JP2016038449A - Electrostatic charge image development toner - Google Patents

Abstract

An electrostatic charge image developing toner having both low-temperature fixability and heat-resistant storage stability and excellent smearing properties, a method for producing the same, and a binder resin for toner.
A toner for developing an electrostatic image, comprising a polyester obtained by polycondensation of a carboxylic acid component containing alkenyl succinic acid and / or alkyl succinic acid and an alcohol component, and a wax, a method for producing the same, and Binder resin for toner.
[Selection figure] None

Description

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

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.
As the binder resin, a polyester resin excellent in low-temperature fixability is used. In order to further improve the performance, it is also considered to use a polyester resin having an alkyl side chain.

For example, Patent Document 1 discloses a toner having a step of forming a raw material component containing at least a polyester-containing binder resin in an aqueous medium or in a solution for the purpose of improving hydrolysis resistance, storage stability, and fixability. A polyester for electrophotographic toners is disclosed which is obtained by polycondensation of an alcohol component and a carboxylic acid component containing at least one selected from alkyl succinic acid and alkenyl succinic acid.
Patent Document 2 discloses a toner containing at least a binder resin, a colorant, a hydrocarbon wax, and a copolymer composition for the purpose of improving transparency in OHP, low-temperature fixability, and blocking resistance. The resin is a resin containing at least a polyester component, and in the endothermic curve at the time of temperature rise measured by DSC of the hydrocarbon wax, the maximum endothermic peak has a maximum value of 55 to 80 ° C., and the copolymer composition Is a graft copolymer of a copolymer and a polyolefin synthesized using one or more monomers selected from styrene monomers and (meth) acrylic monomers, and the polyolefin is obtained by DSC. In the endothermic curve at the time of temperature rise to be measured, the maximum endothermic peak has a maximum value of 90 to 130 ° C., and the density of the polyolefin is 90 to 0.95, and further includes a second resin different from the binder resin, and the second resin is a polyester resin, and a monomer having 10 or more carbon atoms as a constituent element of the second resin A toner having 40 or less alkyl groups or alkenyl groups is disclosed.

Further, in Patent Document 3, for the purpose of effectively preventing toner spent, in an electrostatic image developer comprising a toner and a carrier, the toner is a trivalent or higher polyvalent monomer, A binder resin comprising a polyester obtained by subjecting a monomer composition containing an aromatic dicarboxylic acid and an aliphatic dialcohol to a polycondensation reaction is contained, and the carrier has a resin coating layer on the surface of the core particles. Disclosed is an electrostatic image developer comprising a resin-coated carrier formed, wherein the resin-coated layer is formed by a dry method, and fluorinated carbon is dispersedly contained in the resin-coated layer. Yes.
Patent Document 4 contains a urethane compound in an electrophotographic toner composition containing at least a binder resin and a colorant for the purpose of improving low-temperature fixability and suppressing blocking under voids and high-temperature environments. An electrophotographic toner composition is disclosed.

JP 2007-248582 A JP 2003-84485 A JP-A-5-11495 JP-A-8-6287

As the speed of electrophotographic printing increases, it is necessary to fix with less energy at the time of printing. For this reason, the toner to be used is required to have fixability at a low temperature. 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, because wax has different physical properties and poor compatibility with resin, the wax bleeds out on the toner surface during toner production and storage, so that the storage stability of the toner in a high-temperature environment, so-called heat-resistant storage stability. Gets worse. In addition, the bleed-out wax may adhere to the fixing roller or the like during printing, or the image printed with the toner may be rubbed to cause the image to peel off and become smudged. There is a problem of doing.
An object of the present invention is to provide a toner for developing an electrostatic image having both low-temperature fixability and heat-resistant storage stability and excellent smearing property, a method for producing the same, and a binder resin for toner.

  The present inventors considered and considered that the factors that affect low-temperature fixability, heat-resistant storage stability and smearability are the state of the resin in the toner and the wax as the release agent. As a result, electrostatic charge image development with excellent low-temperature fixability, heat-resistant storage stability and smearing properties is achieved by incorporating a polyester obtained by polymerizing a specific branched alkenyl succinic acid and / or branched alkyl succinic acid into a toner and a wax. It was found that a toner for use was obtained.

That is, the present invention provides the following [1] to [3].
[1] Polyester obtained by polycondensation of a carboxylic acid component containing an alkenyl succinic acid represented by the following general formula (1) and / or an alkyl succinic acid represented by the following general formula (2) with an alcohol component And a toner for developing an electrostatic charge image, containing a wax.

(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] A toner binder resin comprising a polyester obtained by polycondensation of a carboxylic acid component containing the alkenyl succinic acid and / or the alkyl succinic acid and an alcohol component.
[3] Resin particles containing polyester obtained by polycondensation of a carboxylic acid component containing the alkenyl succinic acid and / or the alkyl succinic acid and an alcohol component, and release agent particles containing a wax. A method for producing a toner for developing an electrostatic charge image, comprising: a step I for obtaining an aggregate X comprising an aggregate X in an aqueous medium; and a step II for fusing the aggregate X.

  According to the present invention, it is possible to provide a toner for developing an electrostatic image having both low-temperature fixability and heat-resistant storage stability and excellent smearing property, a method for producing the same, and a binder resin for toner.

[Toner for electrostatic image development]
The electrostatic image developing toner of the present invention comprises a carboxylic acid component and an alcohol component containing an alkenyl succinic acid represented by the general formula (1) and / or an alkyl succinic acid represented by the general formula (2). Polyester obtained by polycondensation and wax.
Hereinafter, the “electrostatic image developing toner” may be simply referred to as “toner”. In addition, the “alkenyl succinic acid represented by the general formula (1)” may be referred to as “branched alkenyl succinic acid” in the present specification, and “the alkyl succinic acid represented by the general formula (2)”. This is sometimes referred to as “branched alkyl succinic acid”.

The reason why the toner for developing an electrostatic charge image of the present invention is excellent in low-temperature fixing property, heat-resistant storage property and smearing property is not clear, but is considered as follows.
The toner for developing an electrostatic image of the present invention contains a polyester having a portion derived from a specific branched alkenyl succinic acid and / or branched alkyl succinic acid, and a wax. The branched alkenyl succinic acid used in the present invention has a branched alkenyl group represented by R ¹ R ² CH—, and the branched alkyl succinic acid used in the present invention is represented by R ³ R ⁴ CH—. Having a branched alkyl group. Since the branched alkenyl group in the branched alkenyl succinic acid and the branched alkyl group in the branched alkyl succinic acid have one branched portion, a straight-chain alkenyl group having 2 or more carbon atoms or a straight-chain alkyl group having 2 or more carbon atoms is bifurcated. It takes the form of a shape.
Thus, it is considered that a structure having two straight-chain alkenyl groups having 2 or more carbon atoms or straight-chain alkyl groups having 2 or more carbon atoms strongly interacts with a wax having a hydrophobic hydrocarbon moiety. In addition, it is considered that the dispersibility of the wax in the resin can be improved, and that it is possible to hold the wax molecules once taken in. The toner thus obtained is considered to be excellent not only in low-temperature fixability but also in heat-resistant storage stability. Furthermore, it is considered that the wax is prevented from being detached from the toner and adhering to the fixing roller or the like at the time of fixing during printing, and the obtained printed matter is also excellent in smearing property.

(polyester)
The polyester used in the present invention is obtained by polycondensation of a carboxylic acid component containing a branched alkenyl succinic acid and / or a branched alkyl succinic acid with an alcohol component. In the present invention, polyester is used as a binder resin for toner.
The polyester used in the present invention may be an amorphous resin or a crystalline resin (crystalline polyester). Here, the crystallinity of a resin such as polyester is the crystallinity defined by the ratio between the softening point and the maximum endothermic peak temperature by a differential scanning calorimeter (DSC), that is, “softening point / maximum endothermic peak temperature”. Expressed by an index. Generally, when the crystallinity index exceeds 1.4, the resin is amorphous, and when it is less than 0.6, the crystallinity is low and there are many amorphous portions. In the present invention, “crystalline polyester” refers to a polyester having a crystallinity index of 0.6 to 1.4, preferably 0.8 to 1.2, more preferably 0.9 to 1.1. “Amorphous resin” refers to a resin having a crystallinity index greater than 1.4 or less than 0.6.
The above “maximum endothermic peak temperature” refers to the temperature of the peak on the highest temperature side among the endothermic peaks observed under the measurement method conditions described in the examples. If the maximum peak temperature is within 20 ° C. from the softening point, the maximum peak temperature is the melting point of the crystalline resin (crystalline polyester), and the peak with the difference from the softening point exceeding 20 ° C. is glass of amorphous resin. The peak is attributed to the transition.
The crystallinity of the polyester used in the present invention can be adjusted by the type and ratio of raw material monomers, production conditions (for example, reaction temperature, reaction time, cooling rate) and the like.

