JP5988727B2 - Method for producing toner for developing electrostatic image - Google Patents

Description

  The present invention relates to a method for producing an electrostatic charge image developing toner and an electrostatic charge image developing toner obtained thereby.

In the field of electrostatic charge image developing toner, with the development of electrophotographic systems, development of toners corresponding to higher image quality and higher speed is required.
As a method for controlling the particle size and reducing the particle size in response to higher image quality, agglomeration coalescence method (aggregation fusion) is used to obtain toner by agglomerating and fusing fine resin particles in an aqueous medium. The toner is manufactured by the above method.

For example, Patent Document 1 discloses an electrostatic charge developing toner having at least a crystalline polyester resin and a colorant and having a specific dielectric loss rate for the purpose of improving low-temperature fixability, high density image, and fog suppression. As a method for this, a resin particle dispersion in which binder resin particles containing a crystalline polyester resin are dispersed and a colorant dispersion in which a colorant is dispersed are mixed, and an aggregating agent is added thereto to form aggregated particles. A method for producing a toner is disclosed, which includes an aggregated particle forming step and a fusion / union step in which the aggregated particle is heated and fused and united while adding an acid and a surfactant.
In Patent Document 2, for the purpose of obtaining a developer having high image quality and good particle size distribution, a flocculant is added to a dispersion liquid containing fine particles containing a binder resin and a colorant to cause aggregation and fusion. In the manufacturing method of the developer that forms toner particles, a manufacturing method is disclosed in which each pH of the dispersion before adding the flocculant, the dispersion after adding the flocculant, and the dispersion after fusing satisfies a specific relationship. Yes.
Patent Document 3 discloses a step of emulsifying a binder resin containing polyester in an aqueous medium for the purpose of obtaining toner particles having a high degree of circularity, and the emulsified particles in the obtained emulsion are subjected to glass transition temperature + 20 ° C. An electron having a step of agglomerating at the following temperature, a step of adding alkyl ether sulfate ester salt or alkyl sulfate ester salt to stop aggregation, and a step of heating the aggregated particles at a specific temperature to unite A method for producing a photographic toner is disclosed.

JP 2009-75342 A JP 2009-122694 A JP 2008-164808 A

By using a release agent in the toner, the fixing temperature of the obtained toner can be lowered due to its melting characteristics. Thereby, the power consumption of the printing machine can be reduced, and a toner suitable for high-speed printing can be obtained. However, a toner containing a release agent also has problems such as toner scattering that causes toner to scatter in the printing press and reduced heat-resistant storage stability that is stable during high-temperature storage.
An object of the present invention is to provide a toner for developing an electrostatic image having both good low-temperature fixability and heat-resistant storage stability and less toner scattering, and a method for producing the same.

  The present inventors have considered the factors that affect the fixing temperature, heat resistant storage stability, and toner scattering in the presence and state of the resin and release agent constituting the toner. As a result, the agglomerated particles including the resin particles and the release agent particles are fused in an aqueous mixed liquid containing an anionic surfactant having a specific polyethylene glycol portion and adjusted to a specific pH. The present inventors have found that an electrostatic charge image developing toner having both good low-temperature fixability and heat-resistant storage stability and little toner scattering can be obtained.

That is, the present invention provides the following [1] and [2].
[1] Aqueous mixed solution containing aggregated particles containing resin particles (A) and release agent particles, and an anionic surfactant having a polyethylene glycol moiety having an average addition mole number of ethylene oxide of 1 or more and less than 8. A toner for developing an electrostatic charge image, having a step of fusing the aggregated particles in the aqueous mixed solution under the pH after and / or while adjusting the pH at 25 ° C. to 5.1 to 6.1 Manufacturing method.
[2] A toner for developing an electrostatic image obtained by the production method according to [1].

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

The method for producing a toner for developing an electrostatic charge image according to the present invention comprises an agglomerated particle containing resin particles (A) and a releasing agent particle, and an anion having a polyethylene glycol moiety having an average added mole number of ethylene oxide of 1 or more and less than 8. After adjusting and / or adjusting the pH at 25 ° C. of the aqueous mixed solution containing the surfactant to 5.1 to 6.1, the aggregated particles in the aqueous mixed solution are fused under the pH. The process of carrying out.
Here, “after the pH of the aqueous mixture at 25 ° C. is adjusted to 5.1 to 6.1 and / or while adjusting, the aggregated particles in the aqueous mixture are fused under the pH” When the pH of the aqueous mixture is adjusted to 5.1 to 6.1 after the pH of the aqueous mixture is adjusted to 5.1 to 6.1, the aggregated particles in the aqueous mixture are fused under the pH, and the pH of the aqueous mixture at 25 ° C. is 5 One or both of the cases where the aggregated particles in the aqueous mixed solution are fused while adjusting to 1 to 6.1. The specific method for measuring the pH of the aqueous mixture at 25 ° C. is the same as the specific method for measuring the pH at 25 ° C. of the dispersion of the aggregated particles (2) described later. It is calculated | required by the method of description.

The reason why the toner for developing an electrostatic charge image obtained by the production method of the present invention can achieve both good low-temperature fixability and heat-resistant storage stability and little toner scattering is not clear, but is considered as follows.
In the present invention, when the aggregated particles containing the resin particles (A) and the release agent particles are fused in an aqueous medium, the pH of the aqueous mixed solution containing the aggregated particles at 25 ° C. is 5.1 to 6. Adjusted to 1. When fusion is performed at a pH in the weakly acidic range, fusion between the resin particles (A) occurs rapidly. For this reason, since the fusion is completed before the release agent is melted or separated, the release agent is exposed to the toner surface even if the release agent is blended so much as to be effective for low-temperature fixability. It is considered that the heat storage stability is good and toner scattering is also suppressed.
On the other hand, when the liquid property is weakly acidic, the stability of the particles is lowered, and not only the fusion between the resin particles (A) but also the fusion between the aggregated particles is promoted. However, the inclusion of an anionic surfactant having a polyethylene glycol moiety with an average addition mole number of ethylene oxide of 1 or more and less than 8 prevents fusion of aggregated particles due to its steric repulsion and electrostatic repulsion. In addition, the generation of coarse particles is suppressed. Therefore, it is considered that a toner having a uniform particle diameter is obtained and toner scattering is small.
Hereinafter, each component and process used in the present invention will be described.

[Resin particles (A)]
In the present invention, the resin particles (A) preferably contain a crystalline polyester (a). When the resin particles (A) contain the crystalline polyester (a), the content of the crystalline polyester (a) in the resin particles (A) is a viewpoint that improves low-temperature fixability of the toner and a viewpoint that prevents hot offset. From the resin constituting the resin particles (A), 1 to 50% by mass is preferable, 5 to 40% by mass is more preferable, 10 to 30% by mass is further preferable, and 13 to 25% by mass is still more preferable. -20 mass% is still more preferable.

(Crystalline polyester (a))
In the present invention, the crystalline polyester (a) is a ratio between the softening point and the maximum endothermic peak temperature measured by a differential scanning calorimeter (DSC), (softening point (° C)) / (maximum endothermic peak temperature (° C)). The crystallinity index defined by is 0.6 to 1.4, and from the viewpoint of improving the low-temperature fixability of the toner, 0.8 to 1.3 is preferable, and 0.9 to 1.2 Are more preferable, and those of 1.0 to 1.2 are more preferable.
The crystalline polyester (a) preferably has an acid group at the molecular end from the viewpoint of improving the emulsifiability of the resin. Examples of the acid group include a carboxy group, a sulfonic acid group, a phosphonic acid group, and a sulfinic acid group. Among these, a carboxy group is preferable from the viewpoint of achieving both the emulsifiability of the resin and the storage stability of the obtained toner.

The melting point of the crystalline polyester (a) is preferably 50 to 150 ° C., more preferably 55 to 130 ° C., and further preferably 60 to 90 ° C. from the viewpoint of improving the low-temperature fixability of the toner and improving the heat-resistant storage stability. Preferably, 60-80 degreeC is still more preferable.
From the same viewpoint, the softening point of the crystalline polyester (a) is preferably 50 to 140 ° C, more preferably 55 to 130 ° C, still more preferably 60 to 110 ° C, and still more preferably 60 to 85 ° C.
From the same viewpoint, the number average molecular weight of the crystalline polyester (a) is preferably 1,500 to 50,000, more preferably 2,000 to 10,000, and further preferably 3,000 to 5,000.
The acid value of the crystalline polyester (a) is preferably 5 to 30 mgKOH / g, more preferably 10 to 27 mgKOH / g, and more preferably 15 to 25 mgKOH / g from the viewpoint of improving the emulsifiability of the resin and improving the heat resistant storage stability. g is still more preferable, and 17-25 mgKOH / g is still more preferable.
In addition, crystalline polyester (a) can be used individually or in combination of 2 or more types.
In the present invention, the melting point, softening point, number average molecular weight and acid value of the crystalline polyester (a) are determined by the methods described in the examples. When two or more kinds are used in combination, the melting point of the crystalline polyester (a) having the largest mass ratio in the crystalline polyester (a) contained in the obtained toner is the melting point of the crystalline polyester (a) in the present invention. The melting point. When all have the same ratio, the lowest value is set. A softening point and a number average molecular weight are calculated | required by the method as described in an Example as a mixture of crystalline polyester (a).

The crystalline polyester (a) can be produced by subjecting an acid component and an alcohol component to a polycondensation reaction at 120 to 250 ° C., preferably in the presence of an esterification catalyst as necessary.
Examples of the acid component include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, trivalent or higher polyvalent carboxylic acids, anhydrides of these acids, and alkyl esters having 1 to 3 carbon atoms. Of these, aliphatic dicarboxylic acids are preferred from the viewpoint of improving the low-temperature fixability of the toner and improving the heat-resistant storage stability.
Specific examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid, azelaic acid , N-dodecyl succinic acid, n-dodecenyl succinic acid, etc. Among them, from the viewpoint of improving the low temperature fixability of the toner and the heat resistant storage stability, one kind of sebacic acid and 1,12-dodecanedioic acid Or 2 types are preferable, and sebacic acid or 1,12-dodecanedioic acid is more preferable.
Specific examples of the alicyclic dicarboxylic acid include cyclohexane dicarboxylic acid.
Specific examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid and the like.
Specific examples of the trivalent or higher polyvalent carboxylic acid include trimellitic acid and pyromellitic acid.
These can be used alone or in combination of two or more.

Examples of the alcohol component include aliphatic diols having 2 to 12 carbon atoms in the main chain, aromatic diols, hydrogenated products of bisphenol A, trihydric or higher polyhydric alcohols, etc. Among them, the crystallinity of polyester is promoted. From the viewpoint of improving the low-temperature fixability of the toner, an aliphatic diol having 2 to 12 main chain carbon atoms is preferred.
Among the aliphatic diols having 2 to 12 main chain carbon atoms, α, ω-linear alkanediols are preferable from the viewpoint of promoting the crystallinity of the polyester and improving the low-temperature fixability of the toner. The thing of 6-12 is more preferable.
Specific examples of α, ω-linear alkanediol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptane. Examples include diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, and the like. From the viewpoint of improving, one or two of 1,6-hexanediol and 1,9-nonanediol are preferable, and 1,6-hexanediol or 1,9-nonanediol is more preferable.
Specific examples of other aliphatic diols having 2 to 12 main chain carbon atoms include 1,2-propanediol, neopentyl glycol, 1,4-butenediol, and the like.
Specific examples of the aromatic diol include 2 carbon atoms of bisphenol A such as polyoxypropylene-2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane. -3 alkylene oxide adducts (average number of added moles of 1 to 16).
Specific examples of the trihydric or higher polyhydric alcohol include glycerin and pentaerythritol.

  The alcohol component can be used alone or in combination of two or more. From the viewpoint of promoting the crystallinity of the polyester, the alcohol component contains 80 to 100 moles of an aliphatic diol having 2 to 12 carbon atoms in the main chain. %, And more preferably 90 to 100 mol%.

As an esterification catalyst, a tin compound, a titanium compound, etc. are preferable from a viewpoint of performing a polycondensation reaction efficiently, A tin compound is more preferable, Di (2-ethylhexanoic acid) tin, dibutyltin oxide, etc. are mentioned.
Examples of the titanium compound include titanium diisopropylate bistriethanolamate.
Although there is no restriction | limiting in the usage-amount of an esterification catalyst, 0.01-1 mass part is preferable with respect to 100 mass parts of total amounts of an acid component and an alcohol component, and 0.1-0.6 mass part is more preferable.

  As a method for producing the crystalline polyester (a), the polycondensation reaction is preferably carried out by placing an acid component and an alcohol component in a reaction vessel and maintaining them at 140 to 200 ° C. for 5 to 15 hours. A method of obtaining the crystalline polyester (a) is preferred by adding the oxidization catalyst and maintaining the reaction at 140 to 200 ° C. for 1 to 5 hours to proceed the reaction, reducing the pressure to 5.0 to 20 kPa and maintaining for 1 to 10 hours. .

