JP2015166810A - Manufacturing method of toner for development of electrostatic charge image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method for obtaining toner for development of an electrostatic charge image, which realizes all low-temperature fixability, heat-resistant storage, and hot offset resistance, and the toner for development of electrostatic charge image obtained by the method.SOLUTION: [1]Provided is a manufacturing method of toner for development of an electrostatic charge image including the following steps (1) to (3) of: (1) obtaining an aqueous dispersion liquid of resin particles I by mixing an aqueous dispersion liquid of resin particles A which have a number average particle diameter measured by an electron microscope of greater than or equal to 10 nm and less than 50 nm, and contain an amorphous polyester (a), with an aqueous dispersion liquid of resin particles C containing a crystalline polyester (c) to cause the particles to aggregate; (2) obtaining a dispersion liquid of resin particles II by mixing the aqueous dispersion liquid of the resin particles I obtained in step (1) with an aqueous dispersion liquid of resin particles B which contain an amorphous polyester (b) to cause the particles to aggregate; and (3) fusing the resin particles II obtained in step (2). [2] Provided is toner for development of an electrostatic charge image, which has a core and shell structure, the core being obtained by fusing the resin particles A which have a number average particle diameter measured by an electron microscope of greater than or equal to 10 nm and less than 50 nm and contain an amorphous polyester (a), with the resin particles C containing a crystalline polyester (C), and the shell being obtained by fusing the resin particles (B) containing the amorphous polyester (b) with the core.

Description

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

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 a method for obtaining a toner having a narrow particle size distribution and a small particle size in response to higher image quality, an emulsion aggregation method (aggregation coalescence) in which fine resin particles are aggregated and fused in an aqueous medium. The toner is manufactured by one method or a cohesive fusion method.

For example, Patent Document 1 discloses a surface active as a polycondensation catalyst in the presence of a polycondensation resin for the purpose of obtaining a resin particle dispersion that is stably emulsified and dispersed in an aqueous medium with low energy and improving toner properties. A step of polycondensation of a polycondensable monomer using an acid having an effect to obtain a polycondensation resin-containing material, and the polycondensation resin-containing material is dispersed in an aqueous medium, and the median diameter of the resin particles is 0.00. There is disclosed a method for producing a resin particle dispersion for an electrostatic charge image developing toner, comprising a step of obtaining a resin particle dispersion having a particle size of from 0.5 μm to 2.0 μm.
Patent Document 2 discloses core particles containing a binder resin and a colorant for the purpose of improving heat storage properties, low-temperature fixability, and filming resistance and suppressing the occurrence of image defects, and the core particles. An electrostatic charge image developing toner having a shell layer covering the surface, wherein the binder resin includes at least one of a crystalline polyester resin and an amorphous resin, and the shell layer has a volume average particle diameter. Including amorphous resin fine particles having a glass transition temperature of 65 ° C. or higher, and the content of the amorphous resin fine particles is in the range of 5 to 25% by weight with respect to the weight of the core particles. Disclosed is a featured toner for developing electrostatic images.

JP 2006-323126 A Japanese Patent Laid-Open No. 2007-3840

In order to increase the speed of electrophotographic printing, there is a need for a toner having a low temperature fixability that can be fixed with less energy. In order to realize such low-temperature fixability, a toner containing a crystalline polyester having a characteristic that the viscosity rapidly decreases at the melting point has been studied as a binder resin. However, since this crystalline polyester is exposed to the toner surface or compatible with the amorphous resin used at the same time, the storage stability when stored at a high temperature, that is, the heat-resistant storage stability is reduced, or the offset is high at high temperatures. There was a problem that occurred. For example, attempts have been made to improve by using a core-shell structure as in the above-mentioned patent document, but these toners cannot sufficiently meet the requirements.
The present invention provides a production method capable of obtaining a toner for developing an electrostatic image capable of achieving both low-temperature fixability, heat resistant storage stability and hot offset resistance, and a toner for developing an electrostatic image obtained by the method. This is the issue.

  The present inventor considered that the factors that affect the low-temperature fixability, the heat-resistant storage stability and the hot-offset resistance in the core-shell type toner depend on the formation state of the core portion. Low temperature fixability by agglomerating resin particles containing amorphous polyester and resin particles containing crystalline polyester to form a core, and further aggregating and fusing the resin particles containing amorphous polyester In addition, it has been found that an electrostatic charge image developing toner excellent in heat-resistant storage stability and hot offset resistance can be obtained.

That is, the present invention provides the following [1] and [2].
[1] A method for producing an electrostatic charge image developing toner, comprising the following steps 1 to 3.
Step 1: An aqueous dispersion of resin particles A containing amorphous polyester (a) having a number average particle diameter measured by an electron microscope of 10 nm to 50 nm and resin particles C containing crystalline polyester (c) Step of mixing and aggregating the aqueous dispersion to obtain an aqueous dispersion of resin particles I Step 2: An aqueous dispersion of resin particles I obtained in Step 1 and resin particles containing amorphous polyester (b) A step of mixing and aggregating the aqueous dispersion of B to obtain an aqueous dispersion of resin particles II Step 3: a step of fusing the resin particles II obtained in Step 2 [2] having a core and a shell, The core fuses resin particles A containing amorphous polyester (a) having a number average particle diameter measured by an electron microscope of 10 nm to 50 nm and resin particles C containing crystalline polyester (c). And the shell is An electrostatic image developing toner obtained by fusing resin particles B containing amorphous polyester (b).

  According to the present invention, a production method capable of obtaining a toner for developing an electrostatic charge image capable of achieving both low temperature fixability, heat resistant storage stability and hot offset resistance, and a toner for developing an electrostatic charge image obtained by the method are provided. Can be provided.

The method for producing an electrostatic charge image developing toner of the present invention includes the following steps 1 to 3.
Step 1: An aqueous dispersion of resin particles A containing amorphous polyester (a) having a number average particle diameter measured by an electron microscope of 10 nm to 50 nm and resin particles C containing crystalline polyester (c) Step of mixing and aggregating the aqueous dispersion to obtain an aqueous dispersion of resin particles I Step 2: An aqueous dispersion of resin particles I obtained in Step 1 and resin particles containing amorphous polyester (b) Step of mixing and aggregating the aqueous dispersion of B to obtain an aqueous dispersion of resin particles II Step 3: Step of fusing the resin particles II obtained in Step 2

The reason why the toner for developing an electrostatic charge image obtained by the production method of the present invention is excellent in low-temperature fixability, heat resistant storage stability and hot offset resistance is not clear, but can be considered as follows.
In the toner production method of the present invention, resin particles A containing amorphous polyester (a) having a very small particle size and resin particles C containing crystalline polyester (c) are mixed and agglomerated to form a toner core. Get. The resin particles A of the amorphous polyester (a) having a very small particle size are uniformly aggregated on the surface regardless of the shape of the resin particles C of the crystalline polyester (c), and are further hydrophilic. Since it has an ester structure, it is considered that it is easily plasticized by an aqueous medium and becomes a film. In the toner production method of the present invention, it is possible to suppress exposure of the crystalline polyester (c) to the surface by covering the core with a shell of resin particles B containing the amorphous polyester (b). Conceivable.
Furthermore, the resin particles A having a small particle size and containing an aqueous medium have a low affinity with the crystalline polyester (c) and can be fused even at a low temperature. It is considered that the low-temperature fixability can be improved while maintaining the hot offset resistance and the heat resistant storage stability.
The present invention will be described below.

[Step 1]
In step 1, an aqueous dispersion of resin particles A containing amorphous polyester (a) having a number average particle diameter measured by an electron microscope of 10 nm to 50 nm and resin particles C containing crystalline polyester (c). Are mixed and agglomerated to obtain an aqueous dispersion of resin particles I.

<Aqueous dispersion of resin particles A>
Resin particle A contains amorphous polyester (a).
The number average particle diameter of the resin particles A measured by an electron microscope is 10 nm or more and 50 nm or less from the viewpoint of low temperature fixability, heat resistant storage stability and hot offset resistance. By using resin particles having a particle size in this range, the resin particles can be easily fused even at low temperatures, and compatibility with the crystalline polyester (c) can be prevented.
The number average particle diameter of the resin particles A is preferably 10 nm or more, more preferably 20 nm or more, still more preferably 25 nm or more, and preferably 50 nm from the viewpoint of low-temperature fixability, heat resistant storage stability and hot offset resistance. Hereinafter, it is more preferably 40 nm or less, still more preferably 35 nm or less.

≪Amorphous polyester (a) ≫
The amorphous polyester (a) used in the present invention is preferably obtained by condensation polymerization of an alcohol component containing an alkylene oxide adduct of bisphenol A and an acid component, for example.
In the present invention, the amorphous polyester is defined by the ratio of the softening point and the maximum endothermic peak temperature (softening point (° C.) / Maximum endothermic peak temperature (° C.)) in the measurement method described in the examples described later. The polyester has a crystallinity index of greater than 1.3 or less than 0.6, preferably greater than 1.3 and 4 or less, more preferably 1.5 or more and 3 or less.

(Alcohol component)
The alcohol component which is a raw material of the amorphous polyester (a) preferably contains an alkylene oxide adduct of bisphenol A.
The alkylene oxide adduct of bisphenol A is represented by the following formula (I).

(In the formula, RO and OR are oxyalkylene groups, R is preferably at least one selected from ethylene group and propylene group, and the average value of the sum of x and y per molecule is preferably 1 Or more, more preferably 1.5 or more, preferably 16 or less, more preferably 8 or less, still more preferably 4 or less.)

  Specific examples of the alkylene oxide adduct of bisphenol A represented by the formula (I) include 2,2-bis (4-hydroxyphenyl) propane polyoxypropylene adduct and 2,2-bis (4- Hydroxyphenyl) propane polyoxyethylene adduct and the like.

  The amount of the bisphenol A alkylene oxide adduct is preferably 60 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more in the alcohol component from the viewpoint of heat-resistant storage stability of the toner. For example, it is 100 mol% or less, More preferably, it is 100 mol%.

Examples of alcohol components other than the above include aliphatic diols having 2 to 6 carbon atoms, and trivalent or higher alcohols such as glycerin.
The aliphatic diol having 2 to 6 carbon atoms is preferably an aliphatic diol having 3 to 6 carbon atoms having at least one secondary hydroxyl group from the viewpoint of improving the low-temperature fixability of the toner. The aliphatic diol preferably has 3 to 4 carbon atoms from the viewpoint of improving the low-temperature fixability of the toner. Specific examples of the aliphatic diol having 3 or more and 6 or less carbon atoms having one or more secondary hydroxyl groups include 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, , 3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1, Examples include 4-hexanediol and 1,5-hexanediol. Among these, from the viewpoint of improving the low-temperature fixability of the toner, at least one selected from the group consisting of 1,2-propanediol and 2,3-butanediol is preferable, and 1,2-propanediol is more preferable. .

(Acid component)
The acid component that is a raw material of the amorphous polyester (a) preferably contains an aromatic carboxylic acid from the viewpoint of heat resistant storage stability of the toner.
The aromatic carboxylic acid is preferably an aromatic dicarboxylic acid.
The aromatic dicarboxylic acid is preferably isophthalic acid or terephthalic acid, more preferably terephthalic acid.
The aromatic carboxylic acid may contain a trivalent or higher aromatic carboxylic acid. The trivalent or higher valent aromatic carboxylic acid is preferably 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, or pyromellitic acid.