<Carboxylic acid component>
The carboxylic acid component that is a raw material monomer of the polyester used in the present invention contains an alkenyl succinic acid represented by the following general formula (1) and / or an alkyl succinic acid represented by the following general formula (2). From the viewpoint of further improving the low-temperature fixability of the toner, alkenyl succinic acid represented by the following general formula (1) is preferable. Branched alkenyl succinic acid and / or branched alkyl succinic acid 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 independently from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner and the smearability of the printed matter. It is 2 or more, preferably 3 or more, more preferably 4 or more, 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 and heat-resistant storage stability of the toner and the smearing property of the printed matter, the total carbon number of the branched alkyl group or branched alkenyl group is 9 or more, preferably 10 or more, more preferably 12 Or more, more preferably 14 or more, and 24 or less, preferably 22 or less, more preferably 18 or less.
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.

The branched alkenyl succinic acid is selected from internal olefin, maleic acid, maleic anhydride, and fumaric acid from the viewpoint of improving steric hindrance, improving low-temperature fixability of toner, heat-resistant storage stability, and smearability of printed matter. It is preferable that it is obtained by binding one or more of the above by an ene reaction, and from the viewpoint of ease of production, it is preferably obtained by binding an internal olefin and maleic anhydride by an ene reaction. . 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 any of an alcohol derived from petroleum and an alcohol derived from natural raw materials.
Naturally derived primary aliphatic alcohols include those made from coconut oil, palm oil, palm kernel oil, soybean oil, rapeseed oil, beef tallow, lard, tall oil, fish oil, and the like.
Examples of the naturally occurring primary aliphatic alcohol include 1-nonanol, 1-decanol, 1-dodecanol, 1-tetradecanol, 1-hexadecanol, 1-octadecanol, 1-eicosanol, 1 -Docosanol, 1-tetracosanol, etc. are mentioned.
As the solid catalyst, a solid acid catalyst is preferable from the viewpoint of increasing the reaction rate of the dehydration reaction.
From the viewpoint of increasing the reaction rate of the dehydration reaction, the solid acid catalyst preferably contains at least one element selected from aluminum, iron, and gallium, and more preferably contains aluminum. Specific solid acid catalysts are preferably γ-alumina and aluminum phosphate.
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 48% by mass or less from the viewpoint of improving the low-temperature fixability of the toner, heat-resistant storage stability, and smearability of the printed matter. Preferably it is 40 mass% or less, More preferably, it is 38 mass% or less, More preferably, it is 37 mass% or less. The lower limit of the content is preferably as small as possible, and is 0% by mass or more.

Any known method can be used to obtain a branched alkenyl succinic acid by utilizing an 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. Used (see JP-A-48-23405, JP-A-48-23404, US Pat. No. 3,374,285, etc.).
The ratio of the number of moles of internal olefin charged / the number of moles of at least one selected from maleic acid, maleic anhydride and fumaric acid is preferably 0.8 or higher, more preferably 0.9 or higher, and still more preferably 0.95. Or more, preferably 3 or less, more preferably 2 or less, and still more preferably 1.5 or less.

As described above, an alkenyl succinic acid mixture containing an alkenyl succinic acid represented by the 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 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.
The alkyl succinic acid represented by the formula (2) can be obtained by hydrogenating the alkenyl succinic acid represented by the formula (1), more preferably by hydrogenating the alkenyl succinic acid mixture. It is 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.
The content of the alkyl succinic acid represented by the 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 in the alkyl succinic acid mixture.

The alkenyl succinic acid in which both the linear alkenyl group of R ^{1 and} the linear alkyl group of R ² in Formula (1) have 4 or more carbon atoms, and the linear alkyl group of R ³ and R ⁴ in Formula (2) The total content of alkyl succinic acids each having 4 or more carbon atoms is an alkenyl represented by the formula (1) from the viewpoint of improving the low-temperature fixability of the toner, heat-resistant storage stability, and smearability of the printed matter. Preferably it is 10 mass% or more with respect to the total amount of a succinic acid and the alkyl succinic acid represented by Formula (2), More preferably, it is 35 mass% or more, More preferably, it is 40 mass% or more, More preferably, it is 50 mass%. Further, it is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 80% by mass or less.
The total carbon number of the branched alkenyl group represented by R ¹ R ² CH— in 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 linear alkyl R ^{3 R} 4 ^CH- total number of carbon atoms of the branched alkyl group represented by a 14 or more 24 or less R ³ or R ⁴ in alkenylsuccinic acid and wherein the number of carbon atoms is 6 or more (2) The total content of alkyl succinic acid having 6 or more carbon atoms in the group is an alkenyl represented by the formula (1) from the viewpoint of improving low-temperature fixability of toner, heat-resistant storage stability, and smearability of printed matter. Preferably it is 1 mass% or more with respect to the total amount of a succinic acid and the alkyl succinic acid represented by Formula (2), More preferably, it is 10 mass% or more, More preferably, it is 20 mass% or more, More preferably, it is 30 mass%. That's it, and Preferably 70 wt% 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 formula (1) or the alkyl group of R ² is 2 or less, and the carbon of the linear alkyl group of R ³ or R ⁴ in formula (2) The total content of alkyl succinic acid having a number of 2 or less is an alkenyl succinic acid represented by the formula (1) from the viewpoint of improving low-temperature fixability of toner, heat-resistant storage stability and smearability of printed matter. Preferably it is 60 mass% or less with respect to the total amount of the alkyl succinic acid represented by Formula (2), More preferably, it is 50 mass% or less, More preferably, it is 45 mass% or less, More preferably, it is 40 mass% or less, Furthermore, Preferably it is 30 mass% or less. The lower limit of the total content is preferably as small as possible, and is 0% by mass or more.

The total content of branched alkenyl succinic acid and branched alkyl succinic acid in the carboxylic acid component, which is a raw material monomer of the polyester of the present invention, improves the low-temperature fixability of toner, heat-resistant storage stability, and smearability of printed matter. From the viewpoint, it is preferably 3 mol% or more, more preferably 4 mol% or more, still more preferably 5 mol% or more, and preferably 50 mol% or less, more preferably 30 mol% or less, still more preferably 20 mol%. % Or less.
Examples of the carboxylic acid component used in addition to the branched alkyl succinic acid and the branched alkenyl succinic acid include dicarboxylic acid and trivalent or higher polyvalent carboxylic acid. Among them, dicarboxylic acid is preferable. More preferably, a carboxylic acid is used in combination. These carboxylic acid components 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 acid component 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.
The aliphatic carboxylic acid is preferably an aliphatic carboxylic acid having 2 to 18 carbon atoms from the viewpoint of improving low-temperature fixability and heat-resistant storage stability of the toner. The number of carbon atoms of the aliphatic dicarboxylic acid is preferably 2 or more, more preferably 3 or more, and preferably 18 or less, more preferably 6 or less, from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner. is there.
Aliphatic carboxylic 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 Among them, 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.
Examples of the trivalent to pentavalent aromatic carboxylic acid include trimellitic acid, 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid, and the like. Among them, the heat resistant storage stability of the toner is improved, and the image density of the printed matter is increased. From the viewpoint of improving, trimellitic acid is preferable.

<Alcohol component>
Examples of the alcohol component that is a raw material monomer of the polyester used in the present invention include aliphatic diols, aromatic diols, and trihydric or higher polyhydric alcohols. These alcohol components 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.
From the viewpoint of improving the low-temperature fixability of the toner, an aliphatic diol having 2 to 6 carbon atoms is preferable, and ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-pentanediol, 1,5 -At least one selected from the group consisting of pentanediol and 1,6-hexanediol is preferred, and 1,2-propanediol is more preferred.
The alcohol component contains an aliphatic diol, preferably an aliphatic diol having 2 to 6 carbon atoms in an amount of 80 mol% or more from the viewpoint of improving the low-temperature fixability of the toner, heat-resistant storage stability, and smearing properties of the printed matter. The content is preferably 90 to 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 a positive number, and the sum of x and y is 1 to 16, preferably 1.5 to 5.)