(Amorphous polyester (c))
From the viewpoint of improving the low-temperature fixability of the toner, the viewpoint of improving the heat-resistant storage stability, and the prevention of hot offset, the resin particles (A) may further contain an amorphous polyester (c) in addition to the crystalline polyester (a). It is preferable to contain.
In the present invention, the amorphous polyester (c) is a polyester having a crystallinity index of more than 1.4 or less than 0.6.
The amorphous polyester (c) preferably has a crystallinity index of less than 0.6 or more than 1.4 and 4 or less, more preferably 0.6 from the viewpoint of improving the low-temperature fixability of the toner. Less than or 1.5 or more and 4 or less, More preferably, it is less than 0.6 or 1.5 or more and 3 or less, More preferably, it is less than 0.6 or 1.5 or more and 2 or less. The crystallinity index can be appropriately determined according to the production conditions such as the type and ratio of the raw material monomers, the reaction temperature, the reaction time, and the cooling rate.
The total amount of the crystalline polyester (a) and the amorphous polyester (c) in the resin particles (A) is preferably 50 to 100 in the resin constituting the resin particles (A) from the viewpoint of improving the low-temperature fixability of the toner. It is 80 mass%, More preferably, it is 80-100 mass%, More preferably, it is 90-100 mass%. The mass ratio ((a) / (c)) between the crystalline polyester (a) and the amorphous polyester (c) in the resin particles (A) improves the low-temperature fixability of the toner and improves the heat-resistant storage stability. 1/99 to 50/50, preferably 5/95 to 40/60, more preferably 10/90 to 30/70, and 13/87 to 25 from the viewpoint of preventing hot offset. / 75 is more preferable, and 13/87 to 20/80 is still more preferable.

  As the amorphous polyester (c) that can be contained in the resin particles (A), the same polyester as the amorphous polyester (b) described later can be preferably used. A resin having the same composition as that of the amorphous polyester (b) may be used, or a resin having a different composition may be used, and the use of the resin having the same composition controls the cohesiveness of the resin particles (A) and This is preferable from the viewpoint of improving the low-temperature fixability of the toner.

Amorphous polyester (c) is a method similar to amorphous polyester (b) described below, and preferably comprises an acid component and an alcohol component in the presence of an esterification catalyst, a polymerization inhibitor or the like, if necessary. It can be produced by a polycondensation reaction at 180 to 250 ° C. The preferred acid component and alcohol component are the same as the amorphous polyester (b), and two or more kinds may be used. Specifically, as the preferred acid component, dicarboxylic acid, trivalent or higher polyvalent Examples thereof include carboxylic acids, acid anhydrides thereof, and alkyl esters having 1 to 3 carbon atoms.
As the dicarboxylic acid, terephthalic acid, fumaric acid, and succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms are preferable. As specific examples of succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, dodecenyl succinic acid and acid anhydrides thereof are preferable. Moreover, as a polyvalent carboxylic acid more than trivalence, trimellitic acid and its acid anhydride are preferable.

  Examples of alcohol components include aromatic diols, and carbons of bisphenol A such as polyoxypropylene-2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane. A number 2-3 alkylene oxide adduct (average addition mole number 1-16) is preferable, and polyoxypropylene-2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene-2,2-bis (4- One or two kinds of hydroxyphenyl) propane are more preferred, and two kinds are more preferred.

As an esterification catalyst, a tin compound, a titanium compound, etc. are preferable from a viewpoint of performing a polycondensation reaction efficiently, A tin compound is more preferable, Di (2-ethylhexanoic acid) tin, dibutyltin oxide, etc. are mentioned.
Examples of the titanium compound include titanium diisopropylate bistriethanolamate.
Although there is no restriction | limiting in the usage-amount of an esterification catalyst, 0.01-1 mass part is preferable with respect to 100 mass parts of total amounts of an acid component and an alcohol component, and 0.1-0.6 mass part is more preferable.
Examples of the polymerization inhibitor include tert-butylcatechol. The amount of the polymerization inhibitor used is preferably 0.001 to 0.5 parts by mass and more preferably 0.005 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of the acid component and the alcohol component.
The glass transition temperature, softening point, number average molecular weight and acid value of the amorphous polyester (c) are preferably in the same range as the amorphous polyester (b).

  The amorphous polyester (c) may be used alone or in combination of two or more, and is softened from the viewpoint of improving the low-temperature fixability of the toner, the viewpoint of improving the heat-resistant storage stability and the prevention of hot offset. It is preferable to contain two types of polyesters having different points. When two types of polyesters having different softening points are polyesters (c-1) and (c-2), respectively, the softening point of one polyester (c-1) is preferably 70 ° C. or higher and lower than 115 ° C., and the other polyester The softening point of (c-2) is preferably 115 ° C. or higher and 165 ° C. or lower. The mass ratio ((c-1) / (c-2)) between the polyester (c-1) and the polyester (c-2) is preferably 10/90 to 90/10, and 50/50 to 90/10. More preferred.

The resin particle (A) is a resin other than the crystalline polyester (a) and the amorphous polyester (c), for example, a styrene-acrylic copolymer, an epoxy resin, a polycarbonate, and a polyurethane as long as the effects of the present invention are not impaired. A resin such as
The resin particles (A) may contain a charge control agent as long as the effects of the present invention are not impaired. Moreover, you may contain additives, such as reinforcement fillers, such as a fibrous material, antioxidant, and anti-aging agent, as needed.

(Coloring agent)
The resin particles (A) may be particles made of resin alone, or may be colorant-containing resin particles containing a colorant, but contain a colorant from the viewpoint of sharpening the particle size distribution of the toner. It is preferable to be a colorant-containing resin particle containing a colorant.
When the resin particles (A) are colorant-containing resin particles, the content of the colorant is from 1 to 100 parts by mass of the resin constituting the resin particles (A) from the viewpoint of improving the image density of the toner. 20 mass parts is preferable and 5-10 mass parts is more preferable.

As the colorant, pigments and dyes are used, and pigments are preferable from the viewpoint of improving the image density of the toner.
Specific examples of the pigment include carbon black, inorganic composite oxide, chrome yellow, benzidine yellow, brilliantamine 3B, brilliantamine 6B, Bengal, aniline blue, ultramarine blue, copper phthalocyanine, phthalocyanine green, and the like. Phthalocyanine is preferred.
Specific examples of the dye include acridine series, azo series, benzoquinone series, azine series, anthraquinone series, indico series, phthalocyanine series, and aniline black series.
A coloring agent can be used individually by 1 type or in combination of 2 or more types.

(Production of resin particles (A))
The resin particles (A) are produced by a method in which the above-mentioned optional components such as the resin containing the crystalline polyester (a) and the colorant are dispersed in an aqueous medium to obtain a dispersion containing the resin particles (A). Is preferred.
Examples of a method for obtaining a dispersion include a method in which a resin or the like is added to an aqueous medium and a dispersion treatment is performed using a disperser or the like, and a method in which an aqueous medium is gradually added to a resin or the like to perform phase inversion emulsification. From the viewpoint of improving the low-temperature fixability of the toner, a method using phase inversion emulsification is preferred. Hereinafter, a method by phase inversion emulsification will be described.

First, the resin containing the crystalline polyester (a), the alkaline aqueous solution, and the optional components such as the colorant are melted and mixed to obtain a resin mixture.
When the resin containing the crystalline polyester (a) is composed of a plurality of resins, a mixture of the crystalline polyester (a) and other resins may be used in advance, It may be obtained by adding at the same time when adding, melting and mixing. For example, when the resin containing the crystalline polyester (a) contains the amorphous polyester (c), the crystalline polyester (a), the amorphous polyester (c), the alkaline aqueous solution, and the above optional components A method of melting and mixing the toner to obtain a resin mixture is preferable from the viewpoint of improving the low-temperature fixability of the toner.
In mixing, it is preferable to add a surfactant from the viewpoint of improving the emulsifiability of the resin.

  Examples of the alkali in the alkaline aqueous solution include hydroxides of alkali metals such as potassium hydroxide and sodium hydroxide, and amines such as ammonia. From the viewpoint of improving the emulsifiability of the resin, potassium hydroxide, hydroxide Sodium is preferred. Moreover, 1-30 mass% is preferable, as for the density | concentration of the alkali in alkaline aqueous solution, 1-25 mass% is more preferable, and 1.5-20 mass% is still more preferable.

Examples of the surfactant include nonionic surfactants, anionic surfactants, and cationic surfactants. Among them, nonionic surfactants are preferable, and nonionic surfactants and anionic surfactants are preferred. It is more preferable to use an active agent or a cationic surfactant in combination, and it is more preferable to use a nonionic surfactant and an anionic surfactant in combination from the viewpoint of sufficiently emulsifying the resin.
When a nonionic surfactant and an anionic surfactant are used in combination, the mass ratio of the nonionic surfactant to the anionic surfactant (nonionic surfactant / anionic surfactant) is: From the viewpoint of sufficiently emulsifying the resin, 0.3 to 10 is preferable, and 0.5 to 5 is more preferable.

Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl aryl ethers such as polyoxyethylene lauryl ether or polyoxyethylene alkyl ethers, polyethylene glycol monolaurate, Examples include polyoxyethylene fatty acid esters such as polyethylene glycol monostearate and polyethylene glycol monooleate, and oxyethylene / oxypropylene block copolymers. From the viewpoint of improving the emulsifiability of the resin, polyoxyethylene alkyl ethers are Among them, polyoxyethylene oleyl ether is preferable.
Specific examples of the anionic surfactant include dodecyl benzene sulfonic acid, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium alkyl ether sulfate and the like, and in particular, from the viewpoint of improving the emulsifiability of the resin, dodecyl benzene sulfone. Sodium acid and sodium alkyl ether sulfate are preferred.
Specific examples of the cationic surfactant include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like.

  The content of the surfactant is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin constituting the resin particles (A). 0.5-10 mass parts is still more preferable.

  As a method for obtaining a resin mixture, a resin containing crystalline polyester (a), an aqueous alkali solution, and the above optional components, preferably a surfactant, are placed in a container, and the resin is melted uniformly while stirring with a stirrer. It is preferable to mix them.

  When the resin containing the crystalline polyester (a) contains the amorphous polyester (c), the temperature at which the resin is melted and mixed is preferably equal to or higher than the glass transition temperature, to obtain homogeneous resin particles. Therefore, the melting point of the crystalline polyester (a) is more preferable.

Next, an aqueous medium is added to the resin mixture and phase inversion is performed to obtain a dispersion containing resin particles (A).
As the aqueous medium, those containing water as a main component are preferable. From the viewpoint of environmental properties, the content of water in the aqueous medium is preferably 80% by mass or more, more preferably 90% by mass or more, and further 95% by mass or more. Preferably, substantially 100% by mass is even more preferable, and 100% by mass is even more preferable. As water, deionized water or distilled water is preferably used.
As components other than water, organic solvents that dissolve in water such as alkyl alcohols having 1 to 5 carbon atoms; dialkyl ketones having 1 to 3 carbon atoms such as acetone and methyl ethyl ketone; and cyclic ethers such as tetrahydrofuran are used. Among these, from the viewpoint of preventing the organic solvent from being mixed into the toner, an alkyl alcohol having 1 to 5 carbon atoms that does not dissolve the polyester is preferable, and methanol, ethanol, isopropanol, and butanol are more preferable.

  The temperature at which the aqueous medium is added is preferably equal to or higher than the glass transition temperature of the amorphous polyester (c) when the resin containing the crystalline polyester (a) contains the amorphous polyester (c). From the viewpoint of obtaining resin particles, the melting point of the crystalline polyester (a) is more preferable.

  The addition rate of the aqueous medium is from 0.1 to 50 parts by mass / 100 parts by mass of the resin constituting the resin particles (A) until the phase inversion is completed from the viewpoint of making the resin particles have a small particle size. Preferably, it is 0.1 to 30 parts by weight / minute, more preferably 0.5 to 10 parts by weight / minute, and 0.5 to 5 parts by weight / minute. Is even more preferable. There is no restriction | limiting in the addition rate of the aqueous medium after phase inversion.

  The use amount of the aqueous medium is preferably 100 to 900 parts by mass, and 150 to 500 parts by mass with respect to 100 parts by mass of the resin constituting the resin particles (A) from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation step. More preferred is 170 to 300 parts by mass. From the viewpoint of improving the stability of the resulting resin particle dispersion and facilitating handling, the solid content concentration is preferably 10 to 55% by mass, more preferably 17 to 45% by mass, and still more preferably. It is 20-40 mass%, More preferably, it is 25-35 mass%. In addition, solid content is the total amount of non-volatile components, such as resin and surfactant.

The volume median particle size of the resin particles (A) in the dispersion containing the obtained resin particles (A) is preferably 0.02 to 2 μm. From the viewpoint of obtaining a high-quality toner, 0.02 to 1.5 μm is preferable, 0.05 to 1 μm is more preferable, and 0.05 to 0.5 μm is still more preferable. Here, the volume-median particle diameter is a particle diameter at which the cumulative volume frequency measured by the volume fraction is 50% when calculated from the smaller particle diameter, and is specifically determined by the method described in the examples. It is done.
Further, the coefficient of variation (CV value) (%) of the particle size distribution of the resin particles (A) is preferably 40% or less, more preferably 35% or less, and more preferably 30% or less from the viewpoint of obtaining a high-quality toner. Is more preferable, and 28% or less is even more preferable. The CV value is a value represented by the following formula, and is specifically obtained by the method described in the examples.
CV value (%) = [standard deviation of particle size distribution (μm) / volume median particle size (μm)] × 100

[Releasing agent particles]
The release agent particles preferably contain a surfactant from the viewpoint of improving the cohesiveness. The content in the case of using the surfactant is 0.01 to 10 parts by mass with respect to 100 parts by mass of the release agent from the viewpoint of improving the cohesiveness and the heat resistant storage stability of the obtained toner. Preferably, 0.1-5 mass parts is more preferable.
The volume median particle size of the release agent particles is preferably 0.1 to 1 μm from the viewpoint of improving the heat-resistant storage stability of the obtained toner and suppressing the scattering of the toner in a printing machine such as a printer. -0.7 micrometer is more preferable and 0.2-0.6 micrometer is still more preferable.
The CV value of the release agent particles is preferably 15 to 50%, more preferably 20 to 40% from the viewpoint of improving the heat-resistant storage stability of the obtained toner and suppressing the scattering of the toner in a printer such as a printer. Preferably, 25 to 35% is more preferable. The volume-median particle size and CV value of the release agent particles are determined by the same method as that for the resin particles (A), and specifically by the method described in the examples.