  In the acid component, the amount of the aromatic carboxylic acid is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 35 mol% or more, from the viewpoints of reactivity and heat-resistant storage stability of the toner. Preferably, it is 90 mol% or less, More preferably, it is 70 mol% or less, More preferably, it is 50 mol% or less.

Acid components other than aromatic carboxylic acids include fats such as oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, alkenyl succinic acid, etc. Aliphatic dicarboxylic acids; cycloaliphatic dicarboxylic acids and the like. Of these, aliphatic dicarboxylic acids are preferred from the viewpoint of low-temperature fixability and heat-resistant storage stability of the toner. Specifically, the aliphatic dicarboxylic acid is preferably at least one selected from fumaric acid, sebacic acid, adipic acid, and alkenyl succinic acid, more preferably fumaric acid or sebacic acid, more preferably fumaric acid. is there.
In the acid component, the amount of the acid component other than the aromatic carboxylic acid is preferably 5 mol% or more, more preferably 30 mol% or more, still more preferably 50 mol% or more, from the viewpoint of heat-resistant storage stability of the toner. Further, it is preferably at most 80 mol%, more preferably at most 70 mol%, further preferably at most 65 mol%.

The softening point of the amorphous polyester (a) is preferably 60 ° C. or higher, more preferably 75 ° C. or higher, further preferably 90 ° C. or higher, from the viewpoint of low-temperature fixability and heat-resistant storage stability of the toner. Is 120 ° C. or lower, more preferably 110 ° C. or lower, and still more preferably 105 ° C. or lower.
The glass transition temperature of the amorphous polyester (a) is preferably 30 ° C. or higher, more preferably 35 ° C. or higher, still more preferably 40 ° C. or higher, from the viewpoint of low-temperature fixability and heat-resistant storage stability of the toner. Preferably it is 110 degrees C or less, More preferably, it is 70 degrees C or less, More preferably, it is 50 degrees C or less.
The acid value of the amorphous polyester (a) is preferably 5 mgKOH / g or more, more preferably from the viewpoint of improving the dispersibility of the crystalline polyester in the aqueous dispersion, the low temperature fixability of the toner and the charging stability. Is 15 mgKOH / g or more, more preferably 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 viewpoint of reducing the compatibility with the shell, the number average molecular weight of the amorphous polyester (a) is preferably 1000 or more, more preferably 2000 or more, and still more preferably 3000 or more. The number average molecular weight is preferably 7000 or less, more preferably 5000 or less, and further preferably 4000 or less, from the viewpoint of improving the low-temperature fixability of the toner.

  From the viewpoint of reducing the compatibility with the shell, the weight average molecular weight of the amorphous polyester (a) is preferably 3000 or more, more preferably 6000 or more, and further preferably 7000 or more. The weight average molecular weight is preferably 10,000 or less, more preferably 9000 or less, and further preferably 8500 or less, from the viewpoint of improving the low-temperature fixability of the toner.

In order to improve the low-temperature fixability of the toner, the resin particles A may contain the crystalline polyester (a2) to the extent that the effects of the present invention are not impaired.
As crystalline polyester (a2), the crystalline polyester illustrated by the dispersion liquid of the resin particle C mentioned later can be used. The content of the crystalline polyester (a2) is preferably 0% by mass or more, more preferably 1% by mass or more, and still more preferably 5% by mass or more with respect to the resin particles A from the viewpoint of low-temperature fixability of the toner. In addition, from the same viewpoint, it is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.

In the polyester resin constituting the resin particle A, the content of the amorphous polyester (a) is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, and still more preferably. Is 100% by mass.
The polyester-based resin means an amorphous polyester and a crystalline polyester.

[Production method of polyester]
There is no restriction | limiting in particular in the manufacturing method of polyester, ie, said amorphous polyester (a), Although it can manufacture by a well-known method, polyester is obtained by the polycondensation reaction of an alcohol component and an 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) salt is more preferable from the viewpoints of reactivity, molecular weight adjustment and resin physical property adjustment. preferable.

  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.

[Polymerization inhibitor]
The polymerization inhibitor is not particularly limited, but 4-t-butylcatechol is preferable.

The polycondensation 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.
In addition, for example, all monomers are charged together to increase the strength of the resin, or divalent monomers are first reacted to reduce low molecular weight components, and then trivalent or higher monomers are added and reacted. The method is preferably used. It is also preferable to accelerate the reaction by reducing the pressure of the reaction system in the latter half of the polymerization.

[Method for Producing Aqueous Dispersion of Resin Particle A]
Although there is no restriction | limiting in the method of obtaining the aqueous dispersion liquid of the resin particle A, From a viewpoint of obtaining the resin particle with a narrow particle size distribution, it is the method of adding an aqueous medium to an amorphous polyester (a) and carrying out phase inversion emulsification. It is preferable to add a water-based medium to a solution containing the base-treated neutralized amorphous polyester (a) and an organic solvent, and perform phase inversion emulsification.
Hereinafter, the method will be described.
In the present specification, the “aqueous dispersion” means that the medium in which the resin is dispersed may contain a solvent such as an organic solvent, but water is preferably 50% by mass or more, more preferably 70% by mass or more. More preferably, it is 90% by mass or more, more preferably 99% by mass or more, and still more preferably 100% by mass. Further, hereinafter, when simply described as “resin”, it refers to both amorphous polyester and any other resin. Further, hereinafter, when simply described as “resin”, it refers to both amorphous polyester and any other resin.

  The resin aqueous dispersion containing the amorphous polyester (a) is prepared by mixing the amorphous polyester (a), an organic solvent and water, and if necessary, the crystalline polyester (a2), a basic substance, and a surfactant. After stirring, it can be suitably obtained by removing the organic solvent by distillation or the like. Preferably, after the amorphous polyester (a) and, if necessary, the crystalline polyester (a2) and the surfactant are dissolved in an organic solvent, water and further a basic substance are mixed if necessary. In addition, when stirring a mixture, arbitrary mixing stirring apparatuses, such as an anchor wing | blade, can be used.

The amorphous polyester (a) contained in the resin particle A is preferably treated with a basic substance.
The equivalent ratio of the basic substance to the acid of the amorphous polyester (a) is preferably 0.2 or more, more preferably 0.6 or more, still more preferably 0.8 or more, from the viewpoint of increasing the hydrophilicity of the resin. In addition, it is preferably 3.0 or less, more preferably 1.5 or less, and still more preferably 1.0 or less.
The product of the molar amount of acid groups of amorphous polyester (a) per gram of amorphous polyester (a) and the molar amount of basic groups of basic substance per gram of amorphous polyester (a) (mmol ² / G ² ) is preferably 0.10 or more, more preferably 0.11 or more, still more preferably 0.12 or more, and further preferably 0.13 or more, from the viewpoint of low-temperature fixability. From the viewpoint of property, it is preferably 0.20 or less, more preferably 0.15 or less, and still more preferably 0.14 or less.
The molar amount of the acid group of the resin such as the amorphous polyester (a) can be obtained by the following formula.
Molar amount of acid group (mmol / g) = resin acid value (mgKOH / g) / 56
Here, the acid value (mgKOH / g) of the resin refers to the acid value of the resin before the treatment with the basic compound, and is based on the measurement method described in the examples.
In addition, the molar amount of the basic group of the basic substance per 1 g of the resin such as the amorphous polyester (a) can be obtained by the following formula.
Molar amount of basic group (mmol / g) = [(addition mass of basic substance (g) × 1000) / equivalent of basic substance (g / mol)] / mass of resin (g)

  The molar amount of the basic group of the basic substance per 1 g of the amorphous polyester (a) is preferably 0.20 or more, more preferably 0.30 or more, and still more preferably 0.34, from the viewpoint of low-temperature fixability. From the viewpoint of heat-resistant storage stability, it is preferably 0.50 or less, more preferably 0.45 or less, and still more preferably 0.40 or less.

(Basic substance)
Examples of the basic substance include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide, and nitrogen-containing substances such as ammonia, trimethylamine, ethylamine, diethylamine, triethylamine, triethanolamine and tributylamine. A salt substance is preferable, and ammonia is more preferable from the viewpoint of dispersion stability and aggregation.

Further, the aqueous dispersion of the resin particles A contains a molar amount of acid groups of the amorphous polyester (a) per 1 g of the amorphous polyester (a) and a base of a basic substance per 1 g of the amorphous polyester (a). Amorphous polyester (a) was obtained by base treatment so that the product (mmol ² / g ² ) with the molar amount of the functional group was 0.10 or more and 0.20 or less. It is preferable to obtain the polyester (a) by dispersing it in an aqueous medium.

≪Phase inversion emulsification≫
A method of dispersing the amorphous polyester (a) in an aqueous medium is a method of adding a water-based medium to a solution containing the base-treated amorphous polyester (a) and an organic solvent and performing phase inversion emulsification. It is preferable.
The base-treated amorphous polyester (a) may be a mixture with a surfactant. The equivalent ratio of the basic substance to the acid of the amorphous polyester (a), the product of the molar amount of the acid group and the molar amount of the basic group, and the preferable range of the molar amount of the basic group are as follows: This is the same as the above range.

(Aqueous medium)
As the aqueous medium, those mainly containing water are preferable.
Examples of components other than water include aliphatic alcohols having 1 to 5 carbon atoms such as methanol, ethanol, isopropanol and butanol; dialkyl (carbon atoms 1 to 3) ketones such as acetone and methyl ethyl ketone; and water such as cyclic ethers such as tetrahydrofuran. Examples include organic solvents that dissolve. Among these, from the viewpoint of preventing mixing into the toner, alcohol-based organic solvents such as methanol, ethanol, isopropanol, and butanol that do not dissolve the resin can be more 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% by mass or more, still more preferably 95% by mass or more, and even more preferably 100% by mass. . The water is preferably deionized water or distilled water.

The temperature at which the aqueous medium is added is preferably 20 ° C. or higher, more preferably 30 ° C. or higher, further preferably 50 ° C. or higher, and still more preferably 60 ° C. or higher, from the viewpoint of improving the emulsion stability of the resin. Moreover, it is preferably 85 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 75 ° C. or lower.
From the viewpoint of obtaining resin composition particles having a small particle size, the addition rate of the aqueous medium is preferably 0.1 parts by mass / 100 parts by mass with respect to 100 parts by mass of the amorphous polyester (a) until the phase inversion is completed. Min. Or more, more preferably 0.5 parts by mass / min. Or more, still more preferably 1 part by mass / min. Or more, still more preferably 5 parts by mass / min. Or more, still more preferably 5.5 parts by mass / min. Also, preferably 50 parts by weight or less, more preferably 30 parts by weight or less, more preferably 20 parts by weight or less, still more preferably 10 parts by weight or less, and even more preferably 9 parts by weight. / Min 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, with respect to 100 parts by mass of the amorphous polyester (a), from the viewpoint of obtaining uniform resin particles in the subsequent aggregation step. More preferably, it is 200 mass parts or more, More preferably, it is 300 mass parts or more, More preferably, it is 400 mass parts or more, Preferably it is 2000 mass parts or less, More preferably, it is 1500 mass parts or less, More preferably, it is 1000 mass parts Part or less, more preferably 700 parts by weight or less, still more preferably 500 parts by weight or less.
Further, from the viewpoint of obtaining uniform resin 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. 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. Moreover, More preferably, it is 80 / 20-95 / 5, More preferably, it is 85 / 15-90 / 10.