As the alkylene oxide adduct of bisphenol A represented by the above formula (I), specifically, a polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4- Hydroxyphenyl) propane polyoxyethylene adduct and the like.
Specific 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 viewpoint of molecular weight adjustment and physical property adjustment, the alcohol component may appropriately contain a monovalent alcohol, and the carboxylic acid component may appropriately contain a monovalent carboxylic acid compound.

<Molar ratio of alcohol component to carboxylic acid component>
The molar ratio of the alcohol component and the carboxylic acid component (carboxylic acid component / alcohol component), which is a raw material monomer for the polycondensation reaction, is preferably 0.50 or more, more preferably from the viewpoint of reactivity, molecular weight adjustment, and physical property adjustment. It is 0.7 or more, more preferably 0.85 or more, and 1.50 or less, more preferably 1.3 or less, and further preferably 1.15 or less.

<Physical properties of polyester>
The glass transition point of the polyester is preferably 50 ° C. or higher, more preferably 53 ° C. or higher, and still more preferably 55, from the viewpoint of improving the durability, low-temperature fixability and heat-resistant storage stability of the toner and improving the image density of the printed matter. It is preferably at least 70 ° C, more preferably at most 70 ° C, more preferably at most 68 ° C, and even more preferably at most 65 ° C.
The softening point of the polyester is preferably 60 ° C. or higher, more preferably 75 ° C. or higher, and still more preferably 90 ° C. or higher from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner and improving the image density of the printed matter. Moreover, it is preferably 140 ° C. or lower, more preferably 130 ° C. or lower, and further preferably 120 ° C. or lower.
In addition, when using 2 or more types of polyester mixed, the glass transition point and softening point are the values obtained by the method of an Example description as a mixture of 2 or more types of polyester, respectively.

Polyesters may be used alone or in combination of two or more, and two or more polyesters having different softening points from the viewpoint of improving low-temperature fixability of toner, heat-resistant storage stability, and smearability of printed matter. It is preferable to contain, and it is more preferable to contain two kinds of polyesters having different softening points by 5 ° C. or more.
Of the two types of polyesters having different softening points of 5 ° C. or more, when the polyester having a low softening point is polyester L and the polyester having a high softening point is polyester H, the softening point of polyester L is preferably 70 ° C. or more and less than 110 ° C. The softening point of H is preferably 110 ° C. or higher and 165 ° C. or lower. The mass ratio of the polyester L to the polyester H (L-form / H-form) is preferably 95/5 to 10/90, more preferably 95/5 to 60/40, still more preferably 90/10 to 60/40, Even more preferably, it is 90/10 to 70/30.
In the present invention, at least polyester L among polyester L and polyester H is preferably a polyester obtained by polycondensation of a carboxylic acid component containing a branched alkenyl succinic acid and / or a branched alkyl succinic acid and an alcohol component, More preferably, the polyester L and the polyester H are the polyesters.

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

The acid value of the polyester is preferably 5 mgKOH / g or more, more preferably 15 mgKOH / g or more, from the viewpoint of stabilizing the dispersed resin particles and making the toner having a small particle diameter a sharp particle size distribution, and heat resistant storage stability of the toner. More preferably, it is 20 mgKOH / g or more, preferably 40 mgKOH / g or less, more preferably 30 mgKOH / g or less, still more preferably 25 mgKOH / g or less.
From the same viewpoint as described above, the hydroxyl value of the polyester is preferably 1 mgKOH / g or more, more preferably 2 mgKOH / g or more, still more preferably 3 mgKOH / g or more, and preferably 70 mgKOH / g or less, more preferably 60 mgKOH. / G or less, more preferably 50 mgKOH / g or less.
The softening point, glass transition temperature, number average molecular weight, weight average molecular weight, acid value and hydroxyl value can be easily adjusted by adjusting the raw material monomer composition, molecular weight, catalyst amount, etc., or by selecting reaction conditions.

(Production method of polyester)
The polyester is obtained by a condensation polymerization reaction between an alcohol component and a carboxylic acid component. The polycondensation reaction is preferably performed in the presence of an esterification catalyst, and is more preferably performed in the presence of an esterification catalyst and a pyrogallol compound from the viewpoints of reactivity, molecular weight adjustment, and resin physical property adjustment.

<Esterification catalyst>
Examples of the esterification catalyst suitably used for the condensation polymerization include a titanium compound and a tin (II) compound having no Sn-C bond, and these may be used alone or in combination of two or more. it can.
As a titanium compound, the titanium compound which has a Ti-O bond is preferable, and the compound which has a C1-28 total carbon number alkoxy group, an alkenyloxy group, or an acyloxy group 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) is more preferable from the viewpoints of reactivity, molecular weight adjustment, and resin physical property adjustment. .
The abundance of the esterification catalyst is preferably 0.01 parts by mass or more, more preferably 100 parts by mass with respect to the total amount of alcohol component and carboxylic acid component, from the viewpoints of reactivity, molecular weight adjustment, and resin physical property adjustment. Is 0.1 parts by mass or more, preferably 1 part by mass or less, more preferably 0.6 parts by mass or less.

<Pyrogallol compound>
A pyrogallol compound has a benzene ring in which three hydrogen atoms adjacent to each other are substituted with a hydroxyl group, and pyrogallol, gallic acid, gallic acid ester, 2,3,4-trihydroxybenzophenone, 2,2 ′, Examples include benzophenone derivatives such as 3,4-tetrahydroxybenzophenone, catechin derivatives such as epigallocatechin and epigallocatechin gallate, and gallic acid is preferred from the viewpoint of reactivity.
The abundance of the pyrogallol compound in the condensation polymerization reaction is preferably 0.001 part by mass or more with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component subjected to the condensation polymerization reaction from the viewpoint of reactivity. Preferably it is 0.005 mass part or more, More preferably, it is 0.01 mass part or more, Preferably it is 1 mass part or less, More preferably, it is 0.4 mass part or less, More preferably, it is 0.2 mass part or less. is there. Here, the abundance of the pyrogallol compound means the total amount of the pyrogallol compound subjected to the condensation polymerization reaction.
The mass ratio of the pyrogallol compound to the esterification catalyst (pyrogallol compound / esterification catalyst) is preferably 0.01 or more, more preferably 0.02 or more, still more preferably 0.03 or more, from the viewpoint of reactivity. , Preferably 0.5 or less, more preferably 0.3 or less, still more preferably 0.1 or less.

The condensation polymerization reaction between the alcohol component and the carboxylic acid component can be performed, for example, in the presence of the esterification catalyst in an inert gas atmosphere at a temperature of 120 ° C. or higher and 250 ° C. or lower. The following is preferred.
For example, in order to increase the strength of the resin, it is preferable to add all monomers to the reaction system at once. In order to reduce the low molecular weight component, the divalent monomer is first reacted, and then the trivalent or higher monomer is added. 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.

(wax)
The toner for developing an electrostatic charge image of the present invention contains a wax as a release agent.
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. You may use a wax individually by 1 type or in combination of 2 or more types.
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 viewpoints of improving low-temperature fixability of the toner, improving heat-resistant storage stability and improving gloss of printed matter. Is 110 ° C. or lower, more preferably 105 ° C. or lower, and still more preferably 100 ° C. or lower.
The content of the wax is based on 100 parts by mass of the total amount of the polyester from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner and the smearing property of the printed matter, and improving the dispersibility in the resin. And preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more, still more preferably 2 parts by mass or more, still more preferably 3 parts by mass or more, and preferably 20 parts by mass or less, more Preferably it is 15 mass parts or less, More preferably, it is 10 mass parts or less.

[Method for producing toner for developing electrostatic image]
The method for producing the toner for developing an electrostatic charge image of the present invention is not particularly limited, and can be produced using either a melt pulverization method or a wet production method. Among these, the toner of the present invention obtains, in an aqueous medium, an aggregate X containing the polyester-containing resin particles and the wax-containing release agent particles from the viewpoint of smearing of the printed matter. It is preferably produced by a method having Step I and Step II of fusing the aggregate X.