(Release agent)
As release agents, low molecular weight polyolefins such as polyethylene, polypropylene and polybutene; silicones having a softening point upon heating; fatty acid amides such as oleic acid amide and stearic acid amide; carnauba wax, rice wax and candelilla wax Plant waxes such as beeswax; animal waxes such as beeswax; mineral / petroleum waxes such as montan wax, paraffin wax, and Fischer-Tropsch wax. These release agents can be used alone or in combination of two or more.
The melting point of the release agent is preferably 65 to 100 ° C., more preferably 75 to 95 ° C., and still more preferably 75 to 90 ° C., from the viewpoint of improving the low-temperature fixability of the toner and the heat-resistant storage stability. 80-90 degreeC is still more preferable.
In the present invention, the melting point of the release agent is determined by the method described in the examples. When two or more kinds are used in combination, the melting point of the release agent having the largest mass ratio among the release agents contained in the obtained toner is the melting point of the release agent in the present invention. When all have the same ratio, the lowest value is set.
The amount of the release agent used is a resin from the viewpoint of improving the releasability of the toner and improving the low-temperature fixability, improving the heat-resistant storage stability, and suppressing the scattering of the toner in a printer such as a printer. 1-20 mass parts is preferable with respect to 100 mass parts of resin which comprises particle | grains (A), and 2-15 mass parts is more preferable.

(Manufacture of release agent particles)
The release agent particles are preferably obtained as a dispersion of release agent particles by dispersing the release agent in an aqueous medium.
The dispersion of the release agent particles is preferably obtained by dispersing the release agent and the aqueous medium using a disperser in the presence of a surfactant at a temperature equal to or higher than the melting point of the release agent. As the disperser to be used, a homogenizer, an ultrasonic disperser or the like is preferable. What is necessary is just to set dispersion | distribution time suitably with the disperser to be used.
As the aqueous medium and the surfactant used in the production, those used for obtaining the resin mixture are preferably used.

  The solid content concentration of the release agent particle dispersion is preferably 7 to 50% by mass, more preferably 10 to 40% by mass from the viewpoint of improving the dispersion stability of the release agent particles and facilitating handling. %.

[Anionic surfactant having a polyethylene glycol moiety having an average addition mole number of ethylene oxide of 1 or more and less than 8]
In the present invention, an anionic surfactant having a polyethylene glycol moiety having an average addition mole number of ethylene oxide of 1 or more and less than 8 is used.
The average number of moles added of ethylene oxide improves the stability of the aggregated particles and the fusing property of the resin particles, improves the low-temperature fixability and heat-resistant storage stability of the resulting toner, and suppresses toner scattering. 1 or more, preferably 1.5 or more, more preferably 1.8 or more, and still more preferably 2 or more. Further, from the viewpoint of improving the stability of the aggregated particles and the fusing property of the resin particles, improving the low-temperature fixability and heat-resistant storage stability of the resulting toner, and suppressing toner scattering, it is less than 8, and less than 5 Preferably it is 4 or less, more preferably 3 or less. From the same viewpoint, it is preferably 1 or more and less than 5, more preferably 1.5 or more and 4 or less, still more preferably 1.8 or more and 4 or less, and even more preferably 2 or more and 3 or less.
Moreover, if the average added mole number of a polyethylene glycol part is the said range, the part derived from alkylene oxides other than ethylene oxide may be included in the polyethylene glycol part in a block or randomly. Preferable alkylene oxide other than ethylene oxide includes propylene oxide.

Examples of the anionic surfactant having a polyethylene glycol moiety include sulfate ester salts and sulfonate salts having an average addition mole number of ethylene oxide of 1 or more and less than 8, and sulfate ester salts are preferred.
As the sulfate ester salt, polyoxyethylene alkyl ether sulfate, polyoxyethylene polyoxypropylene alkyl ether sulfate and the like are preferable, and polyoxyethylene alkyl ether sulfate is more preferable.
Examples of the alkyl group of the polyoxyethylene alkyl ether sulfate include linear or branched alkyl groups having 8 to 18 carbon atoms.
Specific examples of the polyoxyethylene alkyl ether sulfate include polyoxyethylene lauryl ether sulfate and polyoxyethylene oleyl ether sulfate. From the viewpoint of suppressing toner scattering, polyoxyethylene lauryl ether sulfate is preferable.
Moreover, as said polyoxyethylene alkyl ether sulfate, a sodium salt, potassium salt, lithium salt, etc. can be used, A sodium salt is preferable.
Examples of the sulfonate include polyoxyalkylene alkyl sulfosuccinate.

  Specifically, the anionic surfactant having a polyethylene glycol moiety is preferably an anionic surfactant represented by the following general formula (1).

In formula (1), R ¹ represents an alkyl group having 8 to 16 carbon atoms, n represents an average number of added moles of ethylene oxide, 2 to 3, and M represents ammonium or an alkali metal. The alkali metal is preferably sodium, potassium or lithium.

  Anionic surfactants having two or more polyethylene glycol moieties having different average addition mole numbers may be used in combination, and in that case, the total average addition mole number is preferably in the above range. The total average added mole number can be obtained by a weighted average, that is, the sum of the product of the average added mole number and the content ratio of each active agent.

  The addition amount of the anionic surfactant having a polyethylene glycol portion is 1 to 20 with respect to 100 parts by mass of the resin in the aggregated particles from the viewpoint of suppressing the generation of coarse particles and reducing the residual of the surfactant. Mass parts are preferable, 1-10 mass parts is more preferable, 1-5 mass parts is still more preferable, and 1.5-5 mass parts is still more preferable.

[Resin particles (B)]
In the present invention, the resin particles (B) preferably contain the amorphous polyester (b) from the viewpoint of improving the low-temperature fixability of the toner and the heat-resistant storage stability.
The glass transition temperature of the resin particles (B) is appropriately determined depending on the glass transition temperature of the resin such as the amorphous polyester (b) constituting the resin particles (B) and the type and amount of the additive. From the viewpoint of improving low-temperature fixability and improving heat-resistant storage stability, it is preferably 45 ° C or higher, more preferably 45 to 70 ° C, still more preferably 50 to 70 ° C, and still more preferably 55 to 65 ° C. .

The resin particles (B) preferably contain 70% by mass or more, more preferably 80% by mass of the amorphous polyester (b) from the viewpoint of improving the low temperature fixability of the toner and improving the heat resistant storage stability. More preferably, the content is 90% by mass or more, still more preferably 95% by mass or more, and still more preferably 100% by mass.
The resin particles (B) may contain, along with the amorphous polyester (b), well-known resins usually used for toners, for example, resins such as styrene-acrylic copolymers, epoxy resins, polycarbonates and polyurethanes. Good.
The resin particles (B) can be obtained by the same method as the method for producing the resin particles (A) described above, but the same alkaline aqueous solution, surfactant, and aqueous medium can be suitably used. .

The volume median particle size of the resin particles (B) in the dispersion containing the obtained resin particles (B) is preferably 0.02 to 2 μm. From the viewpoint of obtaining a high-quality toner, 0.02 to 1.5 μm is preferable, 0.05 to 1 μm is more preferable, and 0.05 to 0.5 μm is still more preferable.
In addition, the coefficient of variation (CV value) (%) of the particle size distribution of the resin particles (B) is preferably 40% or less, more preferably 35% or less, and more preferably 30% or less from the viewpoint of obtaining a high-quality toner. Is more preferable, and 28% or less is even more preferable. The volume median particle size and CV value of the resin particles (B) are determined by the same method as that for the resin particles (A), and specifically by the method described in the examples.

  The solid content concentration of the resin particles (B) in the dispersion containing the resin particles (B) is preferably 7 to 7 from the viewpoint of improving the stability of the resulting resin particle dispersion and facilitating handling. 50 mass%, More preferably, it is 10-40 mass%, More preferably, it is 20-40 mass%.

(Amorphous polyester (b))
In the present invention, the amorphous polyester (b) is a polyester having the above-mentioned crystallinity index of more than 1.4 or less than 0.6.
The amorphous polyester (b) preferably has a crystallinity index of less than 0.6 or more than 1.4 and 4 or less, more preferably 0.6 from the viewpoint of improving the low-temperature fixability of the toner. Less than or 1.5 or more and 4 or less, More preferably, it is less than 0.6 or 1.5 or more and 3 or less, More preferably, it is less than 0.6 or 1.5 or more and 2 or less. The crystallinity index can be appropriately determined depending on the production conditions such as the type and ratio of the raw material monomers, the reaction temperature, the reaction time, and the cooling rate.
As the amorphous polyester (b), an amorphous polyester (b) having an acid group at the molecular end is preferable. Examples of the acid group include a carboxy group, a sulfonic acid group, a phosphonic acid group, and a sulfinic acid group. Among these, a carboxy group is preferable from the viewpoint of facilitating emulsification of the polyester.

  The amorphous polyester (b) can be produced by subjecting an acid component and an alcohol component to a polycondensation reaction, preferably at 180 to 250 ° C., in the presence of an esterification catalyst, a polymerization inhibitor or the like, if necessary. it can.

Examples of the acid component include dicarboxylic acids, trivalent or higher polyvalent carboxylic acids, acid anhydrides thereof, and alkyl esters having 1 to 3 carbon atoms. Among them, dicarboxylic acids are preferable.
Specific examples of the dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, sebacic acid, fumaric acid, maleic acid, adipic acid, azelaic acid, succinic acid, cyclohexanedicarboxylic acid, etc. Among them, fumaric acid, terephthalic acid And succinic acid are preferred.
As the succinic acid, a succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms is preferable, and specific examples thereof include dodecyl succinic acid, dodecenyl succinic acid, octenyl succinic acid, and the like. . Of these, dodecenyl succinic acid and its acid anhydride are preferred from the viewpoint of improving low-temperature fixability.
Specific examples of the trivalent or higher polyvalent carboxylic acid include trimellitic acid, 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid and the like. Among them, trimellitic acid is used from the viewpoint of preventing hot offset of the toner. And acid anhydrides thereof are preferred.
An acid component can be used individually or in combination of 2 or more types.
From the viewpoint of preventing hot offset of the toner, the amorphous polyester (b) is an acid containing a trivalent or higher polyvalent carboxylic acid and an acid anhydride or an alkyl ester thereof, preferably trimellitic acid or an acid anhydride thereof. It is preferable to use at least one amorphous polyester (b) obtained by using the components.

As an alcohol component, the thing similar to the said alcohol component used for crystalline polyester (a) is mentioned. Among these, it is preferable to use an aromatic diol from the viewpoint of obtaining amorphous polyester, and polyoxypropylene-2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene-2,2-bis ( It is more preferable to use an alkylene oxide adduct having 2 to 3 carbon atoms (average number of added moles of 1 to 16) of bisphenol A such as 4-hydroxyphenyl) propane.
An alcohol component can be used individually or in combination of 2 or more types.

As the esterification catalyst used in the production of the amorphous polyester (b), from the viewpoint of efficiently performing the polycondensation reaction, a tin compound, a titanium compound and the like are preferable, a tin compound is more preferable, and di (2-ethylhexanoic acid) tin And dibutyltin oxide.
Examples of the titanium compound include titanium diisopropylate bistriethanolamate.
Although there is no restriction | limiting in the usage-amount of an esterification catalyst, 0.01-1 mass part is preferable with respect to 100 mass parts of total amounts of an acid component and an alcohol component, and 0.1-0.6 mass part is more preferable.
Examples of the polymerization inhibitor include tert-butylcatechol. The amount of the polymerization inhibitor used is preferably 0.001 to 0.5 parts by mass and more preferably 0.005 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of the acid component and the alcohol component.

The glass transition temperature of the amorphous polyester (b) is preferably from 50 to 80 ° C., more preferably from 50 to 70 ° C., from the viewpoint of improving the low-temperature fixability of the toner and improving the heat-resistant storage stability. ° C is more preferable, and 58-67 ° C is still more preferable.
From the same viewpoint, the softening point of the amorphous polyester (b) is preferably 70 to 165 ° C, more preferably 80 to 140 ° C, still more preferably 90 to 135 ° C, and still more preferably 100 to 130 ° C.
In addition, when using 2 or more types of amorphous polyesters (b) in mixture, the glass transition temperature and the softening point are as described in the examples as a mixture of 2 or more types of amorphous polyesters (b). The value obtained by the method.