(Organic solvent)
As the organic solvent, from the viewpoint of improving the dispersibility of the resin, when represented by a solubility parameter (SP value: POLYMER HANDBOOK THIRD EDITION 1989 by John Wiley & Sons, Inc), preferably 15.0 MPa ^1/2 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, more preferably 22.0 MPa ^1/2 or less.

Specific examples include the following organic solvents. The parentheses on the right side of the name of the next organic solvent are SP values, 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 toner particle size distribution, heat resistant storage stability, durability, and low-temperature fixability, a ketone solvent and an acetate solvent are preferable, and at least selected from the group consisting of methyl ethyl ketone, ethyl acetate, and isopropyl acetate. One is more preferable, and methyl ethyl ketone is more preferable from the viewpoint of heat resistant storage stability of the toner.

  The mass ratio of the organic solvent to the amorphous polyester (a) (organic solvent / amorphous polyester (a)) is preferably 0.03 or more from the viewpoint of heat resistant storage stability, durability and low-temperature fixability of the toner. More preferably, it is 0.05 or more, More preferably, it is 0.1 or more, Preferably it is 5 or less, More preferably, it is 1.5 or less, More preferably, it is 1 or less, More preferably, it is 0.8 or less, More More preferably, it is 0.6 or less.

(Surfactant)
Examples of the surfactant include nonionic surfactants, anionic surfactants, and cationic surfactants. Among these, from the viewpoint of resin dispersibility, nonionic surfactants and / or anionic surfactants are preferable, and anionic surfactants are more preferable.

Nonionic surfactants include polyoxyethylene alkylaryl ethers such as polyoxyethylene lauryl ether, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters such as polyethylene glycol monolaurate, oxyethylene / oxypropylene Examples thereof include block copolymers, and among these, polyoxyethylene alkyl ethers are preferred from the viewpoint of emulsion stability of the resin.
Examples of anionic surfactants include alkylbenzene sulfonates such as sodium alkylbenzene sulfonate, alkyl sulfates such as sodium alkyl sulfate, and polyoxyalkylene alkyl ether sulfates such as sodium polyoxyalkylene alkyl ether sulfate. Among these, from the viewpoint of emulsion stability of the resin, sodium alkylbenzenesulfonate 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 resin dispersibility and resin emulsion stability, polyoxyethylene alkyl ethers and polyoxyalkylene alkyl ether sulfates are preferable among the surfactants, and polyoxyalkylene alkyl ether sulfates are more preferable.

You may have the process of removing an organic solvent from the dispersion obtained by phase inversion emulsification after phase inversion emulsification.
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% 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 composite resin, 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 at the reduced pressure and distill it 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 composite resin, it is preferable to distill off at a constant temperature and pressure.

After the phase inversion emulsification or the step of removing the organic solvent, a step of mixing a surfactant with the aqueous dispersion obtained in these steps may be included.
The amount of the surfactant added in this step is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the amorphous polyester (a), from the viewpoint of low-temperature fixability and heat-resistant storage stability of the toner. More preferably, it is 1 mass part or more, More preferably, it is 1.5 mass part or more, Preferably it is 6 mass parts or less, More preferably, it is 5 mass parts or less, More preferably, it is 4.5 mass parts 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 solid content concentration of the aqueous dispersion of resin particles A used in the production method of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably It is 40 mass% or less, More preferably, it is 30 mass% or less, More preferably, it is 25 mass% or less.

<Aqueous dispersion of resin particles C>
Resin particle C contains crystalline polyester (c).
≪Crystalline polyester (c) ≫
The crystalline polyester means a polyester other than the amorphous polyester, and specifically, defined by a ratio between a softening point and a maximum endothermic peak temperature (softening point (° C) / maximum endothermic peak temperature (° C)). The polyester has a crystallinity index of 0.6 or more and 1.3 or less, preferably 0.8 or more and 1.2 or less, more preferably 0.9 or more and 1.1 or less. In crystalline polyester, the melting point is the maximum endothermic peak temperature.

The alcohol component which is a raw material for the crystalline polyester (c) preferably contains an aliphatic diol having 2 to 6 carbon atoms.
Of the aliphatic diols having 2 to 6 carbon atoms, aliphatic diols composed only of primary hydroxyl groups are preferred from the viewpoint of improving the low-temperature fixability of the toner.
Specific examples of the aliphatic diol having 2 to 6 carbon atoms include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6 -Hexanediol etc. are mentioned. Among these, 1,6-hexanediol and ethylene glycol are preferable from the viewpoint of low-temperature fixability of the toner, and 1,6-hexanediol is more preferable.

  Other aliphatic diols are preferably aliphatic diols having 3 to 6 carbon atoms having one or more secondary hydroxyl groups, and preferably 3 to 4 carbon atoms from the viewpoint of improving the low-temperature fixability of the toner. Specific examples of the aliphatic diol having 3 or more and 6 or less carbon atoms having one or more secondary hydroxyl groups include 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, , 3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1, Examples include 4-hexanediol and 1,5-hexanediol. Among these, from the viewpoint of improving the low-temperature fixability of the toner, preferably, at least one selected from the group consisting of 1,2-propanediol and 2,3-butanediol, more preferably 1,2-propane. Diol.

  The acid component of the crystalline polyester (c) is a free acid, an anhydride of these acids, and an alkyl ester having an alkyl group having 1 to 3 carbon atoms that can be used as a raw material for producing the polyester. It is preferable to include.

  The carboxylic acid component may contain one or more of dicarboxylic acid, monocarboxylic acid and trivalent or higher carboxylic acid.

Dicarboxylic acids include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, alkenyl succinic acid, and the like; phthalic acid And aromatic dicarboxylic acids such as isophthalic acid and terephthalic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. Of these, aliphatic dicarboxylic acids and aromatic dicarboxylic acids are preferred, and aliphatic dicarboxylic acids are more preferred from the viewpoints of low-temperature fixability and heat-resistant storage stability of the toner. Specifically, sebacic acid, fumaric acid, adipic acid and alkenyl succinic acid are preferable as the aliphatic dicarboxylic acid, and isophthalic acid and terephthalic acid are preferable as the aromatic dicarboxylic acid.
The aliphatic dicarboxylic acid is preferably from 2 to 18 carbon atoms, more preferably from 2 to 12 carbon atoms, still more preferably from 4 to 12 carbon atoms, preferably from the viewpoint of low-temperature fixability and heat-resistant storage stability of the toner. Is preferably sebacic acid, adipic acid, or sebacic acid from the viewpoint of improving the low-temperature fixability of the toner.

  As monocarboxylic acid, for example, aliphatic monocarboxylic acid is preferable, and as aliphatic monocarboxylic acid, carbon number of 8 or more and 22 or less is preferable, carbon number of 10 or more and 20 or less is more preferable, and stearic acid is preferable.

Examples of the trivalent or higher carboxylic acids include aromatic carboxylic acids such as 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, and pyromellitic acid.
Examples of other acids include unpurified rosin, purified rosin, and rosin modified with fumaric acid, maleic acid, acrylic acid, and the like.

The softening point of the crystalline polyester (c) is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, and still more preferably 70 ° C. or higher, from the viewpoint of low-temperature fixability and heat-resistant storage stability of the toner. Preferably it is 140 degrees C or less, More preferably, it is 100 degrees C or less, More preferably, it is 80 degrees C or less.
The melting point of the crystalline polyester (c) is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, still more preferably 70 ° C. or higher, and preferably 140 ° C. from the viewpoint of low-temperature fixability and heat-resistant storage stability of the toner. Hereinafter, it is more preferably 100 ° C. or less, and further preferably 80 ° C. or less.
The acid value of the crystalline polyester (c) is preferably 1 mgKOH / g or more, more preferably from the viewpoint of improving the dispersibility of the crystalline polyester in the aqueous dispersion, the low temperature fixability of the toner and the charging stability. It is 10 mgKOH / g or more, More preferably, it is 15 mgKOH / g or more, Preferably it is 40 mgKOH / g or less, More preferably, it is 35 mgKOH / g or less, More preferably, it is 30 mgKOH / g or less.

  The number average molecular weight of the crystalline polyester (c) is preferably 1000 or more, more preferably 2000 or more, and still more preferably 3000 or more, from the viewpoint of low-temperature fixability. The number average molecular weight is preferably 12000 or less, more preferably 10,000 or less, and still more preferably 7000 or less, from the viewpoint of improving the low-temperature fixability of the toner.

  The weight average molecular weight of the crystalline polyester (c) is preferably 3000 or more, more preferably 6000 or more, and further preferably 7000 or more, from the viewpoint of low-temperature fixability. The weight average molecular weight is preferably 50000 or less, more preferably 40000 or less, and still more preferably 20000 or less, from the viewpoint of improving the low-temperature fixability of the toner.

  The content of the crystalline polyester (c) is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 80% by mass with respect to the resin in the resin particles C from the viewpoint of low-temperature fixability of the toner. In addition, from the same viewpoint, it is preferably 100% by mass or less, and more preferably 100% by mass.

In order to improve the low-temperature fixability of the toner, the resin particles C may contain amorphous polyester (c2) to the extent that the effects of the present invention are not impaired.
As amorphous polyester (c2), the amorphous polyester illustrated by the dispersion liquid of the above-mentioned resin particle A can be used. The content of the amorphous polyester (c2) is preferably 0% by mass or more, more preferably 1% by mass or more, and further preferably 5% by mass or more with respect to the resin particles A from the viewpoint of low-temperature fixability of the toner. From the same viewpoint, it is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less.

  There is no restriction | limiting in particular in the manufacturing method of the said crystalline polyester (c), It can manufacture by a well-known method. The manufacturing method of crystalline polyester can be suitably performed in the same range as the above-mentioned polyester manufacturing method.

The polyester resin such as crystalline polyester (c) having an acid value contained in the resin particles C is preferably treated with a basic substance.
In the resin particle C, the equivalent ratio of the basic substance to the acid of the crystalline polyester (c) is preferably 0.1 or more, more preferably 0.2 or more, and still more preferably 0, from the viewpoint of increasing the hydrophilicity of the resin. .3 or more, preferably 3.0 or less, more preferably 1.5 or less, and still more preferably 1.0 or less.

The product of the molar amount of the acid group of the crystalline polyester (c) per 1 g of the crystalline polyester (c) and the molar amount of the basic group of the basic substance per 1 g of the crystalline polyester (c) (mmol ² / g ² ) is preferably 0.03 or more, more preferably 0.04 or more, still more preferably 0.05 or more, from the viewpoint of low-temperature fixability, and preferably 0.0. It is 10 or less, more preferably 0.07 or less, and still more preferably 0.06 or less.
The molar amount of the basic group of the basic substance per 1 g of the crystalline polyester (c) is preferably 0.05 or more, more preferably 0.10 or more, and still more preferably 0.15 or more, from the viewpoint of low-temperature fixability. From the viewpoint of heat-resistant storage stability, it is preferably 0.40 or less, more preferably 0.30 or less, and still more preferably 0.20 or less.
As said basic substance, the thing similar to the illustration by the resin particle A is used preferably.
There is no restriction | limiting in the method of obtaining the aqueous dispersion liquid of the resin particle C, The method similar to the illustration in the resin particle A is preferable.

  The solid content concentration of the aqueous dispersion of resin particles C is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 40% by mass or less, more preferably It is 30 mass% or less, More preferably, it is 25 mass% or less.