(Process I)
Step I is a step of obtaining the aggregate X by aggregating the resin particles containing the polyester and the release agent particles containing the wax in an aqueous medium.
The particles constituting the aggregate X may include particles other than the resin particles containing polyester and the release agent particles containing wax.
In Step I, it is preferable to use an aqueous dispersion (a) obtained by dispersing resin particles containing polyester in an aqueous medium as a supply source of the resin particles containing polyester.
It is preferable to aggregate the resin particles in the aqueous dispersion (a) to obtain the aggregate X.
It is preferable to add a flocculant for efficient aggregation. In addition, aggregation may be performed after adding additives such as a coloring agent, a charge control agent, a release agent, a conductivity adjusting agent, a reinforcing filler such as a fibrous substance, an antioxidant, and an anti-aging agent. The additive can also be used as an aqueous dispersion.
Next, an aqueous dispersion and an additive are demonstrated.

<Aqueous dispersion>
This aqueous dispersion can be suitably obtained by a method including an emulsification step, preferably a phase inversion emulsification step, by adding an aqueous medium and, if necessary, a surfactant to polyester.
In addition, the aqueous dispersion is obtained by mixing polyester and an organic solvent to obtain a mixture (step 1), adding an aqueous medium to the mixture, and phase-inverting and emulsifying to obtain a crude dispersion of resin particles (step). 2) The organic solvent is distilled off from the crude dispersion to obtain an aqueous dispersion of resin particles (step 3), and the surfactant is mixed with the obtained aqueous dispersion (step 4). Thus, it can be suitably manufactured. However, Step 4 may be omitted, and Step 3 may be omitted without using the organic solvent of Step 1.
Next, steps 1 to 4 will be described.

[Step 1]
In step 1, polyester and an organic solvent are mixed to obtain a mixture.
From the viewpoint of improving the dispersibility of the amorphous polyester as the organic solvent, it 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), and isobutanol (21.5); acetone (20.3), methyl ethyl ketone (19.0), methyl Ketone solvents such as isobutyl ketone (17.2) and diethyl ketone (18.0); ether solvents such as dibutyl ether (16.5), tetrahydrofuran (18.6) and dioxane (20.5); Examples thereof include acetate solvents such as ethyl acetate (18.6) and isopropyl acetate (17.4). Among these, from the viewpoint of improving the dispersibility of the polyester, 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, and more. More preferred is methyl ethyl ketone.

  From the viewpoint of improving the dispersibility of the polyester, the mass ratio of the organic solvent to the polyester (organic solvent / polyester) is preferably 0.03 or more, more preferably 0.05 or more, and still more preferably 0.1 or more. Also, it is preferably 5 or less, more preferably 1.5 or less, still more preferably 1 or less, still more preferably 0.8 or less, and still more preferably 0.6 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; trimethylamine, ethylamine, diethylamine, triethylamine, triethanolamine, and tributylamine. Of the organic base. Among these, from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner and the smearing property of the printed matter, a neutralizing agent having a pKa of 12 or less is preferable, and a neutralizing agent having a pKa of 10 or less is preferable. More preferred is a neutralizing agent having a pKa of 8 or more from the same viewpoint. Of these, ammonia (pKa = 9.3) and triethylamine (pKa = 9.8) are preferable, and ammonia is more preferable.
From the same viewpoint, the neutralization degree of the polyester neutralizer is preferably 60 mol% or more, more preferably 70 to 100 mol%, still more preferably 80 to 100 mol%, and still more preferably 90 to 100 mol%. More preferably, it is 95-100 mol%. 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.
The said mixture can be obtained by mixing polyester mentioned above, the organic solvent, and the neutralizing agent as needed.
In the method for producing the mixture, the order of adding the respective raw materials is not limited, but it is preferable to mix the neutralizer with the polyester 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, and reducing the viscosity of the solution. 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 is preferably 0.5 hours or more, more preferably It is 1 hour or longer, preferably 5 hours or shorter, more preferably 3 hours or shorter.

[Step 2]
Step 2 is a step of adding a water-based medium and, if necessary, a surfactant to the above mixture, and phase inversion emulsifying to obtain a crude dispersion of resin particles.
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, an organic solvent that does not dissolve the resin is preferable from the viewpoint of preventing the toner from being mixed. Among these, alcohol-based organic solvents such as methanol, ethanol, isopropanol, and butanol can be preferably used.
From the viewpoint of improving the emulsion stability of the resin, the content of water in the aqueous medium is preferably 80% by mass or more, more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass, and 100% by mass. Even more preferred. 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 50 ° C. or higher, further preferably 60 ° C. or higher, and even more preferably 65 ° C. or higher, from the viewpoint of improving the emulsion stability of the resin. Also, it is preferably 90 ° C. or lower, more preferably 85 ° C. or lower, still more preferably 80 ° C. or lower, and still more preferably 75 ° C. or lower.
From the viewpoint of obtaining resin composition particles having a small particle diameter, the addition rate of the aqueous medium is preferably 0.1 parts by mass / min or more, more preferably 100 parts by mass or more with respect to 100 parts by mass of the polyester until phase inversion is completed. 0.5 parts by mass / min or more, more preferably 1 part by mass / min or more, still more preferably 3 parts by mass / min or more, still more preferably 4 parts by mass / min or more, and preferably 50 parts by mass or more. / Min or less, more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less. 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 150 parts by mass or more, and still more preferably 200 parts by mass with respect to 100 parts by mass of the polyester from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation process. Or more, more preferably 300 parts by mass or more, still more preferably 400 parts by mass or more, preferably 2000 parts by mass or less, more preferably 1500 parts by mass or less, still more preferably 1000 parts by mass or less, and still more preferably. Is 700 parts by mass or less, more preferably 500 parts by mass or less.
Also, from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation step, the aqueous medium is added so that the mass ratio of the aqueous medium to the organic solvent (aqueous medium / organic solvent) is 70/30 to 98/2. It is preferable to do. From this viewpoint, it is more preferably 80/20 or more, still more preferably 85/15 or more, more preferably 95/5 or less, still more preferably 90/10 or less.

Examples of the surfactant include nonionic surfactants, anionic surfactants, and cationic surfactants. Among these, from the viewpoint of dispersibility of the polyester, 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 the 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.
From the viewpoint of the dispersibility of the polyester and the emulsion stability of the resin, polyoxyethylene alkyl ethers and polyoxyalkylene alkyl ether sulfates are preferable among the surfactants, and polyoxyalkylene alkyl ether sulfates are more preferable.

[Step 3]
Step 3 is a step of obtaining an aqueous dispersion of resin particles by distilling off the organic solvent from the crude dispersion.
The method for removing the organic solvent is not particularly limited, and any method can be used. However, since it is dissolved in water, it is preferably distilled. 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 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 used while stirring. Further, from the viewpoint of maintaining the dispersion stability of the polyester, 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 and distill off. 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, it is preferable to distill off at a constant temperature and pressure.

[Step 4]
Step 4 is a step of mixing a surfactant with the obtained aqueous dispersion.
Specific examples and preferred examples of the surfactant to be added in Step 4 include the same as those mentioned in Step 2.
The amount of the surfactant added in Step 4 is the total amount of the surfactant added in Steps 1 to 4 from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner and the smearing property of the printed matter. The amount is preferably 50% by mass or more, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass, and still more preferably 99 to 100% by mass.
Further, the amount of the surfactant added in Step 4 is preferably 0.5 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 polyester from the same viewpoint. Further, it is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less.

When the surfactant is added, it is preferable to stir with a commonly used mixing and stirring device such as an anchor blade or an external circulation stirring device.
When a mixing stirring device such as an anchor blade is used, the peripheral speed of stirring is preferably 20 m / min or more, more preferably 40 m / min or more, still more preferably 60 m / min or more, and still more preferably, from the viewpoint of dispersibility. Is 80 m / min or more, preferably 200 m / min or less, more preferably 150 m / min or less, and still more preferably 100 m / min or less.
The temperature at the time of addition of the surfactant in step 4 is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, further preferably 20 ° C. or higher, from the viewpoint of dispersibility of the surfactant in water, etc. Preferably it is 50 degrees C or less, Preferably it is 40 degrees C or less, Preferably it is 35 degrees C or less.

