R ³ R ⁴ CH— is each independently 9 to 24. X and Y Are each independently a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, or a group that is bonded to each other via an oxygen atom to form an acid anhydride.   The electrostatic image developing toner according to claim 1, wherein a mass ratio (core / shell) of the core part and the shell part is 100/5 to 100/60.   In the carboxylic acid component (H-ac), the total content of one or more selected from alkenyl succinic acid represented by the general formula (1) and alkyl succinic acid represented by the general formula (2) is 3 mol. The toner for developing an electrostatic charge image according to claim 1, wherein the toner is 1% or more and 20 mol% or less.   In the carboxylic acid component (H-ac), the content of the aromatic dicarboxylic acid is 50 mol% or more and 90 mol% or less, and the alcohol component (H-al) is an aliphatic diol having 2 to 6 carbon atoms. The toner for developing an electrostatic charge image according to claim 1, wherein the content is 60 mol% or more.   The alkenyl succinic acid is selected from an internal olefin obtained by dehydrating a primary aliphatic alcohol having 9 to 24 carbon atoms in the presence of a solid catalyst, maleic acid, maleic anhydride and fumaric acid 1 It is contained in an alkenyl succinic acid mixture obtained by combining more than one species by an ene reaction, and the alkyl succinic acid is contained in an alkyl succinic acid mixture obtained by hydrogenating the alkenyl succinic acid mixture. The toner for developing an electrostatic charge image according to any one of claims 1 to 4. In the general formula (1), the straight chain alkenyl group of R ^{1 and} the straight chain alkyl group of R ² both have 4 or more carbon atoms, and R ³ and R ⁴ in the general formula (2) In the carboxylic acid component (H-ac), the total content of alkyl succinic acid having both straight chain alkyl groups of 4 or more in the carboxylic acid component (H-ac) is the alkenyl succinic acid represented by the general formula (1) and the general The toner for developing an electrostatic charge image according to claim 1, wherein the toner is 10% by mass or more based on the total amount of the alkyl succinic acid represented by the formula (2).   In the carboxylic acid component (H-ac), which is a raw material monomer of the polyester (H) contained in the shell portion, the alkenyl succinic acid represented by the general formula (1) and the alkyl succinic acid represented by the general formula (2) Alkenyl succinic acid represented by the general formula (1) in the carboxylic acid component (L-ac), which is a raw material monomer of the polyester (L) contained in the core part, and a total content of at least one selected from acids And the difference from the total content of one or more selected from the alkyl succinic acid represented by the general formula (2) (shell part-containing mole number-core part-containing mole number) is 3 mol% or more and 20 mol% The electrostatic image developing toner according to claim 1, which is as follows. The method for producing a toner for developing an electrostatic image according to claim 1, comprising the following steps 1 to 3.
Step 1: Step of aggregating resin particles (X) containing polyester (L) and release agent particles containing wax in an aqueous medium to obtain aggregated particles (1) Step 2: In Step 1 Step of aggregating resin particles (Y) containing polyester (H) to the obtained aggregate particles (1) to obtain aggregate particles (2) Step 3: Aggregate particles (2) obtained in Step 2 Process of fusing to obtain core-shell particles