  The number average particle diameter of the resin particles C measured by an electron microscope is preferably 30 nm or more, more preferably 50 nm or more, and still more preferably 80 nm or more, from the viewpoints of low temperature fixability, heat resistant storage stability and hot offset resistance. Moreover, it is preferably 200 nm or less, more preferably 150 nm or less, and still more preferably 130 nm or less.

<Aqueous dispersion of resin particles I>
The aqueous dispersion of the resin particles I is obtained by mixing and aggregating the aqueous dispersion of the resin particles A containing the amorphous polyester (a) and the aqueous dispersion of the resin particles C containing the crystalline polyester (c). can get.
In addition, a reinforcing filler such as a colorant, a charge control agent, a conductivity adjusting agent, an extender pigment, a fibrous substance, or the like is further added to a mixed liquid obtained by mixing the dispersion liquid (hereinafter also simply referred to as “mixed liquid”). The additives may be aggregated after adding additives such as an antioxidant and an antioxidant. The additive can also be used as an aqueous dispersion.
Further, in the aggregating step, an aggregating agent can be added in order to effectively agglomerate.

(Release agent)
The release agent is preferably used as a release agent particle dispersion liquid dispersed in an aqueous medium from the viewpoint of dispersibility and cohesiveness with resin particles.
The addition amount of the release agent is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass, from the viewpoint of dispersibility in the resin with respect to 100 parts by mass of the total amount of resin used in the resin particles I. Part or more, more preferably 1 part by weight or more, still more preferably 3 parts by weight or more, preferably 10 parts by weight or less, more preferably 7 parts by weight or less, and even more preferably 5 parts by weight or less. .
Release agents include low molecular weight polyolefins such as polyethylene, polypropylene and polybutene; silicone waxes; fatty acid amides such as oleic acid amides; carnauba wax, rice wax, candelilla wax, wood wax, jojoba oil, etc. Plant waxes; animal waxes such as beeswax; mineral and petroleum waxes such as montan wax, paraffin wax, ozokerite, ceresin, microcrystalline wax, and Fischer-Tropsch wax. Among these, paraffin wax is preferable from the viewpoint of availability. These mold release agents can be used alone or in combination of two or more.

(Coloring agent)
There is no restriction | limiting in particular as a coloring agent, A well-known coloring agent is mentioned, According to the objective, it can select suitably. Specifically, carbon black, inorganic composite oxide, chrome yellow, hansa yellow, benzidine yellow, selenium yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brilliantamine 3B, Brilliantamine 6B, DuPont Oil Red, Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C, Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue (Copper Phthalocyanine), Phthalocyanine Green, and Malachite Various pigments such as green oxalate; acridine, xanthene, azo, benzoquinone, azine, anthraquino System, indigo, thioindigo, 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. When adding a colorant, the addition amount is preferably 0.1 parts by mass or more, more preferably 1 part by mass with respect to 100 parts by mass of the total amount of resin used in the resin particles I from the viewpoint of improving image quality. As mentioned above, More preferably, it is 3 mass parts or more, Preferably it is 20 mass parts or less, More preferably, it is 10 mass parts or less, More preferably, it is 5 mass parts or less.

(Charge control agent)
Examples of the charge control agent include a chromium-based azo dye, an iron-based azo dye, an aluminum azo dye, and a salicylic acid metal complex. A salicylic acid metal complex is preferable from the viewpoint of charge stability and availability of the toner. . Various charge control agents may be used alone or in combination of two or more. When the charge control agent is added, the amount added is preferably 0.1 parts by mass or more, more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the total amount of resin used for the resin particles I from the viewpoint of improving the image quality. 3 parts by mass or more, more preferably 0.5 parts by mass or more, preferably 8 parts by mass or less, more preferably 3 parts by mass or less, and still more preferably 1 part by mass or less.

(Flocculant)
As the aggregating agent, a quaternary ammonium salt cationic surfactant, polyethyleneimine, or the like is used in the organic system, and an inorganic metal salt, an inorganic ammonium salt, a divalent or higher metal complex, or the like is used in the inorganic system. .
Examples of the inorganic metal salt include metal salts such as sodium sulfate, sodium chloride, calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate; polyaluminum chloride, polyaluminum hydroxide, and Examples thereof include inorganic metal salt polymers such as calcium polysulfide. Examples of the inorganic ammonium salt include ammonium sulfate, ammonium chloride, and ammonium nitrate.
When the flocculant is added, the addition amount is preferably 60 parts by mass or less, more preferably 20 parts by mass or less, with respect to 100 parts by mass of the resin used in this step, from the viewpoint of environmental resistance characteristics of the toner. More preferred is less than or equal to parts by weight.
In order to cause uniform agglomeration, the flocculant is preferably added after being dissolved in an aqueous medium, and is preferably sufficiently stirred at the time of addition of the flocculant and after completion of the addition.

The solid concentration of the whole mixture used in step 1 is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, in order to cause uniform aggregation. Is 5% by mass or more.
From the same viewpoint, the temperature in the system in Step 1 is equal to or higher than “softening point of resin constituting tree seed particle I—75 ° C.” (temperature lower by 75 ° C. than the softening point, the same shall apply hereinafter) and tree seed particle I is configured. It is preferably below the softening point of the resin.
In the present invention, the softening point when two or more kinds of resins are used is a temperature obtained by weighted averaging the softening points of all the resins by the mass ratio.

  Note that additives such as a colorant and a charge control agent may be mixed in advance with the resin containing the amorphous polyester (a) when preparing the resin particles, and each additive is separately added in a dispersion medium such as water. A dispersion liquid may be prepared, mixed with the resin particles A containing the amorphous polyester (a) and other resin particles, and subjected to aggregation. When the additive is mixed in advance with the resin containing the amorphous polyester (a) when preparing the resin particles, it is preferable to melt-knead the resin containing the amorphous polyester (a) and the additive in advance. .

The volume median particle size of the resin particles I obtained by the above steps is 3 μm or more, preferably 3.5 μm or more, more preferably 4 μm or more, from the viewpoint of low temperature fixability and heat resistant storage stability. Further, from the viewpoint of low-temperature fixability and heat resistant storage stability, it is 8 μm or less, preferably 7 μm or less, more preferably 6 μm or less.
A volume average particle diameter is based on the measuring method as described in an Example.

<Pre-fusion>
After the aggregation, it is preferable to pre-fuse the obtained resin particles.
That is, after the agglomeration, an aggregation terminator is added as necessary, and then subjected to a preliminary fusing step to fuse the resin particles in the aqueous dispersion to obtain an aqueous dispersion of the resin particles I. It is a process to obtain.
In the preliminary fusion, the resin particles obtained by the aggregation can be fused by heating.
Here, the preliminary fusion means that a plurality of resin particles A existing inside the resin particles are fused to form a core.

The pre-fusion temperature is selected from the viewpoints of low-temperature fixability, heat-resistant storage stability and hot offset resistance, and from the viewpoint of target particle size, particle size distribution, shape control, and particle fusing property. The glass transition temperature is preferably 5 to 50 ° C lower, more preferably 10 to 40 ° C lower, and still more preferably 13 to 30 ° C lower.
Moreover, the temperature for pre-fusion is preferably 5 to 50 ° C. lower than the glass transition temperature of the amorphous polyester (a) from the viewpoint of low-temperature fixability, heat-resistant storage stability and hot offset resistance, and 10 to 40 The lower temperature is more preferable, and the lower temperature is more preferably 13 to 30 ° C.
Moreover, the temperature for pre-fusion is preferably 20 to 70 ° C. lower than the glass transition temperature (melting point) of the crystalline polyester (c) from the viewpoints of low-temperature fixability, heat-resistant storage stability and hot offset resistance, It is more preferably 30 to 60 ° C lower, and further preferably 35 to 50 ° C lower.
Specifically, from the same viewpoint, the fusing temperature is preferably 20 ° C. or higher, more preferably 25 ° C. or higher, more preferably 30 ° C. or higher, and preferably 50 ° C. or lower, more preferably 40 ° C. It is below ℃.

The stirring speed is preferably a speed at which the resin particles do not settle.
When an aggregation stopper is used, a surfactant is preferably used as the aggregation stopper, and an anionic surfactant is more preferably used from the viewpoints of availability and operability. Of the anionic surfactants, it is more preferable to use at least one selected from the group consisting of polyoxyalkylene alkyl ether sulfates, alkyl sulfates, and linear alkylbenzene sulfonates.

[Step 2]
In step 2, the aqueous dispersion of resin particles I obtained in step 1 and the aqueous dispersion of resin particles B containing amorphous polyester (b) are mixed and aggregated to obtain an aqueous dispersion of resin particles II. Get.

<Aqueous dispersion of resin particles B>
Resin particle B contains amorphous polyester (b).
≪Amorphous polyester (b) ≫
As the amorphous polyester resin (b), those obtained by polycondensation of an alcohol component and an acid component containing an alkylene oxide adduct of bisphenol A are preferable.

(Alcohol component)
The alcohol component which is a raw material of the amorphous polyester (b) contains an alkylene oxide adduct of bisphenol A.
The alkylene oxide adduct of bisphenol A is represented by the following formula (I).

(In the formula, RO and OR are oxyalkylene groups, and R is preferably at least one selected from an ethylene group and a propylene group, and the average value of the sum of x and y per molecule is preferably 1 or more. More preferably, it is 1.5 or more, preferably 16 or less, more preferably 8 or less, and further preferably 4 or less.)

  Specific examples of the alkylene oxide adduct of bisphenol A represented by the formula (I) include 2,2-bis (4-hydroxyphenyl) propane polyoxypropylene adduct and 2,2-bis (4- Examples thereof include a polyoxyethylene adduct of hydroxyphenyl) propane, and a polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane is preferable from the viewpoint of expressing the effects of the present invention.

  The amount of the alkylene oxide adduct of bisphenol A is preferably 60 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, in the alcohol component from the viewpoint of heat-resistant storage stability of the toner. More preferably, it is 95 mol% or more, Preferably it is 100 mol% or less, More preferably, it is 100 mol%.

Examples of alcohol components other than the above include aliphatic diols having 2 to 6 carbon atoms and trivalent or higher alcohols such as glycerin.
The aliphatic diol having 2 to 6 carbon atoms is preferably an aliphatic diol having 3 to 6 carbon atoms having one or more secondary hydroxyl groups from the viewpoint of improving low-temperature fixability of the toner. The aliphatic diol having 3 to 6 carbon atoms having one or more secondary hydroxyl groups preferably has 3 to 4 carbon atoms from the viewpoint of improving the low-temperature fixability of the toner. Specific preferred examples of the C3-C6 aliphatic diol having one or more secondary hydroxyl groups include 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 2, 3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4 -Hexanediol, 1,5-hexanediol, etc. are mentioned. Among these, from the viewpoint of improving the low-temperature fixability of the toner, at least one selected from the group consisting of 1,2-propanediol and 2,3-butanediol is preferable, and 1,2-propanediol is more preferable. .

(Acid component)
The acid component which is a raw material of the amorphous polyester (b) preferably contains an aromatic carboxylic acid from the viewpoint of heat resistant storage stability of the toner.
The aromatic carboxylic acid is preferably an aromatic dicarboxylic acid.
The aromatic dicarboxylic acid is preferably isophthalic acid or terephthalic acid, more preferably terephthalic acid.
The aromatic carboxylic acid may contain a trivalent or higher aromatic carboxylic acid. The trivalent or higher valent aromatic carboxylic acid is preferably 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, or pyromellitic acid.