The number average molecular weight of the amorphous polyester (b) is preferably 1,000 to 50,000, and preferably 1,500 to 10,000 from the viewpoint of improving the low-temperature fixability of the toner and improving the heat-resistant storage stability. More preferred is 2,000 to 8,000.
From the viewpoint of improving the emulsifiability of the resin, the acid value of the amorphous polyester (b) is preferably 6 to 35 mgKOH / g, more preferably 10 to 35 mgKOH / g, and still more preferably 15 to 30 mgKOH / g.

  The amorphous polyester (b) may be used alone or in combination of two or more, and is softened from the viewpoint of improving the low-temperature fixability of the toner, the viewpoint of improving the heat-resistant storage stability and the prevention of hot offset. It is preferable to contain two types of polyesters having different points. When two types of polyesters having different softening points are polyesters (b-1) and (b-2), respectively, the softening point of one polyester (b-1) is preferably 70 ° C. or higher and lower than 115 ° C., and the other polyester The softening point of (b-2) is preferably 115 ° C. or higher and 165 ° C. or lower. The mass ratio ((b-1) / (b-2)) between the polyester (b-1) and the polyester (b-2) is preferably 10/90 to 90/10, and 50/50 to 90/10. More preferred.

  In addition, in this invention, what modified | denatured each of crystalline polyester (a), amorphous polyester (b), and (c) can be used in the range which does not impair the effect. Examples of methods for modifying the polyester include grafting with phenol, urethane, epoxy, etc. by the methods described in JP-A-11-133668, JP-A-10-239903, JP-A-8-20636, and the like. Examples thereof include a method of forming a block and a method of forming a composite resin having two or more resin units including a polyester unit.

[acid]
In the present invention, the acid is suitably used for adjusting the pH at 25 ° C. of the aqueous mixed solution used in the step of fusing the aggregated particles to the range of 5.1 to 6.1.
Although there is no restriction | limiting in the acid used, From a viewpoint of adjusting pH efficiently and fuse | melting an aggregated particle efficiently, an inorganic acid is preferable and a mineral acid is more preferable.
Examples of the mineral acid include hydrochloric acid, sulfuric acid, nitric acid and the like, hydrochloric acid and sulfuric acid are preferable, and sulfuric acid is more preferable.
When using an acid, it is preferably used as an aqueous solution, and the concentration is preferably 0.1 to 2N. Here, “N” represents the normality of acid (the number of moles of acid / liter multiplied by an equivalent).

<Method for producing toner for developing electrostatic image>
The method for producing a toner for developing an electrostatic charge image according to the present invention comprises an agglomerated particle containing resin particles (A) and a releasing agent particle, and an anion having a polyethylene glycol moiety having an average added mole number of ethylene oxide of 1 or more and less than 8. After adjusting and / or adjusting the pH at 25 ° C. of the aqueous mixed solution containing the surfactant to 5.1 to 6.1, the aggregated particles in the aqueous mixed solution are fused under the pH. It has the process to do.
The agglomerated particles used in this step are the step (1) of obtaining the agglomerated particles (1) by mixing the resin particles (A), the release agent particles and the aggregating agent in an aqueous medium, and the step (1). The agglomerated particles (2) obtained by the step (2) of adding the resin particles (B) containing the amorphous polyester (b) to the agglomerated particles (1) obtained in step (2) to obtain the agglomerated particles (2) It is preferable that
In the step of fusing the aggregated particles, the aggregated particles (2) may be at least 10 ° C lower than the glass transition temperature of the amorphous polyester (b) and not higher than 10 ° C higher than the glass transition temperature. It is preferable that the step (4) be performed at a temperature to obtain fused core-shell particles.
The anionic surfactant having a polyethylene glycol moiety is added before the aggregated particles are fused. Although it is an optional step, it is preferable to include a step (3) of adding an anionic surfactant having a polyethylene glycol moiety after the step (2) and before the step (4).
Furthermore, in one or both of step (3) and step (4), it is preferable to adjust the pH at 25 ° C. to 5.1 to 6.1 by adding an acid, and in particular, suppress the formation of coarse particles. However, from the viewpoint of suppressing the toner scattering property, it is preferable to adjust the pH at 25 ° C. to 5.1 to 6.1 by adding an acid in the step (3).

That is, it is preferable that the method for producing an electrostatic image developing toner of the present invention includes the following steps (1) to (4).
Step (1): Step of obtaining aggregated particles (1) by mixing resin particles (A), release agent particles and flocculant in an aqueous medium Step (2): Aggregated particles obtained in step (1) ( Step 1) Addition of resin particles (B) containing amorphous polyester (b) to obtain agglomerated particles (2) Step (3): Add anionic surfactant having the polyethylene glycol moiety Step (4): Holding the agglomerated particles (2) at a temperature not lower than the glass transition temperature of the amorphous polyester (b) by not less than 10 ° C. and not more than 10 ° C. Step of obtaining Further, preferably, in one or both of step (3) and step (4), an acid is added to adjust the pH at 25 ° C. to 5.1 to 6.1. That is, after adjusting the pH of the aqueous mixture at 25 ° C. to 5.1 to 6.1 in step (3) and / or adjusting the pH of the aqueous mixture at 25 ° C. to 5.1 to 6 in step (4). While adjusting the pH to 1, the aggregated particles in the aqueous mixed solution are fused under the pH to obtain fused core-shell particles.
Hereinafter, each step will be described.

[Step (1)]
Step (1) is a step of obtaining aggregated particles (1) by mixing resin particles (A), release agent particles and aggregating agent in an aqueous medium.

In this step, it is preferable to first mix the resin particles (A) and the release agent particles in an aqueous medium to obtain a mixed dispersion.
In addition, although it is preferable to mix a coloring agent as an arbitrary component, the coloring agent may be mixed as a separate particle by itself, and may be contained in the resin particle (A). ) From the viewpoint of controlling the cohesiveness of the resin particles (A).
In this step, resin particles other than the resin particles (A) may be mixed. As resin particles other than the resin particles (A), resin particles containing amorphous polyester are preferable, and those having the same composition as the resin particles (B) are more preferable.
There is no restriction | limiting in order of mixing, You may add any in order and may add simultaneously.

In 100 parts by mass of the mixed dispersion, the resin particles (A) are preferably 12 to 40 parts by mass, and more preferably 20 to 30 parts by mass. The aqueous medium is preferably 55 to 88 parts by mass, more preferably 65 to 80 parts by mass.
Moreover, 1-20 mass parts is preferable with respect to 100 mass parts of resin which comprises a resin particle (A) from a viewpoint of improving a color density, and, as for a coloring agent, 5-10 mass parts is more preferable.
From the viewpoint of improving the releasability of the toner, the viewpoint of suppressing toner scattering, and the viewpoint of improving the heat resistant storage stability, the release agent particles are 1 to 100 parts by mass of the resin constituting the resin particles (A). 20 mass parts is preferable and 2-15 mass parts is more preferable.
The mixing temperature is preferably 0 to 40 ° C. from the viewpoint of aggregation control.

Next, the particles in the mixed dispersion can be aggregated to suitably obtain a dispersion of aggregated particles (1). It is preferable to add a flocculant for efficient aggregation.
As the flocculant, an inorganic flocculant such as a cationic surfactant of a quaternary salt, an organic flocculant such as polyethyleneimine, an inorganic metal salt, an inorganic ammonium salt, or a bivalent or higher metal complex is used.
Examples of the inorganic metal salt include metal salts such as sodium sulfate, sodium chloride, calcium chloride and calcium nitrate, and inorganic metal salt polymers such as polyaluminum chloride and polyaluminum hydroxide. Examples of the inorganic ammonium salt include ammonium sulfate, ammonium chloride, ammonium nitrate and the like, and ammonium sulfate is more preferable.
The amount of the flocculant used is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, more preferably 40 parts by mass or less, based on 100 parts by mass of the resin constituting the resin particles (A), from the viewpoint of improving the heat-resistant storage stability of the toner. Preferably it is 30 mass parts or less. Further, from the viewpoint of improving the cohesiveness of the resin particles (A), it is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably with respect to 100 parts by mass of the resin constituting the resin particles (A). 5 parts by mass or more. Considering the above points, the amount of the flocculant used is preferably 1 to 50 parts by mass, more preferably 3 to 40 parts by mass, and still more preferably 100 parts by mass of the resin constituting the resin particles (A). Is 5 to 35 parts by mass.

  As an aggregating method, an aggregating agent is preferably added dropwise as an aqueous solution to a container containing a mixed dispersion. The flocculant may be added at one time, or may be added intermittently or continuously. However, it is preferable to perform sufficient stirring at the time of addition and after completion of the addition. From the viewpoint of controlling aggregation and shortening the toner production time, the dropping time of the aggregating agent is preferably 1 to 120 minutes. Moreover, 0-50 degreeC is preferable from a viewpoint of aggregation control.

  At the time of agglomeration, from the viewpoint of controlling the particle size of the agglomerated particles and suppressing the formation of coarse particles, the temperature in the agglomerated system is 25 ° C. or lower than the glass transition temperature of the resin constituting the resin particles (A) The temperature is preferably 25 ° C. or more and 15 ° C. or less higher than the glass transition temperature, more preferably 35 ° C. or more and 5 ° C. or less higher than the glass transition temperature. It is preferable to confirm the progress of aggregation by monitoring the volume-median particle size of the aggregated particles in the temperature range. The volume median particle size is monitored by the method described in the examples.

  The volume median particle size of the obtained agglomerated particles (1) is preferably 1 to 10 μm from the viewpoint of reducing the toner particle size and reducing the amount of scattering of the obtained toner in a printer such as a printer. More preferably, it is 2-9 micrometers, More preferably, it is 3-6 micrometers. The CV value is preferably 30% or less, more preferably 28% or less, and still more preferably 25% or less. The volume-median particle size and CV value of the aggregated particles (1) are specifically determined by the method described in the examples.

[Step (2)]
Step (2) is a step of obtaining aggregated particles (2) by adding resin particles (B) containing amorphous polyester (b) to aggregated particles (1) obtained in step (1). is there.
In this step, a dispersion of resin particles (B) containing amorphous polyester (b) is added to the dispersion of aggregated particles (1) obtained in step (1) to obtain aggregated particles (1 It is preferable that the resin particles (B) are further adhered to the particles to obtain aggregated particles (2).

Before adding the dispersion containing the resin particles (B) (resin particle (B) dispersion) to the dispersion containing the aggregated particles (1) (aggregated particles (1) dispersion), the aggregated particles (1) An aqueous medium may be added to the dispersion for dilution, and it is preferable to add an aqueous medium. By adding the aqueous medium, the resin particles (B) can be more uniformly attached to the aggregated particles (1).
When the resin particle (B) dispersion is added to the aggregated particle (1) dispersion, the aggregating agent may be used in order to efficiently attach the resin particle (B) to the aggregated particle (1).
As a preferable addition method in the case of adding the resin particle (B) dispersion to the aggregated particle (1) dispersion, a method of simultaneously adding the coagulant and the resin particle (B) dispersion, the coagulant and the resin particle (B ) A method of alternately adding the dispersion liquid, and a method of adding the resin particle (B) dispersion liquid while gradually raising the temperature of the aggregated particle (1) dispersion liquid. By doing in this way, the cohesiveness fall of the aggregated particle (1) and the resin particle (B) by the coagulant | flocculant density | concentration fall can be prevented. From the viewpoint of improving the productivity of the toner and from the viewpoint of easy production, it is preferable to add the resin particle (B) dispersion while gradually increasing the temperature of the aggregated particle (1) dispersion.

  The temperature in the system in this step is included in the resin particles (A) from the viewpoint of improving the low-temperature fixability of the toner, improving the heat-resistant storage stability, and suppressing the scattering of the toner in a printer such as a printer. It is preferably 5 ° C. or more lower than the melting point of the crystalline polyester (a) and 2 ° C. or more, more preferably 5 ° C. or more lower than the glass transition temperature of the amorphous polyester (b). When the aggregated particles (2) are produced in this temperature range, the low-temperature fixability and heat-resistant storage stability of the obtained toner are improved. The reason for this is not clear, but because the agglomeration of the aggregated particles (2) does not occur, the generation of coarse particles is suppressed, and the crystallinity of the crystalline polyester (a) can be maintained. Conceivable.

  The addition amount of the resin particles (B) is selected from the viewpoints of improving the low temperature fixability of the toner, improving the heat resistant storage stability, and suppressing the scattering of the toner in a printer such as a printer. The mass ratio of the resin particles (A) (resin particles (B) / resin particles (A)) is preferably 0.3 to 1.5, more preferably 0.3 to 1.0, still more preferably 0.00. An amount of 35 to 0.75 is preferred.

  The resin particle (B) dispersion may be added continuously over a certain period of time, may be added at a time, or may be added in a plurality of divided portions. It is preferable to add them continuously or in several divided portions. By adding as described above, the resin particles (B) are likely to selectively adhere to the aggregated particles (1). Among these, it is preferable to add continuously over a certain time from the viewpoint of promoting selective adhesion and the efficiency of production. The time for continuous addition is preferably 1 to 10 hours, and more preferably 3 to 8 hours, from the viewpoint of obtaining uniform aggregated particles (2) and shortening the production time.

  The volume median particle size of the aggregated particles (2) obtained in the step (2) is preferably 1 to 10 μm, more preferably 2 to 10 μm, and further preferably 3 to 9 μm from the viewpoint of obtaining a high-quality toner. 4 to 6 μm is more preferable. The volume-median particle size of the aggregated particles (2) is specifically determined by the method described in the examples.