The solid content concentration of the aqueous dispersion obtained through the production process of the aqueous dispersion including Step 1 to Step 4 is preferably 3 by appropriately adding water from the viewpoint of the stability of the dispersion and ease of handling. It is at least 5 mass%, more preferably at least 5 mass%, even more preferably at least 15 mass%, preferably at most 40 mass%, more preferably at most 30 mass%, still more preferably at most 25 mass%.
From the viewpoint of toner productivity, the volume median particle diameter (D ₅₀ ) of the resin particles containing polyester in the obtained aqueous dispersion (a) is preferably 50 nm or more, more preferably 70 nm or more, and still more preferably. Is 90 nm or more, more preferably 100 nm or more, still more preferably 110 nm or more, preferably 250 nm or less, more preferably 220 nm or less, still more preferably 200 nm or less, still more preferably 180 nm or less, and still more preferably 150 nm or less.

[Release agent particles]
As described above, the electrostatic image developing toner of the present invention contains a wax as a release agent. Therefore, in Step I, it is preferable to obtain the aggregate X by aggregating the release agent particles together with the resin particles (a). 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 mold release agent, optionally the surfactant, and the aqueous medium in advance using a mixer such as a homomixer or a ball mill.
As the aqueous medium, those used when obtaining the resin particles (a) are preferably used.

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 (a) can be used. From the viewpoint of improving the cohesiveness between the release agent particles and the resin particles, a cationic surfactant is preferable.
The content of the surfactant in the release agent dispersion is from the viewpoint of improving the dispersion stability of the release agent particles, improving the cohesiveness of the release agent particles at the time of toner preparation, and preventing release. Preferably it is 0.05 mass% or more, More preferably, it is 0.1 mass% or more, More preferably, it is 0.4 mass% or more, Preferably it is 5 mass% or less, More preferably, it is 3 mass% or less, More preferably Is 2% by mass or less.
From the same viewpoint, the content of the surfactant in the release agent dispersion is preferably 0.2 parts by mass or more, more preferably 1.0 parts by mass with respect to 100 parts by mass of the total release agent. More preferably, it is 2.0 parts by mass or more, preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less.

The solid content concentration of the release agent particle dispersion 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. In addition, it is preferably 50% by mass or less, more preferably 40% by mass or less, and further 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 preferably from the viewpoint of obtaining uniform agglomerated particles in the subsequent agglomeration process, from the viewpoint of improving the low temperature fixability and heat resistant storage stability of the toner and improving the smearing property of the printed matter. It is 100 nm or more, more preferably 200 nm or more, further preferably 300 nm or more, preferably 1000 nm or less, more preferably 800 nm or less, still more 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 the particle size distribution of the toner, heat resistant storage stability and gloss of printed matter, an inorganic flocculant is preferable, and an inorganic metal salt is particularly preferable.
Examples of the inorganic metal salt include at least one of sodium sulfate, sodium chloride, calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, and aluminum chloride, preferably calcium chloride. The valence of the central metal of the inorganic metal salt is preferably divalent or higher from the viewpoint of the particle size distribution of the toner, heat resistant storage stability, and gloss of the printed matter.
When the flocculant is added, the addition amount is preferably based on 100 parts by mass of the resin particles containing polyester from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner and improving smearing properties of the printed matter. 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, further preferably 0.01 parts by mass or more, still more preferably 0.1 parts by mass or more, and still more preferably 0.2 parts by mass or more. Moreover, it is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, further preferably 1 part by mass or less, still more preferably 0.8 parts by mass or less, and still more preferably 0.5 parts 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 the addition.

In the aggregation step, the solid content concentration in the system is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more, 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.
In the coagulation step, from the viewpoint of uniformly dispersing the coagulant and causing uniform coagulation, the temperature during addition of the coagulant is preferably 10 ° C or higher, more preferably 15 ° C or higher, and further preferably 18 ° C or higher. In addition, it is preferably 40 ° C. or lower, more preferably 35 ° C. or lower, and further preferably 30 ° C. or lower. The holding temperature after adding the flocculant is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, still more preferably 47 ° C. or higher, preferably 65 ° C. or lower, more preferably 60 ° C. or lower, still more preferably. Is 55 ° C. or lower.
After aggregation, an aggregation terminator may be added as necessary. In addition, when using an aggregation terminator, it is preferable to use a surfactant as the aggregation terminator, and it is more preferable to use an anionic surfactant. Of the anionic surfactants, it is more preferable to use at least one selected from the group consisting of alkyl ether sulfates, alkyl sulfates, and linear alkylbenzene sulfonates, and it is more preferable to use alkyl ether sulfates. .

<Colorant>
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, Indigo dyes, phthalocyanine, aniline black, polymethine, triphenylmethane dyes, diphenylmethane dyes, thiazine, and include various dyes of thiazole, and the like. These can be used alone or in combination of two or more.
From the viewpoint of improving the image quality, the amount of the colorant added is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and still more preferably with respect to 100 parts by mass of the resin particles containing polyester. 1.0 parts by mass or more, more preferably 2.0 parts by mass or more, 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 5 parts by mass. It is below mass parts.
This 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-based azo dyes, iron-based azo dyes, aluminum-based azo dyes, and salicylic acid metal complexes. Various charge control agents may 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 0.3 parts by mass with respect to 100 parts by mass of the resin particles containing polyester from the viewpoint of improving the image quality. Part or more, more preferably 0.5 part by weight or more, still more preferably 0.6 part by weight or more, and preferably 8 parts by weight or less, more preferably 7 parts by weight or less, still more preferably 5 parts by weight or less. More preferably, it is 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 300 nm or more, and preferably 800 nm or less, more preferably 500 nm or less.

(Process II)
Step II is a step of fusing the aggregate X.
The temperature in the system in Step II improves the target toner particle size, particle size distribution, shape control and particle fusing property, low-temperature fixability of toner, heat-resistant storage stability, and smearability of printed matter From the viewpoint of making it, it is preferably 70 ° C. or higher, more preferably 75 ° C. or higher, and preferably 100 ° C. or lower, more preferably 90 ° C. or lower. The stirring speed is preferably a speed at which the aggregated particles do not settle.

<Post process>
By appropriately subjecting the fused particles obtained in step II to a solid-liquid separation step such as filtration, a washing step, and a drying step, the electrostatic image developing toner of the present invention can be suitably obtained.
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 adjusted to 1.5% by mass or less, more preferably 1.0% by mass or less, from the viewpoint of chargeability.
An external additive may be added to the obtained toner 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 diameter of the external additive is preferably 4 nm or more, more preferably 8 nm or more, and preferably 200 nm or less, more preferably 50 nm or less, from the viewpoint of the fluidity of the toner.
When the external additive is added, the addition amount is preferably 0 with respect to 100 parts by mass 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. .1 part by mass or more, more preferably 0.2 part by mass or more, further preferably 0.5 part by mass or more, still more preferably 1 part by mass or more, and preferably 8 parts by mass or less, more preferably 5 parts by mass. It is not more than part by mass, more preferably not more than 4 parts by mass, still more preferably not more than 3 parts by mass.

When the electrostatic image developing toner of the present invention is produced by a kneading and pulverizing method, for example, it includes a step of melt-kneading at least a raw material containing polyester and wax, and a step of pulverizing the obtained kneaded product. It is preferable.
The method for producing the toner by the kneading and pulverization method is not particularly limited. For example, polyester, wax, and a colorant used as necessary are mixed uniformly with a mixer such as a ball mill, and then sealed. Step of melt kneading with a kneader, single-screw or twin-screw extruder, etc., and this melt-kneaded product is pulverized with a jet pulverizer such as a fluidized bed jet mill and an airflow jet mill, a mechanical pulverizer such as a turbo mill, etc. And a step of cooling as necessary before the pulverization and a classification as necessary after the pulverization. For the cooling, pulverization and classification, any of the methods usually performed in the melt pulverization method can be used. An external additive may be added to the toner obtained by the kneading and pulverization method for the purpose of further improving the fluidity. The external additive is as described above.

(Physical properties of toner)
The volume-median particle diameter (D ₅₀ ) of the toner of the present invention is preferably 3.0 μm or more, more preferably from the viewpoint of improving low-temperature fixability, heat-resistant storage stability, and smearability of printed matter. 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, still more preferably 7.5 μm or less, and even more preferably. Is 7.0 μm or less, more preferably 5.5 μm or less.
Further, from the same viewpoint, the coefficient of variation (CV value) (%) in the particle size distribution of the toner is preferably 40% or less, more preferably 35% or less, and further preferably 30% or less. From the viewpoint of improving productivity, 5% or more is preferable, 10% or more is more preferable, and 15% or more is still more preferable. 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

In relation to the above-described embodiment, the present invention discloses the following toner for developing an electrostatic image, a method for producing the same, and a binder resin for toner.
[1] Polyester obtained by polycondensation of a carboxylic acid component containing an alkenyl succinic acid represented by the following general formula (1) and / or an alkyl succinic acid represented by the following general formula (2) with an alcohol component And a toner for developing an electrostatic charge image, containing a wax.