In the acid component, the content of the aromatic carboxylic acid is preferably 50 mol% or more, more preferably 55 mol% or more, and still more preferably 60 mol% or more, from the viewpoint of heat-resistant storage stability of the toner. Is 100 mol% or less, more preferably 85 mol% or less, still more preferably 70 mol% or less.
In the acid component, the content of the aromatic dicarboxylic acid is preferably 50 mol% or more, more preferably 55 mol% or more, still more preferably 60 mol% or more, from the viewpoint of heat-resistant storage stability of the toner. , Preferably 90 mol% or less, more preferably 85 mol% or less, still more preferably 70 mol% or less.
In the acid component, the content of the trivalent or higher aromatic carboxylic acid is preferably 0 mol% or more, more preferably 10 mol% or more, and still more preferably 20 mol in the acid component from the viewpoint of heat-resistant storage stability of the toner. % Or more, preferably 40 mol% or less, more preferably 30 mol% or less.

Acid components other than aromatic carboxylic acids include fats such as oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, alkenyl succinic acid, etc. Aliphatic dicarboxylic acids; cycloaliphatic dicarboxylic acids and the like. Of these, aliphatic dicarboxylic acids are preferred from the viewpoint of low-temperature fixability and heat-resistant storage stability of the toner. Specifically, as the aliphatic dicarboxylic acid, fumaric acid, sebacic acid, adipic acid, and alkenyl succinic acid are preferable, and fumaric acid and sebacic acid are more preferable.
The content of the acid component other than the aromatic carboxylic acid in the acid component of the amorphous polyester (b) is preferably 10 mol% or more, more preferably 20 mol% or more, from the viewpoint of heat resistant storage stability of the toner. Preferably it is 30 mol% or more, Preferably it is 50 mol% or less, More preferably, it is 40 mol% or less, More preferably, it is 38 mol% or less.

The softening point of the amorphous polyester (b) is preferably 60 ° C. or higher, more preferably 80 ° C. or higher, further preferably 100 ° C. or higher, more preferably 115 ° C., from the viewpoint of low-temperature fixability and heat-resistant storage stability of the toner. Further, it is preferably 135 ° C. or lower, more preferably 130 ° C. or lower, and further preferably 125 ° C. or lower.
The glass transition temperature of the amorphous polyester (b) is preferably 45 ° C. or higher, more preferably 55 ° C. or higher, further preferably 58 ° C. or higher, from the viewpoint of low-temperature fixability and heat-resistant storage stability of the toner. Preferably it is 110 degrees C or less, More preferably, it is 80 degrees C or less, More preferably, it is 70 degrees C or less.
The acid value of the amorphous polyester (b) is preferably 5 mgKOH / g or more, more preferably from the viewpoint of improving the dispersibility of the crystalline polyester in the aqueous dispersion, the low temperature fixability of the toner and the charging stability. Is 10 mgKOH / g or more, more preferably 15 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.

  The number average molecular weight of the amorphous polyester (b) is preferably 1000 or more, more preferably 2000 or more, and further preferably 3000 or more, from the viewpoint of reducing the compatibility of the resin particles I with the resin. . The number average molecular weight is preferably 7000 or less, more preferably 5000 or less, and further preferably 4000 or less, from the viewpoint of improving the low-temperature fixability of the toner.

  The weight average molecular weight of the amorphous polyester (b) is preferably 3000 or more, more preferably 6000 or more, and further preferably 7000 or more, from the viewpoint of reducing the compatibility of the resin particles I with the resin. . The weight average molecular weight is preferably 10,000 or less, more preferably 9000 or less, and further preferably 8500 or less, from the viewpoint of improving the low-temperature fixability of the toner.

The polyester resin constituting the resin particles B is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 99% by mass from the viewpoint of heat-resistant storage stability of the toner. Including above. The polyester resin constituting the polyester resin particles is preferably composed only of the amorphous polyester (b).
The glass transition temperature (Tg) of the polyester resin constituting the resin particle B is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, and still more preferably 58 ° C. or higher, from the viewpoint of heat-resistant storage stability of the toner. From the viewpoint of low-temperature fixability, it is preferably 110 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 70 ° C. or lower.

  There is no restriction | limiting in the method of obtaining the aqueous dispersion of the resin particle B, The method similar to what was illustrated by the method of obtaining the aqueous dispersion of the resin particle A mentioned above is preferable.

The amorphous polyester (b) contained in the resin particle B is preferably treated with a basic substance.
In the aqueous dispersion of the resin particles B, the equivalent ratio of the basic substance to the acid of the amorphous polyester (b) is preferably 0.2 or more, more preferably 0.6 from the viewpoint of enhancing the hydrophilicity of the resin. More preferably, it is 0.9 or more, preferably 3.0 or less, more preferably 2.0 or less, and still more preferably 1.2 or less.

The aqueous dispersion of the resin particles B contains a molar amount of acid groups of amorphous polyester (b) per gram of amorphous polyester (b) and basic groups of basic substances per gram of amorphous polyester (b). From the viewpoint of low-temperature fixability, the product (mol ² / g ² ) is preferably 0.10 or more, more preferably 0.11 or more, and still more preferably 0.12 or more. From the viewpoint of storage stability, it is preferably 0.20 or less, more preferably 0.15 or less, and still more preferably 0.14 or less.
In the aqueous dispersion of the resin particles B, the molar amount of the basic group of the basic substance per 1 g of the amorphous polyester (b) is preferably 0.20 or more, more preferably 0.00 from the viewpoint of low-temperature fixability. It is 30 or more, more preferably 0.33 or more, and from the viewpoint of heat resistant storage stability, it is preferably 0.50 or less, more preferably 0.45 or less, and still more preferably 0.40 or less.

The aqueous dispersion of resin particles B is preferably a molar amount of acid groups of amorphous polyester (b) per gram of amorphous polyester (b) and a base of basic substance per gram of amorphous polyester (b). Amorphous polyester (b) was obtained by base treatment so that the product (mmol ² / g ² ) of the molar amount of the functional group was 0.10 or more and 0.20 or less, and neutralized amorphous polyester It is obtained by dispersing (b) in an aqueous medium. Further, the method of dispersing in an aqueous medium is preferably a method in which an aqueous medium is added to a solution containing the base-treated amorphous polyester (b) and an organic solvent, followed by phase inversion emulsification. The preferred conditions for phase inversion emulsification are the same as in the case of the resin particles A described above.

  The number average particle diameter of the resin particles B measured by an electron microscope is preferably 3 nm or more, more preferably 10 nm or more, and further preferably 20 nm or more, from the viewpoints of low-temperature fixability, heat-resistant storage stability and hot offset resistance. Moreover, it is preferably 80 nm or less, more preferably 60 nm or less, and still more preferably 40 nm or less.

<Production of aqueous dispersion of resin particles II>
An aqueous dispersion of resin particles I and an aqueous dispersion of resin particles B containing amorphous polyester (b) are mixed and aggregated to obtain an aqueous dispersion of resin particles II. In this step, the resin particles B are agglomerated and coated on the surface of the resin particles I.

The amorphous polyester (b) to be mixed is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and further preferably 5 parts by mass or more with respect to 100 parts by mass of the resin particles I obtained in the step 1. Yes, preferably 200 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 60 parts by mass or less, and even more preferably 30 parts by mass or less.
From the viewpoint of low-temperature fixability and heat-resistant storage stability of the toner, the mass ratio (a) / (b) of the amorphous polyester (a) to the amorphous polyester (b) is preferably 100/70 or more, more preferably Is 100/50 or more, more preferably 100/20 or more, preferably 100/1 or less, more preferably 100/3 or less, and still more preferably 100/5 or less. Moreover, Preferably it is 100 / 70-100 / 1, More preferably, it is 100 / 50-100 / 3, More preferably, it is 100 / 20-100 / 5.
The difference between the glass transition temperatures of the amorphous polyester (a) and the amorphous polyester (b) [glass transition temperature of (b) −glass transition temperature of (a)] is the low-temperature fixability and heat-resistant storage stability of the toner. In view of the above, preferably 3 ° C. or higher, more preferably 7 ° C. or higher, further preferably 10 ° C. or higher, still more preferably 14 ° C. or higher, preferably 40 ° C. or lower, more preferably 30 ° C. or lower, Preferably it is 25 degrees C or less.

The average particle size of the resin particles II obtained in step 2 is a volume-median particle size from the viewpoint of uniformly fusing in the subsequent step 3 to produce toner particles, preferably 3 μm or more, more preferably 3.5 μm. More preferably, it is 4 μm or more, preferably 10 μm or less, more preferably 8 μm or less, and still more preferably 7 μm or less.
From the same viewpoint, the temperature in the system in the step 2 is equal to or higher than the “softening point of the resin constituting the core—75 ° C.” (temperature lower than the softening point by 75 ° C., the same applies hereinafter), and the softening of the resin constituting the core. It is preferable that it is below a point.

[Step 3]
In step 3, the resin particles II obtained in step 2 are fused. That is, after adding a coagulation terminator to the aqueous dispersion of resin particles II obtained in Step 2 as necessary, and then subjecting it to a fusion step, the resin particles II in the aqueous dispersion are fused. This is a step of obtaining an aqueous dispersion of fused particles.
In step 3, the resin particles obtained in step 2 can be fused by heating.
Here, the fusion includes an amorphous polyester (b) in which a plurality of resin particles I existing inside the resin particles II are fused to form a core and the resin particles I are agglomerated and coated. The resin is fused to form a shell, and the core and the shell are appropriately bonded to form a core-shell structure.

The temperature to be fused in Step 3 is selected from the viewpoints of low-temperature fixability, heat-resistant storage stability and hot offset resistance, and from the viewpoint of target toner particle size, particle size distribution, shape control and particle fusing property. It is preferably 5 to 50 ° C. lower than the glass transition temperature of the resin, more preferably 10 to 40 ° C., and still more preferably 13 to 30 ° C.
Moreover, it is preferable that the temperature to be fused in Step 3 is 10 to 50 ° C. lower than the glass transition temperature of the amorphous polyester (a) from the viewpoints of low-temperature fixability, heat-resistant storage stability and hot offset resistance. It is more preferably ˜40 ° C. lower, further preferably 13-30 ° C. lower.
Moreover, it is preferable that the temperature to be fused in the step 3 is lower by 30 to 70 ° C. than the melting point of the crystalline polyester (c) from the viewpoint of low-temperature fixability, heat-resistant storage stability and hot offset resistance. The lower temperature is more preferable, and the lower temperature is more preferably 38 to 50 ° C.
Moreover, it is preferable that the temperature to be fused in Step 3 is 20 to 60 ° C. lower than the glass transition temperature of the amorphous polyester (b) from the viewpoint of low-temperature fixability, heat-resistant storage stability and hot offset resistance, 25 It is more preferably ˜50 ° C. lower, and further preferably 28˜40 ° C. lower.
Specifically, from the same viewpoint, the fusing temperature in the step 3 is preferably 20 ° C. or higher, more preferably 25 ° C. or higher, still more preferably 30 ° C. or higher, and preferably 50 ° C. or lower, more Preferably it is 40 degrees C or less.

The stirring speed is preferably a speed at which the resin particles do not settle.
When an aggregation stopper is used, a surfactant is preferably used as the aggregation stopper, and an anionic surfactant is more preferably used from the viewpoints of availability and operability. Of the anionic surfactants, it is more preferable to use at least one selected from the group consisting of polyoxyalkylene alkyl ether sulfates, alkyl sulfates, and linear alkylbenzene sulfonates.