The degree of circularity of the agglomerated particles (2) obtained in the step (2) is 0.920 to 0.970, preferably 0.930 to 0, from the viewpoint of suppressing toner scattering in a printing machine such as a printer. .960, more preferably 0.940 to 0.950. The circularity of the aggregated particles (2) can be measured by the method described later.
The pH at 25 ° C. of the dispersion in this step maintains the fusing properties of the resin particles and the stability of the aggregated particles, that is, the fusing properties of the resin particles and the stability of the aggregated particles, and prevents the fusion between the aggregated particles From the viewpoint, 5.5 to 7.0 is preferable, and 5.3 to 6.5 is more preferable.
In addition, pH of the dispersion liquid in this invention is a measured value in 25 degreeC calculated | required by the method as described in an Example.

[Step (3)]
Step (3) is a step of adding an anionic surfactant having the polyethylene glycol moiety. In step (3), it is preferable to adjust the pH of the dispersion to 5.1 to 6.1 by adding an acid to the dispersion of aggregated particles (2) obtained in step (2).
The addition amount of the anionic surfactant having a polyethylene glycol moiety is 1 to 100 parts by mass with respect to 100 parts by mass of the resin in the aggregated particles from the viewpoint of suppressing the generation of coarse particles and reducing the residual of the surfactant. 20 mass parts is preferable, 1-10 mass parts is more preferable, 1-5 mass parts is still more preferable, and 1.5-5 mass parts is still more preferable.
The temperature at which the surfactant and acid are added is not limited, but is preferably 10 ° C to 60 ° C, more preferably 20 ° C to 57 ° C, still more preferably 25 ° C to 57 ° C, and even more preferably 25 ° C to 45 ° C. It is.
In this step, when an acid is added, the surfactant and the acid may be mixed and added, or may be added separately. When adding separately, which may be added first, from the viewpoint of suppressing the generation of coarse particles, it is preferable to add an acid after adding a surfactant.
In this step, when an acid is added, the pH of the resulting dispersion is lowered because the acid is added, but the fusion property of the resin particles and the stability of the aggregated particles are maintained. From the viewpoint of preventing fusion of the resin, it is preferable to add an acid such that the pH of the dispersion at 5.1C is 5.1 to 6.1, more preferably 5.3 to 5.9, and 5.3. -5.7 is still more preferable, and it is still more preferable to add an acid so that it may become 5.3-5.5.

[Step (4)]
In step (4), the agglomerated particles (2) are maintained at a temperature not lower than 10 ° C. and not higher than 10 ° C. below the glass transition temperature of the amorphous polyester (b) to obtain fused core-shell particles. It is a process. It is preferable to carry out so that the final pH at 25 ° C. in step (4) is in the range of 5.1 to 6.1. If no acid is added in step (3), the acid is added in this step. It is preferable to add.
In this step, the particles in the aggregated particles (2), which are mainly physically attached to each other, are fused and integrated to form core-shell particles.

From the viewpoint of improving the fusibility of the agglomerated particles and from the viewpoint of improving the productivity of the toner, in this step, the glass transition temperature of the amorphous polyester (b) is preferably 10 ° C. or higher. Preferably, the temperature is kept at a temperature not lower than 8 ° C., more preferably not lower than 6 ° C., more preferably not lower than 5 ° C. In addition, from the viewpoint of suppressing the scattering of toner in a printer such as a printer, in this step, the temperature is preferably a temperature not higher than the glass transition temperature of the amorphous polyester (b), preferably 10 ° C. or less, more preferably 8 The temperature is maintained at a temperature not higher than ° C, more preferably not higher than 6 ° C, and still more preferably not higher than 5 ° C.
In addition, from the viewpoint of improving the heat resistant storage stability of the toner and suppressing the scattering of the toner in a printer such as a printer, in this step, the temperature is maintained at a temperature lower than 5 ° C. below the melting point of the crystalline polyester (a). It is preferable to keep the temperature at 7 ° C. or lower.

Further, from the viewpoint of improving the fusing property of the aggregated particles, the viewpoint of improving the heat-resistant storage stability of the toner, the viewpoint of suppressing the scattering of the toner in the printer such as a printer, and the viewpoint of improving the productivity of the toner, Is preferably maintained at a temperature not lower than 5 ° C lower than the glass transition temperature of the resin particles (B), and preferably not higher than 10 ° C higher than the glass transition temperature.
In addition, from the viewpoint of suppressing the scattering of toner in a printer such as a printer, in this step, it is preferable to keep the temperature below 5 ° C. below the melting point of the release agent, and keep it below 7 ° C. Is more preferable, and it is still more preferable to hold | maintain at the temperature below 10 degreeC.

In this step, the temperature is preferably maintained at 55 to 70 ° C, more preferably 57 to 67 ° C, and still more preferably 58 to 65 ° C, from the viewpoint of improving the fusibility of the aggregated particles.
The pH at 25 ° C. of the dispersion in this step maintains the fusing properties of the resin particles and the stability of the aggregated particles, that is, the fusing properties of the resin particles and the stability of the aggregated particles, and prevents the fusion between the aggregated particles From a viewpoint, 5.1-6.1 are preferable, 5.3-5.9 are more preferable, 5.3-5.7 are still more preferable, 5.3-5.5 are still more preferable.
In this step, when an acid is added, it is preferable to add the acid so that the pH of the dispersion after adding the acid is 5.1 to 6.1. More preferably, 5.3 to 5.7 is still more preferable, and it is still more preferable to add an acid so that it becomes 5.3 to 5.5.

The holding time in this step improves the fusion property of the aggregated particles, the viewpoint of improving the heat resistant storage stability of the toner, the viewpoint of suppressing the scattering of the toner in the printer such as a printer, and the toner productivity. From the viewpoint, it is preferably 1 to 24 hours, more preferably 1 to 18 hours, and further preferably 2 to 12 hours.
In this step, when an acid is added, it is preferably added within 3 hours after reaching the holding temperature, more preferably within 2 hours, and further within 1 hour. preferable.

In this step, it is preferable to confirm the progress of fusion by monitoring the circularity of the generated core-shell particles. Circularity is monitored by the method described in the examples. When the circularity reaches 0.955 or more, the cooling is performed and the fusion is stopped. The roundness of the finally obtained core-shell particles is 0.955 to 0.995 from the viewpoint of suppressing toner scattering in a printing machine such as a printer and improving the cleaning property, and 0.958 to 0.005. 985 is preferable, 0.960 to 0.980 is more preferable, and 0.965 to 0.980 is still more preferable.
The circularity of the fused core-shell particles is 0.01 compared to the circularity of the aggregated particles (2) from the viewpoint of improving the heat-resistant storage stability of the toner and suppressing the scattering of the toner in a printer such as a printer. It is preferably larger, more preferably larger than 0.012, and still more preferably larger than 0.015.
In this step, it is considered that by increasing the circularity by 0.01 or more, the encapsulation by the shell is improved, the heat resistant storage stability is improved, and the scattering of toner in a printing machine such as a printer is suppressed.
The BET specific surface area of the fused core-shell particles by the nitrogen adsorption method is 1.0 to 5.0 m ² / g from the viewpoint of suppressing scattering of the obtained toner in a printing machine such as a printer and improving the heat resistant storage stability. more preferably from 1.0~2.5m ² / g, still more preferably ^{1.5~2.0m 2 / g, 1.8~1.9m 2 /} g and still more preferably more.

From the viewpoint of obtaining a high-quality toner, the volume-median particle size of the core-shell particles obtained in this step is preferably 2 to 10 μm, more preferably 2 to 8 μm, still more preferably 2 to 7 μm, and still more preferably 3 to 3 μm. The thickness is 7 μm, more preferably 4 to 6 μm.
The volume-median particle size of the fused core-shell particles obtained in this step is preferably not more than the volume-median particle size of the aggregated particles (2). That is, in this step, it is preferable that the core shell particles do not aggregate and fuse. The circularity, the BET specific surface area, and the volume median particle size of the core-shell particles are determined by the same method as that for the toner particles, specifically, the methods described in the examples.

[Post-processing process]
In the present invention, a post-treatment step may be performed after the step (4), and it is preferable to obtain toner particles by isolating the core-shell particles.
Since the core-shell particles obtained in the step (4) are present in the aqueous medium, it is preferable to first perform solid-liquid separation. For solid-liquid separation, a suction filtration method or the like is preferably used.
It is preferable to perform washing after the solid-liquid separation. When a nonionic surfactant is used in the production of the resin particles (A) and (B), it is preferable to remove the added nonionic surfactant, so the cloud point of the nonionic surfactant In the following, it is preferable to wash with an aqueous solution. The washing is preferably performed a plurality of times.
Next, although it is preferable to dry, the temperature at the time of drying is preferably set so that the temperature of the core-shell particle itself is 5 ° C. or more lower than the melting point of the crystalline polyester, and is set so as to be 10 ° C. or more lower It is more preferable. As a drying method, it is preferable to use a vacuum low temperature drying method, a vibration type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method, or the like. The water content after drying is preferably 1.5% by mass or less, more preferably 1.0% by mass from the viewpoint of suppressing scattering of the obtained toner in a printing machine such as a printer and improving heat-resistant storage stability. Adjusted to:

  The degree of circularity of the toner particles obtained in this step is preferably 0.955 to 0.985 from the viewpoint of improving heat-resistant storage stability, suppressing scattering in a printing machine such as a printer, and improving cleaning properties. More preferably, it is 0.955-0.980, More preferably, it is 0.964-0.980. The circularity of the toner particles can be measured by the method described in the examples. The circularity of the toner particles is a value obtained by the ratio of the circumference of a circle equal to the projected area to the circumference of the projected image (ratio of the circumference of the circle equal to the projected area / the circumference of the projected image). The more spherical the particles are, the closer the circularity is to 1.

  The volume median particle size of the toner particles obtained in this step is preferably 1 to 10 μm, more preferably 2 to 8 μm, still more preferably 3 to 7 μm, from the viewpoint of improving image quality and improving productivity. More preferably, it is 4-6 micrometers.

The CV value of the toner particles is preferably 30% or less, more preferably 27% or less, still more preferably 25% or less, and still more preferably 22% or less, from the viewpoint of improving image quality and improving productivity. .
The BET specific surface area by the nitrogen adsorption method of the toner particles is preferably 1.0 to 5.0 m ² / g from the viewpoint of suppressing scattering in a printing machine such as a printer and improving heat resistant storage stability, and is preferably 1.0 to 2.5 m ² / g and more preferably, still more preferably ^{1.5~2.0m 2 / g, 1.8~1.9m 2 /} g and still more preferably more.
The volume median particle size, CV value, and BET specific surface area of the toner particles are determined by the methods described in the examples.

<Toner for electrostatic image development>
(toner)
Although the toner particles obtained by drying or the like can be used as they are as the toner of the present invention, it is preferable to use toner particles whose surfaces have been treated as described below as electrostatic charge image developing toner.

  The softening point of the obtained toner is preferably 60 to 140 ° C., more preferably 60 to 130 ° C., and still more preferably 60 to 120 ° C. from the viewpoint of improving low-temperature fixability and improving heat-resistant storage stability. . The glass transition temperature is preferably 30 to 80 ° C., more preferably 40 to 70 ° C., from the viewpoint of improving low-temperature fixability and heat-resistant storage stability.

  The toner obtained by the method of the present invention has a core-shell structure, and amorphous polyester (b) is preferably contained in the shell part in an amount of 50 to 100% by mass, more preferably 70 to 100% by mass, and still more preferably 90 to 90%. Contains 100% by mass.

(External additive)
In the toner for developing an electrostatic charge image of the present invention, the toner particles can be used as the toner as they are, but it is preferable to use a toner obtained by adding a fluidizing agent or the like to the toner particle surface as an external additive.
Examples of the external additive include inorganic fine particles such as hydrophobic silica, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, and carbon black, and polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Of these, hydrophobic silica is preferred.
When the surface treatment of the toner particles is performed using the external additive, the amount of the external additive added is preferably 1 to 5 parts by mass, more preferably 100 parts by mass of the toner particles before the treatment with the external additive. It is 1-4 mass parts, More preferably, it is 1.5-4 mass parts.

  The electrostatic image developing toner obtained by the present invention can be used as a one-component developer or mixed with a carrier and used as a two-component developer.

  In relation to the above-described embodiment, the present invention discloses the following method for producing an electrostatic image developing toner and electrostatic image developing toner.

<1> Aggregated particles containing resin particles (A) and release agent particles, and the average added mole number of ethylene oxide is 1 or more and less than 8, preferably 1.5 or more, more preferably 1.8 or more, and still more preferably. 2 or more, preferably less than 5, more preferably 4 or less, still more preferably 3 or less, preferably 1 or more and less than 5, more preferably 1.5 or more and 4 or less, still more preferably 1.8 or more and 4 or less. The pH of the aqueous mixture containing an anionic surfactant having a polyethylene glycol moiety that is 2 or more and 3 or less is 5.1 to 6.1, preferably 5.3 to 5. 9, more preferably 5.3 to 5.7, and even more preferably after adjusting to 5.3 to 5.5, and / or while adjusting, the aggregated particles in the aqueous mixture are fused under the pH. Electrostatic process Manufacturing method of the image developing toner.