(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 alkenyl succinic acid in which both the straight-chain alkenyl group of R ^{1 and} the straight-chain alkyl group of R ² in Formula (1) have 4 or more carbon atoms, and R ³ and R ⁴ in Formula (2) The total content of alkyl succinic acids in which both straight chain alkyl groups have 4 or more carbon atoms is based on the total amount of alkenyl succinic acid represented by formula (1) and alkyl succinic acid represented by formula (2). The electrostatic charge image developing toner according to [1], wherein the toner is 10% by mass or more.
[3] The alkenyl succinic acid is obtained 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. Alkyl succinic acid mixture obtained by combining one or more selected from alkenyl succinic acid mixture obtained by ene reaction and obtained by hydrogenating said alkenyl succinic acid mixture The electrostatic image developing toner according to [1] or [2], which is contained therein.
[4] The total carbon number of the branched alkenyl group represented by R ¹ R ² CH— in 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 chain of R ² The total carbon number of the alkenyl succinic acid having 6 or more carbon atoms in the alkyl group and the branched alkyl group represented by R ³ R ⁴ CH— in 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 straight chain alkyl group is based on the total amount of alkenyl succinic acid represented by formula (1) and alkyl succinic acid represented by formula (2). The electrostatic charge image developing toner according to any one of [1] to [3], wherein the toner is 1% by mass or more.
[5] The alkenyl succinic acid in which the carbon number of the linear alkenyl group of R ¹ in formula (1) or the alkyl group of R ² is 2 or less, and the linear chain of R ³ or R ⁴ in formula (2) The total content of alkyl succinic acid having 2 or less carbon atoms in the alkyl group is 60% by mass with respect to the total amount of alkenyl succinic acid represented by formula (1) and alkyl succinic acid represented by formula (2). The electrostatic image developing toner according to any one of [1] to [4], wherein:
[6] The electrostatic image developing toner according to any one of [1] to [5], wherein the alkenyl succinic acid and the alkyl succinic acid are contained in the carboxylic acid component in an amount of 3 mol% to 50 mol%. .
[7] The toner for developing an electrostatic charge image according to any one of [1] to [6], containing an aliphatic diol having 2 to 6 carbon atoms in an alcohol component of 80 mol% or more.
[8] The electrostatic image developing toner according to any one of [1] to [7], further comprising a polyester having a softening point different from that of the polyester by 5 ° C. or more.

[9] Of the polyester and the polyester having a softening point different from that of the polyester by 5 ° C. or more, the content ratio (polyester L / polyester H) of the polyester L having a low softening point and the polyester H having a high softening point is 95 / The toner for developing an electrostatic charge image according to [8], which is 5 to 60/40.
[10] The electrostatic image developing toner according to any one of [1] to [9], wherein the wax has a melting point of 70 ° C. or higher and 110 ° C. or lower.
[11] The electrostatic charge image according to any one of [1] to [10], wherein the content of the wax is 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the total amount of polyester. Development toner.
[12] The electrostatic image developing toner according to any one of [1] to [11], wherein the wax is one or more selected from paraffin wax, ester wax, and amide wax.
[13] Polyester obtained by polycondensing a carboxylic acid component containing an alkenyl succinic acid represented by the following general formula (1) and / or an alkyl succinic acid represented by the following general formula (2) and an alcohol component. A binder resin for toner.

(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.)

[14] Polyester obtained by polycondensing a carboxylic acid component containing an alkenyl succinic acid represented by the following general formula (1) and / or an alkyl succinic acid represented by the following general formula (2) with an alcohol component. An electrostatic charge image comprising: a step I for obtaining an aggregate X comprising a resin particle containing a resin and a release agent particle containing a wax in an aqueous medium; and a step II for fusing the aggregate X. A method for producing a developing toner.

(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.)

[15] The method for producing a toner for developing an electrostatic charge image according to [14] above, wherein the alkenyl succinic acid used in Step I is obtained in Step A below.
Step A: An alkenyl succinate represented by the general formula (1) is formed by combining an internal olefin having 9 to 24 carbon atoms with one or more selected from maleic acid, maleic anhydride and fumaric acid by an ene reaction. Step 16 of obtaining an acid [16] The electrostatic image developing toner according to [15], wherein the internal olefin used in Step A has a content of olefin having a double bond at the 2-position of 48% by mass or less. Manufacturing method.
[17] The method for producing a toner for developing an electrostatic charge image according to the above [15] or [16], wherein the internal olefin used in the step A is obtained in the following step.
Step: Step of obtaining an internal olefin by dehydrating a primary aliphatic alcohol having 9 to 24 carbon atoms in the presence of a solid catalyst [18] The alkyl succinic acid used in Step I is obtained in Step B below. The method for producing an electrostatic charge image developing toner according to any one of [15] to [17].
Step B: Step of obtaining an alkyl succinic acid having an alkyl group represented by the general formula (2) by hydrogenating the alkenyl succinic acid obtained in the step A

  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 diameter 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 T.A. Instruments Japan Co., Ltd.), the temperature is reduced from room temperature (20 ° C.) to 10 ° C./min. The sample cooled to 0 ° C. was allowed to stand for 1 minute as it was, and then measured while raising the temperature 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) Melting point Using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of a sample was weighed into an aluminum pan and up to 200 ° C. The temperature was raised, and the temperature was cooled to 0 ° C. at a temperature lowering 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. Of the endothermic peaks observed, the temperature of the peak with the largest peak area was taken as the melting point.
(4) 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 The temperature was raised to 0 ° C., and the temperature was cooled to 0 ° C. at a rate of temperature drop 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.
(5) Crystallinity Index The ratio between the softening point and the maximum endothermic peak temperature measured as described above, that is, “softening point / maximum endothermic peak temperature” was calculated and used as the crystallinity index.

[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 Mn and the weight average molecular weight Mw 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 (manufactured by Sumitomo Electric Industries, Ltd., trade name: FP-200) 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.) Manufactured; 2.10 × 10 ³ , 7.00 × 10 ³ , 5.04 × 10 ⁴ ) were used as standard samples.
Measuring device: CO-8010 (trade name, manufactured by Tosoh Corporation)
Analytical column: GMH _XL + G3000H _XL (both trade names, manufactured by Tosoh Corporation)

[Volume Median Particle Size (D ₅₀ ) and CV Value of Toner]
The volume median particle size of the aggregated particles was 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 condition: 10 mg of a toner measurement sample is added to 5 mL of the dispersion, and dispersed for 1 minute with an ultrasonic disperser, and then 25 mL of electrolyte is 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 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 Scientific Laboratory), a sample 5 g was dried at a temperature of 150 ° C. and in a measurement mode 96 (monitoring time 2.5 minutes / variation width 0.05%). The solid content concentration (mass%) of the sample was measured.
Solid content concentration (% by mass) = (W / W0) × 100
W0: Sample mass before measurement (initial sample mass)
W: Sample weight after measurement (absolute dry weight)

[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” (manufactured by Mitsubishi Pencil Co., Ltd., width: 18 mm, JIS Z1522) is attached to the image portion of the printed matter, and the fixing is set at 30 ° C., separate from the fixing roll of the fixing machine. After passing through a roller, 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.

[Heat resistant storage stability of toner]
10 g of toner was placed in a 50 ml polycup and held for 24 hours in an environment of 55 ° C. and 60% RH. After that, on a powder tester (manufactured by Hosokawa Micron Co., Ltd.), 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. Then, 10 g of toner was placed on the sieve A and vibration was applied for 60 seconds. About the value ((alpha)) calculated from the following Formula, fluidity | liquidity was evaluated based on the following evaluation criteria. Larger numbers are preferable.