[Post-process]
By appropriately subjecting the fused particles obtained in the step 3 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 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.

Further, an external additive may be added for the purpose of improving fluidity. Examples of the external additive include silica fine particles whose surface is hydrophobized, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, and inorganic fine particles such as carbon black; polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin, and the like. Fine particles can be used.
The number average particle size of the external additive is preferably 4 nm or more, more preferably 6 nm or more, still more preferably 8 nm or more, and preferably 200 nm or less, more preferably 100 nm or less, from the viewpoint of toner fluidity. More preferably, it is 30 nm or less.

  When the external additive is added, the addition amount is preferably 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. 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and further preferably 2 parts by mass or less.

[Toner for electrostatic image development]
The toner for developing an electrostatic charge image of the present invention has a core and a shell, and the core includes a resin particle containing an amorphous polyester (a) having a number average particle diameter measured by an electron microscope of 10 nm to 50 nm. A is obtained by fusing resin particles C containing crystalline polyester (c), and the shell is obtained by fusing resin particles B containing amorphous polyester (b).
The polyester resin particles are preferably derived from an aqueous dispersion of the above polyester resin particles.
The core is preferably resin particles I shown in the aqueous dispersion of resin particles I described above.

The volume-median particle size of the toner for developing an electrostatic charge image of the present invention is preferably 3 μm or more, more preferably 3.5 μm or more, and further preferably 4 μm or more, from the viewpoint of high image quality and productivity of the toner. Further, it is preferably 10 μm or less, more preferably 8 μm or less, and further preferably 7 μm or less.
The mass ratio between the core and the shell is preferably 100/70 or more, more preferably 100/50 or more, still more preferably 100/20 or more, and preferably 100/1 or less, more preferably 100/3 or less. More preferably, it is 100/5 or less. Moreover, Preferably it is 100 / 70-100 / 1, More preferably, it is 100 / 50-100 / 3, More preferably, it is 100 / 20-100 / 5.
The thickness of the shell is preferably 1 nm or more, more preferably 10 nm or more, still more preferably 15 nm or more, and preferably 100 nm or less, more preferably 50 nm or less, still more preferably 30 nm or less.
The difference in glass transition temperature between the core resin and the shell resin (the glass transition temperature of the shell resin−the glass transition temperature of the core resin) is preferably 3 ° C. or higher, more preferably 7 ° C. or higher, and even more preferably 10 ° C. As described above, it is more preferably 14 ° C. or higher, preferably 60 ° C. or lower, more preferably 40 ° C. or lower, still more preferably 30 ° C. or lower, and even more preferably 25 ° C. or lower.
Further, the softening point of the toner is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, and preferably 160 ° C. or lower, more preferably, from the viewpoint of low-temperature fixability, heat-resistant storage stability, and charging stability of the toner. 150 ° C. or lower, more preferably 140 ° C. or lower.
The electrostatic image developing toner of the present invention can be used as a one-component developer or as a two-component developer mixed with a carrier.

In relation to the above-described embodiments, the present invention further discloses the following method for producing an electrostatic image developing toner and electrostatic image developing toner.
<1> A method for producing a toner for developing an electrostatic charge image, comprising the following steps 1 to 3.
Step 1: An aqueous dispersion of resin particles A containing amorphous polyester (a) having a number average particle diameter measured by an electron microscope of 10 nm to 50 nm and resin particles C containing crystalline polyester (c) Step of mixing and aggregating the aqueous dispersion to obtain an aqueous dispersion of resin particles I Step 2: An aqueous dispersion of resin particles I obtained in Step 1 and resin particles containing amorphous polyester (b) Step of mixing and aggregating the aqueous dispersion of B to obtain an aqueous dispersion of resin particles II Step 3: Step of fusing the resin particles II obtained in Step 2

<2> The number average particle diameter of the resin particles A is preferably 10 nm or more, more preferably 20 nm or more, still more preferably 25 nm or more, and preferably 50 nm or less, more preferably 40 nm or less, still more preferably 35 nm or less. The method for producing a toner for developing an electrostatic charge image according to <1>.
<3> In the alcohol component of the amorphous polyester (a), the alkylene oxide adduct of bisphenol A is preferably 60 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, The method for producing a toner for developing an electrostatic charge image according to <1> or <2>, preferably 100 mol% or less, more preferably 100 mol%.
<4> The softening point of the amorphous polyester (a) is preferably 60 ° C. or higher, more preferably 75 ° C. or higher, still more preferably 90 ° C. or higher, and preferably 120 ° C. or lower, more preferably 110 ° C. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <3>, further preferably 105 ° C. or lower.
<5> The glass transition temperature of the amorphous polyester (a) is preferably 30 ° C. or higher, more preferably 35 ° C. or higher, still more preferably 40 ° C. or higher, and preferably 110 ° C. or lower, more preferably 70. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <4>, which is not higher than ° C, more preferably not higher than 50 ° C.
<6> The acid value of the amorphous polyester (a) is preferably 5 mgKOH / g or more, more preferably 15 mgKOH / g or more, still more preferably 20 mgKOH / g or more, and preferably 40 mgKOH / g or less. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <5>, which is preferably 30 mgKOH / g or less, more preferably 25 mgKOH / g or less.
<7> In the polyester resin constituting the resin particle A, the content of the amorphous polyester (a) is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 98% by mass or more. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <6>, further preferably 100% by mass.
<8> The equivalent ratio of the basic substance to the acid of the amorphous polyester (a) is preferably 0.2 or more, more preferably 0.6 or more, and still more preferably 0.00 from the viewpoint of enhancing the hydrophilicity of the resin. 8 or more, preferably 3.0 or less, more preferably 1.5 or less, and still more preferably 1.0 or less, for developing an electrostatic image according to any one of <1> to <7> Toner manufacturing method.
<9> The aqueous dispersion of the resin particles A includes a molar amount of acid groups of the amorphous polyester (a) per 1 g of the amorphous polyester (a) and a basic substance per 1 g of the amorphous polyester (a). The product (mol ² / g ² ) of the basic group with the molar amount is preferably 0.10 or more, more preferably 0.11 or more, still more preferably 0.12 or more, and further preferably 0.13 or more. The toner for developing an electrostatic charge image according to any one of <1> to <8>, which is preferably 0.20 or less, more preferably 0.15 or less, and still more preferably 0.14 or less. Method.
<10> The molar amount of the basic group of the basic substance per 1 g of the amorphous polyester (a) is preferably 0.20 or more, more preferably 0.30 or more, still more preferably 0.34 or more, The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <9>, which is preferably 0.50 or less, more preferably 0.45 or less, and still more preferably 0.40 or less.
<11> The aqueous dispersion of the resin particles A includes a molar amount of acid groups of the amorphous polyester (a) per 1 g of the amorphous polyester (a) and a basic substance per 1 g of the amorphous polyester (a). Amorphous polyester (a) base-treated so that the product (mmol ² / g ² ) of the basic group with the molar amount of the base group was 0.10 or more and 0.20 or less was obtained. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <10>, which is obtained by dispersing a high quality polyester (a) in an aqueous medium.
<12> The method of dispersing in the aqueous medium is a method of adding a water-based medium to a solution containing the base-treated amorphous polyester (a) and an organic solvent, and performing phase inversion emulsification. <1> A method for producing a toner for developing an electrostatic charge image according to any one of to <11>.
<13> The basic substance of the aqueous dispersion of the resin particles A is preferably an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide and potassium hydroxide, and ammonia, trimethylamine, ethylamine, diethylamine, For electrostatic image development according to any one of <8> to <12>, which is at least one selected from nitrogen-containing salt substances such as triethylamine, triethanolamine and tributylamine, and more preferably ammonia. Toner manufacturing method.

<14> The softening point of the crystalline polyester (c) is preferably 60 ° C or higher, more preferably 65 ° C or higher, still more preferably 70 ° C or higher, and preferably 140 ° C or lower, more preferably 100 ° C or lower. More preferably, the method for producing a toner for developing an electrostatic charge image according to any one of <1> to <13>, which is 80 ° C. or lower.
<15> The melting point of the crystalline polyester (c) is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, still more preferably 70 ° C. or higher, and preferably 140 ° C. or lower, more preferably 100 ° C. or lower, The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <14>, further preferably 80 ° C. or lower.
<16> The acid value of the crystalline polyester (c) is preferably 1 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, and preferably 40 mgKOH / g or less, more preferably Is 35 mgKOH / g or less, more preferably 30 mgKOH / g or less, The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <15>.
<17> The content of the crystalline polyester (c) is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 80% by mass or more, with respect to the resin in the resin particles C. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <16>, preferably 100% by mass or less, and more preferably 100% by mass.
<18> Product of the molar amount of the acid group of the crystalline polyester (c) per 1 g of the crystalline polyester (c) and the molar amount of the basic group of the basic substance per 1 g of the crystalline polyester (c) (mmol ² / G ² ) is preferably 0.03 or more, more preferably 0.04 or more, further preferably 0.05 or more, preferably 0.10 or less, more preferably 0.07 or less, still more preferably. Is 0.06 or less, The manufacturing method of the electrostatic image developing toner in any one of <1>-<17>.
<19> The basic substance of the aqueous dispersion of the resin particles C is preferably an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide and potassium hydroxide, and ammonia, trimethylamine, ethylamine, diethylamine, The method for producing a toner for developing an electrostatic charge image according to any one of <18>, wherein the toner is at least one selected from nitrogen-containing salt substances such as triethylamine, triethanolamine, and tributylamine, and more preferably ammonia. .

<20> The volume median particle size of the resin particles I is preferably 3.5 μm or more, more preferably 4 μm or more, and preferably 7 μm or less, more preferably 6 μm or less, <1 The method for producing a toner for developing an electrostatic charge image according to any one of> to <19>.
<21> The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <20>, wherein the obtained resin particles are pre-fused after aggregation in Step 1.
<22> The temperature to be pre-fused is preferably 5 to 50 ° C., more preferably 10 to 40 ° C., further preferably 13 to 30 ° C. lower than the glass transition temperature of the amorphous polyester (a). <21> The method for producing a toner for developing an electrostatic charge image according to any one of the above.
<23> The pre-fusion temperature is preferably 20 to 70 ° C., more preferably 30 to 60 ° C., and further preferably 35 to 50 ° C. lower than the glass transition temperature (melting point) of the crystalline polyester (c). The method for producing a toner for developing an electrostatic charge image according to any one of <21> and <22>.