<2> The method for producing a toner for developing an electrostatic charge image according to <1>, wherein the aggregated particles are aggregated particles (2) obtained by the following steps (1) and (2).
Step (1): Step of obtaining the agglomerated particles (1) by mixing the resin particles (A), the release agent particles and the aggregating agent in an aqueous medium. Step (2): Aggregation obtained in the step (1) The step of adding the resin particles (B) containing the amorphous polyester (b) to the particles (1) to obtain the agglomerated particles (2) <3> The step of fusing the agglomerated particles includes the following steps: (4) The method for producing a toner for developing an electrostatic charge image according to <2>.
Step (4): The aggregated particles (2) are preferably at least 10 ° C lower than the glass transition temperature of the amorphous polyester (b), more preferably at least 8 ° C lower, more preferably at least 6 ° C lower than the glass transition temperature. More preferably, the temperature is 5 ° C lower than the temperature, and preferably 10 ° C higher temperature or lower, more preferably 8 ° C higher temperature or lower, still more preferably 6 ° C higher temperature or lower, even more preferably 5 ° C higher temperature or lower. The electrostatic charge image development according to <3>, which has the following step (3) after step <4> step (2) and before step (4): Of manufacturing toner.
Step (3): Step of adding an anionic surfactant having a polyethylene glycol moiety <5> In one or both of step (3) and step (4), an acid is added to adjust the pH at 25 ° C. to 5. 1 to 6.1, preferably 5.3 to 5.9, more preferably 5.3 to 5.7, and even more preferably 5.3 to 5.5, described in <3> or <4> A method for producing a toner for developing electrostatic images.

<6> The content of the anionic surfactant having a polyethylene glycol moiety is 1 to 20 parts by mass, preferably 1 to 10 parts by mass, more preferably 1 to 100 parts by mass with respect to 100 parts by mass of the resin. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <5>, which is 5 parts by mass, and more preferably 1.5 to 5 parts by mass.
<7> The method for producing a toner for developing an electrostatic charge image according to <6>, wherein the anionic surfactant having a polyethylene glycol moiety is an anionic surfactant represented by the general formula (1).
In the formula, R ¹ represents an alkyl group having 8 to 16 carbon atoms, n represents an average addition mole number of ethylene oxide and is 2 to 3, and M represents ammonium, tetraalkylammonium or an alkali metal.
<8> The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <7>, wherein the resin particles (A) contain an amorphous polyester (c).
<9> For electrostatic image development according to any one of <3> to <8>, wherein the volume-median particle size of the fused core-shell particles is equal to or less than the volume-median particle size of the aggregated particles (2). Toner manufacturing method.

<10> The resin particles (A) contain a crystalline polyester (a) having a melting point of 50 to 150 ° C, preferably 55 to 130 ° C, more preferably 60 to 90 ° C, and still more preferably 60 to 80 ° C. <1>-<9> The manufacturing method of the electrostatic image developing toner in any one of.
<11> The glass transition temperature of the amorphous polyester (b) is 50 to 80 ° C, preferably 50 to 70 ° C, more preferably 55 to 70 ° C, and further preferably 58 to 67 ° C. The method for producing a toner for developing an electrostatic charge image according to any one of <3> to <10>.
<12> Resin particles (A) contain crystalline polyester (a) and amorphous polyester (c), and resin particles (B) contain amorphous polyester (b), <1> to <11> The method for producing a toner for developing an electrostatic charge image according to any one of the above.
<13> The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <12>, wherein a post-treatment step is performed after the step (4) to isolate the core-shell particles to obtain toner particles.
<14> The content of the crystalline polyester (a) in the resin particles (A) is preferably 1 to 50% by mass, more preferably 5 to 40% by mass in the resin constituting the resin particles (A). The method for producing a toner for developing an electrostatic image according to any one of <1> to <13>, preferably 10 to 30% by mass, and more preferably 13 to 20% by mass.
<15> The toner particles have a circularity of 0.955 to 0.985, preferably 0.955 to 0.980, more preferably 0.964 to 0.980, <1> to <14>. A method for producing a toner for developing an electrostatic image according to any one of the above.
<16> The melting point of the crystalline polyester (a) is 60 to 90 ° C., and the glass transition temperature of the amorphous polyester (b) and the amorphous polyester (c) is preferably 50 to 80 ° C., more preferably The method for producing an electrostatic image developing toner according to any one of <1> to <15>, wherein the toner is 50 to 70 ° C, more preferably 55 to 70 ° C, and still more preferably 58 to 67 ° C.

<17> The crystalline polyester (a) has an acid component composed of an aliphatic dicarboxylic acid and an alcohol component composed of an aliphatic diol. The amorphous polyester (b) and the amorphous polyester (c) have an acid component. <1> to <16>, comprising at least two of terephthalic acid, fumaric acid, dodecenyl succinic acid and its acid anhydride, trimellitic acid and its acid anhydride, and the alcohol component is an aromatic diol A method for producing a toner for developing electrostatic images.
<18> The crystalline polyester (a) is composed of one or two acid components of sebacic acid and 1,12-dodecanedioic acid, and alcohol components of 1,6-hexanediol and 1,9-nonanediol. Amorphous polyester (b) and amorphous polyester (c) are composed of one or two kinds, and the acid component is terephthalic acid, fumaric acid, dodecenyl succinic acid and its acid anhydride, trimellitic acid and its acid anhydride The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <17>, wherein the alcohol component is an aromatic diol.
<19> The crystalline polyester (a) has a softening point of 60 to 85 ° C., and the softening points of the amorphous polyester (b) and the amorphous polyester (c) are 70 to 165 ° C., preferably 80 to 140 ° C. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <18>, wherein the toner is at 90 ° C., more preferably 90 to 135 ° C., and still more preferably 100 to 130 ° C.
<20> The crystalline polyester (a) has a number average molecular weight of 3,000 to 5,000, and the amorphous polyester (b) and the amorphous polyester (c) preferably have a number average molecular weight of 1, The electrostatic charge image developing toner according to any one of <1> to <19>, which is from 000 to 50,000, more preferably from 1,500 to 10,000, still more preferably from 2,000 to 8,000. Production method.
<21> The glass transition temperature of the resin particles (B) is 45 ° C. or higher, preferably 45 to 70 ° C., more preferably 50 to 70 ° C., and still more preferably 55 to 65 ° C. <1> to <20> The method for producing an electrostatic charge image developing toner according to any one of
<22> The temperature maintained in the step (4) is 5 ° C. or lower, preferably 7 ° C. or lower than the melting point of the crystalline polyester (a), preferably any one of <1> to <21> A method for producing the toner for developing an electrostatic image according to claim 1.

<23> The temperature maintained in the step (4) is not less than a temperature 5 ° C. lower than the glass transition temperature of the resin particles (B) and not more than 10 ° C. higher than the glass transition temperature, <1> to <22 The method for producing a toner for developing an electrostatic charge image according to any one of the above.
<24> The temperature maintained in the step (4) is 5 ° C. lower than the melting point of the release agent, preferably 7 ° C. or lower, more preferably 10 ° C. or lower, <1> to <23 The method for producing a toner for developing an electrostatic charge image according to any one of the above.
<25> The temperature maintained in the step (4) is preferably 55 to 70 ° C, more preferably 57 to 67 ° C, and still more preferably 58 to 65 ° C, and any one of <1> to <24> A method for producing the toner for developing an electrostatic image according to claim 1.
<26> The time held in the step (4) is preferably 1 to 24 hours, more preferably 1 to 18 hours, and further preferably 2 to 12 hours, <1> to <25> A method for producing the toner for developing an electrostatic image according to claim 1.
<27> A toner for developing an electrostatic image obtained by the production method according to any one of <1> to <26>.

  Each property value of polyester, resin particles, toner, etc. was measured and evaluated by the following method.

[Polyester softening point, crystallinity index, melting point and glass transition temperature]
(1) Softening point Using a flow tester (manufactured by Shimadzu Corporation, trade name: CFT-500D), 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) Crystallinity index Using a differential scanning calorimeter (manufactured by PerkinElmer, trade name: Pyris 6 DSC), a sample cooled from room temperature (25 ° C.) to 0 ° C. at a temperature lowering rate of 50 ° C./min is left still for 1 minute. Then, the temperature was raised to 180 ° C. at a temperature raising rate of 10 ° C./min. Among the observed peaks, the temperature of the peak with the largest peak area is defined as the endothermic maximum peak temperature (1), and the crystal is expressed by (softening point (° C)) / (maximum endothermic peak temperature (1) (° C)). The sex index was determined.
(3) Melting point and glass transition temperature Sample heated to 200 ° C. using a differential scanning calorimeter (PerkinElmer, trade name: Pyris 6 DSC), and cooled to 0 ° C. at a cooling rate of 50 ° C./min. Was measured at a heating rate of 10 ° C./min. Among the observed endothermic peaks, the temperature of the peak having the maximum peak area was defined as the maximum endothermic temperature (2). In the case of crystalline polyester, the peak temperature was taken as the melting point. In the case of an amorphous polyester, when an endothermic peak is observed, the temperature of the peak is measured, and when a step is observed without a peak being observed, the tangent indicating the maximum slope of the curve of the step and the step The temperature of the intersection with the extended line of the base line on the high temperature side was taken as the glass transition temperature.

[Glass Transition Temperature of Resin Particle (B) Containing Amorphous Polyester (b)]
When measuring glass transition temperature about resin particle (B), the solvent was removed from the resin particle (B) dispersion by freeze-drying, and the obtained solid was measured by the above method.
The freeze-drying of the resin particle (B) dispersion is carried out using a freeze dryer (manufactured by Tokyo Rika Kikai Co., Ltd., trade names: FDU-2100 and DRC-1000), and 30 g of the resin particle (B) dispersion at −25 ° C. For 1 hour, at -10 ° C for 10 hours and at 25 ° C for 4 hours, and dried until the water content was 1% by mass or less. The moisture content was measured using an infrared moisture meter (trade name: FD-230, manufactured by Kett Science Laboratory Co., Ltd.) for a 5 g sample after drying, a drying temperature of 150 ° C., and a measurement mode 96 (monitoring time 2.5 minutes / variation). Width 0.05%).
The method for measuring the glass transition temperature was the same as the method for measuring the glass transition temperature of polyester.

[Number average molecular weight of polyester]
The molecular weight distribution was measured by gel permeation chromatography and the number average molecular weight was calculated by the following method.
(1) Preparation of sample solution Polyester was dissolved in chloroform so that the concentration was 0.5 g / 100 ml. Subsequently, this solution was filtered using a fluororesin filter having a pore size of 2 μm (trade name: FP-200, manufactured by Sumitomo Electric Industries, Ltd.) to remove insoluble components to obtain a sample solution.
(2) Molecular weight distribution measurement Chloroform was flowed as an eluent at a flow rate of 1 ml / min, and the column was stabilized in a constant temperature bath at 40 ° C. 200 μl of the sample solution was injected there for measurement. The molecular weight of the sample was calculated based on a calibration curve prepared in advance. The calibration curve at this time shows several types of monodisperse polystyrene (monodisperse polystyrene manufactured by Tosoh Corporation; molecular weights 1.11 × 10 ⁶ , 3.97 × 10 ⁵ , 1.89 × 10 ⁵ , 9.89 × 10 ^4. 1.71 × 10 ⁴ , 9.49 × 10 ³ , 5.87 × 10 ³ , 1.01 × 10 ³ , 5.00 × 10 ² ) were used as standard samples.
Measuring apparatus: HPLC LC-9130NEXT (trade name, manufactured by Nippon Analytical Industrial Co., Ltd.)
Analytical column: JAIGEL-2.5-HA + JAIGEL-MH-A (both trade names, manufactured by Nippon Analytical Industrial Co., Ltd.)

[Acid value of polyester]
It measured according to JIS K0070. However, the measurement solvent was chloroform.

[Volume Median Particle Size (D ₅₀ ) and CV Value of Resin Particles, Release Agent Particles]
(1) Measuring apparatus: Laser diffraction type particle size measuring instrument (manufactured by Horiba, Ltd., trade name: LA-920)
(2) Measurement conditions: Distilled water was added to the measurement cell, and the volume-median particle size (D ₅₀ ) was measured at a temperature at which the absorbance falls within an appropriate range. The CV value was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume median particle size) × 100

[Solid content concentration of resin particle dispersion]
Using an infrared moisture meter (FD-230), 5 g of the resin particle dispersion was measured at a drying temperature of 150 ° C. in a measurement mode 96 (monitoring time 2.5 minutes / variation width 0.05%). The solid content concentration was calculated according to the following formula.
Solid content concentration (% by mass) = 100-M
M: moisture (%) = [(W−W ₀ ) / W] × 100
W: Sample mass before measurement (initial sample mass)
W ₀ : Mass of sample after measurement (absolute dry mass)

[Moisture content after drying of toner particles]
The moisture content of the toner particles after drying was determined by using an infrared moisture meter (trade name: FD-230, manufactured by Kett Science Laboratory Co., Ltd.), drying the sample 5 g, drying temperature 150 ° C. and measurement mode 96 (monitoring time 2 .5 minutes / range of fluctuation 0.05%).