  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]
A 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 to obtain a layer thickness of 1.5 mg / cm ² . The unfixed image thus obtained was fixed at a temperature not lower than the minimum fixing temperature and at 180 ° C. at 300 mm / sec to obtain a printed matter.
The obtained printed material was loaded with a stainless steel weight of length × width × height = 3 cm × 3 cm × 6.5 cm and weight 500 g, and was 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 (a) to (e)]
The double bond position of the internal olefin was measured by gas chromatography (hereinafter abbreviated 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.
The apparatus and analysis conditions used for the measurement are as follows.
GC apparatus (trade name: HP6890, manufactured by HEWLETT PACKARD), column (trade name: Ultra-Alloy-1HT capillary column 30 m × 250 μm × 0.15 μm, manufactured by Frontier Laboratories), detector (hydrogen flame ion detector) (FID)), injection temperature 300 ° C., detector temperature 350 ° C., helium flow rate 4.6 mL / min.

[Distribution of alkylene compound (f)]
The distribution of the alkylene compound (f) was evaluated 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 (product name: Calcoal 8098, manufactured by Kao Corporation) in a flask equipped with a stirrer, and 1050 g of γ-alumina (STREM Chemicals, Inc.) as a solid acid catalyst 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 internal olefin (a) having a carbon number of 18% and an olefin purity of 100%. The double bond distribution of the obtained internal olefin (a) is as follows: C1-position 0.7 mass%, C2-position 16.9 mass%, C3-position 15.9 mass%, C4-position 16.0 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, in an autoclave made by 1 L Nitto High Pressure Co., Ltd., 542.4 g of internal olefin (a), 157.2 g of maleic anhydride, antioxidant Chelex-O (manufactured by SC Organic Chemical Co., Ltd., Triisooctyl phosphite) 0.4 g Then, 0.1 g of butylhydroquinone was charged as a polymerization inhibitor, and pressure 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 reaction 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 target 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 (b) 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 (b) 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 (a) used in Production Example 1 was changed to the internal olefin (b). 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 (c) 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 (c) is as follows: C1 position 0.3 mass%, C2 position 37.1 mass%, C3 position 35.2 mass%, C4, 5-position total is 27.4 mass %Met.
Next, alkenyl succinic anhydride (c) was obtained in the same manner as in Production Example 1, except that the internal olefin (a) used in Production Example 1 was changed to the internal olefin (c). 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 γ-alumina used in Production Example 1 was 10% by mass relative to the raw material alcohol [1-octadecanol (product name: Calcoal 8098, manufactured by Kao Corporation)], the reaction temperature was 280 ° C., and the reaction time was 10 An internal olefin (d) having 18 carbon atoms was obtained in the same manner as in Production Example 1 except that the time and distillation conditions were 148 to 158 ° C./0.5 mmHg. The double bond distribution of the obtained internal olefin (d) 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 (a) used in Production Example 1 was changed to the internal olefin (d). 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 (e) 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. In the resulting double bond distribution of the internal olefin (e), the C1 position was 0.3% by mass, the C2 position was 40.8% by mass, and the total of the C3 and C4 positions was 58.9% by mass.
Next, alkenyl succinic anhydride (e) was obtained in the same manner as in Production Example 1 except that the internal olefin (a) used in Production Example 1 was changed to the internal olefin (e). 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))
By using propylene tetramer (trade name: “Light Tetramer” manufactured by Nippon Oil Corporation), fractionation was carried out under heating conditions of 183 to 208 ° C. to obtain an alkylene compound (f). Distribution of the obtained alkylene compound (f) 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 (a) used in Production Example 1 was changed to the alkylene compound (f). The average molecular weight of alkenyl succinic anhydride (f) determined from the acid value was 268.

[Production of polyester]
Production Examples 7-12 and 14-19
(Production of polyesters L-1 to L-6, L-8 to L-11, and polyesters H-1 to H-2)
The dehydration pipe | tube equipped with the fractionating pipe | tube which let the raw material monomer of polyester other than trimellitic anhydride, esterification catalyst, and gallic acid shown in Table 1-Table 3 and gallic acid pass the hot water of 98 degreeC, and stirrer And a 5-liter four-necked flask equipped with a thermocouple, kept at 180 ° C. for 1 hour in a nitrogen atmosphere, then heated from 180 ° C. to 210 ° C. at 10 ° C./hour, and then at 210 ° C. for 10 hours. Polycondensation was performed. Then, after trimellitic anhydride was added and reacted at 210 ° C. for 1 hour, the reaction was further carried out at 210 ° C. under a reduced pressure of 10 kPa to the softening point described in Tables 1 to 3 to obtain a polyester. . The physical properties are shown in Tables 1 to 3.

Production Example 13
(Production of polyester L-7)
The raw material monomer of polyester other than trimellitic anhydride, esterification catalyst and gallic acid shown in Table 1 were put into a 5-liter four-necked flask equipped with a nitrogen introduction tube, a stirrer and a thermocouple, and in a nitrogen atmosphere. The temperature was raised to 235 ° C., followed by condensation polymerization 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 to the softening point shown in Table 1, Obtained. The physical properties are shown in Table 1.

[Production of resin aqueous dispersion]
Production Example 20
Into a 3 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen introduction tube, 150 g of polyester L-1 obtained in Production Example 7 and 75 g of methyl ethyl ketone were charged, and 70 ° C. for 2 hours. And 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. . While maintaining at 70 ° C., 675 g of ion-exchanged water was added over 77 minutes while stirring at 280 r / min (peripheral speed 88 m / min), and phase inversion emulsification was performed to obtain a crude dispersion of resin particles. While maintaining the temperature at 60 ° C., methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion of resin particles. Thereafter, the aqueous dispersion was cooled to 30 ° C. while stirring at 280 r / min (peripheral speed 88 m / min), and then the anionic surfactant “Emar E27C” (polyoxyethylene lauryl ether sodium sulfate, Kao Corporation 16.7 g, 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 Examples 21-30
In Production Example 20, a resin aqueous dispersion was obtained in the same manner as in Production Example 20, except that the polyester used was changed to each of polyesters L-2 to L-11 obtained in Production Examples 8 to 17. .

Production Examples 31-32
In Production Example 20, a resin aqueous dispersion was obtained in the same manner as in Production Example 20, except that the polyester used was changed to each of polyesters H-1 to H-2 obtained in Production Examples 18 to 19. .

Production Example 33
In a flask equipped with a stirrer, 600 g of amorphous polyester L-1, 6 g of polyoxyethylene lauryl ether “Emulgen 150” (nonionic surfactant, manufactured by Kao Corporation), 15 mass% sodium dodecylbenzenesulfonate aqueous solution “ Neoperex G-15 "(anionic surfactant, manufactured by Kao Co., Ltd.) 40 g, 48 mass% potassium hydroxide aqueous solution 20 g is added, and the mixture is heated to 98 ° C. with stirring and melted, and mixed at 98 ° C. for 2 hours. Thus, a resin mixture was obtained.
Next, while stirring, 1088 g of deionized water was added dropwise at 98 ° C. at a rate of 6 g / min to obtain an emulsion. Next, the obtained emulsion was cooled to 25 ° C., and the obtained emulsion was passed through a 200 mesh (mesh 105 μm) wire mesh. Thereafter, deionized water was added so that the solid content of the resin particle dispersion was 20% by mass to obtain a resin aqueous dispersion.

Production Example 34
In Production Example 33, a resin aqueous dispersion was obtained in the same manner as in Production Example 33 except that the polyester used was changed to the polyester of polyester H-2 obtained in Production 19.

[Production of colorant dispersion]
Production Example 35
Mixing 50 g of copper phthalocyanine “ECB-301” (manufactured by Dainichi Seika Kogyo Co., Ltd.), 5 g of nonionic surfactant “Emulgen 150” (polyoxyethylene lauryl ether, manufactured by Kao Corporation) and 200 g of ion-exchanged water Then, the mixture was dispersed for 10 minutes at 25 ° C. using a homogenizer to obtain a colorant dispersion containing colorant particles. 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 release agent dispersion]
Production Example 36
Paraffin wax (manufactured by Nippon Seiwa Co., Ltd., trade name: “HNP0190”, melting point: 85 ° C.) 50 g, cationic surfactant (trade name: “Sanisol B50” manufactured by Kao Corporation) and ion-exchanged water 200 g was heated to 95 ° C., and the paraffin wax was dispersed using a homogenizer, and then dispersed with a pressure discharge type homogenizer, and a release agent dispersion containing release agent particles having a solid content concentration of 20% by mass. Got. The volume median particle size of the release agent particles was 550 nm.