<24> In the alcohol component of the amorphous polyester (b), the alkylene oxide adduct of bisphenol A is preferably 60 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and even more. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <23>, preferably 95 mol% or more, more preferably 100 mol% or less, and even more preferably 100 mol%.
<25> The softening point of the amorphous polyester (b) is preferably 60 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 100 ° C. or higher, still more preferably 115 ° C. or higher, and preferably 135 ° C. Hereinafter, the method for producing a toner for developing an electrostatic charge image according to any one of <1> to <24>, which is more preferably 130 ° C. or lower, and further preferably 125 ° C. or lower.
<26> The glass transition temperature of the amorphous polyester (b) is preferably 45 ° C or higher, more preferably 55 ° C or higher, still more preferably 58 ° C or higher, and preferably 110 ° C or lower, more preferably 80. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <25>, which is not higher than 70C, more preferably not higher than 70C.
<27> The acid value of the amorphous polyester (b) is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, further preferably 15 mgKOH / g or more, and preferably 40 mgKOH / g or less. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <26>, preferably 30 mgKOH / g or less, more preferably 25 mgKOH / g or less.
<28> In the aqueous dispersion of the resin particles B, the equivalent ratio of the basic substance to the acid of the amorphous polyester (b) is preferably 0.2 or more, more preferably 0.6 or more, and still more preferably 0. The electrostatic charge image development according to any one of <1> to <27>, which is 0.9 or more, preferably 3.0 or less, more preferably 2.0 or less, and still more preferably 1.2 or less. Of manufacturing toner.
<29> The aqueous dispersion of the resin particles B contains a molar amount of acid groups of the amorphous polyester (b) per 1 g of the amorphous polyester (b) and a basic substance per 1 g of the amorphous polyester (b). Of the basic group with the molar amount of the basic group (mmol ² / g ² ) is preferably 0.10 or more, more preferably 0.11 or more, still more preferably 0.12 or more, and preferably 0.00. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <28>, which is 20 or less, more preferably 0.15 or less, and still more preferably 0.14 or less.
<30> In the aqueous dispersion of the resin particles B, the molar amount of the basic group of the basic substance per 1 g of the amorphous polyester (b) is preferably 0.20 or more, more preferably 0.30 or more. More preferably, it is 0.33 or more, preferably 0.50 or less, more preferably 0.45 or less, still more preferably 0.40 or less, according to any one of <1> to <29>. A method for producing a toner for developing an electrostatic image.
<31> The aqueous dispersion of the resin particles B includes a molar amount of acid groups of the amorphous polyester (b) per 1 g of the amorphous polyester (b) and a basic substance per 1 g of the amorphous polyester (b). Amorphous polyester (b), which was subjected to base treatment so that the product (mmol ² / g ² ) of the basic group with the molar amount of 0.10 or more and 0.20 or less, was obtained, and neutralized amorphous The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <30>, which is obtained by dispersing the quality polyester (b) in an aqueous medium.
<32> The method of dispersing in an aqueous medium is preferably a method in which an aqueous medium is added to a solution containing the base-treated amorphous polyester (b) and an organic solvent, and phase inversion emulsification is performed. The method for producing a toner for developing an electrostatic charge image according to any one of 1> to <31>.
<33> The basic substance of the aqueous dispersion of the resin particles B is preferably an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide and potassium hydroxide, and ammonia, trimethylamine, ethylamine, diethylamine, For electrostatic image development according to any one of <28> to <32>, which is at least one selected from nitrogen-containing salt substances such as triethylamine, triethanolamine, and tributylamine, and more preferably ammonia. Toner manufacturing method.
<34> The number average particle diameter of the resin particles B measured by an electron microscope is preferably 3 nm or more, more preferably 10 nm or more, still more preferably 20 nm or more, and preferably 80 nm or less, more preferably 60 nm or less. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <33>, more preferably 40 nm or less.

<35> In step 2, the amorphous polyester (b) to be mixed is preferably 1 part by mass or more, more preferably 3 parts by mass or more, with respect to 100 parts by mass of the resin particles I obtained in step 1. Preferably it is 5 parts by mass or more, preferably 200 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 60 parts by mass or less, and even more preferably 30 parts by mass or less, <1> to <34> The method for producing a toner for developing an electrostatic charge image according to any one of the above.
<36> In step 2, the mass ratio (a) / (b) of the amorphous polyester (a) to the amorphous polyester (b) is preferably 100/70 or more, more preferably 100/50 or more, and further Preferably it is 100/20 or more, preferably 100/1 or less, more preferably 100/3 or less, still more preferably 100/5 or less, and preferably 100/70 to 100/1, more preferably 100. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <35>, which is / 50 to 100/3, more preferably 100/20 to 100/5.
<37> The difference in glass transition temperature between the amorphous polyester (a) and the amorphous polyester (b) [glass transition temperature of (b) −glass transition temperature of (a)] is preferably 3 ° C. or higher. Preferably it is at least 7 ° C, more preferably at least 10 ° C, even more preferably at least 14 ° C, preferably at most 40 ° C, more preferably at most 30 ° C, even more preferably at most 25 ° C, <1> A method for producing a toner for developing an electrostatic charge image according to any one of to <36>.
<38> The average particle size of the resin particles II obtained in step 2 is a volume-median particle size, preferably 3 μm or more, more preferably 3.5 μm or more, still more preferably 4 μm or more, and preferably 10 μm. Hereinafter, the method for producing a toner for developing an electrostatic charge image according to any one of <1> to <37>, which is more preferably 8 μm or less, and further preferably 7 μm or less.

<39> The temperature to be fused in the step 3 is preferably 5 to 50 ° C., more preferably 10 to 40 ° C., further preferably 13 to 30 ° C. lower than the glass transition temperature of the polyester resin, <1 >-<38> The manufacturing method of the electrostatic image developing toner in any one of.
<40> The temperature to be fused in Step 3 is preferably 10 to 50 ° C., more preferably 12 to 40 ° C., more preferably 13 to 30 ° C. lower than the glass transition temperature of the amorphous polyester (a). The method for producing an electrostatic charge image developing toner according to any one of <1> to <39>, which is low.
<41> The temperature to be fused in the step 3 is preferably 30 to 70 ° C., more preferably 35 to 60 ° C., further preferably 38 to 50 ° C. lower than the melting point of the crystalline polyester (c). 1>-<40> A method for producing a toner for developing an electrostatic charge image according to any one of <1> to <40>.
<42> The temperature to be fused in step 3 is preferably 20 to 60 ° C., more preferably 25 to 50 ° C., and further preferably 28 to 40 ° C. lower than the glass transition temperature of the amorphous polyester (b). The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <41>, which is low.
<43> The temperature to be fused in step 3 is preferably 20 ° C. or higher, more preferably 25 ° C. or higher, still more preferably 30 ° C. or higher, and preferably 50 ° C. or lower, more preferably 40 ° C. or lower. <1>-<42> The manufacturing method of the electrostatic image developing toner in any one of.

<44> An electrostatic charge image developing toner obtained by the production method according to any one of <1> to <43>.
<45> Resin particle A containing amorphous polyester (a) having a core and a shell, and having a number average particle diameter measured by an electron microscope of 10 nm or more and 50 nm or less, and crystalline polyester (c The toner for developing an electrostatic charge image is obtained by fusing the resin particles C containing), and the shell is obtained by fusing the resin particles B containing the amorphous polyester (b).
<46> The volume-median particle size of the electrostatic image developing toner is preferably 3 μm or more, more preferably 3.5 μm or more, still more preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less. The toner for developing an electrostatic charge image according to <45>, more preferably 7 μm or less.
<47> The mass ratio of the core to the shell is preferably 100/70 or more, more preferably 100/50 or more, still more preferably 100/20 or more, and preferably 100/1 or less, more preferably 100. / 3 or less, more preferably 100/5 or less. The electrostatic image development according to <45> or <46>, preferably 100/70 to 100/1, more preferably 100/50 to 100/3, and still more preferably 100/20 to 100/5. Toner.
<48> The thickness of the shell is preferably 1 nm or more, more preferably 10 nm or more, further preferably 15 nm or more, and preferably 100 nm or less, more preferably 50 nm or less, still more preferably 30 nm or less, <45 The toner for developing an electrostatic charge image according to any one of> to <47>.
<49> The difference in glass transition temperature between the core resin and the shell resin (the glass transition temperature of the shell resin−the glass transition temperature of the core resin) is preferably 3 ° C. or higher, more preferably 7 ° C. or higher. Is 10 ° C. or higher, more preferably 14 ° C. or higher, preferably 60 ° C. or lower, more preferably 40 ° C. or lower, still more preferably 30 ° C. or lower, even more preferably 25 ° C. or lower. <45> -The toner for developing an electrostatic charge image according to any one of <48>.
<50> The softening point of the toner is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, preferably 160 ° C. or lower, more preferably 150 ° C. or lower, and still more preferably 140 ° C. or lower. <49> The toner for developing an electrostatic charge image according to any one of the above.

  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 the 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)).

[Softening point and glass transition temperature of resin]
(1) Softening point Using a flow tester “CFT-500D” (manufactured by Shimadzu Corporation), a 1 g sample was heated at a heating rate of 6 ° C./min, and a load of 1.96 MPa was applied by a plunger. The nozzle was extruded from a nozzle having a 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 peak temperature of endotherm Using a differential scanning calorimeter “Q-100” (manufactured by TI 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 maximum 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 peak temperature of endotherm and the tangent indicating the maximum slope from the peak rising portion to the peak apex.

[Volume Median Particle Size (D ₅₀ ) of Aqueous Dispersion of Colorant, Charge Control Agent, Release Agent]
(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.

[Number average particle diameter of aqueous dispersion of resin particles]
(1) Measuring device: Transmission electron microscope (TEM) JEM-2100 (manufactured by JEOL Ltd.)
(2) Pretreatment: Cu mesh with an elastic carbon support film (manufactured by Oken Shoji Co., Ltd.) is hydrophilized (300V3 minutes) in an ion cleaner ion cleaner JIC-410 (manufactured by JEOL Ltd.), then solid A sample mixed with a 0.1% by weight sample solution and a 2% by weight sodium phosphotungstate solution (manufactured by Merck & Co., Ltd.) is placed on the sample, and the excess sample is removed with filter paper. did.
(3) Measurement conditions: TEM (JEM-2100), acceleration voltage: 80 kV, convergence aperture: 1 (Φ200 μm), objective aperture: 1 (Φ60 μm), SPOT size: 1, α selection: 3
(4) Analysis conditions: For the TEM image taken in (3), using an image analysis processing device (Nireco Co., Ltd.) Luzex IID, under the condition that the total number of processed particles is 500, the projection surface property of the particles The corresponding equivalent circle diameter was calculated and the number average particle diameter was determined.

[Solid content concentration of aqueous dispersion of resin particles, colorant, charge control agent, release agent]
Using an infrared moisture meter “FD-230” (manufactured by Kett Science 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 sample was dried and the moisture content (% by mass) of the sample was measured. The solid content was calculated according to the following formula.
Solid content concentration (% by mass) = 100-M
M: moisture (mass%) of sample = [(W−W ₀ ) / W] × 100
W: Sample mass before measurement (initial sample mass)
W ₀ : Mass of sample after measurement (absolute dry mass)

[Low-temperature fixability of toner]
The toner was mounted on an apparatus in which the fixing machine of the copying machine “AR-505” (manufactured by Sharp Corporation) was improved so that fixing outside the apparatus was possible, and a printed matter was obtained in an unfixed state (printing area: 2 cm × 12 cm, adhesion amount: 0.5 mg / cm ² ). After that, using a fixing machine (fixing speed 300 mm / sec) adjusted so that the total fixing pressure becomes 40 kgf, the fixing roll temperature is gradually increased from 80 ° C. to 240 ° C. by 5 ° C., and unfixed at each temperature. A fixing test of the printed matter in the state was performed. A cellophane adhesive tape “UNICEF Cellophane” (Mitsubishi Pencil Co., Ltd., width: 18 mm, JIS Z1522) is pasted on the image portion of the printed matter, passed through a fixing roller set at 30 ° C., and then the tape is peeled off. It was. 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 roller that exceeded the minimum fixing temperature. The lower the minimum fixing temperature, the better the low-temperature fixing property. As the fixing paper, “CopyBond SF-70NA” (manufactured by Sharp Corporation, 75 g / m ² ) was used.