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

[Circularity of aggregated particles and toner particles]
-Preparation of dispersion: The dispersion of aggregated particles was diluted with deionized water so that the concentration of aggregated particles was 0.001 to 0.05% as a sample dispersion. The toner particle dispersion was prepared by adding 50 mg of toner particles to 5 ml of 5% by weight polyoxyethylene lauryl ether (trade name: Emulgen 109P, manufactured by Kao Corporation) and dispersing the mixture for 1 minute with an ultrasonic disperser. Then, 20 ml of distilled water was added and further dispersed with an ultrasonic disperser for 1 minute to obtain a dispersion of toner particles.
Measuring device: Flow-type particle image analyzer (manufactured by Sysmex Corporation, trade name: FPIA-3000)
・ Measurement mode: HPF measurement mode

[BET specific surface area of toner particles]
A BET specific surface area was measured under the following conditions using Micromeritics FlowSorbIII (trade name, manufactured by Shimadzu Corporation).
-Toner particle sample amount: 0.09 to 0.11 g
・ Deaeration condition: 40 ° C., 10 minutes ・ Adsorption gas: Nitrogen gas

[PH of the dispersion of aggregated particles (2) at 25 ° C.]
After taking 15 g to 25 g of the dispersion into a sample bottle with an internal volume of 50 ml, gradually cooling to 25 ° C., and stirring the dispersion, using a pH meter (trade name: Seven Go pH meter SG2 manufactured by METTLER TOLEDO). The pH was measured at 25 ° C.

[Evaluation of low-temperature fixability of toner]
Using a commercially available printer (trade name: Microline 5400, manufactured by Fuji Xerox Co., Ltd., J paper A4 size), the toner adhesion amount on the paper is 0.42 to 0.48 mg / cm ² . The resulting solid image was output without being fixed at a length of 50 mm, leaving a margin of 5 mm from the top edge of the A4 paper.
Next, the same printer with a variable temperature fixing device was prepared. The temperature of the fixing device was set to 100 ° C., and fixing was performed at a speed of 1.5 seconds per sheet in the A4 longitudinal direction to obtain a printed matter.
In the same manner, the temperature of the fixing device was increased by 5 ° C., and the fixing was performed to obtain a printed matter.
500 g of a mending tape (product name: Scotch Mending Tape 810, width 18 mm) cut to a length of 50 mm is lightly pasted from the margin at the top of the printed image to a solid image. A weight was placed and pressed once back and forth at a speed of 10 mm / sec. Thereafter, the affixed tape was peeled off from the lower end side at a peeling angle of 180 degrees and at a speed of 10 mm / sec to obtain a printed matter after the tape was peeled off. Thirty sheets of high-quality paper (Oki Data Co., Ltd., Excellent White Paper A4 size) are placed under the printed material before tape application and after peeling, and the reflected image density of the fixed image before tape application and after peeling is measured. Measurement was performed using a colorimeter (manufactured by GretagMacbeth, trade name: SpectroEye, light emission condition; standard light source D ₅₀ , observation field of view 2 °, density reference DINNB, absolute white reference), and the fixing ratio was calculated from the following formula. .
Fixing rate = (reflected image density after peeling tape / reflected image density before applying tape) × 100
The temperature at which the fixing rate was 90% or more was defined as the minimum fixing temperature. The lower the minimum fixing temperature, the better the low-temperature fixing property.

[Evaluation of heat-resistant storage stability of toner]
20 g of toner was put in a wide-mouthed polybin having an internal volume of 100 ml, sealed, and allowed to stand for 48 hours in an environment at a temperature of 53 ° C. Thereafter, it was allowed to stand for 12 hours or more while being sealed at a temperature of 25 ° C. and cooled. Next, a sieve having a mesh size of 250 μm was set on a powder tester (made by Hosokawa Micron Corporation, trade name), and 20 g of the toner was placed thereon, and the mixture was vibrated for 30 seconds, and the amount of toner remaining on the sieve was measured. . The smaller the value, the better the heat resistant storage stability of the toner.

[Toner scattering evaluation method]
The following operations were all performed in an environment of room temperature (25 ° C.) and a relative humidity of 50%. First, 0.7 g of toner and 9.3 g of a silicone ferrite carrier (manufactured by Kanto Denka Kogyo Co., Ltd., average particle size: 40 μm) are placed in a cylindrical polypropylene bottle (Nikko Co., Ltd.) having an internal volume of 20 ml, 10 times vertically and horizontally. Shake and stir. Then, it stirred for 10 minutes with the ball mill.
An external developing roller apparatus in which a developing roller (42 mm in diameter) mounted on a commercially available printer (Oki Data Corporation, trade name: Microline 5400) was taken out and remodeled to be rotatable was used. The developing roller of the external developing roller device was rotated at a speed of 10 revolutions / minute, and the developer (mixture of toner and silicone ferrite carrier) was adhered onto the developing roller. After uniformly attaching, the rotation was once stopped. The rotation number of the developing roller was changed to 45 rotations / minute, and the number of scattered toner particles when rotated for 1 minute was measured with a digital dust meter (manufactured by Shibata Kagaku, model: P-5).
The toner scattering property was evaluated from the number of scattered toner particles. The scattering property is better as the number of scattered toner particles is smaller, indicating that toner scattering is suppressed.

[Production of polyester]
Production Example 1
(Production of crystalline polyester X1)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, and 3936 g of 1,9-nonanediol and 4848 g of sebacic acid were added. While stirring, the temperature was raised to 140 ° C., maintained at 140 ° C. for 3 hours, and then heated from 140 ° C. to 200 ° C. over 10 hours. Thereafter, 50 g of di (2-ethylhexanoic acid) tin was added, and the mixture was further maintained at 200 ° C. for 1 hour. Then, the pressure in the flask was lowered and maintained at 8.3 kPa for 4 hours to obtain crystalline polyester X1. . Table 1 shows the softening point, crystallinity index, melting point, number average molecular weight, and acid value of the obtained crystalline polyester X1.

Production Example 2
(Production of crystalline polyester X2)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, and 2419 g of 1,6-hexanediol and 4957 g of 1,12-dodecanedioic acid were added. While stirring, the temperature was raised to 140 ° C., maintained at 140 ° C. for 3 hours, and then heated from 140 ° C. to 200 ° C. over 10 hours. Thereafter, 30 g of di (2-ethylhexanoic acid) tin was added, and the mixture was further maintained at 200 ° C. for 1 hour. Then, the pressure in the flask was lowered and maintained at 8.3 kPa for 3 hours to obtain crystalline polyester X2. . Table 1 shows the softening point, crystallinity index, melting point, number average molecular weight, and acid value of the obtained crystalline polyester X2.

Production Example 3
(Production of amorphous polyester Y1)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 3322 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, Polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane (31 g), terephthalic acid (662 g) and dibutyltin oxide (10 g) were added, and the temperature was raised to 230 ° C. with stirring in a nitrogen atmosphere. After maintaining the time, the pressure in the flask was further lowered and maintained at 8.0 kPa for 1 hour. After returning to atmospheric pressure, the mixture was cooled to 190 ° C., 685 g of fumaric acid and 0.49 g of tert-butylcatechol were added, maintained at 190 ° C. for 1 hour, and then heated to 210 ° C. over 2 hours. Further, the pressure in the flask was lowered and maintained at 8.0 kPa for 4 hours to obtain amorphous polyester Y1. Table 1 shows the softening point, crystallinity index, glass transition temperature, number average molecular weight, and acid value of the obtained amorphous polyester Y1.

Production Example 4
(Production of amorphous polyester Y2)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 1750 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, A nitrogen atmosphere containing 1625 g of polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, 1145 g of terephthalic acid, 161 g of dodecenyl succinic anhydride, 480 g of trimellitic anhydride, and 10 g of dibutyltin oxide Under stirring, the temperature was raised to 220 ° C. and maintained at 220 ° C. for 5 hours. After confirming that the softening point had reached 120 ° C., the temperature was lowered to stop the reaction, and amorphous polyester Y2 was Obtained. Table 1 shows the softening point, crystallinity index, glass transition temperature, number average molecular weight, and acid value of the obtained amorphous polyester Y2.

Production Example 5
(Production of amorphous polyester Y3)
The inside of the four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 3004 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 996 g of fumaric acid, 2 g of tert-butylcatechol and 8 g of dibutyltin oxide were added, heated to 210 ° C. over 5 hours with stirring in a nitrogen atmosphere, held at 210 ° C. for 2 hours, and then at 8.3 kPa. The amorphous polyester Y3 was obtained by reacting until the desired softening point was reached. Table 1 shows the softening point, crystallinity index, glass transition temperature, number average molecular weight, and acid value of the obtained amorphous polyester Y3.

[Production of resin particles and release agent particles]
Production Example 6
(Preparation of resin particle (A-1) dispersion)
In a flask equipped with a stirrer, 90 g of crystalline polyester X1, 300 g of amorphous polyester Y1, 210 g of amorphous polyester Y2, 45 g of copper phthalocyanine pigment (trade name: ECB301, manufactured by Dainichi Seika Kogyo Co., Ltd.), polyoxyethylene oleyl Ether (nonionic surfactant, trade name: Emulgen 150, manufactured by Kao Corporation) 8.5 g, 15% by weight sodium dodecylbenzenesulfonate aqueous solution (anionic surfactant, trade name: Neoperex G-15, Kao Corporation) 80 g and 5 mass% aqueous potassium hydroxide solution (266 g) were added, and the mixture was heated to 98 ° C. with melting and melted, and mixed at 98 ° C. for 2 hours to obtain a resin mixture.
Next, 1116 g of deionized water was added dropwise at a rate of 6 g / min while stirring to obtain an emulsion. Next, the obtained emulsion was cooled to 25 ° C., and a dispersion of resin particles (A-1) was obtained through a 200 mesh (mesh 105 μm) wire mesh. Table 2 shows the solid content concentration of the obtained resin particle (A-1) dispersion, the volume median particle size of the resin particle (A-1), and the CV value.

Production Example 7
(Preparation of resin particle (A-2) dispersion)
In a flask equipped with a stirrer, 90 g of crystalline polyester X2, 300 g of amorphous polyester Y1, 210 g of amorphous polyester Y2, 45 g of copper phthalocyanine pigment (trade name: ECB301, manufactured by Dainichi Seika Kogyo Co., Ltd.), polyoxyethylene oleyl Ether (nonionic surfactant, trade name: Emulgen 150, manufactured by Kao Corporation) 8.5 g, 15% by weight sodium dodecylbenzenesulfonate aqueous solution (anionic surfactant, trade name: Neoperex G-15, Kao Corporation) 80 g and 5 mass% aqueous potassium hydroxide solution 274 g were added, heated to 98 ° C. with melting and melted, and mixed at 98 ° C. for 2 hours to obtain a resin mixture.
Next, 1109 g of deionized water was added dropwise at a rate of 6 g / min while stirring to obtain an emulsion. Next, the obtained emulsion was cooled to 25 ° C., and a dispersion of resin particles (A-2) was obtained through a 200 mesh (mesh 105 μm) wire mesh. Table 2 shows the solid content concentration of the obtained resin particle (A-2) dispersion, the volume median particle size and the CV value of the resin particle (A-2).

Production Example 8
(Preparation of resin particle (B-1) dispersion)
In a flask equipped with a stirrer, 390 g of amorphous polyester Y1, 210 g of amorphous polyester Y2, 6 g of polyoxyethylene lauryl ether (nonionic surfactant, trade name: Emulgen 430, manufactured by Kao Corporation), 15% by mass dodecyl 40 g of sodium benzenesulfonate aqueous solution (anionic surfactant, trade name: Neoperex G-15, manufactured by Kao Corporation) and 268 g of 5% by mass potassium hydroxide are added, and the mixture is heated to 95 ° C. and melted with stirring. The mixture was mixed at 95 ° C. for 2 hours to obtain a resin mixture.
Next, 1145 g of deionized water was added dropwise at a rate of 6 g / min while stirring to obtain an emulsion. Next, the obtained emulsion was cooled to 25 ° C., passed through a 200-mesh wire mesh, deionized water was added to adjust the solid content to 23.5% by mass, and the resin particles (B-1) A dispersion was obtained. Table 2 shows the solid content concentration of the obtained resin particle (B-1) dispersion, the volume median particle size of the resin particle (B-1), and the CV value.

Production Example 9
(Preparation of resin particle (B-2) dispersion)
In a flask equipped with a stirrer, 600 g of amorphous polyester Y3, 6 g of polyoxyethylene lauryl ether (nonionic surfactant, trade name: Emulgen 430, manufactured by Kao Corporation), 15% by mass aqueous sodium dodecylbenzenesulfonate (anion) Surfactant, trade name: Neoperex G-15, manufactured by Kao Corporation) 40 g and 5 mass% potassium hydroxide 247 g are added, and the mixture is heated to 95 ° C. and melted with stirring, at 95 ° C. for 2 hours. By mixing, a resin mixture was obtained.
Next, 1165 g of deionized water was added dropwise at a rate of 6 g / min while stirring to obtain an emulsion. Next, the obtained emulsion was cooled to 25 ° C., passed through a 200-mesh wire mesh, deionized water was added, the solid content was adjusted to 23.5 mass%, and the resin particles (B-2) A dispersion was obtained. Table 2 shows the solid content concentration of the obtained resin particle (B-2) dispersion, the volume median particle size and the CV value of the resin particle (B-2).