[Production of charge control agent dispersion]
Production Example 37
50 g of 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. Then, 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
240 g of the resin aqueous dispersion of polyester L-1 obtained in Production Example 20, 60 g of the resin aqueous dispersion of polyester H-1 obtained in Production Example 31, and 8 g of the colorant dispersion obtained in Production Example 35 Then, 15 g of the release agent dispersion obtained in Production Example 36 and 2 g of the charge control agent dispersion obtained in Production Example 37 were placed in a 3 L container, and 100 r / min (peripheral speed 31 m / min) with an anchor-type stirrer. Min) was added dropwise at 20 ° C. over a period of 30 minutes. Then, it heated up to 50 degreeC, stirring. Aggregates x having a volume median particle size of 5 μm were obtained after 3 hours. Then, a dilute solution obtained by diluting 4.2 g of anionic surfactant “Emar E27C” (manufactured by Kao Corporation, solid content: 28% by mass) with 37 g of deionized water was added as an aggregation terminator. Obtained. 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. As a result, fused particles were formed, and then slowly cooled to 20 ° C., filtered through a 150 mesh (mesh 150 μm) wire mesh, suction filtered, and washed and dried to obtain toner particles. .

(External addition process)
Hydrophobic silica “NAX-50” (manufactured by Nippon Aerosil Co., Ltd., number average particle size 40 nm) 1.0 part by mass, hydrophobic silica “R972” (Nippon Aerosil Co., Ltd.) with respect to 100 parts by mass of the toner particles. Manufactured, number average particle size 16 nm) 0.6 parts by mass, titanium oxide “JMT-150IB” (manufactured by Teica Co., Ltd., number average particle size 15 nm) 0.5 parts by mass, ST, A0 equipped with a stirring blade 10 L A Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) was added and stirred at 3000 rpm for 2 minutes to obtain a toner. Table 4 shows the evaluation results of the obtained toner.

Examples 2-7 and Comparative Examples 1-4
The resin aqueous dispersion of polyester L-1 used in Example 1 was changed to the resin aqueous dispersion of polyesters L-2 to L11 obtained in Production Examples 21 to 30 as shown in Table 4, and Examples 1 except that the resin aqueous dispersion of polyester H-1 used in 1 was changed to the resin aqueous dispersion of polyester H-2 obtained in Production Example 32 as shown in Table 4. A toner was obtained. Table 4 shows the evaluation results of the obtained toner.

Example 8
As in Table 1, the resin aqueous dispersion of polyester H-1 used in Example 1 was changed to the resin aqueous dispersion of polyester H-2 obtained in Production Example 32 as shown in Table 4. The toner was obtained. Table 4 shows the evaluation results of the obtained toner.

Example 9
The resin aqueous dispersion of polyester L-1 used in Example 1 was changed to 180 g, and the resin aqueous dispersion of polyester H-1 used in Example 1 was a resin of polyester H-2 obtained in Production Example 32 A toner was obtained in the same manner as in Example 1 except that the aqueous dispersion was changed to 120 g. Table 4 shows the evaluation results of the obtained toner.

Comparative Example 5
The resin aqueous dispersion of polyester H-1 used in Example 1 was changed to the resin aqueous dispersion of polyester H-2 obtained in Production Example 32 as shown in Table 4, and the mold release used in Example 1 was used. A toner was obtained in the same manner as in Example 1 except that the agent dispersion was not used. Table 4 shows the evaluation results of the obtained toner.

Example 10
100 parts by mass of the polyester L-1 obtained in Production Example 7 and the polyester H-1 obtained in Production Example 18 in the proportions shown in Table 4, a negative charge control agent “Bontron E-81” (Orient Chemistry) 1 part by mass of Kogyo Kogyo Co., Ltd., 5 parts by mass of copper phthalocyanine “ECB-301” (manufactured by Dainichi Seika Kogyo Co., Ltd.), and paraffin wax (manufactured by Nippon Seiwa Co., Ltd., trade name: “HNP0190”) “Melting point: 85 ° C.) 2 parts by mass were sufficiently mixed with a Henschel mixer, and then melt kneaded at a roll rotation speed of 200 r / min and a heating temperature of 80 ° C. in a roll using a co-rotating twin screw extruder. The obtained melt-kneaded product was cooled, coarsely pulverized, then pulverized with a jet mill, and classified to obtain toner particles having a volume-median particle size (D ₅₀ ) of 8 μm.

(External addition process)
A toner was obtained by performing the same external addition process as in Example 1 on 100 parts by mass of the toner particles. Table 4 shows the evaluation results of the obtained toner.

Example 11
The polyester aqueous solution of polyester L-1 obtained in Production Example 20 of Example 1 was changed to the resin aqueous dispersion of polyester L-1 obtained in Production Example 33, and the polyester obtained in Production Example 31 was obtained. A toner particle was obtained in the same manner as in Example 1 except that the resin aqueous dispersion of H-1 was changed to the resin aqueous dispersion of polyester H-2 obtained in Production Example 34. The toner was obtained by performing the same external addition process as in Example 1 on the part. Table 4 shows the evaluation results of the obtained toner.

  From Table 4, it can be seen that the electrostatic image developing toners of the examples are all excellent in low-temperature fixability, heat-resistant storage properties and smearing properties as compared with the electrostatic image developing toners of the comparative examples.

  The electrostatic charge image developing toner of the present invention is excellent in low-temperature fixability, heat-resistant storage property and smearing property, and therefore can be suitably used as a toner used in electrophotography. According to the present invention, a toner having such characteristics can be produced efficiently.

Claims (10)

A polyester obtained by polycondensation of a carboxylic acid component containing an alkenyl succinic acid represented by the following general formula (1) and / or an alkyl succinic acid represented by the following general formula (2) and an alcohol component, and a wax: A toner for developing an electrostatic image, comprising:

(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 alkenyl succinic acid in which both the straight chain alkenyl group of R ^{1 and} the straight chain alkyl group of R ² in Formula (1) have 4 or more carbon atoms, and the straight chain alkyl of R ³ and R ⁴ in Formula (2) The total content of alkyl succinic acid having 4 or more carbon atoms in the group is 10 mass relative to the total amount of alkenyl succinic acid represented by formula (1) and alkyl succinic acid represented by formula (2). The toner for developing an electrostatic charge image according to claim 1, wherein the toner is at least%.   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 image according to claim 1, wherein the toner is for developing an electrostatic image. The total carbon number of the branched alkenyl group represented by R ¹ R ² CH— in 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 alkenyl succinic acid having 6 or more carbon atoms and the branched alkyl group represented by R ³ R ⁴ CH— in formula (2) has a total carbon number of 14 to 24 and a straight chain of R ³ or R ⁴ The total content of alkyl succinic acid having 6 or more carbon atoms in the alkyl group is 1 mass relative to the total amount of alkenyl succinic acid represented by formula (1) and alkyl succinic acid represented by formula (2). The electrostatic charge image developing toner according to claim 1, wherein the toner is an electrostatic charge image developing toner. An alkenyl succinic acid in which the carbon number of the linear alkenyl group of R ¹ in 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 formula (2) The total content of alkyl succinic acid having 2 or less carbon atoms is 60% by mass or less based on the total amount of alkenyl succinic acid represented by formula (1) and alkyl succinic acid represented by formula (2). The toner for developing an electrostatic charge image according to claim 1.   The electrostatic image developing toner according to claim 1, wherein the alkenyl succinic acid and the alkyl succinic acid are contained in the carboxylic acid component in an amount of 3 mol% to 50 mol%.   The toner for developing an electrostatic charge image according to any one of claims 1 to 6, comprising an aliphatic diol having 2 to 6 carbon atoms in an alcohol component of 80 mol% or more.   The electrostatic image developing toner according to claim 1, further comprising a polyester having a softening point different from that of the polyester by 5 ° C. or more. A toner comprising a polyester obtained by polycondensation of an alkenyl succinic acid represented by the following general formula (1) and / or a carboxylic acid component containing an alkyl succinic acid represented by the following general formula (2) and an alcohol component. Binder resin.

(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.) Contains a polyester obtained by polycondensation of an alkenyl succinic acid represented by the following general formula (1) and / or a carboxylic acid component containing an alkyl succinic acid represented by the following general formula (2) and an alcohol component. A toner for developing an electrostatic charge image, comprising: a step I for obtaining an aggregate X containing resin particles and a release agent particle containing a wax in an aqueous medium; and a step II for fusing the aggregate X. Manufacturing method.

(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.)