[Toner hot offset resistance]
In the low temperature fixability test, the temperature at which hot offset was first observed on the fixing roller was taken as the hot offset temperature. The higher this temperature, the better the hot offset resistance.

[Heat resistant storage stability of toner]
A 25 mL container (diameter: about 3 cm) was charged with 5 g of toner and allowed to stand for 84 hours in an environment of temperature 50 ° C. and humidity 75%. The degree of occurrence of toner aggregation was visually observed every 12 hours, and heat resistant storage stability was evaluated according to the following evaluation criteria. The longer the time during which no aggregation is observed, the better the heat resistant storage stability.
(Evaluation criteria)
A: Aggregation is not observed after 60 hours, but aggregation is observed after 84 hours.
B: Aggregation is not observed after 48 hours, but aggregation is observed after 60 hours.
C: Aggregation is not observed after 36 hours, but aggregation is observed after 48 hours.
D: Aggregation is not observed after 24 hours, but aggregation is observed after 36 hours.
E: Aggregation is observed after 24 hours.

[Production of polyester resin]
Production Examples 1, 2, and 4
(Production of amorphous polyesters A, B and D)
Equipped with thermometer, stainless steel stirring bar, flow-down condenser, and nitrogen inlet tube, raw material monomer of polyester resin other than fumaric acid and sebacic acid (only production example 4) shown in Table 1, esterification catalyst and esterification co-catalyst The flask was placed in a 10-liter four-necked flask and heated to 235 ° C. over 2 hours in a mantle heater in a nitrogen atmosphere. Thereafter, it was confirmed that the reaction rate reached 95% or more at 235 ° C. Thereafter, the mixture was cooled to 180 ° C., 4-t-butylcatechol, fumaric acid, and sebacic acid (Production Example 4 only) were added, and the temperature was raised to 210 ° C. over 2 hours. Then, after reacting at 210 ° C. for 1 hour, the reaction was performed at 40 kPa until reaching the softening point shown in Table 1, and amorphous polyesters A, B and D were obtained.

Production Example 3
(Production of crystalline polyester C)
The polyester resin raw material monomer, esterification catalyst and esterification co-catalyst shown in Table 1 were placed in a 10-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser and a nitrogen inlet tube, and a nitrogen atmosphere In the mantle heater, the temperature was raised to 135 ° C. and then raised to 200 ° C. over 10 hours. Furthermore, it was made to react under reduced pressure of 8 kPa for 2 hours, and the crystalline polyester resin C was obtained.

[Production of aqueous dispersion]
Production Example 5
(Production of aqueous dispersion A-1 of polyester resin particles)
A 3 L container equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen introduction tube was charged with 150 g of amorphous polyester resin A and 75 g of methyl ethyl ketone, and dissolved at 70 ° C. over 2 hours. A 20% by mass aqueous ammonia solution (pKa: 9.3) was added to the resulting solution so that the equivalent ratio of the basic substance to the acid of the resin was 0.90, and the mixture was stirred for 30 minutes.
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. While maintaining the temperature at 70 ° C., methyl ethyl ketone was distilled off under reduced pressure. Thereafter, the aqueous dispersion was cooled to 30 ° C. while stirring at 280 r / min (peripheral speed 88 m / min), and then an anionic surfactant “Emar E27C” (manufactured by Kao Corporation, polyoxyethylene lauryl ester) 16.7 g of sodium tersulfate (solid content 28% by mass) was mixed. Thereafter, the solid content concentration of the dispersion was measured, and ion-exchanged water was added so as to be 20% by mass to obtain an aqueous dispersion A-1 of polyester resin particles. Table 2 shows the physical property values of the obtained aqueous dispersion.

Production Examples 6-14
(Production of aqueous dispersions A-2 to A-5, B-1 to B-3, C-1 and D-1 of polyester resin particles)
An aqueous dispersion of an amorphous polyester resin and a crystalline polyester resin was obtained in the same manner as in Production Example 5 except that the equivalent ratio of the resin and the basic substance was changed as shown in Table 2 in Production Example 5. It was. Table 2 shows the physical property values of the obtained aqueous dispersion.

[Preparation of release agent dispersion]
Production Example 15
50 g of paraffin wax “HNP9” (manufactured by Nippon Seiwa Co., Ltd.), 5 g of cationic surfactant “Sanisol B50” (manufactured by Kao Corporation, alkylbenzyldimethylammonium chloride, solid content 50 mass%) and 200 g of ion-exchanged water Was heated to 95 ° C., and the paraffin wax was dispersed using a homogenizer, followed by dispersion treatment using a pressure discharge type homogenizer to obtain a release agent dispersion containing release agent fine particles. The volume median particle size (D ₅₀ ) of the paraffin wax was 550 nm, and the solid content concentration was 22% by mass.

[Production of colorant dispersion]
Production Example 16
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 are mixed. Then, it was dispersed for 10 minutes using a homogenizer to obtain a colorant dispersion containing fine colorant particles. The volume median particle size (D ₅₀ ) of the colorant fine particles was 120 nm, and the solid content concentration was 22% by mass.

[Production of charge control agent dispersion]
Production Example 17
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 for 10 minutes using a sand grinder to obtain 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 was 400 nm, and the solid content concentration was 22% by mass.

[Manufacture of toner for developing electrostatic image]
Example 1 (Production of Toner 1)
192 g of aqueous dispersion A-1 of amorphous polyester, 48 g of aqueous dispersion C-1 of crystalline polyester, 8 g of colorant dispersion, 10 g of release agent dispersion, 2 g of charge control agent dispersion, and deionization 52 g of water was placed in a 3 L container, and 150 g of a 0.3 mass% calcium chloride aqueous solution was added dropwise at 30 ° C. over 30 minutes while stirring at 100 r / min (peripheral speed 31 m / min) with an anchor-type stirrer. Then, it heated up to 30 degreeC, stirring. It was held at 30 ° C. until the volume median particle size was 4.5 μm. At 5 hours, the volume median particle size reached 4.5 μm. Thereafter, a dilute solution obtained by diluting 2.1 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, and the temperature was again raised to 30 ° C. After heating, the temperature was maintained at 30 ° C for 1 hour. Thereafter, 60 g of an aqueous dispersion B-1 of polyester resin particles was added as a toner shell and dispersed by stirring. Next, the temperature was raised again to 30 ° C., and 30 ° C. was maintained for 1 hour from the time when the temperature reached 30 ° C. Thereafter, a dilute solution obtained by diluting 2.1 g of anionic surfactant “Emar E27C” (manufactured by Kao Corporation, sodium polyoxyethylene alkyl ether sulfate, solid content: 28 mass%) with 37 g of deionized water as an aggregation terminator. Added. Next, after maintaining the temperature at 30 ° C. for 1 hour from the time when the temperature was raised to 30 ° C., the heating was terminated. As a result, fused particles were formed, and then slowly cooled to 15 ° 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 Nippon Coke Kogyo Co., Ltd.) was added and stirred at 3000 rpm for 2 minutes to obtain a toner. Table 3 shows the evaluation results of the toner.

Examples 2-3, 5-11 and Comparative Examples 1-2 (Production of Toners 2-3, 5-13)
Except that the types and amounts of the aqueous dispersions A-1 and B-1 of the amorphous polyester and the aqueous dispersion C-1 of the crystalline polyester as the core material used in Example 1 were changed as shown in Table 3. In the same manner as in Example 1, a toner was obtained. The total amount of the aqueous dispersion used as the core raw material was 240 g as in Example 1, and the amount shown in Table 4 was used for the aqueous dispersion used as the shell raw material. Table 3 shows the evaluation results of the toner.

Example 4 (Production of Toner 4)
After adding the aggregation terminator, a toner was obtained in the same manner as in Example 1 except that the step of holding at 30 ° C. for 1 hour was changed to the step of holding at 55 ° C. for 1 hour. In addition, after core formation and shell formation, both were maintained at 55 ° C. for 1 hour. Table 3 shows the evaluation results of the toner.

Comparative Example 3 (Production of Toner 14)
A toner was obtained in the same manner as in Example 1 except that an aqueous dispersion of crystalline polyester was not used. Table 3 shows the evaluation results of the toner.

Comparative Example 4 (Production of Toner 15)
A toner was obtained in the same manner as in Example 1 except that the aqueous dispersion for shell was not used. Table 3 shows the evaluation results of the toner.

  From Table 3, it can be seen that the electrostatic image developing toners of the examples are all excellent in low-temperature fixability, heat-resistant storage stability, and hot offset resistance as compared with the electrostatic image developing toners of the comparative examples.

  The toner for developing an electrostatic image obtained by the production method of the present invention can be used suitably as a toner used in electrophotography because it can achieve both low temperature fixability, heat resistant storage stability and hot offset resistance. According to the method of the present invention, a toner having such characteristics can be produced efficiently.

Claims (11)

A method for producing an electrostatic charge image developing toner, comprising the following steps 1 to 3.
Step 1: An aqueous dispersion of resin particles A containing amorphous polyester (a) having a number average particle diameter measured by an electron microscope of 10 nm to 50 nm and resin particles C containing crystalline polyester (c) Step of mixing and aggregating the aqueous dispersion to obtain an aqueous dispersion of resin particles I Step 2: An aqueous dispersion of resin particles I obtained in Step 1 and resin particles containing amorphous polyester (b) Step of mixing and aggregating the aqueous dispersion of B to obtain an aqueous dispersion of resin particles II Step 3: Step of fusing the resin particles II obtained in Step 2   2. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein in the step 3, the fusing temperature is 10 to 50 ° C. lower than the glass transition temperature of the amorphous polyester (a).   3. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein, in the step 3, the fusing temperature is 30 to 70 ° C. lower than the melting point of the crystalline polyester (c).   The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 3, wherein in the step 3, the fusing temperature is 20 ° C or higher and 50 ° C or lower.   The difference between the glass transition temperatures of the amorphous polyester (a) and the amorphous polyester (b) [glass transition temperature of (b) −glass transition temperature of (a)] is 10 ° C. or higher and 40 ° C. or lower. Item 5. A method for producing a toner for developing an electrostatic charge image according to any one of Items 1 to 4. The aqueous dispersion of the resin particles A contains the molar amount of the acid group of the amorphous polyester (a) per 1 g of the amorphous polyester (a) and the basicity of the basic substance per 1 g of the amorphous polyester (a). The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 5, wherein a product (mmol ² / g ² ) of the group with a molar amount is 0.10 or more and 0.20 or less. The aqueous dispersion of the resin particles B contains the molar amount of the acid group of the amorphous polyester (b) per 1 g of the amorphous polyester (b) and the basicity of the basic substance per 1 g of the amorphous polyester (b). The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 6, wherein a product (mmol ² / g ² ) of the group with a molar amount is 0.10 or more and 0.20 or less.   The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the resin particles B have a number average particle diameter measured by an electron microscope of 10 nm or more and 80 nm or less.   An electrostatic charge image developing toner obtained by the production method according to claim 1.   A resin particle A including an amorphous polyester (a) having a core and a shell, and having a number average particle diameter measured by an electron microscope of 10 nm or more and 50 nm or less, and a crystalline polyester (c) A toner for developing electrostatic images, obtained by fusing resin particles C, wherein the shell is obtained by fusing resin particles B containing amorphous polyester (b).   11. The electrostatic charge image development according to claim 10, wherein a difference in glass transition temperature between the shell resin and the core resin (glass transition temperature of the shell resin−glass transition temperature of the core resin) is 10 ° C. or higher and 40 ° C. or lower. Toner.