Production Example 10
(Production of release agent particle dispersion)
In a beaker having an internal volume of 1 liter, 480 g of deionized water, 4.29 g of alkenyl (mixture of hexadecenyl group and octadecenyl group) dipotassium succinate (trade name: Latemul ASK, Kao Corporation, effective concentration 28% by mass), and carnauba wax 120 g (manufactured by Kato Yoko Co., Ltd., melting point 85 ° C., acid value 5 mg KOH / g) was added and stirred. While maintaining the mixed liquid at 90 to 95 ° C., using an ultrasonic disperser (trade name: Ultrasonic Homogenizer 600W, manufactured by Nippon Seiki Seisakusho Co., Ltd.) for 30 minutes, the mixture was cooled to 25 ° C., Deionized water was added to adjust the solid content to 20% by mass to obtain a release agent particle dispersion. The volume median particle size of the release agent particles was 0.494 μm, and the CV value was 34%.

[Production of toner]
Example 1
(Preparation of Toner 1)
<Step (1): Production of Aggregated Particle (1)>
200 g of resin particle (A-1) dispersion, 53.9 g of deionized water, and 34 g of release agent particle dispersion were added to a 3 l four-necked flask equipped with a dehydration tube, a stirrer and a thermocouple at a temperature. Mixed at 25 ° C. Next, while stirring the mixture, an aqueous solution in which 17 g of ammonium sulfate was dissolved in 175 g of deionized water was added dropwise at 25 ° C. over 5 minutes, and then the temperature was raised to 55 ° C. so that the volume median particle size of the aggregated particles was 4 It was kept at 55 ° C. until it became 3 μm to obtain aggregated particles (1).
<Step (2): Production of Aggregated Particle (2)>
33 g of deionized water was added to the dispersion (total amount) of the aggregated particles (1) obtained in step (1), and the temperature of the dispersion of aggregated particles (1) was cooled to 49 ° C. Next, while increasing the temperature of the dispersion at 49 ° C. at a rate of 1.6 ° C. per hour, 127 g of the dispersion of resin particles (B-1) is dropped at a rate of 0.5 ml per minute to obtain the aggregated particles (2). Obtained. Table 3 shows the volume-median particle size, circularity, and pH of the dispersion of the obtained aggregated particles (2). Moreover, the temperature of the dispersion liquid after completion | finish of dripping was 57 degreeC.
<Step (3): Addition of surfactant to dispersion of aggregated particles (2) and adjustment of pH>
To the dispersion (total amount) of the aggregated particles (2) obtained in the step (2), an aqueous solution of polyoxyethylene (2) sodium lauryl ether sulfate (anionic surfactant, trade name: EMAL E-) at 57 ° C. 27C, manufactured by Kao Corporation, solid content 27% by mass, average added mole number of ethylene oxide 2) 10.2 g and an aqueous solution mixed with 2284 g of deionized water were added. Thereafter, 2.0 N sulfuric acid was added so that the pH at 25 ° C. was 5.3.
<Process (4): Fusion process of aggregated particles (2)>
The dispersion liquid of the aggregated particles (2) whose pH was adjusted in the step (3) was heated to 65 ° C., held at 65 ° C. for 3 hours, and the particles were fused to obtain core-shell particles.
<Post-processing process>
Next, the dispersion is cooled to 25 ° C., and the solid content is separated by suction filtration while being kept at 25 ° C., washed with deionized water, and then placed in a vacuum low-temperature dryer (ADVANTEC Toyo Co., Ltd., model name: DRV622DA). And dried at 33 ° C. to obtain toner particles (moisture content of 0.5% or less after drying). Table 3 shows the circularity, volume median particle size, and BET specific surface area of the obtained toner particles. 100 parts by weight of the toner particles, 2.5 parts by weight of hydrophobic silica (trade name: RY50, manufactured by Nippon Aerosil Co., Ltd., average particle size: 0.04 μm), and hydrophobic silica (trade name: Cabo Seal TS720, manufactured by Cabot Corporation) Toner 1 was obtained by putting 1.0 part by mass of (average particle diameter; 0.012 μm) into a Henschel mixer, stirring, and passing through a 150-mesh sieve. Table 3 shows the performance of the obtained toner.

Example 2
(Preparation of Toner 2)
Toner 2 was produced in the same manner as in Example 1 except that sulfuric acid was added so that the pH in step (3) was 5.9. Table 3 shows the physical properties of the obtained aggregated particles (2) and toner particles, and the performance of the toner.

Example 3
(Preparation of Toner 3)
Toner 3 was prepared in the same manner as in Example 1 except that sulfuric acid was added so that the pH in step (3) was 5.2. Table 3 shows the physical properties and toner performance of the obtained aggregated particles (2) and toner particles.

Example 4
(Preparation of Toner 4)
In the step (3), an aqueous surfactant solution to be added is a polyoxyethylene (3) sodium lauryl ether sulfate aqueous solution (anionic surfactant, trade name: EMAL 20C, manufactured by Kao Corporation, solid content 25% by mass, ethylene oxide Toner 4 was prepared in the same manner as in Example 1 except that the aqueous solution was a mixture of 11.0 g of average added mole number 3) of 11.0 g and 2284 g of deionized water. Table 3 shows the physical properties and toner performance of the obtained aggregated particles (2) and toner particles.

Example 5
(Preparation of Toner 5)
Toner 5 was produced in the same manner as in Example 4 except that sulfuric acid was added so that the pH in step (3) was 5.9. Table 3 shows the physical properties and toner performance of the obtained aggregated particles (2) and toner particles.

Example 6
(Production of Toner 6)
Toner 6 was produced in the same manner as in Example 4 except that sulfuric acid was added so that the pH in step (3) was 5.2. Table 3 shows the physical properties and toner performance of the obtained aggregated particles (2) and toner particles.

Example 7
(Preparation of Toner 7)
A toner 7 was produced in the same manner as in Example 1 except that the steps (3) and (4) were changed as follows.
<Step (3): Addition of Surfactant to Aggregated Particle (2) Dispersion>
To the dispersion (total amount) of the aggregated particles (2) obtained in the step (2), an aqueous solution of polyoxyethylene (2) sodium lauryl ether sulfate (anionic surfactant, trade name: EMAL E-) at 57 ° C. 27C, manufactured by Kao Corporation, solid content 27 mass%) 10.2 g and an aqueous solution mixed with 2284 g of deionized water were added.
<Process (4): Fusion process of aggregated particles (2)>
The dispersion of the aggregated particles (2) obtained in the step (3) is heated to 65 ° C. and held at 65 ° C. for 1 hour, and then 2.0 N so that the pH at 25 ° C. becomes 5.3. Prepared by adding sulfuric acid. Thereafter, the particles were held at 65 ° C. for 2 hours to fuse the particles to obtain core-shell particles.
Table 3 shows the physical properties and toner performance of the obtained aggregated particles (2) and toner particles.

Example 8
(Production of Toner 8)
In the step (3), the addition amount of polyoxyethylene (2) sodium lauryl ether sulfate aqueous solution (anionic surfactant, trade name: EMAL E-27C, manufactured by Kao Corporation, solid content: 27% by mass) to 16.6 g A toner 8 was produced in the same manner as in Example 1 except for the change. Table 3 shows the physical properties and toner performance of the obtained aggregated particles (2) and toner particles.

Example 9
(Preparation of Toner 9)
In step (3), the amount of polyoxyethylene (2) sodium lauryl ether sulfate aqueous solution (anionic surfactant, trade name: EMAL E-27C, manufactured by Kao Corporation, solid content 27 mass%) added to 5.5 g A toner 9 was produced in the same manner as in Example 1 except for the change. Table 3 shows the physical properties and toner performance of the obtained aggregated particles (2) and toner particles.

Example 10
(Production of Toner 10)
Toner 10 was produced in the same manner as in Example 1, except that the dispersion of resin particles (A-1) used was changed to a dispersion of resin particles (A-2) in step (1). Table 3 shows the physical properties and toner performance of the obtained aggregated particles (2) and toner particles.

Example 11
(Production of Toner 11)
Toner 11 was produced in the same manner as in Example 1 except that in the step (2), the dispersion of resin particles (B-1) to be used was changed to a dispersion of resin particles (B-2). Table 3 shows the physical properties and toner performance of the obtained aggregated particles (2) and toner particles.

Comparative Example 1
(Preparation of Toner 12)
Toner 12 was produced in the same manner as in Example 1 except that sulfuric acid was added so that the pH in step (3) was 5.0. Table 4 shows the physical properties and toner performance of the obtained aggregated particles (2) and toner particles.

Comparative Example 2
(Preparation of Toner 13)
Toner 13 was produced in the same manner as in Example 1 except that sulfuric acid was added so that the pH in step (3) was 6.2. Table 4 shows the physical properties and toner performance of the obtained aggregated particles (2) and toner particles.

Comparative Example 3
(Preparation of Toner 14)
In the step (3), 2.8 g of an aqueous surfactant solution to be added was mixed with 2.8 g of sodium lauryl sulfate (anionic surfactant, trade name: EMAL 0, manufactured by Kao Corporation, solid content: 100% by mass) and 2284 g of deionized water. A toner 14 was produced in the same manner as in Example 1 except that the aqueous solution was used. Table 4 shows the physical properties and toner performance of the obtained aggregated particles (2) and toner particles.

Comparative Example 4
(Preparation of Toner 15)
In the step (3), the surfactant aqueous solution to be added is dehydrated with 18.4 g of sodium dodecylbenzenesulfonate aqueous solution (anionic surfactant, trade name: Neoperex G-15, manufactured by Kao Corporation, solid content 15 mass%). Toner 15 was produced in the same manner as in Example 1 except that the aqueous solution was mixed with 2284 g of ionic water. Table 4 shows the physical properties and toner performance of the obtained aggregated particles (2) and toner particles.

Comparative Example 5
(Production of Toner 16)
In step (3), the surfactant aqueous solution to be added was deionized with 5.5 g of sodium alkyldiphenyl ether disulfonate aqueous solution (anionic surfactant, trade name: Perex SS-H, manufactured by Kao Corporation, solid content 50 mass%). Toner 16 was produced in the same manner as in Example 1 except that the aqueous solution was mixed with 2284 g of water. Table 4 shows the physical properties and toner performance of the obtained aggregated particles (2) and toner particles.

  From Tables 3 and 4, the electrostatic charge image developing toners of Examples 1 to 11 are all low temperature fixability, heat resistant storage stability, and toner scattering compared to the electrostatic charge image developing toners of Comparative Examples 1 to 5. It turns out that it is excellent in all of suppression of.

  The toner for developing an electrostatic image obtained by the production method of the present invention has the characteristics that both good low-temperature fixability and heat-resistant storage stability and toner scattering are small, so that it is electrophotographic, electrostatic recording, electrostatic It can be suitably used as a toner for developing an electrostatic charge image used in a printing method. According to the method of the present invention, a toner having such characteristics can be produced efficiently.

Claims (10)

25 ° C. of an aqueous mixed solution containing aggregated particles containing resin particles (A) and release agent particles, and an anionic surfactant having a polyethylene glycol moiety having an average addition mole number of ethylene oxide of 1 to less than 8. A method for producing a toner for developing an electrostatic charge image, comprising the step of fusing the aggregated particles in the aqueous mixed solution under the pH after and / or while adjusting the pH in the solution to 5.1 to 6.1 Because
The aggregated particles are aggregated particles (2) obtained by the following steps (1) and (2),
A method for producing a toner for developing an electrostatic charge image, wherein the step of fusing the aggregated particles is the following step (4).
Step (1): Step of obtaining the aggregated particles (1) by mixing the resin particles (A), the release agent particles and the flocculant in an aqueous medium.
Step (2): A step of adding the resin particles (B) containing the amorphous polyester (b) to the aggregated particles (1) obtained in the step (1) to obtain the aggregated particles (2).
Step (4): The agglomerated particles (2) are held at a temperature not lower than 10 ° C lower than the glass transition temperature of the amorphous polyester (b) and not higher than 10 ° C higher than the glass transition temperature. Process for obtaining attached core-shell particles After step (2), before the step (4), comprises the following steps (3) The method of manufacturing a toner according to claim 1.
Step (3): Step of adding an anionic surfactant having the polyethylene glycol moiety The toner for developing an electrostatic charge image according to claim 1 or 2 , wherein an acid is added to adjust pH at 25 ° C to 5.1 to 6.1 in one or both of step (3) and step (4). Manufacturing method. The electrostatic image development according to any one of claims 1 to 3 , wherein the content of the anionic surfactant having a polyethylene glycol moiety is 1 to 5 parts by mass with respect to 100 parts by mass of the resin in the aggregated particles. Toner manufacturing method. The average addition mole number of ethylene oxide contains an anionic surfactant having a polyethylene glycol moiety is less than 5 1 or claim 1 manufacturing method of the electrostatic image developing toner according to any one of 4. Anionic surfactants having the polyethylene glycol moiety is an anionic surfactant represented by the following general formula (1), the production method of the toner according to any one of claims 1 to 5 .

(In the formula, R ¹ represents an alkyl group having 8 to 16 carbon atoms, n represents an average added mole number of ethylene oxide and is 2 to 3, and M represents ammonium, tetraalkylammonium or an alkali metal.) The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 6 , wherein the resin particles (A) contain an amorphous polyester (c). The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 7 , wherein a volume median particle size of the fused core-shell particles is equal to or less than a volume median particle size of the aggregated particles (2). The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 8 , wherein the resin particles (A) contain a crystalline polyester (a) having a melting point of 60C to 90C. The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 9 , wherein the amorphous polyester (b) has a glass transition temperature of 50 to 70 ° C.